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Theory of Poole-Frenkel conduction in

low-mobility semiconductors
a a b a
G. A. N. Connell , D. L. Camphausen & William Paul
a
Division of Engineering and Applied Physics, Harvard University,
Cambridge, Massachusetts, 02138, U.S.A.
b
Laboratoire 'Electrostatique et de Physique du Metal, CNRS-
Cedex No. 166, 38, Grenoble-Gare, France

Version of record first published: 20 Aug 2006.

To cite this article: G. A. N. Connell, D. L. Camphausen & William Paul (1972): Theory of Poole-
Frenkel conduction in low-mobility semiconductors, Philosophical Magazine, 26:3, 541-551

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 Theory of Poole-Frenkel Conduction in Low-mobility
Semiconductorst

By G. A. N. CONNELL, D. L. CAMPHAUSENS and WILLIAM PAUL

Division of Engineering and Applied Physics, Harvard University,
Cambridge, Massachusetts 02138, U.S.A.

[Received 13 December 1971 and in final form 5 April 19721

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ABSTRACT
A new expression is derived for the current produced by a high electric field
in a low-mobility semiconductor, taking into account the mechanism of
Poole-Frenkel emission from a Coulombic trap, the mobility of the carrier
after emission into the conduction band, and the zero-field statistical distribu-
tion of carriers between conduction band, donor states and compensating
acceptor states. Differences between these and earlier formulae are examined,
and arguments presented for the different regimes of applicability. Recent
data on amorphous germanium are considered, using the various formulae,
and it is concluded that high-field transport measurements alone are
insufficient to define uniquely the parameters of such theories.

5 1. INTRODUCTION
THE probability of occupation of a donor site in a semiconductor is
reduced in an electric field, a phenomenon first noted by Frenkel
(1938 a, b), and since employed as the basis for the explanation of the field
dependence of the conductivity in many insulating materials and, more
recently, in amorphous semiconductors (Jonscher 1967, 1971 a). The
exact form of the J-F characteristic depends on the shape of the potential
well around the donor site and upon the behaviour of the electron in the
conduction band after emission. However, the necessary condition under
which the effect may be observed may be generally stated : the increased
probability of emission due t o the lowering of the potential barrier by the
field must be significantly larger than the probability of impact ionization
of the site by sufficiently hot electrons. This condition, analysed in some
detail by Jonscher (1970), clearly requires materials with low mobilities,
and explains why the effect has not been reported in the common
crystalline semiconductors.
Theoretical treatments of the problem follow Frenkel, who calculated
the lowering of an isolated Coulombic barrier in an electric field. This
__. ____-___
f Work supported by the D.E.A.P., the ONR and the ARPA.
$ Present address : Laboratoire dElectrostatique et de Physique du Metal,
CNRS-Cedex No. 166, 38-Grenoble-Gare,France.
 542 G. A. N. Connell et al. o n the
approach, however, has several weaknesses. The peak in the barrier
height of an isolated well in the direction of the field F occurs a t a distance
xm(F ) from the centre of the site. To avoid the problem of the interaction
between adjacent wells and a concomitant modification of x,, a lower
bound is placed on the separation of the sites. Since x,, increases as the
field decreases, there exists a minimum field F , below which the theory,
based on a single-site approximation, is inapplicable.
At absolute zero an electron may only escape from its donor site by
tunnelling through the barrier in the direction of the field. At any non-
zero temperature there is in addition the probability that the electron will
be emitted over the reduced barrier or by tunnelling from an excited state
in the well. The field-assisted conductivity therefore has two components.
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Tunnelling must dominate a t sufficiently high fields a t any given tempera-

ture and will be more prominent at lower temperatures. We may expect
then an upper bound on the field above which field-assisted thermal
ionization, i.e. the Poole-Frenkel mechanism, will not be applicable. It is
evident that a t the lowest temperatures, the range of field over which the
Poole-Frenkel mechanism may apply tends to zero.
The behaviour of the electron after emission has received many different
treatments. The two most common approximations are either that the
carrier is trapped at the adjacent well or that it is trapped after a constant
period of time. Hill, on the other hand, has argued that in an amorphous
semiconductor, where the scattering probability is high, the drift velocity
of the electron is proportional to F1I2(Hill 1967, 1971 b). We will examine
these various approaches and attempt to assess the regimes for their
validity.
Many derivations of a Poole-Frenkel expression for conductivity suffer
from the defect that they fail to consider the equilibrium occupation
statistics for the material in zero field. An exception is the work by
Simmons (1967), who pointed out that the apparent Poole-Frenkel
constant, p, in the expression for the current (see $ 2.3)

