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Semiconductor Physics

and Applications

M. BALKANSKI
Universite Pierre et Maire Curie
Paris, France

and

R. F. WALLIS
University of Cal(fornia
Irvine , Cal(fornia, USA

OXFORD
U NIVERSITY PRESS
OXFORD
Nl\ER TT Y 'RESS
~rc:tl I.H~n
I n Stree t. Oxford OX2 hDP

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Balkawki, Minko, 1927-
Semiconductor physics and a pplications/ M. Bal.kanski 'llld R.F. Wallis.
p. em.
Includes bibliographical references and imlex.
I. Semlc nductors. I. Walli . R. F. (RiclnrJ Fisher). 1924-11. Titk. Ill . ri'S.

QC611 . BJ SS 2000 537.6'22 -ck21 ll0-03~4Sl

ISBN 0 ll) :-151741 h Hardback


ISBN 0 19 51740 to: Paperback

Types~l hy N~:wgen lmagin" S '. . , p . . .


Printed in 1-••. 1t 8 .· 1 · "' )stuns ( l Ltd. l hl' llll<ll, Imkt
~· 11 am
un acid-free paper hv •
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~ .>,I l
Preface

In. rec_e nt . ears thcr' have been rem a rka bl , dva nccs in hi gh I
thd I have I cvoluttOnrzcJ telccommunica tions. c ffi!)Uting ~d . ~elm . logy
'>l nge~
and 'e·~t -· . 1 0 ·
r Ieva . evrccs such a field IT t .. · ,. n tn 1· . rn at1on
. . 't , . ·,. e cc t r ansi~tors . In tegra ted
~ "~u r ·.. ln~rc: o processors. and _electroma!'lnetic rauiation J tecto r~ a nd
~ m~_ttei . ::t v~ played key roles 111 this revolution . In large meas re the e
~ "' ctic:_ IM~ed u pon semrco nductor. as the active mate ri·'ll It .. h
fo re es. cntJal tor the furth er development of hi.oh techrlol ·c .th I re-
·k · e ogv at yo ung
wo t crs entcnng the field be well tra ined in the ph\/sics arld . ~- I' . f
- , ·, d ~ · J · c appieations
semiLOil udors and that an up-to-date well-writte n Lextb k ·
the-e t · b ·1 bl · · oo covenn o
s Opics e ava1 a e. It is our hope and intent ion that the presen~
v lume satisfies this need.
T he material included in thi s book falls in to two categories:
I. the basic physics o f semiconductors:
2. app_licatio~s ofsemi~onductors to practical devices with emphasis on the
baSIC physical pnnctp]es upon vv·hich the devices opera te.

The part on the basic p hysics starts with a discussion of the composit ion
and structure of semiconductors. Nex t come chapters on the basic theorv of
electronic energy bands and o n the detailed characteristics of energy ba~d
111 pure. bulk emiconductors. The effects of impurities on electronic state
are then discussed . Chapters on sem icond uctor statistics and lattice
vibrati o ns in semiconductors precede a chapter on charge-carrier scattering
and transport. In the next chapter the effects of surfaces on semiconductor
properties a re treated . Optical properties form the subject matter of
C hap ter l 0. The part o n basic physics concludes wit h a chapter on mag-
neto-optical phenomena a nd no nlinear electro-optical effects.
The part on applica tions is no t a n enti ty sepa rate from the part on basic
physics. The vario us a pplieu topics are accompa nied by references to the
basic topics to which they a rc most closely related. The first applied chapter
covers p- n junctio ns a nd their use as rectifiers and capacitors. Then fo llo\v
chapters on bipolar j unct io n tra nsistors a nd on semiconductor lasers and
other photodevices. The importance of semiconductor interfaces is
expanded upon in chapters o n the electro nic, lattice dynamical. optical. and
transpo rt pro perties of heterostructure. The book concluues \\ ith a
l:hapter on meta l-ox ide-sem icond uctor field effect tra nsistors ·;tnd one l)ll
device applications of heterostruc tu res.
This book is intended to serve as a textbook for a co urse Ln . mt-
conduc tor physics and applications at the advanced undergradm t .tnd
beginning graduate levels. It is assu med tha t the reader has comma nd 1.. fth~
basic material in qua ntum mecha nics. stat istical m d1an i c~. ami ekctn.-
m ag netic theory. It is desirable, but not cssenti·d. tha t th r ~td -r be
acquainted with elementary solid state physics. Example am1 \t.: IL'I · .tr ·
Preface

i• dud ,d t emphasize particular points and provide an apprecia~ion of the


m·tgnttu e 0 'the phy ical quantities encounte_red. Extensive use 1·· made of
'll!~res c enha nc: the clarity of the presentation and to establish contact
, 7th experimental r ·ulls. At the beginning of e~ch chapter there is a
ummary f kc. idea - dev loped in tha t chap~er. Thts su~mary enables the
_ der to get a quick impression of the rnatenal covered m the chapter and
1
he imp rtant qua lita tive re~ ult s. Problem sets appear at the ends of the
chaplet .
ln Tiling tbi · b k w have benefited from a number of prior works.
Thev indud lntro lucti 11 to Solid Stale Physic. · by C. KitteL Solid State
Pln,-· 1c by H. Ibach and H. Li.ith. Electronic Structure and the Properties of
Soiuls by W. A. Harris n, 'uney of Semiconductor Physics by K. W. Boer,
fntrolu ·fiou ro Applied Solid State Physics by R. Dalven, Semiconductor
Phy. ics by K. Se ge r, >miconducwrs by R. A. Smith. Ph_y·sique des Semi-
col/duel >w ·s er de 0111posants Electroniques by H. Mathieu, Physics and
Techno! y of Semi ·onduclor Devices by A. S. Grove. Physics of Semi-
t n lu l Or Devices by S. M. Sze, Fundamentals of Solid-State ElecTronics by
C.-T. Sah, Solid State Eleclronic Devices by B. G. Streetman. Quantum
Proces:es in Semiconductors by B. K. Ridley, Ware !vfechanics Applied To
Semiconductor Heteroslructures by G . Bastard, Quantum SemiconducTor
S!mc.:.fures by C. Weisbuch and B. Vinter, and Principles (~l Optics by
M . Born and E. Wolf.
Fina lly, the authors wish to express their appreciation to Jeannie
M . Brown ·whose diligence and patience in typing the manuscript made
possible the production of this volume.

Paris M.B.
Irvine R.F.W.
December 1999
Contents

1 Basic characteristics of semiconductors


1
1'.1 Qualitative J1rt1perties
1.2 Composition of semiconductors
2
1.3 Structure or solids
2
1.3. 1 Crystalline and a morphous rorms
2
1.3.2 Lallicc a nd hasis
3
1.3 .3 Bravai s lattices
3
1.3.4 Crystallographic terminology
5
1.3.5 Structures or semicond uctors
6
1.4 Chemical bonding in semiconduct o rs 10
1.4.1 Diamond structure semiconductors
10
1.4.2 Zincblcnde structure semiconductors
II
1.4.3 [IJ - VI layered semiconductors I)
1.4.4 Wurtzi te struet ure semiconductors 14
1.4.5
IV- VI semiconductors 14
1.5 Growth or pure semico nductor crystals 14
Problems 16
References 16

2 Electronic energy bands: basic theory 17


2. 1 Schr6dinger equation 18
I
"-·-
') Electrons in a periodic potential 20
2.3 Schrodinger equation for a periodic potential 22
2.4 Expansion of the eigenfunction in plane waves 24
r_)
2.5 Bloch 's theorem
2.6 Electrons in a weak periodic potential 26
28
'2.7 Brillouin zones
Energy bands and energy band gaps 30
v~
Tight binding method
35
2.9
35
2.9 . 1 Wannier fuJ1ctions
36
2.9.2 LC AO method
41
Problems
42
References

Electronic energy bands: semiconductors 43


3
-44
3.1 Spin--orbit interaction .
., iun interaction and pscudopotcntwb -+o
~ Electron
-+ l
3.2.1 Orthooonalizcd plane wave method
"' ..n
3.2 2 Pseudopotentialmcthod
Contents

L
m dft)n eke ron mtcracl i )11
3
54
1 .Hartre • mt:tbo
54
-:3:.2 !lartrec -Fod. mctho
si ty f unt.:tional me l d 55
. clled eke! r me st· tcs 57
57
.4 58
r. knee han 60
.ndudi n b.tn 62
tnchkndc tr ld ur cmiconductors 63
E ·tt:ndL(.l k p meth cl 64
onpnrabolic bands: the Ka ne model 65
66
3 )- Encrg_ band truct r f r r ific ·emiconductors
.5. 1 lementa l emi ' onductors 66
. -.2 Ill- Y emic nduct rs 67
II- VT and IV- VI emiconductors 68
3. dific·tti n nergy band gap 68
., .6.1 cmicondu t r alloys 68
3. ).2 Tempera ture and pressure dependence of
band gaps 69
3.7 Amorpho us semiconductors 70
Problems 71
References 71

4 Kinematics and dynamics of electrons and


holes in energy bands 73
4.1 Group velocity
4.2 Inverse effective mass tensor 75
4.3 Force equation 76
4.4 Dynamics of electrons 7
4.5 Dynamic of holes
4.6 Experimental determination of effective masses:
cyclotron re on::~nce in semiconductors
4.6.1 Cyclotron resonance of conduction lectrons
in Ge and Si 'I
4 ·6·2 ydotron resonance of ho les in Gc and Si
-'
4·6·3 Effe~tive masses of carriers in compound
scrntconductor ....
4 -7 ExpcrimL'nt·tl
. . ' dete rrnm
· <tl
. ton
·- ol·earner
. char!!;e :wd
LOnccntratt on: Hai l effect
Problems
References

5 Electronic effects 0 f . ..
'\ . . . 1mpur1hes
·1 Qu.dnat t v~.: as 11 . .1 . 1• .
'i 2 ·· . . l:l S L) llTI p ll I t IO:S
Ut cct t~.>L· 111' 1'>'> lhcury .
Cont nt

-. 1 onur rmpu r rl i · rn :, rnd JL

- ~ I l:: I il:c l nl ll t r~urclu i L1flstunt Lnu-u url.r c


'\ ' alk•) 1 rbn inter~rt.:t i 11 11
54
n 11 impuritrc · in Til emicondu\..lm<,
- . 'i
cceptnr impuriti c~
IJ
ell corrcc ti 111 a nd deq) leve l\
band '7
Pmhlems I} ,

References 9
99

6 Semiconductor statistics
101
6. I Intrin. ic cmiconductors
6. 1.1 Spherical parabolic energy ba nds 102
6.1 .2 Ellipsoida l energy hands 103
6.1.3 Multiple valence bands 106
6.2 Extrinsic semico nductors 107
6.2.1 Dono r impuritie. 109
I 10
6.2.2 Acceptor impurities
113
6.2.3 Compensa ted semiconductors
I 15
6.2.4 Majority and minority carriers
I 16
6.2.5 Contribution of excited impurity states
11 7
Problems
119
References
119

7 Lattice vibrations in semiconductors 121


7.1 Equations of motion 122
7.2 Monatomic linear chain 125
7. 3 Diatomic linear chain 126
7.4 Three-dimensional cry tals 129
7.4. 1 Elastic continuum theory 129
7.4.2 Three-dimensional lattices 131
7.5 Lattice dynamica l models for semiconductors I33
7.5.1 Homopolar semiconductors 134
7.5.2 Heteropolar semiconductors 135
7.5.3 First-principles methods 139
7.(i Normal coordinate transformation 140
7.7 Vibrational specific heal 141
7.'6 Anharmonic effect s 143
7.'6. I Thermal expansion 143
7.'6.2 Thermal co nducti vity 144
7 _9 Impurity effects on lattice vibrations 145
7. llJ Piezoelectric effects 14,'
7.11 Effects of stt-c ·s-induced atomic displacements 1-N
Problems ISO
Ref~:•rences 151
Contents

Charge carrier scattering and


153
transpor properties
.I impl· phcnnmcn 1 1 gica l introd uction to transpo rt
enm:oru.J u ·tors 154
1
~ 1.1 Ek tric c nd u ·ti n c rrent 154
1.2 c)
11 ludi\ it_ ..:rre uw ma::
157
.I.' D 1ffu t(n c rr nt 159
~U .4 Dis l<ll;cmcn t cun"'nl 160
, .l 1 '1: ._ ltzmann qu· tion a nd its .:;olution 161
L'J Flcdric;JI conJuctiVLLY c. nd mobility 163
, .4 En1ng) depend nee f the relaxation time 167
k.- R Ia ation t1 me r sp..:cific Tattering mechanisms 169
.S. l l 111i1ed impu rity scat tering 169
'. 5.2 'cutrn l imp urity . cal tering 174
'.: .3 Laltic vibntional scatlt:ring 174
Ma!!11et tran r rt pr pc r tie~ 186
.6. 1 Magnet rc. istance 186
'. ·- Hall ffe t 189
.7 Thermoelectric phenomena 192
8. 7.1 Thermoelectric pov.:er 192
8.7 .2 Thermoelectric device .. 194
8.8 Th rmal conducti vi ty 195
8.9 Semi-insulating semiconductors 196
8.9.1 Pure GaAs 196
8.9.2 Impure GaAs: shallow impurities 196
8.9.3 Impure G aAs: deep impurities 197
8.10 Hot carrier phenomena 198
8.10.1 Distribution function in high electric field s 198
8.10.2 Gunn effect 199
8.10.3 Field ionization ~00
8.10.4 Impact ionization 200
R.ll Variable-range hopping conductivitv 203
Problems ~ •
203
References
20~

9 Surface properties of semiconductors 205


9 .1 Surface eff'ect s o n e1ec·t.tome
· states
_ ~ l)
9.1.1 earl y rre" ..,., . t
9 I ., . . ~'" ec ron approximation 2011
. ·- Ttght bmchng method _I
9.2 Surfaccefi'cct · 0 11 1 . .
:s att~ec vtbratiot1 21:
~11 I S · .
·-· urtacc acou ' lic mod, . 21 .:'
9-, ') S . . . I.: S
·-· - Ut h~.:e opt teal modes
21 '
Y._ 3 Surt'a~.:c vibntion· I . .
__ I
Y.2.4 ·xne,-·,n 'I ,t modes tn real semil' unJu 't r:-.
,, · 1entu obsl' rv· · . .
'l . .ttwn lll surttl't'
, . \J )rattonalmodcs
9.~
• Surlacc re,:ombinatit)n
.::_I
• roblems
Rl'f('rcnces
Cont nt
Ill

10 Optical properties of semiconductors


227
Ill. I I 't ndam ·nt al.., 11f k~ t rc nn ,,~net1c rc r tn<.
IO I . I I <~ \ ~.: ll' scqu at inll '-
f'rnpaga ticn (•f ar elcct rtqlla •nc ttc ave in a
1
10. I
L nducting mcuJU m
2 IJ
10. I .3 Ort1ca l constant:.
2:\_
I 0. I .4 Dielectric l'unctiun o f a crystal
2
l 0. I 5 Optica I s pcctroscorie~
214
10.2 Intrinsic intcrhnnJ absorp tion
235
10.2. I A b. tHption cociTicicnt
_]
10.2.2 Transition probability
237
I 0.2 ..\ Oscillator strengt h
240
10. 2.4 Excitons
241
10.2.5 Burstein- Moss effect
241
10.2 6 Indirect interhand absorption 242
10.2.7 Extri nsic interband absorption 244
10.2.8 Interband absorpti on in amorphous
sem icond uctors 244
I 0 ..\ Optical properties of free carriers 245
I 0 ..\. I Free carrier absorption 245
10.3.2 Free carrier rellectivity 249
I 0.4 Absorption due to electronic transitions of impurities 250
I 0.5 Optical properties due to latt ice vibra tions 25 1
I0.5. I Dielectric response of polar lattice vibrations r1
I 0.5.2 Latlicc vibration absorption 255
10.6 Rad iative recombination 256
10.6. I lnternal q uantum efficiency 256
I0.6.2 Carrier lifetime limited by band-to-band
recombination rs
I 0. 7 Surface polaritons 261
I 0.7. I Surface plasmon polaritons 263
10. 7 .2 Surface optical phonon polaritons 26)
10.7.3 Experimental observa ti on of surface polaritons 263
10.8 Light scattering 264
10.8. 1 Brillo uin scattering 264
10.8.2 Raman scattering 265
I 0.8. ~ Anharmonic effects on Rama n spectra 274
IO.R.4 Light sca tterin g clue to clectroni( exci tations 275
276
10.9 Photoemission
276
I0.9. 1 Direct photoemission
277
I0 .9.2 In verse photocmission
278
10.9.3 Surface state energies
278
Problems 27')
References

11 Magneto-optical and electro-


281
optical phenomena
Frequency-dependent conductivity tensnr
" ',
II. I
Contents

, electromagnetic wave in the


Pn 1a • ttlnn t 1 , 111
a,,ndil: field
J'fl; t: nc I; 1) 1 • I m c
2R4
.
__ 1 01 1.! tudin~d pn)paga uun. k II Bn 284
11
1 I."' .., 1 ~tn r pr pagJ.tt n. k .l B o
1,; . 285
1 ressiL)ns ~ r magnetodtspersJOn
II M.11.:ro ..:optl · l · ·
·tnd ma •11 u-.tbso rpti n 286
·-.I L 111 ..'iluuinal p ropagati, n: Faraday configuration 286
ll.J.2 1 ran , ~.:r e propaga tio n: Voigt co nfiguration 288
114 F< radLI r tali n Jue t mt raha nd tra nsit ions 289
11.4.1 . Ia ... lLi..t1111 d 1 r r F a raday rotutio n due to
l"rce arricr., 289
11.4.2 Com.lu ~ti' it ten · r d duced from the
B llzm< nn cq uat i n 290
11 .4.3 n;1ly ·i · >f th effective ma:s obtained by
Far day rotation 291
11.4.4 C, clo tron reso nance abso rpti o n 292
11 .5 I ctr nic ei ~ens tat e in a con tant magnetic field 293
11.6 Quantum mechanical theory o f cyclo tro n resonance 295
11 .7 Jntcrband magneto-abso rpti on 298
ll. Electro-optical effects 300
11 .8.1 Pockcls effect 300
I 1.8.2 Kerr effect 301
11 .8.3 Franz- Keld ysh effect 301
11 .9 Modulation spectroscopy 303
Problems 304
References 304
12 P-N iunctions in semiconductors 307
12. 1 Abrupt junction a t thermal equilibrium
30
12.1.1 Space charge region 309
12. 1.2 Charge density varia tion
310
12. 1.3 Diffusion potential JII
12. 1.4 Electric fi eld in the space charoe reoion .113
12. 1. 5 Electronic ener"\' b·tnd . . th e "' 1 . 31-J.
w· . 0 - < s 111 C space C Htrgc l"l:glOn
12. 1.6 tdth of the space charoe reoion 3 15
12.2
~~·~ 7 Physical interpretati o n l~f th; Dehye lenl.!th 3]
Jli11Ctton under '' Ill•·tppJ te ' d vo.I ta oe
r ."'
.., -' I ~
1- .2.1 Qualitative e!Te·t
1 ~ . 2._? F ~; s 0 an apphed vo lta!!e J t~
orward hias: n-t . ~
1') .., 1 R . YPt regton btased ne va tt\ ch
> • • .

- ·-·· everse ht as: n - ty ,., . 0 · . _ ::' -


p ?4 Q . .. . ·. Pl: lee ton htascd P~'sttt\'d _
--·-· u,tltt ..tlt vc dcsc r t . r· . .
·. . .
bl.t~ed . 'P ton o u trrcn t 11 0 \·\ m a
.Jili1L'[IOI1
I I'") .
-·-.) Q uan tit a tive trntrn ~ _. .
·. . . .
bl.t . ' c 111 ,) J l:ll !'l\.'n t tlL''' m a
. st d JIIH<.:Itun
12.3
Jrad ed P n j unl: tion
I_ 4 p N .
I") .lllllllton L';II1'1L'l· l · tl1l:L'
- .4 . 1 Stnra !!:. .. ·
<. '

~ ~.4.~ •. ~ L L , l p;ll: t(;,t JIL't'


I ransiti(111L" II) 'IL' , .
12 4 ~ ' • ' .tnL:c
l\ppltc;tt inn:-. ,,f
11 n iun~.· ttn 11 Lap; ~,. ,ll'll. .
1 11
o n tent
v
S \ al •nd 1• r . t ~ dn nan d /u1
n
12 51 J\\ul:111ch · h1 .1J... Ill\ n
12 .2 /·ncr hr '<1 k n
Problems
Rd~ ren e. 1:\6
H7
13 Bipolar iunction transistor
339
13.1 Fabrication of tran:--1stor~
34f)
13.2 Ph ysical basis of the BJT
341
13.3 DC characteristics of the B.IT
342
13.3. 1 Injected minority ca rrier concentrati o n<;
342
13.3.2 Currents in the BJT
344
13.3.3 Current !!ain in the BJT
347
13.4 Small-signal characteri stics o f the B.IT
350
Problems
351
References
352
14 Semiconductor lasers and photodevices 353
14.1 General features of s timulated emission 354
14.2 Physical basis o f semiconductor lasers 355
14.2. 1 Qualitative aspects 355
14.2.2 Optical gain in direct gap semiconductors 355
14.2.3 Tra nsparency current density 3n0
14.2.4 Current d ensity gain relationship 362
14.2.5 Threshold condition in a Fabry- Perot cavity 363
14.2.6 Light-emitting diodes 364
14.3 Photodetectors 364
14.3. 1 Photoconductive gain 364
14.3.2 Responsivity and detectivity 366
14.4 Solar cells y.,~

Probl(.>ms 369
References 369

15 Heterostructures: electronir.: states 371


3T2
15.1 H eterojunctions 373
15 .2 Free charge carrier transfer
373
15 .3 Triangular quantum we ll
377
15.4 Square quantum well 377
1
15.4. 1 Conduction electron energy 1eves 380
15.4.2 Hole energy levels 3S2
D ' nsitv-of- states or quantum wells 3X2
15.5 c J . • · ·tntum wells
15 .6 Excitons and shallow impuntJes m qu~ ) ;>:.t
15.7 Coupled quantum wells an d supel · ·lattices- 3t\.t
1 - 7 1 Double-wdl structure 3 ~ :'
). . . .· d ·c coupled quantum w~lls
15.7.2 Superlatllces: pe l JO I ., , 3,'
15.8 Modulation doping of heleros trucluJes .3,'
IS.9 .
Self-consistent . . level calcula twn s
cne1gy- WO
IS.ION - 1- P- 1 structures 39_
Problems '\CP
-
References
Contents

Phonons in superlattices 393


16
I fl. I U~l lltatlv(.; a r eel . o f pho nons in surerlaltice. 394

j fi.2 Ll.l
L
·tiL L"L nt 111 uum theory of low-frequency modes 94
I l ._~ ieh::tric C n llll llllll'l theory f o ptical modes 397
lh.4 1icro · 1 i~.: the 1ry of optical modes 40()
16.4 I inea r chai n model 401
16.4.2 hrcc-di mcn ·i )llal models 403
Problem 403
Reference 404

17 Optical properties of heterostructures 405


17.1 ptic· I a b orpti o n due to electronic Iran itions 406
17. 1. 1 lntrasuhband transitio ns 407
1 .1. 2 Tn t r ·ubband tra nsitions in the arne ba nd 407
I .1.3 lntcrband transitions 409
17. 1A lnt rband optical Iran itions in superlattice. 414
17.1. 5 Optical ab rpti on by cxcitons in hetcrostructures 414
17._ Pho toluminescence in two-dimensio nal sys tem. 417
17.2. 1 Experimentaltechnique 417
17.2.2 Quantum well luminescence 41 (
Problems 419
References 420

18 Transport properties of heterostructures 421


18.1 Effects of a constant electric field 422
18.1 . 1 Electric field parallel to the interfaces: £11.\' 422
18. 1.2 Electric field perpendicular to the interfaces: £11: -E3
18.2 Effects of a constant magnetic field 42 :
18.2. 1 Energy levels and wave function s ..J25
18.2.2 Magnetic-field-dependent den it y-of-sta tes ..J-2
18.2.3 Magnetoco nductivit y in a 20 hetero ~ truclllre 42
18.2.4 yclotron resonance 431
Problems
-'32
References
432

19 Metal-semiconductor devices 435


19.1 Metal-oxiuc-sL·miconduct )J' capa~.:itor
..J3o
19.1 .1 Effect of applied bias on c·ncrgv banos
4.•
ll.J . I ·-, Bi·1cS· c1~Lpen
, d- enL'eOJCapHL'ilance
. · .
19 · I ·-~ · v·1ILI'It' t' ·
• 1011 tl capat'ltance \'C'rsus \' O it:l~ un,,
• 4-tt
IY. l.4 Applicatiun~ of t·l1•' 111 ~1 ' 11 . l . -
C:: ' -0 \lt L'-St'l111C(ll1ull-.'( t r
.l
19.2
• ' ~ 444
M L<d-s~.:mJl'LincluL·h, r J iocle
l lJ"l I E Tb ··
·-· ljUI I . IIL1111 ch<H<JL'kristics or lh'1.: M ' , .. l .
I') "l , C .. . l l ll u
·-·- lll r nt unuer ;tpplit'cl \ lllta ~ ..-
~t:{al-o.xid ·-scmit·onducl ll' lidd L'ficL·I I r;msi'-lt)f
I J.l . l lnl roduui\1 11
i'J I~ DCch ·11·· 1 · ·
. ·- • .ll.:t'riSIII.:~t>t'lh · I( .TI
Co VI

Prubl ms
Reff."r nee.

20 Applications of semiconductor
heterostructures 457
2 1. 1Device · v ith transport parallel to the inll:rfaccs:
fiel d ciTe t tr· nsistor 458
20. 1.1 Anal) is o f ph ysJC<11 proce cs 4
20 .1 .2 Ana lys is o f device performance 460
2U.l .J . emico nduct or insul ato r ~e micont.luctN
lielcl effect tran sistor (S TSFET) 461
20.2 D e' ices with transport perpendicular to the interfaces 4o 1
20.2.1 Heteros tructure double-barrier di ode 462
20.2.2 Heterojunction bipolar transisto r 463
20.3 Quantum well laser 464
20.3. 1 Double-heterostructure lasers 464
20.3.2 Single quantum well (SQW) lasers 465
20.3.3 Multiple quantum well (MQW) lasers 467
20 .4 One-dimensional and zero-dimensional quantum structures 468
20.4.1 Theoretical background 469
20.4.2 Fabrication techniques for I D a nd OD structures 470
20.4.3 Electrical applications of lD and OD structures 471
20.4.4 Device based on I D and 00 structures 473
20.4.5 I 0 and 00 optical phenomena 473
20.4.6 I D and 00 o ptical devices 474
20.5 Devices based on electro-optic effects in quantum
475
we ll structures
475
20. ~. I Quantum-confined Stark effect
475
20.5 .2 Quantum wel l modulators
476
20.5.3 Self-electro-optic-effect devices
477
Problems 478
References
479
Index
teristics of •
uctors

eas
General Properties
11 ndtu·ror j - neither a good insulator nor a very !lood conductor 1.1 Qualitative properties
tric urren t. ~

h tl c 11 ical resis fi l'il\' of semiconductor generally decreases strongly


' tlh inLrea i g temperature, whereas the resistivitv of a metal
g n 'rail~ increases weakly \:Vith increasing temper;ture.
A micondu tor can be an e/emenr, such as Si or Ge, or a compound, 1. 2 Composition of semiconductors
uch a G · As or InSh.
Solid emi o nductors can exist in the crystalline or amorphous form. 1.3 Structure of solids
A lunice 1 periodic a rray of points in space.
A hasir; I ' a s t of atoms associated with each lallice point.
Semiconductors can crystallize in the diamond, =inch/ende, Jrurt=ire. or
oth r \ fructures.
Th bondi11g between atoms in a semiconductor can be covalent, ionic, or 1.4 Chemical bonding in semiconductors
mixed.
Layered s miconductors can interculate foreign atoms or molecules.
ry p ure . emiconductors can be produced by the :one refining method. 1.5 Growth of pure semiconductor crystals

T h hi t ry o - mico ncluct o rs elates back to the nineteenth century. The


d rec in re -ista nce of sil ver sulfide with increasing temperature v. as
n ti ed by Mi chael Faraday ( 1 ~33) . Selenium was found to be phot o-
nductinQ: b W . Smith ( 1873), and the rectifying properties oflead sulfide
w r bserved by F. Braun (1 874). During World War ll silicon found
appli tion a. a rectifier in radar. By far the mo. t important event. how-
eve . was the discovery of transistor action in germanium by J. Bardcen and
W. H. Brattain in 1948 , which ushe red in the exp losive development of high
technology based o n semiconductors that continues to the present clay .

1.1 Qualitative properties


S m1cond uctors can be distinguished from other ma terials by a number of
pb y~tca l properties. one of the most important or which is the electric
rc~ i . ti vi ty fi or the difliculty with which an electric current ca n pass thro ugh
Basic characteristics of semiconductors

. ·. 1 d r tl c ·111fl·uu , 1 Lt:
. , ol· a n electric field. Materials t:an be t:las-
. . . .
the matert•1 un c . . -u l'lt . rs for vvhich the resist1v1ty IS very high ·
. . d . l 0 three call: go n e~. Ill ~ ' •. .
·tilt: 111 . b.. . l vlty is v ry low: and semiconductors, for whjch
t I. for whiCh t e rest 1
me 1 s. . . . x . te · v· lue and is highly temperature dependent.
tl1 tsttvlt I . mtermeula 11 . . ..
e_ n.::s · .- .
1 • n tenlJJeratureresistlvJtlcsofthesethreetype~of
I I T , 1nlues 10 1 t1~ I u
Ill'' I tl )ptL~ • . . ·~ 111 T able 1.1. The temperature dependences of the
malcrtal c.lle gtven . . . - ~ · , l"f]' · F
I II '' . . . • f. "t·l ·· nd ·em 1Lond uctorSdlt:CJUtteCI erent. ormetalsthe
res 1 ·u \ 'II te o mt: s .l • . . . .. . • .
d d nee is t)' J11Call y weak and the reslstn·Jty mcreases with
temperature epen e . d h ·
. . tur" ( jn 1 1). For semJCL>n uctors t e oppos1te is
mcrea-.mg tempera -=-· · . .. _ . .· •. .
· h . The tempera ture dependcm:c 1s strong ctndthe resistivity
Ly 11ca 11 y I t:: ca e. . . .. . . , . .
for the 111 ' l parl decreas w1th mc rea smg tem~erc1ture ( ~1g. l.2). A
num b r o f tl1 I. a ·p ct · of the elec tncal properties of semiconductors
·hould he mentio ned :
1. n n- hmi b havio r a nd recti fy ing effects;
T
... large imp m ity ffect ; .
Fig. 1.1
3. b th p ~ j ti e and negative charge earners:
R ' SJ ·tiVll}' Ycrsus remperJture ror a 4. high therm oelectric povver:
01 1.31. s. sensitivity to light- production of photovoltage and change m
resista nce.
Detail ' concerning th sc effects will be found in later chapters.
3

1.2 Composition of semiconductors


Which so lids are semiconductors? Among the most important are the ele-
ments silicon (Si) and germanium (Ge). which appear in group IV of the
T periodic table of the elements. Carbon in various fo rms ca n be i.l semi-
Fig.1.2 conductor. Other elemental semiconductors a re selenium (Se) and tell-
R c~i. ll\1!\ \'Crsu l emp<!rature for a urium (Te), which a ppear in group VI.
emicond ucLO r . The list of compounds which are semiconductors is ve ry large. Tt includes
the 111- V compounds, formed from gro up Ifl and gro up\/ "lements. ·uch
as GaAs and I nSb; the II- VI compounds such as CdS, C dSe. and ZnSe: the
Ill- VI compounds such as GaS and InSe: and the IV- VI co11po unds uch
as PbS and PbTe. Many ternary compounds such as Cu • 2 chalcopyrite)
are also semiconductors. Organic compounds which ·trc semiconductor::;
mclude anthrace~e . C 14H 10 , ·mel polyacetylene, (CH ),.
Many propert1es of scmi~.:onductors are drasticallv m d ili d b) the
presence of impurities. In silicon, fo r exa mple. the e l~ctri ~ l ·md L ptical
properties can be ignificantly cha nged by the addition ~'~r i mpurili _. :u ·h a~
boro n or arseniC. T he process of deliberat elv ad din .... k.n ,, n impun11 :.. in a
controlled m·Hmcr is kno .
. . . · ,
d . ' -· .
wn as opmg. In compound ' L'nt tL'On u ,'(Clf ·
J .
devntl1ons lrom stoich· ~ . , . -- . .
wmett y ca n attect tht'lr pmpertt

1.3 Structure of solids


1.3.1 Crystalline and amorphous forms
Solids l:an t:xist in the n '. . . .
form the "11 0 . . . ):.t.tllme ur thL' a nw rrh~)US "''1111. In th
' ' ms 01 1ons · 1 r ~. . . t.
ran<•(.' urd~;:r 1·11 ll . • , ' t: dll<lllgl'l.. Ill ~~ pcril t.h ' arr.t~ IL'. th Ill!
'=' IIC svs tt·rn I !h
-· · n t' amorphous fo r m th 'II.' 1 n I
Structure of solids

1i l It rmctl h Lh~ ra pitl u li ng 11!


l1

ai ~~) it} high r tha n. J 11.1 p i'\~o: . h ther a


tmpl' i u_ ..,talline r am rph u kpcnds o n how it
ln 1he folll \ mg U l..,CU S IO ll e sha ll r cus on c stalline
r · a m lrph( u. s '111ico nd uct r will be di T us ~.:d in a latt::r

men t )J the at m::.. in a n iJ I crystal is specified by the crystal


. . . characten zed by t\ o elements: a lattice and a
ttl e 1 ~1 pen dtc arra. o f points in pace. A basis is a set of points
1 ntlcall} to each lattice point. Choosing one point of the lattice
r :!in. the po it i n v t r R({) of a n arbitrar !a ttic point can be
d l

( 1.1 )

\\her a,.a~.a3 ar n nc plana r vector ca lled the primitive translation


vectors and f ,. ~ f 3 r integer tha t take on all integer values and are
referred to llecti vely , f. T he primitive transla tion vectors are the
harte. t tra n lati n · t rs in their respecti ve directions tha t carrv one
point fthe lattice int a nother point of the la ttice. They fo rm the edges of
a parallelepip kn wn a n a primitive unit cell whose periodic repetition
generates th entir la tti . If a 1• a 2 • a 3 are chosen to form a right handed
triple. i.e .. th . alar t riple product a 1 · (a 2 a:,) is positive. then this triple
product i the' lume r! 0 of the primitive unit cell :

( 1. 2)
L~ L
It hould e mpha sized th a t neither the primitive translation vectors nor
th prim it i e unit cell are unique for a given lattice. Three possible pairs of
primitive tra n ~lation vecto rs for a two-dimensional Bra va is lattice are
z:
Fig.1.3
h vvn in Fig. 1.3. F urthermore, for c uhic lattices, the primitive translation Lattit:e points of a space latt ice in two
vector ' m·i_ not be orthogonal, and the primiti ve unit cell may not have the dimensio ns with possihle pairs of
·hap f a cube . This is the case fo r both the fcc and bee lattices. In general, primitive translatio n vectors.
there exist uni t cells which are no t primitive and whose volume is larger
than that of a primitive unit cell. or particular interest is the conventional
unit cell which h as the symmetry o r the crystal system to which the lattice
belongs. Thus, fo r fcc a nd bee lattices the conventional unit cell is a cube, c
requcn tl • referred to as the elemental cube. The conventional unit cell is
characterized by three axes a , h, c that coincide with three noncoplan_a r
J gcs o f the cell that meet a t a corner and three angles n. d, ~~ between patrs ,
,
axes as shown in Fig. 1.4. The magnitudes a, b, c oft he axes are the lattice
f1(if().,"J._ - - - - - - - -
constants. , -C.: "
' II

A (I:__ _ _ _ _..Y

1.3.3 Bravais lattices


It \\ as -.1 (J\'-.'Il by Bravais that there are 14 possible lattices in three- Fig.1.4
J IInt..:nsi unal -.pac ' .A tabulatt.on o f t I1e Bra va1s a t t c~s an d crys r <-•~ l s" )l s' tCITI S
. It. f\_stai .I Xt: ll. hc ;uld ~t ll :!k'" · 1·
. . f emicond uctors
Basic choroctenstlcs o s
f . the 7 crv
,> I . Bt;J\';J i.· { ;tlltL C~ (ll
lal 'Y tcms
Table 1.2 I ll ~
-

Restriction<> on LOnvcntional cell

a=h = c
(I = j = '! = 9()-
f; 1 ~:c-o.:cntc: rcd
hody-o.:o.: tt len:d
priml llVC a = h :f c
t tragnn I n = :-J = ~f = 90'
bod -centc c·d
p t im t t1 I 'C o # h f= c
ha>e-c~.-mtcrcJ Lt = ,j = I= 90"
faLc-..:c nt cn.: I
h <.ly-ce ntered
primit ive u = b =fc c
(l = d= tJO' .- = 110·
rnmitive a= h=c
= -, <
mg< n:tl
Fig.1.5 " = d 12(1' f; 90
-,10\ 'llltOnJI JnJ pnmllt' e umt ..:db pri 111 it i \t: a ~ h :f c
mon chmc
rhe fac~-.:entercd cuh1c l:.tttJcc.
base -center d ( =.., = 90 # j

triclini..: primitive a =fc h -"-c


Cl # ,1 # ~·

is give n in Table I .2. Three of tbe Bravais lattices are cubic: simple cubic
(s ), face-centered cubic (fcc), and body-centered cubic (bee). Another one
is hexagonal. The face-centered cubic lattice is shown in Fig. 1.5 and the
hexagonal lattice in Fig. 1.6.
Example l.l: Body-centered cubic lattice
Describe the positions of the atoms in a body-centered cubic lattice
Fig.1.6 and specify one or more sets of primitive translation vectors.
om·entt na l and primitive unit cell. of Solution. The body-centered cubic lattice (bee) consists of a simple
Lhe he ·agonal lalliL·c:. cubic lattice with additional points, one at the center of each lattice
cube . The additional points constitute a second simple cubic lattice
(Fig. 1.7) .
The corner points of the original simple cubic lattice a rc center
points of the second simple cubic lattice. Hence. ea h point ora b uy-
centered cubic lattice has surroundings that are identical i th · l1f
eve:y other point. which i a prope;ty characteristic L f a Bra' ai:;
a
lattice. A po, sible set of primitive translation veer c i_ given ! :

.-
~-~- = a(~ ,O.O) , a2 = a(~.~.!). and a~ = u(O.O.l ) as sh .l\\'11 in
u ' I Ig . I .R. A more symmetric set is given hy a 1 = a(~, ~. - ~ l
a) = a(~ . ! . ~). and a.; = u(- t - {,~)as shl; \<vn in ig t.'"i.J. h
• I I • --

-~ -
'
angle hetwcen a pair of the l~ttlet:- p~imitiv~~ tr·m..;hri n H' 'tM t:;
-----·- 109' :2X'.

lnsimpkcrvsl't! ·- ' I ,
... ' . '

.
. S SilL 1 as l10
1 SC Ol the ll1CtalliL· eki11L' t1(S Ll pp
I ~·~ IS
llt:lt:
. J '
l)11ly lltH:; at l11. , . • ·. . . .
f lth.llfl !1.

I 1.. - .tssoci,tkd With a ~nen LttiiL\.' PL)Inl ln m ,,~,.. 'rn-


p LalCd crystals · ·I 1· . . ~ .
l
Fig.1.7
. · .· IlK lll tng thnse L)t all sCmic,\rhluct . r ·, th rt: IS Ill tho~n
r \.II mtcrp~!ICl l il l ll il'. l:l il1c' I' l llli lll j! ll1t: .ttom a~!\Ocl'lt -·t .·111I .
1"' 11 •d a h·" l \ -l.c ttl ~o: r •d u thtc ll t: '.. ti h· 1 . 1 , .· . · · '. cl ''' a g1wn !attic~? point. 1. • .. t hL 1' l I
\: l l!•.L ' ~ .t )d:o.J ~ . 1\ prnnttiv · · .. . . · •
t.hll.:s tht.: hash . Tl , . l unit_u:llu)nLttns tilL· ~:tm,: numb ·r
h.: ctlunts ut LhL· basts arL· idcnuti,.: I h_
true ure of solid

The r ition Ctl r or till '''" ••ton inlhl: h.lsis


; ·
( I 3)
•n bech '>Cn ... uch tha t ( < d ' / '· 1., < 1 Tl
tl . b . . - t .c :! .cl - . 1Ccom plctc
11.: "l at 111 m Ill cell ( i::. specified by
lf

R(l n) = R(l) + R(h· ). ( 1.4) '

'
a,

ry. tal struc tu re = la ttice + basis

Fig. 1.8
1.3. Crystallographic terminology Primitive transla tion vector~ l·or the
hndy-cc ntcrcd cubic Bravui latlice
The t r ~( l) i. a translation vector of the la trice. The crystal as viewed which connect the lat tice point at the
from n~ pom t r appear exact! the same as viev..·ed from another point 1.1 origi n to lattice poinb a t two ..:ube
gi\"en b) corner · and one cube center

,. I = ,. + R (f') . ( 1.5)

In other w rd . tr n la ting the crystal by R(e) leaves the crystal invariant.


A lattice direction ca n be defined in terms of a translation vector

( 1.6)

\\here a. b, c w re introduced at the end of Section 1.3.2 and n 1.n 2 , n 3 are


integer r placi ng P1 • 1:'1 . •. The lattice direction from the origin to the
.. -. . .

endpoi nt of T(n ) i designated by enclosing in square bracket s the values of


n t . IIJ.. I13 for th e shortest translation vector parallel to T(n ) : [n 1n 2 n,]. If a
coeffici nt n, is negati ve, it is designated by placing a bar over it: IIi.
rta in la ttice directions can be transformed into one another by sym-
metry p ration s of the crystal. Such directions are called equivalent. In a Fig. 1.9
ubic cry ta L the directions [100]. [010], (001]. [TOO]. [OIO], [OOI] are Primiti\'e translation ,·ectors of the
uivalent a nd arc designated collectively b y ( 100). For a general set of body-centered cubic Ialli ·c conne..:ting
the la ttice point at the origin w lattice
quivalent directions, one chooses the ni .11 2 , n 3 values for one of the points a t three cuhe cente rs.
direction a nd encloses them in angular brackets.
A lattice plane is determined by the intercepts of the plane on the crys-
tall ographic axes and is specified by the Miller indices. Ordinarily. one uses
th axe that coincide with the edges of the conventional unit cell and
ex pre. s s the intercepts in units n 1 .~z 2 • n 3 of the lattice parameters a, h. c.
he Mill r indices h , k , 1 are obtained by ta king the reciprocals or n,. ll~. 113
and multiplying them by the smallest number that clears the fractions. The
lattice plane is designated by the Miller indices enclosed in parentheses:
(hid ). If a n index is negative, a bar is placed over it. It should be noted that
ht;re I i~ not the same as in Eq. ( 1.1 ).
. A set ofcrystallographically equivalent planes is identified by the Miller
111 li t!s f r u ne of the planes enclosed in curly br~ckcts {!1/d}. Thus, the set

ol e4 ui v:.~ en 1 pia ncs ( 100 }. (0 10), (00 I), (I 00). (0 10 ). (00 I) of a ~.:ub1c latt1ce
. f ·conductors
Basic characteristics o sem•
_ f-ty-cenll.:rcd c.uhic and hcxagonal laltitc'\
h ,lf:J\ l i!fl tiL r,tri1 111C IC.l~ 11 , t.:
Table 1.3
Face-centered Hexagona l
(/1
(3 J:i;:~ )u2 c
4 3
.!.~ a·' ( v'3/ 2}lr (
4/ a-' -1,i 1crc
12 6 (c .:> a )
uj/2 a (c > a )
(, 2(c .-- J'Jo1
, dbtanct.:
{I
c(c < v'3a )

, repres n1e d lle..'"·t1vely by ' 1UO l . The smallest


. distance between
. . a pair of
1
.
p.uallel (llh.t plane in a ubiL crystal of lattice con tant a IS g1ven by
({

d,;.., = J h- '1 ( I. 7)

Th Bra,·< i. !attic that occur most frequently among semiconductors


ar the fac - ntercd cubic lattice and the hexagonal lattice. The primiti,·e
and conventional unit cell of these two lattices are shown in Figs. 1.5 and
1.6. resp cti ely. Th ir characteristic parameters are given in Table 1.3.

1.3.5 Structures of semiconductors


With these preliminaries out of the \:1,-'ay, we can now discuss the structure·
of the important types of emiconductors.

1.3.5.1 Group IV semiconductors


Group IV semiconductors such as Si and Ge crystallize in the diamond
structure which consists of two interpenetrating fcc lattices displact?d with
respect to each other along the (Ill) direction by one q uarter the body
Fig. 1.10 diagonal of the elemental cube. There are two a toms per primitiv ' unit cell
on enttonal unit cell or the diamond and there is a center of inversion midway between two neare 't neighbor
~t ructure .
atoms. The diamond structure is illustrated in Fig. 1.10.
Example 1.2: Crystal ··tructure of diamond
Describe the diamond structure and its Bravais lattice.
Solution. The Bravais lattice of the diamond structure i. fac -c rlt t.' r"'d
cubic. A symmetric set of primitive transhtion vec tors ·un t:thn rl
he ."t = a(O,! · D- tl~ = a(.l;. 0. *). a3 = a(-L t O) . The an...,l Dd\\ n
p<.ursof vet.:tors is60o . The,;olunieoftheprtmtti\'~unit~ ni, 11 ~ h
dtamond
. structur~
.- c ons1s 1s u two mterpcnctratut!! tac '-1.: nt ' J
c , · . t' · - •
cubtc lattu.:L: displ· d · h ~ L. J
. _ · · c~ce Wtt respect to one anoth r ·tl 111!! .hl' Pl' ~
dla!!onal
~ . ot the cubi Lee · ~ 11 b · - -
yonequarterot t ht'len!! tl 't th dl.t~\11.1
1
, hebastscllnsistsot't\.voatomslocakdata(O.O.O ~a n 11 1 1 . 1. f h•
LOordmalton numh. . 1 · t . q J
. \.:t, w 11c 11s thc number ufth n •·tre't n 'IE! b 1
anatnn1tnthestru<:t -- ··r 1" '
. 1 : lite, Is nur. he numbl-rol'n t- r ·.tr t n 'I •h
Is I_. The max11num ,110 -· 0 · t· .
0 Y11·l. 1_L1 :o.ph~..·rcs
. _· . t
1s U ~4
P rlJOno ava 1lahkvolun ,•\\htdtl.lllb
1 1 · ·I ·. ,_ ..
o-74 1·urctsJnt,!,kkchu
.. · . ·- ' " 11 '- lJs ~•g:nriH:antl\ mall·r 1h. n h
' -· ·rh - I
~ ' ILl . l:llL\11\.'S[Ill'lg_hbllf'\ !'th ·ltr ( I ll ~
Str ct re of solids 7
r l ll~. ~ - ). <-1( - l . 1 . I) , 1 ( I I
1
I
n () () ) 1 I -1 I I • .J • 4 • 4 I.
tt 1( • . I ). a(~ . .: . (I , " ~ . 0. ~). o(O, '. . ~) . rc'ir ' ·-
h~.:t\ ~ '11 fh.:.trc L ll ~l gh ho r honcl-; is IOlJ -2R' .

I~
urc1
. lhta B r~l\ ai s httl ' 'b .
. ,.· : , L~ ecd uset 1lccn\lronmcnt:-.or .
t lt.: hasL dtl~ I 111 one ntatlon . Til l-s s··ti"LI' "tLtl· '. . I
- • " ~ 1 . , n ;Hur<-~
'·'' nt btmd tng.

1.3 5.2 emiconductors


Jll \ nu ndu tor- ~ uch a a As a nd lnSb crystallize in the zincblende
tru · ur · \ htch i. deriv d from the diamond structure by making the two
interpen tr_ung f~c !attic different as shown in Fig. 1. 11. For ex:1mple. in Fig. 1.11
i-a. o"le k latttce onrams the Ga atoms and the other fcc lattice con- Con ventiona l un it cell or th..: 1.incblcnde
tam. th <\. atom . There is n center of inversion between nea rest nei!!hbor struclur..:.
at m · be au e the e two a to ms are different. About each atom of a~oi ven
. pecie. . a)- Ga. th re are four eq uidistant atoms of the other specie; As,
arranged at th corners of a tetra hedron. In each elemental cube there are
fo ur mole ular u nit· of GaAs.

Example 1.3: C rystal structure of zi ncblende


D crib th r_ tal structure ofzincblende (cubic zinc sulfide) and its
Bra' at latti
olution. T he Bravais lattice of the zincblende structure is face-cen-
t red ubic. The face-centered cubic lattice is formed by add ing to the
-irnpl cu bic lattice one point in the center of each square face. Any
p in t can b considered to be either a corner point or a face-centered
p int or an of the three kinds of faces (bottom. top and side) of a
imp! ube. Hence, the face-centered cubic lattice is ·1 Bravais la ttice.
T he primitive unit cell of the face-centered cubic crystal is rhom-
boh dra l as seen in F ig. 1.5 a nd has three of its edges coinciding with
the primiti ve translati~n vectors. The conventional unit cell is a cube.
Th primitive cel l ha s one quarter of the volume of the co nvent ional
ell and has less symmetry.
The zincblende structure consists of two interpenetrating fcc lat-
tices displaced from each other by one-qua rter of a body diago nal.
The S atoms are placed on one fcc la ttice and the Zn atoms on the
other fcc lattice. as in Fig. 1. 7. There a re four mo lecules of ZnS per
onventional ceiL The b;sis attached to each point o f the latt ice is
ZnS, wi th respective coordinates of the atoms: S = a(O, 0. 0) and
Zn = a (1, t. t). The ZnS structure does no t have inversio n symmetry.
Th diamond structure is obtained from the zmcblende structure
by ma king all atoms the sa me species.

Exercise. Describe the crystal structure of lnAs, which has a lattice


·o stant 11 = 6JJ48 A (see Fig. 1. 11 ).
Basic characteristics of semiconductors
q of the primitive unit cell and the number
ta) Wh,l l are the ol ume ) wo .
nf atom , in il'. . _ 3/ 4 = 55 .3 k', where a 1 = a(O. ~. ~) ,
, cr. ~ln - Ia, · a;. x a,l - ll ·· -
"-(I~.O. ' ) . a,= a(~-1 -0) :twoat ms ., . . ,
a_ (_ - . 1, f) b~t veen tvvoletrahedr al bonds knowmg that
(b) Calculatle tl_letl~ntgbetwcen Lwo ody diagonals of a cube.
the ang e IS la . h, . b .
-d··tgonal vectors. takmg t e cu . e center as
n. wer. Two b o d r I< . r-l. . . · ,r
. . 1). d - I - I. 1), each w1th length v 3 m unrts ot J-.
o n gt n. ar {1- 1· an · . . ;::;; F. · -
~ · b t 11 their ndpomts 1s 2v 2 . . rom tngonometry.
The d1stw ce e " ' r:;
coo.·:. H· • c = - V 2. a = h = V 3.
r-l
c·1 - tr + 112 - "'tt/J
-
- ~ - . 3 cos U. c s (} = - 1.0 = l 09o 2~'.
8 3
= - - · rl e conventional unit cell'?
(c) 11 w manv at m ar 111 1
Ans,~er. Fr0 ;n Fig. 1.1 I. there are:
4 compl te o atom.
6
I, • atoms in faces
' x 8I
c
• atoms at corners
8 atoms

(d) Wha t arc the number and separation rt of nea~est neighbors?


Answer. 4 nearest neighbors: r1 = /3a j 4 = 2.62 A
(e) What are the number and separation t] of seco~d neighbors'?
Answer. 12 second neighbors; r 2 = aj v2 = 4.28 A (same a · for
nearest neighbors of the fcc lattice)

1.3.5.3 11- VI semiconductors


CdS, a Il- Vl compound. typically occurs in the wurtzite struc ture which
consists of four interpenetrating hexagonal lattices. t-vvo occupied by Cd
atoms and the other two by S atoms. There are four ·tt oms per primiti\·e unit
cell and no center of inversion . Each atom is surrounded b .. fuur nearest
neighbor atoms of the opposite species located at the c·orners of a t trrt-
hedron a shown in Fig. 1.12.
As we have seen previously. the zincblende ·tructure con·i·c t' t \O
interpenetrating face-centered cuhic sublattices. one subb ttic b ing di,:;-
1 t
placed with respect to the other by i a. a. a. where a is the lattice consl mt.
The wurtzrt structure (Fig. 1.1 2) can be viewed as n n'i ting f l\\ -
interpcne_trating hexagonal close-packed (hq)) structur s. on~ fL r a ·h )f
th atomrc components. The hcp structures are displaLC \\ ith r . p 'LI l)
one anoth~r alone: the a, -axis by an amount uc vvhere u is a p~tf<l!ll t r) 1tlu:
order of..,J 1It) · Lt s·hOlll
11 b e noted that the hcp st ructure is not.t Br.t\ u l.uw: ·
hut con.:;Ist
.· · · s· ~11' t wo- mterpenctratmg
· · hcxa glmul Brava L I.Htll.:~.: . 1. l.t ·c, I
r ~lattve to Il"",·ttl ,')t)l er
" . b y a vector d given
. ~ by

d 1 .
Fig. 1.12
= I
1 a, + 3' tt~ t-
1
2 " :..

\\'u i l lik 'I I U\.lil f C \ \iu\\lll g l\ i<: whcrcu 1 .a~ anda . . , . ,.


. . -' . ' .tit~ 11\.lWn m hg. I b . The'' u rt 1l t' trul..l\lf
l '' lu.:ur.d c n"ITIHlnl!!ll l 11 t: .tLh 1 ~ 11 ~ lont;tins lour I Ill , . .. . .. .
·d: t l ll JI - , . _. . ll(kltdr.tttng h .:xa g llnal Br.. t\ ilh l.r ltl ·•·
pu I tlllllllvc unit.:L·ll.
tru tu r of soltd

1 mil mductor ·
1
r '~h.:h a~ ' d , a n In,\~ n y.,talli 7e in Ia crcJ stru ·-
1
.
tth \,mnus_polytypes n ssihlc Jcpench ng nn tl e ·t· ck in 1
number (1[ at m . per primitive unit cell can he r ur or
lg l l the r ll~ l) pe
'1111~.: )tH.Jut:ll r consiqing of metal atnms and chal OQen
n c, th~ m ta l at m · lie in two-dimensional sheets and : tre
r h_ chemt al_ b nds. Pairs of metal sheets arc connected by
n het\\e n patr: of metal atoms. one atom or a pair beinf! in
I the thcr at ) !ll bei ng in the other sheet. The chalcof!cn at;ms
Fig. 1.13
rr ngcd m l\\l -di men ic nal sheets and are bound by chemical
La yered 'tructun.: .
m tal atom in a<.ljac nt metal sheets. Each metal , hcet is che-
und l an ther m ta l sheet on one side and to a ehalcogcn sheet
t'n h th r. ·acb chalc gcn ·beet, on the o ther hand. is chemically bound
onl) t th~ adjacent meta l :-.heet. There. ult is a sandwich of four sheets. a
pair l)f metul :hect n th inside and a pair of chalcogen sheets on the
out id . i . h \\'n in Fi~. l.l4a . Also shown (Figs. 1.14b and 1.14c) are
, ie\\ rom ab ve ·m d rrom the side of the hexagonal array of chalcogen and
metal .nom-. in adja nt heets. Chemical bonds do not exist between
·and\\ iLhes. Sand icb s are bo und together by weak van der Waals forces
to fom1 th cry ·tal. T he sp a ing between successive sandwiches is called a
van der Waals ga p.
The phy'\ical pr p ertie_ of la ye red compounds are strongly an isotropic.
The ~ material are n t mccbanically strong. If a shear stress is applied in a
direction parall J t the . beets, the sand\:viches will slide with respect to
ach ther and. in fact, can be pulled ofT like onion peeL.
Theel ctrical c nducti ity is also anisotropic . The conductivity is typi-
cally hi!!h \\ithin the plane of the sheets a nd very low· perpendicular to it.

a)

::~
Sc

( b) ( C)

Fig. 1.14
Schema til: rcpr6cntation of tl1' ln. ·
strul:turc: (a) Structure l,f J ·an<..h \ tl'h
com lklS ·d or l \\ ll In ~he: \) ht'l\\ ·.·n l \\l)
Se shect:-.. l h) H ·xag<"lllal Ltrr<t\ ol ~
~UhS:ll1dl\ id1 CLlll!'>i~lt!l!;!. fa IJ.l 'l'fll
In :tml s. ,11 ···ts '1 ..:1H:d fr( m .t b ' '
(c) Cha ir-hl..c d ·format11 n l !thL·
h exa~o n~d ~t rr.t~
. . f emiconductors
Basic charactenshcs o s
;\ rur n:pn:~entativc l:Ubic cmicond UClllr<. <l l ro
tanl. IP
Table 1.4 l.ult i..: ·
<.: <' fl (/
"'
Rt:f Material SI rlll:t u re {/
Ret
ruLlurc (I

543 ,,
5 (i"i Z nS zincbtendc 5423 b
Jr .. nl''' J
<I

5.43 1 h ZnSc Lincblende 5.661 b


i .:h l ~ndc zincbtende
'i.(11 l b Z nTc 6.082 h
() 142 b dS zi n~.:blcncle 5.X:~.2 h
'i 447 h CdSc Li ncble ncle f)052 b
5 (J4( h CdTe zi ncblende 6.423 h
ZliKhkndr.!
6. 130 b PbS rocksa lt 5.935 b
7. tm.hh:mk
llrtc..bh.:nJc (l.04i\ h PbSc rocksalt 6 152 h
mchknuc (i.4 74 h PbTe rocksal! 6.353 b

~~ Ktttd ( 19 '(1
b \ c113mantd :.md Hamann (I lJ 7Y I

Comment. In the proc . ~ o r intercalation. foreign atoms and even


m k cule. :111 ea. ily be introduced into the van der \Vaals gap. The
physical propertie · o f the material ca n be dras tically modified by
intercalation. When lnSe is intercalated with Li, as shO\vn in Fig. 1.15.
fore ·ample. its conductivity increases markedly as a result of free
cle trons donated by the Li a toms. The Li ions 'vvhich arise can
diffuse easily \vithin the van der Waa ls gap.
1.3.5.5 IV-VI semiconductors
IV- VI semiconductor such as PbS and PbTe crystallize in the rock salt
structure, Fig . l.l <\ vvhich consists of two interpenet rating fcc lattices
Fig. 1.16
displaced along the ( 100) direction by one-half the edge of the elemental
Rock. alt . tru ·tun::.
cube. There are two atoms per primitive unit cell and each atomic site is a
center of inversion .
Lattice constants for representative semiconductors are gtven m
Table 1.5 La ttice con ta nt n and the c{a Ta ble· 1.4 and I .5.
rauo f r repre;;enLati ve wunzite struc-
ture ·cmiconJucto rs at roorn t mpcra-
turc r~t!'tcr Wed3mant<.:l and Hama nn
1979) 1.4 Chemical bonding in semiconductors
'l<lterial <I
1.4.1 Diamond structure semiconductors
C/ !1

1. s 3.8 1'1 1.64 The bonds between nearest neighbor atums in Si and G arc .o\ ·tknt.
' d. 4. 139 1.62 : lectronpair bonds as described by Pauling ( ]1.)60). Each :1wm r 1de~ ,tt tht'
C...dS~ 4. 31N l .tu centerolatetnhedro
. . _ ~ n <~. nu..~·IS bouncl to 10 , L1r nearest ne1·ghbl r I ·J J J ( h ~
cot ners of the tetnhe ·1·- T h·- . . 1 1
(.ound tn
. . ' u o n.
manv c·trbo 11 ~
l ste trah edralboncltn~u s r he"Jm:l\r~·• " t hl
· · ~ - .- 1.. ll
. . •· < compounds and 111 the di:tm c~n d ll>nn 1 I c..aiL• 111·
!Tidy be under tood · · f' 11
Ge are '
.
.ts o n\vs. The ~lectwnJL' L·onfig urau L' Jll I

C: ( l.,f (2s t {"l.p) ~


Si : ( Is)- (2s ) ~ (2p/' (J., i2 \ 3p) ~
Ge . ( I s\ ~ \. "',· ) ~
J - ·
~ )r' , , · ) ~ (
-r• \·'·' -"P
,,
-t ) ,.
Chemical bondi ng in semiconductor 11
th I tr. I IUrdt:l'trnns. t ,\-cleLir th <l n d tv.l f1-el ll rc n
1,11 ' .tLh 1 thee C11 ur d e Iro n. can he pa trt: .vtth a
1
I '"'PP . tlt: "Ptn nan •tghhon ng at m tor rm an lectrt n
n:pr~o:'>~:nt the clcdr ns l ' d N~. 1hen t 1c e lcctr n pair b nct
111 n. fot exa mple. e m b . represen ted . _mholi ·a lly hv
. .
·+ Si · __. · Si : . i .
~laniLally, the b nd strength is determined by the overlap of
rhllal of·t-hc tw elect.~·on o n neighbo ring atoms . Thi s overlap
nl..tnLt:d b) promotmg a n s-e)ectron to a p-state. For Si. the
J:Ltro n ·onfigu ra ti n is ls ) 2., )2 (2p/' (3s) (J p( Le t the 3s
2

t h~tal be dcno~ed b)~ s, fJ, . p_,. P~· One can "hybridize" these
1
t 1 for~n .SJr hybnd orb1tals < r t~trahedral orbitals by constructing
the flit"\ mg hn a r o mb111atto n. (Pauling 1960):

Prt = ~( + p , + p,. P~ )
I.Pt 2 = ~ ( . + P\· - p , - P:)

I.Pr.l = ~ (s- P.\ + Py - P~ )


lf.'t4 = 1(s - Px - P.r - P: .

The tetrah dral orbitals have their maximum amplitudes along the direc-
rion to th rners o r a tetrahedron whose center is at the origin of coor-
dinate of the o rbita ls. If t\ o such orbitals are centered on neighboring
atom and o ri nted along the line connecting the two atoms, a very large
overl p of the orbitals occurs. which leads to a correspondingly large
bond tr ngth for the electron pair bond between the atoms. The angle Fig. 1.17
between an · pair of bonds or a given a tom is I 09"28'. Such bonds are sp 3 te trahedral o rbita ls.
tr m ly trong. as indicated by the great hardness and resistance to shear
f diam nd.

