Journal of Non-Crystalline Solids 35 & 36 (1980) 819-824

North-Holland Publishing Company

DEFECTS IN AMORPHOUS SEMICONDUCTORS

David Adler
Department of Electrical Engineering and Computer Science
and Center for Materials Science and Engineering
Massachusetts Institute of Technology
Cambridge, M A 02139
U.S.A.

The energies of low-energy defects in tetrahedrally coordinated, pnictide, and chalcogenide amorphous semiconductors are
estimated. Both nonintimate and intimate charged pairs are
considered. The sign and value of the effective correlation
energy is estimated in each case and the variation of the
Fermi energy with electronic correlation is calculated.
Although the Fermi energy is storngly pinned for nonintimate
pairs with a negative effective correlation energy, it unpins
when the -'airs are intimate.

INTRODUCTION
Recent advances in our understanding of the electronic structure of amorphous
semiconductors have followed from the postulate that well-defined defects are
present in these materials (Street and Mott, 1975), and, in fact, since some of
these defects have a low creation energy, they can be present in concentrations
sufficiently large to control the transport behavior (Kastner et al., 1976). Of
course, the existence of defects in crystalline solids are well known and of
great importance, but the constraints of long-range periodicity limit their
nature. Nevertheless, defects such as vacancies, interstitials, and substitutional impurities often control the transport behavior of crystalline semiconductors,
and the entire semiconductors, and the entire semiconductor industry exists only
because of the ability to fabricate inhomogeneous materials with well-defined
defect profiles. Freed from the constraints of periodicity, amorphous solids can
exhibit a much wider range of defects. Even in a one-component materials, we can
envision strained bonds (with incorrect bond length or bond angle), atoms with a
variety of non-optimal coordinations, and positively and negatively charged ions
with varying average spatial separations.
In multi-component alloys, weaker bonds
can form instead of stronger. By their very nature, amorphous solids are ordinarily metastable, a transition to the lower-energy crystalline phase being retarded by a potential barrier which is essentially inaccessable below the glasstransition temperature of the material. Local relaxations can take place, but
long-range crystallization does not occur. The disordered state is quenched in
by rapid cooling or by direct depositions from a vapor or plasma phase onto a cold
substrate. Consequently, the defect structure critically depends on the method
of preparation. However, it is now clear that despite the enormous number of
defect possibilities, identical preparation conditions do yield reproducible
electronic properties, and the basic reason for this is the chemical nature of the
atoms which constitute the material.
It is the purpose of this paper to analyze the lowest-energy defects expected in
covalent amorphous semiconductors, to make a zeroth-order estimate of the creation
energies and the electronic structure of these defects, to estimate the effective
correlation energy in each case, and to discuss the expected variation in Fermi
energy with electron concentration for chalcogenides, pnictides, and tetrahedrally
bonded amorphous semiconductors.

819

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Do Adler / Defects in Amorphous Semiconductors

CHALCOGENIDES
Kastner et al. (1976) showed that a particularly low-energy defect exists in
amorphous chalcogenide alloys, a valence alternation pair (VAP), consisting of a
positively charged three-fold-coordinated chalcogen and a negatively charged