where 1 ( E -~ e , ) I is the defect ionization energy and P is the field, could be

altered by a factor of two, since the parameter m ranged between 1 and 2
depending on the model chosen for the compensation of donor and
acceptor centres in the evaluation of carrier densities. An additional
difficulty comes from the common assumption that if data are fitted by an
expression of the form occ exp ( - E / k T ) , with a single activation energy
E,this must mean that a single discrete impurity energy level exists. We
shall show that such a conclusion is not unique. Thus, unless the precise
density of states of the semiconductor is available (which is not the case for
most insulators and amorphous semiconductors), apparent discrepancies
of the order of a factor of two may be anticipated in the comparison of
 Poole-Frenkel Conduci ion in Low-mobility Semiconductors 543

theoretical and experimental parameters. Some authors have attempted

to explain such discrepancies in terms of an effective temperature
(Jonscher 1971 b). Although this approach may not be incorrect, the
data a t present available already fit within the above-stated accuracy,
without departing from the conventional framework.
In $ 2 we develop an expression for the conductivity, enhanced by the
electric field, and in 9 3 we compare the results with experimental data
obtained in various laboratories on amorphous germanium. I n parbicular,
we re-examine work analysed by Hill (1971 c) and point out the difference
in the conclusions that arise from the basic physical differences in our
treatments of the emission probability and carrier motion. Unfor-
tunately, the data themselves are not able to differentiate between the
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results of the two approaches, and therefore the choice of a particular

formula must be based on whether it is physically reasonable.
Our discussion throughout will be limited to the Poole-Frenkel enhance-
ment of the conductivity, i.e. the modification of the emission probability
from a single isolated site. I n a real material, parallel conduction
mechanisms will exist to a greater or lesser extent a t any temperature.
The description of the conductivity over the complete temperature range
therefore requires a knowledge of the field dependence of these other
mechanisms. Our limited approach must be applied with caution and
can only be compared meaningfully with experiment in regions where other
mechanisms can be neglected. It is obvious that the temperature range
over which this condition is satisfied might be severely limited in some
materials.

$ 2 . THEORETICAL
DEVELOPMENT
2.1. Statistical Considerations
The probability of occupation of a donor site in zero field is determined
a t any temperature by the density of states and the total number of
electrons per unit volume in the system. I n an amorphous semiconductor
the density of states in the conduction band is not known and in addition
it is often postulated that a continuous tail of localized states extends
from the conduction band edge to lower energy (Cohen 1970 a, b).
Nevertheless, a single activation energy for conductivity or in some cases
carrier production is found in many such materials over a limited
temperature range. However, this need not imply the existence of a
discrete donor level.
For example, consider a model semiconductor with a density nd of donor
states per unit energy in the range Ed to ed - 8e. If N , is the density of
acceptor levels, then charge balance requires that

where n is the density of electrons in the conduction band and ef is the

 544 Q. A. N. Connell et al. on the

Fermi energy. If the density of states in the conduction band is written

as g,(e) ( e - e C ) P , then ef may be expressed as
N

(2)

when eC-ef$>kT. N , represents the effective density of states in the

conduction band, which may easily be evaluated in the case of a crystalline
semiconductor ( p= 0.5) but must be treated as an undetermined para-
meter for an amorphous material.
Equations ( 1 ) and ( 2 ) are solved most easily under certain limiting
conditions. When
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N , < <n&T

we obtain the following expression :

n = (nd2v,7cT[1 - exp ( - 8e/kT)])1/2

exp
(Zc)
-

which in the limit of small 8e reduces to the well-known expression for a
single donor level (Blakemore 1962). When
n < N , < n,kT
the solution is
n,flckT
n= [ l - exp ( - Se/kT)]exp
N,
An inspection of these expressions indicates that for this simple model a
single activation energy wiIl be obtained over a limited temperature range
despite the continuous distribution of donor levels, but the interpretation
of the activation energy wilI depend on the degree of compensation and the
temperature range in which the measurements are made.
I n an amorphous semiconductor we expect the statistics to be compli-
cated, and the activation energy for carrier production need not be
described by the analogue of either of the above extremes. The proba-
bility of emission from a donor level into the conduction band in zero field
for a limited temperature range will in general be approximately

where fl, is the total density of donors, A( T )is a parameter describing the
effective density of states in the conduction band and the degree of
compensation and 1 < m < 2 . This is evident in the models considered by
Blakemore (1962),and has also been noted by Fritzsche (1972). We now
consider the enhancement of Po by the electric field.
 Poole-Frenlcel Conduction in Low-mobility Xemiconductors 545