Comment. Starting with an isola ted silicon atom in the 3s23p2 ground
-tat co nfigurati o n, an energy of 3.5 eV is required to promote an s
el ct ron to a p state yielding the 3s3p' configuration. The direction s of
maximum amplitude o f the sp 3 orbitals along the four tetrahedral
axe are shown in Fig. 1. 17. When electron pair bonds are formed
between neighbo ring atoms with sp 3 orbitals, a substantial amount of
energy is gained that offsets the promotional energy and yields a net
binding energy. The bonds between a given atom and it s four nearest
neighbo rs are shown in Fig. 1. 18. The angle B between bonds of
109' 28' is extremely resistant to deformation .
0

1.4.2 Zincblende structure semiconductors


Fig. 1.18
We already noted th at th e zincblende structure, like the diamond structt~re, Elcctrun pair bonus he l\H'~n a St at m
c ntain s two interpenetrating fcc lattices. This suggests that the bondm.g a nd its fo ur ncun:st n..:i to:h h'-lr,.
i~ primarily ovalent with sp·1 orbitals pa rticipating in the electron patr T he arr0\l sin li alL· ' I ·tr•' ll ' Pin
b nd . akino GaAs as an example, the Ga and As atoms ha ve the electron o ri..:nl ~tt ic•n
Basic characteristics of semico nductors
2

Gn: (Is~ (3pt (4s)1 (4p)


(2.\. 2 (2p)l1 (3s)1

As : ( l..)-, (2s 1- (?p )(o (. 3s )2 (' -~ p )(, (4 s )1 (4


. p )3

, , nd l f ur •Jectr ns beyond closed shells. However


d no t ~.:< rrl: 11
\' IliL I1
· til. l·tltcr ilui.lJO n by transfernng one electron trom an As
. . " •

~can ac 1liL\C 1,.; • • • • •


. l 'L ,,. .,, t nl!i hbo r G·t at m y1eldmg an As 10n and a Ga- ion.
( l Ill 1 11
L ... .... - , •

\\'hl'n thi 1.; th. ne for :.til Ga- s pa1rs. each atom m the ~rystal has four
lectnm beyL~nd Jo ·ed shell · nJ t_e trah~dral ele_ctron pa1r bonds can be
onstructed u:;ing sp" hy bri d l rb1tals JUSt as 111 the group lV semi-
1
on ucl r . We an theref re r fer to the bond in Ga - As as a covalent
bond. On the ther hand, three electrons can be transferred from a Ga atom
t an A at m t yield Ga 1
A --- . Each a tom is an ion with only closed
:h 11 , t f 1 ctr n ·. H ence. the bo nd in G a- ~+ A .. - -- can be regarded as an
ionic bond. Th actual bond is a mixed bond containing both covalent and
i mic chara ter.
The chemical bond between two atoms A a nd B can be described by a
molecular orbital ': given by (Coulson el a/. 1962).

( 1.9)

wh re · A and 8 are atomic orbitals centered on atoms A and B. respec-


tively, and>. is a va ria tional parameter. For the case that A and B refer to As
and Ga <Horns, respectively. :Pr~ and r..p 8 are sp 3 hybrid orbitals oriented
along the line between nearest neighbor As a nd Ga atoms. The orbital part
of the wave function Ill for the two electrons of opposite spin forming the
electron pair bond is

w= 1( 1)'1(2)
= [r..pA(l) + A:Ps( I )J[ .-~(2) + A<tJs( :2 )] . ( 1.10)

Multiplying out the right hand side of Eq . ( 1.9) gives

'lJ = 'P.~ ( l) r..pA(2) + >.[ A( l )r..p s (2) - :PA () ( s( l ))


' A~ 'Ps(l) t,as(2). l !.II )
ln the first term
. I , . on t h e nght
·
hand side of Eq. (1.1 ) bo th I l'tnws
Mt: oca 11zed on ·:t to A · .
b t ' m · Ill the second term they a r ~v nh dt.'tnP ut d
e ween atoms A 'tnd B d . .
atom B. · ' · an Ill the last term they ~tr b th I L.tltzl'J L1 !1
The value or ,\ r . · . .
are lonlize i Ies 111 the ' ·mge )t 0 :::; A S . Fl)r ,\ = tl, t -.rh ·I •..:tn.. n
Tht:se ~·ts~s< 'o)'~. atom A. \\rhile for ,\ = ~ . thev an:· k 'JiiZl'd 'n ..It m .
' • .... ~.:c 11 espond t 0 . . ·
PUle 1Y 1on1c bon is . F(H' /\ _ 1. ~a~.:h k ·tr n t::-
_
cquall" shar•"<·l h -
c twe~.:n the A . .1 B
<~nu atoms, ·md ,,. h<l \ · .1 purd · .d nt
J ..... .
h ll1d .
If a scm ico nclucto r I1 . . 1I1
( )'rnup tv y . " s t' com position .-1' /3''
' ut VI dement) · 1 B ·
mcnt), thl' ~tat · . , 11 .• . . · .tn<. ~ ~ th~..· ca tt n ~n.HIJ
ll, ~.: l.:i.:ll\IL' ch ·u ,
L ~ - I ~l lHJ ( f i llf1 d t Ill
Chemrco l bonding in emiconductors 13
-
' l1 lll! ' r) . llld ll'llll' ll \
• 1,11nc• , ·r ' l "' L"lllpn nnd
, ., ..
-~·n ti -
•'11 fod )'l(\,:! 1

\ I (

OA~ AJ.A, () 47 ll .llK


() ..j, '
GaA' 11.4(1 ll.(,k
() I InA' 0,.:19 f) hX
() _(],' ZnTc 0.4 5 049
( 6:-\ CdTc 0.4 7 0.49
0. ' A ISh 0.44 0 .6\1
0.-!9 CiaSh 04_1 0 .()9
l).4l{ lnSb 0.46 ()_Mi

h_ ( ul n d a/. 1962)

( 1.12)

\\here e 1 the magn itude of the electron charge. The quantity N takes on the
\'alue 4 for group I . emiconductors, 5 for Ill- Y semiconductors, and
6 for 11- VI semi o nductors. Since group IV semiconductors have pure
v. lent bond . A = 1 and QA = QB = Q_ The 111- V and II --VI semi-
onduct r bav A i= 1 and QA = - Q 8 i= 0. The bonds have a partial ionic
-haracter and a re therefore mixed bonds. The magnitudes of the static
ffi ti' e ch.. r_ for a number of compound semiconductors are gi ven in
Table 1.6. An a lternative treatment of ionicity has been given by Phillips
(197.) .

1.4.3 Ill-VI layered semiconductors


In a lay red compound such as InSe, each In atom is bonded to three
ncar t n ighbor Se atoms which lie in a plane and one nearest neighbor In
at m wh ich lies on a line perpendicular to this pla ne and connecting the two
In atoms . These four a toms are located at the corners of a distorted tet-
rahedron _Each Se atom , on the other hand , is bonded directly only to three
n arest neighbor In atoms. This bonding can be understood by noting that
In a nd Se a to m h ave three and six electrons, respectively. beyo nd closed
hell ·:
6
In : ( ls) 2 (2.~f (2p) 6 (3si (3p) 6 (4s/ (4p) (5.s/(5p)
6
Se : ( b / (2s) 2 (2p) 6 (3sr~ (3p) (4.s/ (4p'(

B. tra nsferring o ne electron from an Se atom to a neighboring In atom


accordin g to the equation
. . • t-
in -+ · Se : ____. · ~ n ·-- + - ~e :·
v.e obtai n fo ur electrons on the In " ion and five electrons on theSe+ ion .
Four v / • hybrid orbitals can be constructed on each ion. In the case of In- .
1

Wurtzite tructure semiconductors


1.4.4
The 11 _VI mateJ ial zn occur. in both _the zincblen?e a~d ~vurtzite true.
tures Cd i.: a II- VI em1 onduc torwh1ch occurs pnmanly m thewunzite
·true t ur . Th electronic configurations of the atoms are
2 6
Cd : (1.\)2 (~ )~ 2p )( (3s) (3p) (4.s/ (4p) 6 (5s/
6 2 4
S : (1 )2 (2 ~ (2p (3s) (3p)

corresponding to two and ·ix electrons beyond closed shells for Cd and S.
re p ti ely. B tran. fen·ing two electrons from an S atom to a neighboring
Cd atom according to
. Cd . + . s:... + . . .- +
---------> • C~d .2- s
we obtain four electrons on each ion and the possibility of four tetrahedral
bonds per atom using sp 3 hybrid orbitals. The orientation of the tetrahedra
in succes ive layers of the wurtzi te structure differs from that of the zinc·
blende structure.

1.4.5 IV-VI semiconductors

The rock salt structure in which the lead chalcoeenides PbS. PbSe. anJ
Pb!e crystallize is typical of strongly ionic material~ u has NaCJ and KBr.
Tht~ suggests that the chalcogen atoms acquire tvvo I tr ms from nei.:-h·
bo~mg ~b ato~1s and become doubly negatively h rged with closed sh 11
ele~tromc _con1Igurations similar to those of th halid ions in the alkah
halide. · Smce Pb has four electrons beyond c1 ·~;;d sh 11 ·. we ha\'e. fd
example. ·

. ~b · +· ~: ____,. ·Ph .='+ +: .. :--. !. I.~

Although the bond'10 . .. . ,.


n11 nan tl ~ , , n~·
there is ev· j" . ~ 111 the lead salts seems t h
llen e (Smith 1968) I . n.t .•
. m c n~l l'll
cha racter lnd d . t 1at the h mh g .11
. ec 111 none 0 fth b 111 lhn:-
purely cov·•lent ' . c compound ' t'mtc n ud r·1 th
< or purely IOnic.

1.5 Growth of .
. .. .
1 he\.:uncentration r· pure semiconductor cry
.· . .
an Ius.: of~e . lmpullllcs IS a n~ s nli tl h ·t
. . . tn•cundul·lL)rs l ·. h,
II)C 111pU . . •L
I"I[\' . ' . [IS l L r f1)fL' I p f( till t
. L:nntent F .
· liithenrt,H\?. th m.Jt 1i.tl
Growth of pure e miconductor crystals 15
cr) t<t lhn ~ J • ect -. 11ch as cl t!!> l :)Cal i '11" an • 2
tth J1_rc cntttmc -.iii · n is tl c b<.I.,IS f:n the pro 1 cti m 0
lnen g ~I Ar r
r ~llllt.: nduct )rJc ices. Nootherma1cri·llca n l <llCh it.
rtJ.IT1 1ffif'UTllJCs r JO q l·[ess i ofl enreq Ired.
101 ' " p~1rc ~ol_ cr ·stallin sili on btain d by hydr gcn
I . '' hKh IS a ltq 1d that an b . is tilled manv tim es i 11 ord r
Hea ter
du.:on thus pr d u d i- melted a nd a -inl!lc ~ rvstal is >r )Wn
ne of the main di ' cui ie in a hieving -ingle crystals or
n. L c ntr lhng the temp rature gradient necessary to
J)K<.Hi n. -.: 1 ly u-ed method is the Czochralski method in
Cr) tali.- t u h d to the melt and the crystal is "pulled" from it
I. thdra' in g the seed a . hown in Fig. 1.19. The small single Fig. 1.19
d 1 mounted n a rotating axi and is put in contact with the Diagra m of th~: Czochrai· ki meth d of
the liqmd. Th temperature gradients are adjusted in such a wav cryc La[ growth .

th~ r I grO\\ th occur .. at the surface of the seed. Crystals of diameter~s


up lt : km are obtaina ble b thi method. At present the standard dia-
meter u ed fo r microelectronic applications range from I 0 to 15 em.
In the Czochral ki method a possible ource of pollution is the crucible.
At rhe melting poin t of si licon (1418 C). the crucible is always chemjcally
attacked and p llute the melt. An effective way of removing the impurities
i to use the zone refining method or floating zone method developed by ,I Shie!J
Prann and . ho n in Fig. 1.20. One starts with a single crystal or poly-
cry talline ilic n ingo t. A narrov·/ cylinder on the bottom of the ingot is
heated by a coil a ttached to a high-frequency generator. The local induction .··'
,. _, .
heating forms a narrow molten zone. By slowly moving the heating coil ..: ·- <
/,

upward . a lo displacement of the molten zone takes place followed by ., " .. : .


olidification. Once the whole polycrystalline ingot has been passed
through b th molten zone, one obtains a single-crystal ingot. By repeating
thi roce man times one can obtain extremely pure material. Silicon
·ith imp uri ty levels as low as 10- 10 can be produced by zone refining. Such
extraordinary purity bas made possible the development of modern elec-
tr nic and computer technology to the extent we know it today. ---++- Monocry ~tal
To understa nd the basis of zone refining consider a solid in equilibrium
with it liquid phase. The impurity concentration is cL in the liquid phase SecJ
and c in th so lid phase. The segregation coeftlcient K of the impurity is
d fined to be the ratio ofcL to cs : Support

CL
K = - . (1.14)
cs Fig. 1.20
Diagram of the Ll)I1C refinin g methlld or
In general K is much larger than unity, impurities being more soluble i.n the crystal purification .
liquid than in the solid. Let the impurity concentration in the starting mgot
be ·o. The initial molten zone also has impurity concentration co, but the
first solid sel!m nt obtained after the passage of the molten zone has the
ncentratio~1 c' =co/ K . If K > 1. the solid segment has a lower impurity
\ nc ntration than initially. As the molten zone progresses, It becomes
enri h d with impurities until its impurity concentration reaches the value
Kc<,. urther motion of the molten zone through the crystal g.JVeS no
additional purilication.
c1 = cu/ K ,

\\here ~ 1 4 Ljf. Clearly, if both K and S are large, very significant


punlh.. ation can be achieve

Problems
1. Prov tha t in a cubic crystal the direction [hk f] is perpendicular to the plane
(hf.::C) . Ca n thi demons tration be !!eneralized to all crystal systems'.1
DeL rm in . th direction perpendicular to the (Ill ) plane of the tetragonal
la ttice.
3. Iden tify the plane \Vith maximum density of atoms in a fa ce-centered cubic
la ttice. Show that the maximum proportion of the available volume \vhich can
be filled b, hard spheres in a face-centered cubic lattice is 0.74. What is this
proportion for a bod y-ce ntered c ubic lattice?
4. The lattice constant of the di amond form of carbon is 3.567 A. Given that the
0

density is 3.516gjcm 3, calculate the number of atoms in the elemental cube. Is


your result consistent with the diam o nd structure'!
5. Carbon also cr:ystallizes as gra phite w.hich belongs to the hexagonal system.
[f the lattice constants are a = 2.41 A. and c=6.70A. and the densit'¥ is
3
2.25 g,icm . how man y atoms does the primitive unit cell co nt ain') How n{any
i~terpenetrating hexagonal Brava is lattices does the graphite tructure have'!
6. For Cd~ m the wurtzite structure the lattice constants are specilied by
u = 4.14 A and c = 1.62 a. Calculate the density of the crvstal ·:m d the volume
of the primitive unit cell. What is the numbe~ of neare~t nei!!hbors and the
distance between them? How ma ny ato ms does the primitive u~it cell contain.'

References
C. A. Co ulson . L B R -d ·. lD 0 ,-~
(I%:!). · · e ei, anc . Stocker. Proc. Ro1· . , ~ 1c. (L ndon ) A27 , -'=' ·

· Kittel, lntroducti
ew York, t<.JR6).
II to Solid S tar!! PI · ·· · · SI.."lll
1_1.\IO. '
di.tl n (Jl hn \\'IIi:'~-
l. Paulin~, The Nat ure o( t/r > C l . ·. 1 - . . 11 ni\ersit)
Prc!is, Ithaca, I960). · ( l e llt/W Bond. 1 htrd ed ttt on ( orn.:

W. J . Pfann, in Solid S t 1 . H
!Academic Press N - \Jll (' Phi 'SI C'.\, Vol. ~- eds. F t.:it unJ urnru
J -. . . . , · · ew • o rk , 1957 ).
. . Phtlltps, Bond~ und B I .
I'J7 3J. . Wl c s 111 S l:'mit·onductnrs l '<to '111tl.
R. A. Smith ~-c . · . I
'I1 . . . 11111 unc llctorv ( C· b . :1 -
· Wc1Bn1antel and . .t m rll gt' Un tversity P r •s 1
Vnlug, Berlin. 1')7l) ). Hamann. Grundlugr"ll tier F,•vtl.. ''f'
ne gy and •

ery

Key deas Bands and gaps


Th 1g n t H~.:s or an ele tron nll)Ving in the periodic potential of a crystal
re Bl 1 1/a/cs \\ ho e enero · igenvalues can only take
c rl m, !lowed \alu~s I ing in energr hands. .
Ek:t:tr 11 m \·e as if th i ns are instantancoi.tslv '
at rest . 2 .1 SchrOdingerequotion
The 1 (lUrier expan. 1on o r a p~:: riodic pO!cntial involves sums over wave 2 . 2 Electrons in o periodic potential
ectors called retiJ mcal larrice vectors.
l11e dectroni eigen ' ta te. are determined by solving the Schriidinger 2 .3 Schrodingerequotion foro periodic
l'£flltltion for a period ic potential. potential
The de11 ·iry o.felecrronic stare. ink-space for crystal volume n is 2.4 Expansion of the eigenfunction in plane

(2~)-'.
wove$
g(k) =
Each eigenfunction of an electron moving in a periodic potential 2.5 Bloch'stheorem
con i t of a plane ll'avl:'jacwr and a periodicfunctionfactor.
:'\ weak p riodic potential perturbation leads to strong scattering of 2.6 Electron$ in o weak periodic potential
el ctrons wi th wave vectors k satisfying the Brag~? cunthtion
1
k ·/~/ = ~~~- where G is a reciprocal lattice vector.
The plane which bisect the reciprocal lattice vectors G, the Bragg planes. 2.7 Brillouinzone$
ncl se spaces called Brillouin zones.
The dcgcncrac, of the zero order states \k) and \k - G ) at the 2 .8 Energy bonds and energy bond gaps

Brillo uin zone boundary is lifted in degenerate perturbation theory.


h p n urbed energies Ek are split at the Brillouin zone boundary by
an amo unt ~ \ Vc \, leading to a discontinuity or gap in Ek which
:::.eparate t\VO energy hands. In the reducfd ::one scheme, all of the
n rgy bands can be represented within the
range or vvave vectors in the first Brillouin zone.
When~the electron - ion interaction is strong, the tight hinding or LCAO 2.9 Tightbindingmethod

method provides the electron wave functions as series of functions


localized about the nuclei. The localized functions can be represented
by Wmmier_/imctions or by atomic orbitals.
. bands: basic theory
El ctrontc energy
. . Ill\ such a.., rectifiers that we now associate with ·ern·
II •h ·tpp1 alit h . 1-
It
• ,H' ~ • · , . ~fa r back as t e ntncteenth centurv it .
~t )f~ hac.1 1
,\.: n 11 t 11
JV
. . - , Wet,
~..: n u~.; · i p en t ofquantum mechamcstn the late 1920sth
ntil tcrL 11e l 'vL 1 1 at
1
' ' u : r r the e r perti s became understood. A. H. Wi i<·
th 1)' I ~ 1 ;lsJS Ill . . . >On
P 1 •\. th dectr me band theory of crystals developed b
\. ··d l 1 - 1l . f' .~ d )
, . . b". Pllli ·d wthc understandmg o sem1con uctors. Propertie
F I I d. ,;,ll 'fi . f I . I . . 'S
• . :.. e n g.1. 11• L tempen t ure cocl tctent. o e ectnca . resJstJvitv- folio',,.
1
tb; 11 ·~ theory. The key 1ngred1ents are the Bloch states
h reth ctge stJtes of an electron moving in the periodic p~tential of a
cr tal. The energi s of the Blo h ta les cannot take on aJI posstble values.
b; l arc r slricted to certain all \Ved regton s or bands sep_arat~d from one
Jlo c..l n~r~. nanJ
;.mother by f rbidd n regi ns or band gaps as shown m F1g. 2.1. The
. llowed en ro} hand are a na logous to the pass bands of an electric
~ransnu::.::,ion Une and are ha racteristic of any wave propagating through a
peri die structur (Brillo uin l_ 5'' ). . . .
In a pur emi nd uct r w1thout defects and at 0 K , certam bands are
Fig. 2.1
11 wed n ·rg\ han anJ forb idden completely full f l ctrons and the remaining bands are completely empty.
c!nerg) gap of,m el 'Clr n 111 a p ri lie A we shall s e later, th is situation corresponds to an insulator. If the
p t..:n llal. tempera ture of the crystal is raised . electrons will be excited from filled
bands to empty bands leading to partial occupancy of these bands. Under
these circumstances. the crystal becomes a semjconductor with a con-
ductivity that increases r·otpidly with increasing temperature as more and
more electrons are excited into originally empty bands. The underlying
basis for these statements will become apparent as we proceed .

2.1 Schrodinger equation


An ideal crystal consists of an infinite array of ions loca ted at or near lattice
sites and an assembly of electrons moving in the field of the ions. The basil·
properties of Crystals fOliO\\' from the d yn;m ics oft hese j n teracting system~.
In order to solve this dynamical problem. we first write down the nHnplere
Schrodinger equation that includes electron- electron electron- ion. and
ion- ion inte~actions. We then introduce the approxima~ion that enable~ us
to find solutions corresponding to the difrerent aspects f he beha\illf 11
the . crvstal·
J •
electi·Onl·c mo· l.ton, wmc
· · motton.
· · tn
a nd thetr · · ~\'tth
· t rncttOih
vanous perturbations including external fields.
The complete S h10
. . c .··d·mgcr equat1on.
for 11 elecrr n.~ anti.\ t '1!1S can 1.t·l.'
111
written terms or the electronic coordinates r 1• ••.• r anJ th~ illflll
coordmate R 1 , · · · .. R l\' ,ls
.,

I~
L
II .\' '
fjI -
v- _I
. + l , tR
_I
-
v,. -
n _
- c-
II
~
[ 1
i = l - 111 L 2M .
I.. = I I.
/.. + -' i.L
/- l
t_

I ii
1 . •• • R ~, )

+ V,.;(,.I
. • . . . •
,. · R I . . . . ' R \')] \V
II ' = Elf! ,

where lht.: fir ' t t ~ .


et m on the 1 ·I' t . · .
the second is th . - c t Ltnd stc.k Is tlw km ·t
.
l1L)f1 S,
'·I . 'l . .
~ cc ton lnl~ra ~ · . IC ,-.11
t: "I Ill'! ' '1' "\ I' t I
~ ... ·:::-. n 1 1 ·It n~ l h.' 1
c 1 t\ n Pfllcntnl lh·· . . .
. ' • '- illll r t h I:> tit ' ILlll h 11 Ill ,
Schrodinger equation 19
111 11
~ntct<.~ ctinn pnh.:ntial. In the third tc rm . t, 1 is
1 'll

·trn 1!\ ' ,tn d f. a nd the prim · t'll the sum mea n~ that
/I" ' cl utkd. T ltc :-pin ·1Wb1t interaction and othe r
IIC lllllllkd j',lr l ht.: prt'. t.:lll.
t Hl 111.1:->. 111 IS sma ll r by a ractor o r at least I /1 ROO than
. ti1L 'IL'cl rl n m o tion is in general much faster than that of
u.tr '11 J i..,t ri t uti _n adjust cont inuously to thl' positio ns
,tt ~lll) 111. ta n t I t 1111e can be a::;sumcd tu be the same as
1. "er a t r ' l. hi · assumpti o n i ca lled the adiabatic
a 10n Bl n~ ;.md_ I "'nhcimer 1927) . It ca n he ex p ressed by writin g
-----•a• ... "I~ ·nlunctt n W a · a p roduct of fun ctions of the electron ic
,., . . . r,. repre en ted collecti vely by r . a nd the ionic coordi·
. R . r·pr ' en t d collecti ely by R:

'I! (r . R) = d r. R);;( R). (2.2)

\Ye c l<.H a panial pa ration of the electronic and io nic coordinates has
b en aclw?-.. db) the a diabatic approximation.
The fundi n 1.:' r. R) is the electronic eigenfunction and is a function of
the lectronic ourd ina tes r as variables with the ionic coordina tes R
app anng a. fixed parameters. It sa tisfies the electronic Schrodinger
equation

[-t li2 \';


1=l _ /II
71 L"
- i.i= J
1 e2
~
1
+ Vc,(r. R)
'1
l (r, R) = E, (R )7/;(r. R). (2.3)

\\her E<.(R ) is th lectronic energy eigenvalue a nd is a function oft he ionic


o rd inat R. The function <;(R ) is the ioniceigenfunction and is taken to
. au f) th a proxima te equation

(2.4)

\vher ¢> (R ) = Et:( R ) + Vii( R) is the effective potential energy of the ions
and E i · the tota l energy eigenvalue. Eq uatio n (2.4) is the ionicSchrodinger
equation and arises whe n Eq . (2 .2) is substituted jnto Eq . (2 .1), Eq. (2 .3) is
used. and the terms

ar neglected. The latter terms represent the nonadiobotic coupling of the


electronic and ionic motions.
L p to this point the io nic coordinates R in Eq . (2.3) arc arbitrary. If the
i n cu py the sites R 11 of the equilibrium crystal structure, the potenttal
V,., (r. Rq) beco mes a periodic potential with the periodicity of the crys ta l
lattice.
Electronic energy bands: basic theory
0
• Electrons in a periodic potential
r 22
_ ·c()nuudor r stal the periodicity of the perfect cry, tal is 1.
In a r ·• I ~et 1l . . . . I d cI •
. J'Htritit:s uc· nc1es. mtcrstttla s an other defect and b
ruptcli l1~ 111 • • . . . . . v
·l1 r tlion ul the nuclei about thetr equthbnum po iti n •
th~ t I1crma \1 '
I . . . 5. 1n
. . ·s ·tis · t modera te temperatures these devtattons f
, , II -pr pared L rom
peri 1 dic t: lea tit cha.ng:s 111 the dectron~c energtes t~at are relattvely ·mall
• . . . .

.,,llt can ben •glectcd 111 !tr ·t approxtmatwn. The pnmary problem is then
he Ill 1 rion of the ele tr ns in t~1e field of the. periodic potential of the
p itivt: 1011 ._. a ·h of which provtdes an_attractive potential as shown in
Fig.2.2
Plll n 1, 1, , 1 0~k 1~0lat.: I i n. r i&. 2.2 . To si mpl ify the pr blem even turther, w_e neglect the Coulomb
int~.;ractions b twee n the lcctr n and focus on a smgle electron movine in
a peri dit: potential V( r ) wh ~re ,. is the position vector of the electr~n.
Schemati diagram;:; reri die potentials along lines containing ions and
\ 'frl
bet\ een pla n ~· f i n. ar , hown in Figs. 2.3 and 2.4, respectively.
Th periodicit c ndition ati sfied by V(r ) is

V(r + R(t) ) = V(r), (2.5)

where R(e) is a lattice vector given by Eq. ( 1.1 ). Any periodic function can
be expanded in a Fourier series. For V(r) we can write
Fig. 2.3
f\ tcntial al ng a line of ions. V(r) =LV GeiGr , (2.6)
G

\'(r)
where G is a reciprocal lattice vector which can be determined m the
following way. Replacer by r + R( ) in Eq. (2.6):

V(r + R(l:.')) = L1 c e iG (r - Rtll) = L1 ceiG'r eiGRt•) . ( ~.7 1


r G G

Now substitute Eqs. (2.6) and (2.7) into the periodicity condition, Eq. (2.5):

Fig. 2.4
P lcntial along a lint:: between planes of
1() 11 <..

In order for Eq (I 8) t 0 b .
· -· e vahd for all values of r. '.Ve must have

e i(iR( I = I.

MakinguseofEll·1· (I · I ) , we o b tam
.

from which follows

G · u; = ~1rn, [
i = I")\
~ -~
(2 11
where the L u· ..
. I ctnlttu.:s nur, · " " ' · 11
ol Eqs. (2 . 1!) is I t: Hlh.:gu S. lt can h > ea o jl~· \ ~.:nrkd th tlthl? , ctlttl l'
Electrons in a periodic potential 21

2rr
h - = - 2n a1· - a 1, (2. 13)

lu ne ~ f the primitive unit cell given hy Eq. ( 1.2). The vectors


h~.: pri1~iti:,'~ translation vectors of the reciprocallallice . They
th" p ntmtlve translation vectors of the direct lattice by the

a; · b 1 = 2rr6u. i. j = I. 2, 3 (2.14)
h Kro necker delta (Du = I if i = j , 0 if i =F f).
oeffi ·ients o ft he periodic potential , V c, can be obtained by
in,·crtin.; the u ·ier series in Eq. (2.6). The result is

Vc = - 1
flo
1·cell
d .) rV(r) _,,,.
·c (2.15)

w~ n te that Vo is simply the average potential over a primitive unit cell.


Example 2.1: Primitive unit cell of the reciprocal lattice
Deriv the r lation between the volumes of the primitive unit cells of
the reciprocal and direct lattices.
olution. The volume n, of the primitive unit cell of the reciprocal
Iallie i given by

sing the expressions


2n
h2 =no ·'
- a' x a 1
,
we obtain
(1n)2
f2,. = ~ - lbl · [(a3 a,) (al a2)]1.
26 X X X

The theorem of vector analysis concerning the vector triple product


gives
(a 1 x a 1) x (a 1 x a 2) = [(a 3 x a 1) · a2]a1 - [(a1 x a,) · al]a2
= [(a 3 x a,)· a2]a,.

Combining this result with the condition


b 1 • a 1 = 2n,

we obtain
b ds · basic theory
Electronic energy an .

u b~tJtuting
lal . (a2 ;-< a~) l = no
m ' I.J ( 1 21 'It: ds the de ired result
. ( 27r)~
n,. =~

\ •h th< l th, \ olume of the primitive unit cell o_ft~~ reciprocal


tttt.:s
< t · ei in ·e dyproporti nal tothevolumeofthepnmitJveunitcell
t (the direct Ia ticc.

2.3 Schrodinger equation for a periodic potential


In dealing with th dynami . of electrons in crystals, we shall be primarily
c ncern d. irh electron en rgies on the order of a few eV. The de Broglie
wavelength ,\ is rela t d t the energy E by
h'2
E =--.,,
2m>.""
where hi, Planck's constant and 1n is the electron mass. For the energies of
interest,>. is on the order of a lattice spacing, so diffraction effects will be
important and the wave picture of the electron must be employed through
the Schrodingerequation.
In the coordinate representation. the momentum operator pis related to
the gradient operator V by p = - inV. where fi = h/21f . The Schrodinger
equation for an electron moving in a periodic potential fl' (r ) is
H·. (r) = E ·(r), (1.1 )
where

H = Ho + V(r), (2. 1 ~ 1

Ho is the kinetic energy operator given by


-, -,
H 0 = p- = _ !i-v- l~-19 '
2111 2111 '
n "' ·
.v - ts. .the Laplaci·m .
' 0 peiator, and f (r) I.S the eioenfuncti n. Onlv IC .. 1
r L1 1··e\\
specwl cases of th , · d. · ·
b . t: peno Ic potential can the hr "ding r ~quanon
b

e so1vect analyttcall 0 · Q\
exp· d. . y. ne can, hO\vever, obtctin a f rmal soluuon ·
an mg '1/.1. '') m ct -ser'I Cs
(c ·I ~
. ~ o f' f unctions
. ,
tormmo. . . ,_
·t c rnpl te · ·t. A p~t rlJI.L
<LI y co nvenient set f tl11. e, l lf
the rre ,1 or s purpose consists of th io nfunc.:til ns \ (r '
c e ectron Hamiltonian J-1 e
(1,

llo \ (,.) = r:·0 \ (,.).


where r:o JS 1 free elect
· l1c . .
one ·ecs th·:~t . ron ene 1gy ugcnvalue. \Vit h HIJ "1\ II t:l\ Ey (.2 till.
' P1.1ne w·tve ·~ ·
' s cunst1tute ·olutions.· t·' Ly 1 , ,
\-·-

\ (,.) = c'" ,..


Schrodinger equation for a periodic potential 23

( 2.22)

r /. has c01~ ..tant components that are convenien tly ::.pccincd


oundarycond1t1ons. One starts with the crystal in the fo rm of a
t"''"'"'~"~, \ Jth edge l en_!! t~1 s L1, L1. L3 a nd periodically reproduces the
11 ll the space 1. hlkcl. The original crystal se rves as a unit cell
ry tal. and o ne n::quires that the eigenfunction x( r ) satisfy the
md1t1 ) 11.

\ (r + 1;ar) = x(r' , i = l , 2.3 (2.23)

\\her ,la~l = L;. the ; are integers. and the a; are the primitive transla-
u n \cdor.
quation (1. - 1) is the periodic boundary condition of Born and
\Oil K ann:in. Sub -rituting Eq . (2.21) into this equation yields

(2.24)

Jfw writ k in the form


(2.25)

wh re th b; are the primitive translation vectors of the reciprocal lattice,


and use Eq. (2.14). we obtain

e2rriN,p 1 = \ (2.26)

ur
111; (2.27)
p;=-y ,
1 i

where the 111; are integers. Equation (2 .25) can now be written as

m1 m2 m 3h (2.28 )
k = - hl + - h?+- I
N1 N2 - N3 .

which is the specification of k according to periodic boundary conditions.


It should be noted that the volume associated with one k value in reci-
procal space is

(2 .29)
~flk = .I r \[hl · (h2 X h3)] \
N,N21\ 3
and tha t N = N N N is the number of primitive unit cells in the c rysta l.
1 2 3
Sine lb . (b x b ) \ is the volume of the primitive unit cell ofthe reciprocal
1 2 3
la ttice, the numbe r of k values in the latter volume is given by

lh1 · (h2 X h3) \ = N . (2.30)


~nk
Electronic energy bands: basic theory

hHthc.:t rd .tl, .,nuit


...
er of allowedwavevectorskinaprimitiveunit
b fl·. . . ee1l
. .oc.··tll·tttice
recrpt · i .qu·. I to the
. . num er o cttt1ce s1tcs m the cry. t·a .
1 1h, 1
racrr.;tal ofmacr . c prcs1z . th1s 1s a very large number, on the order of
·ud·n·· nu 11ber. ..
t 1 Ie 1 r ·r Hn the wav peri die boundary
. . conditions
d . are introduced th·at
c t . are ncl!lec ted. If one 1s on 1y mtereste Ill the bulk properr
- . d .h te'i
, rc 1 , tals. the rror assocrat_e wrt the use of periodic
!· r c 1 dlti Ih 1 xtremeJy small and IS more than compensated b
tl e ci ·nou ~implificati n f Lhe ~:n~thematics relative to that require~
hen "Ul face c.:f <.:fo' arc treuted exphcrtly.

E ·ample 2.2: Densi ty-of- ·tate in reciprocal space


Deriv~.: an e pre· 1011 f r the density-of-states in reciprocal space.
'olution. The q mntit. ~Dk i the volume in reciprocal space asso-
ciated \ ith ne k vatu a pecified by periodic boundary conditions.
The in er f ~nk i th number of k values associated with unit
lume in r ciprocal ·pace, or in other words. the density-of-states in
r cip rocal (k). From Eq. (2.30) we have

Since the volume oft he primitive unit cell of the reciprocal lattice 0,. is
lhr · b1 x b3l.

N
g(k ) = -
n,. .
But we saw in Example 2.1 that

so

g(k) = Nn~ = ~
( -') 7r ) ·' (2rr) · '
where 0 is the volu f h .
account f . h me 0 . t e crystal. If we introdu e , f< tor o1 2 w
or t e two pOS ' tbl ·· · · · .
the density-of- t ·~ tes . sl de oncntat1ons ot ele t r n ·p111. w·· htal!l
· " · me u mg spin

(,..
g ,, " ) == -
n, .
4Tt·1

2.4 Expansion of th .
Tt e e•genfunction in plan a es
l Pancwave
1 ·t· t"·
co mpkte set ,·,1 d cs that ,.:onstituk the JO"nfun ll
r . terms )r h' -
ull Hamiltonian H . "·' w Ich \ 'e c·m e p:m I ·tn ·•-
. Lll.:h :tn '\ . ,· .
1.: puns1 n 1 l.Ju" d ~nt l
Bloch's theorem
2
n m1 < fa I l1Uric r ~ n l.!" i.l (""~ p r·
J1rl d (C Ill p 'fl( fie f.1ULJild;lrV
ta the I rm

t·( r ) -= C (!..k'A'.
(2.31 )
"
(k a r~ the ex pa nsio n cocnlcicnts and k is a \Nave
db) pen tl1c bounJ a ry condition , k = ( 111 1; ..v 1)h, +
11h' \- h_· rn q . (2.2R). Substituting Eq. (2.3 1) into the
n r lJU~~lJ lfl. . -. 17)_ and using the expansio n of the period ic
1 I m Fl uncr ·cne,. f q . (1. 1). yi tel

2m C(k)e'"·r + .2:;: L VcC(k ei(G+k )·r = £ L C( k )eikr _


~ k k

(2.32)
In tht: cc nd term on the left hand ide o f this equation, we make the
·uh tituuon k' = G - k a nd o btain

LL G (k ) i(G+k,. = LL VGC(k' - G )eik' r


G k G k'

= L L VcC(k - G )e;,..,.• (2. 33)


G k

\\here th Ia t fo rm re ults from the replacement o f the dummy summation


\ariabl k' y the dummy ' Umma tion variable k.
The hrodinger equation can now be rew ritten in the form

L{
k
1
11'2 k / 2m )C(k ) + L~ G
cC(k - G) - EC(k ) } cik·r = 0. (2. 34)

For th i eq uati o n to be va lid for a n arbitrary val ue of r . we must set the


c fficie nt of each factor c;",. equal to zero:

(t/-!r / 2m)C(k ) L VGC (k - G) - EC(k ) = 0. (2.35)


G

Add itional eq ua tio ns in volving the coefficients C (k - G) can be obtained


b 1 replacing k by k - G and G by G' in Eq. (2.35) and considering all values
fG. Since ""e have infinitely many reciproca l lattice vectors G. we have an
infinite set of linea r homogeneo us algebraic eq uation s in the coefficients
C(k - G ). For a nontrivial solution to exist, the detern1inant of the coef-
ficients C (k - G ) must be zero . This secularequation specifies the allowed
eigenvalue of the energy E for a given va lue of k. ln practice. the deter-
minant is made finite by restricting the values of G employed to those with
nngnit ude less than some specilicd value. The na ture of the solutions to the
sec ular eq uation is disc ussed in Section 2.9.

2.5 Bloch's theorem


Wen te from Eq . (2.35) that a given k is coupled to only those k's that differ
f'rum it by a reci procal la ttice vector G. We can therefore pick a particular k
b nds. basic theory
Electronic energy a .
6 . . n rewrite q. (2 .31) in the form
a. 'l tailing p HOt a
•drl = L C(k - G')ci(k - G )·r

[L
G

= ,P· r C(k - G)e - i(lrl· (2.36)


G

. Ir' JU'l ~.; hrm.:L t on the right hand side of Eq. (2.36) is a
h q- ntn_ •
f . 1•1 n 1 ,. w1th the pe nodicity of the cryst,dlattice, as may be
< • . . . , , • •
• J"
pc 1 1u mt.: _, • E 29 W I ·
\ n' ~.:d hy r plt.lCi g . by,. + R( f) and usmg q. ( . ). e ca I this periodic
fundi n 111. (')

(2.37 )
G

a d " rit
\ ( r ) = e ik. ·I" Uk ( r ) . (2.3S J

Equation (2.38) on ti tutes Bloch's theorem, which states that the eigen-
function of an elect ron moving in a periodic potential consists of a plane
wave factor and a periodic function foetor. An eigenfunction of the fom1
(2.38) is called a Bloch function (Bloch 1928).
Comment.lfthe position vector r is augmented by a lattice translation
vector R(e), the Bloch function '1/.Jk.( r) is changed only by a phase
factor. To demonstrate this, let us replace,. by r + R( t) on both sides
of Eq . (2 .38) which states Bloch's theorem:

'1/Jk(r + R(C)) = e ik. ·(r,-R(f )) uk ( r + R(


Since uk(r) is periodic with the periodicity of the lattice,

and we can write

· k(r R (e)) = eik. (r R(l )) uk (r )


= e ik R( lc/"'.ut.. (r)
= e ik ·RI\() IJik.
· r )
\ 1' .

Thus. t!k(r . R (f)) 15


.. . . . . . J
tiplied b 1 sunply the ongmal Bl och I undt n n (r) m 1 •
Y t 1e phase facto . 1k R(il · •
· 1 e · wh1ch is inck p nd nl ol r

2.6 Electrons in k
F . . . a wea periodic potential
OI sem ico nducto rs and .
the one-ckctn 11 . . 111 cli1_ ther oliu. thl.'pr r
. . u l'lgen t ut t" , •.
l: Pll.: sscd in ·q . (
2 3 . •~'- h.ms hy m an::. I I h~.: b 1 ·
lh;: c'•rrl'spnndin ' S ·- ~~J '.~.:q.utrcs hundred::. f p l.m.' l
g · 1. h roc( Ill ~ 1 . .
C4ll.llll , lj
Electrons in a weak periodic potential 27

1 •t h • t m . dll'finiit to cxtr<~ct the e~se ntial ph ysics in ,,


' n td Lhi ' · )mphcltlion we consider a weak potential that
Iltllhati n t heory . We thcrl·hy obtain analytic results from
· 11p )rtant 1h sica] principles can be deduced.
he r )tcn tial I '(r ) as a perturbati on , the zero-order eigen-
th\.' c hr ·dinger equatio n. Eq. (2 . 17) . a re plane waves

(0 ) ( )
r
I ,.,_I' I (2.39)
··
~ . = -vTI e " · = k) '

lu me of the crystal. and the zero-order energy eigenvalues

E (o) = n-,,-
I I I

(2.40)
k 2m ·

ummg f r th e moment that the state of the wave vector k is not coupled
b_· the p ten tial to another state of eq ual energy, we can write the perturbed
rn rgy eig nvalue to second order as

(
ki V( ·)ik) + ""' (ki V(r)ik')(k' i V(r) \k ) (2.41)
I ~ E (O) - £ (0 ) ,
k' k k'

\'h r

(2.42)

Substituting Eq. (2 .6) into Eq. (2.42) yields the relation

(2.43)

Using this result, Eq. (2.41) becomes

(O) ""' VcV- c (2.44)


Ek = Ek + Vo +~ (Ol (Ol ·
G Ek - Ek - G

Taking the complex conjugate of Eq. (2.6) and noting that V(,.) is real, we
have

V(r) = v • (r) =L V~e-iG···


G

which, upon replacing the dummy summation variable G by - G, becomes

v(,.) = L v~ u-e'G·· . (2.45)


G
. bonds: basic theory
Electrontc energy
. d ('"' 4'i) l!ivcs the result
'lnlf a ring Cq ·. (-.6 Ml -· - ~
(2.46)

J ) ·an thl!n be rew ritten as


d!H n ( - 44
~ v(i 2 1

= l:.k + Vo + 4
· l Ul I

Ek £ !OJ - E (OJ , (2.47j


G k k- G

, ' 0) (0 )
which i c rr~.;d to O(f 'c; a'> long_as ~k Ek - G·
Th .. lirst rdcr c rrected eig ntunctiOn has the form

,(OJ ~ (k' l V(r)Jk) .1 (O) •


lf'J. (r) = 'IJ'k ( •·) +0 (0) (O) /Jk' (•)
E" - £",
k'

. ro) ~ vG. . ,/ o) ( )
= . k (r ) + 0 (OJ (OJ u k - G r · (2.48)
G Ek - Ek - G"

Making u e of the fact that \ 0) r ) is a plane wave as given by Eq. (2.39). we


can rewrite Eq. (2.48) as

J ikr {1 ~ Vc -iG·,·} (2.49 )


'lj;k ( ,. ) = me +0
vn
(OJ (0) e
G Ek - Ek - G

which has the Bloch form of a plane wave modulated by a periodic function
uk(r) given by

uk(r) = _ 1 { 1
. Jn
+"""'
0 £ (0) -
VG*
£ (0)
e 1G·r
. } . (2.50 )
G k k- G

2.7 Brillouin zones


The periodicity of the system in real space leads to a periodic di,isil111 L)f
wave vec~or space into Brillouin zones. Within a given zon th ' nergy of an
electron IS a cont" • . ~ . · ·,
. . muous 1unction of energy but undeP,. ~ a iJ::>l'"Onllnut 1·
~r.ossmg a zone boundary. The Brilloui~ ~one is am =s t u fuJulncept in
llh1
t e lepresentatiOn of l ~ . .
W . e ectromc state m crvstals.
eig c .nov./ .dtscuss· th,e a. bove results 111. •detail. . he perturb<:d enl'·r'•' ::.
1
~~.:nvuuegtvenbyE (/ 4 , . . , - . . , d·r
term v. d · .q . - · 7)contamsaconstant . htltJud rh l u ~rl r
0 111
term is 11' . c1· ~:cond ord er term that is wave vec-t r lkp ·nd ,nl Tllc' I' t tl •
egc~ttve at k - 0
chc · £ (01 s· - anc1 bec mes larve in m· gnitudt: ::. E u •1PP rl:t-
" c· , mce there ·, . ,
numher ::~r .·
I
. •s. " Isum O\'er G .m::;. tl-.·• (~ .-P
stngulantte~ 111
~
th~.:r .. '" Jll 111
tint!·
. ~·
en~::rgy. As·111 -1. .· . t le ex.pr~:ssion for the . 'l. ll1d r I 'f ·!lUI
' ' dr s•tu·tt• 11 .1 1-
Eq (2.49) II' .1 . ' • PP Ies tu 1 ·n r
the pc rt urh~J 'll!l..ll t~ndi 'll ::! '
· ' stnguhrity ~ h '•th'
wavl' state 1.. _ (,' . ' · U\.'cur~ lor G - G 1 th ' ..1 111 t I ·I · .
I •o In the p . t ·b .
strong '>t:all~.:rin • <J . \:I" Lll .eJ L"tgentun~.. ltl n Jt , \. ,.
l '

g 1 th~: ~:lectrotl I'"· Ill l 1 1.1tl· "'


(J
Brillouin zones 29
the -mgula ri L_'.

' .51

· i1.111 fo r the unperturbed ener<:rv !liven


~-- ._

ua tion for the plane in wave vector space that


1 d th~ rec1pr c· ! lattice · tor Go. It is the famous Bragg condition for
the J- r nt call ring fplane waves by a periodic structure. The perpen-
d. I r h1 e t r plane is known as a Bragg plane. We note that k = Go / 2
-~ 11 1 Eq. ( ~ (0 l -: £ -to)
' - 51_ a n th·at- £_Go/2 Go/ 2 f rom E·q. (2.51
· ). -
mcc there IS a Bragg condltton for each G, the Bragg planes divide wave
\ector pace into zones which arc called Brillouin zones. The first Brillouin
zone enclose the rigin and is the smallest volume entirely enclosed by the
Bragg plane ofr ciprocallattice vectors drawn from the origin. The second
Brillouin zon onsis ts of those portions of volume just outside and con-
tiguou w1th the first z.o ne which, when translated by appropriate reciprocal
lattice vector , \viii exactly fill the first zone. Third and higher zones can be
de cribed in a similar manner. It can be shown (Ziman 1972) that the
olum of ch Brillouin zone is the same as that of the primitive unit cell of
th r ciprocallattice. Consequently, we deduce from Eq. (2.30) that each
zone o ntai ns values of the wave vector k allowed by periodic boundary
o nditio ns, where N is the number of primitive unit cells in the crystal. The Fig. 2.5
fi r t thr Brillouin zones for a two-dimensional square lattice are shown The first three Bri llouin zont::s of a
two-dimensional square lattice.
in Fig. 2.5.
Example 2.3: Brillouin zone
De cribe the construction of the Jirst Brillouin zone for a face-
ntered cubic lattice.
Solution. The primitive translation vectors of the face-centered cubic
lattice with lattice constant a are given by

They can also be written in terms of orthogonal unit vectors.\·, _f,-, i as

a 1 = 2I a ( x, + y, )_,

The volume of the primitive unit cell is

These primitive translation vectors can be combined with Eqs. (2.12)


and (2 . 13) to give the reciprocal lattice vectors G,

G - 2n
- ,[PI ( - X. - y- +:::-' ) ' --
+ l2( X. + _)'- - ::") + f' 3( X~ , -
- )' :::--·)] ,
ll
b nds. basic theory
Electronic energy a .
_ all integer values. From the form f these
.., .
111
·h··r~ ach of 1 1 12 1
' ' h'
cc iproL:allattice of a face-centered cubic lat-
. c ec that t e r r· ' .
e I• rs :-. · d uh·c lat tice. The two sets o G s With smalle t
tic 1." a hody-cc 1tere t:
o z~r n~lgnitudc are:

.... 2.• (-:\ - .i· + .:).


±~ ,/
X - 1'- :).
.

"
± -~,
a -\,
±=-a -"' ±21fa- 2:.\GI
')7r - =~- "'(21f) ·
a

Tb perp ndicul, r bi~ d r planes of these two sets ofG's arc specified
by the equation
3r.
±I -kx + kr- k :: ) = -,
(I ' . a
3r.
±(kx + k.r + k::) = -,
a

and

27r 27r
±kx = - , ±k-- = -.
({
u

The boundary of the first Brillouin zone of the face-centered cubic


lattice has contributions from all 14 of these perpendicular bisector
planes as can be seen in Fig. 2.6.
The first Brillouin zone is the smallest volume centered at the origin thar
is bounded by perpendicular bisector planes. It has the form of the Wigner-
Fig.l.6
Th.: fi r t Brill uin zone of the Seitzprimitiveunitcell for a body-centered cubic lattice and is uniquely spc·
face- entered ubic lattice with ome cified by the symmetry operations of the crvst·tl !at tic'. Points of high
!'high ymmetry inuicat d by symmetry denoted by r. L X. etc .. are shown. in Fig. _.6.

2.8 Energy bands and energy band gaps


lnordertogetfurtherinsightintotheetTectofth p ri i ' p 1 t ntia l nt ,:
energy eigenvalues of an electron, we need to mod if) 1ur pr · dun.: in )rd ~
t handle the de gene1acy .. l occurs 111
t1at . zero rd rat th Bn·11 ('l11·11 Ztll. 1
boundarv' where E4· - (J- ...cd) 1s
.
satisfied . We ust J ~'11 rat plnu r b·tll•111
theory and r
·.
.
ocu~ on the two deot:nera te st a ks A nd A
~ 1 11 •
\\· hd~
neglectmgalloth - ·· Tt1e two eq uationsofthe
::. - h.& r ll·n '" ·
·sct cfEq _, ,,:-.H
L

.,.. t:Is.
thesl: two states are

( l' iO)
-,. I· ·o - D" C k ) 1 (t o 't\1\' - I

.,
£ l 'J I
(~,. . I
\) E,. l , A
Ene gy bands and energy band gaps
31
U.\llc nI 1 an nlri\ ial , !uti m is

: II
1•J. I .II
,_ 0.
01 (2.54 )
Vo - k
I. " "

11 equa ti n 1!.1 \'l: ·


t

+ _1 {£/.10 + £ I.'01G, ± [( /..


( I)
-
(OJ
£1. - G,) + 4 jl G
2
,J Jt}. (2.55) IG
~ 0 k

• tmportant · n ~:q u ence of this result is that, as £ !.( 1 and £ 1°1 Fig. 2.7
· f ~ k - G0 Energy Ek as J functi on o f k n.:a r the
m qua I. t he tv\'~ s I t~t1 n . orE~; come no closer together than 2jVc,J degeneracy point1Go.
In lh r \ l rd. ther~ 1· a d t:c ntmUity or forbidden energy gop in the energy
H.:r u k cun tlrtt ~ cpa rates two allowed energy bands. States of electro~·s
propagatmg through the cr tal do not have energies in the forbidden
'ner!!y gap.
To desLribe the bt:havior oft he energy eigenvalue more precisely near the ,_
~'2iv·(·l
I

degenera • point k = ~ Go. ,~,. c let q = k - *Go and use Eq. (2.40) to elim- I ' '•
in te k fr m Eq. (2.55). The result is -
I

-
(2.56)
' 2IV!c,l
~dL
v)ivc. I
A q --> O.E~.: __, V + £~,G6± / Vc0 / .Forsmallq,weexpandthesquareroot
in E . (_.56) in Taylor series and obtain
Fig. 2.8
The first three allowed energy bands in
1.:- Vo (2.57)
the extended zone scheme.

wh re (} i the angle bet\-veen Go and q.


The b havior of E~; as a function of k is illust rated . chematically in
fi g. -· 7 for a particular value of B. Two bands of allowed energies are
epa rated by an energy gap t :l{ whose magnitude is 2/ VGo /. The wave vector
at whtch the gap occurs is specitied by the Bragg condition contained in
Eq. (2 .52). and it therefore lies on a Brillouin zone boundary. Note that the
c/ dependence forces £ 1, to be normal to the zone boundary itself.
Each nonzero reciprocal lattice vector can give rise to an energy gap. The
fir t three allowed energy bands and the gaps between them are shown in
Fig. 2.~ for a one-dimensional system. Except for the lowest energy band.
the energy bands are split into tv.:o parts. one lying in the domain of negative , ()
wave vector. and the other in the domain of positive wave vectors. This '

behavior is a feature of the extended zone scheme depicted in Fig. 2.8.


-k
An alternative procedure, which in some ways is more attractive. is the
reduced zone scheme. It is obtained by using appropriate reciprocal lattice Fig. 2.9
vector~ to translate the parts of an energy band that lie in an outer Brillouin The tir~t IIHL·..: ..lllt>\\..:d · L·rg\ hantl m
znn mto the first Brillouin zone as shown in Fig. 2.9. In this way, all of the the: redun:d Ll•ne ~dlt•n ..:.
. bands: basic theory
Electronic energy
s an her ' presented within the s~me ran~e of wave vect P i . The
cm:1 g h. nd. eJ·ustificd by notmg that 1f the wave vector k' f
J d:t.:( 1 e t:h meLan
r~ u~.: (r) di cr fr om another wave vector k by a reci proc-,
th 1 d1 tu ndJlHl '!.' c1

111 1• C \ ed r G
k' = k + G. (2.58)

1 nb Ill!! Eq. (:!.3· ). we e tb c1 t

\, (r ) = e'k ' uk' (,.) = eik1· ciG ·r uk ' ( ,. ) .


1

(2.59 J

ThL' factor t ·'G ,. ha the pcriodi ity of the crystal and so does the function
u,.( r ) defined by

llk (r ) =e ' tG' r ( )


uk' ,. = e
iG'·r ( )
Uk+ G r . (2.60)

Con equentl

The Bl ch functions ·l k(r) and k+c(r ) are therefore equivalent.


To complete the justifica tio n of the reduced scheme, we show that the
energy eigenvalue is a periodic function of k with the periodicity of the
reciprocal lattice. If the fo rm o f the Schrodinger equation in Eq. (2.35) is
modified by replacing G by G' and k by k-G. the result is
2
(k - G) C(k- G) +"'"" Vc ,C(k- G- G' ) = Ek C(k- G). (2.62)
2
:
... m L
G'

where the dependence of the energy eigenvalue on k is explicitly indicated.


Since Eq . (2 .62) stands for an infinite number o f equatio ns corresponding
to the infinite number of values ofG, there is an infinite number of solutions
for Ek and the associated coefficient s C( k - G ) which we la bel by an index 11
having the values 1, 2, 3, .. . :
172
2m (k - Gl ·c " (k - G) L I\,-•C11 (k - G - (;' ) = E nk n(k - G).
G'
(2.631

The i~dex 11 is the band index, and the va lues of £ 111. for giY n 11 ami v;tri-
ou -~ fo rmthe nth energy ba nd . The co rresp nd ina 811. ·h funL"£IL111 ~
specthcd bv Eq (/ 16 ) . c-
- - . · - ·- are des1gn·:tted 1j,11k(r ). .
establi ·sh the peii.·OltCtt
lo _. j' ·
y I
··
£ we modi f the hr l tem '1 11 t h · l'll
hand stde of Eq. C' 63) b . · . 11
..
1...
_ ·· G' ith '
- ~ . .d . -· Y tnt1 oducmg b G ' and : ummm\! l .. r .1 0~
sc~.:on term by letting G" = G + G' . Th~· resul t i.
li ~
~-
7: 2111
(k.
-
G ' )2( . (k
" - G V• . , ·
r

+ L
-
C/ '
l 'c;"
(,'
• (!..
1/ -
II,
} = 1"-··" I'·
\ 1\
nergy bands and nergy band gap
3
II 1.!1 \ L

I 1
, ) (~r, (, '
I r," (;] "( It - G 'i

E,.~. ( II It· - I )
12 6 _)

= En!.C,(k - G) .
(2.66)
If\ ru e A in q. (1.. ) by the reciprocal lattice ector G " and set
n
r _- G + G' nL., = G ' G" . tI1e resu It can be cxpres::;cd as

f= !i"J. ,_
[1m (k - R t 0k - A.k - If' + r, k - -K- (k - K ')
]
C11 (k - K')

= E11k - G'' u(k- K ). (2.67 )

in e both G and K in Eq . (2.66) and (2.6 7) pan the space of reciprocal


lattiCe vector 't d since G' and K' are dumm y summation variables
. panning the · m space, we see that Enk- G '' and Enk are eigenvalues of the
arne matrix. If there is no degeneracy of bands at k, then

(2.68)

for an~ alu of G" and therefore Euk is periodic in reciprocal space. This
re ult an be ex tended without difficulty to the case where k is a point of
£ n ra y .

hav thus established the justification for the reduced zone scheme. c
whi(h is the scheme most commonly used in the discussion of electronic
n rg band s. In Section 2.5 we noted that the number of values of the wave
't'Cl · k all wed by periodic boundary conditions i, equal toN, the numher
f primitiv unit cells in the crystal. Since the Bloch functions in a given
nergy band are distinguished by their wave vectors, it follows that there are r
~ M
Bloch functions in an energy band . Each Bloch state can be occupied by
tw lectron. of opposite spin in accordance with the Pauli principle. so 2N
electron can occupy a given energy band.
pecially important for semiconductor physics are the t:tce-centered
cubic and hexagonal lattices. The first Brillouin zone of the former is given Fig. 2.10
in Fig. 2.6 and that of the latter in Fig. 2.1 0. The zone-center point (k. = 0) is Brillouin zone r,,r the hexagLmal l.ll! i ·e.
denoted by r. Particular points of high symmetry on the zone boundary
and in certain directions within the zone are labeled by letters as shovm.
Example 2.4: The Kronig- Penney Model
Develop analytic solutions to the Schrodinger cq uation for a periodi(
p ll:ntial consisting of an array of square-well potentials.
Solution. Consider a one-dimensional periodic potentiaL V(.\·) =
V r + a ). huving lattice constant o and represented by the
b nds · basic theory
ElectroniC energy a .
, arra h wn in Fig. 2.11. The one-dimen"iional
·quHC- s,.c 11
1 •
· . ·
' .. _1 • ~ c . ualJOn for thts case ts
, chn utngcr t1

- lil d2~, (.· ) + V(x}tf,'(.-.:) = £¢,(x).


'2.111 dx- ·
· tl , energy e;:i a n value and ·t/1(X) is the eigenfunction.

-
\\-hen.. F t 1
\: < 1 - h where ~ (.x) = 0. the eigenfunct 10 n is a
~ , . . .
· 11 0
In LI rcg1 . .
t linear ~.:ombmation r pla ne \\/aves travelling to the nght and to the
left:
Fig. 2. 1 .
p I nll I ent:r.,.., d Ill~ Kn.,nJg P.:::nll\!) ..) 1(.\ ·) _- A c,;,h + 8 (;" - i,h .
m d I.
The en rg eig n a 1ue is rda ted to (3 by E = f1 2 .A~ /2m or
rJ = J2mEjtr. . . .
Tn the th r r gion -h < .r < 0, wtthm the barner, the solution is of
the f rm
'IfI 2 ( .\·) -- c?nx
~
+De- ''-'" '

where Vo- E = /7 2 a."2 / 2m or (\' = J2m(Vo- E)/17. At each dis-


continuity of potential, the eigenfunction must satisfy the boundary
conditions that it is continuous and has a continuous first derivative
with respect to the coordinate. For the discontinuity at x = 0. we have
t 1 (0) = 1 2(0)
,.rt (0) = 'if'S(O).
where the primes indicate first derivatives with respect to argument.
For the discontinuity at x = - h, the boundary conditions are
1(-b) = 1h (-b)
• /1 (-b) = ·zt;; (- b).
The eigenfunction must also satisfv Bloch's theorem which for pre-
sent purposes can be written as J

'th (a - h) = eika t!J l (-b)


"·~(a - b) = ei/,a «l1 ( - h).

The boundary condition at x =- h then become


7- ikll I I
t l,' IJ \{/ -
L1) = If'~( -/J)
,- il..a ,, ( ,
(. 1/.'1 (/ - h) = ·~( - h ).
lf one no\v utilizes rl ·
. 1e expansiOns oft ·1 (x) and '' (.Y
one obta1n -

A B= C + D
i1j(A - B) = n(C' _ D)
e ik"( .,·'t-' .I_ Be . '(
i [,, /') 1 ' " A\ , · · ,,,. r t
Tight binding method 35

- 1
~
,
I-) - n ()
\-J 1t ·-.
I 1( II
7! - 2 7!
hi = fl.
'"" - ('
t lh
- c""
- i.-le- '" '' I l II h - ne _,,,, r\e' 'h
Fig. 2.12

I 1 • th~? determina nt give. th quation The Lh:pcndcncc ot the functiOn


( p/ 1a) sLn (.1u) + co~ ( 1a ) nn iu with
(\ ~ - ,{! I' = :.rr(l Iafler Kr n1g and Pen ney
l'c (A. a) = 7 l1 sinh ( 1h) sin [.J a- h)J 1'>:\ 1).
_n
+ osh ( r~ h ) cos[.J (a - h)].

111 or
tnd 1 ar fu n ti ns the en rgy eigenvalue E. this equation
. p ·cihe the dependenc of Eon the v.rave vector/.:. 15
'
A implc re ult arist:s if o ne pas. e_ to the limit b _. O, v0 --... in '
' ''
uch a \U~ that the quantity m V0 ha/ 1i approaches the finite va luep:
2 I

cos (ka) = P sin (3a ) + cos (3a).


'3a
Thi rc ~u J t c rrespond s to a potenti<ll V(x ) consisting of a periodic
array o f delta functions . Since the left hand side lies in the interval - I 11 2rr 3n 4rc
ka
to I f r real k. . the allowed values of E are those that cause the right
hand id to lie in that sa me interval. They correspond to the heavily Fig. 2.13
dra \.vn ra nees of rJa in Fig. 2. 12. Note that the forbidd en ranges Plot of energy in units of :r2h 2 f1 mac
b me : ma llcr as E increases. Figure 2. 13 shows the allowed bands versus reduced wan:: vector forth..:
Kronig- Penncy model with p = 3-:r/ ~
of en r __ E (k ) eparated by gaps at the zone boundaries. (after Kittel 1986).

