High‐field hopping mobility in disordered molecular solids: A Monte Carlo study

of off‐diagonal disorder effects

Yu. N. Gartstein and E. M. Conwell

Citation: The Journal of Chemical Physics 100, 9175 (1994); doi: 10.1063/1.466672
View online: http://dx.doi.org/10.1063/1.466672
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 High-field hopping mobility in disordered molecular solids: A Monte Carlo
study of off-diagonal disorder effects
Yu. N. Gartstein a) and E. M. Conwell
Center for Photoinduced Charge Transfer, Chemistry Department, University of Rochester, Rochester,
New York 14627 and Xerox Webster Research Center, 114-40D, Webster, New York 14580
(Received 8 October 1993; accepted 8 February 1994)
In the model of high-field hopping studied extensively by Bassler and collaborators, disorder arising
from the varying intersite wave function overlap (off-diagonal disorder) was incorporated by
random assignment of an overlap decay rate to each site independently, admittedly an arguable
procedure. We have carried out Monte Carlo simulations incorporating· assignment of a random
overlap to each bond. The assumptions of a Gaussian density of states and a Miller-Abrahams type
of elementary jump rate were retained. We find the value and field variation of the mobility to be
quite sensitive to the model of off-diagonal disorder considered. However, the results of our
simulations may also be fitted by an exponential dependence of mobility on the square root of field
for some ranges of field and parameters of the disorder.