2.2. Field-enhanced Emission Probability

Frenkel's original discussion of the barrier lowering of a Coulombic
potential showed that the binding energy of an electron would decrease
with an applied electric field?. Jonscher (1967) has pointed out that for
the Schottky mechanism the barrier is lowered uniformly in all directions
of carrier motion in the hemisphere centred on the field direction so that
the probability of escape from the electrode is enhanced by an angular
independent quantity. He showed that the Poole-Frenkel effect is more
complicated and for a Coulombic po$ential the barrier is lowered by an
amount which depends on the angle 8 between the direction of escape and
that of the applied field, i.e.
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E ~ - E ~ ( ~ ) = E ~ - E ~ - / ~ F ~. ' .~ C. O. S .' / (4)

'~,
where the Poole-Frenkel constant /3 is ( e 3 / m ~ o ) 1 / 2 The
. probability of
emission in an electric field into the forward hemisphere, is therefore,
using eqns. (3) and (4),

where CL = /3F1i2/mkT. Hill has suggested the approximation that the

barrier in the reverse direction is raised by the same factor as it is decreased
in the forward direction (Hill 1967, 1971 b). Strictly speaking, this ,

approximation is not appropriate. The barrier in the reverse direction,

on the single-site model, is infinitely thick. The energy required to ionize
an electron into the conduction band is an increasing function of its
distance from the donor site in the reverse direction. The escape proba-
bility in the direction B is then given by the expression

s: v-47

where
e e2
, E , = E ~ - E and
~ A E = e F x cos 8--
47r0z-
For small fields, lim P(8) = Po(0) =
F -+O mkT
Furthermore, a numerical integration of the expression for P shows that
the ratio (p(s)~Fpo'B~)
6 0-06 for all fields. The integration over the

t We recognize but ignore the possibility that a quadratic Stark effect might
lead to a net increase in the ionization energy at very low fields.
 546 G. A. N. Connell et al. on the
entire hemisphere in the reverse direction, using Po(6) as a valid approxi-
mation, leads to the probability of emission

[l - ( a + 1) exp ( - a ) ] 2-
PO .
a

We note that the necessary conditions on the low- and high-field behaviour
of the escape probability, namely that
lim P , = lim P, = *Po and lim P , =0
F+O F+O F+a,

respectively, are maintained.

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The total probability of emission in a field can now be written as

while the difference in the probabilities for emission in the forward and
reverse direction is
A P = P F - P R = [ a c o s h a - s i n h a ] - .2PO . . . (6)
a2

We are now in a position to calculate the enhancement of the conductivity.

2.3. Field-enhanced Conductivity

We must first consider the fate of the electron after emission. Consider
the case in which an electron emitted with thermal velocity in the reverse
direction is trapped a t an adjacent centre without intermediate scattering.
The distance travelled is independent of field and the current J is propor-
tional to the difference between P , and P,. The functional form of the
current is therefore given by eqn. (6). I n the limit of small a , J-F1j2
and the characteristic is non-ohmic. Hill attempted to reconcile this with
the linear dependence found a t small fields by assuming that in amorphous
materials the carrier escapes into a ' diffusive region ' where the drift
velocity vD is proportional to F1I2and he further claims that J - v D h P .
I n the limit of small a , he obviously finds J - F (Hill 1967, 1971 b).

-
We believe that this approach is invalid for the following reasons.
First, vD F1'2is valid when a carrier is accelerated over a certain distance
and then trapped without intermediate scattering events. However,
with a drift mobility of 0.1 cm2/v-sec and a field of 104V/cm, a carrier
will be trapped in 5 x 10-lo s if the centres are 50 A apart ; using a typical
relaxation time of the order of 10-13sec, we then find that during this
period 200 scattering events have taken place. Hence the relaxation time
approximation, which leads to the familiar dependence of the drift
velocity on field, that is, vD F , is applicable.
N
 Poole-Frenkel Conduction in Low-mobility Xemiconductors 547