2.9 Tight binding method


Thl: xpansion of Bloch wave fun ctions in a series of plane waves converges
w 11 ir the electron- ion interaction is weak, i.e. , the electron energy
und rgoes onl -y a small chan!!e as a res ult of the interaction. It is of interest
~ ~

to con ider an alternative method, the tightbindingmethod, which is partic-


ular] , appropriate \vhen the electron- ion interactio n is strong and the
electro n::, ·ue tightly bound to the positive ions. In this method the electron
wave function is expanded in a series of functions th a t are localized about
the vario us nuclei of the crystal.

2 .9.1 Wannier functions


One can con truct a set o f localized function s by taking suitable linea r
combinations of Bloch functi ons t1.'11J. (r ). The res ulting functi o ns, t:allcd
Wannierfunctions. are defined by

w"(r - R (P)) = i\' - ! L e- ik R(I l l/)"k(r) (2 .69 )


k
. bands: basic theory
Ele ctromc ene rgy
_ . . p r unit cell. The fact that '~'n is a function of
t•{)f l h~' C'' t e >I. . lHlh~
t: ,l 1 01 • h d
-.ccn h y usi ng Bloch s t eorem an wntmg
..

!'
r Rl 1) 111 1~ ca t:

= N- _ e -·ikR(rl e. ikr link ( r )


11 '11 (1'- R ) 0
k

iL c/ktr Rf ill"k (r - R(l )), (2. 70


k

wIltf \\(: ll 'L\''' Ll ed the periodicity of u",.(r ). One can use the orthonorm-
L '-' • ,

,tim fth Blu:h funct i n _ , ·11 ,.(r) to show that Wanmcr functiOns centered
n ditTercnl Ia ticc it s are o rth ogo nal:

I.( 3rl\ ' (r - R (()) 11' 11 (r - R(£')) =


, . . 1.1 ' ·

Ea ch Wan ni r fun tion is loca li zed about the lattice site entering into its
d fi nit i1 n. Th is can be easi ly demonstrated for the special case of a simple
cubic !attic with u11 ,.(r ) independent of k: ll11k (r ) = llno( r ) . Then

The function
In\

f' x) = Sll1 X
X X

is a localized function that has its maximum at .\' = 0 and decays in an


Fig. 2.14 o cill atory fashion as .\' ~ ± . This behavior is s h~.)wn in Fig.~-~~.
he un li n ( 111 )lx plotted \ero u · x . Although the orthogonalit of \Va nnier functions localized lH1 different
latt ice ·ites i a desirable property. they are of limited use in energy band
C'tlculati ons. be a use the d esired quantities. the Bloch sta t ·s. must ~
known in order to calculate the Wannier functions. R u ; urse is thacf:w
made to alternative fo rms of localized functi o ns.

2.9.2 LCAO method


A conven ien t se t of localized functions is comp )~cd t at mic orbital~
,_, r. wh~re,.,. d~.ignates th e type· of atom and i rh\. part1 ul t r.lt~1 m~<.: ~t.ll d
that a tum (Is, 2s. 2fJ,. etc.). A ti~Zht binding BIL,d• fun ·ti~ n t -~.. · (rl ''
L' ons tru~:t ed ha ving the- t'c rm ~

I .
'''J.. ,_, (r ) ___ , (,,/.. R '"I l ''
~ !L 1- ""
Tight binding method 37
1\ ( tns~\ era l Blnch ftJJKtion"~clf )rbital. Lentercd
h ' n i n F i !L 2. 1s
11 .1 re
I

n
tnd cncrn\'
:::-.
CJ ~IZ 'I~V·\IU-'
< t:s·. o f tlne IJ
namll. to nJan
.
arc
1111! a hne<LJ' ~ mhinat:ion ofth Bloch fur1ClJ.')J1S . ' I • r
• . ' . 1, " ·'"' or
/'; and r · nd chonsmg: the c 1ett!Lients to mimmize the
I th ~. : Hamdtoman subject to the normalization condi-
tun~tll.. ll . T h conditiOn for achieving this result is that the
Jmmantal quatiun be sa tisfied:

(2. 75)

nt l1f the Hamiltonian matrix!:::! in Eq. (2.75) are designated bv


n.: giYcn b_ ~ · Fig 2.1s
C o ntributions to several k = 0 Bloch

H .-,n.'J' = j ·w~. . (r ·)
· h ~ti I .
H ·1 hk ,.,(r)d 3 r..
't" . X I (2.76)
functions of Is, 2s. a nd 2p- o rbi tals o n
adjacent atomic sites.

\\here the Hamiltonia n for His given by Eq. (2.18). The elements of the
overlap matrix~ ar designated by S,,-1,,.,, , and are given by

(2.77)

lt hould be emphasized that in general S"1.,,.,, is not the Kronecker 6,"-n.'i'


becau atomic orbitals ~.p, 1 ( r - R(f!K) ) and <p,c'i'( r - R( f!'K' )) centered on
different nu lei a re not orthonormal. ln principle, the size of the matrices!:::!
and ~ i infinite. but in practice, one truncates the matrices by including only
a finit n umber of occupied and nearby unoccupied atomic states.
Th x ression for H ,. 1.,,'i' in Eq . (2.76) can be rewritten using Eq. (2.74):

H "i.r;'i ' = /V
I ;· [ ' e - Lr ik R (t r;) • (.
'P"i I -
R(''f't,,·))] H

x [4,>;'"'1'' '\o,'!'(r - R ( e' no'))] d 3


r. (2.7R)

A uming periodic boundary conditions, we change the variable of inte-


gration from r tor' = r- R( l'f.;,) :

/ J1 t\ l. ,t +1 1. 1 _
-
~,y / ' [ '
L.,.; e-ik·R(£~<), 11 • .(r')] J-1
'rf;.J
. . I

I ~""" ik lR (1)1 R (I;' )- R (I> ))


= - L.,.; L.,.; e
N I I
Electrontc energy bands : basic theory

. . 1 = " _ f a nd have made use of Eq. ( 1.4). The o;;um vert


\ · rc ,.t: a . e sel,d·· tclv to y1·eJd a factor o f' 1Y wh.1c h cance
.. Is· t he fac tor 1 ,V
b~: d nc Immc JU J
can . e 011 the dummy mtegrat1on vanable r . we obtain
- . . . , · •

Drur pmg l 1le pnm

' IIi R (l ti) - R(ClJ; J]


H,. . i ,..'1' ==- L_., e

(2.80 .1

An anal 1 simila r 1 that just given can be applied to the overlap


integr· 1 S,o,,.,.. ,· define b Eq. (2.77) . The result is

. ,
S111.,.,,. ='L (;) k ·IR(l ;;' J- R(Ot; )j

-
f

<p ~ i ( ,.) :p"'I'(,. - R (P,....') + R (0 tl,)) c/"1r .


J (2.8 1)

We see that S i.,;'i' consists of a sum of terms containing either one-center or


two-center integrals depending on whether R(f.,..! ) = R(Or; ) or R(tn.') =f.
R(Orc) . re -pectively. Their eva luation can be conveniently carried out using
spherical coordinates for the one-center integrals and elliptic coordinates
for the two-center integrals. The latter can be reduced to certain basic two-
center integrals using the rela tions developed by Slater a nd Koster ( 1954).
Since the two-center integrals decrease exponentially with increasing
separation of the centers, it is customary to neglect these integrals for
centers with separation greater than some chosen\ alue.
Consistent v.·ith the spirit of the tight binding procedure, one can
express the potential energy V(r ) in the Ha milto nian Has a sum of atomic
potentials:

1 (r) = 'L>.:,.(r- R( C,.;) ).


"''

~hiere 1 ~ (!·) is t~e potentia.! due to ~ucleus h:. We cnn th n group rb t.::nn::> l)f
11
the lol\ov..mg way after malong the repbc~mt.nt ,. - Rt r. ---'· r :

/-1 = Ho + t ,,- ( ,.) + L u ·" (,. - R (I ";; n) l- ,·_·l

lf we now ·r · . th· 1 . . t' 1ht '


.· . . < ss umc .11 t 1e a tom1c l.)l'hltal .-, (rl i an~.:l!.! ·n UIH.:LI n
LllcJmJc Hamtltoni· 1-1 · ) . 'T' · '
<~n n ,,,;(,. with cncrg~ i:;cmc.du • . L ·n 4 · 1-·
- , .,
f rH .
'"·"' '' Cd ll ht' rcwntten a s

II,. •'t' ::-


,, . . . , '
I ,., , t-, I
J '" I •
Tight binding method 39

(2.R5)
contuin three-center integraL in which ( 11 1,-" . { 1,-'
IJ J.rfTcrent.
II II
~n I two-center
.
integral. in which e"thI er
I K -:/; t.K = _
o,,-. ~mce the three functions -t;,(1·).
r) ar all I calrzeci functr ms. the three-center integrals are
II compared t th t\·VO-center integrals, \vhere t\VO fthe tlu-ee
fun tll'n ngly ovcrlal n the ame center. Consequently the three-
center 1111 gral are fn.·ttuentl ' neglected . The results of Slater and Koster
can be u ed to red u e the two-center integrals appearing in V1.u;'i' to certain
bas1c mteQral-.
In order to cal uJate the energ band structure for a given material. it is
nece aD to have \ a lues for the basic integrals entering into V,.; ...' i' and
,;... , The e value are determined in the empirical method by choosing
them ·o that experimental data reflecting the band structure are repro-
duced . In the ab initio method , the basic integrals are calculated from
tabulated atomic rbitals and atomic potentials such as those of Herman
and Skillm n ( 1963) a nd Clementi and Roetti (1974). Typically, the results
of the ah initio method do not agree well with experimental data for semi-
ond uctor-. o recourse is then made to a semi-empirical method in which
the ba ic integrals are multiplied by scale factors to produce ·tgreement with
ex peri men t. In many cases. the in traduction ofjust a few scale factors leads
t go d r ult .
Example 2.5: Calculation of a simple energy band
Consider a one-dimensional, periodic array of hydrogen atoms. all in
th l.1 tate. with lattice constant a. Calculate the energy as a function
of the vva v ector k.
Solution. Since there is only one atom per primitive unit cell. the basis
index K and atomic state index i each take on only one value. We
can drop r.: and take i = Is. The determinantal equation given b
Eq. (2 .75) reduces to the simple equation

L f
eikl u ; ·
.
Y~s(x, y, ::)[1-/o
+ ~ v(.Y _ f'a.y . .:)Jtp r-(x - fitt, .l',.: )d r
3

(I

-- E~k '~
,iklu
(:
; · u ;'' (Y )l . .Z) I.'l J 1 (x
r Is · ' . · r ·
- f a. )', z)d

1
r.
I .

Utilizing the result


[Ho + n(x, y, .:) ]:P I ~ (x,y, .:) = r rs'? L-(Y,r,.:)
Electronic energy ban ds.· basic theory

-1
.
nd ::.epara tmg .u t the terms with e= 0, we obtain

I 1.\ - I.
I
(~· r - ) ' n(x - f!'a,y,.::)<pJs(x.y,.::)d 3r
'fl.l ·'·· ·- ~
t' f O

+L ei/Jo ;· . 1 Jx, y, z) [c: 11 + ~ v( x - f.' a, Y, .: )]


1 , i( l f fQ

/ :p 1s(.r - l!a,y, :::)d 3 r

= Ek [1+ L
J ;io l)
eikfa
'
j cp~_,(x, y, z):PJs(x- fa,y, .::)d 3 r],
\ here w h · v as umed that the atomic orbital 'P~s(x, y, z) is nor-
ma li ed to uni ty. We now restrict ourselves to nearest neighbor
o rlaps. Letting

i)_, = ./ cp 1Jx, y, z)u(x ±a. _v. z):pL~(x, y, z)d 3r


K1s = . / :p~s(x,y, .:)v(x + a,y, z):pls(x + a,y, .:)d 3r
=.I<p~_Jx,y, -)v(x- a.y, z):p 1,(x- a,y, z)d 3r

S~s = / <p;,(x,y, .:)cpJs(x ± a,y, z)d 3 r ,

and solving for Ek, we obtain

')
E~-: = E1s _ k [1 1.. + K 1,coskaJ.
+ 1 -t-. 2S-Is COS ~a

Tak_ing v(x, y,.:) to be the Coulomb potential - e 2 / r. \Ve can evaluate


the Integrals to give (Pauling and Wilson 1935)

e-1
- e- n( a+ D ).
.
K.Is=

\J'.
1.7':! r--r--------.~ -
as

~ - 1.>-;
\ : S Is = e - D ( I + D + JI D-)) ,
\
'
'

I IS 1 '":--l--L.__ _.L_
l~
'
where D = a jaB and aH is the Bohr radius .
-2 () 2
4 Let us consider the particular cast.' D = - _Th~~ tnt .! I! th ·n ·''
th e v·tlues f 0 ~9 ~
/..a . ' " • I =- __) 99 Ry, K = - 0 0X09 R l
~ • • till
I

Withrl, =- 1 0Rv theb -·11 . . II 1'£' . t .


F"1 · J· t: av1oro ;. as a lunctt n )I,
(l g~ ;} 6 - Note that the band width I.\ Ht
4
2
·' '·
• . . _ ·'~,JI =
~.: 1llllun 1s r· ..
O.OI) Ry. ft is mterestinl!, th :11 thL' ~..·n
1 1-
It \.'
~
, dl.t 10 Jc Ill wave \'I..'L' tL)r l'llr all \\ a \ ' 'll ·.t' ill
Problem
It h h :tVt\l r ·).L eu r ~ n n 1y n ear th '/nne

. . pr, 'i ~ a v· Iua l'lle pict urc or how encrgv


'" l,ll- <.l dll11 "ar l roue.ht ~ tooe
::: t\1 ~- t l)101111t1CLr
r . I '' l'll•
rc ml1mtd. fa r J p~trt. . th St .
, . ·1 h at 1 d l -· . t . ' ·
r.. 11 111 e !ll a 1s are
. The degeneracy. - o l the
. ei2:cnv·duc
~ • r'; IS · _ eq ua~1 to t 11e
l t11e H 111 the cr t:::t l 1 •• tl1e num b e r o ,- pm111t1vc · · · unit
I'
• L • .... . .

atun apprua c h each o ther • th e ove1·1·1p o f t\1C a t Ol111C ·

v
• <

111.:e and the m teg ra L " · J h. and K 1" increa se in ma!lnitude


n t·1 nt 1 de r a:-.e~ . T he degeneracies arc then rem ov~d. a nd .
~
n1 ' I hr ade m; u t into a band. The widths of the ba nds
the '.ttlic~ c n. ta nt d ec reases. Since there is one state for each
,.. the t 1tal nu mbe r of orbital states in a band is N. Therefore
ro Interatomic dbtance
t<.tkin mt ccount spin . 2. c\··ctrons can be accommodated in a band. jus~
a m th n~.:.HI) fr electron pi ct ure . Fig. 2.17
. chern3tlc repre en tation of the e nergy bands as a function of atomic Energ y bamb as a fun cLic n of a tom ic
sqxtra tio n for tetrahedrally bound
-.t:pJratJ 111 for tetra hed ra lly b o und se miconductors such as Si and Gc is
semicond uctors like Si <.md Gc .
~h1\\ ll in Fig . 2.1 7 . A t th quilibrium se p a ration r 0 there is a forbidden
energy gap £1!. betw n th e occupied and the unoccupied sta tes that results
from th,.: \P' hy rid iza tion .

Problems
I. ho~ that cxp(ik · R({ )) i. an eigenvalue and the Bloc h function 1.-'k (r ) is
an eigenfunction of th e -rys ta l translation operator T defin ed by Tr =
r - RU ).
Find the ncrgy ga p at the co rner point (1r j a. Tr/ u) of th e Brillouin zone for a
quare la ui c in t\\·o dimen . ion ·with the crystal potential

I' (x. y) = - 4 Vu cos (2rn) a) co. (2Tr_r/ a).

3. on. it! r the diamond . truct ure a nd its reciprocal lattice associated with the
twenti nat cuhi c cell. Let he he a primitive translation vector of this
rc ·ipr ·al lattice. .
(· ) how that the Fo urier co mponent VG of th e crystal po tent1al seen by an
el ctron i zero for G = 2b, .
(bJ Demon trate that the energy gap vanishes at the zo ne bound~ry plane
normal to the end of the vector h, in the first order approx1mat1on to the
or th e wave equation in a peri od ic lattice . .
~ luti ons
(l:) '.·ing Eq . (2.35). where the o nly equations to be retamed are those that
~.: ntain both coenicienh C(~G) - · ·
and C'( - ~C). show that the potenual
· · 1· '"I' Ll" 11/ ·tt th e zone
energy 2 V0 cos Cx creates an ene1gy g.tr o L:X• t.: -' - o <
. dboundary. - 1 b· 1d at /· -- () fc>l- the Kro , m!l- · Pennev~
4 . F111 the enerl!v - - o l the · o\vest energy· ,11
. · ·' · - · l « I For- -th1. s case J

m1 del \\hen thL: potent tal energy 1. · a delta lund lOll .tl1l P ·
find the hand. l.!.a
~ p at. k = '
E·, . · ·. . . · . h 'd tl1 0 f t )C t-ll.. t a 11 0\VC1d
1
5. Bv ·1ppl y1nl! success1ve appro:x1mat10ns. esu m<~te t e WI :r
h~n • E a~d the forbidden gap l~g for the Kroni g- Penncy model w1th P = "t
.

nd u - 3 A.
h. Pr \ .:
<
th ~ t the Wannier fun cti ons centered at different la tticl; sites are
Il l I IJgnnal
Electronic energy bands: basic theory

References
1-. Bl ch. z P!ll'Sik 52,555 (1928).
,... . Ho ·n an 1 J R . Or cnhe1mer. Ann. Phys. 84. 457 (1927); !Vf· Born and
•v
K. H· .ln ~ . _,·,onlico 1 ·~r1.J('fJIT n f Crystal
. Lallices (Oxford Umver ity Press,
l "4)
x.Lru. . . . P . .
f .I
9"'>· W ' P·
L. B Jlh1 in. 4nn. Pln·s 17, 88 (I. ~~) . me 1 opagatwn m enod[(· Struuures
cc nd ~.:"cilt · n ( Dov PubltcatiOnS, New York, 1953). •
1 . 1e nli anJ . R etti, ~10111ic Dat~t. and N~cl~ar Da~a T~hles J4, 17? {1 974 ).
F Herman a11d ktllm.-~n. Atomtc Structwe Calculatzons (Prentice-Hall
md '\\ J It .. . J., 1963). '
c. itt I, fntrodllc'tion to Solid State Physics, Sixth edition (John Wilev
N ~w ork. J98 ). ...
R. L. Kr nig and W. G. Penney. Proc. _Roy. Soc. (London) 130, 499 (193J).
L Paultng :md . B. Wilson. Jr.. lntroductwn to Quantum Mechanics (McGraw.
Hill. Nc\ York. ll35).
J. . Slater and G. F . Koster. Phys. Rev. 94, 1478 (1954).
A. H. Wilson, Proc. Roy. Soc. (London) 133, 458 ( 1931 ).
J. M. Ziman. Principles of the Theory of Solids. Second edition (Cambridge
U niversity Press. Cambridge. 1972).
e r y bands:

ductor

Energy bands in
t 'miconduc to r at 0 K has it Faience bands completely full of semiconductors
dr n and it conduuion hands completely empty. Betwee-n these
b 1d i. thl: fundam elllal h md gap.
Orbital nd ~pin angular momema of electrons interact to modifv 3.1 Spin -orbit interaction
th 1r encrg~ level ~ ·
The 11i.: ti\·e I dr n- i n potential can be represented hy a 3. 2 Electron-ian interaction and
p. ·udopoumtial onsisting of attractive and repulsive parts. pseudopotentiols

Electron interact with one another through the Coulomh interaction. 3.3 Electron-electron interaction
In the flarrree-Fock m ethod the Pauli exclusion principle leads to
the xclum'~e interaction between electrons. In the densityjlmctional
method th nergy of interacting electrons is a functional of the
electron density n(•·).
Excited ta te energies can be calculated with the aid of the electron
etrcnerg_r nperator that combines the effects of exchange and
CO IT e ] ti 11 .
The k · p method provides the energy £ 11,. as a function of \A.-'ave vector k 3.4 The k · p method

n ar a hand extre111u111 without calculating the entire band structure.


A IIOJU/faenerate hand with extremum at k = 0 in a cubic crystal has an
isolropic 4fectil'e mass. A degenerate band with extremum at k = 0
111 a cubic crystal exhibits ll'arping of the constant energy surfaces.
A band \Vith extremum at k ::f- 0 in a cubic crystal has an unisotropic
ef(ec tire mws.
Silicon and germanium have indirect gaps with extrema or valence
3.5 Energy bond structures lor specific
semiconductors
and conduction bands at different k values. The majority of 111- V.
11- VL and IV- VI semiconductors have clirecl gaps with extrema of
valence and conduction bands at'' = 0. 3.6 Modification of energy bond gaps
Energy band gaps can be modified by changing the tcmpermure, by
appl_ ing pressure or stress, or by forming an alloy.
3.7 Amorphous semiconductors
Disorder in the atomic arrangement produces an amorphous
Sl:'micvndw.:tor.
. bands: semiconductors
ElectroniC energy
. . Wit h ut d viations from periodicity ha c th.
ur-- ·cmlc n uLtors . f t
• l: h· ..1·w. tic that a t the a bsolute zero o temperature al l cnergv
un rt,tntc ai.IC c . . . . d I I· f
. · lu IIH! c. certain ban are compete)' ull of cl ctron
"'J

1 ·tnds up tl) .Jill1 me .. Th ·


' h· d r high r energy are completely empty. ere IS a gap bet vc n
tn I .tn · 0 ....
the hiuhe ·t 1tile
.. d b an an t e o t tom ed ge of the
d d h b
thc op ~.:<.Ige ' I ~ .
md Thic; t'Ta 1, ca ll ed the fundamental gop. The electrons
I , c"t em p tv _ t1 , · c . . . .
l up ing the h)~ est tilled band~ ar~ strongly lo~a llzed _ a bout md 1vidual
·. dar termed core el ectrons. 1 he electrons 111 the h1gher filled bands
11llL l I .Ul . . .
, .. tlizcd than o re lectr ns and part1c1pate 111 covalent bonds
.tn.: 1e"s lo. .
bel\\ en atom:- The e I ctr n a r valence electr~ns. and the bands they
ccup)- are valence ba nds. F r rea ons th at will become clear later.
the bands that are cmp t • t 0 K are conduction bands.
Th general di cu · ·i n f ncn!y bands in Chapter 2 presents the basic
c 11 pt' tb· t undcrli nergy band theory , but omi ts a number of effects
that ha c igni fi ant impact on the energy hand s of real semiconductors.
h ff ts tha t w di s uss in this chapter a re the spin orbit interaction. the
1 tr n- i n inter::tction and p eudo potenti als. a nd the electron-electron
interaction. The characteristics of the energy bands of typical semi-
LOnductors are presented and a na lyzed with the aid of k · p perturbation
theory.

3.1 Spin-orbit interaction


An electron possesses both orbital and spin a ngu lar momenta . The~e two
forms of angular momentum interact through their associated magnetic
moments to modify the energy of the electron. This interaction is th basis
for the familiar LS coupling in atoms. For an electro n c f position vector
r and momentum p moving in a central potential V (r ). the spin- orbit
interaction energy is given by (Thomas 1926)

H w, = ~(r)L · S ,
where L is the orbital angular moment urn opera to r ,. p, S i · th spin
angular momentum operator 41i<r. <r is the Pauli ·pin matri'\ H' tor. ·md

~( r) = _ 1_, -, ~ dT . (3.- l
2m- c.:. r dr
. For a general potenti al the spin- orbit co ntri buti 1 11 t thL' Hamilt ia n 1S
g1ven by

II
H ,." =- - £T • V I , "
4m2c2 p
.
' '
..l . ·"

whcre
.
Vis~ th c gJ , ..<~C1le
· • •
nt operator. f:/ ., should b ., 1·d t th • H. milt 1 11 1•111
g1 vcn bv Eq p 15) Tl . ." · . t 1
th .· _· . - : · le pJ csenL·eolthcspet·d )fli l!ht c m/1" 11 11... 1 LI.L
c pm ~ I bit lntcrac l!on is a n:: la ti vist iL· ell TL
onunent. The . · . . . .
·('' · . . s 11.. ln OJ 1)II ln tc rac t l n IS ()111.: ~I ' 'I
c H.:ds \V IH::n ·t 1·t ·I
·. · . ' tcc lJ Onm \'L ··inthl.''ilrl)11" hlL'tlli·ll
nuc 1l: l , lh ~ reed .. . . "'
L.tll .tppln;n:h tha t l l l lw.ht . .t nd II. mu
<
in -orbit 1 ere 1on

I Till Ill lh ~ \'<: n e c qu :I t l lll Ill . , I - l. .


· L 1 rt l l h!LI
I I'I t IlC D I L.l . I . -
• L I C :I IJ 'l<;lJ c e qu .J tJ n n whi ch . a lt ~r
n~nts. La kc.: s the fnrm

( VI "( r )

1 -- rnp nr..: nt '> pin r.l is the 2 x 2 unit nnt ri x. a nd

0
I - (
0j -i)
0 .

Th r t two term.· re the kinet ic and potential energies , the third and
ft urth t~rms Me the r la tivistic corrections to the kinetic energy and
r ltenl!ai energy (th arwin correction), and the fifth term ~;epre­
-,ent. the pin orbit co upling. The relativi stic corrections become
import nt ~ r heav" nuclei .

in e th mag nitud of both the potential and its gradient are very large
near the nucleu s. tb . pin- o rbit int eraction tends to reflect atomic char-
acten lie. In pa rti ular. the energies of j = ~ and j = ~ atomic le vels are
pbt b)- th in-o rbit interaction. Thi s s itu~1tion carries over to energy
band in cry tal ·· a m ay be readily seen in the tight-binding picture. For
1
xamplc, en rgy bands derived from) = andj = ~a tomic levels are split.
Example 3.1: Spin- orbit splitting of valence bands
Di u the sp in- o rbit splitting or the valence hands m Si, Ge,
and ln Sb .
. olutinn. Semiconductors such as Si and Ge have the diamond
tructure. The structures oft he valence band s arc similar in diamond,
Si . and G , with the po int o f maximum energy at k = 0. This point has
ene rgy F1 a nd is called the band edge. The valence band edge states
are d ri ved fro m p-like atomic states and would be threefold degen- E
erate in the absence of .- pin. With spin th e degeneracy is six-fold
without spin- o rbit interaction . Introducing spin- orbit interaction
I ads to a splitting or the V::llence band edge into two band edges: an
upper band edge associated with fourfold degenerate Prlike states
and a lower band edge associated with two-fold degene rate pr like
states.
When k f- 0, the Pl hands split into two doubly degenerate hand s
ca lled light and heav ~ hole ha nd s. The energy difference between the
p1and Pi ha nds at k = 0 is denoted hy .6.,11 • A schematic representation
oT the v~lence band splittings is shown in Fig. 3.1. For diamond the Fig. 3.1
va lu of .6, is .. . _ 0.006 eV, which is much less than the fundamental Valence bands uc:ar til-: 13nlkHnn /<In ·
11

gap o 5.4cV . As the atomic constituents become heavier. the spin-


sc:mtCll!ld uctors 11 1l h -;pi n n rh1 t 'Phttm~
tJ rbit sp iJtting increases and the fundamental gap decreases. ForGe, 6 ",. The band.'> .· dhl\\ n ~II"<" th.: ht'a\ ) h,) k
6 ", ,~ U.3cV and £" c::= 0.74eV. JnSb has a spin orbit splitting of (h/t), light h0k ( //1) . •111d r th> lf ( 111)
(J k2l:V whtch is si~nilicantly larger than its fundamental gap of hamk E;tch lxmtl " lh•uhl ) d.: g ~m:1at.:
bands. semiconductors
ElectroniC energy ·
• tra t 1 th ·ituation in Si and Ge. In semiconduct r
(1:23 CV , Ill ~011 . . . . .
ht:'l\ 'v demen t , the spm orbtt sphtttng ts one of the
compl)sc o r ~ - _.
. Jr Jet 'rmm m the hand structure.
iml rtant f aL 1l

3. Electron-ion intera ction and pseudopotentials

11 th electron· r · ry,·tal Jrc dealt with explicitly in an energy band


cak lalion. the electron w n interaction is simply the Coulomb interaction
du Ll thl: pustllvc nuclei T r ·tting all the electrons, however. is very dif-
tiettlt analytically and ve ry computer-intensive numerically. Part of the
rea on or th 1 • diffi .ult i · that the wave functions of the loosely bound.
m re e:tended cle tro ni tates must be orthogonal to the wave functions
f Lh tit!bt 1 und . more localized core states. Furthermore. the electron-
ion pot~ntial is n t ·weak in the core region , so pla ne waves are a poor
appr xima tion there. If the extended stale wave functions are expanded in
t rm · of ian v 'lVe . it may take an enormous number of plane waves to
achie ·e c re t· te orthogonalization and to properly account for the strong
electron- ion potential in the core region.

3.2.1 Orthogonalized plane wave method


A way of handling the orthogonality problem \Vas pointed out by Herring
(1940) who proposed the orthogonalized plane wave method (OPW
method). If jk) denotes a plane wave of wave vector k and jc) a core state.
the orthogonalized plane wave Jk )onv is given by

Jk) 0 pw = Jk) - L (elk) jc) . ( 3.4)

where the summation is over all core states. It is ea ily s en that Jk)0 p 11 rs
orthogonal to any core state Jc' ):

(c' Jk)0 pw = (c' jk)- L (cJk)(c'Jc)


l'

= (c' Jk) - L,. (cjk)l·<"<


= (c ' jk) - ((·'Jk) = 0. l3.5)
. The exact wave function fo r an extended eJ ctr n .\.r~tnJc-J
m a sene of OPWs or the form

I¢" Plf' ) = ""'


L C( k - G llk - G I /'H '
G
when.: G' is -1 ~ · . th
S .. . · ' n:: tproca 1 1atttce vector. ~ ubstitu!IOll 111[ '
chrod mgcr cqu<ttion , Eq . (~ . 1 7 ). and u:-.e 0f Eq . J.~

L C( k - G' )I( HI) + I ')Jk - G ) - \llk


(, ~

= '(;' C (k G L' jk G) \l 'lk


lectr n-ion int t. d
erac 10" an pseudopotentials
47
th l' 'r ~tal . a rr sufficiently lpc~li7eu sn that
lin I ) j<'} - r, jc)

1 nt \) I k . ' <tin!.!. th ·1t 11 · . I


k .
·melle energy Opt>ratnr
u Js l l e
.I~) anJ laklllg the scalar product or Eq (1 7) ··tl I
. • '

"' G ' J \\ e L) bt.IJn


. · -. \\·1 1 t1c

fl 2 ,
tk- G) [-") (k - G t8( ·c· (k - G' /V/k - G )
_ 1// ' '

- ""-;-' , ( ·lA- G )(k - G'ic)l


= LG EC(k - G )[ cr.·· - "
~
' (c/k - G ,\ (k - G' jc)]. ( .3.9)

:xpJoiting thr Kr ne ker deltas and rearranging terms, Eq. (3.9) becomes
,~

- t/.. - G t (k - G ' )
_/11
G
= EC( k - G'),
(3.10)
wh re

(3.11)
c

In o rdinate space. we have

I R(r. r' ) = L (E - c,.):p;.(r) <pc(r' ).


('

where ; A r ) i a core state orbital.


T h quantity V R is a potential operator that is nonlocal and energy-
dependent. It is repulsive in character, because for extended electronic
tates, E > c · It therefore tends to cancel the electron- ion potential V
\\'hich is a ttractive in character. Consequently, the effective potential
V + VR appearing in Eq. (3.10) tends to be weak, a fact which was
ex ploited by Phillips and Kleinman ( 1959) in their development of
the pseudopotential method.

3. 2. 2 Pseudopotential method

The effective potential V + V R is known as the pseudopotential Vps:

v"s = v + vR. (3.12)

Jn terms of the pseudopotential, Eq. (3 .10) can be rewritten as

L HcJ;'( k.)C{k - G') = EC(k - G), (3.13)


G'
. bands: semiconductors
Electronic energy

hi? e
IT;. ('· _ G 12 0(. (' ' + (k - G \ Vps\k - G') f3.l4 J
/1 c,, (k)=- 2nl
" . J,1

. the ro les of G and G'. The fact that VP\ is weak


lrt' c mll.:n.; Ihinge0
nd e ' . . tl . the t~ o uri er components o f VP' are smalL except
re l , nlean 1U
c mp 1 • • •• \l'lttice vectors. and the convergence of the series
r the: r t k \ rectproc.t ' .
r I o,.,,., h utcl be raptd.
m q. (_· !) or] . ~ .'nd Kl inm a n. we take the coeflicients C(k - G J that
11
1

Folio~ mg P 11 1P5 ' .


.. ., E (~ 13 ) a n 0 fi n the function
sat1 1) q. - ·
\k(r ) = L C( k - G) \k- G ) . ( 3.1 5)
G

(l\6 )
,.

Substituting this form fo r 1 ?r w) into the Schrodinger equation


H\ fP11i) = E \¢fP''v) yields
H\xk) - l.":\c\xk)H\c) = E \xk)- L (c\ -xk)E \c) (3.1 71
c

Using Eq . (3.8) and rea rranging, we get

[H + ~(E - ,,.)\c)(ci ] \Xk) = E \u )

or, using Eqs. (2.18), (3 .11), and (3.1 2).


(3.\Q)
[Ho + Vps}\Xk) = E 1\k) -
W e see that \xk) sa tisfies a Schrodinger-like equatio n \\·ith the pseudl)·
p otentia l as the effecti ve potential a nd the eige nval ue given by rhc e.\•H:t
eigenvalue£. \ k) is kno wn as the pseudowavefunction . "inc T"r is ,~-e~tk.
1
1 1
I X~< ) can be expanded in a rapidly co nvergent series l)fplanc.: \ ,1\ I?S. Thts 1 . '
computa tionall y much less dema nding task than tht ·olution ,f Eq. (~·.
in which the full po tentia l V appears a nd fo r vvhid1 a plan'\\ ,l\' , \r••m•l ll
i much less rapidly conve rge nt. . . .
There still rema ins the no ntri via l pro blem L f acru.tll_ ~.: bW 10111g: th~
.. ,.td :) t t . 1 N · 1 i J·n'llli' 11t
Psc • l po en •a . o t onl y ts the pseudop ten tial m nl · .tn ~ r '" ..
on the energy eige nvalue £ .it is also no t umq uc Zim.tn I - In ~ r:tcu~~
111 1111
much use has been made of local fo rms 0 fthe pseud p l ·nu.tllh.t l l' • "
parameters chosen to fit experimental data . b ur r ·~.. 1tl n nl c .tl ll nn
have become common.

3 ·2·2·1 Empirical pscudopott·ntial method


~ part il:ttlarl y ::.imple ap prL)ac h ((\. hen
cl ::. ~ UIIIC::. that lh~: p-;1.:' Llcl UIH I n t1:1
. I ~.·an be pr
El ctr n- ion interaction a nd pseudopotentials
49

I r• rJ = L "•· ,.- R ( fl,-)) _


I~

hl bindi ng Ill thnd. The Fourier tnnsform ()(- 0



vfl·' (I ·) tl1CI1
.
,

(3.21 )

l hl \ ol me of the cr st::ll . This expression can be recast as

-iG R(t J j d Jn :,.(r - R (flh· ) ) c - i(r' (r - R I~))

= / L e - i(I·R(f I L e rG·R(,·) ; · d 3r 'v,c( r ')e - iG·r ' '


(3.22)
I ,...

\\her \\ hav a ·sumed periodic boundary conditions. The sum over egives
th number or unit cells N by Eq . (2.9). With the introduction of

1· - (G )
. = -11( ; ·
(/1· r v .(r)e
. , - a'·'
·r .
(3.23)
' 0
- "0 . ''· '

Eq. (1_1_) come

(3.24)

\\ h r fi e i the number of a tom in the primitive unit cell.


Th F urier transfo rmed atomic potential v~;( G ) is known as the pseu-
dopotential form factor ro r atom fC For semiconductors having the
diamo nd or zinchl ende structure. it is convenient to choose the origin of
rd inate- midway between the two atoms in the primitive unit cell at
th pom . t· a (l" , l8 , l)
R . Th en R( I ) -- - a (l
s , lR , l) · d R(?)
8 an - -- + a (!8 , !8 , !)
s .
ub titution of these values into Eq. (3.24), setting T = a(k . k, k), and
taking n, = 2 gives the result

(3.25)

wh -re ts(G ) = Hn
1 (G ) + v 2 (G )] and ·t 11 (G) = 1 (G ) - u2( G )] are tbe Hv
ymmetric and ~ntisymmetric form factors, respectively. The quantities
S (G ) = cos G - r and S 4 (G ) = sinG· r arc the symmetric and antisym-
mctric structure factors. respectively. Since the t\vo atoms in the unit cell of
the diamond structure a re the same species, 7' 1(G ) = v2 ( G ) and u,.J(G) = 0.
>nsequently.

VP·' (G ) = tJs ( G ) cos G · T. (:~.26 )

hen and Bergstresser ha ve calculated the band structures near the


f unJamental energy gap for a large number of semiconductors having the
diamond or z.incblcnde structure. They chose the form factors to fit optical
. bends . semiconductors
ElectroniC energy ·

_ d 1. l the ma llcsl three or four nonzero values of jG 1 wer


:.~t·• Jnd to un I,., .- . II - e
: ' , >d co nvcr~cnce of the rec1proca att1ce vector um
ufllCJCnt 10 gJVC g t ~ cr f h . - .
er J 1 not include the C11ect o t e spm- orbJt interac-
1et r r~su 1t , I10\\ e\ •
li n r 11 n olal effects.
, le ~ . Band r 1cturc of ZnSe
., an p ~· 2· r
Is u: th d~.: erminati n o f the band structure o ZnSe by the
mpiric·li pseud 1potcntia l method (~PM~. .
olution. The r . ud p tcntlal Hamlltoman IS
')
11- 7
H1 = - - V'- + v,,_,(r).
" 2m

Making u - orEq. (3.2 5), the pseudopotential Vf' (r) for a zincblende-
~tructur emi nd uctor can be expressed as a Fourier series invol-
in g. ymm tric and antisymmctric pscudopotential form factors and
tru tur factc rs.

Vp.1 (r ) = "
~ . · (G) vs (G )
' [s·') iS'1 (G'_1v_." (G) ]eiG·r.
jGj~Go

where Go is a cutoff reciprocal lattice vector. Both the symmetric and


antisymmetric structure factors contribute for a zincblende st ructure
rna teria \.
For the determination of the form factors, only the first five reci-
procal lattice vectors which have squared amplitudes ofO. 3. 4. 8. and
11 in reduced units are considered (Chelikowsky and Cohen 1976).
Larger reciprocal lattice vectors are assumed to give negligible con-
tributions to the pseudopotential. The symmetric ·tructure l~1ctor for
G2 = 4 is zero and the antisvmmetric structure factor for G: = 0 and
G = 8 is zero. One can take 'Vs( O) = 0, since it is a constant con-
2

tribution to all energy levels. Thus, there are three s_·m metric and
three antisymmetric form factors to be specifled. p ro imate form
factors are determined by comparison o[ experim n tal op i al data
wtth the calculated ba nd structure.
The band structure is obtained by calculating th roL t · of thc
secular equation derived from the Hamiltonian mat i\.. The matri \
for the ~incblende structure is complex, since th matri: dem 11 [~ of
the ~ntisy_mn:etric potential are pure imaginar} . Th pwccdurc
conststs ol adJusting the band structure in succ s t\'e ' t p.- tl) ake It
consistent with the experimental results. One s tarL \\ lth J JtL.ll11 )nd-
~t ruc\ure_ semicoJ~ductor for which the mat r·x im I t.:J 1" r~.d .!lld
- 0 -0 111 stze, lor exampk. G . R Recti\ 11y .mc h-, ,H~fl1 1 ~' 1 ()ll
mcasuremen t ·11-e l t:s·ed 1o est nnak
-
thc- en ro\ dtft• 'II • 1...v~ l \ \ ~.:··~.,
'c\
_ - L

vanous dectronic states in the Brillouin z '11 I ·I nl.'.tr th .


hand gal) <·1re fit ·bY(1elermtnm\!.
· · the I' rm 'IL'l<lrs l•' 1 n 1t h' l I •1
rydb • · H · ~ • · '
b , ~ ·g.. avtnQ found the pokntial fo r c, t'~l1~: 11 J ' ·~ \
. y kt:epLng: the same symmctri · puknt ial .mJ .1 1.111 1111
ymml:lnt: put t·· 1 · 1l ·
. , . e_n 1' 1 · 1 ohta m th.: P•'kntJat I t
f> .lf"IH.: SYlllllll' lflL' ) . .
· I Okn lt;tl and 11 LT ·..1 cs dh: mu
El ctron- io n inter ction and pse d opo te ntiols 51
l~l tl r r ,' .
...... - - to \ \1 1h in ll.lll ' T he ha nd
al ulall.' ac '•""~r I l l~' t I•' tl11·-~ prOLl:l!UI'l:
~ . shown
IS
(>

4
2
al pseudopo enti a l rnethnd
-2
li · tted tr atm cnt of sem ico nduc tor energy ba nds has been
--4
~" k · ·:1nd C o he n ( 1976) wh o included bo th the spin o r bit -6
1 n nl cal t rms 111 the p seud o po tcnti a l. T he ma tri x elements
-R
r 1 H<tm illo ni a n give n by Eq. (3.3) were ca lcula ted with
s. ln rd r t inc lude spin effects, the sta te indices that
q ('A) mu ~ t bt: a ugmented by s pin state indices s a s fo llows:
I~\ I \) · Ic) - t lc ) = ic)Is). The m a trix elements o f H_, 0 then
A r ~ X U.K I r
ZnSt:
[! nn
Fig. 3 .2
JIG· , = 1k- G ·J Hsolk - G's' ) Ba nd structure of Z nSe by the em p irica l

- L (k- GsJHsolcs") ( s" Jk - G's' ) pseudopo tcntial method (after


Chelikowski a nd Co hen 1976).

+L L (k - GsJcs" )(cs" IHso Jc 's"' )(c's'" lk - G's '). (3.27)


(_'." r·' .,w

Sin th p in- o rbit interaction is s tro ng o nl y nea r the nucleus of a n


atom. the d minant co ntribution to the matrix element co mes from the last
t rm imoh •ing the double sum . Writing

H \'0 = A . U , (3.28)

wh r
11 ,
A= --
2 -, v J· X p, (3.29)
4m e-
we have to a go od a ppro ximatio n

H(/ G'., • ::::: (s lu Js') · L L (k - GJc)(cJAJc') (c ' lk - G').


(''
(3.30)

The ex treme localiza tion o f the spin- o rbit interaction has the ad d itiona l
conseq uence th a t we ca n write A as a s um of a tomic co nt ributi o ns.

(3.31 )

Since th e co re index c denotes both th e electronic stale f and the lattice


site ff\, o f the core sta te a tom , the o nl y sig nif1cant co ntributio ns to (ciA Jc')
are th ose fo r whic h c and c' ha ve th e same la ttice site a s o ne of the terms in
Eq . (3.3 1) fo r A. W e can therefo re rew ri te Eq. (3.30) fo r H ;';',_G's' (k ) as

H~~, .c•,, (k ) '::: (sJu ls') · LL L (k - GJtt'h:.)( fi·>JA JI't>)


I /1 (K

x (t'enlk - G' ). (3.32)


. bands. semiconductors
ElectroniC energy ·

Lcl u -.: .d er l l1e


11 ,.,
111 •• gi v n by

_ I: (k _ G itf'fi· ) (t'f'h·.[k - G' )


,
-
- L -!f'·I ;· .- li k- G.J r,n..,,,,.(_',.- R(Ln.,))d 3r
{'

.
I
. e'u.- G' l·•·' ;,~< ( r
I
- R ( tK.))t
. I'· r I

' ;rc; Cl' JR fi.! J ' (k. - G)l· -(·k. - G') (3.33 I
= L-t - . , e '" ''· ,

where

J,~(k = / eikr tp;) r)d 3r , i = l. t' (3.34 )

i ~ the Fouri r tran sfo rm of the orbital '-Pit•(r) for core state i of atom tt. The
sum over an now be carried out with the aid ofEqs. ( 1.4) and (2.5) to yield

S = 0N1 ei(G- G' R (t· ) ! '". (k-G .)1~~


·(k-G'_
.) . 1 3-
(... ))

At this point we restrict ourselves to core states that are p-states. which are
the most important core states for semiconductor band structure calcula-
tions (Chelikowsky and Cohen 1976). It can then be shown (Weisz 1966.
Bloom and Bergstresser 1968) that the integral h. (k) is proportional to lki.
Combining the magnitudes of k - G and k - G' with angular contributions
from (k-G [c), (c [A lc') and (c '[k - G' ) gives a factor (k-G ) x (k-G l
in the expression for H~~·. G's' (k). U tiJizing this result to get her with Eq . (3.35).
we can rewrite Eq. (3 .31) in the form (Chelikowsky and Cohen 1976)

H~~' G '_,. , (k) ~ (k-G) x (k- G' )(s [a [s' )


{ - i.\s[cos( G - G') · r] ,\··• sin [( G - G' . rJ} . (3.36 \

where we have restricted ourselves to diamond and zin bl n j ·structures. r


is defined just before Eq . (3 .25). and

( _.,' ·-""'

. The quantities .\r and A.:! contain the contrihuti n from rhL' r:tdtal
mtegrals Involving· a· to I11s 1 <~nc
• 1"'!. Ill
· t 11e pnmilt · . plt• rh ''-
. . .v umL L·ell. In pnnd
may
,
b·· c·1I 1 d t'
l: ' u ate rom tabulated atomic l rbit ·d ·. hut i prJ 'I I(· ·
'
Hl'

usuallv' needs" ..to au·JU S t th em to yield


. · ·nl .
gUlld a!.!.reem Ill\ JLh l p ·fllll
Nonlocal d!ects cun be included bv addin-g l l th~.; )le-al .t ,11111 ~· p;;·udl'"
potentt::tl a term of th ·· r· . . . ~ '
l: 01m LCh elikowsk y ~tnd 1h n I '

I·' vdr. E) = L -I I (E)/ \I) p


I ll

where ·4 ' (F· ) ·1s an cncr , , 1 1


lat ing the l'!l'.. . -<.. epl: nu~..·nt \\ell dL'l Lh .
LLt ,. , .111
ol ~..·ur , " 1•. 11 l:S . J
Electron-electron mt roctio n 3
ntum •' lllpnncnt. ll h .: nil'n t t rm fur/;( 1) 1, / ,( t - I
r f I ' R f 'tr s~m ict~nduLt r a pp lic~l it1 n · f~.:a n
a_ I uc... 0 · I • -') · T JlC CJlldlllltlcs
. . · · .·L ( /:.• ) CtJ' I11 tllll
.
~ho. entt Ill c p •rimcntal data . T he rnat ri clem .nts f
\.: pl:t.:lt 1 p iLI1e \\': t\'C tall.'.. h ~nc the l<>rm

1\ _ G ') = 4~t
n<J J.i
l ) P, ( cosO~; G, k <;')

' S' (G' I - G )F ; ( k - G. k - G '), (3.3L)

\ ~)lw11e p rat m . P, (x ) is a Leoendrc pol" no mi·ll f.l7 _


. e -' < • k - G.k- G'
' e n k - G a nd k - G ', S' ( G'' - G ) i. the structure factor for
F, (k - G. k - G'' ) i · a somew·hat comp licated function of
' sci functil n.:.
n nh.cJ.l p ·eud p lentia l method has pro\'ed to be a very powerful
p lOL dur· J r cal ula tmg acc urall:: energy band structures of semi-
co1dU l )f . um ~ro u s ·pe i 1c examples are presented in Sectio n 3.5.

3. 2.2.3 Ah initio pst•udopotentials


The pseudop tt: ntia l th at have been discussed so fa r have in volved param-
ett:r · that ure dete rmined by fi tting experimenta l data for the crystal being
tudt d . A c n ptually more sa ti sfactory procedure is to avoid data fo r the
f) ·u.tl and u e o nl y da ta fo r the individual constituent atoms. Pseud o-
potential _ ne rated in thi s way a rc known as ab initio pseudopotentials.
The) can b \'ie\\ed as producing truly predicti ve calculati o ns for crystals.
et r ah initio p eudopo tcn ti a Is (Bac he let et a/. 1982) has been d veloped
for e\e ry ato m fro m H to Pu . They can be used advantageo usly in the
non! al p. eudo potenti a l method a nd in procedures to be discussed in the
ne ·t Lion which include th e electro n-electron interac tion explicitly.
\Ve om: have in ha nd tbt.: ingredients fo r a one-electron theo ry of
1111 nd uctor ba nd structure. By o ne-electron theo ry we mean a theory in
which the eigenfuncti on fo r .N electro ns is approxima ted by an antisym-
mctriLc.:d prod uct of o ne-electro n eigenfunctio ns. However. the electron-
lectr n interacti on ha s no t yet been taken explicitly into acco unt.

3.3 Electron-electron interaction


p to thi s point we have trea ted o nl y a single electron a nd have o bt ained a
Hamil toni an. H 1 (r ), which invo lves the coordinates of onl y tha t o ne elec-
tr n. We know. however. tha t electro ns interact with one another through
the Co ul omb interac ti o n. It is therefo re neL:essary to dea l explicitly with
th coo rdinates of a ll /V electrons 111 the system ,., , r 2. 1'3· . . . - r.v. The
Hamill m ia n then ta kes the fo rm

( 3.40)
b nds. semiconductors
Electronic energy a .
. tl . ·ct:< 11 ·)summation means that the terms for; --= 1..
rnnc on c . . are
., of the Coulomb mteractwn terms enormou
rhe pre I.: n~L: . . . 1\
, th\; pr bll:m beca use the_ Hamiitontan IS no longer cparabl~
. e·t'·l term involving the coordmates of only ne elec-
f tt: rrn , ... . .
ur... must then c made to approximation methods. some of
,., e cri lx: .

.3. Hartree method


In Lle Hanree method. the '-ele_ctron eigenfunction is expressed as a
r duel of 10 -ckctron igenfunctJons :Pn(r ):

(3.41 )

Each electro i a ssumed to move in the average field due to the other
lcdr . Th eil!enfuncti on 'Pi(r ) then satisfies the Hartree equation

(3.42 )

where the sum over j need not be restricted to j =J:. i, because the volume
element oft he integral cancels the singular term. There is an equation of the
form (3.42) for each occupied state :Pi(r ), so we have a set of coupled
nonlinear integra-differential equations. They can be solved by iteration on
a computer by inserting~ an initial couess for the .. J·(r ) into the Co ulomb term.

3.3. 2 Hartree-Fock method


There is a fundamental difficulty with theN-electron ft n til n given by the
simple product in Eq. (3.41 ). It does not satisfy the Pauli exclusion principle
that a given electronic state can be occupied by at most ne I ·ctron. In th~
H_artree-Fock method, this difficulty is remedied by ' nti g th..: \'-ekct r~ 11
etgenfunctlOn as a Slater determinant of one-electr n ·u n 'ti n::;

1 (1·1 )n , (.1·1 ) .,; \ ( I'J t1 \ { .\ I )


"I (I'.: )ClJ (s_; ) .,..~ , tr ;: < ' t .:

where ( v) ·.. · ·
· ' Js a spm eLgL'nfunctio n. If two el L'tr n u
1
·{ · )
'
1
n·;(.\ ). then two c c t· . b . .
· ·h " , .
ts cs. l he Pault p .· .- 1 .
umns ecomc tdt.·ntu:al. :md th tl
·rl " tmup e ts tlll:rct"ore ohL'YuJ
l~ ( ne-dect rot r . . . .
cxpcct·ttl ~ l·1 . I 1 _unl"I!Ons t.,.'; (r L·~•n ht: lk tnn tn
l• v •• Lit.: t I I H .
Li o ••s ·,n ll . ( •..: an·uhvman ,' l[J ' Ill \l''
L

· h: -r, 1· ) Th ~· \.trt,llH•nal
,. ·. · .
cakubt tu n l·.td
Electron-electron int ra tion 55

47ruL (d 'rl.,;i (r') !- . I ·'I } .,.J;{r)

'\"' I
1 • 1I - I

!-' 1,I y{ ·' ) .


I .
( 'P1 . 1 . . i( l" )
I
I,. - I ,. I 1(r)·
I . =- E ' "· t'. r· ) I 't' I . (3 .44 )

or
.l nne the ll a rtree- F ck C(lll"-llion~
• " tl1'·lt
• detet·m'
. me tl1e onc-
Ltln: .;,(r) . T he last term on the left hand side is a new term
change term . 1t a ri,se from the direct Coulomb term preceding
r rrang m~nt ", (r ).pi(r ) --+ - ri (r') :p, (r) . In other words. th~
nd 1 are m tercha nged and a minus sign is added .
h.mge term can be rewritten in the form

.! d\' v. .x(r. r' );pi(r' ). (3.45)

'here
_.2
l l c.ni l\ 1" '). =- ~ <.p1' ( r ') (: ;p1 (r). (3.46)
i 4nt:olr- r' l
i the exchange operator. It is both a nonlinear and nonlocal operator, a fact
"hich complicat s the solution of the Hartree- Fock equations. They can be
oh ed exactly for a system
- of free electrons.. the one-electron functions
eing plane wav . Exchange leads to an effective repulsion between elec-
trons ofpara ll I pin (Seitz 1940). Some of the physical consequences ofthe
Hanree- Fock method , however, are not satisfactory (Kittel 1987, Ashcroft
and Mermi n 1976).

3.3.3 Density functional method

A significant advance in the treatment of the electron- electron interaction


wa made b y Hollenberg and K o hn (1964) and by Kahn and Sham (1965).
H hen be rg and Kohn showed that the energy of an interacting electron gas
in a n ext rna! pote ntial is a functional of the electron density n(r). Mini-
mization of the energy functional with respect to va riations in n(r) leads to
th e orrect gro und state energy. Kohn and Sham shO\·ved that, if n(r) for an
J -electron system is ex pres ed in terms of one-electron functions o.p;(1·) by

N
n(r) = L !:,o; (r)j 2
. (3.47)
i= l

the minimization of the energy functional lea ds to a set of equations, the


Kohn-Sham equations, that determine the one-electron functions . By treat-
ing exchange in the local density approximation (LOA) and introducing
th~ co rrela tion energy F~._. which accounts for the difference between the
Hartre"- J-ock energy and the exact energy, Kohn and Sham obtained the
b ds. semiconductors
Electronic energy an ·

l.!quati n
.
1
1
n (r' )
~ d 3r' + J-l n·(n(,.)) } <pl(r) = E ;i_p;(r ), ( 3.4~ )
{ Ho + J ,., + 47rf I. !r - r'l

\here r ., i . the clectr n- t n potentiaL

. d(11 XL' (11 ))


I'·" (n ) = I
(:IT
(3.49 )

( ) ·t th n .- 1 ctron exchange and correlation energy. The


and f .n 11
ex hange part r fL \c(n ) a · derived by Kohn and Sham has the form

1.22 db
I'·'· (n) = - -
r_,(-
11 )
ry ergs. (3.50)

The quantity r. (n) i. the radius of a spher containing one electron


expressed in units of the Bohr radius as and given by

r~ ( n ) =
3 ll/3 · -I · (3.51 1
· [ 4rrn(r) as

The correlation part has been estimated to be (Wigner 1934)

f.l r -
_ -
0.88
r,.(n) + 7 .8
[I + r5 (n l
rvdber 0_s...
3 (r, (n) + 7 .8) · ...
~ ~ )
l. -'·--

Other forms for both the exchange and correlation potenti· L have been
suggested.
The density functional formalism of Hohenberg, Kohn. and Sham g.in~s.
in principle, exact results for the electronic gro~nd stat n rgy and for
structural and lattice dynamical properties ~hat ar d ~termi ncd b) that
energy. Computational difficulties generallv fore the u e f the LD
(Wendel and Martin 1979 Yin and C~hen 19'82) or Quantum I )nt · ark'
1

methods (Fahy et a/. 1990). Representinl:?: the elec tron ion intcrad ivn )
ab initio pseudopotentials and using the~LOA. Yin ami ( t h n l)bta tn~d
val~~ · for the lattice constant a. bulk modulus Bo. a nd ht: t\ • lll.'f\!. £ ·
ofstltcon and germanium that are presented in ab k I 1 ;(.·tht'r \\i th th'-'

Table 3.1 C ·tll:uht . 1 . 1 r:xpenment:t


. · . n>nst:tnt. bu ll- m•JUIII
. . ' · ' ~l .lrll llatltl·.:
lor ~thcon •·tnd g~tm.tntum alter 't 111 and Cohen IYX2l
1 • • ·( - ·••

Lallin· cunstaul ,1
Bulk uwdulu' 8 11
(A)
(t-.lh.tr)
('a! h .. p . l '; t k' .
St 5 .-1 ~ I
"-'"'~') O.lJX
G\: ~ ()5:' 5o. ::: II 7 1 0 ,.,
Th A p metho 57
I ~h ' ·n~~ml.'nt hl' t ' 1.c " n llh::o
' t.) and L.' J1C ntn~
. nt ts vcr
n I f l ' ls )11,1 1 lj ~( l d r\) f F
'"
'' ~
lectronic states

an e I lht: Pfl' j)Crties o r :-, miconductnrs are excited I -


h ~' "ph)
[ ha cr ll'lal
· m lc in prOJ.1Crtics' suc-11
' '·•s·· el,t:: C·t·· l e ec
I I C<l con-
Ic• •l { rp tli..Jn . A l ~ h o u g h the density runcti onal meth ud
t: y utli.! go d results l l r !!round sta te pro perti s such as the
nt tnJ bul k m, d ul us. as \-vc ha ve seen in tl1e 11 ,.,,,.· , l .. ·
.... 0 IS sec 1ton . It
·
"llahle r ult ' G r enen!:V ~- ~
ga ps and o tl1et- 1) 1·o pe 1·t 1·es " . ·
In VO 1VJIH!
·
. Fore :.tm _k . the L DA calculatio ns r 't'' in and ' ohcn vield
n g~ gap I 0.48 e ''l nd 0.47 eV ror Si and Ge. rcspecti~re l y,
t,:;mltca nLly I - th an the ex periment a l values of 1. 17 eV and

n altcrn,Hi\ e a pp r ac h to the excited state pro blem is based on the


J 't~rmm.tti( n )r quasiparticle energi s E nk thro ugh the olution of the
t.:hri1dlllg'r-like eq ua ti n

[Ho + I . i Vli l d r' L ) r, r' ; £ 111.:)]


3
, 11 k(r')

= Enk ''nk(r), '


(. .).)
- ., )

\\ h re J ·If i tl e average Coul o mb (Hartree ) potential due to the electrons,


and ._,(r. r ': E,k) is the electro n self-e nergy opera to r. The Iau er operator
c ntai n ~ the d Te ts o f excha nge and correlation. It has been evaluated with
suffi 1 n t accu racy to yield signi fica nt results fo r semiconductors by
H ~ bert en a nd Lo uie ( 19tl6). T hey obtained the values of 1.29 eV and
. 5 cY f r the minimum energy ga ps ofSi a nd G e, respectively, which a re
in mu h b tt r ag reement with the experimental values than the LDA
rc ult of Yin a nd Cohen . A number ofint erba nd transiti on energies were
cc I ulat d that arc in good overall ag reement with experiment fo r both Si
nd G . Simila r re ·ul ts have been o btained for the III - V compounds AlP,
aP. lnP. AlAs, GaAs. InAs. A!Sb , G aSb. and lnSb by Zhu and Louie
( I 9 1). The energy eigenva lues as functi o ns of wave:: vecto r were calcula ted
by Hybertsen a nd Lo ui e for the valence ba nds ofGe. The results are in good
agr ment with experiment.

3.4 The k · p method


It wa. stated in the introduction to this chapter th at the top of the va lence
band and the bo tto m of the conducti on hanJ are separa ted hy the funda-
mental gap. Electro ns in the cond uction band and holes in the valence ba nd
tend to acc umul a te in the vicinity of their respecti ve ha nd ex trema in
acco rda nce with sta ti stica l mechanical distribution la ws. It therefore
pr e~ U'-> ful to ha ve a procedu re fo r developing the energy versus wave
\'e t )r relatio nship E nk near a hand ex tremum witho ut ca lcul a ting the
ent1 re ha nd structure. T he k · p method i. such a procedure.
d 5 . semiconductors
Electronic ene rgy b an ·

3.4.1 Nondegenerate bands


· c·J1 a. pte r! an electron in free space has an energy-wa
• , \ :t: h uve <;cen t 11 -·
. c tor rel.ltl no:;hi that i i ·otropic.

(3.54

\'h~:re k:. = k- k~ + k"j . By differentiating this expression twice with


r r ·ct to J, , one btain.
I t/ 2 Eo
m = tz 2 dk 2 .
(3.55 )

On the th r hand, the r suits that will be presented for energy bands in
emi ndu toru frequently exhibit an anisotropic relationship between
en rgy and wave vector, so that the energy is not simply a function of the
magnitude ot k. but depends separately on k,., kr. k: . One must then define
an invene effective moss tensor whose elements for band n are given by

I 8 2 Enk
1) (3.56)
( Jn '
11 JIV
11 2 EJk ,JJk v .

In general, these elements are not constants, but are functions of k ,. k ,. k: .


Of particular interest are the values of the elements at band extrema. as
discussed above. A derivation of Eq. (3.56) will be given in Chapter 4.
Let the energy band of interest have an extremum at wave vector ko.
At a nearby v.'ave vector k. the Bloch function can be \vritten as

( ·)
. nk ( I
·) _
- e ikO" I' ()!:ik·r link 0 - D.k I , (3.57 )

where !:1k =k - ko . Substituting Eq . (3 .54) into the Schr6dinger equation.

[ p-
2m + J (r ) ·. nk(r) =
') ] Enk r ,nk •·) . (3.5 )

where Pis the momentum operator and J' (r ) is the r n li p1t 111 i~ I. '' ·
obtain

P2
[ 2m
liko . P
m
h!:1k. p
111
+ /z2(ku + !:1k )2
,.,
-Ill
+I

,.
lu ,,,,

= £1/l..u ~J..II"J..o I .:'11.. (I').