+
singly coordinated chalcogen.
In their notation
this pair is represented C '
3
CI-.
The creation energy of a VAP is just U, the additional coulomb repulsion
arising from the presence of the extra electron on the C I- site. U represents the
difference between the ionization potential of the chalcogen atom and its electron
affinity, screened by the dielectric response of the material.
Crude estimates
for ehalco~en atoms suggest that U is of the order of 0.5-1.0 eV, so that we might
expect 10 I- 102cm -3VAPs in chalcogenide glasses under ordinary conditions
Vanderbilt and Joannopoulos (1979) carried out much more sophisticated calculations on defects in amorphous Se and showed that the zeroth-order estimates of
Kastner et al. (1976) must be modified in order to obtain realistic estimates of
the defect energies.
Basically, two important effects must be taken into account.
Firstly, ion-ion repulsive terms due to nearest-neighbor interactions prove to be
important contributions to the total energies, an effect which favors lower coordination.
This correction can be expressed as zR, where z is the coordination
number of the defect center.
The repulsive terms do not affect the creation energy of VAPs to first order, since the average coordination of a VAP is the same as
that of a chalcogen in its ground state.
However, they do affect the magnitude of
the effective correlation energy and, more important, they increase the energy of
a C3 center relative to that of a C1 = so that the nature of the lowest-energy
neutral defect is at present unclear.
Secondly, Vanderbilt and Joannopoulos
(1979) showed that, unique to singly coordinated chalcogen atoms, the possibility
of ~ bonding contributes an additional energy decrease that depends on the nearest
neighbor configuration.
This results from the freedom of the singly coordinated
atom to rotate its charge distribution around the axis of its only bond.
The
effect can be modeled by a renormalization of the bond energy of a C I center.
Although sophisticated calculations now exist for Se, there is still some value
in improving the original estimates of Kastner et ai.(1976) because of the inherent simplicity in performing these estimates on a wide range of materials.. This
has been done for isolated defects in chalcogen, pnictide, and tetrahedrally
bonded atoms in Table I. Both neutral and charged centers have been considered
Note that the repulsive-term correction simply renormalizes the values of bond
energy, E , and bonding-antibonding energy difference, A, in the original estimates of PKastner et al., the former decreasing to E 1 Z E - R and the latter increasing to E 2 ~ ~ ~ .
Vanderbilt and Joannopoulos foun~ R = 0.4 eV for Se, a
value sufficiently large so that E 2 becomes greater than E 1 (although E_ > A).
This results in the CI center having lower energy than the C3 , a conclusion consistent with an analysis of EPR experients (Bishop et al. 1977).
Kastner et al. (1976) also suggested that in certain materials the C3 + and C I-_
centers would be spatially near each other, or intimate (IVAPs), resulting
in a
still lower creation energy (at the expense of some entropy).
When the two centers are separated by random distances, they are called non-intimate (NVAPs).
The
creation energies and effective correlation energies of low-energy NVAPs are given
in Table II.
In binary alloys, heteropolar bonding is assumed to predominate.
In
all of these calculations, the values of the appropriate bond energy, repulsive
terms, and correlation2energy are simply treated as parameters, except that the
greater strength of sp and sp 3 bonds relative to pure p bonds is explicitly taken
into account.
In each case, U represents the screened value of the ionization
potential of the positively charged atom reduced by the electron affinity of the
negatively charged atom.
In certain cases, this parameter is expected to be
larger than the estimates for chalcogenides given above.
These are labeled U* in
Table II.
It is interesting to note that all values of both AE and Uef f can be
expressed in terms of only five characteristic (positive) energies; E 4 ~ P - 4B is
positive because pnictide atoms ordinarily prefer p bonding to sp 3 bonding while
E 5 H 2E I - E 4 is positive because Group-IV atoms ordinarily bond tetrahedrally

82]

D. Adler / Defects in Amorphous Semiconductors

rather than with twofold coordination

(Adler, 1978).

Table I
Zeroth-Order Energies and Probably Electronic Nature of Isolated Defects
Defect Center
Chalcogen Atoms:

Pnictide Atoms:

Electronic Nature

E1

Acceptor

C3

E2

Donor

CI+

E1

Acceptor

C3+

-E 1

C I-

EI+U

(Spin)

(Spin)

Electron Trap
Hole Trap

C 3-

EI+2E2+U

Donor

P2

E1
3
~E 4 + E 2

Deep Traps (Spin)

P4
+
P2

Tetrahedrally Bonded Atoms:

Total Energy

CI

E1

Donor

(Spin)

Electron Trap

P4 +

E4-E 1

P2-

E1 + U

Deep Trap

P4-

~E4+EI+2E2+U

Donor

T3

E3

Deep Traps (Spin)

T2

E5

Deep Traps

T3+

E3

T2+

E5+E p

T 3-

EI-E4+U

T 2-

E5+U

Acceptor

(Spin)

Deep Donor
Donor (Spin)

Notation
E
P
A ~

~ Energy of a p bond
Excess energy of an antibonding orbital relative to
a bonding orbital

E 1 _= Ep-R
E2 - +R

z s-p promotion energy

E 3 Z EI+B

Z Excess energy of an sp 3 bond or sp 2 bond relative to

a p bond

E 4 ~ P-4B
E 5 ~ 2EI-E 4

R ~

Repulsive term per nearest neighbor

U z

Correlation energy resulting from an excess electron on

an atomic site

The most important issues in any analysis of the transport behavior of covalent
amorphous semiconductors are the values of AE and the sign of Uef f. If AE is
small for any possible defect center or VAP, a sufficient density will ordinarily
be present to control the transport behavior.
If Uef f > O, VAPs will predominate,
resulting in the suppression of unpaired spins under ordinary conditions (Anderson, 1975) and a strong pinning of the Fermi energy (Adler and Yoffa, 1976). For
chalcogenide alloys, there seems to be no doubt theoretically or experimentally
that Uef f is negative, no matter whether the lowest energy defect is C3 or CI;
since both E 1 and E 2 are in the range 1.2-1.6 eV for Se (Vanderbilt and Joannopoulos, 1979), it is clear that both U-2E 1 and U-2E2 are negative.
In binary alloys, it appears clear that the creation energies of VAPs other than C3+-C I- are
larger and thus fewer will ordinarily be present.
In all of the examples in Table
II involving chalcogen atoms, however, it appears likely that Ueff < 0. Note that