Second, it is inappropriate to use AP in the process Hill postulates since

carriers emitted in the reverse direction still receive momentum from the
field in the forward direction even in this so-called diffusive regime.
We believe that the more plausible explanation of the field dependence
of the conductivity is the following. The carriers after emission are
scattered frequently before finally being trapped. Therefore, carriers
emitted in the forward and reverse hemispheres will contribute in the same
way to the current. The current can then be written

J = nepP = 2 A (T)epa-2( 1 + a sinh a - cosh a ) exp (s) (7)

In the limit of small fields, eqn. (7) becomes
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J = A ( T ) e p exp - p, );C
which shows normal ohmic behaviour. This is a necessary condition for a
single-well model. I n high fields

pp1'2
J =B ( T ) e p m k T P - l exp -
(
E&-E,
mkT ) ( z)37112,

which, apart from the parameters m in the exponent, is very similar to

previous expressions given for the Poole-Frenkel mechanismt.
In eqn. (7) the mobility may be temperature dependent. In the
extended states of an amorphous semiconductor, Mott (1969) and Cohen
(1970 a, b) suggest that the mobility may be written as
eu2
p=-
6k T
v,1, . . . . . . . . (8)

where a is of the order of an interatomic distance and vel a typical electronic

frequency ( 1015 Hz). This formula applies under the assumption that
N

nearest-neighbour jumps are most probable, but it may easily be

generalized to a summation of contributions of the same functional form
when longer jumps are also allowed. On the other hand, for a hopping
regime Mott gives

where vpll is a typical phonon frequency ( - 1013 Hz), W is the hopping

energy, R is the most probable hopping distance and CL is the decay constant
for the wave function of the localized state (Mott 1969). Other formulae
for p, similar to (9), have been derived under different assumptions about

7 In an actual case, in which the single-siteapproximation may not be valid

at low fields, the fact that our expression yields J - P as P-tO does not by itself
justify our approach.
 548 G. A. N. Connell et al. on the
the nature of the states involved. However, substitution of these
expressions into (7) leads to the same functional dependence of J on F .
For example, in the particular cases of (8) and (9), the resulting activation
energy E is either ( e , - ed)/mor W + ( e , - e d ) / m ,and the two mechanisms
therefore may only be differentiated by the magnitude of the mobility
calculated from the conductivity.

3 3. DISCUSSION
The analysis of the temperature and field dependence of the conductivity
in terms of expressions like eqn. ( 7 ) is most conveniently carried through
by adapting the technique outlined by Hill (1971 a). (Note that in his
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paper fig. 3 is in error, since the ordinate corresponds to J,-1Tl-2. As a

consequence, it is seen from eqn. (5) of his paper that the sign and magni-
tude of the slope of the line in this figure are not related to the activation

I I

I 1
1.0 10
NORMALIZED FIELD 3

Normalized current (8) versus normalized field (9)

for a sample of electro-
lytically prepared amorphous germanium (EDC-1).

energy.) As an illustration of the applicability of the Poole-Frenkel

theory in its present form, we have analysed some of the published data on
various types of amorphous germanium (Camphausen, Connell and Paul
1971, Croitoru and Vescan 1969, Morgan and Walley 1971). The results
of such an analysis on as-deposited electrolytic germanium (EDC-I),
 Poole-Frenkel Conduction in Low-mobility Xemiconductors 549

prepared in our laboratory, are shown in the figure. By reducing eqn.

(7) to a two -variable form

$= 1+ 9sinh 9-cosh F,

where the normalized current$ and the normalized field F are

mkT
' = 2 A ( TJ ) e p (J--)2 exp (s) , 9= cL,

the results may be plotted in such a way that experimental data obtained
a t different temperatures fall on the same curve. The line through the
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points is then the theoretical expression for the current given by eqn. (7).
The parameters in eqn. (7) obtained from the analysis are presented in the
table. As expected, the quantity m lies between 1 and 2 but it is difficult
to take the analysis any further, since the temperature dependence of
A(T ) is unknown for an amorphous semiconductor. However, assuming
that A ( T )is a constant A , we find for EDC-1 that mE, as defined in the
previous section, is 0.15 ev. We have already observed that the inter-
pretation of the activation energy E depends on the type of conduction
after emission. If we assume that A 1017 N and W < (6, - cd)/m
(e.g. in amorphous silicon, LeComber and Spear (1970) found W=O.Olev
in three samples), then p (100 K) N em2 V-1 s-l. We note that this
value for the mobility is in the range, suggested by Cohen (1970), for