I. INTRODUCTION tics) and uses a Miller-Abrahams type ansatz for Vij' the
elementary jump rate between sites i and j with energies Ei
Charge transport in disordered molecular solids, and in and Ej' respectively.6 We write this
molecularly doped polymers in particular, is the subject of
much experimental and theoretical activity. (For recent re- _ {eXP[(Ei- E)lkTJ, Ej>Ei
Vij- Vo W ij 1 ,,,:::, (2)
views, see Refs. 1 and 2.) Despite the wide diversity of the , EJ"-"'E 1
chemical and physical structures of these materials, there are
where the prefactor Vo mUltiplies the quantity Wij= W ji rep-
some features found frequently, although by no means uni-
resenting the electron overlap. For an isotropic medium
versally, in their transport. One such feature is the possibility 6
Wij=exp( -2yR i) for a pair of sites Rij apart. To allow for
of fitting the dependence of the mobility f.L on the electric 7
off-diagonal disorder Pautmeier et at. assumed sites i and j
field intensity E over a range of fields with In wx £1I2. This
make independent contributions according to
was first proposed by Gill in an empirical formula to fit
experimental data for poly(N-vinyl carbazole), specifically3 (3)
where a is the distance between nearest neighbor sites, the
(1)
sites assumed to be on a cubic lattice. fi and fj are assumed
to vary randomly in uncorrelated fashion according to the
where Ao is a low-field activation or barrier energy, f3 a con- distribution
stant, k the Boltzmann constant, T the absolute temperature,
and (lITeff)=(lIT)-(lITo), To being the "intersection"
temperature.
The frequently found exponential dependence of f.L on For numerical computations ya was generally taken equal to
£112 suggests the possibility of a unified description. An at- 5. 1,7,8
tractive attempt at such a description is the application by Extensive Monte Carlo calculations of Bassler and
Bassler and co-workers l of a version of the model widely co-workers l ,8 using Eqs. (2)-(4) have led them to conclude
used for disordered semiconductors. 4 ,5 This model describes that, over a range of high fields, their calculated mobility is
the charge transport as hopping of electrons or holes between well described by the expressions
sites with diagonal and off-diagonal disorder. By diagonal
disorder is meant a distribution of the energies of the carriers f.L(o.,"i"E)=f.Lo exp[ -(2o.I3?J
on the hopping sites, which is assumed to be Gaussian with eXP[C(o.2-l2)E1I2J, I;=: 1.5
variance (J'. Off-diagonal disorder represents the variation of (5)
X { exp( C( 0. 2 -
2.25)E 1I2 ], l< 1.5'
intersite electronic wave function overlap arising from both
positional and orientational disorder of nonspherical mol- where o.=a,/kT and
ecules. In the formulation described by Bassler, the off-
(6)
diagonal disorder is also given by a Gaussian attached to
each site, with variance I. !-Loo being the mobility of the system without disorder. The
In addition to the Gaussian distributions this formulation quantity !-Lo exp[ - (2o./3)2J represents the ohmic mobility.l
assumes a low density of charge carriers (Boltzmann statis- The constant C = 3 X 10 -4 (cInN) 1/2. It has been reported that
the field and temperature dependence of f.L for various
-jOn leave from Department of Thermal Physics, Uzbekistan Academy of samples over wide ranges of E and T are well fitted by
Sciences, Katartal 28, Tashkent 700135, Uzbekistan. Eq. (5).1
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12 Feb 2016 00:27:25 © 1994 American Institute of Physics 9175
 9176 Yu. N. Gartstein and E. M. Conwell: High-field hopping mobility
It is important to understand to what extent the Monte
Carlo results and formula (5) are sensitive to the details of
the model. A feature of the model that warrants further in-
vestigation is the particular form of the introduction of off-
diagonal disorder. Since off-diagonal disorder arises from
positional and orientational disorder of the transport mol-
ecules, we believe that the quantities W ij and W ik for differ-
ent j and k should in general be uncorrelated. The splitting of
the overlap parameter Wij into independent contributions
from the sites i and j in Eq. (3), on the other hand, results in
a correlation between all hops to or from a given site. In
terms of percolation theory, the resulting transport calcula-
tions resemble "site percolation."s,9 The case we believe is
more representative is "bond percolation," where the differ-
ent bonds adjoining a given site are uncorrelated. From per-
colation theory it is known that the results for the two cases
differ, the detailed difference being dependent on the actual
"bond" distribution involved. 9,lO What is more important,
the attempt to mimic positional and orientational disorder by
random decay rates in Eq. (3) may lead, as will be discussed
later, to overestimation of the contribution from longer hops
in the sense that the rate of such hops can be implausibly
high.
In this paper we present and analyze results of Monte
Carlo simulation of hopping in high fields between sites on a
cubic lattice with off-diagonal disorder described by a single
parameter ~ij for each bond. The elementary jump rate is
again taken from Eq. (2), with diagonal disorder character-
ized by a Gaussian distribution, but Wij will be given by
Wij=exp(~ij)exp(-2yRi)' -r~~ij~r,
~ij being a random variable. The separable form (7), with the
off-diagonal disorder represented by a separate factor, is sug-
gested first by consideration of smail displacements of the
hopping sites from their positions on a lattice. Second, in
Ref. 11 electronic overlap for nonspherical molecules has
been calculated and shown to be separable into angular and
spatial parts for intermolecular distances of interest. The re-
sults presented in this paper are obtained with ~ij uniformly
distributed between - r and r. This gives a broad distribution
of a kind frequently used in the theory of disordered
semiconductors. s We have also studied Gaussian distribu-
tions of ~ij and found similar results. From studies of 9hrnic
conductivity9,lD it is known that different bond distributions
can lead to different mobilities. Since the actual bond distri-
butions are unknown, we also explore the consequences of
modification of the distribution (7) by taking
Here ~;j is another random variable which will be chosen to
allow for either a more uniform bond distribution or a distri-
bution with more weight on unfavorable bonds.
The disadvantage of taking W ij in the separable form (7)
is that it takes a great deal more computer time to incorporate
other than nearest neighbor jumps. In this paper we restrict
ourselves to nearest neighbor jumps on a cubic lattice, which
has frequently been used in percolation studies. s,9,lo For the
systems we consider 2 ya = 10 is quite large and the tempera-
tures usual for experiments are not low, T=200-300 K. l ,2
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This means that in order to reach a regime of variable range
hopping4 one needs very large disorder. Including other than
nearest neighbor hops would not therefore practically speak-
ing affect our results for small and moderate disorders, a
conclusion that has been checked independently. For very
large disorders the results presented should be considered as
indicating trends. That is consistent with the main purpose of
this paper, which is to study sensitivity of Monte Carlo re-
sults to the model of off-diagonal disorder and not to propose
another fitting formula for experimental data. This sensitivity
is already easily seen for small disorders by comparison of
. our results and results of Bassler and co-workers.
The results of our simulations are presented and dis-
cussed in Sec. ill after a brief introduction to the simulation
procedure and units used in Sec. II.
II. THE SIMULATION PROCEDURE
The simulations have been performed on a sample con-
sisting of 1000x40x40 sites with periodic boundary condi-
tions in the y and z directions, while the electric field is
applied in the x direction. The random walk simulation pro-
cedure is similar to that described in Ref. 1 though differing
in some details. In particular, because we are interested here
in asymptotic (steady-state mobility) behavior and in order to
save computer time, the dwelling time of a carrier on a given
site is taken simply as the reciprocal of the sum of all jump
rates from this site. This yields a correct result for a total
travel time in the limit of a large number of hops. Note that
with our procedure we have been able to reproduce the mo-
(7) bility vs field results described by Basslerl for the case of
purely diagonal disorder.
Particles start their motion at randomly chosen sites at
the left x boundary of the sample. The motion is terminated
after the particle executes a specified number of hops or
reaches the right x boundary. Measuring the particle dis-
placement in the x direction and knowing the total travel
time we can find the drift velocity of the particle. The result-
ing mobility is determined by averaging over 100 particles.
The results presented in this paper are obtained from the
averaged drift velocity, such averages demonstrating more
"stable" behavior with respect to statistical scatter of the
data than averaging of the inverse velocities. The "terminat-
ing" number of hops for each particle has been varied from
104 to a few million, depending on the degree of disorder. To
avoid situations with a particle executing a giant number of
"useless" fast hops within a pair of very large Wij' the num-
ber of allowed successive hops between the same sites has
(8) been limited to 10 (compare to Ref. 12). After that number of
hops these sites have been considered as a cluster from
which hops to all other available sites are taken into account.
We have found that the simulation results are practically
the same for different disorder realizations so long as disor-
der is weak or moderate (most results in this paper). We
suppose this is due to the fact that particles start their motion
at random sites and each particle then sees virtually its own
"realization" of disorder on its trajectory. For moderate dis-
order in a sample of our size the probability of even a partial
coincidence of the trajectories of two particles is small. Thus,
averaging over a large number of particles actually implies
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 Yu. N. Gartstein and E. M. Conwell: High-field hopping mobility 9177

