BAND THEORY &

CONDUCTIVITY
Recal l from Chapter 7
that si ngl e atoms have
thei r el ectrons arranged
i n stabl e energy l evel s
or orbi tal s around the
nucl eus
These energy l evel s or
orbi tal s are
characteri zed by the
quantum numbers n, l
and m
l
, and get cl oser
together as move
fur ther from the nucl eus
These orbi tal s can be
descri bed by a l adder
model or energy l evel
di agram as shown here,
where each l i ne
represents an orbi tal
that wi l l hol d 2e-
HOW ELECTRONS ARE ARRANGED IN
SINGLE ATOMS
E
n= 1, l= 0, m
l
=0
n= 2,
l= 0,
m
l
=0
n= 2, l= 1,
m
l
=1, 0, -1
n= 3,
l= 0,
m
l
=0
n= 3, l= 1,
m
l
=1, 0, -1
n= 3, l= 2,
m
l
=2, 1, 0, -1, -2
n= 4, l= 2,
m
l
=2, 1, 0, -1, -2
n= 4, l= 1,
m
l
=1, 0, -1
n= 4,
l= 0,
m
l
=0
Recal l from Chapter 7
that si ngl e atoms have
thei r el ectrons arranged
i n stabl e energy l evel s or
orbi tal s around the
nucl eus
These energy l evel s or
orbi tal s are characteri zed
by the quantum numbers
n, l and m
l
, and get
cl oser together as move
further from the nucl eus
Thi s model can be
descri bed by the pi cture
shown here, where each
ci rcul ar orbi t represents
an energy l evel
HOW ELECTRONS ARE ARRANGED IN
SINGLE ATOMS
When atoms come
together to form
mol ecules, they share
el ectrons
When thi s occurs,
according to Mol ecular
Orbi tal Theory, the
atomi c orbi tals on the
two atoms are mi xed to
form mol ecul ar
orbi tals, whi ch are
then shared by the
mol ecule
Thi s can be modeled
pi ctorall y as shown
here
HOW ELECTRONS ARE ARRANGED IN
MOLECULES
E
Formation of Mol ecular Orbi tals can be model ed
mathematically by consi dering what occurs when the
wavefunctions that describe the orbi tal s are added
(constructive i nterference) and subtracted (destructive
i nterference)

HOW ELECTRONS ARE ARRANGED IN
MOLECULES
EXTENSION OF MO THEORY TO A LARGE
COLLECTION OF ATOMS, AS IN A SOLID
Thi s Mol ecul ar Orbi tal approach can be extended beyond two
atoms to three, four, fi ve, etc.
Each atom added to the mol ecule contri butes an atomi c
orbi tal to the formati on of mol ecular orbi tals. However many
atomi c orbi tals mi x, that s how many mol ecular orbi tals form

When Avogadros Number
of atoms have mixed their
atomic orbitals, the
molecular orbitals can no
longer be considered as
discrete orbitals separated
by DE, but now form a
BAND of energies
In sol i ds, the el ectrons
resi de i n energy bands
rather than orbi tal s
The bands represent a
range of energi es, rather
than a si ngl e di screte
energy l i ke an orbi tal
These bands form vi a the
mi xi ng of atomi c orbi tal s
from each atom i n the
col l ecti on
The l ower fi l l ed band i s
cal l ed the Val ence Band,
whi l e the upper empty band
i s cal l ed the Conducti on
Band
The energy separati on
between these two bands i s
cal l ed the Band Gap, E
g
BAND THEORY
This zoomed in image shows how bands are
composed of HUGE numbers of individual orbitals
crammed into a small energy space. The DE
between these individual orbitals is ~10
-23
eV, too
small to measure, thus why we represent this
collection as a BAND
Conduction Band
Valence Band
E
E
g