The It · p method 59
I th~.: tal, nltn is JWnde~cn~rat I
d •"~•-dcr a . t le p~rt urh ·d energ y cun

nm~ l n the su m mean , the term n' = 11 ,· 5 excl Ul1cc:1 . lftl1e eneruv
n trcmum at k = ko. the term linear in 6.k must vanish, so th:;t
1/·(0.k 2
= Lu/.. 11 + ----'-
2111
+ 17 ~ "D..ko!::.lq ~ ~ (nkoiPuln ko )(n ko JP.dnk 0 )
1 1

m- L L E E . (3.61)
ol n' nku - · n'k n

From th ddi niti n of the inverse effective mass tensor,

(3 .62)

and u ing Eq. (3.61 ), we obtain

( /11 )
117
II jJ 1/

(3.63)

The principal contributions to the sum over 11 1 typically arise from those
stat w·ith E,1'kf) closest to E,1k"·
Example 3.3: Efrective mass for a spherical, parabolic band
Evaluate the inverse effective mass ratio for a spherical, parabolic
band.
Solution. Take the semiconductor to be cubic with band n derived
from an s-like state at ko = 0 and bandsn1 fromp-like states at ko = 0.
From symmetry, (s0 jpy jx 10) = (s0 jp 1 jy10) = (sO jpj::- 0) = P,,., (O),and
1

all other matrix elements of p 1, are zero. Then,


2
.111) - [I 2 ~I JP,p'(O)j ];. (3.64)
( -m .. -
.I jl l/
+m L..
f'
, E,n
.
- Ep'O
(If//' '

If the states sO andpO correspond to the conduction band edge and the
valence band edge, respectively, and we neglect all other p-like states
at k0 = 0, we obtain the approximate result (Kane 1957)

2
_'_!_!_) - [ I - 2 I p Sf' ( ()) 1 ] 1: (3 .65)
- -1
( m~
s fill
m E,g ul"''
d . semiconductors
Electronic energy b an s .
E quation (3 .65) is particularly u eful for
where £ ,u - ro.
£'-~ = - h . . .
· · ·ond uctor such as JnSb. T e energy as <l funct1 n of
11'11 rQ\\ g p e tlliC . .. • h .
' r take the: form charactenstic ot a sp encaL parab lie
,·ave 'e t
b.l.ll .
? ~
Irk"'
£,, = E,o + - - , (3.66)
" 2111'

'' h~:n.:
-= - - =--= - .
m· m.~ , m,T m __

and k.- = k \2 + k I: + k : . As the energy gap increases the effective mass


-

al oin rea ·e .

3.4.2 Valence bands of Si and Ge


Turning now to the case for which band n is degenerate at its extremum k0 ,
we label these bands by n = 1, bz, ... and the corresponding eigenvalue
energy by E t>ku. We foc us on the valence bands of Si and Ge whose maxima
are at ko = 0, so 6.k = k . The bands are triply degenerate in the absence of
spin considerations. Applying degenerate perturbation theory. we must
deal with nondiagonal second order matrix elements having the form

H = 11'2 " ' ' (6ikoik ·Pi ko )(Pko Jk · p jb;ko) l.3. 67'.l
I}
m 2 ~
f
Ei::k u -
Et k u .

The perturbed energy eigenvalues Ep(k) are then specified by the secular
equation

H,l - ..\ Hr;, HI :.


H21 H:.?c - ..\ H .,_J, = 0. {3.68 )
H31 Hn H.~.' - ..\
where..\ -- EP (.k) -
1~2 ,
" '' -
,/?-111. u ti·1·IZtng
· the symmetry pro ert.·t es ol·s·1 am·i
Ge, one can reduce Eq. (3.68) to the form (Dresselhaus eta/. 195 5)
Lk~ + M (k>: k.!) _ .-\ /1/f.; rk. , \/.. ,/.._
NkJ;,
U·;:' + l'vl (k ; + k }) - /\ ,\ k k-
Nk J.;.k:
N k ,k: Lk: + \1 (k ~ - k ,-

where the quantities L M · . . . 111


E4 . ~ 3.67 ). · · · · N mvolve pa rt1cul tr n1l~r 1 cltat rat._.
T properlv.J tr·e·•t t-11 l:" \1'1
. ICI1C " b I I' ..
t:ompouncl SC t1t ·c j • . c an :\ l t a nd J<:
<l

I Oil( llL' tOrs 1t . ·


orbit int net · . , . · · Is n e L·cssary tP ta t. 11 Ll t
to n ciS gtven by E
111 1 ·b· . - q . (.J .) ). \\1t h tl \. 111 lu t 1
L 'l ' . ,.
~.:xc luclin g thcs · ,
~ tltnter· .1·
• · • Ol t 1 1
de gL'Ilcr~tt· 1~ 1 , . . <lL ton , tn~..· 6 p- lt k.e \ ,tkn ·
c . 11.. "~Pitt orb 1t ·111 1 ·
era ltL n spl it. II l'i 1 ~
The A p method 61
~I 11· 1\\'11- t · IJ l 1Cl!l.: ll 'r(ll '
' ~·'1
and :t . /.1 -·
• "- '' the fnrm (Drcssclhaus 1·t a/. I~S S.I
1

II If~
~ \ '\ II
,\ ' ,, ~. 1 //
() II...._!!_ ~lh
- ll q If 21/ ' llo I ll
~\o l
!!.!.·· ,
H11 I~ .}]
.\ II
\ ~ '" '
~ Ill
~
II;_
,\ !:£ • II · '!lll p II r/1 = 0.
\ h
1 •. - ~ 1111 - 11 - ~ u ,~
\1 1 J/Jl ~~ - ~ HI
0
1!11 -
!.f...__i!!_. ._,f,._ clf..u
\::. "· h '"
_ !J.J.·~
\ h 0 ~- H ..
1 - - .-':. > ., - ,\ I
r 70 )

l the 'Plll- or it ·plitting between the iJn andj


11 2
states at k = 0.
In t ttl n the !nom nt~m o perator.p must be replaced by the operator
• - p- I 4mc- )u · V l Jl1the matnxelements inEq.(3.67)andtheterm
!t/... - _mmu. t be ·tdd to>. to give the energy eigenvalue Ep(k ). o!T
0[()
0 11
. . f the secular equation to o rder k. 2 may be obtained by
crm td nng only the 4 4 block in the upper left corner and the 2 x 2 block
in thr lower right rner. The two 2 x 4 strips neglected in this approx-
imation affect th soluti ns only to order k 4 j 6 w. Solving the 4 x 4 deter-
mmantal quati n gives the result
: Heavy
E .3 -, (k·) = Ak -
~
± [B-k
1 4 '
+ C - (k r-k\ •·-
1 1 ?
(). 71 ) 011 '--~~
- '_,,. . ._-__-..,....::~ .
' holes
_./ 0 I I

010
\\ h r
Fig.3.3
2 \.1 ) li:. / 2m ( ).72a) Constant energy contours in the (I 00)
plane in k·space for the two flu ted energy
surfaces of the valence band of Si.
(3.72b )

(3 .72c)

't h lu tion specified by Eq. (1. 71) occur twice for each value of k. This Heavv
d ublc degeneracy ( Kramers degeneracy) is a consequence of time-inver- holes·
i ) 11 ymmetry and the fact that crystals of the diamond structure possess
a c nter o inver~ion (Kittel 1987).
Th n. tant energy surfaces described by Eq. (3. 71) are nonspherical for
C i= 0 and are referred to as fluted or warped surf~-tces. The intersections of
th sc surfaces \.vith the ( 100) plane ink-space are plotted in Fig. 3.3 for
. iii ·on and Fig. 3.4 for germanium.
Turning now to the 2 2 determinantal equation, its solution can be
written as
Valence
(3.73) band

Fig.3.4
wher A is given by Eq. (3 .72a) provided~"" is small compared to Eg, and a
nstanl energy n uto urs in the tl OUl
t•vo-f ld degennacy due to time-reversal symmetry is present. Since the plane in k-spa.:e fl>r tht: tw\.1 tlu t ·d t.>n,l g)
band d scri hed by Eq. (3 .7 3) is split off at k = 0 from the bands described by surf<tce> of the v:d IK"t: band ot" e(.d. a
:.q. (3 7 1) by the spin orbit interaction, it is referred to as the split-off band. Dressel haus t'l a/. J li'i) )
Electronic energy bands : semiconductors

'tlle val nee ban d constants A. B . C for Si and Ge have ecn


Tht.: va Iuc 1 (
. d r· vel tr 11 resonance measurements (Orcsselhaus et a/
dctt:nm n~ I on: . . . .
JtJS.5·Dc terc!al 195J). Recent ~a luesarcgJvcnmTable_J.2 . Wenotethat
. L·on i t nt ~i t h the tact that the curvature of the valence band
.I I] ·g;lli\L.
. . k _ 0 Q 11 ca n a] ··o show that B < 0. The plus sign 1·n
l . ncgctll\(: <11 - • ' . •· '
q _. 71 ) Cl rre. p nd. to he'IVY holes. wh~reas. the mmus sign corresponds
. ltgh hole . Th vatu of the sptn- orbit sp llt-~ff parameter 6. ~, can be
e munc by <.;pectr ·c pic measurements. It I_s found to be 0.045 eV
f ) f 1 aud 0.297 cV [ r Ge Boer 1990). A schematic plot oft he heavy hole.
1i Itt twk, and pli t- band s is given in Fig. 3.5.
0

3.4.3 Conduction ba nds of Si and Ge


Theoretical calcula ti on (Herman 1954) show that the conduction band
minima of i nd do not occur at k = 0. In the case of Si. there are
·ix mmirn of the same energy at ko = ( ±ko. 0, C)) . (0 . ± kn. 0). and
(0. 0. ±ko ). \ h re k 0 is about 0.8 of the way to the Brillouin zone boundary
in the r direction. Such minima arc often referred to as va lleys. One can
then ay th at the Si conducti on band has six va lleys. Even though Si is cubic.
a Lhange 6.k parallel to k 0 is not eq ui valent to a change perpendicular to
H k 0 , since. if ko = (±ku. 0, 0) , (nkoiPxln'ko ) =/= (nkolP ~· l n'ko ) = (nko!P: /n'ko).
Consequently, the expre sions for the inverse effective mass ratios become
Fig. 3.5
He ' hole (lrhL light holt: (lh). and m m
plit-o[ ( o) energy bands for diamond -= -= 1 (3.74)
struct ure semiconductors. The Kramers m( m ~·x
degeneracy i indicated by the up a nd
d wn a rrows.

.,' ..-)
~
.
( . .I .

The relation of energy to wave vector i.

k,.

T~e surfaces of constan t energy a re ellipsoids of re\ luLit1n \\ ith nw 't r ,In 1
mmor axes proportional to vrnl' and m respectin:h Tht: 'lt fr n:'tanl
energy su r . I i
- r aces. ISs lOWn chematical ly in Fig. 3 . .
I • .

lnthecaseofG~ tl . . . f . ... b·tnd lltp 'IJ th.tt 1·tt ·IIH!


Fig. 3.6 111
) .. . c, let c:: ..ue our condudton J ~

Jllblant ~.: nc r 'Y 'u rlatt:l> fvr th~.:


.~ I du ectl ons as shown in Fig. 3.7. T he band ~d ' :-. .tr t the Bnltt' 1111
z ne boundary (L · ) B .
•)nd uct1on ham! ,.f i, . .. . · pomt · _ rotat111g the L'0oriina Le 1
I lt!S 1 ll g ·1 (J\J] j'
clO · ...
I. · _ Ctrcctton, one ca n show th· L the- n r!! _,
re.tttonotEy
. L

,. I ' . ' ' . . . 6 IS v.thd for the cu ndUL'tio h.tnJ l r


(~7 ) ." .. • ~ •
r •rl r rn.tl
\a ues ol nl, and III "
For s·t ·a nJ '.
Gc, Ill • .
. ( t' ~l) lhe elltrs
L
111
ruuhy b·tlt T l
. t:. , . 1l: m·tJur- Lo- min,)r ' I . .. .
cln i'> Ol ropyoft h · II ' . . . 1 1. 111
c l: 1ps td .
Thek p meth d 63

de structure emiconductors

.mel tructure~ l'' ?incbl. 11 d, . .


~ c ::..t ucturc ~ llllconcluctors
lh•' J k.td I ( r ·suit-.. tin! a. re qua 1ltat•ve
• • L
. . to th '> C
- · 1y Similar
ft r _d ramond '> tructure materials. However the lack of a
nrn th~Lrnchl n e structurele·uJs toc t.:r·t·.
• L
f'
aJne1ectsont1e
.
1
tha t• arc n t ~ und 111 the_ diam ond structure -
r.: · 1
. r 0 1 examp c,
1
blC Kramer d generacy 1 di ffe rent in the two case ·. If we
Kramer ct~gcnc_ra testates by up and down arrows (loosely,
~)~ rela ted t ~pm dtre~tion). the Kramers degeneracy for
n n . -.truct ur 1 · pe~ Ified by £ ( ,k)=E(l, k ) and
E . - k). T hese relatiOns do not hold for the ziocblende
l"lr \\hi_h v. _ha e E (T , k ) = £( [, - k ) and E (l . k ) =
Fig. 3.7
. \ c theret rc a rnvc at the qualitative picture shown in Fig_3.8
Constant energy surfaces for the
f1r th~.: al nee band .T he b havior of the bands shown implies that th~re is conduct ion band of Ge.
a !"near. plittine n_ ar ~ = 0. This is. in fact. the case. The splilling is spe-
ctfiLd b~ th ontnbutJOns (Dr s. elhaus 1955)
E
I I
k-J,-
\= \·X-) j:: }2
1 1
(3.77a)

(3.77b)