Parameters describing the conduction in amorphous Ge in the Poole-

Frenkel regime

Temp.
Sample range m ktp (100 K ) Remarks
(OK) (cm-l V-l s-l 1
EDC-1 78-170 1.51 1014 Electrolytic
E-95 94 1.42 Electrolytic
E-97-2 78-130 1-51 N 1014 Electrolytic
Croitoru 78-92 1a55 Evaporated
and
Vescan
(1969)
Morgan 35-80 2.5 1017 Evaporated
and :approx.)
Walley
(1971)
 550 G. A. N. Connell et al. on the
conduction by percolation or by hopping in localized states and thus is in
agreement with the model for amorphous germanium described by Connell
and Paul (1971) and Camphausen et al. (1971).
The table also includes the results of similar analyses on several of our
other samples and on the published work of Croitoru and Vescan (CV)
(1969) and Morgan and Walley (MW) (1971). I n the range of tempera-
ture over which the data were fitted, m is close to 1.5 for all the samples
except that of MW, and E is close to 0.15 ev for all the samples except
that of CV. I n fact, the fit of eqn. (7) to MWs work was significantly
poorer than the otherwise typical result shown in the figure, and we
suspect that the large power density (of order 1-10 W dissipated
in their samples during measurement raised the sample temperature above
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ambient. Similarly the value of E for CVs material was obtained from
fig. 2 of their paper and is considerably less accurate than our results.
On the other hand, the product of A p is significantly larger in evaporated
material (MW) than in electrolytic material, but whether this difference
corresponds to significant differences in the mobility p or in the density of
states parameter A cannot be resolved without further experimentation.
However, such a difference does not affect the internal consistency of our
analysis but rather suggests an area in which further work is crucial.
The present formulation of the Poole-Frenkel theory is able to explain
the conductivity of several types of amorphous germanium for tempera-
tures between 50 K and 150 K. However, this is not necessarily a unique
explanation, since the expression given by Hill, namely J P112AP, N

satisfactorily describes the J-F characteristics when different values for m

and E are used (for example compare his analysis of MWs work). As is
evident from 3 2, the two approaches lead to different conclusions as to the
nature of the conduction in the base of the conducting band and although
we have argued that his formulation is not applicable in this case, the
question will be definitively answered only when drift mobility measure-
ments become available. We therefore urge that the interpretation of the
field-dependent conductivity be treated with caution and whenever
possible be supported by supplementary measurements.

REFERENCES
BLAKEMORE, J. S., 1962, Semiconductor Statistics (Pergamon), pp. 135-136.
CAMPHAUSEN, D. L., CONNELL, G. A. N., and PAUL,W., 1971, Conference on
Amorphous Semiconductors a t Ann Arbor ; J . Non-Cryst. Solids (to be
published).
COHEN,M. H., 1970 a, J. Non-Cryst. Solids, 2, 432 ; 1970 b, Ibid., 4, 391.
CONNELL,G. A. N., and PAUL,W., 1971, Conference on Amorphous Semi-
conductors at Ann Arbor ; J . iVon-Cryst. Solids (to be published).
CROITORU,N., and VESCAN,L., 1969, Thin Solid Films, 3, 269.
FRENKEL,J., 1938 a, Phys. Rev., 54,647 ; 1938 b, Tech. Phys. U.S.S.R., 5, 685.
FRITZSCHE,H., 1972, Electronic Properties of Materials, edited by R. H. Bube
(McGraw-Hill) (to be published).
 Poole--Frenkel Conduction in Low-mobility Xemiconductors 551

HILL, R. M., 1967, Thin LJolid F i l m s , I,39 ; 1971 a, I b i d . , 7, R57 ; 1971 b,

Phil. Mag., 23, 59 ; 1971 c, Ibid., 24, 1307.
JONSCHER, A. K., 1967, Thin Solid Films, 1, 213 ; 1970, J . Phys. C, 3, L159 ;
1971 a, J . Vac. Xc. Tech., 8, 135 ; 1971 b, J . Phys. C , 4, 1331.
LECOMBER, P. G., and SPEBR,W. E., 1970, Phys. Rev. Lett., 25, 509.
MORGAN, M., snd WALLEY,P. A., 1971, Phil. Mag., 23, 661.
MOTT,N. F., 1969, Phil. Mag., 19, 835.
SIMMONS, J. G., 1967, Phys. Rev., 155, 657.
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