BAND THEORY
Conduction Band
Valence Band
E
E
g

The magni tude of the the
Band Gap i s determi ned by
how wel l atomi c orbi tal s
overl ap i n the materi al .
How wel l atomi c orbi tal s
overl ap i n the materi al i s i n
turn determi ned by the si ze of
the atoms i nvol ved.
Orbi tal s on smal l er atoms can
overl ap better, whi l e those on
l arger atoms don t overl ap as
wel l . Thi s i s basi cal l y due to
the fact that i n smal l er atoms,
the nucl eus i s wi thi n cl oser
reach of the other atom s
el ectron cl ouds/orbi tal s.
The magni tude of the Band
Gap determi nes what type of
materi al resul ts a
conductor, semi conductor or
i nsul ator.
BAND THEORY
Bondi ng between smal l er
atoms results i n better
orbi tal overl ap, whi ch i n
turn results i n stronger
bonds
Stronger bonds mean that
the el ectrons are held
more ti ghtly by the
material
Thi s i s turn transl ates i nto
a l arger Band Gap, and
usually an Insul ator
The example i l l ustrated
here i s for Carbon i n the
Di amond form
Conduction Band
Valence Band
E
E
g
= 5.5 eV
C
C
C
C
C + 3 C
e
-
The degree of
orbital overlap
is visualized
here by the
arrow
signifying the
distance
from the
valence
electron on
the central C
to the nucleus
on an outer C
BAND THEORY
Bondi ng between medi um
si zed atoms resul ts i n
sl i ghtl y worse orbi tal
overl ap, whi ch i n turn
resul ts i n sl i ghtl y l ess
strong bonds
Less strong bonds mean
that the el ectrons are
hel d a l i ttl e l ess ti ghtl y by
the materi al
Thi s i s turn transl ates i nto
a mi d range Band Gap, and
usual l y a Semi Conductor
The exampl e i l l ustrated
here i s for Si l i con, al so i n
the Di amond form of a uni t
cel l
E
Conduction Band
Valence Band
E
g
= 1.1eV
Si
+ 3
Si
Si
Si
Si
Si
The degree of
orbital overlap
is visualized
here by the
arrow
signifying the
distance
from the
valence
electron on
the central Si
to the nucleus
on an outer Si
e
-
BAND THEORY
Bondi ng between l arge
atoms resul ts i n poor
orbi tal overl ap, whi ch i n
turn resul ts i n weaker
bonds
Weak strong bonds mean
that the el ectrons are
hel d l oosel y by the
materi al
Thi s i s turn transl ates i nto
no Band Gap, and a
Conductor
The exampl e i l l ustrated
here i s for a-Ti n, al so i n the
Di amond form of a uni t cel l
E
Conduction Band
Valence Band
E
g
= 0 eV
4
The degree of
orbital overlap
is visualized
here by the
arrow
signifying the
distance
from the
valence
electron on
the central Sn
to the nucleus
on an outer Sn
Sn
Sn
Sn
Sn
e
-
Sn
In general , the el ectrical resi stance of a ci rcuit component or
devi ce i s the rati o of the vol tage V to the el ectric current I:



If you take i nto account the nature of the materi al making up
the component, what you re real ly measuring i s the resi sti vity,
whi ch i s the resi stance R ti mes a rati o of the cross secti on of
the material A to the l ength of the component L



Conductivity i s the i nverse of resi stivi ty
CONDUCTIVITY
R =
V
I
=
R A
L
=
1

We wi l l consi der how temperature and i mpurities/defects
af fect the conductivity of a metal
Metals have no band gap, so thei r conductivi ty i s determined
sol el y by el ectron mobi lity, that i s, how freel y the el ectron can
travel through the material
When you i ncrease the temperature of a metal , the thermal
energy causes the atoms to vi brate more, i ncreasing the
l atti ce vi brations or phonons, whi ch i nteract and scatter the
el ectrons, thus decreasing the mean free path of the
el ectrons, hi ndering the el ectron mobi l ity and i ncreasing
resi stivity. Thus conductivi ty goes down.
AFFECTING CONDUCTIVITY
OF A METAL
Rai si ng the temperature of a metal i ncreases the l atti ce
vi brations whi ch scatter el ectrons, i ncreasing resi stivity and
l owering conductivity
TEMPERATURE AFFECTS ON A METAL
Low Temperature High Temperature
e
-
e
-
See this website for more information as well as video simulations

http://regentsprep.org/Regents/physics/phys03/bresist/
Bendi ng or deforming a metal changes the l attice, that i s, the
atoms are moved i nto di f ferent posi tions. El ectrons thus get
scattered as shown.