~ r the light a nd heavy hole bands with C a constant. The effect of these
·ontrit ution i to shift the maximum of the valence band slightly avvay
fr m k = 0. Tnt rband magneto-optical experiments on InSb (Pidgeon and
r ve. 1969) have shown that the valence band edge is raised by . . ._ 10 5eV Fig. 3.8
HeaYy hole (hh), fight hole (/h). and
corrc pondi na t a very small value of C. This shift is not evident in the split-off (so) energy bands in the [11 OJ
nergy band figures for zincblende structure semiconductors shown in direction for zincblcnde structure
_ub.cqu nt fi gures. Henceforth, vve shall neglect C in our analysis. semicond uctors. The arrows distinguish
It h :.~. be o rne customary in discussing the valence bands of zincblende difrereut Kramers states.
' tru ture emiconductors to use the dimensionless Luttinger band param-
ter. ~ 1• ,_ , r >which are related to the Dresselhaus parameters A, B. C by
I
2111 Ill 111
, =--1 A, _ ,1 -- -
/_ - !i'1- B,
-
..
~~~ - [I-:1 C2
=:,2 + 8 2]2 . (3.78)
fi-

Th nergies of the light and heavy hole bands are specil1ed by the
ex pression

, ? ~
(3. 79)
,, ,,
X (k ; k ;: + k ;:k; + k; k; )]- }.
re th and - signs refer to light and heavy holes, respectively.
We n< te that the condition for spherical bands is 'Y2 = )3- Values of the
Luttinger parameters are presented in Table 3.3.
In the cas of Ill- Y scmicondudors such as GaAs and InSb, the mini-
mu m fthe c nduction band is at k = 0, and there is no linear splitting such
d . semiconductors
Electronic ene rgy b an s .
, ~ -.,., for Ill V and II VI 1inchlcnd~.:
p ·t r· tm t: le l 'i I I· 1• ' lructure
' ' rr w s Jl)69, Lawaetz 1971. Bl.ier 191)0)

':·I --, ~
-~~

11 5 Z nS 2.54 0.75 1.09


II Of>
() 7~ I 57 Z nSc 3.77 1.24 1.6 7
I 75 Z nTe 3.74 1.07 1.64
I 01
l ::!5 CdTL: 5.29 1.89 2.46
ll·N
~ ., . :! g6 H!!.
.,
- 4U - 21 .0 -20.7
.... 57 HgSe - 26.0 -13.7 - 13.2
u94 l 12 HgTe -1~ . 7 - 10.2 - 91)
lnP 5. 15
Jn•\s 211 4 '3 q j

In b Jl5 l.f.5 15.6

as in the valenc and . A ·plitting does appear in third order ink and is
giv n by (Dre l h~u s 19 ·s)

(3.80)

where C 1 is a constant related to the spin- orbit interaction. This splitting is


also too small to be observ·1ble in the energy hand figures of this chapter.
The conduction bands of GaAs and lnSb are therefore very nearly sphe-
rical. GaP, on the other hand , ha s conduction ba nd minima along the six
( 100) directions as in Si. The minima are so close to the zone boundary at X
that a camel's back structure appears.

3.4.5 Extended k · p method


The k · p method outlined in the preceding sections is valid only in the
vicinity of an energy band extremum. The method can be modified. how-
ever, so that it provides accurate results over the entire Brillouin zone. Tht>
starting point is the observation that the periodic functions llnk) r ) form a
complete set in terms of which mn· periodic function with the periodicit) of
the_crystal Ia ttice can be expanded . 1n particula r. one can ' pand lin~; tr) in a
senes of the u11~;,, ( r),

Unk(r) = L Cn·(k o) ll
II'
11 'k,,(r l.

where. the. codficie11 l s' c."' l(o arc the element s


. (·'· ) -
l) t thl: . ..
~~!!~t1\ • ·t ot ~ l
)f rh1.'
Hamtltontan matrix ~

(nt,ko l ~ 6.k. · p!nJ k 11 ) (lltikp J D.A . p I I

1
L'll tku (ntkol-;~ /'' -"
(n~ ko l ~ ~k. · p jn1k.o)
The 1\ · p method 65
I ll.!~ num hn 1r hands i~ included in th e H <.u niltnnian
0 Jt""atH 11 f hr ]at tcr leads to <ICCllra\e l'I1Cfl'V hands over·
'='~
Ulll I 1llL'.

h.l'> ht:e n 10'\ l1 ited hy C ardona and Pollak ( 1966) for Si


la. they determined interhand matrix elements ofp for up
h ~ then ( l nstrLKted a I 5 15 Hamiltom a n rnatrix whose
1 ~:.1\ e yuite go xi results for the valence and conduction
I, t:lllir wn ~ -

34 nparabolic bands: the Kane model


n1ple f th . xact k · p method is the Kane model (Kane 1957)
\\ Jud11 a ·ed on th e scrvation from perturbation theor.Y that the hand s
ha,in-= the greatc t intl uence on a gi ven band are those that are closest in
rnerg_ l) tha t ban d. In the Kane model one focu ses on a particular band
and in lud in t h Hamiltonian matrix only that band and those other
band. close t to it in energy. Exact diagonali zation ot' the resulting matrix
1nve. resu lt Cor th e energy bands that include nonparabolic effects. i.e.,
2
:orrection to th energ_ of higher order than k .

Example 3.4: K a ne model for a tvvo-band system


Evaluate E11 k fo r two bands n = c and n = 'U , assuming that the band
e. trema a re at k =
Cl.
olution. he secular equation for the determination of Enk takes the
form

~ k ·., (cO ip lt 0)
E,.o - ,\
I = O, (3.83)

wh ere /\ = E iik - h 2 k 2 / 2m. Expanding the determinant yields a


uad ratic e4uati o n in,\ whose solution is

[(£,, _£," )' +4(>


) l

>. = I{
2 E ,o + E, o l(cOiplvO)IY]'}
(3.84)

Expansion of the square root in Eq . (3.84) leads to the series solutions


for the conduction and valence band energi es:

2 4 4
, _ , 17 2 (k · l(cO \p lv0) 1) __ 1i (k ·i(c0 iplnO)I) + ... (3.85a)
A , - E,{J + -111-" Ed! --
E' oO 111
4 (E.:co - E~ "o )3

2 4 4
, !i 2 (k · l(cO\p iv0) \) fi (k ·i(cOiplvO)I) (3.85b)
\ . = E,.o - -;
111-
E-:,0 - E dJ + 4IJ1 (E cO - E dJ ) .1

The first two terms on the right hand sides of these expressions give
th e energy to order k 1 and constitute the parabolic approximation.
. emi conductors
Elect ron 'c energy b o n d s. s
4
. the right hand sides are of order k and are non-
T he th u·d term, n - ~ h k
. . N o t ~ from q. (3.84) t at as -----. x. ., .A ~~ lkl. a
arab ol lc corredtons. c
P . b 1ic beha vior. Plots of the band energies\ and..\
thstmctl · n np. ra t1 · _ _ . . '
01 ~ . nd 11 n p·1rabohc cases are shown 111 Fig. 3.9.
~ rThe
th~.!K~arJ
anc m
ICdeal c·an b•" c'x nanded to include the conduction band
... · F · _ . . . •
. . d hea y hoi hands and the spin-orbit spht-off band
l1e I tg11 ,t n . - . . d. I' d -
(Kan 195 7). A 4 4 Ha m ilto man ~natnx 1s 1agona Ize to yield the
foll \! ing band cnergie lo o rder k-:

E . ·k =E
' ( ) g
fi~ k 2 [ l +2P- ( -2. +
+-_-
2m
2
I
3m Ee Ee + ~'"
) l
J
(3.86a )
, ~ r.us k • olid

(3.86bj

2 2
£ , -n-k-- ( l - - 4P_- )
(3.86c)
1' - 2m 3m£'<

(3.86d)

In Eqs. (3.86). Pis the momentum matrix element between conduc-


tion and valence bands. The quantities P2 / mEg and P2 / m( Ez + ~'"
are typically large compared to unity for material s s uch as ]nSb. The
effective masses of the v2 and split-off (so) bands then ha\·e the proper
negative signs . The neglect of higher band interactions leads to an
incorrect sign for the 'ul band effective mass.

3.5 Energy band structures for specific semiconductors


Detailed energy band structures have been calculated fL)[ a large number of
semiconductors. In thi s section we present band struc ture- for repre-
sentative elemental and compound se mico nductors an d d i · u:;· the qu:Ill-
tative feature of the individual structures.

3.5.1 Elemental semiconductors

The energy band structure ofSi for th e principal Ji r d1 n in th ' Bnl l~' u 111
zone 1s J1rcse t i · F·1g.
· 11 ec Ill
· 3. 10. - The ma xunum . 11 th upp ·nnot tdkJ
(valence) band ccurs at the r point ( k = 0 ). ~tnd t h • mminHnliOt'th ·lln, ~>l
(!lllJ)l \! ( ., d .- . . ' t th .
J LOI1 LILli0\1) hand OC ur ~ ak) llg the .\ ,j j t:l'LI I U Llil U l \.
way to the zo ne b 1 1 - - . ~ . h,tr·
. c um ary . fh1s IS ~111 xam pl I .tn ind1rect ap l.
actenzed bv the ext 1·e - .. I
. . •. · rn..t ol t 1c ':llc.·nL·I..' and c r luLl I n nJ t•~-.. ·til''=- t!
Fig. 3 .10 dttler nt pumts in k . -- t . ,, 1
Band < J ruuu,~ •ll' ~ ~ i al t~r t ' li e lik• l w~ k
,. 1• , . · _-space. I he magnit u k ,r th · 11 •
\,JL:llL .mdcundu ct1 1 b· J' 111
_,,,J ' " ' '~ '' I'J76J _ _ l n .tnL :--.at r, , Pm IL'11 tp •ro.tLUlt: 1 1 I
gap ,Jt thl: J Politi i-. 3.45 l'V at 5 K .
nerg band str ct res for specific e mico nd uctors
67
1
I i . ~ ){) I h,l! 1he \ <1h 1v h·)!l•i ·tt r~' · · J
. .• ' ' ' ~ l 'i c.:g n ~: r a le .
frcml, IL llllJl: Jr' '> l atcs \\'hich ~Ire not "Pill h the c uhi .
phl h th~.: sp m < rbit interact! n. but th~: latte r Is too
phtt mg that 1s ' \, cnt -111 tbc s -- ·-ti~ ) 1- tl 1- _ "
I · • ~.: c 1c 1gu1 c.: . ,~-, ~ one
11th; r J10111 !. the ._. llllll ' tr . i. reduced rrom cuhic and the
Jl. I. C\ IU ·n t for lbc I' X and rL directions . Every band
t I J _ull} ~ ~ ·~e rate he \ ttl. c of the Kramers de•,~nerac;
) 111111 t Jy Jnd th presence of a center of inversio n

. tructu re c r Ge is s l~0 \\~1~ in Fig. 3.11. It is qualitatively


but t hc r ~re . ome sJgnllJc·tnt ditTerences .As in the case
1
t 1 I.
I nc banu ma. m1um occurs at the I' point. However. the L A r .:.\ X f../.K I r
r~nd mmm um IS at the L-point. i.e .. at the Brillouin zo ne
PtlUI n~ the [111 ] d irection . The order of the r l and r~ band s is Fig.3.11
Band structure or Gc (after ChclikowsJ-,
re\ rs mpared to i. bu t the fundamenta I energy gap is still indirect and and Cohe n t':l76). ·
cqu.!ll;) 0.67t:V at r m temperature. The spin- orbit splitting of the
upp rm t 'alene ba nd i 0.3 eV and is clearly seen in Fig. 3.ll. The
minrmu11 dm:t: t gap at r between valence and conduction bands is 0.90 cV.
light!) larger lh a n the indirect gap.
n
In the cquen e of h mopolar materials such as in column IV of the :>-2
pen Jil: table. the fundamental gap is largest at the top for diamond '"'
~ -4
:>-.
(£,,~54 eV) a nd decrease · going down the column until o-Sn is reached. OJ)

~ -6
c:
\\ hich ha. ze ro funda m nta l gap and whose band structure is shown in ~
-8
ig. 3. ! ::!. 10
- 12

L A f L\ X UJ•.' [ r
Wave vector k
3.5.2 111 - V semiconductors
Fig. 3.12
helik "" ky and Co hen have calculated the energy band structure of the Band structure of o -Sn (after
IJl V cornp unds corresponding to all possible pairings ofGa and In w·ith ChelikO\\·sky and Cohen 1976).
P. A. _and b. The band structure of GaP is shown in Fig. 3.11. It is similar
t thal f i in that the minimum energy gap is indirect and occurs bet'vveen
the r int or the valence band and a point ncar the Brillouin zone
b un ary in the rx direction of the conduction band. The band structures
of th o ther five compounds are very similar to one another. Specifically. 6
th minimum energy gap is direct and occurs at the r point for each of them. 4
· a n example. the band structure of GaAs is shown in Fig. 3.14. In 2
ad dition to the principal conduction band minimum at [, there is a sec- ()
·- ..,
nd a ry minimum at the L-point. The order of these two minima is the >
0 - -

rev r fthat found in Ge (Fig. 3.1 1). ~-4


Th e ·pin orbit splitting of the valence bands of GaAs at f is clearly ~ -6
~.: \ ident in Fig . 3.14 as the separation oft he r 7 and fx bands. The splitting of
u.: - !{

the upper val nee band f:-: ask becomes difrerent from zero can be seen in - 10
th rJ and rx directions. This splitting is a consequence or the IO\vcred - 12 L-~~~----~~----~
) metrv when k is finite. The band structures of other III V semi- L A r ~ x ex ~ r
n uct~rs :.uch a GaSb. InP. lnAs, and lnSb arc qualitatively similar \~ht \ 't' \'c' l'!llr k

t that fGaAs. Just as with the group lV materials, the fundamental gaps Fig. 3.13
f II I compound:-. become smaller and smaller as one goes down the Hand structure ur ia P (al'ter
PCJ'! ( di t:.tble . Chelikowsk\ and ' hen 19761.
. emiconductors
Electronic energy b on d 5 · 5
... . b·•nd gJ Jl' .tlld ~ pill orbi.t splitting~ in eV of group IV. III "
l bl 3 4 Dm:d .a mi liWi re~.; 1 ' . . '
a e • . 1t low temperature (alter Bur5.tcm and Fgli I" ;:
I. ::! ,, d 1\' VI cmJCo ll<1uc 1_o.rs , " '
IT 1 :-\6. Bf>cr 1990) -
. Jf d cJna l "7 {lJ
l • H •·•rt· i<>o
. n 19~ 0 . K Jttc I

£"" 6 ., ,, II -VI and IV VI £";,


-~
l'
~ --
().()()6 ZnS (cubic) 3.78 fl.llli 7
3.45 () 04 5 ZnS (hex) lSI I O.IIXIi
(I 74 tJ .90 0.297 ZnSe 2.!Q U.-103
Gl!
() 0.73 ZnTe 2.39 0.9i
-sn CdS
~ 3.0 2.515 ()fJ62
AlP ..,
, J
-· CdSc U\4 ll.41fi
AlA> .......... -·-
1.65 0. 75 CdTe 1.61 0.811
2.35 2.Y0 () 0 ' HgS so (J.32
UL I. 2 o.:-4 HgSe so IJ.58
Ga b 1.?1 0.S I 0.76 HgTc so 1.1!5
lnP 2. 19 1.42 0.11 PbS 0.29
Fig. 3.14
In lSI .42 0.43 PbS~: 0.16
Band ~truclur ·of GaA. (aftt:r
In b l.OJ 0.2 3 OJQ PbTe ()[':)
Chc:h!wl\sky and Cohen J 97n).
SnTe 0.3

3.5.3 II-VI and IV-VI semiconductors

The II - VI and IV-V I compounds e se ntially comprise the Zn, Cd. Hg. Pb.
and Sn chalcogenide and some oxides. The II - VI materials crystallize in
the zincblende or wurtzite structure, whereas the IV- VI materials crystal-
lize in the NaCI structure. An example of band structure is that of ZnSe
shown in Fig. 3.2. It closely resembles that of GaAs. The band structure of
L A r il X U,K I r HgTe is given in Fig. 3.I5 and is seen to be like that of n-Sn. Hovvever. the
k mercury chalcogenides may have overlapping valence · nd conduction
Fig. 3.15
bands and be semimetals as discussed in Section 3.6.1 . A tabulation of
Band str ucture of HgTe (after Cohen valence-conduction band gaps and spin- orbit splittings oft he vaknce band
and Chehk01 ki 19 , ). is given in Table 3.4 for a variety of semiconductors.

3.6 Modification of energy band gaps


We have seen that under the sa me ex perimental conditi on · the energy banJ
gap varies fr om one semiconductor to another. For ~- in:n material the
band gap ca n be changed by heavy doping with imp urities or b~ alloyin~
~•th another semiconductor or by varyit;g the t mp rature 1 r a pr l~ 1 0 ~
stress. In thi s section we examine these method s o m dil\ tn!! th t'J;lll i gar-

3.6.1 Semiconductor alloys


Modification of e er y band gaps 69
h~.: h.111d l!ap
. . II
,,r .
- ~ ., 111 11
~ _•
-
' " ; 1 c o ntttlllt l ll · 1 nLI 1 m nl
111.11 '' O\• •.tht:\ '' lna tt 111 Wi. t ,1 L1 11l1Pt)'> tliun i , ltn c~u if ~ 1' 7n
that lrl.: ' <H IL: 1 'l \ ~ 11 •. ·J 111 >-
. ' ~.: \.:d i Y ' -;a me ;JI O mt c radi i ·tnJ :::. 3 ()()
t cngth to lh' th1rJ c )mtitu 11 1 1_. _ t
. 01 \ \'O con ·ttl uents
2 .6() ..__.____,.________ ___,_
(I 0.~ ().4 n r. n. 1n
E .' l:\ .87 )
~r Ec ,.) tic 'tgna t c a n a ,·erage over difTc rcn 1 micro ·co pic Fig. 3.16
1 a g.!\ en composi tio n _,._An example of linea r
L )!1 1st ' Ill \ 1tl_
Dc pc nd t iK t: \>I ban d ga p un
com posit ion r.. r Zn e I '(J fter
th hand gap ' 1Lh ·o m positio n is given in Fig. 3. J6 for the L·trat h £'/a/. 19-7)
When the ha ractcri ·tic pa rameters o r the two co -
n
I.
. (' 1 .
1g111 1cant_· different. bowing of the bandQap occurs.. as sl
. 1O\\ ,n
~ 2.70 ZttSc
[i r the ~s t em Z nT _ , 1 _,. Bowing can be described by the

(3.88)
2. I 0 l-.'--"'-''---'..::::::.= =:::::.:::.._____.._j
wh r' E 'I t the ba n e.ap ' ith bowing anu his the bowing parameter. 0 0.2 0.4 06 0 8 1.0
for man) -.emi ond u tor a lloy . hi. positi ve (Boer 1990). The band gap or X

th 'allo~ for a !2iY n om positi o n is then smaller than the linear gap E.,(x ) at Fig. 3.17
that ·ompo iti n. , - Dependence o f band gap o n
In ome, mt .ond uctor a ll oys with na rrow gaps. more profound changes compo siti o n for ZnT e, Se 1_ , (after
Lara ·h e1 a!. 1957)
oc ur in the ban "tructurc a a functi o n of composition. Of particular
intere tis H g 1 "Cd , T vvhose band structure fo r three di ffe rent composi-
ti n ~ i . how n in ig. 3. 18. If a ba nd gap i defined by b. £= £ (f 6 ) - E (fx )
__\)."
*
Jt k = 0. th n C.,.£ fo r pu re C dTe is + L6 eY co rrespo nding to a semi- E.. =0 __ . - · - . E-?0
c nd uctor. A t a certain intermedi ate compositi o n b.£ is zero, corre- - -' - - ~ 0 - - - - - - -~
:p nd in g to a ga plcss semico nductor, and fo r pure H gTe, b.£ is negati ve_
~ -- I~\ -
~,·(\ tio
. :C. E orr ·pond s to the fundam ental gap defin ed as the difference in energy
f th I we t empt y sta te and the highest filled sta te o nl y if b.£ ~ 0. If
j.£ < 0, it is no lo nger the fund amental gap. The latter is zero for cam-
?\A ~
p iti(.: n \\ ith 6 £ < 0. becau e the lowest empty band and highest ftlled X

ba nd are the x ba nd s th at to uch at k = 0. Thus, HgTe appea rs to be a


Fig. 3.18
gaplc · scm ic nducto r like n -Sn. H owever, there is a fine point that must be D ependence o f ba nd struct ure on
menti n d. Since HgTe lack · a center of inversion , there are terms linear in composition x or pressure p for
k that rajsc the valence ba nd edge above it value a t k = 0 and produce a Hg. 1 , Cd ,Te (after Boer 1990) .
m·tll overla p of the va lence and co nducti o n bands. The result is a semimetol
\-\ ith both electro ns in the co nductio n ba nd and holes in the valence band
pr sent.
noth cr interesting system is the alloy Pb 1_, Sn,Te. In PhTe the con-
ducti on and va lence bands a re L (, a nd L c,, respecti vely, whereas in SnTc
they are reversed. L (; and L(, . As .\' increa. es. the gap decreases until it
re;_ ch s 1.ero at x = 0.62. For x > 0.62 the system is again a semiconductor
( immock et ul. 1966 ). Thi behavio r is shown in Fig. 3.1 9. It provides a
ha-; i ~ for desi!!nin !! material s with specific band ga ps.

3.6. 2 Temperature and pressure dependence of band gaps Fig. 3.19


D ep ·nde nce ,,f' b.ll1 I gap L>ll
The hand oap in semiconductors is dependent on cryst a l bo nding and cu tnJh ):>t li ('!l ft_) r Ph 1 ,: n, '(.tftcr

btttcc-: m ~ta n t. Bo th o f thesc parameters cha nge when the temperature T L>imnwc k. r1 u!. I J )(-!)
Electroni c energy bonds : semiconductors

~I . , T he change in band gap is described hy


r pressure p c Mngc · ~


w "
= (.E)
__!I.
'" T
(DE.
6. T + ~
f'
.J
(/]
") 6-p.
T
!3 .89 )

The va lues of ((J Eg/ T )i, are typically ""' - 40 meV /K and those of
(t)E.jcJp r,..., 10 meV /k bar. _ _
C n:idering fir t th effec t ot temperature, one t_mds that_the band gap
de rea es uadratically with Tat very low T a~1d l~nearly With Tat room
temperat ure. This beha i r i ··illustrated forGe 111 Fig_- 3.20 and is ~elated to
dt'ec ts on the hand tru ture due to thermal expansiOn and lattice vibra-
tions. Empi ricall~, the band gap as a function of temperature can be
repre ented by (Var bni 1967)
0 100 200 ~00

T! K)
AT 2
Eg( T) = Eg(O ) - B + T (3.90)
Fig. 3.20
Dependence of band gap on te mperature
for e (after 1acFarlane er a!. I 57) . where A and B are constants.
The d pendence of the band gap on pressure can be complicated if the
band edge. at different symm etry points move in opposite directions as
the pressure increases. An example is GaAs, '<Vhich is shown in Fig. 3.11.
The band edge at r moves upward relative to the valence band edge.
wherea the edge at X moves do\vnward . As a result, the minimum band
gap is direct at pressures below 8 x I 04 atm and indirect at pressures
above 8 x 104 atm. The resulting dependence of the minimum band gap on
pressure for GaAs is given in Fig. 3.22.
Application of uniaxial stress to a cubic crystal reduces the symmetry and
!!) splits the light and heavy hole bands at k = 0. The number of equivalent
0 conduction band minima is reduced if the stress is in a suitable crystal-
lographic direction.
Fig. 3.21
Depende nce of band ed ge on pressure
for GaAs (after Boer 1990)
3.7 Amorphous semiconductors
In addition to the crystalline state a semiconductor such a , Si 'an exist in the
amorphous state in \vhich the atoms do not form ·1 period ic ar ray·. but an:
disordered . The absence of periodicity means that BloL·h· thet.lrem TIL)

3000
/ Gai\.s .?Ugc.'

s :woo
I
100()

() ..j()
~ ()
Prt·,s ur.: 1 I0 1 c~ lul l
Fig. 3.22
References 71
11 th 11 lh \ , 1\ ~ \ CL" hll " I1111 '' r :1 ~nnd qu a ntum
. .
IS 1111
t Itc c-.-.. "1 11 11..' 1 ·nt sh 111·t 1.
2.0 r----r---r--r---.--,
'
l , . . · ; •ngc (lrlh.: r n:n1;11ns thai the cl cc-
l.lll::-. I !.t in-. t i s grn-;s lea tun:-; . Ban d cdg-l' 'i. ho\\·'C c r. a rc ICJ
I d h,wd g.tps :Ire lln I ~'IH!.t:r clearl y dctincd. States whl1SC
IX
Ill\ ~i ln~l 1.\ ha t had been the l'nrbidden gap ma y have ' ,,
\.I r.ItiH.:r t han I Ill' C.\ lcndcd c haracter or Rlnch slate . 1.7
''.the_ ~~ost c~·lm1.11tln amorphous semiconductors. C reating
I l.tttt ~..:. ' ' h ' h IS lclra hedrallv ha nded cJu ·c" ~- -·1 · . , . 1.6
r • • . , • .., t: ,JXd lOll
r ment 'l r a l1 urtnld coordination 0 1- 11 •. . , ·t . hb >
,r , , , ., . cdtes ne1g o rs and "' 1.5
~
1 rng bond . IH.: sc blmd. need hl be sat urated and co mbine ~-

m. n \,tlent ;t !Otn s . uch a s H t y ield n-Si:H .


\
1.4
emicl)l1d u t_o r all ys an: frequently used in applications.
I ~- ·mwrph o.u . 1 JC alloys are u seful in solar cells in vievv of 1.3
th:J tc m .a .' ttni Ze perfo rmance by varyi rH!~ the com JlO SI·1lOll
·
. 1.2
Ill cnce ot the _ b and. gap of hydrogenated Si- Ge allovs
H) n o m po Ill n 1. ·hown in Fig. 3.23. •
0.2 0.4 0.6 0.8 1.0
X

Problems
Fig. 3.23
Dependence of band gap on
I. D_d~..nmnt: the e · ec t ~t i n va lue of the Hamiltonian , Eq. (3.40). for a state
compositio n for ll'·Si 1_, Ge<:H (after
111th \\<1\ fu m;~ ' - n g1v n by Eq . (3.41) under the assmnption that the rp;( r)
Mackenzie 1!/ a/. 19R5)
. Jli I~ Lht: Condit t n f rthonormality:

/ ~; (r)~j(r)d ·'r = fl;1.

ht \\ 1hat the ta tio nary condi tio n

tog tber \\'it h the o rthon o rmalit y c nditi o n handled by Lagrange multipliers
lead 1 th..: Hartn..:e equation . Eq. (3.42).
3. Rep a t the ca lculations of problems I and 2 using the 1vave function of
- ll · : .43).
4 Pr ,. tha t the only nonzero con tributi o ns to the excha nge term in the
Han r e- F d equa tions come from electrons of parallel spin .
ak ul ate the energie of the conduction. va lence. and split-off bands of GaAs
a ~ uncti ns o f k usin g Eq. (3.86). Take P = 811/ a. where a is the lattice
n L;1111. and take E~ ( Efr) and .6,, from Table 3.4. Plot the energies versus k
and c mpare the res.ults\.Jualitalively to those for GaAs in Fig. 3. 14. Explain
any ~i~rn i fican t differences.
6. xtend the ti ght binding treatment or Chapter 2 to the case of Ge with two
atoms per unit cell and taking into account the 4s and 4p atomic states. The
re It :,p cific · the va lence: band energies (Reference: Chadi and Cohen 1975).

References
. A. hcroft and N. D. Mermin , Sulid S tate Physics (Holt. Rinehart , and
Win tn n. w York. 1976).
·· B BachdL:t. D . R. Hamann. and M . Schltitcr, Ph_t·s. ReF. 826. 4 I 99 (I ~ ~Q) .
S Bluom and T . K . Bemstresser . .';)o/id State Commun. 6. 4n5 (1968) .
. Ri"ie1, Sune 1• ,: l Semiconductor Phys ics (Van Nostrand Rei nhold.
New Y1 rk. I'NO) . .
Electronic energy bands : semiconductors
. ·fd• ·a!lces 111 £/ectromc.\ and Eleclron Phr.1in. Vol. VII
E Bur, lc Jn ,tntI P E I ' · ll1 , 'i5
.cd . H . Hr ,., ks (, adci111 C Press. cvv Y?rk. 19: )., ..
, 1 1 . 11 nc<.lroscufl l' (i\c.;,ulemlc Press. New York. 1<)69).
1 C ·r l,liH 'l1l l(/1([//11 l ~-,o 196L
d L H PJ ih k '·'/in. R£'1'. 142. ).' (
.
..... . 1 ' ·. 11) .
1 C:.1ruona ·111 r· • ' ' · ' · 8 405 197
. ]' . 1 M 'nhen. Pht ·s . .",'tal . .Sol. 86 . ( 5).
0 . .1 (I1at 1 .tnt . .. · , .. ,, 'i
, 'l
J R ._ w , ~nw 1 " ·k\ a 11 d M 1
· ~· C )hen · ·//n .1. Rt:.\ . B14. 5_6 (1976).
M. L \ •ho..:n an i .T K. Be rg trcsser. Ph)S. Rn. 14L 7S9 ( 1966).- M . L. _Cohen and
1. R . Chclik ' " 1-.y . .lcc lrolliC Struc /ure and Opucal Properltes of .Semicmuluc-
.tors pnngcr- crla . Berhn. . 19RH ' ). . _
R . Dexter. H . J Zeiger <m d B. Ltx . .Phrs. Rer . 104. 637 ( 19)6).
J. 0 Diml11l)Lk. 1. Melngaill . a nd A. J. ~t_rauss. Phrs. Rer. Lell . 16. 1193 119fi6).
G. Drc ·elhaus. Phrs. Rcr. 100. 5XO ( 19))).
G Dre-:.clhaus. . F Kip . and . Kittel. Phys . Rer. 98, 368 (1955).
A. L. .cJw 3 rd. . -. I_kh1 use, a nd H . G. Drickamer. J . Phys. Chem . Solid1 11.
!40 19. 9).
S. Fahy. . W Wang. :.tnd S. . Louie. Ph1·s. Rer. B42, 3503 ( 1990).
'\: . A. Harri n. Elec!ron truct ure am/the Propl:'rties of Solids (W. H. Freeman .
an - ra nci co. I nO).
F. H t:'rm an . Pln ·s . Re r. 93. 12 14 ( 1954).
C. He rri ng. Ph_;.\. Rn 57. 1!6LJ (1940).
P Ho hen be rg and W. K o hn. Phys. R er. 136, B864 ( 1964).
M. S. Hvbert sen and S. G. Louie , Phrs. Rev. 834. 5390 ( 1986).
E. 0 . K ~ ne, J. Phys. Chem . Solids 1. .249 ( 1957).
C. K itt l. /ntro du tiun 10 Solid State Physics, Sixth edition (John Wiley.
New York. 19 6).
C. Kittel. Quantum Th eory o( Solids. Second re ised pnntmg (John Wile~.
New York. 1987), p . 92 .
W. Kohn and L. J. Sham. Phys. Rev . 140, Al133 (1965).
S. Larach, R. E. Schrader, and C. F. Stocker. PI'IJ's. Rev . 108. 587 ( 195h
P. Lawaetz, Pln·s. Rev . B4, 3460 ( 1971 ). .
G. G. MacFarl a ne, T. P. McLea n , J. E. Qu a rringt o n. and V. R o berts. Plt_rs. Rer
108, 1377 (1957).
K . D. Mackenzie. J . R . Eggert. D. J. Leopold. Y. M. Li. S. Lin. a nd \V. Paul.
Phys. Rev. B31, 2198 (1985).
J . C. Phillips and L. Kleinman, Pln·s. R e r. 116, 287 ( llJ:'<)).
C. R ._ Pidgeon and S. H. Groves. Phys . R i!l' . 186. o24 ( 1%9) .
F. Seitz. Modern Theory of Solids (McGra\'>'-Hill. New Y o rk. 1940 ). p. 2-L~ .
L. H. Thomas. f'v'ature 117, 514 ( 1926).
Y. P ._ Va rshni, Phys. Swt . Sol. 19.459 and 20. 9 (!967).
G. W e iSZ. Phv:1. Rev. 149, 504 ( 1966).
H. Wendel a nd R . M . M a rtin . Ph1 ·s. Re r. 819. 5251 ( 197 ).
E. Wtg~er. Phys. Re r. 46. 1002 ( 19.~4).
~ - T. 'nn a nd M. L. Co hen. Phrs. Re r. B26. 5668 (1982\
X. Zhu and S. G. Lo uie. Ph1 ·s . Rei'. 843. 14142 ( l Yl) l)
J. ~1.· z~~nan , Princi( 11C.\' of rlw T!tcorr of S olids. s~,~· onJ ~Jiti m l :unnndg('
L. nJvet slt y Press, Ca mbrid ge. 197 2 ). p. I02 .
•cs and dynamics
ro s and holes in
bands

Electrons and holes in


ron in an energy band can be represented semiclassically energy bands
p 7~·kc1 o fBJ ell state.s that is spmial~r loca/i::ed. The velocity or
l rot the \\ a ve packet IS the group velocitr v, . 4 .1 Group velocity

un.ttu.re o f an ~nergy band is proportional to (J,e inl'erse ejfectil·e


111
Th~: lllrC'r se cf1ert1ve mass t ensor is defined hy 4 .2 Inverse effective moss tensor

An £'.\1£ m ol j(Jrce F acting on a band electron produces a change of its


waw \ ector k with time. 4.3 Force equation

dk
F = 1i.-dt.

\\hich i. analogous to the classical relation of force to time rate of


cha ng o f momentum p:

F = dp.
dt
One therefore defines the crystal momentum to be Ilk. .4.4 Dynamics of electrons
An electric field£ produces an accelerated electron wave packet:

dv2
dt
= -e(-1) .
111 ~
£.

A hole> is an emptr stare in an otherwise filled band. Both the electric 4.5 Dynamics of holes
charge of a hole and its ej(eclive mass are positive.
The effective mass of a charge carrier can be measured by cyclotron 4.6 Cyclotron resonance
l'f!.\0/lW/C(' .

The concentration and charge sign of a charge carrier can be measured 4.7 Hall effect
by the Hall cf/'ecl.
. t' d dynamics of electrons and holes in energy bands
Kmemo 1cs an

One of the~ at urcs that di ·tinguishes semiconduc~ors from metals j . that


the ur ·ent ~.,; rricrs c· 11 include not on!~ electrons m the conduction band.
but. empty -.1 ctrnn tate, or holes 111 the valen~e band . The dynamical
rc p nse of th curren t carriers to external electnc and _magnetic fields is
·trongly ITect by th energy band structure of the semiconductor and is
char· tenzcd b their fDctiv · mass and charge. These parameters can be
detem1 in d by mea ns of cycl tron res nance and Hall effect respectively.

4.1 Group velocity


The wav function rrc, ponding to Bloch states are wave-like in char-
act rand are n n-Io alized . In order to disc uss the motion of an electron
from ne poi nt t another. it i. necessary to form a localized wave packet. so
that th el ctr n can be a signed a particular coordinate at a particular
time.
A wave packet can be created by setting up a linear superposition of time-
dependent Bloch functions of various wave vectors k with coefficients a11,.
that peak at a particular wave vector ko:

(4.1 )

The time-dependent Bloch functions · nk(r, t) can be written as

(4. 2)

where Enk is the energy eigenvalue of the Bloch state. We now exploit the
sharply peaked nature of the quantities a11k by settin2: k = ku + t::.k and
carrying out expansions in powers of D..k: ~

(·l3)

In the case
c of ank.'·r·s rapt
- 'dl Y varymg
. - character requires us t r tain its tu
· 11
dependence on l:ik:

( ~ .5 )

Substituting Eqs. (4.2 - 4.5) into Eq. (4 . 1) gives

where. fo r o ur purp ) " , ·1 · , . 1


.' cses.t ls sutfictentlvau:·un t [ )1\:l.lln II tn·l '.l• 111!!
lcr:n 111 the expansion nf lind .- ). -
fbe ex pres ·ion Wl: ha c obt· - ,
ufwa c vcctorl- d -'llh:dlllf/nl.,,(r.t)reprl:s nt
" O mu ula ll"d b , · 1 ·
ove r k ff " · ,Jn ~m · LJ1 1U t1l.lllll1 I
. \\~ L'l•rls rlkr 1111.' value ll'lh~ ·m ·ll lut Ll
Inver e effective ma ss tensor 75
h.1 I I he e m elo p t.:~ 1 1nc·t ll) n 11a ~ liH.::. a me v· I c to r ' I r and
f.ik I
u ..tkr

(4.71
) ~.:,H, thcrel'o rc be rcg;.~rckd as specifying simplerectilinear
n c packe t I r the ckctron that i:;; characterized hy a velocity
l'

I
Vv. , =-
/1 VJ..o £'
- n r..-r, · (4.8) I'' Brilloum 10ne •
·------~

Tl t. v., is the grou p velocity of the electron wave packet. It is a Fig. 4.1
tlc rate o f t ran ort c fma ss. charge. and energy oft he electron. Graphical representation of v,. and E"k as
functiOn s of wave vector k. , .
S!•. proporlional to the k-gradient of the Bloch state energy. it is
dctt.nmn db) the 1 pe of the £"" versus k curve. Figure 4.1 gives a graph-
r enlation v>: a , a function of k.
Ref.,k I) (r,t)
Comment. Equa ti ns (4.6) and (4.R) specify the time evolution of a
, , ve packet for an electron characterized h:-,.· a group velocity vr:. 1...,...__ u / - + :
g ••• ••

Figure4.2 g1ve a schematic representation ofthe wave packet in real


spat. . At a pa rtic ular time 1. the wave packet has its maximum
amplitude at me value of r. say ro. The spread U.r oft he wave packet
and the width U.k of the region over which a"" is appreciable are
. ubject to th limitation U.rU.k -:::' 1. The wave vector interval U.k
hould b sm all compared to the dimensions of the Brillouin zone, so
Fig.4.2
that £ 111. va ries little over the principal levels appearing in the wave Representation in real space of a wave
packet. i.e .. U. k ~ I / a where a is the lattice constant. The above packet of an electron in the
me nt io ned limit a tion then gives conduction band.

I
6-r-:::' - »a. (4.9)
U.k
Trr spective or the value or r 0 , the wave packet of Bloch states char-
acte rized by !:::,.k « 1/ a is spread out in real space over many primitive
unit cel ls . Thi s behavior is shown in Fig. 4.2.

4.2 Inverse eHective mass tensor


Since a wave packet can be regarded as a semiclassical d~scription of
electron motion, \Ve can make usc of various classical relat1ons between
velocity , force, and energy. Consider the time derivative of vg:

dvg _ d (~. V k E~ nl.: .)


-- -
dt dr h
1 dEnl. (4.10)
= -V~. -- .
li dr

sing the classical relation


dE
--dr = F· v,.. . (4.11)
. . dd mics of electrons and holes in energy bands
Krnematrcs an yn a

· t llef' 1-, ·cFactingontheparticle.wecanrewrite q.(4 . IO)


nnd intro luctn " -
(l.

(4. 12 )

\\ h re we h,tve a. umed tb . t Fi independent of k . Replacing v g on the right


hand ide 0 ~ q. (4. L) it I ti nition in Eq . (4.8). we obtain

d v~
- =-,I l·v /. v k £. ) F Ilk . · (4. 13;
dr n-
lmpari n fE q .(4.1 3)to ew t o n's se~o ndlawof~otion.showsthatthe
quan tit /l 2 \7~ kEn!.· v,.:hich i, a dyad1c , ha s the dJmensJOns of inverse
mas ·. W . . d fi n d th elemen ts of the inverse effective mass tensor for band 11
,. Eq. (3. 2). or a simple parabolic band.

I D2 Enk
-2 -- 2 (4. 14)
m,~ tz Dk .

We see that the curvature of the energy band is proportional to the inverse
effect ive mass. The larger the curvature. the sma ller the effective mass.

4.3 Force equation


Let us re-examine the classical relation given by Eq. (4.11 ). Applying the
chain rule for differentiation to the left hand side yields the result

dk
-d
.I
· V k Enk = F · V'.< .

Eliminating the gradient of the band energy with the aid of Eq. (4.8) and
equating the coefficients of vg o n e·1ch side of the resulting equa ti on. we
obtain

F= ndk 0
(4.151
dt
The quantity 11k is known as the crystal momentu m. Equari n (-+.15) 1 ~
therefo re the analogue of the classical rdation

l~ . 1 (11

where pi ' the classica l momen tum .

4.4 Dynamics of electrons


Co nsider th~.: speL·i· tl ~ . · ~. 0
.
1-IL.. k I £. .)-ht'n ,. . ' Ldse 111 WIIICh th lun.:C' :tri e-. rr lJl • n ... ,
Dynamics of holes 77

Ilk
r, cit - - ·£ - ( 4. IX)

th·rct 'ft? \.:.lUse. Ll \\'U\ C vec t r k to chan ge \Vilh time


C.II1Cllllhlll ' l:q::; . (..f . I J ). 4. l 4 ).and(4 . !7) ~o yi e iJ .

d g
df=- (
-;;;
I ) .£
(4. 19

th.tt tbcdcctron v. a\ pa ket i. acccleratcJ by the electric llcld


n ·~.: l an ~:I Llri urn::nt.
II tne picture ofele trica l onductionjust described is valid for
1lkJ nero) t a nd . n electron of wa ve vector k ~.:an make a
a nearb) m pt:::.- . ta te of different wave vector under the
f a" ~ak. ele tric field. Ho,,·ewr. if the band is completely filled
tr n .... there are n empt _ ·tatcs into which an electron can make a
n. a nd con equ n ll _ the conductivity of a filled band is zero.
thu arrne a t a imple distinction between insulators and conductors.
An Ill ulator ha'l a ll bands up to aod including a certain band completely
filh.:d \\ith ele tr ns at the absolute zero of temperature . All hands above
tbeupp'm1 t fi ll d band are completely empty. and the lowest empty band
~~ ep.trated from the upp rmost filled band by an energy gap£~ » k 8 T,.,
''here T i~ ro m temperature. In practice, Ef!. must be several electron volts
:.1 • r r example, in th a lkali ha Iides.
A onduct r o ntain, at least one band that is partially filled with elec-
tron . If th e~e 1 ctron arise hy thermal excitation across a forbidden
en rg~ ga p fr m ·m o therwise filled hand , the material is a semiconductor.
!\ot tha t u nder thi ' definition. a semiconductor is simply an insulator v..-ith
a relativ ly mall energy gap. ff one or more bands remain partially filled
do"'n to th a bsolute zero of temperature, the material is a metal or a
semi meta l.

4.5 Dynamics of holes


I fan l ctron is excited from a filled energy band to an unfilled energy band.
the empt y ~ra te left in the otherwise filled band is called a hole. Of great
imp rta nc are hole~ lying near the top of the uppermost filled band
(\alene band) of a semiconductor. In assessing the properties of such holes
\\' e ·amine first their wave vector. Since the reciprocal lattice has a center
ofinv r"ion , the full valence hand has a total wave vector of zero . The wave
vec tor k 11 to be associated ,.vith a hole is the diffen:nce between the total
wa v vector of the filled hand and that of a band with an electron of wave
\'~o:CtL r k, . lll1 SS II1 g:

kh = 0 - k l'
= - k,, ( 4.20)

t~ that 1he hole wave vector is not that nf the missing electron, but is the
n~.:g- ti ·e ol' it.
. dd ·cs of electrons and holes in energy bands
Kinematics a n ynaml
. Lh, cnerg , of a h Ie. we observe that as lk,J increa e th
urnuu! n :w. ll1 c . d d h . e
- , , 1.,"'er in the valence ban . an t e energy Ec(k .) ofth·
3 ·a 1 t " t.l t e 111 o t: :- t f h . ' at
t te lc ·re~ cs.
• . H ,• •··ver
...
the total energy o t c system of electron
' .
" th \ ·tlcncc ha 1ncrca -es. by the same amount. ?ecause a the
11
7trc.; rnp:s from its initial htgher energy stat~ .to tts final lower
t· l , 1 Ot.:CIIpi d sta le makes the reverse transitiOn. This scenarro
line the energy o f the h le. E11(kh) , to be the negative of Ee(kr):

(4.21 )

Smcc k1r = - k .. we lrtve

(4.22)

For every tate with wa e vector k, there is another state of equal energy
with wa vector - k (se Figs. 3.5 and 3.8). Consequently,

(4.23 j

As stated above, Ee is a decreasing function of its argument; hence. Eir is an


increasing fun cti o n of its argument. It characterizes a normal particle
whose energy increases as its momentum increases.
In the case of a spherical parabolic valence band, we have

( 4.~-q

where Ev is the energy of the valence band edge and the effective mass m; is
negative. The hole energy then becomes

(4.25 )

It is convenient to rewrite this result as


(a)

.
E.II ('k h)=-£,.+ n2ki
- -' .
?.m,,'.
where
. m'.".is the e tlective
~ ·
mass ot~ a hole. C lea rl v. o n mu t h,n· IIlii ==-I ll ·
Smce Ill IS neo·:tt. .. . .. . ' I\' .
k,. , . . ''.. ~=-' tve. ~'1 1 " ts positive . Plo ts of t:L,(k , and E tA1,) \crsus "·
\ec~ o i di e presented 111 Fig. 4 _3.
1 he next q uestior
' 1 c'·>n , . . . h
'l.:Clns t egroupYeloci. t . l \:it · )f!lh'l'. I Lt·' gn rd'~'·
I
(b)

I I
( -+.-
' ~)
Fig.4.3 Vgh = y; Vk,, Eft {k , ).
(a) Hnk ene rgy /:'~, <tud (h) mi, sing
d~:Ctrut nt·rg~ E, a ~ lunc ti o u s of while that of the missing electron is
a v euor A pai nf hole a nJ
nn ~~m g elt: ·l vn 1 ~ 1nJi.:aLcJ by the
(;H<: Ic~ I
v~.- = - V 1. E (/,
IJ '\ '
Cyclotron resonance expenments in emiconducto r 79

I
v,., - - h V t..n E, i - /. 11 )
I
= - h v /q, E.(' ( k" ) . (4.29 )

~ q. (-4.23) kad · t

= V((h · ( 4.30)

up cl citie of the hole and missing electron are equal.


t prt pert of hole, to be discussed is their charge e11 • The equation
n. Eq. (4.1 , a pp lied to the missing electron is

elk,.
fi - = - e£ . (4.31 )
eli
Replacmg k, by - k:, . ne o btains the equation of motion of the hole

(4.32)

\\here e, = +e. T h t. . the charge of a hole is positive. A hole near the top of
an otherwi ·e fi lled band can therefore be regarded as having both positive
charge and positi e effective mass. An electron near the bottom of a con-
duction band a lso ha . positive effective mass. but negative charge.

4.6 Experimental determination of eHective masses:


cyclotron resonance in semiconductors
tel tro n resonance experiments in semiconductors exploit the classical
m tio n of barged particles in a constant magnetic field. A particle with
harg e, and velocity v will experience a force under the influence of a
mag n tic held B given by the Lorentz expression

(4.33 )

The magnitude of the force for v perpendicular to B is


(4.34)

If the particle has mass m. it executes a uniform circular motion about the
field with radiu s r, an acccleration v 2 j r, and a centripetal force
,
v- (4.35)
F,.= m 7 .

E 1 atinu the two forces, we get for the radius oft he circler :- rnu/le,I B. !he
peri d o f Lh circular motion is T = 2rrrj v. The angular trequency of the
. dd ·cs of ele ctrons and holes in energy bands
KinematiCS an ynaml
h~.; cyclotron frequency and is given by
1Jrtll'l ,..., l:alle d

(4. 61

. h d;J -1c•tl a rticle in free space. a charge carrier in


1
. i h. 11 ·ffective mass m ' has a cyclotron frequency
eB
(4.3 ,)

uhjectcd to an extern' 1 radi· ti o n .field. a ~ar_rier ~n a cyclotron orbit


b. energy 1f the frequency oi the radwt10n tield approaches the
.t bs r --
cvclotr n trequency. Th electric field £ of the radiation should have a
n-onzer comp n nt in the plane of the cyclotron motion. The resonant
ab rpti on of en rg t the cyclotron frequency is called cyclotron reso-
na . To determine th yclotron resonance conditions let us consider the
eq uation motion for a free charge carrier subjected to an external elec-
tromagnet ic field

m· -
dv
( d! ~V) = Cc (£ +VX B) . (4.38)

Here r is the relaxation time of the carriers. vis the drift velocity under the
influence of the electric field£. and the magnetic field oft he electromagnetic
radiation is neglected in comparison with the static magnetic field B.
For plane-polarized radiation with£ = (E~0 , 0. O)e;"'', v = (t ~cn . 'l'~n .0)/
e-'.-; 1 and 13 taken in the .:-direction, the equations of motion become

nt ( - iw (4.39a}

( l)
m ~ - iw +-; u1. = - ec'crB· (4.Jl)b I

Solving for Vx and the current density component } 1 = IIJ, t\ . one caku·
lates the complex conductivity according to

(-l.-Hl
~
~ (J 2 t-"'---i---t--+~-+-~--l where ao
.
= n,.e~' r/ Iii , ·IS the stat1c. co nducti vit\ ·tnd 11 i th i::Jrn· r ·l n·
centratJon . The .. , . . .• • · . ,f lh .
~ __J.__ ___j___:::::J . d . . . powei c~bso1 bed 1. prupor11 nal t th~.o rc:al p.trt
con uc t1 V1ty g 1ven b y
() () '------1----l._

:t (J 0.. 1.0 J.5

Fig.4.4
I' clat1 e J) \ >WcT JbS,q1llu ll V<: l"o u ,
agnd i..: field In Ull llS ( f .J, /..; fu r
1·' " 1lk r"nt 1d<JXJLiu n tim ·~ 111 un h
]
In h g. 4.4 i. ·h WJI tl - .
·' uncttun ur the t · . .
<ot ,,;r Cai LI.T D r~.:~scl h au~ Lf ,tf. J lJ ~~ ) . . I' .. 1c IL'I~tlJVe Pt.IWLT •tb . ] l l L\ dl

.tltc magnetic d I intl'nsit
C lo ron resononc experime nts in semiconductors 8
tunc
/

:; '·
lll"'nts <lO c. clotrn n r '~n n ~tncc ( f lectrons and holes in ...
~ . Ei
rtcd b_ . Dre ·-_cJh aus. . r . Kip. and . Kittel ( 195J. ...
E
. . De ter. H Zeiger. and B. ax ( J<r4. 1956). The ~

dttt ns are dete rn in ·d h_ the cfft:cli ve ma · ur the §


' tigath1 n l-or nl" / m :::::: 0. 1. and ...;= L.5 1O'' rad s ' . 0
e.
r II b = <'60 ' c rre'\po ndi ng to w = u..', . The line width is .f
~
he collision re la\:ation Li m e r. which describes the efTcct of
~_, rn r \ 1th im t rG ctions. ·or cyclotron resonance to be 0 I 000 2000 l,(M )() 4000 5000
Magnetic field (oc r~t d ~)
1 ~cs ·ar. · t ha e the mea n free path of the charge ca rrier
t'' p~m1it the ca rrier t sweep ut one radian of arc around the Fig. 4.5
rhit het\\ en co lli ·ions. T hi s conditi o n i satisfied if u..:, r > 1. To Cyclotron resonance absorption versus
n h r'laxa ti n Limes it i adva ntageous to work with high-purity m agnetic field at 24000 Me s forGe at
liquid hehum tempe rat ures. These req uirements can be relaxed 4 K (after Drcssclhau~ eta/. 1955) .
f high r-fr q u nc radi·ttio n and higher magnetic fields. The
:.111. r tu u din cycl tro n reso nance experiments is essentially the same
a that [i comentional pa ramagnetic resona nce except that the geometry
1 11 di11ed . o that lhe microwave electric field is perpendicular to the
e. temal applied m a gn tic field. Absorptio n of energy under cyclotron
re. onan e condi tion is determined by measuring the changes in the Q
( ualit) fa tor) fa micn1 \· ave cavity in which the sample is placed. The
external magneti fi ld may be va ried in order to obtain the dependence of
the power a orption in the ample on the magnetic field . From the
ab. orpti n "'pectrum this efTective m ass may be obtained . T ypical cyclotron
re onance. pcct ra forGe and Si are shown in Figs. 4 .5 and 4.6. respectively. 1000 2000 3000 4000 5000
Magnetic lield (oersteds)

4 .6. Cyclo tron resonance of conduction electrons in Ge and Si Fig.4.6


Cyclo lro n reso nance absorption versus
The c nductio n ba nd s nea r their extrema in Ge and Si consist of sets of magnet ic field at 24000 Me ' s for Si at
el li p oidal con ·tant energy surfaces located at eq uivalent positions in k- 4 K (after Dn.:sselhaus t'l a/. 1955).
~pace a t r n a r th e zo ne boundary a nd are described by the equation

(4.42)

\\'her m, i the transver e effective m ass and m7is the longitudinal effective
mas.
To discuss the motion of a conduction electron in the presence of a
unif rm static magnetic field 13, we consider the group velocity
v K = ( I / TI ) V k Ek. Making use of Eq. ( 4.42), we find that

Jik 1i ,_ nk _-
v)i \ . = ~ • Vor = _ln_ l 'V'<:: = - .. (4.43)
· m;· "'· m, · rn 1,

r mbin mg the equation of motion given by Eq . (4.15) with the Lorentz


f rce given by Eq. (4.33) and setting v = v>: yields
dk
f7- = - C:' V ,. X 13. (4.44)
dt '
· s of electrons and holes in energy bands
Kinematics and d ynam•c
. . I - ... t·lne 13 = B(sinB.O. cosO). Eliminati ng k r
• T3 t 1 • 1n 1 1c :\..-1' " · . rom
'~ t< k 4 ' tl the au.i of Eq. (4.43). and assummg that v:r varie· a
44 I '1 ·
. , ' ult m tht.: cl cq uatwns

iwt ':sn - w; cos Hv!{y = 0

(4.45b

when.: v.J, = eBjm and w1 = ( Bjrn;. Setting the determinant of the coeffi-
1
cients f Pg.-. · t'g_1 , t~g: equa l to zero gives
O.Q.l W=--+-++--t-+=H---t--;.§":!::"1
(4.46)
x
;:::.
:::.
0 L.:i:.J.__L_,L__L_.J..__L-l-J.--'-- '
-10 0 RO 90 100
nglc in d gn'c in\ 110
whcr \ is the cyclotron frequency . If we define the cyclotron effective mass
plane fr Ol [00 il ' 'I
m:. by
Fig.4.7 eB
Effective mas of conduction electrons w(.= - , (4.47 1
m Ge at 4 K crsus the angle between me
a mal! netic f1eld in the (II 0) plane and
the [00 I] axis ta fter Dresselhaus we tind from Eq . (4.46) that
eta!. \95 ·)
2 2
1) cos 2 () sin (J (4.48i
(-nz*c
= -- +-- .
nr•I
2 n1•·n1¥
1 I

Table 4.1 Electron and hole effective The value of the cyclotron effective mass for conducti on electrons in Gc
masses for silicon and germanium in
units o free electron ma s (after Kittd at 4 K is plotted in Fig. 4.7 for various directions of the magnetic field in a
1986) ( 11 0) plane measured from the [00 I] direction. If on assumes that there is a
set of equivalent constant energy surfaces oriented al ng th (Ill direc-
m; m; ill ;;, n1;,;,
tions in the Brillouin zone, the ~ffective mass param ter can be deri,·ed
Si 0.92 0.19 0.16 0.52 fro.m a fit of the theoretical ex pression of Eq. (4.4 to rh ~ x.peritnental
Gc: 1.59 0.34
pomts. The results are presented in Table 4.1. In Fig. 4.' an~ shown the
0.01:12 0.043
1
results for the angular dependence of the efl"'ccti\ t' ~tt-'' f (oncluL·tit n.
electrons in Si. From these results one may concl ude that rh re is a ~et ' t
1

111
eq LIIV<~Ient constant energy ellipsoids oriented a long th I om dtrectil)flS
the
_ Bn ll oum · zone. The values deduced for the m a . p.tri. mt:ter'
\ · \111
are (lst~l
1 able 4.1.
-,r-
C I tron re o n
x perim nts in emicon ctor 83
resonance o f ho les in Ge an d Si II 14
~

h·tnds . ~r ·~ ·mll ,,1


!1·1HX' • ..c I··.ttl1 ·r Clllllplicat
.:: · .11 · cd ;t s a J ~-I-
I
IJ ll

)~
• · c

I If I\\ -!old l r 1tlal dL '· • ' <·t t "' · - 0 - T ll C 1 Orl!!lnatc


- ' '"=" ·m'r'tC\ · · 11. \(,
I I d · and ·trc · h<tra ~.: tcri zcd b · the cn cn2.y-wavc vec tor
lll l1t} . (J.71. ~ ~ I
\ j
~ , i
- ( ~ - ~ !.2
\ \ (\ 1 k -:-1..--y ) ]~ • (3.7 1) -, 11.24 >/_ ~ N !'-!"

q 3. I) ,.. i\~ · the li l!ht hole band and the plus sign gives

~ 0 20
~fa:
,...... ""'v
tnd. T he wa rp 1ng term. with coelficicnt C 1 make the hole
ani. t r pi c. \V arp ing effects can be includ ed in an
OL
• ~ b) mea n. f the ex pres. ion (Dre ' selh a us e1 a/. ]-l))5)
0.0

0.04
,_
C)
~ - --
,:=

- I 0 0 I 0 2() 30 40 50 lifl 70 80 90 I Oil


Angle in tlt:gree' in r II Ill
Plane lrom LOO II ax 1 ~
(4.49 )
Fig. 4.8
Effe.:tive mass of co nduct io n electrons
in Si at 4 K ve rsu. the angle between
which applies whe n t he magnetic field lies in the (II 0) plane and makes an a mag netic field in the ( 110) plane and
the (00 I] ax is (after Dresselhaus
an le fl \\ ilh the [100] direct ion. In Fig. 4.9 is shown a plot of experi mental Cf a/. 1955).
··y I tr n re nanc data for holes in Ge as a function of the angle e. The
con tanb A, B, Cw reeva luated by fitting Eq. (4.49) to the data. The values
thu det rmin d re given in T ab le 3.2. A similar procedure was ap plied to 040
h I in i \\i th qua lita ti ely similar results (Dresselhaus eta/. 1955). 1-, ~ 0
lU6 ~
It i conveni nt in ca lcul a ting va rious properties to have an isotropic v r-
ci_
appro ·imation for the hole masses . Such an approx im ation is provided by :: 0 . ~2

th ~ II wtng pression fo r the va lence ba nd energies (Smith 1968): ";o2s


::
ls>o-"
v
g
-~0.2~
(4.50) u
"
~0.08

The average light and hea vy hole effective masses are specified by 0.04 _
,
Is
0
_£ - -
-
- 10 0 10 20 30 40 50 60 71l RO 40 lt lO
(4.51a) '\mdc in deorecs in t il m
. plane lw1~ [00 1] a~i'

~ . l} (2111)
Fig.4.9
-=-:;-
111
= {
- A- [B-~ + (C-/6)]2 2 ·
(4.51 b) Effective ma~s of holes in Gc at -l K

Ill"" 11 versus the angk bet ween a magnetiL'


field in the ( II 0) plane and the [UOI]
h expression for the li ght hole effective mass is a rather good approx- axis (a ft er Dresscllutus ,,r tl . l'l55 }.
imation sin<.:e the li!!ht hol e band is nearly spherical. but that for the heavy
h le i I ss a ti s fac~o ry due to the significant warping o_f the heavy hole_
hand 'v~ll' · g t }1e vu 1ues o. f' A . B , an d c t't·onl Table -3__
? , one hnds the values of
11
i ' " an mj,IJ th a t, re li sted in Table 4. 1.
. dd mics of electrons and holes in energy bands
Kinematics an yna

.6.3

ra ·
1 p cr 11. .
he lndu·tJ n 1 ctnneffecuvemassesofiii- Vandli- VIcompound
'ith dJr 1.:1 l! p ,1t k - 0 are li ted in Ta ble 4.2. Comparing the effective
m. s ~.:s , ·ith the orresp nding band gaps in Table 3.2, we see that the
etTecti~c mas" decrea. e a the gap decreases. This behavior is consistent
\'ith the Kan ow I I · s pressed by Eq. (3.65). As pointed out in
Chapter J, GaP ha an indirect gap with conduction band minima verv
clo to the X-p int n th Brillo uin zone boundary in the (100) directio~.
The effe tiv m f onduction electrons is anisotropic with m; = 0.91 111
and m; = 0.25 1JI.
Th effectiv rna es of hole arc determined by the Dresselhaus para-
meter A, B, C or the Luttinger parameters "i't, / ?. , ~fJ.. As noted in Chapter 3
the effective mass depends on the direction of propagation of the Bloch
wave due to warping of the constant energy surfaces. Average or spher-
icalized effective rna es for light and heavy holes can be calculated using.
for example. Eqs. (4.51 ). An alternative method (Lax and Mavroides 1955)
uses the quantities

(4.52 1

and

to express the average light and heavy hole masse a

m;" = ( , -)- 1m
m,,
- ·
=
(
~~ ,
I
- i')- (I
,,~
+ O.OS~iu + O.Ol ~ ~~)- - ,~.

Values
.
of .avera ooe e~e c t 1ve
. h o 1e masses arc g1ven
. . Tahle "+1. _i.
111 , ~1 · ·h )\\ !1
-"" :.o:.
are the spm- orbit ·spl 1't- fT e ft'ect1v
. ma sses m~ · .
'"
Table 4.3 1\ vera oe e ffe~ t . ' I1 0 I . .
. "' ~.: I\ C <::masse~ 111 UJlll S o t· the fr~ •
bdll 1. Ill Ill- Y ' lllcl II VI . .
' semiconduct o rs [aft ·r Ll\\';tL' I L Ill
Ill v 111;;, Ill hit Ill II \'I
GaP '"
0 . 16 0.5 ll ...J6
GaA~ o.o:s 5 U. l ~
Zns .,,.,
/ J '~
l)
Ga . h () 06
ln P
0 .'\ (J l..J Zn TL'
ll .(JX l),.i
ln.i\ -, 11.1125
U. 15 u
0.-t
lnSb 11 .112 1
11.1)~
11 . ~ ll I I
tal deter inatio of carrier ch rge and oncentrotion 85
• t3
n.tal det ermination of carrier charge and
.. ,.,...... ,rratlon: Hall eHect

mc 111 n Lh~lt p r \ ide · useful mfo rm atinn abL)UI current


Hall effect. !l Sid e r :t bar nr
rectangular cro s section in
n~.:tll ll "'~\\'S in _the presence uf' a uniform external magnetic
n 111 hg ~-I r .. Fu r the steady tate sttua tion th e equation of
rr nt ca tTH:r g!\ e n by Eq. (4.3:::;) reduces to
Fig. 4.10
Ill ' v Ex perime nt al c0 nfigurat1 o n f• H the Il a ll
F = - r - = e, £ +.i 1 x B. (4.55)
effec t.

1 cun:cnt de n it y per unit carrier concentration . e, v, and F is


~.:arne r.

nfigurat i .n shown in Fi g. 4.10. let us Ctrst apply an electric field


- i ~ctio n a rallel to the ax is of the ba r. A current will arise in the
f th field"' ith

( 4.56)

Note th.tt.i1~ IS in th e sa me direction for both electrons and holes. Nm:v let us
wrn n a magnetic 1eld in the .:-direction, B:. Carriers are deflected in the
negati\'e y -dire ti 1n, whether electrons or holes, and accumulate on the
f"ront .\.:-fa Cth e bar. At the same time an excess of carriers of opposite
~ ign appear. o n the opposite \\'all creating an electric field component [ 1 .
o te that [ 1 has oppos ite signs for electrons and holes. In the steady state
thi tr:.m verse electric fi eld. call ed the Hall field. gives rise to a force that just
canl.: Is th Lo rent z fo rce due to the magnetic field:

(4.57)

Th l ral current densityj, is given by nj 1\ for electrons and Piix for holes,
where 11 a nd pare the concentrations of electrons and holes , respectively.
The Hall fi eld can now be expressed as

(4.58)

vvhere the Hall coefficient R 11 is given by

I (4.59a)
RH = --
ne

!'or electrons and by


1 (4.59b)
Ru = -
pe

for h( les. Since [ 1 • j\, and B: are experimentally measurable. _an ex?~ri­
mental valu e of RH can be deduced and from it the concentratiOn ot _free
carricrs. F urthermore. the sign of the Hall coefficient gives the s1gn of the
c
tan(:) = -z:-.
'-'r
(4.60)
'-'x

ftaeH !l angl : talt:kclron...-. The gcometr)' is how n in F ig. 4 .1l for electrons and holes. If we substitute
Eq. (4.53) into Eq. (4.54). we obtam
e .r:
[). = -'-.
n1 •
[,Br·
·
(4.611

The quantity e, r/ m; is the proportionality constant between the velocity


component n, and the electric field component Ex- We can write thi~
relation as

(4.62)

where the conductivity mobility J.l is er / m • and is always positive. The


equation specifying the Hall angle now takes the form

(4.631

Coupling an experimentally measured value of [ 1 with th :e of E, and F


enables one to determine both{) and Jl.
Comment. Hall effect measurements are the m t fr qu ~ntly used
procedure to obtain two of the basic chara ct ri. tic or a semi-
conductor: carrier concentration and mobi lit ·. In rd r to sinlrlif~
the a nalysis it is general practice to use a s~1 ~1 pl in th h~ pe l'l ;t
long pa_rallelepiped. Consider as an example a bar c f ·iltc n \\ h l"IS\.'
dunens10ns are: length. 0.01 rn: height. 0.001 rn and \\idtb l O(ll iH
Between the contacts at the ends of the bar a currenL / ,-== l tiOl.\
flow · A magnetic held 6 of 0 . 1 T is appl i . The ' ,JL,1gc <lP[ li'J
~et_ween the e nds o f the bar is 5 V, and th p rHcnt t.tl Jtfl.~."r 1~1.." 111 ·;t·11
s._uJcd 111 the transverse direction is 0.001 V. Th ·~.:kc 111. li IJ ' ' 1' ·h
)00Yfm, . •
£ 1' is I V .m
I , .an d t. h ecurrcntcknstl · '/\hIll 111
~ Tlt'H.dl
"'
codltctent Rfl ·. - .\ ' 'C . . .
Is 10 m · 1 (these dtmcnSil ns h 1 1 11 ) 11l' , fn'nt
Eqs. .. (4 · S<J) · The H·<~ II ang. Ie ts . !!IVt:n
. tw t.t n fJ I 0 l ~~~- I h··
mnblltty 1, : 0.02 111 2/ (Y. ··) _ , l~U . 111 : : (\., ~ S
• • . _. 1 ·' - - . 1111..'~· 1
ll·' ·t i ·1 11!
IS flOSIIIW the C'l .. ·
(, , • , Llll rs mu~t he hoks. The lh k
' - I 0- 1 m ' _ ) .2 I () t , L'111
References 87

· ra h~'li~ cncrg; band \\ith the energy a~ a fundion

(4.64)

• m a:>: at k = 0 and u IS the lattice constant. Calculate


I Ci t] !:~ <i ' a functi o n of !' and plot c~ versus k over the range
1 h'r m 0 = O. lm and a = 4A.
~.t 11e xpr :. i n for Ek as in Problem I , calculate the eHective mass
und1 :m Ck and plor m · ve rsus k over the ra nge 0 ~ k ~ Ti f a.
3 n dectr n movinn in an ~:ncrgy band under the influence of an
I L nL fie ld . A suming no scattering of the electron. calculate the time
i f r the electr n to cross the first Brillouin zone if t: = 10 V fm and
1
= . The inverse o f this time is the frequency of a Bloch oscillation.
4 011p. n.. th . r~ ti v masses for light and heavy holes in Si and in G e that
re ult fr m Eq s. (4.49) and (4.51 ). Take the magnetic field to he in the [110]
din: ·ti('n ({} = 90° ). Also compa re with the experimental values of m;11 =
0.16111. mj,h = 0.53 m for Si a nd m;,, = 0.044m. m;,, = 0.35m forGe.

References
K. W B .. er. Survev o f S emiconductor Physics (Van Nostrand Reinhold,
e\N or k. I 90).
R.N. De. ter H. J. Zeiger, and B. Lax, Phys. Re v. 95, 557 ( 1954); 104, 637 ( 1956).
G. Dre ·elhau . A. F. Kip. a nd C. Kittel, Phys . Rev. 92.827 (1953); 98.368 ( 1955).
W. . H rrison . Eleclronic Struc!Ure and !he Properties of Solids (W. H. Freeman,
a n F rancisco . 1980) .
. Kittel. !nTroduclion to Solid State Physics, Sixth edition (John Wiley,
e\ York. 1986).
P. Lawaetz. Phrs. Rei'. B4, 3460 (1971).
B. Lax and J . G. Mavroides, Ph rs. Rev. 100, 1650 (1955).
R. A. Smith. Semiconduclors (Cambridge University Press, Cambridge, 1968).
Impurities in
m 11-lr pe ,\'<'111i< 'OII(/ucrors provide free ekctrons to semiconductors
trnn band a~d po itively charged donor ions. Acceptor 5.1 Qualitative aspects of impurities
' m p-llpe senl/conduc/or. provide free holes to the valence
n I neg·tti\l.:l~ charge lcccp!or ions.
lwl• mpurilie \ hav i ni7a ti o n energies that are small compared to 5. 2 Effective moss theory
th fundamental gap . Their energy levels and eigenfunctions are \veil
d~.: cd h~ £'/it>cfhe 11/IISS t/ieor)' .
11
Th 1111i\ tropi f)fe ·tire mass of the conduction band in Si and Gecau ·es 5.3 Donor impurities in Si ond Ge
:.1 pli ttmg ~fen rg_ I vels associated with p-I ike hydrogenic states.
A. t of Jl nor level i associated with each conduction band minimum:
i minim<I for i and four forGe.
The \\ <He ve tOr d pendence of the dielectriL constant leads to coupling
bd\\ecn impu rity state. associated with different extrema of an energy
band and a pl itting or degeneracies.
In mat rial .;;uch as InSh, the small effective mass and large dielectric 5.4 Donor impurities in 111-V

n tant I .·td tn a large ejfec/ire Bohr radius of donor le1'f'ls . semiconductors

De&eneracy a nd ll'(llping or the valence bands lead to complicated 5. 5 Acceptor impurities


tructure o (/(_:ceprvr /el'(:/. .
Dap /ere/ centers have energy levels near the midpoint of the 5.6 Central cell corrections and deep levels

fu ndame ntal gap. The ground state ionization energy depends


. ignifi a ntly on the nature of the impurity or defect. Ccnlral cell
'(1/Tt ctions are required in the impurity potential.
t suffici ntly high impurity concentrations, the wave functions of 5.7 Impurity bonds

n ighh ring impurities overlap sufficiently to produce an impuriry


band.

ln pun tie-. ca n hav a dra stic effect on the pn perties or semiconducturs,


pan,cularl . th electrical properties. They can provide adcliti o n:d current
earner-,, uch a o nduction electron or va lence holes, and scattenng
l:c lers \A.'hi h r crt 1rh th e mt tion c r the carriers. Impurities are con-
cn ientl} dassi 1 •d a ·curding to the column of th~ peri odic table- 111 whJch
tJ \!y OCt.Ur.
. ff
Electrontc e ec s 0
t f impurities

ualitative aspects of impurities


5 .1 Q
~ ·t uroup IV :emiconductor such as Si. If a group V
l t u Ct111 IL1eJ 1 tr '1 ...
.
. .. . b. . .
.. dded It Sr the P atoms c,m enter u strtuttonall v int
nt ·uc11 a. 1 a · . . . o
r •tal h ·eph:trH! Si atom Ill t he drar~on~ structure. Pho<;phoru~
· t , be'- c nd c1 ed shells. o[ whrch four can be paired up
tarn · fi1 c1 L 1 0 11 J . . •_
·our ncighbon ng Sr a toms to form four electron-pair
H h I~c ( nm ' n ! . .
nd . 1 h, ri Lh dcctro n is b und to the P ron .a t sufficrently low tern.
p r. tures. ut 1 thermally excit d to the conductto~ band at highe~ tern.
pera l un: , nd j -· therefo. r .un ho und to the P IOn. The srtuat 10n i'.
illustr.tted schema tica lly Ill Frg. 5. 1.
Phosphoru j cLIJJed a dono r im purit.y, be~ausc: it "donates" el~ctrons to
ru tom mtr due d the conduc tron band. Sili~on d ped w1th PIS known as n-type Sr, becau e
tJ utt II) into anSi liJL!it:e to torm the current ca rrier pr vid d by Pa re negativel~i charged conduction elec-
donor .:~.:ntcr P 1on to whil.:h an e:tra tron . Other gr up Vel m nt uch as As and Sb behave very much like p
ck\:lron ~~ \ t:akl) b und .
L t usn con id r a n impurity from group III of the periodic table . uch
;;1 • B, whjch can al· en ter Si substitutionally . Boron contains three elec-
tron::. beyond closed hells and therefore lacks one electron needed to form
electron pair bonds with four nea re t neighbor Si atoms. The missing
electron on the B atom can be regarded as a hole. At sufficiently low
temperatures. the hole is bound to the B atom. At high temperatures an
electron from a far away electron pa ir bond can transfer to the B atom and.
together with the other three electrons, form four electron-pair bonds
between the B atom and it four nea rest nei ghbor Si atoms. The hole is
thereby transferred from the B atom to the far away electron pair bond and
is no longer bound to the B atom. The B atom in this process has become
negatively charged. The situation is illustrated sc hematica lly in Fig. 5. ~ .
Boron is referred to as an acceptor impurity. becau it .. accepts"' elec-
Fig. 5.2
trons from elsewhere in the crystal. Silicon doped\ ith B is kn ovm as p-type
Boron atom introduced substitutionally Si, because the current carriers provided by B a re positiv I_ harged h les.
into a Si lattice to form an acceptor Other group III elements such as AI and Ga behave mu h the ame way as B.
Genter B- ion t which H hole i:. weakly Other impurities of interest are group VI element uch a· and Se. '' hich
b und.
behave as double donors and group II elernent · su h a Zn and Cd. \\hich
behave as double acceptors. If we consider I II- V mic nd u ~t r . repi<Ki ng
a group V atom by a group VL a tom lead to a I nor impurit} . \\ h r a5
replacmg a group III atom by a group II atom yiel t , an acceptor im urir. ·

5.2 EHective mass theory