822

D. Adler / Defects in Amorphous Semiconductors

Table II
Creation Energies and Effective Correlation Energies for Low-Energy NVAPs
NVAP

Neutral Defect

A_~E

Uef f

2C3

U-2E 2

2CIO

U,

U~2E 1

C30-P2

U -(EI+E 2)

2C3

U*

U -2E 2

2P2

U -2E 1

P4+-CI -

2CIO

U + E4

U-E 5

P4+-P2 -

2P2

U + E4

U~E 5

C3+-T 3-

C3-T3

U~-E 4

U,-(E3+E 4)

2T3

U,-E 4

U,-(2E3+E 4)

P4+-T3 -

2T3

U -2E 3

C3+-CI -

C3+-P2 -

even if pnic~ide and tetrahedrally bonded atoms are present in chalcogenide alloys,
Uef f remains negative for the C3+-C I- VAP.
PNICTIDES
As the values shown in Table I suggest, the lowest energy neutral defect in pnictides is very likely P2 rather than P4 . It would be expected that E 1 and E 2 are
again comparable, while E4, dominated by the promotion energy, should be significantly larger than either. The s-p promotion energy is large for Group V atoms,
and although it will be screened somewhat in the solid, the screening should not
be anywhere as large as that for U because it is a neutral excitation.
The existence of ions such as PH4+ suggest that E 5 is positive, although it could be quite
small for pnictides,
Consequently, it is not clear whether the effective correlation energy for the P4+-P2 - VAP is positive or negative.
But in any event, the
density of defects should be considerably smaller in pnictides than in chalcogenide alloys.
The existence of a small equilibrium spin density and an equivalent
concentration of photo-induced spins in amorphous arsenic (Taylor et al., 1978)
suggests that perhaps U and E 5 are about the same magnitude, resulting in comparable densities of P2 centers and P4 + - P2- VAPs.
TETRAHEDRALLY BONDED ATOMS
Because four is the maximum possible covalent coordination using s and p orbitals
only, valence alternation is impossible in tetrahedrally bonded solids. However,
the three-dimensional structural rigidity of tetrahedral bonding together with the
usual techniques used to deposit such amorphous films ensure the existence of
large defect densities.
The lowest energy neutral defects are the two-fold and
the three-fold coordinated atoms, T2 and T3 , respectively.
If E 5 < E3, the T2
center has lower energy than the T~. Crude estimates (Adler, 1978) suggest
that this is indeed the case, although a more sophisticated calculation (Allan and
Joannopoulos, to be published) indicates that the two defects have essentially the
same total energy.
If either of these centers are characterized by a negative
Ueff, the possibility of charge-transfer defects (CTDs) exist. This is clearly
not the case for T2 , for which Uef f = U + Ep, an intrinsically positive quantity.
However, for T3 , Uef f = U - (P - 3B), which could have either sign. Although the
simple estimate of Adler (1978) suggested that Uef f < 0 for T3 centers, the calculations of Allan and Joannopoulos (to be published) clearly indicate a positive
Uef f in this case. If so, isolated charged centers are not present in amorphous

D. Adler / Defects in Amorphous Semiconductors

823

silicon under ordinary conditions, and the observed spin density results primarily
from T3 sites.
Unpaired spins could also result from the presence T2+ - T 3pairs, however.
For the case of amorphous s i l i c o n - h y d r o g e n alloys, m u c h lower defect concentrations
are observed under ordinary preparation conditions.
However, hydrogen is given
off at elevated temperatures, creating both T2 and T3 centers.
Intimate
T3 + - T 3- or T2 + - T 3- pairs (ICTDs) could also exist, the former yielding unpaired spins, the latter being spin-paired.
BEHAVIOR OF THE FERMI

ENERGY

The d e p e n d e n c e of the Fermi energy on electron concentration for isolated defects

depends primarily on the sign of Uef f (Adler and Yoffa, 1976).
If Uef f > 0, the
defects are neutral w h e n the average electron density, n, is unity and the Fermi
energy rapidly near n = i. As shown in Fig, l(a), this v a r i a t i o n is over an
energy range approximately equal to Uef f. On the other hand, if Uef f < 0, charged
pairs are the ground state w h e n n = i. The existence of these charged pairs
strongly pin the Fermi energy, as is shown in Fig. l(b).
(0}
(bl
!
To

,o+0L

il
~o~

~ To ,U

T
n

Fig.

i.

e F as a function

of n:

(a) Uef f > 0;

i
P

(b) Uef f < 0.