Defects can al so scatter el ectrons i n metals, thus i ncreasi ng
resi stivity and decreasing conducti vity.
This shows a Schottky defect, which is a missing atom in the lattice. The
other atoms in the lattice will fill in the empty space, and the electron
gets scattered





e
-
AFFECTING CONDUCTIVITY
OF A METAL
Defects can al so scatter el ectrons i n metals, thus i ncreasi ng
resi stivity and decreasing conducti vity
This figure shows an Interstitial defect, or extra atoms in spaces in the
lattice. These also can scatter electrons.






A Substitutional defect is a different atom in a standard lattice position,
which also scatters electrons as shown
e
-
e
-
AFFECTING CONDUCTIVITY
OF A METAL
An example of i ntentional ly addi ng an i nterstitial defect to a
metal i s addi ng Carbon to Iron Steel. This makes the steel
stronger



An example of i ntentional ly addi ng a Substitutional defect to
a metal i s addi ng Chromi um to Iron Steel. Chromium resi sts
oxi dation/corrosion better than i ron al one, maki ng stai nl ess
steel.





AFFECTING CONDUCTIVITY
OF A METAL
Remember that a Semi conductor has a Band Gap. Thus we
must consi der how changing temperature af fects that Band
Gap.
Raising the temperature of a Semiconductor gives the electrons in
the material more thermal energy. This raises the Fermi Level and
decreases the Band Gap. Thus conductivity increases as temperature
increases for a Semiconductor.
Lowering the temperature of a Semiconductor takes thermal energy
away from the electrons in the material. This lowers the Fermi Level
and increases the Band Gap. Thus conductivity decreases as
temperature decreases for a Semiconductor.
AFFECTING THE CONDUCTIVITY
OF A SEMI CONDUCTOR
E
Fermi
Level,
E
F
E
F
E
F
E
g
E
g
Band Gap E
g
High Temperature

Low Temperature

Room Temperature

When your semi conductor happens to be used i n an LED, as i n the
experi ment we di d thi s week, changi ng temperature al so changes the
I ntensi ty of the LED.
When you connect an LED to a battery, the battery gives electrons enough
energy to move from the Valence Band to the Conduction Band. Another way to
say this is that the electrons are excited by electrical energy from the battery.
LEDs light up as a result of these excited electrons returning to the Valence
Band from the Conduction band and losing energy in the form of visible light.
This is known as Radiative Decay.
The electrons can also lose energy in the form of heat. In this case, the heat is
absorbed by the lattice, which must be able to vibrate to dissipate this heat.
This is known as Thermal Decay.
The Intensity of an LED is a function of how many electrons Radiatively Decay
vs. how many Thermally Decay.
Raising the temperature of a Semiconductor not only gives the electrons in the
material more thermal energy, it gives the entire lattice more thermal energy.
This increases lattice vibrations. In this case, the lattice could still take heat
from decaying electrons.
Lowering the temperature of a Semiconductor takes thermal energy away from
the electrons and the lattice itself. This decreases the lattice vibrations. In
this case, the lattice cannot take heat from decaying electrons, as it cannot
vibrate in this cold state.
AFFECTING THE INTENSITY OF LIGHT
FROM AN LED SEMI CONDUCTOR
Next we consi der how Composition Af fects the Band Gap of a
Semi conductor. In general , the stronger the bondi ng i s i n a
Semi conductor, the l arger the Band Gap. Stronger bonds
mean that el ectrons are hel d more ti ghtly, thus requi ring
more energy i nput to move those el ectrons.
There are two majors ways to change the composition of a
Semiconductor:
Doping
Substitution
AFFECTING THE CONDUCTIVITY
OF A SEMI CONDUCTOR
Dopi ng i s the process of adding a very smal l amount of
i mpurity atoms (1 i n 10
6
) to a material
The i mpurity shoul d be cl ose i n si ze to the ori gi nal material to
avoi d l atti ce mi smatches, but shoul d have ei ther one more or
one l ess val ence el ectron than the ori gi nal material
Dopi ng al ways i mproves conducti vity, as i t l owers the Band
Gap.
There are two types of Extri nsic Semi conductors that resul t
from Dopi ng
P-Type Semiconductors
N-Type Semiconductors