A common. . f'e·atu·1·,.~ of the tmpunty
· · systems d scnhcL . i Ill· rl1c.. pr~:, ndtn•':
sectron ._ ts that o n!.! cte·tl · ·11 . . ~ .
' s t 1 ac urrentcar n crnt accrt .u n ~.:h.lr~'m 1 , in· : trt
thclt
. -~ Jdofunim putt··t Y.·ro n o f' the opp stt. ch~ug . Th~.-' tmp un t}- ':"- 't m t!lll
cone. ponds to a hydrogen-like a tom .
A problen1 or nreat j 111 . . .
po1 tan ce ts to d et rmm tht.• ' ' 1\
1..:11 rgy t'lgcnvalu s r tl .. .
, . . b
·' . .
• · o 1l: tmputlt _ alL)l11. pr perh t.t!.:tn ml
Cnt.:r Yha nd structur . 1 1· 1 · · -
., . . . . . e:~nc Lt ~..ctnc sere 11111g prLlJ'Ll LIL .
erl,tm .t:>pccts Sllnphl y the p r hkm :
I. T he impu ri ty po t . 1·. 1 ·. .
., . . Lll l.l IS \\ t:a !.. . h 'L'.Ilh~ tJ IIlli ll lll
IL e l11..:d hyt )lL' h l.rl j ' [
C II.: c t IIC Cl II'\'-! 11 I of I l_ plc.tl
Effective moss theory 91

I '" I_ ' ,tr) til!! l r a lattice cnn-.tant


t 1 l ''1"\ I ~a J uuL ;tnu nnl~ \\ <n e ector:-. k n ' Hr the
lUll .trl.'. Illlp< na nt 111 the F 'Uri r dccumposition nf the
Lllll.:t l )n .

dt pnh.:ntllt' the thel"'ry that incPrpnrates these simpli-

n 1tent 'a~ ha s h~:-cn carricJ out hy Luttinger and Kohn.


!
utt mg r and Kohn '-;155) is the effective mass theory f
h· l~lrll ng pni_nt o l thetheoryisthcSchrodingerequation
hl. 1 11punt) '' · ' e !unction , ·;( r .

I "1(r ) I p( r)] •,(r = E;v ,(r ). ( 5. I )

1 the irn p urit~ potentiaL I ·1, r ) is the period ic potential of the


tl . ~wd E, i t h encr!!y cigenv:.d ue . Let us first consider donor
impunt c and a nd uction band with minimum at k = 0. Luttinger and
K 1Im expand d t ·,(r ). not in terms of Bloch l'unctions \~.- (r) , but i~ terms
of th functi n

\ nk r ) = eik ·l" 11110 ( r ) ( 5.2)

'' htch arkn \\'n as luttinger -Kohn functions. These functions form a
·ompl t t. hq en:.~ble one to usc Fourier transform techniques unen-
cumb r d by the k-dependence of 1111k r).
B~ ·u tituti ng the expansion

"l'; ( r = L :2...::: AnkX.nk(r)


11 k
( 5.3)

int th hr .. dingt:r equation, Eq. (5.1 ), and making use of the simplifi-
L3 U n ( l (~)listed above. Luttinger and Kohn were able to show with the
aid f c, n nical tran sformations that the impurity wave function can be
\\ nt t n t • good approximation as
(5.4)

The function F, r ) is known as the effective mass wave function o r envelope


function . It sa risfies the effective mass equation.
( 5.5 )

wher £, (- iV ) i obtained by replacing k in the band energy E,-k by the


operator - iV. The impurity potential can be well appwximated by the
o ul omh p tential

(5.6)
Fig. 5.3
R.:present:llll•n ~,r I h.. effl.'-:ti m;h.;
\\·here Zl! i~ the charge of the impurity ion and f is the static dielectric waH~ functil'n or .:rnd pe t"u n~·ti n
t nt f the semiconductor. The functions F,.(r) and ~·i( r) are shown F. t,.) and the impurit~ \ \;l\t' fun-:11 n
l', ,·). <I is the Ll!li~·e l.'l'll wnt
a tiLall in ig. 5.3.
f ·mpurities
Electronic e ff ects o t
· ·t·ttcs for a spherical parabolic band
1 .::; 1• lm! unt\ s • . . .
F.: amp e ~ · · . . ·• ra t"'s assocwted w1th a sphcncal paraboli
find h~.: impnnty c tgt:n~ . '".' ~
. o ul mlh p t ntta l. . .
t 'nJ ,111 . 1.. 1 . : pherical parabobc band wtth effecti e
Ju • n. he ·m: rgy ' ·'
t l can ht: wn tt~::n as

(5.7i

· · , n is ·- t k = 0. The effective mass equation then


1tthL ban d 1111111111 ~11 · 1 L

take the f rm

(5.8)

whic h is th Scbrbdinger equation for a hydrogen-like atom. The


4
eiaen!'unctions are characterized by an etfective Bohr radius a8. which
J is ~1 measure of the orbit size and is given by
2

( 5.9)

- --1----- - n= l
The binding energy of the impurity ground state 1s the effecti\'e
Rvdbera
.; b Rv"
.; given bvJ

0 k 11 2 m*Z 2 e4
Ry* =? = ) -)t;, , . (5 .10)
Fig. 5.4
_m • a '· 2
8
.
2(4u 0 ,rE-
Hyd rogen-like energy spectrum of a
~ h a ll ow donor impurity. The energy eigenvalues are those of a hydrogen-like atom given by

Rv '·
E(nH ) = - ~,
( 5.11 )
::-,
n-,_,
...c
~ ~~rT~~~~~~

UJ where nll is the principal quantum number with the va l 1es I. 2. 3. · · ..


A schematic representation of the energy spectrum is gin·n in Fig. 5.4.
This example is applicable to donor impurities in Ga s.
·A. d'1agram sh owmg
' t·h e 1mpunty
. . ground state reb
. lt\
. t t \,1r lerr·' ·tnd
1..t'
conduction bands for a donor impurity is given in Fig. 5 .5 . We ..:~c th~tt th~
1 11
donor level lies just below the conduction band eJ g . FM ,tn ac P '
impurity the ground state lies just above the va len ~e hand dg ·. lmpunt ~
level s that lie close to the corresponding band cdc · arc~: tl J sha llow levels.
Exercise. Calculate the etTective Bohr ra ·u · o n , nd ~tf~diH?
Rydberg Ry' for a donor impurity in GaAs \\ ith 111 - .ll 111 Z:::: I.
and ( = 12. -
Di lance
Answer. 91 A. 6.6 meV
Fig. 5.5
~chcm;; IJ l Jc' pr t: libllull of t ho! P"~Jtion
llf l hL llllp un\ y gr. JuJ•d ' tal \!'i: Dun<ll"
n ~<~r th\: <.:onuUI. ti• H• ha11d a11d .J<.:<.: i:f11"r"
ll< .11 LIH \ ' ;Jlcm.L b a11 d
Donor irnp riti in S1 and Ge 93
lrll\ \1 lle '" t _ l 'lr·udnut :111 I th:1t the impmity
ll th .-n
'tlr, , ' 1. 11 1! rmcd

purities in Si and Ge
5 1 of ellipsoidal constant energy surfaces

n ri \;S\hen n I"a] · with dunor impurities in Si a nd Gc.


nst~nt cr:crg: : u_rfac . nr the conducti n band are not
hr ud · of re ·o lutto n a specified by q. ( _~ . 76). onsider a
\ 1d ~nl "n.:d at k o The ctli ti vc mass equation in the parabolic
n then t:rk ~ th fo rm

(5.12)

The ani otrop) f the kin Lie energy operator renders it impossible to olve
rlli equation exactl . Recourse must then be made to approximation
method.. uch a_ th va ria tional method (Faulkner 1969). Faulkner has
arried out detail d variational calculations for donor impurities in Si and
e. He determi ned the effective Rydberg to be 31.3 meV for Si and 9.8 meV
for G .
The ani otropy f the kinetic energy operator in the effective mass
quation 2:iv n b. Eq. (5 . 12) causes a splitting of excited states such as
p- tate . hem = 0. tate is split off from them = I states. This splitting
ha.' be n b rv d experimenta lly in Si (Picus et a/. 1956, Aggarwal and
R· m a 19 - a nd in Ge (Reuszer and Fisher 1964) by means of infrared
p tr · p).
e have n ted in Chapter 3 that the conduction band of Si has six
equi,·alent mini ma or ··valley .. along [I 00] directions ink-space. Within the
pre ent th,or •. there is a set of donor levels associat d with each valley. A
gi\ n d no r level therefo re possesses a six -fold degeneracy due to the
multipl \" lley . In the case ofGe, there arc four equivalent valleys located
alo ng [I J I] directions and centered at the L point on the Brillouin zone
b{ und · ry. Each donor level has a four-fold degeneracy due to multiple
Yall ) . A more sophisticated theor . ho''-'S, however, that the multiple
\'alley degeneracies arc split by· interactions hetween valleys, as will be
di cu s d in the fol lowing section.

5.3.2 Volley-orbit interaction


Th effi cti\'e maS!:> tht:ory of impurity states presented thus far assu~es tlu~ t
the d1 J tric con_ta n! is independent of vv·ave vector. In fact. the,dtelectne
on~tant i~ not a constant. but is a function of wave vector k and frequency
...:. r pre~en t purposes tile frequency dependence can be ignored, but ~he
wave \'CCI r d pcndence cannot. The latter dependence leads to couphng
ctv. a n impurity states associated with different extrema of an energy
hand. as in the case of donor impurities in Si or Ge.
Electronic effects of impurities
'd emic )nductor with r equivalent minima in the co
Let us c n t er a . - I ,., 3 . . n-
. b d lo .. 1ted ul wave vectors kow tt - , ....... · .. , 1. If r(k) 1 the
Juctton an ~,;.. . . · · h w · . ..
. d erld~nt d 1eJectnc functiOn, t e euect1ve mass equation
wa e-v~.:dot- ep " . .
. l .,) mu t e 0<Je nerahzed to a set of coupled dtffer ntial
g1 ·en y :q · -5·1-
l

"'lJll ' tion ·

, . 2 r ze1
tt-(k ow - tV',) F (. ·) - ~ F. (r) = EF (
L
• - ,,I"':
-
? ~
II' '
1 ' 1 JJO
~4
- I 7ffo€
(k Or1 - k 0 1)·I (//
I/ -
1
<"t <i• r ),

(5.13,1

,vhere 111 i::. the rl mpo nent of the diagonal effective mass tensor of the
wth mit~~{~um and cp (•·) is the etTective mass function of the J.L·th mini-
mum. Th term in Eq . (5 .13) with I.J =1- tt can be treated as perturbations
wi th (k ) ta ken from theoretical results for Si and Ge (Nara 1965). Using
varia tioml sol Lit ions to Eq. ( 5.13 ), one finds (Baldereschi 1970) that the six-
fold degen rate ground state fo r donors in Si is split into a singlet U 1,
ground state, a doublet(£) excited state, and a triplet ( T2 ) excited state \vith
relative energies given by

E(T2 ) - E(A 1 ) = ~1 = 10 .6meV


£ (£ ) - E (T2) = ~?. = 1.1 meV.

The experimental values of the splitting parameters ~ 1 and 62 derived


from infrared spectroscopy (Aggarw·aJ and Ramdas 1965) are ~ 1 = 11.85.
21.15, and 9.94 meV and .6 2 = 1.35. 1.42, and 2.50 meV for P. As. and Sb
impurities, respectively. The splittings of excited states deri\'ed from ~s. ~p.
and higher hydrogenic states are very small, because the env lope fum:tions
are very spread out in real space and require only ver _mall k in their
Fourier decomposition .
ForGe, the four-fold degenerate ground state is spl it into ·1 singlet (A t
ground state and a triplet ( T 2 ) excited state \Vith ca!cuht d pl ttting

The experimental values of ~ 1 are ~.83. 4.23 an J 0 .3 ~ m V f1r P. ·. and


Sb impurities, respective\v.
,. The ionization encrgie; for the lower !yin£ ' tate: f J . . n 1r 1mpuntic . in
St an? Ge are li sted in Table 5. 1. The ag~- m nt hd\ 1: ·n lh "1 r) ,tnJ
expe t:nnent for the excited st·1tcs is v~:ry l!D • but 1 'l..!ll tfi._·,Ultl) I ·
sattstactory for the Is. tales. For the lattn~th "re t: ad ar kpl..'mkn · 11
the tomzatton energy on th nature ol'the im purit _. 111 .... ) hll n \\ tlh th,
theory so l'ar devel oped .

5.4 Donor im pur•"t•1es ••n 111-V semiconduc o


Ill V '> elllh.:on Jul'lors such as . I . . . ~.. I
. .
ba ncI mtntmum . "' . ,t n tt..>" 1.1
:ttl. _ 0 [' h . .
L lllll1ll til 11 bctnd I
A cceptor •mpuntie 9
Ill , I ; t tt d ' • 1. t11 ·r uv r
l .tt1l ~ n·r l'l(,•J , R,d I.:IC ..: ht

4:.5 53 .
1 \ ,I} - 2.fi
\2 (1 3 1.2 30.
2/'11 II :I IU II : 11.6
:!.p 6 4(1 1.4 (d 6.3
Jp,, 5.4!' -5 5.5 5. 3
'I' .\ 12 J. l 3. 1 3.0
h · I I) I l 26 1:2.76 14.04 10. 19
II T2} .6(1 9 93 '.U\1 9.87
2p, 4 4 4.74 4. 73 4.74
2p I. J 1 73 I. 73 1.7:1
3ru -. 5 2. 6 2.56 2.57
l.r± I. 3 105 1.02 103

·pherical and paraboli . The donor states are therefore described by the
i ·otro pl etfe tive ma eq uation. Eq. (5.8). Similar considerations apply to
d nor Impurities in II I semiconductors. In the case of InSb the con-
duction band effecti v mass i so small (m ' : : : : 0.014m) and the dielectric
con tant i - larg ( :::::. I ) that the effective Bohr radius is exceptionally
large (a 8 - I Oas) and the ionization energy is exceptionally small
(£ 1 ~ 0.-9 meY).
Other [IJ-V em iconductors such as GaP have multiple conduction band
min ima away fro m k = 0. The donor impurity states are described by the
effective rna uation gi en by Eq. (5. 13) and are qualitatively similar to
tho ·eof i .
A ta bu la tion of experimental and theoretical binding energies of
·hallow d nors in Ill- Y and II Yl semiconductors is given in Table 5.2. Table 5.2 Binding energies (mt:V) for
donors in 111- V and II- VI semiconduc-
Ef ctive m theory i seen to give rather good results for shallow
tors (after Watts 1977)
d no rs r placing either theca tion or the anion of the host crystal.
System Donor Theory Experiment

Gai\s Si 5.72 5.84


s 5.72 :\. 7
5.5 Acceptor impurities lnSb Tc 0.59 0.6
CdTe In 11.6 14
Th f'G tive mass theory of acceptor impurity states in Si and Ge is 25.7
ZnSe AI 26.3
complicated bv the degeneracy of the alence band at k = 0. The warping Cl 25.7 26.9
or the con tan\ energy surfaces as described by Eq . (3.71) further compli-
cate the problem. The effec tive mass formalism of Luttinger and
Kohn . nevc rthele s, is able to handle these difficulties in a straight-
forwa rd manner ( Luttinger and Kohn 1955). The effective mass equation
b es a matrix equation obtained by first making the replacement
~ ' .. - i\7,, in the matrix ofEq. (3 .69 ) and adding the impurity potential to
the d iagona l cl ~ 111 nts. This matrix then operates on the column vector of
'Omp r cn t F, (1') of the effective mass wave function. and the result is set
Electronic effects of impuriti es
96
equaltoz r o:

;:_>'2
D'!. f __

' n. Dr cJxD:::

if
-L--M(-) ,+~
i)-, '), )
c
ff-
n":! .Y- o ::- -N - -
arD:::

. 2 ( D2
[j2 o:. - L - - A1 - ,
d::- dx:.
- .\' - -N--
;)'.::::: fJyu:

(5.l4J

wher 111 = -Ze2 j 41fr-n r.


Equation (5.14) represents a set of three coupled pa rtial differential
equations in the three functions F1 (r), F:. (r ). and F~( r) . The spin- orbit
interaction at this point has not been included. To include ir. one applies the
procedure described above to the matrix of Eq. (3.70). The result is a set of
six coupled partial differential equations. Neither set can be solved anal}t-
ically. In tho e cases where the acceptor binding energy is small compared
Theore tica l
to the spin orbit splitting of the valence ba nd, the set of six coupled
B 10.3 9.3 equations can be decomposed into a set of four coupled equat ions and a set
a 10.8 9.3 of two coupled equations. which determine the acceptor states associated
In I 1.4 9.3
TI 13.0 9.3 with the light and heavy hole bands and with the split-offband, respectiwly.
The problem can be simplified by separating th e Hamiltonian matrix into a
spherically symmetric part and a cubic correction (Baldereschi and Lipari
1973).
Variational method s have been a pplied to the solut i n of the accep[(lr
impurity problem (Kohn and Schechter 1955. Mendels n an James 1964).
The ground state is four-fold degenerate, has even parity. -tn :1 b~long~ t '
theirreduciblerepresenrationft; .andh·tsnoradial nod , . Jti ·L meni n rl~
n.o v. B .'///fLI//////I//1///1//////f/11/l
representedbythesymbol (8 + 0).Excitedstateswhich ar p-l i eb I ng_tL'
the r (i, r 7: orr~ representati ns a nd ha ve odd parity. Th number of r<tdl,tl
- 1.0 -' '
'_: ~ Jp nodes vanes. For a given symmetry type and a giY n numba n f n ~.1d '· rl 'f ·
>~ - 2.0
.- ~~ -3s
may be more than one eigenstate. These eigensta te: are di LU1~ ish ·J b~
•'
~-02 ·--~.;..._ 2p addir~.g another index, a in (8 - II) and (R ..:_ ] ~).
§ 3.0 ~+ I ·'·- 2 s . In fable 5.3 are given e ·perimental and the 'fc:ti ·al il' niz.tunn ~.·ner,~I ·
lor ~.iroup III accept or. in G e. Tht·re arc cka rh . 11mifi :mt lilT r m·c ltl
;,!

.2." --4 .11


~-lJ)
11;: IOI1l7..ation energies of the varil)LIS accc-pr . : in '" .l ntr dt ·tilH1 \\lt h d~.
:t -5 ellectlvtnn ~ s re · It l ' l
' su · ne ener~1·es l) l · the
. .
IO\\ -h m n b lUll t.u~.·~ l
f" l 11 11 ,,.
are prc::;cntcd in Fu
111!1 h +< l
• • _ · .
1
'\ (. . , . ~
levd s. fhe J1anty ol 1 t1 c~ 1 eves ~ 1
·-
.
· · ~
e ~- · J ,tnL 1dcntl11ed \\'ll h t he L't1 n·e ·p 11
.
l _.l l
··-1
accort1lll l.! Lll tlcl£1\ L 1111
lead to sek ·tiC\ 11 1 t' . ~
\.. rue~ or opt 1ctl tr~tn . itll ns In I d
f ig. 5.6
sy t_nmt:t.r nf a sub~titutiL)nal siJc lacks a I.' ·ntcl I. I m
1 u~ I)JUI! l<l l l llll Lah.: o: ncq;1c 11 1 lr 111 '-lllon s I l"l\111 the gn'tln l t· t • . II I .
• lal 11.: r DJ,J <.y an J DiJillllud l 'Jil7 1 .. s I I (l ;t l 1 · Ill I ·a [ •d l 1.. ll
( lck Y and 111llllud. IY67 ) 1·1· ·
· L'l l\' ' 111 l 'oS lh I
Central cell corrections and deep level 97
l nrinuum \\ 11h th.: los of the J1ll111 l !!f •up s) mn 'l ry Table 5. 4 R1nohn • 11 r 1 rm ) ••r
ll . ;lC q l ll f~ ill rrr v nJ II "I mtLOO ·
duLior, , ntl l1parJ
he t r ~Heel b
1 1tk 1111ll \' 111J II Vl ·' m i~.: n nd uc ims ·a n
1'!73 )
a) d J1pwa ·he em I 1 _·...: for i a H...l c. IT ctive mass
lllahll! picture the experime nt al r~s ult s r r the bind ing cccptcr
mh r ,rca 'e ch sh wn 111 T a ble _.4. (J ~Ip 7n
oa A Zn 25 6
I R6
r I cell corrections and deep levels Lt 110.1 114
11 the pr cedi ng s c t i o n ~ of this chapter that effecti\'c mass
t the amt.: gr und ·tate io ni za ti on energy for a ll impurities o f
d )l1l r or a~.:ceptor) in a given semiconductor_ since the ioni-
Jept.:nd onl\' on the carrier effecti ve mass and the dielectric
he ho t cr ' nl. The latter properties are little a ffected bv
impt nti l lm\ concentra ti n. -
It r I ar rrom the re ·ul tc· pre. ented in T.1bles 5.1 and 5.2 that the ground
~wt i mvtion nerg) dep nd . . ignilican tl y on the nature of the im~purity.
in~.: 1nrradi~.:ti< n to the effec ti ve mass theory predict ion. The reason for this
dr ~.:rt.:pam.:y is that the impurit potential within the unit cell occupied by
the impurit) cann t be ade4 ua tcly described by a Coulomb potential
.crcened h~ the bu lk d ielectric constant of the host crystal. The impurity
potentral tend to hav a short range component superposed on the
oulomb pot ntia l. Since impurity gro und states are typicall y deri ved
from hydrogt!nic s-states and have v a ve functi o ns that are no nzero a t the
impurity nu leu ·. th~;y are trongly influenced by the short range part of
th pot ntial v..·hi h \aries ·igniflcantly from one impurity to a nother.
£ "\cited . ta te deri ved from hydroge nic p-states, o n the other hand, ha ve
wav func tion that a re zero a t the impurity nucleus a nd are much less
affi t db) th ho rt ran ge po tential. as is evident in the data of Table 5.1.
Th h rt ra nge contribution to the impurity potential is known as a
centra l cell correction. The implementa tion of this correction may be
achi ved by mean. of more sophi sticated theories based o n pseudopoten-
tial . A pa rticularly simple case is that ofisocoric impurities ,.vhich have the
am n umber of core electrons as the a to m of the host crystal. e.g. , P a nd S
in Si tP·mtelides a nd Sah 1974). For these impurities the perturbation
pot ntial is not re ponsible for binding additional core states. Howeve r.
imp urity and host ato ms ha ve different Coulomb and excha nge contribu-
ti n::. of o re electrons to the potential. Taking this effect together '.vith
man '-va lle\· effects into account, a weak short ran ge contribution to the
ciT ctive in; purit y potential can be obtained and incorporated into tl~e Table 5.5 lo niLa tion energies (meV l for
effccti e mas eq ua ti o ns. The res ult s for the ionization energies ofP ~ nd S r_n p a nd S in Si . The s+ and S 0 slates refer
Si ar given in Table 5.5. T he agreement between theory and cxpenment Is to one a nd two elc..:trons bound 10 the
qu ite good . Indi vidual valley- orbit interaction splittings for P, As, Sb and ct:ntcr, respectively (after Pantt'lidt:~ .tnd
Sah 1974)
otht: r donor impurities ha ve a lso been ca lculated. . .
or the case o!' no ni. oco ric impurities the perturbation potenllal brnds Impurity Th ' Of \ f \ptfl lllt:ll l

additional core electrons in the impurity cell and cannot be regarded as 42.4 4' ~
p
weak . In othe r -ystem s a lso. the perturbation potential is stro ng . These S (.'>' n) :!lJ 1 \02 I)

'>~stems irdud vacancies and host atom interstitials. noble metal ato m S(S ' l t>5Q.J hl'
imp urit1 ::.. and transition metal atom impurities. Efl'cctivc mass theory is
Electro ic effects of impurities

. hi b" ·ws -- the defect levels tend to lie toward the <.:entc
n I ng r a p Il<.a c. ~ • . . , . . . r
. g·tp . nd cannot be ascnbed solely to e1ther the alence
o f the f un ;J men t d 1 ' '1
1 c nduction band.
·t r J cfectlcvcl• Jving h are referred to
toward the. centerI of.the gap
I mp u n Y ~
· They pia an important role m ca ta yzmg t e recombination
Ll d eep Ieves. 1 . . .bl h .. .
n Icct r ns• ·•nd ;... 11 ole , but contnbute neghg1 ~
Y to t e eqtuhbnum con _
c~:ntra t ion . of elec ron and holes. Shallow donors a~d acceptors. on the
the r han , conlr 1 th oncentration of current earners and thereby the
electrical conductivity.
A . an example o f d p levels we show in Table 5.6 t_he i?nization energies
r _d t ra 11 ition elem nls in Si (Zunger 19R6). The IOlllZa twn energies are all
e 5.6 i •)Oilall011 ~nerg1 'S (C )
. -., 11 sid~wbly larger th · n the effective mass theory value of "' 0.03 eV.
f
~ ~ . ull 1. .I tran~nion metal dopants in
1 (o.~.fler Zungcr l9c6)
A num b r of approaches have been made to the theory of deep levels.
They includ tigh t binding methods (Hjalmarson eta/. 1980), and Green's
function meth ~ds (Baraff and Schluter 1979, Zunger and Linde felt 1983).
Recent empha. is has been placed on the use of the density functional
approach together with ab initio pseudopotentials (Zungcr and Lindefelt
0.2: 0.30 OT
1983, Zunger 1986).

5.7 Impurity bands


Up to now our discu sian of impurity states has treated the impuritie- a
isolated entities. At a finite concentration n 1 • however. the impurities
have an average nearest neighbor separation of approximately n;' 3
. At
sufficiently high n 1 , "' 10 18 cm- 3 for Si, neighboring impurities are suffi-
ciently close that their wave functions overlap enough to produce a sig-
nificant perturbation of the energy levels. The energy levels broaden Lmt
into a band called an impurity band.
If the impurities were located on the sites of a lattice. th impurity band
would be associated with reciprocal lattice vectors and a n impurit~
Brillouin zone. For group V donor impurities in Si the imp urity hand \\ouki
be half full ifthe two-fold spin degenera y were taken intc1 a count. Such an
impurity band therefore has metallic character ·lnd h uld ·hi hit tintt ·
conductivity even a t very lmv temperatures. This b h<. vi 1r h·ts in fa t b ~n
observed in 11-Ge (Fritzche I ()55) .
, The as.umption of periodicity of the impurit y sit ~s j -. fu1urs . rw t \ ,tli' .
~ o r rea l semtconcluctors. The impurities are disordered Th~ n rgt - ' 1
tmpunty states are not confined by b·md ed~e. , but .u ~pre.td ul (n a a.n
~xtended range characterized by a d e ns it v-of-sta r s function h n h..-rm 1 r '.
rt has been hown ( Andersorl ·
1('~I.')
1
-~'
t h a t ui
~r Sl rL 1t'rL.. t ll I ,,1 J1 l '- 1o col•· •ed
.. states
and the appea rance or in~ ulatini.! character. Th t -.tit ed ..tnd Jeh ~.:alird
states ~~~:e. se parated hy th mobility edge ( Ml' tl 1 I 7) II I\ h. h!tng th'
compostlton or b y other means. the Fe rmi n r -' L"~lll m.t i. ll I'· .
lhrnuf!h the mobility . .
cd ol: .1 t 1· 1
o , • me o -msu ator trans ton
~- h•' ,.
cc n t r<~ t i n ., t \\ 1 1 1
- ' ' 1tL'1l1 e tr~lll"iti o nt~tl-. s pla · t-.;-.;p•d la·d r·l.tlll

I,
Re fere nces 99
1 ''''m' CLh1~ n: bt1 m ct n 1c J crivcd hy Llhscr vin g th;rl
ll the lOll r ICill iilll C~lll llllplln :.tn d r , d ll- CC lh e hlllcllll"
. t:
1 F r rhc '>1.: r cn~.:J 'ou l0m h ~l O c ntial

e -'
(r) = - - - c '/ r ( 5. I h)
-1·:7111,.

hlil1' ~e cree Hng ln gth: pcuficdhyq::·= 4 (311, /7r) 1 ' 3 / uj .a 11


1
1 rll.ilnl~ ifq, < 1. 19/ a u (R o gersl'ta/. llJ 70 )0J

(5.17)

Problems
l ~~~ ula c the d n r io ni za lton energy, the radius of the ground state orbital.
an l til' m1n1mll rn L'P nce ntra ti on for which there will be sufficient orbit al
O\erlar D pr due a n impuritv ba nd in n-lnSb. The dielectric con.·tant f is 18
.tnd the dcctron elfcc tiw mass m: is 0.014m.
1
<tkui.H~ Lhe cf fe t f nonpa raholicity on th e donor ioni zation energy in
n-ln b ming th effect ive ma ss equation

where

p = -i7i V. a nd V;( r ) is the C o ulomb potentiaL Take F, (r) to be a variational


funct ion nf !he form ."1(cxp (- or), where cc is the vari ational parameter. Is the
e~' L f the no nparabo licit y to in crease or decrease the ioni za tion energy'1
J. alcu! at the hinding energy of a donor impurity in Si using the effective mass
eq uation, q . ( 512), a nd a va riatio na l trial functi o n of the form

with oj1 = 47ffudi 2 j me2 • n a nd ,1 va riational parameters, and 1 = 12. Take


the values nl" th e m,", from Tahle 4.1. set k 0 ., = ko 1 = koc = 0. and ignore
the vall ev o rbit interaction. Co mpare your result with that for a sphencal
bamj · - m · = ( m [. m ;-' ) I ·' l .
Will1
4 The el ectric fi eld of an io ni zed impurity is screened by l"ree carriers gtv~ng
ri se to th e !;creened po tential VJr ) = - (e2 j 4rrr0 rr) x exp ( - tf,r), where q, is the
in v rse ~creening length. Using a trial functi o n of the form f!(r) ~ A e:p( -:- or)
in th e v::~n a ti o nal method , calculate the binding energy as a functiOn ol i.f, lor a
dono r impurity in CdTe taking ( = 11 and m;. = O.IOm. Is your result
consistent with the remark ju st above Eq. (5.17)' 1

References
R. L. Aggarwal and A. K. Ramdas , Phys. Rev. AI37 , 602 (1965): AI40. 1246
f 1LJ65J
P W _ And r:-.( n . Ph Fs. R('\" 109. 1492 (195X).
A Bal d resc hi , /'/n·;_ Rn. BJ. 4673 (1970).
00 Electronic effects of impurities

A. Bcddere chi a nd N. 0 Lipari. Phys. Rev. 88, 2697 ( 1973) .


. A. BamJT and M. Schliiter. Phys._ R~v. 819. 4965 ( 1979).
F. Bas. ni. . fado ni~i. and B. PrcgJOSJ. Rep. Prog. P~ys . 37. 1099 (197 4 ).
D. H. D ickey and J . 0. Dimmock. 1. Ph~·s. Chem. Soltd\· 28. 529 (1967).
R. au lk ner, Phy 1· Rcl'. 184. 713 (1969).
H Fn tzsche. Ph. ·s. f. cv. 99. 406 (1955).
H . P. Hj · lmarson. P. Vogel. D . J. Wolford. and J. D . Dow. Phys. Rev. Leu. _
44
8 0( 19 0).
W . K ohn dl . Schechter, Pllys. Rev. 99. 1903 (1955).
J. 1. Lutlingl!r a nd W. Kohn. Phys. Rev. 91. 869 (1955).
K . . M endel u n · nd H . M. James, J . Phys. Chem . Solids 25, 729 (1964).
N. F. lo ll. r/1•. Pln·s. 16. 49 ( 1967).
H . Nara. J. Phr.1. ·~c. Jp11. 20. 778 (1965) .
. T. Pant l ide~ a nd C. T. Sah, Phys. Re i'. 810, 621. 638 (1974).
. . Picu. . E . Burstein. and B. Henvis. J. Phys. Chem. Solids I, 75 (1956).
J. H. Reu zer a nd P . Fisher, Phys. Rev. Al35, 1125 (1964).
F. J. Ro rs. H . C. Gra?osk~ Jr._. and D. J. Har~ood, Plzys. Rev. AI, 1577 (1970).
R. K. \:Vatts. Pomt D(~/ects 111 Crystals (John W1ley, New York. 1977).
A. Zunger, in Solid Srate Physics. Vol. 39. eds. H. Ehrenreich, F. Seitz. and
D. Turnbull (Academic Press. New York. 1986). p. 275.
A. Zunger and U. Lindefelt. Phys. Rev. 827, 1191 (1983).
cto stat1stic

e as
Statistics
ri1H1i. st?micl ndu ·ror free chan:re carriers arise from the excitation
6.1 Intrinsic semiconductors
·I c tron: from the valence band to the conduction band creatino
u I l n ntra tio ns of free electrons in the conduction band and fre~
h I Ill the \ alence b·md.
I til rmal equilibri um the Fermi · Dirac distributionji111ction specifies the
ccupation 1111111! r of a state.
I he den itr-o(sta/c. in an energy band is the number of states per unit
\IJ!ume p r unit energy intervaL
Tht.> intrmsic carrier concenlration enters the /mt· olmass aClion that relates
the on en rration of electrons and holes.
In exrrin. ic . Cl/liconductors the charge carriers arise primarily from 6 .2 Extrinsic semiconductors
impuri tie ·.
Donor impuritie.\ produce an 1z-type semiconductor. In the ji'eeze-out
range the free earner concentration increases exponentially
wit h temperature, but in the saturation range it is nearly constant.
A ccep! vr impurit ie.1 produce a p-trpe semiconduNor.
In a cvmpen.wted semiconductor both donor and acceptor impurities are
pre ent.
In ann-type semiconductor electrons are the majority carriers and holes
are the minoritr carrias. In a p-typc semiconductor the roles of
electrons and holes are reversed.

In rder LO ca lculate properrie - such as electrical conductivity, it is neces-


!'.ary t kn ov> the concentration of electrons in the conduction band and
hole in th valence band . These current carriers can arise by thermal or
optica l e cita ti on or electrons rrom the va lence band to the conduction
band. b y excitation of carri ers from impurity states. or by injection from an
utst l source. In this chapter we focus on ca rrier concenlraltons 111 a
'ien iconductl r in thermal equ ilibrium .
. emtconduct rs can be classified according to the origin of their current
carriers. Ir the carriers arc due primarily tot he excitation of electrons from
th val 1 e band to the conduction band. the semiconductor is intrinsic.
"fh is i-, the si tuation in an ideaL perfectly pure . emiconductor. but it may
Semiconductor statistics
. . . lpur c;;emi comluctor if the temperature is sufficient! .
al 0 ccur lfl .tn Ill , . . . Y
tl lnnd if the current earners anse pnmarily from
1
high . On t 1e o 1e • • . . . "
. ~ . . . th . rnicon d uclo r ts extnnstc. l ts clt:ctncal beha vtor depends on
• • • •
3

trnpunue~. t! .
uon-intrinsic r pertie ' r the mal.enal. ..
Vv.hen h h donor and <tccep tor tmpunttes ared present and have random
A t eqUJ·11·bnum
·
·cm iconduct r is compensate . electron •·
d 1 trt b UtiOII • the .
ar . tran ~ r rred from the dono rs to the acceptors, thus creatmg ionized
don rs and accept r.. If n neutral donors and acceptors remain. one ha~
ideal compensation.
If a . micondu t r c ntai ns impurities whose ground states lie far from
the band edge . the impurities give rise to deep traps. Carriers originating
from ~ h allow impurit ie c· n be captured by deep traps. The result is a semi-
insulating semicond uctor in which the thermal excitation of carriers into the
alen r c nd uct i n band is difficult.

6.1 Intrinsic semiconductors


Let u c nsider an intrinsic . emiconductor with an energy gap Eg between
the valence and conduction band extrema . Since electrons are Fermi par-
ticles. the Fermi-Dirac distribution , fi:D(k ). specifies the occupation
number of a state of energy £1. in thermal equilibrium at absolute tem-
perature T,

(6.1.
Fig. 6.1
Fermi- Dirac distribution function where = 1/ kaT, ks is Boltzmann's constant and EF is the Fermi energy or
plotted against energy E for T = 0 K chemical potential. A plot of the Fermi- Dirac di stribution function versus
a nd T #- OK.
energy is given in Fig. 6.1.
When the temperature Tis zero.fj.-0 (k) = 1 for£,. < EN and_! ro(k) = 0
for Ek > E~. All or the states situated beiO\-\' the zero t mperature Fermi
energy E ) are occupied and all oft he states above Ejl re empt) . The Fermi
energy hes between the occupied and the unoccupi ed sta tes of the system at
T = O.
When 1::k - EF becomes very large compared to /.. 8 T . it is P')ssiblc~
to neglect the quantity + I after the ex ponential in th d n mi nawr L11
E.q . (6 .1)_. The Fermi- Dirac distribution th n red u , s tl th B It 1,wn
dtstnbutiOn

The conccntntion
c 0 ,. e I'ectrons Ill
· the cond uctil n bani n ·t' .... ,
~ t\ 11 l'.

, ~
0-'
17 = :...
q """
'
L .I'FJl ( "I . ) = -- ~---
f..
'
-~L_,_ (' i/A
I
J- T
1..

wh~re th ·um is over . 11 , .


. tl
I S 11: VO 1LI111L'
,
l)f' th ~
" ,
"tall:s tn th L' ~nJ uLti llll l ' an
. e" sh:m , and a Ia ·11 r ot' h·1
l u tthe:-.pt nd egc ncra · ~ .· -'
J s tnl! tl p r M.:n Llllll 1 1
lntrin ic semiconductors 103

= - -- ; · d· 3 k (6.3)
-"
11
( ) .
~ ~Jf;-;:£:-
. k-_-:::
E-r .-+-1

fh ira~ inte~ral in this expression cannot in general be evaluated


r m. H wever.. with certain approximations its analytic eval-
Je.

6.1 .1 Spherical parabolic energy bands

The fir. t a. e \\ e consider is a spherical parabolic conduction band with


e1Tect1ve mas ' m( and energy given by

(6.4)

wh re Ec i the onduction band edge. W e take the temperature sufficiently


I \\ that koT « Ec- EF and approximate the Fermi- Dirac distribution
y

(6.5)

qua ti n (6.3) now becomes

n = -2- ;· t /11
· !{e .l(£F-F,·-h'
· · k 1 '12m·)
•· . (6.6)
(27r )3

Introduc ing spherical coordinates 111 k-space and integrating over the
angle gives

(6.7)

2 2
Changing the variable of integration from k toE = h k /2m;·, we obtain

(6.8)

where

N, (E) = 7r2
l ? ')3/?. E 21 ( 6.9)
2 ( -;;'

i~ the density-of-states in energy for the conduction band, i.e. , th~ number ?f
states per unit volume per unit energy intervaL This quantity ts plotted 111
Semiconductor statistics
0
-t· of en rny £. The free carrier concentratJ n i al~
~~ 6 1 as u f l lt: Jo n c:- E . . n
- · - d . tl · ti'gure It h uld be noted that q. ( 6.8) IS vahd f r a more
repn.: ·en L 111 l L .
. . d ·p'tldence nf E.k - Ec on/.; than that of Eq . (11.4) provided
cnmp I tGtteu1 t; c . ' .~ . __
th~ pnper t:xprcssJ n lor ;\,1 ( L ) I. usc~. , 3 - ~ '
The int grill in Eq (fd~) 1s proportJOn,tl tor (5) - 7r- / "--The result for 11 1,
n= /\!,.(' (fr - / -:._)
(6.1 ())

\\here
(6.11 )
l :!
{If: the effective density-of- states for_the conduction band.
The cf~ ctive den ·ity-of- ·rates N , represents a weighted sum of all the
tates in the conduc ti n band . It is, in fact, the partition function of the
nonint ra ting 1 ctro n cJ'as. The weighting coetncient is the Boltzmann
._ factor which xpresses the fact that the higher the energy of the state in the
-
I
conduction band the lo·wer the probability that the state will be occupied by
an elec tron. A t a given temperature N, represents the effective degeneracy
:;.
, 0 I
<:.~ 0 L__- - - - ' - - - - - - ' of the onduction band regarded as a single level with energy Ec- Because
1 2 the approximations employed lead to the use of the Boltzmann distribu-
fiE tion . the carriers form a nondegenerate system. When the criterion
Fig. 6.2 k 8 T « Ec - EF is not satisfied, the full Fermi- Dirac distribution must be
Den i!y-of- ta tes N<( E) and the product used , and the carriers form a degenerate system. Nondegenerate semi-
,\',( E )exp(-. 1£) plotted again . t conductors are characterized by a relatively low concentration of shallow
energy £.
impurities, whereas degenerate semiconductors have a relatively high con-
centration of shallow imp uri ties. In the Ia tter case the ovt: ria pping of atomic
orbitals of neighboring impurities can lead to the formation of impurity
bands as described in Chapter 5. The Fermi energy can then lie s ufficient!~
close to Ec that degenerate behavior persists to low temperatures.
Example 6.1: Effective density-of-states: conduction band
Calculate the effective density-of-states F,, chan tcrizing the con-
duction bands of semiconductors Ga.As and lnP _
Solution. Substituting the values 11 = 1.055 x 10--- ergs ·tnd ks =
1.38 I0- erg K - I into the expression for the lle ti' • len · it~­
16

of-states in the conduction band. Eq _(6.11). one c- t ·

(Ill'~ ) ~ (
31 1 2
10- t'l - -
T ('Jll
_,
Ill 300
The conduction bands ofGaAs and InP are l 1 a g "1\ J .tppr im.ll ltll
sphcncal and parabolic with dfectivc ma sses 111 cqu,ll w !1 t)(, '', " 11 !
0.077 nl respectively. The correspondin..! e~re ·tl\
J n ttl ,f tJt'.
are 4 _2 -· 10 17 c m- 1 .dl1 d )- __-., 10
1 ~- .
m -. r ~spctl\d_.ltOI-..
Turnino"' now t l 1 hoi es. 111
· t 111: valenc "' banJ . ,, I ·
1\ 1 ' till' ' '
.Th
talelackml!~ ·tnele·t
0 • : •
·
L ~ on . l .1C c IS!rtbutil n ru
1 1· · ' [1\))1 J r ,, I
e cunc e ntlt~twn ul h< ll's pis th ~ n gn · n b~

[l - f i- J. (k \j
lntrin ic emiconductors 105

(k ) - J (6. 1~)
- 111 ,,

lo\\ cmpaaturc a. t1Jlrl')Xi m·'-ltt. 11 "H


1
T ..4"
. . _. . . _ l~
~1 -
.£• , . an d pro-
m th\: c.l. c f I.' nd uc tton ekct ron s . we 11 nd fort he concentra tion

f1 = /J,, j( 1::, -£, I


(6.14)

th dfect i\e d n it '-( r-slates ror holes is given by

( 6.15)

Example 6.2: Effec ti,·e den. ity-of'-states: valence band


ulculate th eff ctivc density-of-states 1- ,. for the valence bands of
a and TnP.
olutioo. ing the value of 1'1 and k 8 given in Example 6.1, one gets

,. = 2.5 I 01\1 m;,"')


( m
3; 2 ( .I_). -
300
l / 'l
em
- 3
.

Th maj r part of the effective den Lity-of-states comes from heavy


hoi '' h masses are 0.5 m and OAn1 for GaAs and loP, respec-
eg:lccting the light hole contribution. one find s that /V,. is
10 1 crn - 3 and 0 . )3 10 19 cm - 3 for GaAs and lnP. respec-
tive] _. at T = 300 K. The contribution of light holes can be obtained
by u ing t he result o r Section 6.1.3.
T he xpr " ion for the conce ntra tions of electrons and holes given by
Eq . ( . I ) and (6.14) invo lve the Fermi energy EF which i: as yet unde-
knnin d. We can elimina te it by multiplying the two expressions together
t iekl
(6. 16 )

where £ '.! = E - £ 1• and n 1 is the intrinsic carrier concentration. Equation


(6. 1()) i. the low of mass action that relates the concentra lions of conduction
I trons and holes in thermal equilibrium, i.e., the product of the electron
and hole conL:entration . in a nondeg~.:neratc semiconductor is constant at a
j v n l mpcrature. It must be emphasized that the law of mass action is very
g ne ral. The basic approximation made is that the separa tio n of the Fermi
n rg_ from the valence and co nduction band edges is large compared to
k,JT. It makes no as~umption about the source or sources of electrons and
h lc., whether by excitation across the gap or by ionization ofimpuritie . In
chcmi:.,try, a similar law controls the concentrations H t and OH ions in or
w· t r.
Semiconductor statistics
. .. , r e:citation across the gap in an intrin ic em·
F tl1e pJrucu 1ar <.:dSt: · l-
or • ~ 1 n in uritie. to be ionized, and charge conser ation
ondlll- { r I 1lCT\: ,tr~.: I b .
l. • . _ r·r m th law of- mass actiOn,
.
we o ta m
r 1r th.ll 1- TJ.

The conL:t.l1l .ttions of c nd uction e~ect ron s and valence ~oles increase
C"i entiall ~.:xpuncnti 11)' ,: ith increasing temper~ture and With decreasing

nergy g:·~p Th1. behavior i primarily _respo nsible ~o~ the chara_cte~istic
temperature dep nd nee of the electncal condu~tJVIt~ of an mtrmsic
miconductor. In Fig. .3 n IS plotted as a functiOn ot temperature for
£~ = l.OeV an me = 171 1, = O.I_n1. .
Ha ing btain d a n expressiO n that gives both n and p, we can no\\·
determine the ~::rmi energy En of an intrinsic semiconductor by equating
the xpressions for n in Eq . (6 .10) and pin Eq. (6.14):

(6.18)

Solving for En yields the result

EFi -- E V + ~I ·Eg + 43 k B T Iog (/11:


m:.) · J (6.19)

We see that a t T = 0 K , the intrinsic Fermi energy lies at the center of the
forbidden gap. As the temperature increases. Eri increases or decreases
depending on whether m" < nz~. or m ; > m~ , respect ively. If m; = m;.. EFi
lies at the center of the gap for all temperatures.

6.1.2 Ellipsoidal energy bands


For the case of a semiconductor such as Si or Ge, we must take into account
th~ fact that the constant energy surfaces of the conduction band are
elhpsoids of revolution. The conduction band energ\· that appea rs in
Eq. (6.6) must be replaced by the corresponding expr n from E I· (3.76): _.::i'
n=
2
( ~)' J d 3ke {EF- E -(fl!/~)[(1;: k~)'m; lk - /... 11 ~ 111 • }.

~n ~ rder_ to evaluate the integra l. we ''spherical i.t " tht: n ·r,;) b:t J by
mtJ oducmg the scale transfornn tion

( ",_' -- ('11/ ;)s: /,


k = Ill") ~-kl' . I
.!
-
_ I
Ill \ . 111 ,. "- ~ - k o =

The co nduction elect ron t:nncelltr~tion then h ~cl !Tit:'

II - -
2 - (11(....!...1)1'2 )! ;· tf
_1_ f.:' , l1 t.1 I
:::! rr ) 111 .
Intrinsic semiconductors 107
" t1 1a '-Phellcal para holic l:nn d . \'vC r ., ,.,·,,.~ L] . (c. -:11
11 . ~ -)

II = <.' 1, - / , I l'
• I
N,'( E 1,<' 1 (I t:. (6.23 )

- ,f_ tate ''(


.. ) is. . c"ivcn b

' I
'( )-- -I ('2mv o. ')
n-
1 77.:!
1;":. !
E -. (6.24)

f-. tall:::; effecti\e ma ,_ m 'D - is related tom; and 117 ; by

( 6.25 )

me out the integrat ion over E in Eq. (6.23) leads to the result

( 6.26)
where

(6.27)

Tf there are r equivalent ex trema in the conduction band , each extremum


contribute:, the amo unt uiven by Eq. (6.26), so the total concentration of
onduct1on el ct rons is then

(6.28)

It hould be noted that Eqs. (6.14) and (6.28) are not restricted to pure
-em i onductors. They apply also to doped semiconductors, but EF is no
1 nger the intrinsic Fermi energy.

Comment. ForGe with density-of-states effective mass for the con-


duction band 0.22 m and heavy hole effective mass 0 .34 m, one obtains
C r the effective density-of-states of the conduction band
1- , = 0.26 : 10 19 cm- 3 and of the valence band Nv = 0.50x
10 19 cm - 3 at T = 300 K. For Si with effective masses miJos = 0.32m
and mi111 = 0.52 m, one has IV,. = 0.45 x 10 19 cm- 3 and N, =
0.94 10 19 cm - 3 at T = 300 K .
For the case of a spherical parabolic valence band, the Fermi energy can
be eliminated from Eqs. (6 . 14) and (6 .28) . The concentrations of electrons
and hole are then specified by Eq. (6.17) with rn;. replaced by mbos and
with a factor d inserted :
l 1)1J1( ~ ~ ·)3 /4 -E~ f2knT (6 .29)
n = p = 2r2(kBT/ 21ftz- · -mn 0 sm,, e ·

6.1.3 Multiple valence bands


In Si and Ge, the uppermost valence bands (light and heavy hole bands)
have dcgl:nerate maxima at k = 0. In the approximation that each of these
Semiconductor statistics
lie. their contributions to the concentration ...
hand . 1. ·piH:rical Hil LI para b ·'
f light at d hea '- hole are
(6.30)

-
N,., = ~., (11lu, /'.B
'· T / 21111t.:2)!< / 2 • (6.31 )

<lnd

(6.32)

wh re

(6.33)

The eflective masses of light and heavy holes are m;11 and 111~11 • respectively.
The total concentration o f ho les is given by

P=P + Ph = (N- ,, + N- ..11 ) e .J( £ , - Er ) . (6.34)

Eliminating the Fermi energy from Eqs. (6.28) and (6.34) yields the Jaw of
mass action in the form

(6.35 )

For intrinsic material, n = p = n; . Then from Eq . (6.35)

n 1· = n =p = [1·JVc (.·N-ul + ,.-, t•h ') ]~e-.


1
1\ - JE./ 2 · (6.36)

Using the expressions for N~ , F.'t· and f/,. 11 given in Eqs. (6.17). (6.31). and
(6.33), respectively, we obtain

l , ., , , I , ,
= 2r2 (ksT/ 2n1i 2 )\ - [m' 1-.( 111 •-' i - + n 1 •.J-'_) ] ~ - n e -.
p , 1
11; (6.3 7i
DOC:> !h hh

. As we have seen in Chapter 3. the light and heavy h \ a lem:e bands of


St and Ge a~e .wm~ped , not spherical and paraboli Ta~in g the ltn\·
temperature hrnn ot the hole distributio n funL·ti o n in . (6. L) and ct)n-
vertmg the sum over k to an integral. we obtain

Fig. 6.4
I • 11 I.HIIL HcrO( ~ u rl o.H.:o.: t n I. pd "
xtn n 1 em1con uct r 109
d/.. llh pu p ·n d ''-'t d .trd, ..,l~lll 'l·hct ' Li lth ·cnll l;l nt ·n ·r •v
p ·tpcn il ' lli.lr l 'lhC..,L' :--urLICC<.. jo.; th e !! LidiC11t P ith ' C 11CI' !! ~.
n ·' dtlk 1 ' II ·l.: dl , i:-- ~j, en hy ~·

dl. , - dl. 1 jV"/.:.',." 1-

1 ,,1\ = r II1\ I.S' d £ ,.


.I
1 ' r =
- I V~.£ •.~. 1
ciS
.
(6.40

I=-~ ;·
( _;r)· . .
dE,. ;· __..
r. (6.41 )

t~ con~tant energy surface of energy £ ,.. ln actual cases


e. t h intcgnls in Eq. (6.41) must be done numerically.

6.2 xtrinsic semiconductors


A h t: nc t d in hapter 5. impurity atoms are an important source of
r in a , miconductor. Since the electron or hole ionization
·harg~.: ~..::un
energ~ ma) h' ma ll compared to the forbidden energy gap. there may
b ·i-=-mlicant thermal production of free carriers at relatively low
t mpcratur . .
'er) gen ' ral ~::X pression for the ratio of electron and hole concentra-
ti n ind ped emi onductorscanbederivedfromEqs.(6.lO)and(6.14)by
r \Hillng th m a

(6.42a )

an
(6.42b)

''here EN i the intrinsic Fermi energy. Taking the ratio of Eqs. (6.42a)
and (6.4_b). we btain

-II == e-·'
~ Jl £ E I
F- "''/ (6.43)
p

I th F rmi energy of the doped material is higher than that of the intri~1sic
rnaterial. the lectron concentration is higher than the hole concentration.
\ h r a if th~..: Fermi energy is lower than that of the intri~1sic material. the
h le ncentration is hieher than the electron concentration.
Th d tJiled staristic;l analysis of impurity levels is complicate~i by_the
a ·t that these states are localized. If there is already one carrier ol a _g,ven_
· ·111 · locahzed
PII1 · · · orb1ta
unpunty · 1, t h t: a dd't'on
'.I
of a ·second earner. ol
3 •

· h · energy as a result of the


· pposne spin to that orbital causes a large c ange 1n
Semiconductor statistics

. n f the two carriers. The binding energy of the second


oulom) l rq u1· 10 · 1 ·
. . · . II , 0 weak that the bound state wtt 1 two earners can be
earner 1 typtc Y s
ign red.

6 .2.1 Donor impurities


]l i nvcment in the d v I pmeot of impurity statistics to use the grand
canonical ensemble of ta li tictl mechamcs (Tolman 1938, Guggenheim
l 9 -3 and berg 1958, T iller and Wallis 1960). The probability that a
on~r impurity tat ha 11 j electrons \vith spin up and n electrons with
spin down i given b
. [ ) -_ C 1[(n! n l) E, - Et( n , nl)j
P n , 11 , (6.44 )

where C i a nornnlization constant and £1 (n T. n 1) is the energy of


the sh te . Th occ upation numbers n and n J can take on the values 0. I.
In a cOt·dance with the discussion in the preceding paragraph. we
shall exclude the possibility that both n and n l take on the value t
simultaneously.
As a specific example, we consider a donor impurity such as phosphorus
in silicon or germanium. The treatment can be easily modified to apply to
acceptor impurities such as boron. The phosphorus atom can have its extra
electron, not needed for covalent band formation , in a localized state with
its spin either up or down. As discussed in the preceding chapter. the ground
state of phosphorus in either silicon or germanium is a singlet with the only
degeneracy due to spin. In the present simplified discussion. v\T neglect the
excited bound states and treat only the ground state and the continuum of
unbound states. The probability that we have one electron localized on a
phosphorus atom is therefore given by

(6.-l: l

Using Eq. (6.44), we obtain

2e 1( l:. F- £)' )

2e .I( £ F- F ;' )

where EJ' is the energy of the donor impurit. . t.tte l!i \ n_ by


E" - E1 ( . · . ~
t - .1. O) = Et(O. I J and we have taken 1
(0. 0 lthe m.·rg) 1 1 the
crystal With the donor electron rem 'ed) ro h r Th~;; qLwnut) P, is th'
occupatio~ factor or the impurity state. Not lhtll it I rh. I th ~lm~· ·''
th~h ennt~Du:ac distribution defined in Eq. ( 1).
. e pro abtltty that th txtra clectrllll of th phosplh ru t •nt I 1 1J1l ~ J
lllll thl: conduction band is give n h y

~J I I / L1 1
~
, - 1- 1- , -=
+ ,e ll., ' ' l I
Extrinsi semiconductors 111

d111g \ i~ h t h. ~cneral ana lysis of Eq. (()4X ). \-VC examine the


1~ nant :>l l LI:l tH)ll in \vhi~..·h EF is suH1ciently below
l that E;'
'1. ~~~en t he _llllpunty level is essentially unoccupied. ncarlv
1mpunt1 .· ~ r IL m zed . and n ::::::: ""·A more precise appraisal C:r
h\ ta"-'_ng 11110 acC(""lUnt the electrons excited from the valence
nduct1 n band. The condition of chan.!c neutrality is then
=
II Jl -j- II+
". (6 .49)

th' con entra tion of ionized donors. For the case under con-
.::: 11". liminating the hole concentration using the law of
I tain

(6.50)

Tln: p\ Jcall~ signifi ant so lution to this quadratic equation is

l
n = 1 [ nd + (nj + 4n j )2.!.] .
J
(6.51 )

Equation (6. - I) i p·trticularly useful when li ef ::::::: n;. If this is not so. we have
the t\\O limit ing ca s 11.1 ~ ni. n:::::: nr1 and 'lei « n;, n:::::: n,-. The first case
c rre-p nd- to a n extrinsic semiconductor and the second to an intrinsic
emiconduct r.
Turning n w t the general analysis of Eq. (6.48). we need a second
relation in o l ·ing the Fermi energy Er. This relation is provided by
Eq. (6._ ) in hich the approximation Ec - Er » k 8 T has been made.
H \Vc\'er, w no longer require that Ej1 - £,... » k 8 T . Hence, Er can be
Jo. lO Ef1 and can even be above it. Noting that the energy E;' of the
impuri t tal is given by

Ej1 = Ec- Er~ , (6.52)

wh r Ed i ' the donor ioniza tion energy. Eq . (6.48) becomes


1'1(/
n = I+ 2e ':i(b. - £·c+ £·~~ l. (6.53)

Eliminating Er - Ec from Eqs. (6.28) and (6.5.3) yields the relation

1r
')

- -- = .!.,·iV
~
, ,
. e - riE,, .
( '
(6.54)
lid - 11

Tw limiting cases of Eq. (6.54) are readily evaluated: ,t3Ert »


l(k 8 T « E,J) and ,.'1£" « I(ksT » Et~)· In the first case, 11 « 11" and one
. nductor tatistics
Sem1co
. mtt e · ,Juti n

(fi.55J
··Hlduction electron concentration increa e
it h im:rca ing temperature. This is the freeze-ou~
I r· 1 r ln 1ht.: t:cLmd case. 11 ::: nd. essentially all the donor
' i . hi. j the saturation range of temperature .
• ( ju tinn eledr n concentration in n-Si
nmpl · · (111 · .
. nJuction elec tron concentratiOn as a funct1on of
al ·tilat I t.: t.: . · · · s· k. E. 0
tcmpcr.ttun.: l·c)rgroup V don r tmpunttes m 1 ta mg c1 = .030eV.
11
_ 0 I)'"" 111 111 = 0.19111 a nd r = 6.
~lutio~.-E~ua~ion ( .5 ) is u qua.d ratic equation inn which can be
ol ·edt gi c the phy icall_ meanmgful result

1
n = 2nJ rI+ (I + 4;,:n) ] - I (6.56 j

where

(6.57)

The limiting cases di sc~ssed above follow from Eq. (6.56) for
T
400 500 600
nc1 I Fi,~ » l and nr1 I R;.
11 « l , respectivel y. Inserting the values of
the material parameters and a ra nge of values of the temperature into
Fig. 6.5
Eq. (6.56). one obtains the dependence of non tempera ture shown in
nducu on electron concentrat ion n
Yer us tem pera ture T for n-Si . Fig. 6.5 for nr~ = 10 1n em - 3 .
It is of interest to obtain an expression for the Fermi energy for thesyst:m
?iscussed in Example 6.3. Substituting the result for 11 given by Eq. (6.:- 6)
mto Eq. (6.28) and solving for Er yields

Er = Ec- ksTlog{ ( rN;/2nt~)[ l + (1 + 4n,rj \',<'11 )1~ }. (6S

In the low-temperature limit. 11" 1N,':tl » 1. and EF i gi\ by

Er ~ Ec - *Ed+
- -
~ k 8 T log.... ( ?.r111y~ ,) •

The Fermi energy Sh 1·t .d . . I ,·tnLl th'-' l'tlll·


.. c s tn1 vvay between the 1mpu rll kv
d Ut.:tton band ccl oe . t T 0 . .. T 1tnW''
to · . .o a = and Ill It tally ris.:s ·t · TinL:r ~ 1 ' .\ ~ ' Lll
Increase. It IS n cc ." - . . l ·I dt,·f·
. 11 · · c s el i Y to take mto acco unt tht: I 1' g ·n ·r,t d 1
m,t y Ill the valence h· d . - I tll''n t
E .. - 1- . ctn tn order to properly rr·1L: · tl •JL rrh r1.. \ L L
- 1- a~ a unctio n or T. '
When holes· 'represent.
·t
th 1 th • 1•l t1
condition of el ectroneutrollt '..I ll. ...,
E trinsic semicondu tor 13
r ndndt' l!l\ cn h ~ l·. L l .... t(' -"'~·
'" anLI ( '' I I

/·., -
;--..
I r.,tl
-1..' i( I I L "l -j
I
( ,., + I\ ··h )t' f(l I '· • )
( A.n 1 J

11. Lquatit. n in. exp ( 1£ 1.· ) which c-111, b·~'" ,S<ll ,,d . · 11 -
" 11 urneJJc a y 1or
lllll'll ll .. , v1Lh tem perature is displayed in F ig. n.A r n-Si
7
1 lll:f!.!_ l•c::- ·ll.. , o ut ha lfwa y between the donor ~levcl ami th~
,tnd edge a t ' ry low k mpcratures and dror s to abo ut the Fig. 6.6
h' 'ncrgy gap at hi gh tempera tures !'o r which k\ I! .T > £"". l- enn i t: n··rg. [I VCI' US lcmpcr,LtUr<.: {
f< r n-Si .
l:ll n k ' tron co ncentrati on n is plotted versus iiW<.'Ts~' tem-
g. 6. 7. N t the clearly defined intrinsic. S<tturalion a nd
m peratu rc. The slopes of the curves in the intrin ·ic
n the . c: m.ilog plot provide values for £~ and £",

)r"'g 111g treatment is applicable to donor impurities in semi-


J"' such < • G s for which the conduction band minimum occurs
. he con ta nt energ: . urfaces are spherical. and r = 1. For those
case uch · ~ i. Ge, a nd 'aP in which the minimum occurs awav from
/.. - 0. th c n 'ta nt energv surfaces are ellipsoids of revolution. r > -1 , and
a m r general tr a tmcnt is required tha t includes the contribution of
~ cned hound . ta te. . Thj treatment is given in Section 6.2.5. 1/T

Fig.6.7
C nduction electron concentration 11
ve rsu- inverse temperatur~ 1/ T fl r
6.2.2 Accepto r impurities
n-Si .
Th treatm nt f acceptor impurities is straightforwa rd if the current car-
r1 r ar reg::trd d a holes. The major complication is the degeneracy of the
\ alene~ band at k = 0 a ociated w·ith the: light and heavy hole ba nd s. We
hall negle 1 \ · r ping eflt:cts and restrict o ur discussion to the case in which
the light and hea \ _ ho i bands a re spherical a nd parabolic.
We u e th .... ra nd canonica l ensemble a nd a procedure analogous to that
empl yed f, r d nor . Onl y those cases in whjch either no hole or one hole
r d n a n acce ptor impurity a re co nsidered. For ho les the energy
h in verted compared to electrons: Ep ____, - Ep, £1 _..... - £ , .
iliLy tha t an acceptor impurit y state ha s p, l light holes with
·pin up. p1 li ght ho les with spin do wn. p 11 f heavy holes with spin up. a nd
Ph h a y holes with spin down c-otn be written as

(6.62)

her Eu is Lh ~ energy of the accepto r impurit y state. The probability that a


I ~-
. ingle ho le i. localized on an acceptor atom is

P(O, 0. 0 . I ) P(O, 0. l , 0) -t P(O. L 0, 0) + P( 1. 0. 0, 0 ) ..


P,~~P~
( --_~O.~O~)~
+~P~(~O .~O~
.O~.~l)~~
P~(O~,(~
) .~l.~O~)~P~(Of.~l.ro~.u~
- )J+~P~(~l.noli,l)
).~O)
( 6.63)
Semiconductor statistics
. inl ) Eq. ( .63) yields
u

(6.64)

r. ana logou. to that u~ed for donors, we find that the


1
1 s i 1 the valence band IS

(6.65 )

when: lla I· t 1 ,_
~ ,~.~n··· ntrali n of acceptor impurities, Et = Ev + £0 and
vV ... • • • '

E,,
i the acceptor i n1zat1 n energy. In Section 6.1.3 It was shown
(Eq. (6.34)) that

p = i-v- ,,, + 1-v-d r)(:_~ d( E,. -EpJ ' (6.66)

when the light and heav hole bands are spherical and parabolic.
Eliminating Ev - EF from Eqs. (6.65) and (6.66) gives

p2 l -
- - = - (N d + N- ch)e - ' jF~u, (6.67)
na- p 4

which is analogous to Eq. (6.54) for donors. The same limiting cases can be
analyzed for acceptors as were done for donors .
Comment. The case of an acceptor impurity such as boron can be
analyzed in the following way (Guggenheim 1953 ). A neutral boron
atom has an unpaired electron in the 2p shell. If a second electron is
added to pair up with this 2p electron and one takes into account the
pair of 2s electrons, the boron ion thus formed has the electron
configuration necessary to form four tetrahedral bonds with four
nearest neighbors. The procedure used for donor in Section 6.2.1 can
be applied, but with emphasis on occupation num bers 11 == I and
n = 2 rather than n = 0 and n = I . For Group III accep tors. n === 0
corresponds to a state with the unpaired 2p el tron r mo\·ed. Thb
state has
_ <
an ene rgy so h1g1
' 1 that it can be neg! ct d. .
f ~sm_g the gr~nd canonical ensemble one can expre ~ th pwb•Ibiht}
0
mdmg a pa1r of 2p electrons (or no hole) n u rt n at m ~IS
e •~C2Er - L.")
I - pI ~ ~7fi:'----r~-"7.'::":::---- ( b.O~ )
4 e d(E, £, ) .:1(1£1 - £ 2 ) -

where E 1 'ind E 1,
.- ' ·~ are the enero-ies of th n = I • n '' == ~ :w ·
re, pect1vely £ " _ E b th •
dcnon11·11 . r ' . b~ , - . :._ - E, · and the fa t r of ~•rr •Jrs 111
erate St-11a' 0 .1 b ec·tus
c e" tl_1e acceptor grou nd ·tal~ i. lUI- 1· 1 IJ li ~-
''' n-
. l.:C <I OUnd n·l 11. 0 f ') ·p ,nd'
to· 1 1 . . . 1'' -rclectr n · n a bt n t 'mt:•Jff<.;' 1.. -
d 10 e that Is I o n ·· ·d . II 'Ill'
l'rec hole~ is tze mto the valence band. th 111 ·ntrJ
x trinsic s mrcon uctors

111 itic 1', d ' li ncJ h y Eq::-. (6 46) and (6 .64) ror don r. ·rnd
n ht! 'n llc n rn the ge ne ral fo rm

(6.70)

and - · ign~ refer to.donors and acceptors, re -pcctrvely


Jt:ger~eracy of tbL· 1mpunt y level. The corresponding
r t he ln.:c earn e r concentration is

n}
p = I + !::'e
I
(6. 71)

6 2.3 Compensated semiconductors


In J compensated semiconductor both donor and acceptor impurities are
pr e1H and distributed randomly. Electrons from the donors will transfer
to th .l~.:t:ept r- thu crea ting ionized donors and acceptors, even at
T = 0 K. Partial mpensa tion means that not all donors and acceptors are (£) (±) (±) (!) (±) (±) (±)
ionized at T = 0 . Ideal c mpcnsa tion means that all donors and accep-
t r: are ioniz d at T = 0 K. In this section we trea t an1Hype semicond uctor
uch .l n- i tl1'H i partially compensated by acceptor impurities.
'j e

Let the con enlra ti ons of donor and acceptor impurities be nr~ and na. G G G G 8 8 8
rep ctivel '.' i th nt~ > n" . We assume, for simplicity, that the impurities are
group I m nt for tbe donors and group III elements for the acceptors . Fig.6.8
t th t mp ratures of interest, k 8 T « Eg. all the acceptor levels are Sl:hematic representation of eh:..:tron
o upied b lectrons transferred from donor impurities as indicated in the transfer from donor to a(ccptor
impurities.
i· gram f Fig. 6.8. Th co ncentra tion of neutral donors is given by n3
17~ = lld - lla - II. (6.72)

where n i th o ncentration of electrons thermally excited to the conduc-


ti n b nd.
F IIO\\ ing the analysis based on the grand canonical ensemble gi~ren in
S ti n .2.1. we can write the fraction of donor levels that are occupied by
le tr ns as

(6.73)
le
1 .
1itf- E,.J

The nergy difference Ec - Er can be eliminated using Eq. (6.28) and the
res ult ·impliti.ed with the aid of Eq. (6.57) to give
_ 1 N ell
. _ •iF.··· = I
l + -rN <e + -c- . (6.74)
2n 11
. ductor statistics
Sem• con
n I rearranging yields
111gE
n(n + lla ) _ N''ff
-J. ( '
(6.75)
II - fl o - II

compensation b)

II- 1' (6.76)


1 + n,,,l + [( I - ~
N '"
) 2 + 4 ..!:L]
11 N" 12
'
\ ·here 11 1 g1v n bJ Eq. (6.- ).
E. ample6.4: Conducti n el ctron concentration with compensation
present
Dcri ·pr 1 n for n with 1111 >> nu i- 0 and ksT « Et~ or
kBT » Ed·
Solution. ln the ver low-temperature limit, 11 is much less than 1111 and
can be neglected compared to the latter. We then obtain directly from
Eq. (6.75) the result

(6.77)

which shows clearly that n decreases as lla increases. In the high-


temperature limit with both n 0 and nd very small compared to""'
Eq. (6.76) can be expanded in Taylor series to give
(6.78)

corresponding to all noncompensated donors being ionized.


The Fermi energy can be calculated by eliminating 11 from
~qs. (6.28) and (6.76) and solving for Er. The res ult is a straight-
torward generalization of Eq. (6.58).

6.2.4 Majority and minority carriers

In previous sections we have seen that electroni tran ttil)ns frorn th


valence
. band to tile cond uction · band mmtnns1c
. . _ . mat n;.tl [ ~a d toe lcctrl,n
111 the conduct"
~ , ,· . ton b'ctn d and holes 111. the valence band. ur hernJOil_. ·· th'-'
t:xcttatJOnofdonor . ·
nnpunttes· · 111
· n-tvpc material and .tL'l: pt r tmpu
· ri ll ·' 111.
p-type
..
matenal.
le-~ds t -. . c1

· ·
o con uctton electron:; aml .tkm:c we~.
1 1 · r~ P~-,
lively. Our dtscu · .1 . . . t· rtlll
. . h ston the L~oncentratJOns of fr ~.: ~:arnl:L' 1!1 t h~ 1,tt . .
°
c.tses. owevcr did '10 t d trJtl J!l'
or ho 1es. 111
- '
n-type nnt .· 1
evclop explicit c:xpressit n h 1 Lh~: ~nnl' 11 .
ri _, lt\•rll
int~.:rb·lnd . . < etta and electrons in p-t Ypl: m:.tkn:d th 11 1 ·
L excttatton We .• . ..:
,
· nnw reme-dy lh1s d ltl: H:IK)

624 1
· · · n-type material
<·onsiJer -
.t '->Cmh.:oncluct 1. . I
-
~..:nergy E . °\\·ll 1 d o nor con · ·n LJ au n
-o/ , .LnL1 no cc nrp . .. __ .
L11S.illlt g "ICL\."[1{ t)r 111lf1Urtll
Extn tc s miconductor 117
I l h~.: \ :1"1 tl it n l th~ llll J1U rit \ cl ·tn •n" :1 1 •
<1Jl 1l
'l1k t s
.tnd I 1c \;tl ·n ·._ I a nd i" 1.'. ssc nt i<tll y c "1111ph.: tc ly
lllo..nn " ill then h ' .;;i tuatcd hct\Wcn tlw dnncH c ncrg · lev:,
II llll l I tho.: l'lllh.ludi ~l n h :tn 1 Er as "P ~clfi ·d hy •q ((, 5LJ).
Ill.::_! t ·mpc n turc thl· dnnGr impurities [1f"OQressi\l:lv inn i/'
r~ :lr p · a nd C\· cntu ~ill~ l'a lls hc k \v the clnnnr cnct:l! . , , ,.,1
"scn tta ll) all dnth)r impurities arc i<..l ll i7cd. and the con-
nn luc t t(l ll clcctr~.,llls is equal to the .;a turati o..l n range va lue :

( 6 .7l))

r l llCt ~Le in th ~ _lcmpcra turc. th e rm;il excitatio n of carriers


p hcc m e smn1l11.:ant and lead ~ t the 11roductit'~ . n o l. llo l". ·
es 111
d
111 .

l)f1 CC I1 ra ti 11 fJ is given by th e Ja w of mass action nn = 11 2


/' I •

arner concentratto n a t the temperat ure of interest.


q. (6.50) that Eq. (6.79l remains a verv
• J

,
1r
p =_!..._ . (6.( 0)
lid

F 1 at ro m tc:: mpera ture the intrinsic carrier concentrati on n, i


I: • J0 "cm ' . Jl the concentration of donors nd is I0 16 cm - 3, the hole
1

c n c:ntrati n f1 a t r om temperature is 2.2 " 104 cm- 3 which is ver, mall


c Jmp;tr d to b th lid a nd ll j . For this reaso n, the conduction electrons in an
n-type material ar ·ailed the majority carriers ami. the holes are called the
minority carriers. Jn the sat uration range the conducti vity of n-type material
depend~ nly o n the do no r impurity concentra ti on; the minority holes give
J negligible ntri bution to the conductivity.

6.2.4.2 p-tJpr material


If' the ·emi nductor is doped only with acceptor impurities, the con-
du ti,it i p-t pe, a nd there are no compensating donor impurities:
" " = 0. Jn th aturation range.
(6.<' I )

· th tem p ra t ure inc reases, interba nd excit·ttion of conduction electrons £


an h I in reases .
Pr edin g as in the case of n-type ma terial. \VC find under typica l con-.
diti<. n that the conducti n electron concentration is much less than that ot Fig.6.9
th hole ·. Consequently, in a p-type material. the majority carriers are holes Density-of-st~II C'~.. Fermi distrihutiLlll.