The s i t u a t i o n is m u c h m o r e complicated for intimate pairs (Adler and Yoffa, 1977).

Firstly, IVAPs and ICTDs can be occupied by 0-4 electrons, so that two values of
Uef f enter.
Secondly, the coulomb forces between the charged centers m u s t be considered explicitly, since, of course, these include the attraction that stabilizes
the IVAP or ICTD in the first place.
Let us call the attraction between the positively and negatively charged center in the neutral state of an intimate pair M.
It is clear that M < U, since the latter is an intraionic rather than interionic
force.
As an example, let us consider the particularly low-energy IVAP C3+ - C lfirst discussed by Kastner et al. (1976); its creation energy is only U - M.
W h e n this IVAP has no electrons present, it is C3 + - C3+ , but because the extra
bond that forms under the transition from CI+ to C3+ , the two C3+ cneters are not
nearest neighbors, but are next-nearest neighbors; thus the coulomb repulsion is
M', a quantity considerably smaller than M.
Similarly, when four electrons are
present on the IVAP, the two C I- centers are again next-nearest neighbors, yielding a r e p u l s i o n of M'.
Both effective correlation energies remain negative, so
that no unpaired spins exist under ordinary conditions.
However, the Fermi energy
unpins.
A detailed calculation shows that in the range of electron densities
0.3 < n < 1.7, Ef lies near T o - IUeffi/2 - (M + M')/2, where T o is the o n e - e l e ~
tron energy of the C3 center and Uef f is the effective correlation energy of the
NVAP (From Table II, Uef f = U - 2E, under the assumption that C1 has lower energy
than C3; otherwise Uef f = U - 2E2. ) As n increases from 1.7 to 2.3, the Fermi
energy then increases rapidly to the v i c i n i t y of T o - IUeffi/2 + (M + M')/2, a
total increase of M + M'.
The overall behavior is shown in Fig. 2.
For ICTDs in tetrahedrally bonded solids, a new possibility exists.
The calculations of A l l a n and Joannopoulos (to be published) indicate that an isolated T3
center has a positive Ueff, so that U > P - 3B.
If, however, M is sufficiently
large that the intimate T3+ - T 3- pair is stable, the Fermi energy should exhibit

824

D. Adler / Defects in Amorphous Semiconductors

Fig. 2.

(a) gF as a function 8f n for an

IVAP;
(b) corresponding density of
quasiparticle
states.

i
Ep2e~

1
1
..
/
i
2
AVERAGE ~UMBER O~ ELECTRONS PER P~m

o~s,TYoFSTATES

more complex behavior, as shown in Fig. 3. Such behavior would show up as four
apparent bumps in field-effect data, rather than the two which are usually observed
(Madan et al., 1976). However, the highest and lowest could well be masked by the
valence and conduction band tails.

Fig. 3

EF as a function of
n for an ICTD with
a positive Uef f.

AvEragENU~eE~a~ELECTRONS
PE~ZCT~
CONCLUSION
The energies and effective correlation energies of a wide range of defects in covalent amorphous semiconductors have been estimated using a crude model. However,
more sophisticated calculations in special cases indicate that higher-order effects can be taken into account by a renormalization of the relevant parameters.
These renormalized parameters can then be used in conjunction with the Fermi energy calculations presented here to determine the dependence of eeff on electron
density. The overall results can be verified experimentally, for example, by
field-effect observations.
This research was supported by National Science Foundation Materials Research
Laboratory Grant No. DMR-78-24185.
REFERENCES
Adler, D., 1978, Phys. Rev. Lett. 41, 1755.
Adler, D., and Yoffa, E.J., 1976, Phys. Rev. Lett. 36, 1197.
Adler, D., and Yoffa, E.J,, 1977, Canad. J. Chem. 55, 1920.
Anderson, P.W., 1975, Phys. Rev. Lett. 34, 953.
Bishop, S.G., Strom, U., and Taylor, P.C., 1977, Phys. Rev. B 15, 2278
Kastner, M., Adler, D., and Fritzsche, H., 1976, Phys. Rev. Lett. 37, 1504.
Madan, A., LeComber, P.G., and Spear, W.E., 1976, J. Non-Crystal. Solids 20, 239.
Street, R.A., and Mott, N.F., 1975, Phys. Rev. Lett. 35, 1293.
Taylor, P.C., Strom, U., and Bishop, S.G., 1978, Phys. Rev. B 18, 511.
Vanderbilt, D., and Joannopoulos, J.D., Phys. Rev. Lett. 42, 1012.