DOPING SEMICONDUCTORS
P-Type Semiconductors are doped semi conductors i n whi ch
the charge carri ers are posi ti ve hol es
These result from dopi ng an i ntri nsic semi conductor (or
possi bl y i nsul ator) wi th a smal l amount of an el ement wi th
fewer el ectrons
Thi s adds an Acceptor Level above the val ence band
El ectrons move easily i nto thi s l evel, l eaving behi nd posi ti ve
hol es to carry charge i n the val ence band
Adding a Group 3A el ement l i ke Al to Si wi l l make a p- type
semi conductor
DOPING SEMICONDUCTORS
E
g
Band Gap E
g
E
Pure Si
Si Doped with Al
Acceptor Level,
New Fermi Level
e
-
+

Here s a Lewis Structure- ish pi cture showing p- type dopi ng of
Si , wi th B i n thi s case
DOPING SEMICONDUCTORS
http://www.halbleiter.org/en/fundamentals/doping/
N-Type Semi conductors are doped semi conductors i n whi ch
the charge carri ers are negative el ectrons
These result from dopi ng an i ntri nsic semi conductor (or
possi bl y i nsul ator) wi th a smal l amount of an el ement wi th
more el ectrons
Thi s adds an Donor Level bel ow the conduction band
El ectrons from thi s l evel move easi ly to the conduction band
Adding a Group 5A el ement l i ke P to Si wi l l make a n- type
semi conductor
DOPING SEMICONDUCTORS
E
g
Band Gap E
g
E
Pure Si
Si Doped with P
Donor Level,
New Fermi Level
e
-
Here s a Lewis Structure- ish pi cture showing n- type dopi ng of
Si , wi th P
DOPING SEMICONDUCTORS
http://www.halbleiter.org/en/fundamentals/doping/
Substitution i s a process of substituting one el ement for
another i n a compound semi conductor.
The el ement you are substituting wi th must have the same
number of val ence el ectrons as the el ement you are
substituti ng for
For example, i n GaAs, a III - V semi conductor, you coul d
substitute Al or In for the Ga, or P or Sb for the As.
Depending on the si ze of the el ement you substitute i n
rel ative to what you re repl aci ng, the band gap wi l l ei ther
i ncrease or decrease
SUBSTITUTION IN COMPOUND
SEMICONDUCTORS
In l ab, we i nvestigated the Band Gap of a seri es of LEDs
composed of GaAs
1- x
P
x
You shoul d have observed that the Band Gap of the LED
i ncreased wi th i ncreasing amount of P
Thi s i s a result of the fact that P i s smal ler than As, so GaP
bonds are shorter and stronger than GaAs bonds, so el ectrons
are hel d more ti ghtly i n these bonds
When el ectrons are hel d more ti ghtly, more energy i s requi red
to move the el ectrons i . e. , the band gap i s l arger
A si mi lar result can be obtai ned by substituting some Al for
Ga
SUBSTITUTION IN COMPOUND
SEMICONDUCTORS
Conti nui ng wi th LEDs composed of GaAs
1- x
P
x
Instead of repl acing some of the As wi th P, replace some As
wi th Sb.
Thi s wi l l resul t i n l onger bonds between Ga and Sb, thus
el ectrons hel d more l oosel y
When el ectrons are hel d more l oosely, l ess energy i s requi red
to move the el ectrons i . e. , the band gap i s smal ler
A si mi lar result can be obtai ned by substituting some In for
Ga
SUBSTITUTION IN COMPOUND
SEMICONDUCTORS
Most materi al s experi ence some resi stance to el ectron fl ow at al l
temperatures
Some materi al s, however, l ose ALL resi stance to el ectron fl ow
bel ow a cri ti cal temperature, T
c.
These materi al s are cal l ed
Superconductors.
In a Superconductor, current can concei vabl y fl ow forever si nce
there are none of the fri cti on or heat l osses associ ated wi th
normal conducti on. However, many materi al s known to
superconduct requi re l i qui d N
2
or He temperatures to functi on, so
conti nuous current fl ow can be expensi ve to mai ntai n.
Superconductors al so repel outsi de magneti c fi el ds bel ow a
cri ti cal fi el d strength H
c
. Thi s i s known as the Mei ssner Effect.
See thi s websi te for more i nfo on Superconductors
http: //www. superconductors. org/
See thi s si te for a vi deo of the Mei ssner Effect
http: //www. youtube. com/watch?v=Xts42tFYRRg

SUPERCONDUCTORS