anJ freL· carria cnnccntratll)l1 \ dStb
'llh..l the minority carriers are conduction electrons. , . cnc:;rgy fl11· n- :.111d r-t~ pe ma t · ti ~ I.
fn - ig. 6.9 arc presented schematic representa ti on~ ot the~ denstt y-of-.
tat ' · Fermi di -rribution, and free ca rrier concentratt ons as JunctiOns of
en m~ fo r n-and p-type semiconductors.

6.2.5 Contribution of excited impurity states


As i cu~ t d in C hapter 5, the donor ground state in Si is six~l.-old degen-
. · · · .l.tl1e~ de"Ciler·tcv
c r~Jte \\ Ithm eftect tve mass theory t c. • J
due to spm
-
1s ne!!lected .

Semiconductor statistics
. .. ,d \\ ith each of the ix conduction band mini
f• , I 'I t.;l<l 1.: • . h d flla.
, • II , orhit 111 t ractt n sp 11ts t e cgeneracy to pr due .
1
r11.: ' •
1 ·lunnol h: .t ~.:\ . - · ~ · "d , . . d· d ei.l
n tate. i.l tnplet T 2 exute st<tt.e. an ~ .oublet £ excit d
·pltlllng is ~ 10 mcV a~d .the 12- £ sphttmg is"' 1 meY. Ir
u~.;h that the sphttmgs are comparable to k T
( ~HI t hem di fied to in~l~de the c~ntributions of~h~
Ul 11 nnore there are addttlonal exctted bound states
i 1 ~ ~ 2 • J.,, ... leveL. These levels are typically sufficientlv
d 1s 'tHH l eLi ,.1 bttnd edge that they can be neglected if r~d 1 « i. l<
In JC th our·fold degeneracy f ~h~ donor. gro~nd sta~e m effective
mas. theory i split by the valley-o~·b1t t~terac~IO~ mto a smglet ground
·t al and a triplet ~:x ited :tate. C n 1derallons s~mtlar to those for Si apply
abo to the contnbution r excited donor states m Ge.
The grand c·.u1 nical n embl enables one to account for the occupancy
f excited state ry ea ily. lf the system has impurity levels of energies
E,k, Eu ... . and oc upati n numbers n"' n p, .. . the probability of the
c urrencc of thi tat in a n ensemble of members containing all different
p ible occupation numbers may be written as (Tolman 1938)

(6.82}

where degenerate level are not accounted for explicitly and we are
focusing on donor impurities. Let us now assume that an impurity ion can
trap only one carrier. Since the values of nk , 11£, . .. are restricted to 0 or I. the
occupation numbers must satisfy one or the other of the constraints
... = 0 (6.83a)

(6.83bl

In the latter case one of the occupation number s is unity and all the others
are zero. The occupation number that is unit y can be any one of them.
however. .The normalized probability that one impurity level is occupied
can be wntten as

(6.84)

where

( ..S5 l
IIJ.., Il , ..

and the .cons•·t1·a· · d ·


< Ill 1 state In Eq. (6 R1b)
lf ar1 · ... - app I1.es•
nnpuntv level 1·5· d . ·· f" 1 wr
~ . each of th "' . · egene ra te With energy £ 1, .md dL·gen r~t ') · ~
·the
- ' v· l, ·ese. deuenen o
t•I I . .
c e eve swtllha vett ' ui.:·u p.tll "lnn unl
h ·tk , l'n
r l, ,
c1 ue unny 111 tu. tl . . . .
n, HI gl vmg nse to g,, i<.kn i ,d ll.: rm 111 th _wn .
1
Takinu into ., .
o « count the deg . . . . p 11 tl 1t~
alternativ furm encutCies ul ·til k\ b.' ·L ~,.· 11 · pre ..

I • I
References 11 9

I - I" ( I - pI ) = - ---==---'-'•_
1
-.,.,---
I + <r ./ ' i(/ - r id .
~, .., ,,
I

,.ith - q. (6.2X) gi,es a rclatinn that det~.:rmin c3 tht:

r /\r
1
L' it £ 1 - 1:, ) = -=-----===---'-1._1--:---c-- (6.88 )
,.,.....er ,l! ! ( f, I - C,.) ·
I olu ti n or Eq. (6.8R) yields the Fermi energy as a functi o n
ture. Th lectron cone ntration can then be calculated from
or \lari u ~ tempentures. Electrons thermally excited from the
...tnd can b acL·ounted ror as in Eq. (6.61 ). Th~ case of acceptor
im ntl can h h ndled in similar fashion.

Prob ems
1. akuhttl.: the onc ~ ntrati0n of conduction electrons and holes in intrin ic Si at
3 lO • m the approx imation of spherical. parabolic valence ha nds. The values
of the required a ramercrs are: Eg = 1.14eV. r = 6, m; = 0.92m, m; = 0.19m,
m 1 = O. lflm. m"" = 0. 2m.
on. id r a am ple of Si doped with As to a concentration " d = 10 17 cm - 3
(a ) Calculate the nLentration of electrons occupying impurity levels at 300 K.
(h) DeduLe th co n entrations of both electrons in the conduction band and
hole in th \'alence band at that temperature.
( ) Oedu tb value of the Fermi energy.
The \'alue of tht: impurity ionization energy £" i · 0.03 cV.
3. For the a f donor impurities find explicit expressions for EF in the two

Ia) ( '!!,)e£, ks T « I (\veak doping)


rV
'
b ( ~~~) E., ' ks T » 1 (low temperature).
r.\'c
4. n. ider n-G e with As impurities and singlet A 1 ground state and tripl.et T1
· g1vcn
exciled sta te ionization energ1es · · T a bl e ).
m ~ I F
. o.r lltJ ---:- 10 em.. - " .',
10
·md
neglectitH! higher bound ·rates. calculate EF as a funct1on of tempel:ttu~e T
ov r th range 0 _ T _ 150 K and plol EF versus T. Calculate II as a lunLIJon
r T nd plot 11 versu T.

References
-· . Gugoenheim . Proc. Phrs . Soc . Lone/. A66, 121 (1~ 53 l· . ·k l95t<).
P. T. Lande berg. Senutonductors
. ·
one1PI10.1p, 11 ~)r.~(lnterscJence
. · · NewYo1,
S. Tei tler and R . F . Wallis, J. Phys. Chen/. So/uls .16. 71 ( 1960 >· . . . 1 Press.
R. . Tolman, Pnnnples . . oj . .s·lafi.\IU
.. ..aI M'l c·haii/CS (Oxford 111VCIS11)
r rd . 193 ).
• •
t1on tn
du t rs

Phonons
t r ''IIi!' llfJfJT'O YiiiWfinn the equatiOnS of llll)tion are linear in the 7.1 Equations of motion
I 'Lllk nt L 111 0 111:?111~ Of the atoms.
11 '' 'lc>d£'.fi·equ211 ·ies of a monatomic linear chain arc confined to 7.2 Monatomic linear chain
nd b,t,,·cn z rn and a maximum frequcncv.
mwl m d ~frequencies oLt diatomic linear ~!win lie in the acoustic 7.3 Diatomic linear chain
m h ( "II" the oprical hronch \l.'ith a gap between the branches.
111lil7llllll lh •or.I provides a simple treatment or long-wavelength 7.4 Three-dimensional crystals
1!' ' i h r:.nion.
11 n di ,pcn i 11 curres are determined by ineluslic newron sca11eri11g. 7.5 lattice dynamical models

h rl ra ng interactions are insufficient to account for the experimental


lla. Th deformability of the electron charge distribution is taken into
• LL{ unt b~ th _h ell model and the hone/ charge mndel. The partial ionic
chara t r of the electron-pair bonds and the effective charge of the
atom i · tah n into account by the def(mnatinn dipo/(> model. The linear
rt'. ponsc! II IC'Ihod provides full phonon dispersion curves without fitting
par:.1m t rs to experimental curves.
In '\ nornwl m odc o( vibratiun all atoms vibrate with the same frequency. 7.6 Normal coordinate transformation

Tht.: \lbrati nal specific heat obeys the Dehye T 3 -hm at low temperatures 7.7 Vibrational specific heat

a nd th Dulong Petit lmr at higher temperatures.


nham1 me effects arc responsible for rhernwlt.!xpansion and di{fit. il'e 7.8 Anharmonic effects

thermal conductiritr.
7.9 Impurity effects on lattice vibrations
lmpuriti ::; and other defects can give rise to /ocali::.ed modt!s.
7.1 0 Piezoelectric effects
Pic:oelecrricitr can increase the elastic moduli and the speed of sound .
7.11Effects of stress-induced atomic
Appl i d . "!I· s.,·can cause shifts and split tings of electronic and vibrational
displacements
en rg) kvels .

. n imp rta nt ~oun.::e of deviation s from period icit .. in a crystal i.s the dis-
pia ·eme nt of an atvm from it s equilibrium position. These dt>\'tatton anse
nat rail fr m the thermal energy of the atoms. If the crystal i in a stabk
n lgu ra ti n. the displ<tcem~nt or an all Ill leads to •t rorce tl~at tend s to
re t re th a t mtl) its equilibrium position. However. the ktnettc energ) ol
the at 111 cau ::, ~ it to OVLrshoot the latter. As a res ult the atom \'Jhrates
l attice vibrations in semiconductors
2
. . .b . osition. The forces of interaction between atoms
about tt equt 1I n u 111 11 . . . I . 'b
. · 'b r Gt iu ns together. g1vtng nse to att1ce v1 rations.
couple the a tomtc VI L

7.1 Equations of motion


A de el pcd in the Bo rn- Oppenheimer appr?ximation. discussed in
Chapter 2 the potentia l energ~' for the nuclear ~otwn, ~( R) : ts g_Iven by ~he
' ttm o f the el~ tr n ic e ne rg tgenvalue, E.: (R ), an? the JOn- Ion mteract100
r ,R) At moder ate temperatures for which· the nuclear
e ne rgy. , \ · · displace-
ments ar mall. we can expand the nuclear potentia 1 energy m powers of
their dtsplacem nl com po nents uo ( ft;:).

tf.>( R ) = rl>o +L 1>0( €h:)t-1u(tK) +~L L 1>,:~ ,3( fn-; e' 1


tl- )
Lt>l'l - l·,;o l'tc.' ii

X u~, \'Pt;: ) liJ ( tn' t;:') + ""'""'


L L ""'
L ;r,
'l'n;h u ;,.., {_t'' t;: t., tull K. II ·)
("

f no f'ti'.t3 (" ;.-;"--(

(7.1)

where
II= R- R (O) (7.2)

and the superscript zero denotes the equilibrium value. The terms up to and
including the quadratic terms are the harmonic terms, while those terms of
higher order than quadratic are anharmonic. Since the right hand side of
Eq. (7.1) is a Taylor series, the coefficients have the interpretation

;r,.
'l'o d
(
Ln-;f..I K.)

=
Ul/0 (
a ) 'V
;r,.

(!..;, )Du,,( t' r~.' ) u=O


I .

3
;r,. 1 -.' (n
'*'o t £" ")
.tK.; f.' t;:; K = ,. ..
oun (£,.,_,)au 3 (f'"''
CI <P .
)EJu_· (f"
, I . (7.3)
. . h·"_
J· u=O

From the symmetry of partial derivatives. we have the rela ti n

if>o.,'J(£1'\,:J!'K.') = <l> Jo(f'l..:':~r~.. ) (7A)

~it,h similar relations for if>n 1h (LH:l'r.-'; f"h·") obtained b y p m lU ting l HO.
f! K {J, and £" K. 11f.
T~e solution of the Schrodinger equation for the n u I~I . Eq. (2.4). is
facthtated by solving the classical problem o f them tion fth nu ·I i. The
classtcal equations of motion are given hy a set fequa!ll. n L r, hn:h thl'se
for nucleus e,.,_, are

with o: = \. v - R , · -..
· ' · · - · estnctmg ou rsel es tn the har ll)fil ~ ll.:ml t ( ll
we eva luate the right h •·llld sic!·~~ l,>t. q . 1' 7 .:>- ) : till l l h t.tln
.

H D~ u .. (lj" )
I I i) { -' =
- •I\ ' ' ( f'•·
n
) -
Equations of motion 12

(f',,') ;lrl: I'Cr ' · St' lha1 all atom" <If· 111
Jtltlp1 llll' llS.t h c r ' L anhclhlr~)r · ·;JCtingnnan y; 1 tnm ; h~n c

( 7.7)

11hcrm r . if all atoms arc chsplaccd rigidly according to


/( j f' h'' ) = ( (~ 1 •
(7 .8 )

n"tanL. n relative motiun of the atoms occur, and no


: hen e,

L
I' .I J
4>,..] t 1-1· ·'1-1') -() 1 = o

L
,.,.,,
<D 0 -1 (th·: ft' 11-' ) = 0. (7.9)

E u U 1 7. ) tat s the condition of infinitesimal translational invoriance


that m.t he ati fied by the force constants <ll ( r;,; f.'t,'). From this con-
ditio! and repla ing by J , \Ve obtain the alternative form

c1>, J ": P"") =- L '<I>~, ( f K; e'"''), (7.1 0)


(' ti'

wh re the prime n the sum denotes that the term with f.' K' = f.l\. is omitted .
e no\\ rewrite the equations of motion in two forms that will prove to
e u ful. in_ Eq. 7.7). Eq. (7.6) becomes

3-u(.J th'.) "" 1 1 f)/


10 = - L 8( .K.; f. l'i, )u:J (t:
I
(J(l <1> 0 1\. ) . (7.11)
l ' K'.j

Eliminating <I> ,J 1\ ; 1\.) from the latter equation with the aid of Eq. (7.10)
]i ld

(7.12)

B th f rms of the equations of motion just obtained are linear homo-


gen o u difrerential-difference equations. This suggests that we seek plane
wav ol Jtions of the form
I
- 2 f11 ( . ) i (q R ( )- .,;t] (7.13)
11 11 ( Pt,:: q, I ) = M ,., '" n h (' ,

in which W ,., ) is a measure of the amplitude of the wave, q is the w~ve


vector, and u. is the angular frequency. Substitution of this trial solutiOn
into Eq. (7 .12) gives the linear. homogeneous algebraic equations

L [D A"-"-'; q) - w 2 6~.1~6ti"' J WJ( n') = 0,


(7 .14)
K' .J
. . miconductors
lattice vibrattons m se
2
\\here

. f h~ dynamical matrix for the crystal. If we impose periodic


ts an dem(:nl L L c · · 1 h 1
· , d.t 1ons 011 th..: , t m1c cltsp acements. t eva ues of the wave
hl undar ' t.:On l ~ , · d - · ··
. 1 )with/\ ~ q. Un e1 penod1c1ty. theforce
·ctor q < n~ "Pt'l 111 cd hyEq · ( - -- . . - ·
1.: ·' II - (';;')de( ~n d nly on the dlllerence t =
c1.Hl tants ~l,, > n.. · E ·
e-
f' and not on
' . .. tel'·' n~cq uen tl y. we can rewnte q. (7.15) With the aid
{ an d { " P<1J,1 -' · ·
of Eq. ( J.l) as

'
D.,~( Hh;q
\L
= ( M ".-k f ".-·)- 2 - .
c;p,~ . J (On~;ftl..')e'q
R
(I_ (7.16)

The 11 m tri i. 1solution of Eq ·. ( 7.14) requires that the determinant oft he


en !ficients of the amplitudes W -J( tt') be zero:

(7.17)

This is the secular equation. If the crystal is three-dimensional and has


r atoms per primitive unit celL the dynamical matrix has dimensions
3r x 3r, and the secular equation has 3r ei!.!envalues for u.r~ for each value of
q. These eigenvalues are distinguished by the branch indexj. For a stable
crystal the eigenvalues must be non-nega tive. The sq uare roots of the
eigenvalues are the frcq uencies of the normal modes of vibration of the
crystal and are design a ted by v..1qj. They are conventionally taken to be non-
negative. A plot of w qi versus q constitutes a phonon dispersion curve. After
the normal mode frequencies are calculated. they may be substituted into
Eq. (7.14) and the corresponding amplitudes ~V (t/ : qj ) determined. The
latter are the eigenvectors of the dynamical matrix.
T_he eigenvectors can be chosen to be orthonormal. A particularly con-
veme_nt choice is designated by e 08 (qj ). for \-Vhich the orrhonormality
cond1t10n tak s the form

L e,.Jqj )en,. (qj' ) = IJ/ .

The property of closure is also sa ti sfied :

( _[ ll
M o natomic linear chain 12

c;tfc ranch . 1 h(' nt hn l\.\ ' hran (' hc'> ha 'l: their atl)mi c di-;-
l['l'lld t •tllar I l l q an I :trL· ·ailed transver e acoustic branches.
I ru11.. lks L<lll he l'lh':-. n ::-;ud'l that the di splaccm ·nts nfthc
'l111.1l ll I h i ~l: I r the oth r. In similar ra
•hton the nnrmal
'J'Itc.tl h r~ltll:h · l·an he classiticd a · lo ncitudinal or tr;:Jns-
l 'I 111 a htgh -symm e t r~ direction . the hrat~·hc~ have a mix~d
t 111'\CI''i • ·haraL·ter.
cmtc nd ULI 0r ()r the diamond or zinc-blcnJc st ructurc
ms pt:r unit II. There are six pho no n branches of which
"11 ·al 'vYith tw o transvc r a nd one longitudinal and three
th l\\ Iran. , erse and one lou!litudinal.

1. onatomic linear chain


llu trat th g neral procedures 2iven in the preceding sections by
1111 k exampl -. Th first case th a t we consider is the monatomic a 1- t 1+1
J nL r h in\\ ith n ar t neighbor interactions. We assume only one atom
Fig. 7.1
pt:T 1rimlll\e unit ell. Both the,.,. index and the o index can he suppressed. Diagram or monatomic linear chain" it h
A dt't=ram nf t h., · ~ t m i · shovd1 in Fig. 7 . l . Referring to the equations of nt~are~ t neighbor interactions.

m 1tion giH~n b E q . 7.11 ). with nearest neighbor interactions only, the


nonzero force o n ta nt. are <I? ( , I ), <I> ( C. C) , and <I> (£, 1 - I ). From
Elj.(7A)an thc p ri dicityofth chain,(P (f, C l )and<P (C. £- l ) mustbe
1ual and have th ·a me value for all . If u( e+ 1) > u( ), we see from
Eq C' 11) that th fo rce constant <I> ( €. I) must be negative in order to
ha\'e the f r na t 111 ' act in the direction of increasing as it should from e,
ph~ -j al con id ration . Setting

<1?{t, , + I = <I>( , f - l) = - a , ( 7.20)

v.eobtain from Eq. (7.10)

<I>( P,f) = 2a. (7 .21)

' io2 the res ults the equations of motion become

/vf
a,- u,.('') = a [u(f+ I )+ u(f - 1) - 2u( )]. (7.22)
fJt-

The elements or the dynamical matrix specified by Eq. (7 .16) are given by

D(q) = -l2a-
I iqu
ae - ae
- icta ]
.M

=~
?a
(I - cos qa )
M
= 4a . " / 2) ,
- sm-(qa
(7.23)
M
. . miconductors
lattice vibrations '" se
t The secular equation. Eq. (7.17), yields the
"here u IS thL la!tice ct:I st an .
normal mode f req ue CIC ~
I

wq = (~) \ in(qa/ 2) . (7.24)

. w·Ive vect r q specified hy the periodic boundarv


a1ut: o r lh ~ < .
= lf = 27fn/ Na. where N ts the number of atom
ThL · • -
. ,
t:ond I 10!1!1 lv, +I) u(i ) are ,_ · .
. l1 c ham
m 1 · .rn d 11 1·s, an integer. I be vectors of. the rec1procallatttce
. G are
.
gtVt:11
b G_
] - -'' 11
1.,.. /[,t· For the case under consideratiOn, Eq. (7.13) for the
displacement reduces t

. ) _ l .f -
U,f (f . { - II
t r;rr i ( qal - c.v•l )
- ~·r e . (7.25 )

If we augment q by a r ciprocallattice vector G. we obtain

''· f ') -_ t~-~


u,1+G ( r, VJ
- ~- rr
r.veif' (q~)af-...:1]
·
1/ 2
4 (j
' J'vl
= 11(/f; t ). (7.26)
n.
0.6 Thus, the physically distinct sets of displacements corresponding to the
0-+ normal modes of vibra tio n can be restricted to values of q in the first
Brillouin zone. There are therefore N normal modes corresponding to the :V
0~------~------+----­ values of q in the first Brillouin zone. One can have longitudinal modes with
- rr / a 0 rrla q
the u( f) parallel to the chain axis or transverse modes \.vith the u([) per-
-+- First Brillouin z.one -1
pendicular to the axis. The force constants for these two cases would in
Fig. 7.2 general be different.
orm, I mode fn.:4ucno.:ic~ vcn.us wave A plot of the normal mode frequencies versus q is shown in Fig. 7.2. Forq
vector for a monatomic linea r chai.n.
small, w,1 increases linearly with q. At larger q, w,1 increases more slowly and
reaches its maximum value at the Brillouin zone boundary. The normal
mode at the zone boundary has atomic displacements that alternate in sign
moving along the chain, but have the same magnitude.

7.3 Diatomic linear chain


No real semiconductor has only one atom per primitive un.it cell. Since
group IV semiconductors as well as 111--V semicondu tors ha\ l\\ L) awm~
Mt M, 1- a - -\ ~er primitive celL one can get a qualitative picture of tho>ir n mn l ,·ibra-
-oJ'\N~W~
(J 2/- 1 21 2/+1 tronal modes by considering linear chains , ith eith r 1 t rn;.lll ng t'on:c
consta~ts or alternating atomic masses. We shall di · us th httt r "'xphL·itl:
Fig. 7.3 and reter the form er to a problem.
I 1 gram ol d1at mic linear chain wit h
altern ating rna ..: .11 1 •md A4" and
onsider the diatomic linear chain, ith alt rn:.tttn ~ m.t . e \/, .wJ \/~
1 ea rt~l n cig hh,lr interact io ns. and nearest neighbor interacti ons as shown in Fi~. ./\ ~ .1 lllll · pt'nl JJ .
bound a rv condr· tr'or1s ··t 1 ·
, J
· ~
• wr 1 ' umt LTlls in the p riod Thl n Hl fl e
1·n1 ·nl
ol the Ioree con ·t· t

. .
s <~n matnx are ol the fllllnwin g f nn:
•T>U. 1: e. ~ ) = •I>U' l· t 1 , ) , h · ..,
' . - ·- = '+'(f , _ ;f 1. 1

<(l ({ , I : I. I) = •1• I. 2; ,
Dia tomi li near cham
127

I 11( / - I. 2) - 2u({_ l )j ( 7 ::!Xa)


,·1· u(i. 2 )
11, ,)1 :: - a [u( l -1 l. 2) + 11({, 1)-2u (l , 2)j.
( 7.2Hb)

f ll1c J) namiGd matrix are

(ll:q) = i\fj" 1
(2!T) . IY2 _;q ) = M ;- 1 (2a)
(7.29a )

(7.29b)

(7.29c)
ht . UJ on ub'tituti 11 int Eq. (7.17) give the secular equation
I 2(T l a
( I +e- 'qa)
I - - uF
J/1 I

1I -
(A1 1 llh_ )'S
(T
2a = 0. (7.30)
I (I + e lqu - . -u.r
1

(Jf, j\12r= 'h

EYaluating the de t m1inant and olving the resulting quadratic equation in


2
ield
....· )

M, 2] I}
'' ( 1-a )',.~
qa 2
MJ
I ~ 4 . , : _lv/~
- I ± [(- I - - Slll~-
Af:_ .~1 1 M1
: (2a)
112

'.M,

I 4i\1 .· 2
[ - M J lA1
2

sm 1..:...
qal ~} ' ( 7.31)
'

l 2
At:oustic
branch
0+-------------~r--
wher 1 i · th r duced mass of the two types of atoms: 0 !!.. q
a
I I I
-=-= - +-. (7.32) Fig. 7.4
/t4 M, M1 Nr>nnal mode frequencies versus wave
vector for a diatomic linear chain.
n islent with the fact that there are two atoms in the primitive unit celL
th re are two branches in the lattice vibration spectrum corresponding to
th plus and minus signs in Eq . (7.31 ). The branch with the minus sign is the Table 7.1 Normal mode frequencies fl)f
acoustic branch labeled byj = I, while the branch with the plus sign is the the di·Homic linear chain a t two values
optical branch labeled by j = 2. The normal mode frequencies ;.Uql and wq2 of the wave vector q
ar the appropriate square roots of the right hand side of Eq. (7.31). They q "-'q l wq~

ar pi tted as functions of q in Fig. 7.4. I

It i · worth while to work out explicit results for certain limiting cases,
namely. q = 0 a nd q = n/a (Brillouin zone boundary). The normal mode
0 0
c~~r
(~~)!
t

frequ n ies are easily evaluated from Eq. (7.31) and are listed in Table 7.1
for th ,",.1 1 > Ah,.
7T

(J C"Y
Ali
.
L t1ce
"b
I ro
t"tons in semiconductors
12 · d. f the atomic displacements for these
tl e. mplllu e o b . .I
1 , ,Jfllll r 1 ai : d Jrl'( 1) and W (2) may be o tatneu from
. , lhc.tmpl1 1Ut:s ·
IJnut n · · .
q 7.14 hi h LIke th form

t! - iqa ) vV (2) = 0 (7.33a j

a I I +e''' ')W( I + (~ -w") W (2) ~ 0 (7.33b )


(M1 1-;.) 2
· B bstitutin 0o the appropriate values of the normal
f r theca eofmtt=r l. Y u . · h
mod fr q uen le· ·mt o et'ther of t hese equati o ns, o ne can d e. te rmme t he
· · b . . W( l ) -111 d W (7) fo r the wave vectors ofmterest. T e
relatwnsh1p etw en " - . . . . . d ( 7
·.
amplitudes - ( 1) an d (2) ofthe physical displacements u(fi 1) dn u f-)
are related to W( l) and W(2) by
I I
- -:;
2
U( l ) = M ~ W(l ) . (2) = IV1 2 ""W(2). (7.34 )

as can be seen from Eq . (7.13). .


To illustrate this procedure, let us consider the acoustic branch for £f = 0.
Then w = 0, and Eq. (7.33a) or Eq. (7 .33b) yields

I I
M~2 W( I ) = .M ~ 1 W(2) .

Eliminating W( I) and JY(2 ) with the aid of Eq. ( 7.34), we obtain

U(l) = U(2) ( 7. 35)

which corresponds to a rigid tra nsla tion of the crvstal. The th r limi ting
cases can be worked out in similar fa shion . The . results ~1re p re-enl d in
Table7.2forthecaseM 1 > M 2 . Wesee thatfortheoptical bra n h l tq= O.
the two atoms in the unit cell move in opposite directi o ns. r th a' ustic
branch at the Brillouin zone boundary. only the atoms o f th hea"i~. r mass
move. whereas for the optical branch. only the a to ms of the light r ma ·s
move.

Exa~ple 7.1: Vibrations of a sq uare lattice


Denve an CXj)ress· .. h
. . ' Ion tOr t e no rmal mode freq uenci _ l)f .1 m 1 na-
tomic simple sc1uare I· tt·· · . . . .
• • · c1 Ice wn 11 nea re. t nerghbor 1rHerm t1 t
Solution. The Ia 1tice is . . d ~ · ·ch
I assume to ha ve lattict:· c on !anl l \\I
t 1e :.:It oms labeled bv in1 ~o , .. 1! " • • • 1 '
.} cocrs r. 111. fhe equatll)IIS t::lt m 11 '11 1.1
Three-dime nsional crystals 129

tT II, l,m t- u, l ,m- 2u, ,IJI) + r(u,_,, , I ··l lit,"' I - 2u,,)


- ,T 7',,, I / '' ,, 1 - ..."l l'1m ) t- r ( r, 1 1'\ Ill ,, I• 111 ) I ' 1111 )
-- L.. •

h1.. 1: II. I' ~liT the \._1' L'Oll1pL)Jll'llt.


. Of l.hsphceJll'-' 111 i\1 . tl
• '- . .
IS lC atomiC
m ..,_._ 1~ !hi.' central lm~ce constant. and r is the noncentral force
• n..,t 1111. Slllcc t~1c equat1ons of motion arc uncoupled . we can take
. '!utll n ~~ r the tnrm

t'i m = U

Jnd

ll t /11 = 0

The equations of motion for the u-displacements yield normal mode


fr q uencies specified by

w
..: -_ 4a
-
[sm
. 2 - (qxa) + -sm-
r . , ((/ra)
- -- J
M 2 a 2 '

while tho ' e for the ·-displacements yield

u.J 2 =4r
- [sm
. 2 - . ., - . , (q- ·-a)] .
(q.ra) - -cr sm- 1

/11 L.. T 2

The wave vector components q_\· q,. lie in the ranae - rr/ 1 to + rr/ a. For
waves propagating in the x-direction, the u-displacement modes are
longitudinal and the v-displacement mod es are tran ve rse. For pro-
pagation in the y-dircction. the assignments are reversed. The model
treated in this example is the Rosenstock- Newell model (Rosenstock
and Ne\vell 19 53).

7.4 Three-dimensional crystals


7.4.1 Elastic continuum theory
Since real semiconductors are three-dimen iona l ·tncl ha ·e at l , t t\ o
atoms per primitive unit celL the sec ular equation th at must he
determine the normal mode freq uencies. - q . (7.17). in vo lv s a et rmi na nt
that i at least 6 X 6 in size. Anal yti c solution of thi -qu a t ion a rc r < . i "l!C
on ly in special cases. so one must use a mpuler r r th 'C n ral ca . h
~itua tion is further complicated by the fa ctthar th in t c r~llom i c intera tic n
are long range, even in homopolar ,·ernicunductor. such as Si and
(Herman 1959). In heteropolar semiconductors ~uch as a A . th Mom
are electrica lly charged ions for which the lon g range Co ulomb int r tl on
must be taken in to account.
. m"•conductors
v"br tio '"
ca e -01. \: ' lll' ch considerable
. .
progress can he made
.
da tic l:On tin uum bm1t where the wavelength of
· h . rger th· n the lattice constant. For a cubic
e m ul: 1a 0 h
th fo rm jq ja << I.
n
·I • • , k ne can t en expand
hi~ c ndlh n t.l e~ .
, ,..· m p wers "f Ra{b) :

~ lln( f,.;) + L
aun(P~)
"·) e +b. K) RJ(o) 0Xi1
!-I

1 . 8 2 u,. (tn.)
+ - ~R(o) R(b) ?- o + .. ·. (7.36)
2~J G ~ ~ X~
· "f

.t t ' . g this e, pa sion into the equations of motion. Eq. (7.12), and
SU b t IUI I1 · f · f
· · tenn s through
retammg . e ond order ' we obtain the equa tlons o motiOn o
elasticity theory

P
a2u(r)
ot2 =
a·u(r)
Ctl i..7x2 + (Ct 2 + C44)
(8oxoy
v(r) 8w(r))
2

+ oxo:
2

8 2 u(r) D2u(r)) (7.37)


+ c44 ( a· J' ,· + az-' ,

plus two other equations obtained by cyclically permuting (u, v, 11') and
(x,y, z). We have expressed u as (u, v, w) , pis the crystal density. and Ctt·
C 12 , and C44 are the elastic moduli in the Voigt notation (Born a nd Huang
1954). The elastic moduli are linear combinations of the second order force
constants <Pa~:~ (€1'\,; f' K.1 ) . In Table 7.3 we present the elastic moduli for a
number of cubic semiconductors.
The equations of motion of elasticity theory, as expressed by Eq . (7.37).
are linear, homogeneous, partial differential equations which dmit solu-
tions of plane wave form

u(r, t) = [u(r,t),v(r,t),w(r,t)] = (U. v. W )eiq·r- tlq " . ( .38 )

w~ere U, ~· Ware amplitudes and cis the speed oft he wav . ub ·titution of
this form mto the equ a t.Ions o f motion
· y1elds
· a set of- three hne.1r h nw-
geneous algebraic equat· · v J h ·1
Ions m . / . W. The secular eq ua t10 \ h1c mu
be solved to provide a no t · ·. l 1 · . • i
n nv1a so ut10n mvolves a 3 3 det mu n.tnl :.t m

Table7.3 Elastic modHli (in fQII d ,


(after Harrison 19tiO. Boer 1990) ynej cm- or IQ lll Nfm~ ; f'Lh \a ri u: cubJ~: uu nJuclM

Cry~tal
c1 1 ('12
44 Crys tal
107.6 1:2.50
Si 16.57 57 7 lnP
<.ie 6.39 7.%
12 X9 In ~
Al!\ s 4 .1\3 0 .7 1
12.02 lnSb
Ga l' . .70 5. ~')
14. 12
6.25 Zn
J !\s II .Xi 7.115
~ . 32
•aSh ~ X-1 . lJ~
..j lll
..J .Q
Three-dimensional crystals
131
ll l t i ~n •n ' '. There <1 r~ th ·reftll"l' t h rce solu tinn" In r ,. . i l nd
n h '11 th~.: '• bra tJnnal SJ"ll'l'trum t\lltt1 . , .. _ . . . .
. ' 1 t ~u c a t:oustu.: . snH.:e 1he
. lq/ '"l'S ' r r\' as lql goes to zero for eal.:h bran~.:h.
11
rtam h1 g,h-svmmetrv dirl'l'lion s· 1"t' .
~. · · prnpc-1ga1Jon. the 'iccuhr
n ,111 h ' I;._Klnred ·tnd · l) t' . 1.
.' _sl u IOns o transverse or longi ludinal
L

"~bl .uncd. We hst a lev.' of these cases:


1 (I m · cr:-.'-' "a"e. [100] propagation direction

II = (0. n,O) = (0. V.Oki<t(r - r, r)


I
,, = (C44jp)"i

hn,,it u ina I wave, [I 00] propagation direction

u = (u, 0, O) = ( U . 0, O) eiiJ(x-c,r )
I
C{ = (Cll/p)2

J. gi tudinal wave, [II 0] propagation direction

u = (u. v, 0) = ( U, V , O)eiq(x .r)f ../ie- iqc,t


I
C[ = [(c., + c, + 2Cl4)/2p]1.

The speeds of acoustic waves such as these three can be measured


experimentally using ultrasonic techniques (Truell et a/. 1969). From the
speeds and the density. the elastic moduli can be determined .

7.4.2 Three-dimensionallattices

The equations of motion for a three-dimensional lattice have the form


specified by Eq. (7.12). The force constant matrices ci> (/!n..• £'/'\,') are 3 x 3
matrices. For a crystal with periodic boundary conditions, the solutions
to the equations of motion can be expressed as plane waves given by
Eq. (7. I 3). If there are N unit cells in the crystal and r atoms per unit celL
the number of independent solutions is 3Nr. i.e., the number of degre~s of
freedom .
An important quantity th a t enters into the calculation o f many lattice-
dynamical properties is the frequency distribution function F(u.. . It is defined
as the number of normal m odes per unit fr quency range and a n b
expressed in term s of the d e nsit y-of-stales in reciproctl space Jeriv d in
Example 2.2,

n (7 .3 )
g(q) = ~ ·
(-11,

where the electron wave vector k ha been rep Ia e i by th ph nc n wa


vector q. In order to obtain F (w) . we need to sum up the numb r fn rma!
. · ·conductors
Lattice vibrations m sem•
2
. _ , . 1 inr• in a _-;hell between __two const~nt fre_qu~ncy
111 J s \i tlh ftequLIH.:te Y ~.. ·e as shown in ftg . 7.5. Thts sum IS gtven
ur I ...." . at ,....,, an I i.JJ dw m q-spclL , ' -
~.: .

)'

F(...; rlr..u = f g(q)d\1


./shell

=- 0 -, ;· d ·q.
\
(21T( shell
F'g. 7.5
C""~n l:lnt frcquen.:} urfaces l
a c \I!Ctor p c. Th element volume between the constant frequency surfaces has a
base dS..! and an altitude dqJ.., ~ a that

/ r(3q = ;· dSU)dq J.. .


J shell

The element of frequency dw is related to dq.1. by

where V qw is the gradient of w and is the group velocity Vg of the normal


mode. One can then write for the element of volume

dw
dSu:dq 1.. = dS,_,_. - .

A simple case is provided by the isotropic elastic continuum with con-


stant speeds of transverse and longitudinal waves c, and c1 • The dispersion
relations are w = c,q and w = c q, and the surfaces of constant freq uency
are spheres. Then for branch},

) . r.,}
dS.; = q- sm () d(} d<P = -~ sin () d() d d.J.
c-.1

where e. c/J are polar angles. The frequency distribution functi on i · gi\ en by

0 1
2~ + \)
F ( ') = (? )3 / " sin(} df1 / " r/0 (
-7!" .fu .fo c c·I
Ow:!(?
I

= 2;2 ci~ t . AO )

Fr<.:LJLu:ncy cTHt)
12
and is proportional to :...'2
Real semiconductors .arc I· , .
Fig. 7.6 phonon speeds Th . e <lstJcally antsLHrop!L' \\'tt h n n · H1 't.tn l
. · c evaluation of Ft ·) . fr ·-
I r~.:qu~ m:y di trihutiu n I um:llli ll ve r,u:, L!llcncles over the entire B _. \w 1equtres accurall: ph t1Ll11 ~,.
11 11
\ ( tun lOne that arc dett:nni n d tth
lll.!l.jUt.: n~ y l' ·· ,blL..:rW ~;:he r I'J77 ).
mentally o 1 theoreti .. .,
c,, 11 Y·. 1 n c 'x··1m P1e ts
1111t:rcsting feature 1, 11
· s11Ll\·vn m ri ~ 1. t
. s lC pl~.:scnct• ur~ H .
pomts ch:.uactcr 17 eJ bv 'J 1 J an ove smgularities tn 1- (
typc:-;ufVanHuvc . rlwrrcJ, = O(Yc~n HL'\c ]t 51) h·r I ' l l ' l ' li"
singu attlJ s 111 1 - · II
vanes as \w, u..'l '. ·: UllL'-LIIllensit'Ha l .., t ·m f 11 'I~·' '
lh.:ar a stngui-JrJ.t\· -. tl d
~ ' . a I -<-\ .I !lU I ll I 1 ' Ill 11 I• ' '
La tti ce dyn amica l mo dels for s mi conductor
133
"'-'I· In lh Itl'l'-dinH:n ... inn ' t1 "\ LI ' Ill ( {/ '1I 1u.: 11:1 'i.·lll ~ U 1;I -
· . '
I} I Il l 1.! <I:- 1- • ..._·1
. · ' C r i It ··tl
· 1' n 111 'i arc 1. stl Ia fl'l j an I lin i 1 · 1n
. 1
In ,1\.' I td .ll h..'l..' \\ ~th I\1,'1'Sl' ' lhC:\li'C:lll th e pntndi~o.· irv or a crv ·t·d
t~.l.~nltl.'al pnml~ in the surfa~.:cs (lr const~nl frcqu-·n ''v
- 11 1.. • •tn d hc nu nl 'illl l.! ulantJcs in th, r·- , , .. J Jstnnutton
. · · ·
. 1 I" 1) ~ L' ll:LJU~.:tll'y
I j llld Ill I d . '"'
t .

.5 Lattice dynamical models for semiconductors


phonon t. th~..· quantum of cncr'T)' l f ·1 1101-111 -1) 111 ) j ~ f · f
• _- . . '"'. ' ' t ll: o gtven requencv.
n ,11 tl ~ - ptmc:ral ta_sks L)l htttcc dynamical theory is to devdop ; 11
un kr t. tnd mg nl e.xpcnmcntal phonon dispersion curves · c , " .. .
' Tl· · · -· , . ,. . . ,1. . ,-<-·q,V\.:JSU S
q l'll \ . 1~.:s~ Lurvcs Lan be determmed by the technique of inelastic
n ·utP 1 s ·a ttenn~. ~ monoenergetic beam ~r neutrons of energy Ei and
"·I' \C ·tt r k , ts ~nCJdent on the crystal of interest . The neutrons interact
"1th th at ms oJ the crystal and are scatter d into a state with enernv E
~md \HI\'e 'ector k , . At the s·tme tim~ a phonon 0f energy 17v..JqJ is cr::ttcd
( toke." process) or destroyed (ant.t-Stokes process). Conservation of
n ~r-= ~ .md cry ·te:li momentum require that

1lu., q.i = Ei - E. Stokes (7.4la )

= E, - Ei anti Stokes (7 .41 b

q = kl- k~ Stokes (7.4lc)

= "~ - ki anti Stokes. (7.4ld)

By measuring the energies and momenta of the incident and scattered


neutron s. one can determine both q and :.Jq i for the phonon that is created or
destroyed .
An alternative technique for obtaining pho non frequencies is based o n
light scattering. Photons replace neutron as the scattered part ides, but the
same conservation lav,:s a pply. Highly m n hroma tic isible light is
typically used. e.g. , from an argon-i o nIa e r. Ho" ever, the wave vector. o f
such photon are so small compared to the Brillouin z ne bound·1ry that
only phonons with wave vector ~ near the zo n center can h tudi ed in ne-
phonon processes . When the frequ enc f the scLHl n.:d light differs fr m
that of the incident light hy the fr quency o f ·1n pticc-11 ph } Jl 11 , th e . cat-
tering proce . . is called Raman scattering. An optical ph 11 11 11 fr ~4uc n c i'
thus determined . 1L on the o ther hand , thL: diffl:ren in frequcn f he
~cattered and incident li!!hl c o rre, p( nd s to the fr q ucncy of ·tn il L u tic
phonon . the process i c;lled Brillouin scattering , and an ac ) U. tiL ph on< n
frequency is determined.
Additional optical techni4ues for the mcasur m t~ t r _p honnn
frequencie5. include the ab ·oq tio11 , cllli ' sion . and ren ~li On In ra red
radiation. A detailed treatnwnt of opt ical tl!chniqu ~ i. r"s ntc J Ill
C hapter I 0.
Lattice vibrations in semiconductors

7.5.1 Homopolor semtconductors


h in ·Ia tic m:utr 11 cattcring t ch niq ue has been employed to .determine
lh~ ph n 11 ui pcrston curves ~f Si ( Dolltng 1962) and ~e (N1lsso~ ~nd
lin 1· 71) \ hkh are di played 1 F1g . 7. 7 and 7. 8, respectively. A stnkmg
fc tun: fthe result··~ the flatne of the transverse acoustic (TA) branch as
it approa he the Brillouin zone unda ry in the [1_00] and also. the (Ill]
direct 1on . Thi 11atnes i difficult t reproduce With a model mvolving
T. ~hort range interatomic in Lera li on · between nearest neighbors and next-
0 0 0 0 neare t neighbors. It has bee n :.-.hown (Herman 1959) that interactions out
to a 1 in luding fifth n ighbor · ar r quired to give a reasonable fit to the
0

expcrim ntal data for


The basic physical reason for the anomalous behavior of theTA branch
X
in Si and Ge seems to be the high deformability of the electron charge
di tribution in these materials. This deformability was taken into account
Fig. 7.7 by the shell model (Dick and Overhauser 1958, Hanlon and Lawson 1959)
Phon,.m spectrum for Si in the [100]
which was first applied to alkali halides. The electron charge distribution is
direction ( fter Dolling 1962 .
represented by a spherical shell about each nucleus. A given she!J is coupled
by Hooke's law forces to the nucleus inside the shell and to the shells about
the nearest neighbor nuclei as shown in Fig. 7.9. In addition there are
interactions between nearest neighbor nuclei.
The equation of motion for the shell model take the form

10
M /i.
EJ2uo: (€h: )
ot- = L { ~~~ (f!),,f'K.') ui3(e'K') + if>~S (f.K,f''""' )q (f',/) }
I ' ~;.' {3
9 (566
0 66 TO
0 6 ( 7 .4~J )
0
0 o 6. o\c
8 6
/6
LO ( .-+~bl
7 '

I
LA
v
'I
6
0

- 4

TA
00 0000
M,. 8 -, - [• 1111 .,....Ill]
b.
2 0
//.1 I'S
b.
0 . iJt - - tl> + (~ . (<J> ) I -
. q) · II -L~ l

, ~o wlu\.:h can he solv u . I


Tl . . . ~.: Ill t le manner d ·I " . .
11.: shell moue! W'IS ' IP I' I . eve oped Ill pr-:\ ll) U s s ·~:lh n.
I) -t-- - - - - l A sutt,,
· · . b- k. cltu1c•~
. lJI.' tl· ' P ~~~t to S1 •.111 l 1 L• b\ chr ,1r1 · . 11
I . .. 1e modd . .. . . ~
\~tth the ex perimental 11 p;_tt,.tllletns !.!a\l: ra thcr l:.l'' I
IA h 1 I lllnun d1s,, · ~
Fig. 7.8 ranch:-. were n::asllll'lll · I t:.I'S.' IL)Il l' lll'\l'S . In rartll.lll
l'li••mJn >~~trun1 l c.r I, · 111 l ho.: I IIIII] A . . ' ) v Well .
\':tl'l<tltun un lll'
I II . ll'pr~>dtll.'l'd
Ulf ·• l t••tt!.t l l 1 J ll ~, .. n , 1111 t c h ll l 'i7 ll S s 1l' m) I 1
~.:
, lllc~ lltl· l'uvaknt buJtd I " LILl' Is thc .holld l' harg~.· I h dl..'l {
dl" I l l d ) I · .
I I L - Up l•l l'l l' llllll d l l
lattice dynamical models for semiconductor 13
11 1! It I 1 ,J h•nh ''llc..' c..: lllltk<tli ; · 1hi -.. char.!!c dis1 nh u t 11111 hy pia in).!
I' '1111 ·ltar_•c h '1\\\.l'll ca ·h pa1r ''' nc;11Ts1 nt:l).!hhnr nu ·I ·i . 1 h .
h n_'~.: 1 L\'UPI ·d h~ J..h .H'k.: ' s law t'nrc~..·s 1u 11t ~se llllcl·1. Cnupling
tnlr'' itt· ·d l' '1\\.: ' II llt'arcst llt'1ghhnr nucki <~nd h~.:1wccn 11 ·ar .._t
11 'J"h l 1 J1tl111 1 ~..·h~trgcs The cquatillns l)r motitlll arc or 1h ' o.;;lln c !.!Cneral
,, 1111 1 th\t 'f 1r the shell llhXkl and may he solved in the s;tmc wa; U \i ll!..!
Fig. 7.9
th~.: tdt.d"·tllc..' ~tpprtl\. i matit111 . The results for the ph< IH.lll di ~ persi <l n-curvc: S~.:h ·m;IIJL r~:pl t.: enl ' l ll>n 1 t hell modd
,f ,bftll1 i hy \\' -her are shown in Fig. 7. 10. We 'iCe that the ;1!!recmcnt 1nt ra cuon,
fie.. I' en the 1r_ and e'\pcriment is cxc..:cllent. Similar results h7.vc b ~~ 11
,, [, t.111 tcd ll r ( ic ( \Vehcr 1977 ).

7.5. 2 eteropolar semiconductors


Phl t lll d ispcrsil1n curves fur a large number of hcteropolar semi-
nduct )rS have b~en obtained by inelastic neutron scattering. Both the
~hellt1 1d I and the bond charge model have been applied to these mate-
ri;1ls. l wever. the theoretical analysis must include the partial ionic
cha r: ctcr ( r the electron-pair bonds and the effective charges on the ions.
The ituati n is somewhat similar to that of ionic crystal such as alkali
halides fc r which the rigid ion model (Kellerman 1941) and the deformation
dipole model (Hardy 1962) have proved useful.
ln the rigid ion modeL the ions arc regarded as nonckf'ormable point
char!!e interacting \.\itb each other through th Coulomb inte-raction.
Short rang repulsive int ractions or the Born- Ma er type are aLo
included. The Born- Mayer interaction has the form
(7 .44)

\V,

I 1

L K

~·hnl) 21 uhJltn~ .:~tkultt Jr·uh


Fig.7.10 II· . Jt•r f , ,111111! 1962 1 JI,~ll11 ind
. s·1: ••) )I' J
Ph on n di~per~ion curves lor L i rt:JC<, ,l' pcni1ll't1\.l t ,t(,l , \ t:

(after Weber I Y77 ).


Lattice vibrations in semiCo nductors
. r· cters \Vhich can, for example. be determined fr m
, here A .m I r1 • re r.t d 111 •
't ,. . tti e l.Ono;;tant and t hL bulk modulus.
the equt l111LUm 1.l L h d r
..1 .1ted 11 Jt.iel which ta kes mto account t e Ctormabtltty
. · ·
,\ 111 lr · .-op h~~ 1~.::, . . . . .
t c ec n)n ·I 1.1. rg"... Lii · tributio n ~tbnut an ton ts the deformatiOn dtpole
0f 1 lt: I t ~.: _ . .
node! ( H.m.ly 1 62 Kaw an i H · rdy I<)69. K unc ~~a/. 197 5 ). ~hts 11_1odel 1s
ha"~.:d 11 the adiabatic. harmo mc, and linear ~1p?le appro~1m~t10ns. 1t
de cribes the Jmg range pa rt ,f the interatomtc lorces, wh1ch IS due to
le tr tatir..: interacticms 1t1 tl ~ tem of ion cores and loosely or tightly
bound 'lectr n ·. A a re ull o l' tb di ,placements of the ions and the dis-
wrti 11 of the elect on di trib uti01r about the ions, an electric dipole
m 111 nt pd(f r.:) is proJuced t lattice site flt>·. whose components can be
xpand d in pO\·Ver serie · in th com ponents of the ionic displacements
u(C;-;.) :

p; 1
( /'i,) = e'(h.·. U0 ( K) + Lf11nti (fK,f h.I)Ll(i({I K1 1 1
). (7.45 )
('t;' d

Here e"' (/{) is the effective charge on ions of type K and mr..-~Ur.:, f ' ~~ ) is the
deformation dipole matrix. The latter can typically be restricted to nearest
neighbor interactio ns. An additional contribution to the dipole moment
arises from the presence of an effective electric field E c'f which polarizes the
ions. If o(/{) is the polarizability of ion K. the total dipole moment can then
be written as

p,.( K) = e"' (K) Ita(Cn;) +L 111nJ(I!K, e'K')u(J (f'rtl) + o-(H)£2 ([ti ).


[','J'

( 7.46)

The effective field is itself determined by the dipole momenr an C'l n be


expressed as

E,~:JJ (fK) = L Bod(fK, f.' r.:' )pJ( e!{ 1 ), t .4 )


{ ' K.' a
El . . ".L'·(£r~ . e'r.:' ) i's th e<tppropnateCoulombcoefficient(K
whereB . . uncl9 1- -l).
tmmatmg the effective field from Eq . (7.46) yields .-

PofK =e 1
(tr)u,. (l:,~) + L~'~~(li(f'r.:,f't/) u ,. t't>:)
{ ' ,,· 1

u (r>) 2.: B .J(I!r.:,. f 'r..-' )p l(t't/ ) .


f'r. ', )

The eq uati ons of motion r .


or the dtsplacemcnts can be\\ nlt~: n t.
. ,2 II,. ({·
;\if 1,U. ,. /-..·) = 2:. t'f> "· 1
(f' , fi l
r.,' '"" )u r(l ti)
I· 1

f' t.' j

- Lt:'(r. ) B., i(l' h )fJ ·(('r')


,, '
, , l ; \

- """)II ' (' r


~ ~ 1 ;,.( t < , t<)8 I. (' 1-.·' , fu ,..,·'')j
I ,, 1 1 1 '',~'' l
Lotti e dynomi 0 1 d 1 f
mo e s or semiconductors
137

Fig. 7.11
l'hron.>n ,iJ ~po.:r" "ll Lt t l VC l <11 l n\h· nlid
<:J rd~:' J')t:nmcnta l dat.J (,dt~r Pm.
,., of. 197 1). " .JiJ Ime~. 15-p<t r,tmc cr
d ·fu1 m· li"ll iprtlo.: mndcl · J,"hcd Ime •
fl I fl .h ll.S 1.0 1.0 OJ\ O.fl 0.4 cco nd-IH!tghh< r c.;~.: n tr;tl fort~: m" eJ
0 .2 fl. ' fl.! (l)
r 100 1 x A II I Oj d\!llt:d line\. fir l - 11CII!h hol '- ·ntrall•lrtc
I II II L
modt:l ( a ll ~.:r Kunc !' I ul. 1rJ'iJ

,, h ' r tl' , 1I h . f' ~-.-') is the- Coree constant matrix for short range i11 teracti ons.
E u.Hi""~n:-. A:-l) and (7.49) arc a set of simultaneous equations in the dis-
pl.!' mc>t t' and dipole moments. Solutions in the form of plane waves witb
\\ :.1 \ · ' ~tor q can be found . tha~ yield the frequency as a functi on of q.
Re::-.u lt It r lnSb arc- shown 111 Ftg. 7.11 together with experimental data
frl1Ill in Ltstic neutron scattering. Paramete-rs that appear in the force
C1.:mstanr and deformation dipole matrices were chosen to give the hest fltto
the' data.
A cQmmc-nt is desirable about the different behavior of the optical mode
frequenc t in homopolar and heteropolar . emiconductors as q ~ 0. In
homopl'dar semiconductors the transverse and lo ngitudinal optical mode
frequencies approach the same value, whereas in heteropolar semiconduc-
tors the trans\'erse optical frequency u.JTO approaches ·t lower value than the
longitudinal optical frequency wuJ. Thi difference in limiting frequencies
arise from the strong interaction of transver 'e optical modes with the
transverse electromagnetic field at wave vectors on the order of -»roJc,
wherecisthe peedoflight.lfthewavevectori trictl yzero. h wever,the
trans,·erse and longitudinal optical mode freq uenci in cubic hetero-
polar emiconductors have the a mc va lue by _ mmetry. When cJ == ·'ro l e.
the splitting of .,;TO and ;,;,.' w become apparent. Since ...:r /1 is v r '
small compared to wave vector. at the Brillouin z nc b undar_. the tran-
sition to identical values or wro and wuJ as q - 0 an not ~ en n th
scaleofFig . 7.11.
The interaction of a transvcr. plic~1 1 pill n( 11 r mall \\a '\'C t ) f ~\-i t h
an electromagnetic '"rave i. co n veni ~ ntl ~ xpr s::. din tam , rth' 111L dtlted
relative displacement w given by

I
(7. -o)
w = ( J1 ; n( J1 u,

·
v.here U is the relative di:,p)aCCI11 11 1 r !he l\\0 lllll ·
. tn a
1it ·
Ul L
11 and \1 i-.
their reduced mass. The eqwili on )J 111 '1tiLHl l'l r H' is

7.51
(7.52)

The parameter 1721 i a modi fled el ctric cha~ge a_n_d is equal to brz (Born and
Huang 1954). while b-22 i am difi d polanzab1hty.
L t us a._ ume tha t w £ and P va ry as exp( - iu-•t). We can then eliminate
w from Eq. (7. ~) u ·ing Eq. (7.5 1) and obtain

P= bTz ) (7.53)
( h2z - L7 11 w-, £.
Introducing this result into the expression for the electric displacement 'D
given by
1) = Eo£+ p = EoE(u-·)£ , (7.54)

where F(w) is the dielectric function , we see that on eliminating P,

E (W ) = 1 + -I ( b22 - bT2 J ) . (7.55)


Eo btt w-

Let us consider the limiting case w ___. oo and E(-.v) ___. E.·.· Then

bn = Eo (Eoo - 1). (7.56)

For transv~rse opt~cal modes of long wavelength and frequency wm. the
macroscopic electnc field E vanishes, so from Eq. (7. 51)

btt = -w~0 . (7.57)


Using this result and settine:~ w = 0 in Eq . (7 .55.), we fi n d t hat

= t:o(
1
b12 s - t: )w~0 • .58 )
where E . = t:(O) Th d. .
·' . e Ielectnc function now takes the form

(· ( ') = t: - + (E, -, r - )w~o


~.
W]·o - w-
W e now take tl1e ct·1vergenc f D
mndes f lo ng wavelen h . ~ 0 . and focus on longi uJ1n II pri ·at
gt and frequency uJLu:
v
· 'D -
- ~'"or (Wtu) V. £. • Ol
For lorP•itLtd .. 1
• "' tn,t waves. V. £ ..
space charge. V . D = 0 C . =I= O. but II the sernic nd u~ t l r
· nsequentlv ( . ) 0.
-· ""'lu -==- a n~ 1
0 -o: , , (,., __ , l...'-' - I , ,
-.\ '\
r "",-T,,
.
- . . . .,- c' ).
lottie dynamical models for semiconductor 139
111 th1 11.' ·ult ''~' th ' l dd one - Sac hs- TeII er re lation

I \

..... rr'
f • ~'/c ...,· ,). Thus. the limiting value~ or 10 and l-<J /11 <IS
k t~.: rmJtlcJ b)· the stat1c and high-frequency dielectric cun. tants.

S First-principles methods

intcd t ut in Chapter 2. the potential energy for the nuclear motion is


~.: tr\ nic ~nnmd stale energy as a function of the nuclear coordinates
plu. th dir ct int~raction between the nuclei. When the nuclei occupy their
qmhbnum p(lSlttons, the electronic ground state energy can be calculated
u Ill.! Bl lch'., theorem and ah initio pseudopotcntials (Bachclet cr a/. 1982)
\\ h ~ p.H meters are determined from atomic data only. When the nuclei
Jre Jt-pla ed from their equilibrium positions. the situation becomes more
L mplicat d and requires a more elaborate analysis .

.5.3.1 Frozen phonon method


F r c rta in normal modes of vibration. particularly those for q = 0 and for
q n th Brillouin zone boundary. the atomic displacement patterns are still
p ri die. but with a unit cell that may be the same size or larger than the
primitive unit cell. One can therefore still use the Bloch theorem to calculate
th lectronic states. By varying the size of the atomic displacements and
tting a parabola to the results. one can obtain the force constants that
control the motjon in that particular mode. The calculation of the fre-
quency of the mode is then straightforward (Kunc and Martin 1981 ).

7.5.3.2 Linear response method


A procedure that provides full phonon dispersion curves without fittine:
parameters to the experimental data i the linear response method (Baroni
era/. 1987. Giannozzi eta/. 1991. Quong and Klein 1992). The first step is to
calculate Bloch functions ·1, (r) using the density functional method in the
LOA as described in Section 3.4.4. One then expand the Hamiltonian in
powers of the ionic displacemen ts to yield a first-order change H (' l {r of the
form
vflr'l ··) + v ' 'l (,·)
.\L
7. 3

where Vh(l )(1·) • r h(l )(r) ' and Jl.\((l ) ( r ) ()I"C the fir t-ord
.
"r hang
.
in th~
electron- bare ion interaction , th e clectr n- clectr n 1nt ract1 n , · nd th
exchange-correlation intere~ction , re. pectively . The hang in I tr 11
concen~ration n ( l ) r ) due to the first-ord r change in th H amill ni ·•n is
given bv

(7. 4)

where/~ is the ermi Dira occupation number ;,.tt1cl Ev i. th Bl ch tat


energy.
Lattice vibrations in semiconductors

Since fl(ll (r through the terms u -, ( n (r)~ and


c )nta ins n( 1l (r )
cl J r(lr'n(r') j 4?TEolr - r'l in Eq. (3.48)._one ~ust s~lve Eqs. ~7.6J\ ~nd
(7 .64) self-consistently 111 order to obtam t~e conveLged values of 11 (r)
1
and fi (Il (r). An important point is that thts procedure handles non local
ab initio pseudopotentials \.Vithout difficulty . The second-order change In
the electronic energy of the system is specified by

E.,,~ ~) = I
L-t.!rII ( IJ j/ b(-l
"""' IlJ) (7.65)
11

where v hU) is the second-order electron-bare ion interaction. Adding the


ion-ion interaction to Ec~~l and expanding in powers of the ion displace-
ments to second order, one obtains the dynamical matrix from which
phonon dispersion curves and other lattice dynamical properties can be
calculated. Phonon dispersion curves for Si obtained by the linear re ponse
method are shown in Fig. 7 .12.

7.6 Normal coordinate transformation


The basic characteristic of a normal mode of vibration is tha t all ·1toms
vibrate ~ith the same frequency when a particular mode is , · ·ired. l n a
harmontc crystal there is no transfer of energy from one n rm~1l m~ ~.k to
another. Each normal mode can be associated with a normal coordinate
Q(qj) which is a linear combination of the physical displa ·m nt ,(' · ·
The normal coordinate transformation which carries the lin (ft. ) int 1 th ·
Q(q; ) IS gl\' CB by

l l
Q(qj) = N : - L M l. e""( lJ.i k - iq·R!'' u., lH.
lhn

' here the cot:l'licicn ts e ( - ) . . .


J , . . · .. 1 . . · "'· fl.! die the eompo m:n ts ol'th ·ig~,.·n ~.: t th
) Jl<~mtc,t matnx mtmduc. I - S. . -
Eq.(7 . llJ) , th~.:i ' "'·· · .. _cl 111 ' _L'L'ltl)J1 7. 1. Usin..! th· dlsliJ' r l.lt 11
ll\t:Jsc lJ,tnsfnrmatJon ~.·an be 'lh~ \\n lL' be
Vibra tional spe ific heat 141

ll (7 .6Xj

th J t 1 1 th(' 1~ dt'Ih'tin!! a ~irst tim~ derivative. Carrying out the normal


d111.111. tra n"l mna11lln w1th the aid or Eqs. (7.1 X) and ( 7.(1 7) viclds the
r~ 111l ·

H = ~ L[Q:!(q i) + L<);;Q2(qj )]. (7.69 )


q,

, that the transformed Hamiltonian is a sum of independent har-


t •

nH n1c 1~ Jll..t lllr terms. The Schri..kiinger equation for the nuclear motion,
q. (.2.-0 . can then:forc be solved by separation of variable . The total
ihra ti 111Jl t>nergy Er is the sum of the harmonic oscillator energie~ asso-
ci:tt \\ ith the normal coordinalt:s .

E/' = L h...;q;(nq, !) , (7.70)


qj

" here the 11q1 are the harmonic oscillator quantum numbers given by non-
negati\e integers. The quantum of energy. n:..Jq.i· of a normal mode of
, ibration is called a phonon.
A phonon can be vievved as a particle-like entity that serves as a carrier of
\'ibrational energy in much the same \'>•ay than an electron erves as a carrier
of electrical charge. The group velocity of a phonon is given by

(7.71)

7.7 Vibrational specific heat


Using statistical mechanics and the energy giv n by Eq. (7.70) nc can
calculate thermodynamic propertie. , such a the sp cific beat and entropy.
as functions or temperature. The first step i. to omp ute the no rmal mode
frequency as a function of \Nave ecto r. The peci!'ic heat ' :t!l then be
evaluated from the average energ_ (£ 1') u ing the rcl at i n

')(£,.) ) ( .72)
c~~ = ( JT n.

where the temperature diffen.:ntiati on i at co nstant volum - · he av n ~


energy can be expressed in term s of the av~rage os ilhtor quan tu m nu mbt.:r
( n 9 , ) by

(E,) - L hv.Jq ; ( (n111 ) +~ ( 7.73 )


Ql
Lattice vibration in semiconductors
- .. 1en(\emble. one obtains
, 'er·w1ng · n,,, l!)\ "'·~r •ol Cc 0l)111L
....

(7.74)

) yie lds the ·pccific heat in the form


0111 buung qs. (7.7- }-( 7 74
fiWqJ .) 1 l!fr,;yJ I";T

s = k B Lq l ( kBT (e"""'oq,/ k n T - I )1 0
(7.75)

At an arbitrar tem p ra turc the calculation of Co requires a numerical


'ilculati n based n a knowledge of the q-dependence of wq;· The e~a­
luation is much implified at both high and low temper_atures o At high
temperatures where ks T > 1i qi for all qj, the right h~m?_side of Eqo (7075)
can be expanded in pow·ers of 1iwq1 / kuT to g1ve the 1Im1tmg result

Cn = ks Llqi

= 3Nrks, (7.76 )

where N is the number ofunit cells and r is the number of atoms per unit cell.
This result is the Dulong-Petit law.
At low temperatures where k 8 T « n:..v111a 1· , only lmv frequency modes
contribute significantly to Cn and elastic continuum theory can be used. We
must recognize, however. that elastic continuum theory yields an infinite
number of normal mode frequencies with no upper bound. whereas a finite
crystal has a finite number of normal modes frequencies. Debye resolved
this discrepancy by imposing a maximum frequency wv on the elastic
continuum modes such that the total number of no rmal mode- eq uals the
total number of degrees of freedom :

j
OJo}/J

F( ·) d~o = 3Nr. ( 0 7)
()

Takinuo the. isotrop·c


1
· ctppi oxnnat1on to an elast1c continut m. \
0
• • • •

Eq. (7 .40) mto this l!quation and solve for wf).


. .. ·

~) ] I '.> .., s )
(' ;
l f2 l.. l

For diamond and zincbl ~ d ~ . . ; ,


h~ ·. 1 . ~;;n cstlucturestheratwO /i r h as th~o: lu ,r c .
w ere u I S t1c lattice can s t · l Tt· ~ . . ' .I
· nn · 1t speeds 0f tnns\ ns ·u•J loll!.!JtuJ II1•1
s0 unL1 waves can be co,dculo . - . •
. .
~
Section 7 4 otncl .ttecl lrom the elastic modul i .rs d nh "' 10
dVCI aged over v· .· . . .
0 • '

· '
It i~ conveni ' nt · ct·. . .utous L1InXtiOns \.>1 pn,r a:.lll• n
0

. • 1.: 111 ISCUSSII1g the , o·j~ - h · h ot I


l'> lic tempc ratur . H k ~ speLl IL' eat tt'l Ill lrt u · 1 11
~.: nown ·ts th ~ D b
c • t e ye temperature h th 1 l.ttl n

/j._,_,/1 - /,. II (-:) .


Anharmonic effe t l.ct3
I '~'Ill )

PhS
21il
PhTl' I (,J Ci:1l\s 145
CdS 21:" (i:-ISh 26')
273 <'dSl· IXO In A s 24~
2.) l dTl' 162 lnSb 200

~ ,, \d"lim! .~
t h~ sum in E4. (7.75) to an integral~
hy mea 1.1s. o f tl1e p11onon
L

Jl·n::.Jt. - (-sta tes. \I>'C can express the spccitic heat in the form

cl = 9Nrk B (T)
8
·'.fo/• H
T .\· e-' d\
4

(e·'· - I ) 2
0

(7.80)

A::. th t "mperature is lowered toward zero. the upper limit on the inte!!ral
can xtended to infinity. The value of the integral is then 4i14 / 15 and

71
4
Cn = -)1- ' NrkB - (T) 3 6
~
.. 5 8 (7.81)
/ ,---- ~ilicon

7/
This is the Debye T 3 -law. It is well satisfied bv solids at vcrv lo\.v tem-
perature . Values of 8 for representative sem-iconductors a;e listed in I /
Table 7.4. As the temperature increases. the specific heat starts to deviate 7/
si£rnificantlv- from the T 3 law. This behavior can be attributed to the exci-
. 7/
200
ration of higher frequency modes. including optical modes, whose fre- 10
Tcmpcratur I Kl
quencies are not well described by elastic continuum theory. The phonon
density-of-states develops peaks due to Van Hove singularities. The specific Fig. 7.13
heat curve flattens out tmvard the Dulong- Petit values as the Dehye tem- Specific heat fSi nd Ge v··r u
a h ~o l utc tcrnper:lture (, ft r Ki tt I
perature is approached. Figure 7.13 shows this behavior for Si and Ge. 19 6).
Further increase in temperature to well beyond the Debye temperature
leads to a renewed increase in the specific heat. This increase is due to
anharmonic effects associated with cubic and higher order term. in the
expansion of the potential energy in powers of the displacements.

7.8 Anharmonic eHects


7.8.1 Thermal expansion
If cubic anharmonic terms a re included in the latti e polential l!n rg_. th '
interaction potential between two ·ttoms bee m , asyrnmctri ·ith r sp ct
to the point of minimum potential. The potential rise. mor rapidl __ , · the
atomic sepa ration decreases hclow the value at minim um potenttal and
rises less rapidly as the separation increas~.:s above t hi. v~ lu . A th rn at
distribution favors the la rger values of separation . This b ha 'i r •· n b
illustrated by considering a diat mic molec ule ,:vith intc:raL'tit. n pot ntial
(7. _)
lattice vibrations m semiconductors
· tlhe potential minimum . Letting II ' = 11 - ur,, we
\\ hct L: ,,, is the scpar tl 'n a . -
h<ne for the a ·erage scpar<JtH111 u
. 1\·e- r ·,,,j kn T dw
f
. - un
u ::; 1111 + f e- 1·,, /t.:IJTdll'
(7.83)
- 1111

To a gL d ·tpproxnnati n w can tend the l ov~e': limits oft he integrals to


<:~nd expand the int gral in powers of .·· retammg only the lowest-order
non a nishing term . T he res ult can be v ntten as
ii = ( I + o T )uo. (7.84)

where n is th thermal expansion coefficient given by


}·yks
0 : : : -J-- . (7.85)
4 -uo
00 We see that o: is proportional to the cubic anharmonic coefficient~( .
0.4
The foregoing treatment reveals no dependence of a on temperature.
00 0.2
0.0
Real crystals. however, exhibit a decrease in a with decreasing T at low
500 -0.2 temperatures. This behavior is associated with the chctnge in normal mode
- 0.4 frequency due to change in volume that is described by the Gruneisen
400 - 0.6
0
parameter ft given by
:lG -0.8
,
~

'00
I
::> 0 5 10 15 20 0
(7.86 )
200
where w; is the frequency of normal mode i . The therma l expa nsion IS
related to the Gruneisen parameters by (Mitra and Massa 19 ~)
0

a= I:r _c r_!_
(il
(7.
; '3Bof2'
- 200 ..__..__..__,__..__..__..__-1-J
no h c'i) · h
0 5 1 150 200 wb ere n 15 1 e specific heat associated \Vith normal moue i and BtJ is the
T( KJ ulk modulus An han11 0 · ·
11ICity enters cr throuah the volum pt:nd n ot
.
h ·
t e norma I mode freq · ~=>
Fig. 7.14 S . uencies and temperature thro uo-h ' 1
The rmal xp a n i n or
Si a , a function
th
em1conductors with th d··-
.- .
d . o ~~ ·
e Idmon or zmcblende struct ur h.l,. n !:!atn e
·
o tem perature: o pe n ci rcle , ermct 1expanswncoeffic ·,. t · ' .. . . - ,
ex p~ri m ~.:nta l data (a fter yon t: l ul., ors· ·b . len SO\eiarangeotlowtemp r·tture .Inth' a e
I , n ecomcs negative ·n I JO K .
1977 ). o lid ur' e. thco re ttca l r~.:w lt as showninFig. ?. I4 . The' .~· -. a~~become~p si t·v .again,lt....., _O ~
( al 't ~ r W an ~c r l'J82)
tran verseacow t" d GiuneJsen pa1ameters lore rtam lo\ -trequ m~
s Ic mo e a re nega tiveandprodu~:e thc n gdti\ J<Hld- Lf, ,.

7.8.2 Thermal conductivity


In s~miconduct:o rs witt .
. . . 1 VCI y low C·t 111 . .·
t:-. pnmaril yassoci·llel .·h. ' erconcentratio nth lfdl1 1
I . . ' l \\tl then, ,, 0 1- _
llt po tcnttal cncr~v . I . )\\ phPnons. rh o.tnh..tnn
l..;l
ll .LS ·I O II~ hetwcen ~,
nl
Pl•\lLICe In[ ···
.
·
I.: I di:tiOn __: OC (\\ ' ·n Ill I Ill I
C . '- •. 1o no ns. Pho . .
cc pt tlltder sp \ :ial .·. , nnns tht' rdv r ha \ 'a Uh. I
I. dill'usi vc rathl'r tJ·,.,~~~ILtllnl1'>l~llll'..:., lhL' flp\ t t ph on I ' Ill I'
1 <1 l ~ llL' 111
· na turl'. ThL· I ·.u ll u (: ,
< "
Impurity effe ts on lottie vibrati o ns
145
T hy Fourier's low of heat conducti o n

{! - - 1.VT.
(7 XX)
lh. thermal conductivity. Ttl derive ' Ill ''XJl "' , ·
. . ' , .. IC~ S I011 OJ lo. Wl' U '{:'
r· .
l..:·tll.'l tL lhL'tlr~ m onc-d11nension. Let 11 ( · ) 11 tl , , . .·
. .\ C 1t: cnctl!y dcnsn v
n n .11 p lllllt x and 1". the speed nf sound
• ·
Tl1 .~ 11 , 1 1 t Jl~
" l:
-
lea u x can be
\ Jtlld1

I
Q= 6 [u (x - ,\) - 11(.\ + ,\)]·1·, . ( 7.R9 )

E I .111 iing u( x ± X) in powers of>. and ret(lining only linear term s. we get

Q = - ~ du VsA = - ~!!!!._ dT r,>.


3 clx 3 dT dx ·
I ciT
= - -3 Cot:,>.-
.. · dx . (7.90 ) - I0
:.<:

Com ·ring Eq. (7 .88) with Eq. (7.90), \;>,'e see that
I
K. = -3 C oV
.. ,\-A. ( 7.91)

An appraisal oft he temperature dependence of l'i. can be made by notin!!


that at low T. Co"" T 3 • v c::::: constant. and.>..-::::: constant, whereas at high 10 10 ~
T. Cn ::= constant. 1.:s c::::: consta nt , and .>.."" 1/ T. The phonon mean free H Kl
path ,\at low Ti s determined by the sample dimensions or the impurity
Fig. 7.15
concentration . but at high Tby the inverse of the mean number ofphonons Th ermal co nd ucli\ it~ 1 10p1 a ll}
iipJ; = l / [exp (nw/ keT)- 1] rv T. The thermal conductivity as a function e nriched Ge vc r u ~ l mpera ture a fter
of temperature is roughly a bell-shaped curve as shovm in Fig. 7.15 for Geba lle a nd Hu ll I - ).
nearly isotopically pure Ge.

7.9 Impurity eHects on lattice vibrations


The introduction of an impurity atom into a semi co nductor ca n take place
either substitutionally or interstitially. We shall focus on the substituti onal
process in which a n atom of the pure crystal i,· rep laced by an impurit y
atom. In general, both the mass or the atom and the force con. !ant · u-
pling it to its neighbor. are changed by the sub, tituti on. In th e a. [
iso topic substitution, only the mass changes. nd er certain c ndition · a
localized vibrational mode arises in vvhich the amplitude of vibrati n i.
large at the impurity site a nd decrea e. exponential! goi no a\ a fr m the
site.
To illustrate the situati on in a simple wa y. let u~ co tLider a m nat01 1ic
linear chain with nearest neighbor interacti ons aml a . inglc i:- topic
impurit y at site f = 0. The equations o f m tion ar . assumin ~ a tim
variation exp( i"..JJt ).

M :.J~ u, + cr( II { . I + II{ I I - '2111 ) = 0. e=I= 0 (7 . _a )

J'vf' :.,} u0 + a( u_, -1 u,1 - luo ) = 0, (7 .:29b)


lattice vibrations in semiconductors
1
A.f' e the ho t mas. and impurity mass. respectively. We
where ;\/ anLl " ar . h h . d h fi
- ~ ..,r N + 1 at ms 111 t e c am an t at xed end
h
as~ume t at th e1.: ... - .
b )undary conditi n!-- . re <~pp lted :
lfN = l/ _ ,v = 0. (7.93)

lutions t 7. 2) tha t sa tisfy Eq. (7 .93) are given by

A _in(N - f)¢ (7.94a)


=
{ Bsin(N
llj
+ fl)dJ. (7.94b)

Substituting either expression for U ji into Eq. (7.92a) gives, for e> 0 or
<- 1,

M u} = 2o-(l- cos dJ) . (7.95 )

To determine A, B, and ¢ , we substitute Eqs. (7.94) into Eq . (7.92b) for


f = 0 and into Eq. (7 .92a) for t = - I. The resulting equations can be
simplified with the aid of Eq. (7.95) to yield

A[2(Q- 1)( 1- cos¢) sin N (b - sin(N + l) c&] + Bsin(N- l )q> = 0


(7.96a )

(A - B) sin N ¢ = 0, (7.96b)

where Q = M' I M. From the second of these equations we have


A= B (7 .97 )
or

sin N = 0. (7. 8)
The case A - B c 01. d
· - respon s to even modes of ibrati n m whil'h
ILl = li p. From Eq . (7.96a) we have

(Q - I)( I - cos ¢) sin N ¢ - cos N Sil1 =0


Fig 7.16
Graphical soluti o n fo r lo ·atizcd
or
vibrationa l m od~.:s . ur c :1 : cot
o.: urvc b : (Q I ) tan ',Jf-· Q > l ;
curve c: (Q - I ) tan t/J/"!.. Q < l : curved : cot iV({> = (Q - I) tan (ci>/ 2). ( 7 9)
- tau ,,,/2 (arter Muntroll and P Its
This equation specifies the . II .
1955)
phical solut 1011 sho"'n. F . cl O\Ved values of ftlr e\ n m I
modes. For ~
Q_ 1 yy
111 tg · 7· 16 ''l'd
1 s• m
• understanJm • _ th r 1
- one h·t tl1 · -
cot Ncp = 0. For 0 , 1 '· e pcrtect Iatric " nh tt ·d
-1 · . - ___.. on\! has ·t h · , · ·
0
Qanci ..J,) arcdownshil'ted b . ' e,l\•y tmpunt~ at 111 . th.: .til
lor(! < l . unchLisa ltght . Yan~mwuntpfO(I /., .• tnJu I '
upsiJit'led h v 'ltl . t111punty atlll11 the •til )\\ I tltr '
J' .anount oro l/1. ' ~ •
LUI Vl·.., lur cnt( J\1, •) . .J •
. . .

1 1
<lh(O
l I)
\ l. hut the t 11 :;:. 1
u h~-:.., rtll
, 1
- tan( o / :2 ) n '\ c r a 11 1 th I
Impurity effects on lottie vibrations
147
- I 11 hat lw" happ~:ncd In th . .. 1 . ,. , .
llo I' d 'b .
• co •ze v1 rational mod . 11
l n ... l mud . I h • .rrrsw r I 7r--.--------------~
e \\11 1 a Clllllpkx va lue o l ,•, 1.(,

C) :.. iT t i(. l .'i


(7. 100)
-':' I 4
..; 11 1 Itt Ill'' th i. f~._wm fnr '' intt..) En"'~' (7 ·99) ·we 0· t)tarn
· Ill
. the limit i 3 u
12
(I - Q ) coth ((/2 ) = 1
(7.10 I ) I I

"hu.:h k t 1111 111 :: the value o r (and hence the value of th .. f · . 1.0 '---~--~-~-...::::::~_)
c 1 eq uency v ra
Fq . ( - _") .tllu. 1 ,, 7. 1(l!l) .· · () () 2 0.4 (1 ,1) 0.~ ' ,(J
Q
Fig. 7.17
(7.102)
Diagram of lm:a li7cd m d~: a nJ perfect
Ia tti ·c freq uenci~:s fo r M' < ,'vi . .._., 15 lht:
The I cali1ed mode. F.frequenC) lies above
. the allowed b·md of the per f'ec1 max imum frequency of the perl e l
b ttic .1. shLnvn 111 1g. 7.17. The displacements of the localized mod are la u ice and Q = \tf' f,\4
•'i \t:ll b'-
:=

.4 (-I )""-' sinh (N - C)( (7 .1 03a ) 1.0


ll · =
{
' A ( - I )N·-t sinh (N +f)( (7. 103b)
·~ 0.5
which describe an essentially exponential decay going away from the
"
impurity atom as illustrated in Fig. 7.18.
The case sin No= 0 corresponds to odd modes with B =- A and I
ILi = - u, . The values of (j; are given by o = nn / N . where n i an in teger,
and are the same as for the perfect lattice with .A f' = M . The frequencies of I I
the odd modes are unaffected by the impurity. This behavior is consistent
with the fact that uo = 0, i.e ... the impurity atom does not move in an odd --0.5

mode.
For a heavy mass impurity, /\If' > M , the normal mode frequencies are
lowered and no localized mod e with frequency a bove the all owed ba nd of
the perfect lattice can appea r in a mo natomic crystal. However. a resonance Fig. 7.18

mode can exist which is not a true no rmal mod , but which can per-i ·t fo r a
D l·placemt:n t pa!lern nr :1 I caliLetl
vt brd ti nal m d .
considerable period of time. It ha s a large amplitude at the impurit, and a
frequency within the allowed ba nd . In the case of a d iatomic or p lyatomic
crystal. the replacemenL of one of the lighter o nstituent atoms by a heavi r
impurity can produce a loca lized mode ,, ith frequency in the forbidden =ap
between acoustic and optica l bra nches. Replaceinent f ' l heavi r · n-
stituent atom by a lighter impurity ca n (l )so lead t a I C'~ l i zc d m d in th
gap. A lighter constituent atom replaced by a o v n li ghter impurity gi
rise to a localized mode with frequency a bov th ma xim um frequen f
the perfect lattice (M aradudin C' l a/. 197 1).
Localized impurity modes in three-dim nsi on· I latti s can b
veniently analyzed with the aid of Green·, funct i n. (Me I I r II <nd otl.
1955· Maradudin e ta/. 1971 ). T he qualita tin: fe·n ur s a e sim.lar to th · c
of one-dimensional la ttices. In a di amo nd st ruct ur s~:m i ondu t H such as
Si. the replacement of a Si atom by a B at m I :1d-. t a tmpu ri t: · mode
localized about the B atom . Such locali zed mode:-. ca n b ' ~t u di "'d hy optit:a l
techniques as disc ussed in Cha pter I0 .
Lattice vibrations in semiconductors

7.1 0 Piezoelectric eHects


me cr , als hu e the pr pcrty tha t if the crystal is strained, an electric
dip 1 m menl ami a - · cia ted elect~ic field develop. This p.henomenon is
all d piezoelectricity. Only cr stal ·without a center of mverston can exhibit
it. nd r the in ver-ions_m m try operation the crystal is transformed into
it ' elf and an hy ·ica l pro perty must be unchanged. The electric dipole
mom nt N/ i an odd function of coordinates. however, so 1\11 = -1\1 under
in er_ ion . n eM = 0 and piezoelectric crystals cannot have a center of
inversion. Thus, ·emic nductors of the zincblende structure such as GaAs
and of the wurtzite structure such as CdS exhibit piezoelectricity. but dia-
mond structure semiconductors such as Si do not.
The coupling between the elastic strain and the electric field is char-
acterized by the third-rank piezoelectric tensor e,-.,1-. according to the relation

(7.104)

where Jn ii is the stress tensor, Cn J"f, is the fourth-rank elastic modulus


tensor, u-, is the particle displacement, and £ 1 is the electric field. The
equations of motion take the form
2
0
p--= L
Un "'"' OJ0-.:3
-
3t2 [3 OXJ

- "'"' 82 u d£.
- L Cn3- 0 . , - z= e.,~.d -.- . .105)
1-r< .\.f 0 .\ 0 h 8.\' i

The
. constitutive
. relatio n mvo
· lvmg
· t h e electnc
. dt.splacement V ~ nd the
d te 1ectnc tensor E0 1. whe 11 · . . . "
· ptezoe 1ectncny ts present is

'D " = 2: , a ud
f a ~. - + Eo
8r
I: . co
0 1 1
'
.1 0 )
!'1-, . I I "

" ., eq ua l ton
Combining this relation with the· M·tx"rell .

yields the c;:q ua Lion

which is to be .so l v·~, t .· I


... ... simu hneo ·I . . .
Asaspl:cifi\.: ex· - I ' . llS}\Vllh [ q . ( .10')
· , dlnp e let u · . ·
S!XIuld axis parallel I 'I - s. LllllSil1L'r lhL \\ lll l L i l L' (~,l! Jl
~ J.. . u tIe : -dire ·t ·
-- ll~L'IIUil ~llld
I)I'LI ()' to · . . . L IL\11. l)l' L'hhtil: \\ ,L
I . - d ,.,.. I I 11 l! I 11 II ' . I . .
1
~
11
LPILI.OL'hxtrictLTt\o · t H; \ -( II'Ccltl)n .th•r •t 1 111
. J .
.Ill d ln g l • L'kmLIIl or
I I) )L' L'l' n . I . . .
Ll~,.• d ' . • ~llU\.(J. ~~ 11\ ' llti )JI,tll I I I
IL ll:l(l(L' h:n. ( IJ

fJI. . I. ql ! (I
Effects of stress -induced a to mic di placement
149
111

d
,_
'11

"'
! ' l '
( 7. I IJI:.l )

n~ll: c'J£
() -- (' 1. -:
) -1-
( , ._
+ tor , 1 - i)_y
I
. (7 I I 0 )

h ~.: the appropriate clastic modulus in the t· t. . ~ 1111-


ltl.l(IIH!:
44 p ..
. ' •
th' 1. ·rn~.: held from th equationiJfmotion ·
yL..,I."t
~
\\I ' obt·dill
1
11 0 <.1 1011 .
-
· t 11e wave
· t:
l.'ytl ~ l i 1l

•))
u-u- - (
) , li-
P ~= C.:~4 --- (7. 111 )
dt - a .r1 ·

'' ith -+4 the effective elastic modulus specified by

(7.112)

Taking the ela stic vvave to have the pla ne wave fo rm

u~( x , r) = U cos(q.Y- u.:t), (7. 11 3)

the di spersion relation is found to be

(7. 114)

where c, is the speed of the w·~ve . Jt is clear that the speed is enhanced by the
piezoelectricity. T ypicall y. the enhancemen t is on the o rder of 1- 3 p rcent.

7.11 EHects of stress-induced atomic displacements


Thea pplica tionof a n ex ternal str s toasemiconductorcrystalpr due sa
number of interesting effects. If the stre s js unif rm pressure. the cry tal
contracts with resulting change in lattice co nsta nt , elec tronic cncrgie __ and
phonon frequencies. The symm try of the cry'ita l i, unchang d . . o th
degeneracies due to symmetry a re unaf!'ectcd . In cubics miconclu tor ~ the
energy gap between conduction and va lence hand. a t th ·· ra nd L pc int :
increa es with increa in g prcs::;ure. whcre<1 S it d cr a · · at th Y p int . ln
th~ case of phonons the frequ encies of T :\ miJdes at -~' a n d L deer ·ts with
increasing pressure, \Vhereas fo r TO mode. a t th fr qu n 1~..:~ in r a:-. .
LO modes show the same he ha vio r as T mod .' excc:rt for i (M :min z
1980).
If a uniaxial stress is applied to a cubic cr. stal. the at ms t pically di. pin l:
in such a way as to reduce the sy mmetry and thcrl'by re movin g degen-
eracies. In addition. di spla emenL wi thin a unit cell can occu Lh : l ar
reft: rrcd to a. internal displacements ur internal strains.
Lattice vibrations in semiconductors

. tre 11e ap[')h d in the [Ill] direction of a diamo nd r


L eta un wxr1l A p·lir r neare ·t-neighbor atoms along that
· ble 11 te ·tructure Lf a 1·
• , t
' . · ·
<

zm
u·r L '
ctitnwtllundergo~Lcla
• , , nge
1 f -e paration whtch wtthm the framework
, , .
. . · t , tl eor)r wmdd b L:l.dt. However, tt turns out that
ot c:lJS teal la ttc Y 1 . ·r
· , . -u· ' t th ~o r is n t .Hdequate
I 1 .

111.1<.:f0. COp! C1LIS Cl y .
to compete y spect y ~d 1 •
Microscopic the ry ·how. that f:..dl IS gJvcn by

(7.115)

'"l1er · the Kleinman internal displacement parameter (Kleinman 1962).


lS . I b I '
ing a latti e-dynami al model with nearest-ne1g ~ or cent.r_a forces
¥Y

ha\ing for c n t·1 nt a, and tetrahedral angular forces havmg force


const;nt aa , o ne can show that (is given by (Harrison 1980)

(7.116)

It is evident that ( = 0 (ac = 4a0 ) corresponds to no internal displacement


and that 6d 1 is then fully described by macroscopic elasticity theory.
whereas ( = I ( a 0 = 0) corresponds to a full cancellation of the elastic
displacement by the internal displacement.
X-ray diffraction can be employed to measure(. One finds that the values
of ( are 0.73 for Si (Cousins et a!. 1982a) and 0. 72 for Ge (Cousins el a!.
1982b).
Application of a uniaxial compressive stress to Si in the [I 00] direction
lowers the energy of the two [100] conduction band minima rei tive to that
of the other four minima. Compressive stress in the [II I J dir crion in Ge
lowers the energy of the [111] conduction band minimum r lativ t th· t f
the other three minima. In the case of the valt:nce bands. unia. ial ' tress
removes the degeneracy of the light and heavy hole band Piku and Bir
1959). Degeneracies of impurity levels can also be removed by unia-.;:ia l
stress. T~e three~ fold degeneracy of the optical phon n: at q = 0 in i a nd
Ge 15 spht ?Y umaxial stress as a result or inequivalent hange in the for~.·e
constants
. .m the r·h1·ee d 1·rec
· ·t·
1ons o f' po 1anzat10n.
· · n opt1· a J m d ,·...'
polanzcd m the direction or the stress and the other twc are poh1n d
normal to the stress.

Problems
I. Consider a nt~-Jimcnsim1··J 1 . . . . . t
as the [Ill j ,. . . .· . ' moe1e lol St that has the same <ItO mil: tl1~lnt n
lll ect ton of the tin ~(' ·1· · hb r
appro xinHtio 11 t . t: -L IIl1L'nstonal crvsw!. In then ~.ue~Hl"tg
wo 1on:c co ' t·
L
'· . · • ·I 111
c rrcspo11 1· ns <~nts (T l •md (T' · tlt ~rn· tt..• diL n_ t i.J
· 1 two diH·· ·•
l lll !?. to l1~: , . . - ' . • -
(a) \V ·t ·· 1 , . r~.nt lh:~trcst - nL'J g hh) J 1.., 1,mct.'
rt 1.: lll\\ II the equatio 11 f' . .
(h) u · . . ~ 0 mut10n f1)r t h • l\\ 0 al m an th t
~mg<~pl.tnc - w·tv· s l . -
- , ·c . u llltnn o lthl· t'orm u ( !) 1/ I'
t.
- I ·-, ., •uve 1 1.l rther ·, ,.,-.'I· •
, . •. · Jcq Llt.'lll'V -'-' a ~ a J'un
\• CI ~ ll ~lffO r rT 1 = I!I!IN j . . .
( ) I I m .tnd , - (I
l' ~~ ~ap ill the j" •
~ I l l'J'C , - - ·- I
-· Rc pL:at pi o bh.;n, I I I rc qu'-lll') '- l l:l' t r un,·.• II ~' h ,llJ II
fit I ' )II I ilh lit. I
. I clllt ,\J . ' IH hlsc llil' . ". \\ t . l l ll n1 S Ill Ilk 0..1 h lt.l
m.ts~c tn hl' tit I
I ' Sl' I I ·' I
R fer nc s 151
11 h t! lh -tl ' 1~ \ • 11 a m on a t m i~ ·h ~1111 1\ith "Ill' , 1t" m , p 11 111 111 .,. 1
11 1 11111
, I

,/u(l) )
l 1 (
_, ..,,r, lu ll) II ( I lf 1('1' -1 ~") l l~ '
- ,,, . - <---J I

rh~ cqu·~ t ll1 n" l~ motinn. The quantities ,.- 1 and ,, 2 arc the 11 rst-n ~::I~hbnr
j tl\l
nd '-·-:nnJ -ne1~hb~ 1 r fpr~~ c~•nstants. Using a plane wave ~nlutton. find the
1 qu ·nc_ \ C r~u~ wave vector n.:lat1o~1 anJ plot this rdatH 1 n for 17::. =- 0.2'irT
1
~nd,. =-.07.rTJ. Is th e ma\.tmum frequency alwa ys at th~ Brillouin 701w
hl•ll nda r .1
~ ,IJ IItng f l 'lll the equalio.ns of motion o f problem 3. pass to the continuum
limit J.nd ,,ht:tlll the _elastiC equation or· mo ti o n. \Vhat is the ~ peed or so und
r r·~o;;ed 11) terms ol ITt. a:-. Af. and a')
~ •\n .:\.pres. it)Jl for the rrequen~y· distribution function in an .1-dirnensi onal
~~ . t.:m is

Cal uh le the frequency di stribution function for the monatomic linear chain
\\ith nea rest-neighbor interactions. The singularity in the result is an example
r a ·m Ht ve singubrity.
6. sing a two-dimensional version of elasticity th eory, derive an expression for
the low-temperature specific heat and obtain an expression for the Debye
temperature in terms of the speeds of longitudinal and tra nsve rse waves.
7. Consider a monatomic linear chain with nearest-neighbor interaction s
characterized b ,• force constant a and with a defect bond between a pair of
nearest neighbors characterized by force constant a'. Derive expressions that
specify the frequency and displacement of a localized mode of vibration. For
what values of a' /a does a localized mode exist?

References
G. B. Bache let, D. R. Hamann. and M. Scbliiter. Ph_rs. R el'. B26, 4199 ( 1 90~) .
S. Baroni. P. Giannozzi. and A. Testa. Pin-s. Rer, Leu. 58. !R61 (1 9 7).
K. W. Boer. Sun•ey ol Semiconductor Phl •sics (Van Nos trand Rcinh ld.
Ne\\' York. 1990).
rv1. Born and K, Huang, Drnamical Theory n( rr sral Lallie s (O xfo rd niversit y
Pre ·s. Oxford, l 954 ).
\\!'. Cochran. Proc. Ro r. Sue. ( ondo n) A253, _60 ( 1959) .
C. S. G. Cousins. L. G.rwald . .1 . S. 0 1 en. B. Selsmark, 'md B. J. Shcld 1 11 . J. Appl.
Crrsrallugr. 15. 154 ( 191<2·:~).
C. S. G. Cousins. L. Gcrw<:.tld , K. Niel s n. J. S. Olsen . B.. lsmark , B. J. -·held tL
and G. E. Webster. J. Pins. CIS, L65l 19 ~2 b).
B. G. Dick and A. W. Ovct:hau ·er. Pl11 ·s. Re t'. 112. 0 (I 58) . .
c- 1·1 1'S ant 11_/(·rIll·(,t··1·t' lnt ernalt n<ll
G. Dolling. in Jnclosric Scal/l!ring 1 ~ / ·. l ·utron. Il· l .)(J
Atomic Eneruy Agen cy. Vienna . 196_). V I. II . p. 37 _
T. H. Geballe and G. W. Hull. Pln •s. R r. 110, 773 19 8).
P. Giannozzi. S. de GirL n..:oli , P. .Pavone. an d' . B:uo111. , P/1· 1 ··· Rl 1'. 843. 723 1
( 1991 ).
J. E. Hanlon and A. W. Lawso n. Phn. Rcr. 113.472 JL 5 ).
J. R. Hard v. Phil. Alag . 7 315 (I 6:2). . .
W. A. Harrison.
J
Eleclrunic .1·)rmcturc and the Proper/1cs o1 n1I 1· ( W · H · r eman ,
San Franci~co, 19)')0).
Lot ice vibrations in semiconductors
11 1 5o/tell· 8 405 ( 1959).
1
Jh:nnan J.P.~"~'· ~'·. pj;, . ..
Rc v. 181. 1272(1969).
\. 1 Karl' an J. R. 1-J,uu. · . A 178 17 ( 1941)
vr K IIerman. !'lo!. Ror oc. (London) . . . :.
c~ Killt.l. ]ntrmlttcl/011 to oltcl Stole Phystcs. Sixth editiOn (John Wiley.
Nt: crk. ll,h)
1--.lc nm<lll. Ph) Re1. 128. _61 ( 196
->·
1

K. Kunc. Jill. Phys. .tri) 8. J ll (1973- 74).


1.-... Kunc and R. M. Martin. Ph.,··. R_e r. B24. 2311 (1981).
K. Kunc. \11 . Balkcln ·ki ·nd M . Nu JJTIOVICJ , Phys. Re v. 81 .2 , 4346 (1975).
K. Ly n. G. L. Sali nger. . . wen · n, and G. K . Whtte. J. Appl. Phys. 48.
~ 65 ( 1 77). .
. . Ma radu in. E. W. M ntrull , G . H. We1ss. and I. P. lpatova. Theon· of
Lolli e n 1·11 un1i ·s in rhe Harm onic Appruximativn. Second edition (Academic
Press, e~ York , Ic 71).
G . Martinez. in Handbook on Semiconductors, Vol. 2, eds. T. S. Moss and
M. Balkanski ( orth-Holland . Amsterdam. 1980).
S. S. Mitra and M. E. Ma a, in Handbook on S emiconducrors, Vol I. eds.
T. S. Moss and W Paul (North-Holland. Amsterdam , 1982).
E. W . Montroll and R. B. Potts. Phys. Rev. 100, 525 ( 1955).
G . Nilsson and G . Nelin , Pln·s. Rev. 83.364 (1971 ).
G . Nils on and G . Nelin . Pins. Rev. 86. 3777 (1972).
G. E. Pikus and G. L. Bir, Fiz. Tverd . Tela I , 1642 (1959): S ol'. Phrs. Solid Srare
I, 1502 (1959). . .
D. L. Price. J. M. Rowe, and R. M . Nicklow. Phys. Re v. 83. 1268 (1971).
A. A. Quong and B. M. Klein. Phys. Re v. 846, I 0734 (1992).
H. B. Rosenstock and G. F . Newell. J. Chem . Phy. . 21. 1607 ( 195.1).
R. Truell, C. Elbaum, and B. B. Chick. Lltrasonic 1Hetlwds in Solid State Phrsics
(Academic Press. New York , 1969). .
L. van Hove, Phys. Rev. 89, 1189 (1953) .
K. HW. Wb anser. Thesis, University of California, Irvine. 1982.
W . e er, Phrs. Rev. B15, 4789 ( 1977).

('
• •
rge carr1er scatter1ng
d transport properties

Key ideas Transport properties


ha rgc C:l rricrs in SC11l icond llCtors arc cha racterizcd by their IIICll/1 (ree 8 .1 Elementarytransparttheor't
p 11/i. rdcnation rime. and mnhilit_r. ·
nc B 1{/::lllll/111 equation governs the behavior or the carrier distrihution 8 .2 Baltzmannequation
/IIII I Titl11.
The moht!it_r of a carrier is proportional to the average re/asation time . 8 .3 Electricalcanductivityandmobility

[ n g ncraJ. the re/axa lion I ime of a carrier depends on its energ.r and on the 8.4 Energydependenceofthe relaxation
nature of the sca!terers. time

• t £1 1/ering IIII..'Chmrisms SUCh CIS those due tO ioni::ed impurilit'S and phonons 8 .5 Reloxotiontimesforspecific
contribute to the relaxation time. scalteringmechanisms

The el clrical conduclil'ily i . modified by an external magnetic .field. 8.6 Magnelolronsportproperties


The Hall efr c 1 enables one to measure the carrier concentration .
The presence of a temperalure gradiem gives rise to the S t:eheck Ljf~·ct. 8.7 Thermoelectricphenameno
An elec!ric current can produce a hemfiux through the Prltier effect.
Free carriers contribute to the !henna/ conductiFity of a semiconductor. 8 .8 Thermal conductivity
Using deep impurilies. semi-in.w!Oling semiconductors can be produced . 8 .9 Semi-insu lotingse micondudors

In high electric field\" , free carriers have a hight'r eff"cctil'(' temperrtll/1"(' 8 .10 Hotcarrierphenomena

and a /mrer mobility. Ncgatire difjt>rential conducriviry can arise that


produces Gunn oscillafions. High-energy canins can generate
additional carriers by impacr ioni::arion.
In disordered semiconduuors at lo\\' tcmperatur ~ . th(' electri a ! S.ll Variable-ra ngehoppir>g nducltvtly

conductivity can have an cxp (- BT - ~ ) depe ndence duet ''ariahlc-


ranJ<e hopping of carriers .

Transpo rtpr perti ~ u ha sclcctriLal nducti \ il p !J ' acrttcta l r letnthe


applicati 11 1..1 f e micond u t rst o dcctro nic d vic . . ln_tht:, cha r _t r \ hall
be ncerneJ wi thth t1, t' <t JUantit y , u ·ht~s I c t nccharl!, tn n:::spcn'
an externally applied l·orcc s uch a s that J 1 l< an cl ·tri_c 1 :d.
The
carrier or electric charge or int e r s t in scmicondu ' t\lrs ar · pn n anly cnn-
ducuon e lectron s and h')lcs.
Charge carri r scattering and transport properties

. henomenological introduction to
8.1 51mp1e P
tran port in semiconductors
We tart our dl. us .1 n f transport with a simple phenomenological
~.: · · . .
approa ~h. When an extern. I rc 1s applted_to a system of free charge
· , tl t:,. carrter · arc disp laced under the mfluence of
earner the field, and a
. _
t re ·ult . The external force may be due to an electnc held producing
curren . d.
an electric onduction curren t. t a concentratiOn gra tent giving rise to a
diffu ion current. or L a thermal gradi nt leading to a heat current asso-
ciated with thermal cond uctivity.

8.1.1 Electric conduction current


To a first approximation a system of free carriers in an energy band can be
considered as a gas of noninteracting charged particles. In the absence of an
external force the charge carriers execute Brownia n motion resulting from
collisions due to the interaction of the carriers with impurities. lattice
vibrations. and other perturbations to the periodic potential. During a
collision, a carrier may undergo a sharp change in direction. but between
collisions its motion is essentially rectilinear and characterized by its mean
speed. For carriers obeying classical statistics, the mean speed is the thermal
speed s,h specified by the law of equipartition.

1 ¥ .2 _ 3k T
2m sth - 1 B ,

or

( 8.1 )

where, m* . is the carrier


. euect1ve
A' ·
mass. In sermconductor
·
·. u has St.· w here
h
t e earner effective mas
. ' ses are on the order ot the free electron mass mo. Ihe
r •

t herma! speed ts on th d f 7
Th e~ average
. ·. e or er o I 0 cm js a t room temp ratur .
th ·
time bet . . . . . .
ween successive colhsions IS t he reloxotron timer L)
r
e earner. It depends h . . J
on the t on t e punty and perfection f rh " mat nal an
emperature T · l 1 . . 1 r: ,
The mea d. . · YPI_ea re axat10n tunes lie in th ran_ I I 0 :;.
n IStctnce a earner t . ' I b . . . ~ h\
givcnby ta\e s e t\vee n~.:o lh s ll n s t · ttsmeonfreepot ·

and typically lie in the .


· .
tl1e d In.:ct1on I an ge I 00- l (-)l"C>A
of a carrie. . . · ., • . 1_n the e:ts .
rsotroprc sc
ttering
dn·eetron with eqL· I I llllmedlatel alll:-r a u IIi i~. n b· all .an
l.t proh'lbilt T · ·r ·
I,o rezero. ' 1
y . h e meonvel o city~.ft h
When an de~.: I ric fi ~ I .
s uh . . ' 1: d £ IS llJ1 r I
· J <.: llua lur~,.·l· F -:: ~ . P lcl at Il l e r 11 • a .tttl
v ' kl~.:it CO
. illpuu("nt
. , ' £
). . l- or a c.:· ·
d l n
~ Ill . :-. ht:l l I
1
llllh j 1 .
"' l r 'Li t ~ n o I II l' ti ~.-•I I "'
•• (
Introduction to transport in semiconductors 155

f11 11 n (. ·~ Eq (4 14))

. "' ·.. -
Ill -

I ntcgra ting this equation from r0 to r0


( r) -
dr
. ~·..
_ (,<..

- t. nne gets
•.l• l vv
. e,.£
l',, (f) = - I. ( 8.4)

Fig. 8.1
This component increases linearly with time between two collisions and is Velocity component vcr. us time for
r tu rn~::d to zero immediately after each collision as shown in Fig. 8.1. a carrie r undergoing colhs wns
Suppose that there are N carriers traveling with speed s in a given
d irection. The number of collisions made by the carriers in a small time
int r val dt is proportional to both Nand dt. H N(t) is the numher of carriers
which have not made a collision at timet. then

N(t)
dN(t) = - - -. dt , (8.5)
r (s)

where r(s) is the relaxation time . Integrating this equation , we have

N(t ) = Noe- ' f r(s) (8.6)

where No = N(O).
The probability P(t) that a carrier has not made a collision at timet is
given by

l
P(t) = - e - 1/ r (s) ' (8 .7)
r(s)

where P(t) is normalized to unity:

(8.8)
l )
ex: P(t)dt = l.

The mean time between collisions (t) is specified by

(t) = .l tP(r )dT = r(s),


(8.9)

so r(s) can be interpreted as the mean free time. Similarly, one obtains the
mean value of the velocity component vn (t) in the form

(v,.) = {


'n.,(t)P(t)dt
Jo
e,. £ eJr(s)
tP(t)dt = - -.,-
= -;;;: I) . /71
(8 .1 0
= ± J.l( s)E,
Charge carrier scattering and transport properties
156

1-
\\here Jl (·' i the fr e carrier mobility gi vcn hy

e1 r(., ) cr(s )
/l·(s) = ---;;;;- - 111 • ·
(8.11)
l
2
The unit of , ar convention llv ta ke n to be cm / (V s). In the Drude model,
1
a ll arrier r a given ma..; have th sa me speed , so r (s) and J.L(s) are con-
·tants f r such carrie r .
he rn ilit i · by efini ti n positive and depends linearly on the
rela ' a tion time. F >r a gi .n semi cond ucto r the effective mass is a known
fixed quantit • . The mobilit y th refore va ries from sample to sample
thrOLw.h its d pendenc on r which is a function of impurity content and
temperature. The hi ghe ~ t alue · of rand hence of f..L arc obtained in very
pure material at low temperature.
In semiconductors \Ve can have positive charge ca rri ers, holes. with
mobility f-lh and velocity v 11 = p ;,£, a nd ne2.a tive charge carriers, conduction
electrons. with mobility JLc and velo~,.;ity v" = - J..Le£. The displacement of
charge ca rriers under the influence of an applied electric fie ld produces an
electric current. The current density j is d fined as the charge crossing unit
-··
surface area per unit time. For electrons and ho les we have
'--

(8. 12a)

(8.12b)

where nand Pare the co ncentrations of electrons and holes, respectively. If


both .electrons and holes are present. the total current j is the sum of the
mdtvtdual contributions, so tha t

j = je .h = a£ . (8. 131

where the electrical conductivity a is given by

a= nef.Le pep;, . ( 8.1-l)

Using Eq. (8. 11) we can re- expre


· '"s the conducttvlly
. . as

rr =e1(17T• +PTh) . (J . L-)


m,. m;,
·quat ion (g.l3) is a micr . ". . . . . -
geneotL semicon :l .. oscoptc st.uemen t ot Ohm 's law Ft r a lw111Q
c uctor slab or 1 , ·h r l ·
volt a!le V ·1pplit;d. engt r and cros:;-sedi( n.d .tr~LI \\ 11 1 •1
sta te; th at. .tcross the length. tht: corneniio;1·tl f rl11 l1f0hm'-· b''

I. = I R. I ...; It'
\Nh.:r~:· I i s· tl1e curreni 11 .
0\\1111.!
~
and R ·-. h
I:-; l C'
.
l'L'SIS! <tn ,; .!,!1\ '11 !"I\

f
R --
lntrodu tion to transport in e micondu ors 157
Tabl~ 8 .1 ~'"'Ill 1 ·mr~rdlu rl Ill• bilitil·~ "' u11 1 " 1.d 1 ., h.rll t·l 1'11\ tq

St { fl' l'l"ll c
IJ'iO xooo }~ flO
4 ' () _:~ no If 10()

IL i a g n ral obsl.'rvation that the mobility of electron, is signillcantly


l1n! 'I than that of holes. This can be attributed at least in part to th~
;;1... ncra lf~, la rger ctlectivc.: masses of holes compared to electrons and the
n l.'r. r la ti\.lllShip of mobility to effective mass contained in Eq . (8 . J l ).
1\h,hJlit• 'S tend to increase rapidly with d ecrea sing temperature a a
• 11- qucnce of longer relaxation times at low temperature than at hi 11 h
temperature. The trapping of free carriers by ionized impurities and the
de ·rea ·cd amplitude of atomic vibrations at low tempera ture both tend
to d c rease the etlecti\'e collision rate and increase th relaxation time.
om representative mobilities at room temperature are shown in
Ta le 8.1.

8.1 .2 Conductivity effective mass


The expression \:ve have obtained for the mobi]jty. ,~1: , contains the
conductivity effective mass m x. For a specific semiconductor it is necessarv
to determine what types of carriers are present and how their band structure
effective masses are related tom' . As a specific exa mple we consider n-Si for
which the conduction electrons arc distributed among six equivalent val-
leys. Two valleys have their minima along each of the x-. y- , and .:-axe at
+x 0 . ±y0 , and :c::0 . Each valley is characterized b a longitudinal effective
mass m t and a transverse effective mass m 1 due to the anisotropy of the
conduction band constant energy urface ~. The total current densit is the
sum of the current densities associated with each aile ,

( . 18)

wherejer is the current density from electrons in the two valleys with minima
along the i-axis, i = .r , y , ::.
If the electric field is in the .\:-direction , the electrons in the two minima
at ± xo are characterized by the long itudinal effective rna s m , whe r a s
the electrons in the four minima at ± .1'(1 a nd ± .:o are charact rizcd b y
the transverse effe ti ve ma. m 1 • We therefore have th e followin g c n-
tributions to the current den ity u sing Eq. (R.l2a):

nr - r,.
·. = 2(n j t1 )ep,. £ = -
. { \
- £
11/t
(• . 19a)
'
.19b )
Charge carrier scattering and transport properties
158
T he total cu rent ensity from Eq . (8.19) becomes

1
j =
t
~3 ( -m,+ 2.)ne
m,
2
r,£. (8.20)

Referrir g back t q. ( .12a) \.Ve see that

I'· · = ~3 (-1
L mf
(8 .21)

which upon comparison with Eq. (8.11) yields the inverse conductivity
effective mass for the conduction band:

m~
I = 31(1me+ m,2) · (8 .22)

For carriers in the valence band we have to consider the heavy hole and
light hole bands which are degenerate at k = 0 and will both contribute to
the conduction process. The current density due to heavy holes with con-
centration Ph and mass mhh is

(8.23 )

while that for light holes with concentration PI: and mass m 111 is
1
. _P e - r"E
leh- , (8.24)
mu,
where we have assumed that the relaxation times for light and heavy holes
have the same value r 11 • ~
The total hole current density jh is

}.h --Jeh
· +lhh
· = ( -Ph + -Pt ) e -r11 E, 1
(8.25 )
m;,h m r;,

which can be written in the alternative form


1
. pe-r11
}j, = - £.
111 ('

where m;. is the conductivit ff .


k s und
!') = 1)1' + fJ 1 Co . Y e ect1ve
·_ mass for val~nL ~ bdncl h
· mpanng Ec1s (8 ?S).
~ · ·-- .tnd (8 ._6). w~ ob ta m .

_I__ Ph Pr
or - - - + -
,. /)111"" /)11/ ill
In equilibrium the cone . . .
tiona! to m 31'2. 1 V :! entr.ttlons ol light and hea\'\ hl J•.., 1 pr 1' -
"' <~nl 'II'"' , n:spl'cti vely, so

I
;-
Ill ~, , , ~,
-Ill ' =
,. ' ., \ .
IIIII - + Ill -
I t Ill
Introduction to transport in semiconducto rs
159
1. Diffusion current

h 'I th' rr_ · L·arric•.· distrihutio n is not uniform in space, the a rricr:-. tend
dtllu L'
. . . rc~wns
lnm1 . ~ . 1.1f high
~ , . to 1·eg1
l'Onccntntt.l1D ·011 s- o f 1ow con-
nlr tllll .
.
Dr II USillll
.
ts Q:lWerncd hv Fick 's hw w11 t'cl1 states tl ttl
~ _ ·· , • .. . 1a
·
1e earner
11 .1,, 1 proplll·twnal to the concentration gndicnt 'J'11c fltt
. . .. ~ ' . xo f.
c1
·
partlc-
ul." ~-- p~.:. ~I carr~J·c_r '. ~: the number. o f ~uch ~arriers crossing unit area per-
pu dr~.tr l.lr hl t_hur dut:dron ofmotiOn 111 untt time. In one dimension Fick'
11" tJ I-.~s the lonn

J Ul = -D dnci
II \' I d.\' • ( 8.28)

' here D; is the diffusion constant for the ith type of carrier. In three
dimen-.ions. Fick's law becomes

(8.29)

Associated \Vith a ftux of charge carriers is an electric current called the


diffusion current whose density ji is e(';J,~i) . For conduction electrons and
holes. we have

(8.30a )
and

(8.30b)

The total diffusion current is

(8 .31 )

When both an electric field£ and concentration gradients are present, the
current densities satisfy

(8. J2a)

(8 .32b)

The mobility f.L is a measure of the e·1se with which a carrier responds to
an electric field , whereas the difru ion consta nt Dis a measure of the eas
with which a carrier responds to a concentration gr·tdienl. From the form of
Eq. (8.32) we see that the quantity Vn j n play the role of an effective "field''
which produces the dilfu sive ri1otion of a carrier. It has been shown
(Einstein 1905) that there is a direct connection , c·tlled the Einstein relation ,
between the mobility and the diffusion const a nt.
If we impose the condition of equilibrium on a semiconductor. ampl .
the current density of each type of carrier must b Zl:f'O. Taking electrons a.
an example. we have from Eq . (8 .32a)

ne11,.£ + eD,.Vn =0
Charge carrier scattering and transport properties

or
llfl ,.f = - D,.Vn . OUJ)
The electric field£. j relat d to the ekctric potential V(r} by£= - V V(r),
o q . (8. 3) become
1/( f i,. "V V = D l! Vn. (8.34)

F urthermor . the c nd uction band edge becomes£( - e V(r), and under


non-deg n rat c nditions, the conduction electron concentration at
point r can be xpr ed by the following modification of Eq. (6.1 0):

11 (r )
-
= N 1 (:'
- i[£ - eV(,. )- Ef·
' • •
(8.35)

Since the Fermi energy Er is the chemical potential of the electrons. in


equilibrium it must be a constant and independent of position . Taking the
gradient of n(r). we obtain

Vn (r) = en(r)V V(r ). (8. 36)

Substituting Eq . (8.36) into Eq. (8.34) yields

f.Le kaT
De = -8 = - - /.Le , (8. 37 )
,' e e

which is the Einstein relation. The corresponding relation for holes is

kaT
D1r = -- p~~. (8.38 )
e
Taking
. into considerat Ion
· h E' · .
t e m ste1n relatiOn. we can re\Ynte the
.
~xpressJOns for the electron and hole current densities !!iven h) E ~s. ( 8.3~)
m the form ~

i. = f.te(en£ + kaT Vn ) (8.39a)

l11 = J.L11(ep£ - kB T Vp) .


Thus. the current densi 1 ·,
sion is ta k ~ ·
.
' Y Is proportiOnal to the mobilitv Hn
en mto account. ·
,,h n fifl"u-

8.1.4 Displacement current

Up to this point we have fot: . . .


mdepe ndent pheno . . used on electnc;,d cPnd ucu a Jinll'-
. menon IJ ·t sv -t . ,
e ectnc field that 0 . .11 . ~ ·. .' ~- s em ot tree c 1rn rs 1.
I ut'IJ'-' "l t~.l .Ill
su "lk 111 tune ol' the J'n rm

£ = £,£-' - '""·{ . . ..Jl)


d'
is . .
I •
a •splacement current
. Sl. t lip Whl)SC JL•nsi l \ . .
. - J.J ~~ =-1 ~ll b)
. 'JV
'" = --
t}{ •
The Boltzmann equation and its solution 16
1 lh electric d tsplocement The electric dtspl ,IL\:111Clll j, rclatt: 1 to
11 · I I h~ the cquatii'IJl

( X. 2)
h , ;., h~, dich::,ctric L·onstant and (fl is the permittivity of' vac uum
· - ' Nm - ). C'Pmbining Eqs. (~.40) ·- (R.42). \Ve obtain
12
Ill

it = - ia .o:....£. 0:~.43 )

ddin2 thi-, n:·:-.ult to the static contribution to the current density l!i ven bv
Eq. (•' L' l i~ lds -~ -

.i = (a - iffouJ)£. (8.44 )

Tit: 1 1I· cement current contribution is important only at relatively hjgh


r quencies such as those found in certain electronic components and in
l ur al phenomena.

8.2 The Boltzmann equation and its solution


In order to go beyond the simple treatment of Section 8.1, it is necessary to
recognize that the relaxation time is in general a function of the energy of
the free carrier. Furthermore. in the presence of an electric field , free
carriers are not in equilibrium. and their distribution over energy is not
specified by the equilibrium distribution function discussed in Chapter 6.
but by a nonequilibrium distribution function that is determined by solving
the Boltzmann equation.
The classical distribution function(( v , t ) specifies the numb r of charge
carriers having velocities in a unit range about the value vat timet. Since
a carrier is characterized by its wave vector k. we replace v by k :
f(v. t) ____. f(k.t ). We shall deal only with spatially uniform ystems, so there
is no dependence of( on the spatial coordinate r of the ca rrier. For the
moment it is assumed that only a ingle type of carrier is pre ent.
A charge carrier moving in a perfect crystal with a periodic potential an
be taken to be in a particular Bloch eigenstate of the p ri die Hamiltonian.
If the periodic potential is perturbed by the intr duction or impuritie or
other flaws or by the vibrations of the nucl i a\ ay from their quilib rium
position . the carrier may undergo a scattering tran. ilion to another Bl h
state.
The distribution function f (k. , r) can change with time t a. a r suit of
collisions or as a result or .an explicit cl r nden e n r r an impli it
dependence due to a dependence of k on r. The t tal dcri a tiv~:. U \i ith
respect tor can therefore he written a.

(8 4 -)

where <.!1. 1 is the time rate or change of l due to collisio ns and th ~ mimts
ciT mil . . · · · . d 1•
sign in front or this term reflects the I act that colltstons tend to 1 uce t le
Charge carrier scattering and transport properties
12
.· . func tion only of the carrier energy £ 11 , as is
ccurancy of ta c k. Lf ./ t.
fr qu ntly th ca · . the
8/ fJf BE" (8.46)
ak" = aE" ak., ·
Bl
8t = O, (8.47)

anJ

dl _ ai [L aEkdko.] - dfl . (8.48)


dt - 8£k rr 8k 0 d! dt col/

From the basic equation of motion given by Eq. (4.15) we have

~dk,1
11
_- F
0' • (8.49)
dt

where F is the external force acting on the carrier, so Eq . (8.48) becomes

df 8f
- =--F·VkEk--
df l (8.50)
dL n8 cit Ek coli .

But from Eq. (4.8), which specifies the group velocity of an electron wave
packet,

1
Vg = tz VkEk. (8.51 )

Substituting this result into Eq. (8.50) yields

df of
dt =f)£ F. Vg -
dfdt ! . (8.521
k col/

In a st~ady state the two contributions to the time depe n d n~e n the right
hand stde cancel, so that

elf
dt = O, ( ~ ..-3 1

and

of F . Vg = ...:._
DE d!' l . ( ...-.J I
k d! ' ""
For small deviations oflfr .. .
that the time ntc - ~J · om the equlltbnum dislri twn u. ' I:'~ urn.
01 ~.: 1 angeofthed ·, ··b · · lilt , , fl. I
proportional to the d .. . _ 1st11 utton luncu n du t
L
I '

. evtatJOn ot th-' d ., .b . . . , uthh


1
num value : '- tstn utt o n t unciit n I 111

·(II
-
1I - I
---
I
- (I ' '
I • ull r .
Electrical conductivity and mobility 163
"" II ' 'r" ' o fth~..·pr~ 1 PI..ll"llt1 11ality um..;t <Jnt i~ th • rcla • l1Pntimc r .
.-4 l ·an t lwn he rcwri t ten a:-

;}f / - t;,
._,-l :- F · v .. - (' .56 )
r' ;~ ·' T

, Ju h 1 the B~)~t7mann equation in the relaxation time approximation. It


1 u ... r l" cm pklst 7ed that a rela xation time cannot al\:vays be defined. pa r-
IlL ul.trl he n the earners are 111 alllsotropic energy bands. A discu , s10 11 of
h f'ltlllfC lll 'Il lS t'1..W lh1.. C:Xi:' tence O f a relaxa tion time can be found in the
.II'IJd. b) R\1lh ( J9l)2) .
r the prl1hlcm of electrical conductivity. the fo rce F is

F = e,.£. (!5.57)

' here c, L the carrier charge and £ is the macroscopic electric field in the
cr} ·tal. The Boltzmann equation becomes

i.J(
BE' k
e, £ · Vg = - f-- -
.fi)
(!5.58)
r

whic h can be rea rranged in the form

. ,. [){
f = JO - er r~£ · v~.
oE~; ·
(8.59)

If we assume that the perturbing electric field is weak, then to first order in
£ .. we ha e

. ·:::: r:(, - e r-£ · v


ato (8.60)
·f n t aE" .!('

which is an explicit so lution for the perturbed distributi on fun tion/ The
d viation off from its eq uilibrium value is proportional to both the electric
field and the group velocity. Thi:s solution can be used to calcula te the
average va lues o f ph ysical quantities of interest uch a vg.

8.3 Electrical conductivity and mobility


The total cu rrent density} is an average of the currents a~~ociated v.:ith the
individual charge carrier- and is gi en by
.6 1)

where n, is the concentrat ion of charge carrier. and the· angular brack l.
denote a sta ti . tica l mechanica l average oft·~:

( _)

The carrier concen tra tion can be exprc, sed in terms of th distribuli n
function. Combining the result f r the gro up cloci t ( ~ q . (X .~ l)) and the
Charge carrier scattering and transport properties
16.4
Boltzmann qua tion (Eq . ( ~ - 0)), we can write

.
j .l d'k = ~-~-~;~ --- e,r (~~~ £ · ~ \hEk
• L
l d'k. (~.63)
The C'n ro Ek i an even function of k. but its gradient is an odd function.
ti
Sine b 1 the relaxnti n timer and the equilibrium distribution functionj[ 1
dtq end on k only thro ugh £ 1( . the second term of the integrand in Eq. (8.63)
is an odd functi n . f k . a nd it~ integral therefore vanishes. Hence.
} fd Jk = j j (1 13k _ T he di st ribution function _is the Fermi-Dirac dis- /rl
tributi on function. T he ca rri er concentration IS gtven by Eq. (6.3):

(8 .64 )

One can ·implify the integral i_n the numerator of Eq. (8.62) by noting
that vg as expressed by Eq. (8. 51) must be an odd function of k. whereasj1) is
an even function. Hence,

If
. vgcI 'k' = JJ · 0/rl - vg v"d -k
~o- ecr'-JEk·E I l·
=
I
-c,.
EJto
T () £k (£ · Vg )Vgcf-1k.

(8.65)

The average value of the group velocity, Eq. (8.62), nmv takes the form

( )
Vg =- 47T-'n,.
e, I '1/u
T f_)£k (£. Vg )Vr:d-'k.
. • (8.66)

The quantit~ (ug) is called the drift velocity which is the a verc ge va lue of the
group veloctty of a scattered carrier in an electric field. B\' vmm tn we s~:e
that 1f k enters
_
r onl),. th.IL)Ug h t h e energy Ek. the onlv n· nvnnL
~ . .~
hmg com-
ponent
. ,
ofu
. g
ts th 'tt
'
pa 11 1 t 1 1 . . . . -. . . ·
ra e o t 1e e ectnc fleld £. It£ 1s m the x-dtredJllll.
Eq. (8.66) can he re\vritten as

( v ~ '; = f v ,,;' = ___e c _ ;· i'£') .(')j.


I) .c ~ l ,~k- (8.6 '7 )
c ' ,, .. T \ k - - I' '
4rr·'nc ')£!.. '-'' ' ·

The mobilitv~ fL is delined


·
h\· tl . I ..
.i 1e 1e at1on

(?·,,)
,-.. ,!
= (e. le )f' ,,
i. I t \.

Comparing Ell'' ( 67
· "· ' -) ) and (8' · 6l') .. o b t:11n
0 • we .

I' = _ _ e ;· . t.· ) U/tl


. . , 1
471 1 }1 . T( ~ )£ /'~ .tl !...
·- { . ( 1.. ,. . ~
fhl.! mnbilitv b · ·
. - -. ~.:. mg prnp nti~l . I -
l11ne bctwcl'n L' 11· . . Il.l lu th · SL':tlt ' 1'1 111! 11111 ·
. c 1:--Iun s Is ion . -
ckl'lnc cnndiiL'livitv fT . . g .tnd lu \\ whl'n t h.: lll ~·
Is ckiirh: ~l h\ ()11 . 1
IT! '\ :1\\ .
.
.

I =- ~·-
Electrical conductivity and mobility 65
' I 1 h '' h n '-·,,mhme I \\ith Eq (.. 61) and (X.6X) yield
(T : - II,Cfl. (X.71 J

I l1 lt.·trihutinn functi,,n/o is the Fermi· Dirac distribution function

(X.72)

, hH:h upt1n ditrerentiation yields

Jj(l ( £") de ~( "' - r::,. I .


i)Ek
=-
[c 1(1:, - , ) + tf - ..
- -t3fr( l 1··
o -. o). (8.73 )

~ub: tJt ution of Eqs. (R.51) and (8.73) into Eq. (8.69) gives the mobility in
the tNm

(8.74

which is valid for both parabolic and nonparabolic bands.


For the special case or spherical parabolic bands with£,. = (112 j 2m* )k2.

t/·
(V~.Ek),.
.
= -m ..• kr , (8.75)

and

fJ· =
')

n-e.
4 7f•311JI'r'" 2
J . r(Ek)/o( l -fo )lr,.d
1 3
· k..
.
(8.76)

Since k ,. is a dummy integration variable, we can replace k_, by ky and by k :,


add the three expressions and divide by 3 to give

.. ,.,d 3 '
2
I' =
fi e!3
12r. 311cl11 - *' ; · . .(
r(£~.)./o I - .1o)"- '' · (8.77)

Introducing spherical coordinates, setting E = (TP. / 2m' )k 2 , and noting that


the integrand in Eq. (8. 77) depend s only on£, we integrate over the angular
variables and obtain in the classical limit

(8.78)

If we define the average value of r (E ) by


fr (E )j;,£1f 2dE
R.7 )
(r ) =. JJj,£ 3n rt£ ,

we can re-cxpress Eq . (8.7X) in the form

fl - e[J (21'.11;') 1!~ (r )j ..f(,l:.'v:. dE. (8 .80)


- 3 7f 2 1lc l11 '
Charge ca rrie r scattering and transport properties
166
T treat the C<.lce f ellip. oidal parabolic bands. one ·'sphericalize-;" the
neroy u -ing the tra nsformati n in Eq. (_6.21 ). The mobility tensor element
II"'' i~ ot tain .d f r m ~q. (8. 0) by replacmgm" bym;, and (r) by (r,.), where
IT.= f l" ' .
1 rder to pr ceed further we must evaluate the integrals in Eqs. (8.79)
and (8.80). h range of integration is from zero to £,, the maximum
en r!! , f th band of interest. For not too large carrier concentrations and
not t~o high t mperatures, the ex ponential decrease of.fo with increasing E
enables us in good approximation to replace Em by infinity. For semi-
conductors with temperatures, carrier concentrations, and effective masses
satisfying the inequality (Tolman 1938)
J

nc
l/ 3
< (m*2rrk T) 2/fi
B
1, (8.81)

it is satisfactory to take/0 to be the classical Boltzmann distribution given


by ~

fo(E) :::: Ke- Ct: - Er ) , (8.82)

:-'here K_ is the normalization constant determined by Eq . (8.64). When the


mequahty 1s not satisfied, the full Fermi- Dirac distribution must be used
in Eq. (8 .77) with the consequence that the intecrrals must be done
numerically. o
Restricting ourselves to the classical case, we find tha t

(8.83a )

n, = 2: 2 (
2
;3•y/2 f .!oE1dE
I
= 4(r.f :J) Jf _ h2
(2m")~/:!
Ke Er
. ~3 b l

Eq uation (~.80) for the mobilit y then becom es

= e (r ) . . '-l )
11 m· t• .
Thi s result is a gcneralizat" . .
ca rriers are ass umed to.h·H).:1 ofo that lor the Drude model In\ hi ·h til ,_.-h,tr~,
case we must k . ave the same r regardless f enl.:'r..!\ I 1 th' >!~·nc·r.tl
. --
o r~.1et to eva luate (r . . 1 hts rr~
. now r( £) 111
Sicle red in the n~xt s• t .
. .. l :C I On. W e ·ee th · t h . .
p.tldfneters. the · tv ~-. .. .t t e rno h1l! t\ 111\ \1 .: 1
, t:la ge n:. •hx·l(j) l . .
cepcnJ
I o n the m<.tter"·J . ' ' '. Lll Ime anJ the ll~lll · n
- . ht . 1 11C c fl e ·t , .
pu• e rnall:n,tl . hut tl , . l IVt: mass IS ~s n ll,dl .t
· 11.: dV~o:r H!. · • )
llllpunth.'s a 11 d oth ,. . . ' l II: cl.\<.t tl cll
ll 1111pcrli:d 11..111~
Energy dependence of the re laxatio n time
167

8.4 E e gy dependence of the relaxation time


.ttl nng l'\ ·nt a current C<lrricr mak.cs a transition frorn the Bloch
1;\ I~' the Bh,~_·h st:lt ' In'!.:') . F1)r the present we restrict oursd c. tn
1 trob nd scattering ft,r \Vhich n' =- 11. The scattering rate W(k - ·1.:') is

1 1 nmni.'J 1ua ntum mechanically from Fermi's golden rule . The rate of
h.lll!..t 1 I the dis tributinn function due to collisions is !liven by

·; I ;·
<< = - { l·V(k ~ k'){ (k )[ I -f (I.:') I
( ''" .
- H'(k' __. k)f (k')[l -f (k)] }d~k' , (8.85)

, 11 ·r the first and second terms on the right hand side correspond to
:c.HL ring t)Ut of state k and scattering into state k . respectively. Note that
the Paul i principle has been taken into account. At equilibrium , the net
c "IIi ·i 10 ratl' vanishes. and \ve obtain the principle of detailed balance:

If (k-- k:').l(,(k)[l -.f{,(k')] - H1 (k' __. k).fi,(k')[l -.f0 (k)J = 0. (8.86

A more convenient form ofEq. (8 .85) can be obtained by using Eq. (8.60),
"':hich we re\Hite as

()"
f = fo- tp(k) ~-~k , (8.8 7)

where

(8.88)

Substituting Eq. (8.87) into Eq . (8.85) and exploiting the principle of


detailed balance yields the result to terms linear in <p

~r
dr
I
mil
= j'{ w(k --" k') [zp (k ) ofo(k) [I - ./o(k' )J- (k') {J~~:.')lo(k)]
8Ek

+ W(k'--" k) [;_p(k) f!/o( k )fo(k')


c Ek

- zp(k') ~;i:.') [I - j(,(k)J] }rt 3k' .


. now use
If we , Eq . (8 .73)
- and again take advantage o f detaile i bab n e
obtain

~- ~ = -jJ ; · W(k - k' )[ (h: - (k')].fo (k )[ l - ;;,(A' ]d Jk' , ( '. 0)


cull ·

which upon making the substitution

W(k --) k')[J - ./l)(k')] = Hl (k,// )[ 1 - /o(k )j g. I


Charge carrie r sea tering and transport properties
1 8

b c me.-

i!f I = -r1;· W (k,J.:' )[ (!.:) ~ i.p(k') ]h(k)[l -Ji)(k)]d k'.


3
(8.92)
{) { ( t l!f •

Again u ·ing E _( '_ 73 . we can revvTite Eq. (8.92) as

J_l == U(o(A) ; · W(k,k') [<p(k) - i.p(k') jd 3 k'. (8.93)


() l coli fj £1, ·

We consider two important cases for which a relaxation time can be


defined (Roth 1992):
1. Elastic or inelastic scattering which is characterized by W(k, k'), being
an even function of k'. This case is referred to as "k-randomizing"'
(Herring and Vogt 1956).
2. Elastic scattering and isotropic energy bands with vV(k __, k') depend-
ing only on the angle between k and k'.
For case (I) we note that since W(k ____. k') and JO (k' ) are even functions of
k' . W(k, k') is also even . On the other hand 'P(k') is an odd function of k'
because Vg is an odd function of k' from its definition in Eq. (8 .51). Con-
sequently, the integral involving i.p(k') in Eq . (8.93) vanishes, and

(8.94)

Use of Eq . (8 .87) yields

81)''1
at m/1
= - U - to )
. .
I
.
f ·
W(k. k )d -'k.
' I
( c .95 )

whi~h upon comparison with Eq. (8 .55) gives the inverse rela -.:ation time in
the lorm

I
r(Ek) = ;· IV(k.k' )c( 3 k ' .

Thus, forca
. se (l)the in\'eJ·se re 1axaLion
- time
- d e pe nds nnh l n tht> 'l'dll n !1'~
rate H/ (k,k'). · · ·
For case
, .- (
(2), we .use
_ ·
the sPleiJ<.:a
1 -· . 1parabohchand
- vn lu "C rr: .. 1i/.. / 111• -··11d
\\lite 'P k ) 111 the lorm

tp( k ) = X(k ) · v~ = X(kl · lik / m" ,


whe re

X(k ) = e, r (E~.; )£
Substitulin~ I hi s cxpr . . - .
~ . -· ~:ssiun ~~~r ;:'(k Inll) Eq . (~ _l ~l '''-' 'bt In

i)~ ~ - h !Jfn\1..) ;·
i it '"" 117 ,jj._-A . II' (J.. . k ' l[X(J.. ) · (k f. )I C
Rela a tion tim es for specific scattering mechanisms 169

r " · h 1 \ ' u_t1 li1l.J th_t' !act that l•'r t•I:Jslll. ta lt ··nn
'- , /·.,.
., , JJk :1111.._1
nL1. ). 1 h ' l l'rm 111 squ:m: hrad.ds c· m he written :1 s

\(l..)k(cllsf1J. x ens. () I. ..x ). ( X.I 00 )

h r · f 11. x ~~ thl.· <tn gk between k and X(k ). The integral over k' is eva luated
u mg sp h ·neal l.',_ll)rdmatc~ with the polar axis in the k-direction . Then
~ f}J. he ~()lllC::\

C(LHJ.x. = l.·osOu.:cosfhx - sintt,. _,.. sinf-J,. _xcos ( J. ' - 0x)· (,'.101 )

Th it:tcgra~ of the term containing cos ('t-- "' - -P x) vanishes becwse bv


a . . . um ptlon n depends only on ek.k' and not on f k': ~

(R.102)

. e of Eqs . (8 .97) and (8.87) yields

ufl
iJl . ·) ;· W(k , k )[I -
= -U - to 1
cose"k']d -k'.
1
(R.103)
,_·u/1

mparing this equation with Eq. (8.55) we see that

I .
l

I =.
r (Ek) W (k,k ) [I - cose,. _k'] d ·k' .
I 1.
(8.1 04)

Hence. for case (2) the inverse relaxation time depends not only on 11-'(k. k' )
but also on the factor I - cos B,. _k' \-vhjch represents the fraction of forward
momentum k that is randomized or lost in each collision. The relaxation
time involved in low-field transport phenomena is the momentum relaxa-
tion time that is specified by Eq . (8.1 04) .
In the classical limit to \Vhich we restrict ourselves, W( k,k 1 ) becomes
equal to W (k ........ k' ) and can be calcul ated by the Fermi golden rule for the
scattering mechanism of interest. We discuss the calculation of both
the scattering rate Hl (/i , k' ) and the relaxation time r (Ek) for a variety of
scattering mech a ni sms.

8.5 Relaxation times for specific


scattering mechanisms
There are a variety of sca ttering pr ._es o r importance in semi-
conductors. They include sca ttering by ic niz d impurities. neutr:.1l impu -
rities, other charge carriers. acou stic piH nons, and optical phonon s. a h
scattering mechani sm leads to a charaGleri<>tic energy dependen ·c: of th '
relaxation time.

8.5.1 Ionized impurity scattering


If the weakl y bound electron of a don o r impurit y uch asP in Si is .' itcd
into the conduction band . the positive impurity i( n that rcm:tin s serves H::. tt
Charge carrier scattering and transport properties

. f" fee ·arrier:. Since we typically deal with ·y ·tern


caltenng cent r r r . . . b C I .
. -1 l oncentr'llion of tree earners, t e ou omb potent 1al
c ntammg a mJ c ~ . , . .
· · · purit ion 1s screened by the free earners. The mter-
du to t he po. tt1ve m1 • ·.
acti n Hamillonian J therefore ol the form
1
- Ze- - qulr - RI
11int (1·) -- , (8.105)
4 7rE J ,,. - Rl e
wber R is t he p itio n ector of the ion, Ze is its charge, E is the dielectric
constant ft h · m iconductor, and lfo is the inverse Debye screening length.
If onl y a ingl type of free carrier with concentration nc is present, q0 is
specified by (Debye and Hi..ickel 1923)

(8.106)

Similar considerations apply to an acceptor impurity such as AI. but in


this case the impurity ion is negatively cbarged and the free carrier is
positively charged.
If we neglect multiple scattering and use the Born approximation.
Fermi's golden rule (Fermi 1950) gives the scattering rate as

( k,k
I)
= h27r I(k I . 2
IH;I/[(r)lk) l o(Ek' - Ek)g(k ),
. I
(8.107)

where the 8-function expresses the fa.c t that the scattering is ela ·tic and the
3
density-of-states g(k ) is S1/(27l") . Taking the Bloch statel k ) as the product
1

of a plane wave function and the periodic function uk (r ). the matrix element
of l-h11 becomes

( 8 . 10~ )

The pr~duct ujA r)uk(r) has the periodicity of the r. tal ~In l can b~
expanded m the Fourier series

u;.(,.)uk(•·) = L f!iGr B~o.·dG ). ~ .I OlJ l


G
In this equation

Bkk G ) --
I (
nI ; ·
e- iG'··· . . '
ll~o.· (r)uk(r )d -' r

and G is a reciproc·ll htt" . l ( .. 10 ')


an<..l evaluating· tl1e . 't JCceJvector. Substituting E I· (~ . 109) m t
~ 111 egr~1 over th 'I -. · ·
l: l: eL trontc C(hlrdtnal . 1~

(k' I H;m(~') lk) = 0 L (;


Bn(G' )rt(k' - k -G' l Jll

whercH(k' - k - G) ·· ~.
rs th~: t-:LlllriLT transii.lrrnn )f II,, r :1\

H(k' -- k _ G)
I = -
I ; ·
~2
I' •14 I. C> rf/ (. 1
1111 I <
',,
Rela ation times fo r specific scattering mechanism 171

\:tt )i n _• intcral.: li(lll pt'll.:nltal th e impnrta nt f-ou rier


mp n ·nt ,11 tho:-' ,,f sn w ll :-.rgumcnt. We m a thcr ·~ ·lie ncg lccl the
,. llkd u m h.la pp ll'rm~ with G /:- 0 . Using spheric!! cnonJm tcs w ith
h 1 !~11 ~LXI · para llel I~) I. k' and placing the impurity ion at the ori gi n,
n lth J t H( /.. ' - I.) is given hy

(R.ll3 1

In thl' a bsence of umklapp terms, we need only deal with the coefficient
B 4 /.. ( l . The periodic function u,.(r) depends weakly on k for the states with
high ca rrier occupancy near the band edge . Hence. we can approximate
u_dl') • u,. r) and from the normalization of lk) obtain Bk'k(O ) :c:: I jrt.. The
matri. element of Hinr simplifies to

2
(k rl H inr( r .) 1k = }{ (k , - k) = - -Ze [ 1, ] . (8 .114)
lk - k'j- + qJ
.-
EoEf'l

Th total scattering rate can now be obtained by substituting


Eq. (8 . 114) into Eq. (8.107) and multiplying by the number of ionized
impurities ¥ 1 :

(8.115)

If we assume spherical parabolic bands, we are dealing with the second or


the two cases mentioned in Section 8.4. The relaxation time is there[t)re
specified by Eq. (8.104) v,;hich. with the aid of Eq. (8.115) and setting
n 1 = N 1 j fl. becomes

(8. 116)

We introduce s pherical coordinates with the polar axis parallel to k and


note that since £,., = t_·k , we must have k' = k and therefore

(8. 11 7)

The inverse relaxation time then takes the form

2
l llj /'[ Ze /fuf ] -
r(Ek ) = 41f211. 2k2 ( t - cosfJ) 1~
1 ( '. I I )
x /5( E,. - £,., )( 1 - cos B)k' dk' sin 0 dO dtp.
Charge carrier scattering and transport properties
172
. . · Lmg /.,, 10
llmm . f·<tv. r f ::,
k
u ·ing Ek' = t/·k' 2 /2m·. and carrying ut the
integra ls o ver Er an ~ give:
~ 1
2
.!!_}_ (~n: ·.) ' j· f· l [
3 2
_l_ _
rf£k) - 4 ;r/i lr
,
. 1 2k- ( 1 - cose) + q0
Zl:' /r:n. 2 ] ~ £l(l - cosO)sin0dO.
' (8.119)

Tb e integ ral over cos fJ can be evaluated by elementary means to yield


(Brooks 1955)

- ) 1J
I+ (li-q0 /8m"Ek)
l
.

(8. 120)
This result is the celebrated Brook s- Herring formula. For small q0 (large
screening length, low carrier concen,tration), the relaxation time is to a good
12
approximation proportional to £;,' . The average value of r(Ek) can be
evaluated starting from Eq. (8.79). The result is

~(4;rto r-)
2
(r ) =
1rn 1 Z 2 e4
x J:' £ 3 [Iog(l +8m*E / n2qJ)- ( 1/ l + ( 1i 2
qJ / 8m~ E )) ] 1
e- 1Ed£
j~ £ 3/1e- SEd£
(8.111 i
The factor in square brackets is a slowly varying function of E. whereas the
3
functionh(£ ) = £ exp( - E)issharplypeaked. Wema_ ther foreobtain
a good approximation by replacing E in the square-brack r d fac tor by its
value at the maximum of h(E ), i.e. , 3k 8 T . The integrals that remain in
Eq. (l:L 121) are proportional to gamma functions: ~

.fo{ E e- EdE =
3 4
f(4) = (ksT )4 r (4) ('. J~2a l

lor ~ £ 312e . Ed£ _ .J- 5/2 f


- ·) (5)2 = (ks T )-
.; -r~ (5 ~

Using the values r( 4) - 6 and f (5/ 2) = (3 / 4) Jr. \\t: bt.tin

4(47rFoc) (~k 8. T ) 3 /~,;nr [


2
(r ) = ( T 2)
n3l2 n,z ~ -1 log I + T :. - --~~-:-:-
o
lL• I - -''
\\' 11 " ' • ., ,,
t: Jc ti = , ,
1-e-n
,
( '4 · k,
The b. I. -"1 (llf 8 and n, replaces ". in
' -
1110 I Jt y ' LSSOCJated v/tJ . . . , . . ' .
1
ob tained by l11LlltJ. nl . E I St:tt:encd 1 0 1lt7~d Ill plll ll_.
t• YIIIQ ~ Ll
~ .
(X 1"~,)
. - -'
t
)~ ('Ji ll :

1
Relo oti n hmes for specifi c co ttering mechanisms 173
'' ll If II l \'1111ra t ur~.· d l' pc nd l'll · · c11 the mnhifil\ i-; l "« nt ;ri ncd rn
I. r ' '.Th • in~..-rt'a: · in llh)hiht _' with inc rc;r-.i;,!! tcnrpnat til l' i"
1 h I I lth til~.· I ~Jd that Cc1U inmh ' l':ltiL'ring ,.., mnn: dl ·c live r r
1h.tn r) r fast <I ITi\.'P'. Hi ghn tempe rat urc~ prnducL:
1 .n ncr ... and I her ·1"\WC larger a vcra~c rl.'lax.a 11 1n t imc a nd hi uhl'r
"'''lltl) . ~
h •n •In - the in' c~o:;c rci:Jxation time has a lt)!,Writhmic divergence
t).
+
:I.e .0
htdl ~~ ,: h.lra · knst~~: (1 1 the bare Couk"~mb interaction . An alternative
(I

m a 1 ' f hminatmg the divergence is prov ided by the Conwell Weisskopf


llt..'tlh"~d ( o n\\ L'll and Weisskopf Jl))O). It is assumed that the Coul omb
dd "~f .1 ~lrli~..·tJiar inn ceases lt) be dkctivc a t a maximum impact param-
IL'r " , ., SL'l: Fig. ~-~) equal to one-half the mean distance between impurit y
Fig. 8.2
I )fl
vcomctry J"o r i ni7l·d imrunl )
callcrin g .
IJ/1111.1 I
= ~ Ill
1/J
(~ . 1 25)

rrespc,nding to hm.n is ·1 mimimum angle 0111 ;11 between k and k ' specified
h) Ridky 19~~)

I
h/Jicl\" = (Z/ k )( Ry' I £~; )1 cot(Hmiu / 2), (8.126)

\\here Ry· is the effective Rydberg. The evaluation of the inverse relaxation
time proceeds as in the derivation of the Brooks- Herring formula except
tha t q0 is set equal to zero and the ra nge oft he integration over eis restricted
e
to Hmiu ~ ~ r.. The result is

(8. 127)

For small impurit y ion concentrations the dominant energy dep ndence of
r(Ek) is£}/~. just as with screened ionized impurity scattering.
The average value of r ( Ek) a nd the va lue oft he mobility can be obtained
in the same manner used in the Brooks- Herring treatment . T he result for
the mobility is

( . '- )

The experimental verification of Eq. (~.124) or q. (R . l ~8) i compll-


cated b severa l factors. In materials such as n-Si and n- e, the en r.s.'
bands ~re ellipsoidal, not spherica l, and it is oece ~sa r ' t rc: pla e n 1, h '
an appropriate density-of-states mass (H am 1955). Ot m ~- i rn~ n~n ­
is the fact that at high temperatu res scattering hy laliiCt 1bra uo ns
dominates. whereas a t very low temperaLUres most of the impuri ti s a r
neutral rather than ioni zed , so neutral impurit y sc-ttt ring mus t
considered.
Charge carrier scattering and tra nsport properties
1 :.4

8.5.2 Neutral impurity scattering


.· . " ltte r db a neutral impurity, there is no long range
If a charue ca t ner t,. - c. . . . . .
c ul m b tnterclc
.
. b
. t. 0 10
10
· v lv J . The effecttve mteract10n potential ts hort
. .
deled b a squa re well potenttal. It IS known that a
ran an d Cd n c m . . .
neutral b dr 0 a to m can bind a second electr?n w1th a bmdmgene~gy Er
of0. 7 R . . B ch j ng the square well P?tent.tal to reproduce ~he bmding
energy £ T. '"' t r '--1sorl'lbl
· (.
v realistic
- ·
relaxatton time can be obtamed whose
·
mver · 1M ' the f rm (Sclar 1956)

(8.129)

The corresponding mobility is

I' -
_ (2m '/n)2c£j.l [ 1 I (k T)2l+ (Er)2I] ·
8
(8.1 30)
,
1Tz- 31fn -
Er kaT
It has a weak temperature dependence with a minimum at T = Er / 2ks.
T his weak dependence on tempera ture is in marked contrast to the strong
dependence of ionized impurity scattering on temperature.
The values of the scattering rate are found to be sma ll unle E Tis small.
Consequently, neutral impurities that bind a carrier into a d ep level will
not act as strong scattering centers and will not be important in determining
the mobility.

8.5.3 Lattice vibrational scattering


8.5.3.1 Acoustic phonon scattering
The v ibrations of the nuclei in a semicond uctor produce ad \iatio n ofthe
carnerpotential from periodicit y that scatters free char_ ~uri r . lf Rand
Ro den.ote the nuclear coordinates in the displaced an- ~4uilihri um Cllll·
figuratl~ns, respectively, we can expand the carrier p t nti ..d in po\\ r s rics
m the displ acements R _ Ro,

V (r, R )= V( r, Ro) (R - Ru ) ·VRl '(r,R )iR- Ro+· · . (l' . J3 1

and stoy with the !~near terms if the displacements a r null. Th~.: fir'\! 1·nn
on the 11 ght hand side of Eq. (8 . 13 1) is the pcriodil t nti~ I tnd th · ~·~. n~. i
te rm IS the deviation f 10111· .· . d'ICil . tl ·akul. tl' tht, r.l 1~, ·1t
. y. Our task 1·
. . peno ·
wh1ch C'lrne r · · ·
. . s .li e sca ttered o ut of ·t part icular Bl ·h '>l..ll b th ... J '' •
1 111011
Fo1 lo nl! wavelength v'b 1 .. 1· _., : . 1nd
.. · .~ . .~ ldl 0 11s~ ,, >> I ) O il e L <lll ll S"''I.l ·ttL"Jl\th ·~o.f\•
'-Ie. u1be thl: v1bnt H)n . · .
• s In te rms ot the strain tens r t ' Jdin . . 1 h

,
( /II'
_
-
1(a"s• I- - '
-:, - .-
- Ux,. iJ \
i Ju ·)
, •
Jl . t ' - r. r,_ I ·-
' ~

"I
Relaxation times fo r specific sca ttering mechanisms 175

'lh d f rm tin potential pr•'\. ' 1urc. lhl· Bluch ~tal~ cn ·rg_ b j..,
.m I • I 111 1 ' " cr ,,f 1111.~ , ·1,, :
I \--,
. ( "., ..k 1,f, ,.c 11 , \- - · U\.1341
...__, ''
!II '

I 11 ~·ul i 1.Ty ~ l ~ ls. •Hlc can simplify this expression tn l!.ive

(H. 135)

\ 11h ~the dilatitm given by

D. = )
L.......J
e
1'1'
= au,
.,
__I o,-)ur I
, iht:
') . (X.I36)
I' C _y ( 1' (!::;

h r spherical bands. c2 = 0.
Since the atomic vibrations of crystals arc described in terms of normal
Jlh)des.\\C introduce normal coordinates Q(qj) by means of the normal
CL1ordinate transformation

u(r) = -r.n
I-
. .
. . .. .
L e(qj)e'q.-Q(qj). (8.137)
VPH qJ.

where q is the wave vector. .i is the branch index restricted to acoustic


branches. and e(qj). is the polarization vector. Equation (8.11.7) is an
adaptation of Eq. (7.46) to an elastic continuum of volume D and
density fl - In the limit q --+ 0. e(qj) is related to e" (qj) in Eq. (7.46) by
e,, (Oj) = (AI,.) L" 1\Ih Fe(Oi). As will be seen later. the important values of
1

q are very small compared to the zone boundary value "/a. so we assume
that this relation holds also for q =I=- 0.
In evaluating matrix elements involving phonon wave functions it is
convenient to introduce creation and annihilation operators a~, and OqJ by
means of the relation

1i
Q(qj) = ( -_- ' -. ,, -) ~ ( oq,. + a
-U-!q I
(8.138 )

where wqf is the normal mode frequ ency. Eliminating Q(qj) from
Eq. (8.137) yields

. 11
u ( r) = ( - --
_)~ "'{e(_qj
~ - - e
). tq·r
uq 1
+ e· r.:;-
(qj )
2p0 qi ,} »q i V uJq I

where we have used the relati ons e( - qj) = e (qj) and -V - qj ) = '-'- '( qj ).
The dilation specified by Eq. (~.136) then takes th e Corm

-'' ( ,
W. r)
··
=_I·(-11-·')· ~ L_
)rA~ £Jt
{q ·
.
e(qj)
.
ju,'q;
t
,., ilq I _ q e'- (v ) (,
J~uq 1
' &