pendent of E. This is not seen in Fig. 2 because the lowest

10.00
fie~d for whic~ data are shown is already fairly high, close to

'" • ~
+
I< ..
+
. . . .
+
<>
+
<>
+
<>
+

<>
10 V/cm. It IS seen, however, that f-L decreases monotoni-
cally with increasing field. For the lowest nonzero r value
~ 1.00
~
8 8 B g Q 0 0 0 shown, r=3.5, the low-field mobility and drift velocity are
c: '"
0 .0.
OJ
.ci 8
'" '" higher than for the r=O case. This is a familiar result from
~ percolation theory;5,9 off-diagonal disorder allows for some
~
u
.Q
~
0.10 .
0 r=O
r=3.5
+ r= 5
more favorable jumps. Apart from the increase in mobility,
the course of the curve for r=3.5 is quite similar to that for
<> r = 8 r=O, ending in essentially saturated behavior at high fields.
.0. r =10 For r = 8, although the initial behavior is similar to that of
r=3.5, there is no longer saturation in v in the field range of
0.01
0 2 4 6 8 10 calculations. The saturation must occur at higher fields.
Frr Rather v goes through a maximum and then decreases. The
more rapid decrease in f-L with increasing field and the ap-
FIG.. 1. Drift .velocity vs FIT, where F=eEalk, for different degrees of pearance of negative differential conductivity have been at-
off-diagonal disorder taken from Eq. (7) with no diagonal disorder. For a =9 tributed to the percolation paths becoming less twisted at
A, F=102 K corresponds to E=105 V/cm. high fields. 13 Regions in which, for example, carriers moved
against the field at relatively low fields may become traps at
high fields. 14,15 The behavior for r=8 is more marked at
averaging over different realizations as well. Of course, these
r= 10, where the mobility for the lowest field shown is de-
arguments would not hold, for example, in situations closer
creased below those for smaller r. To find the increase in f-L
to the percolation threshold where only a few critical paths
predicted by percolation theory, 5 it is necessary to go to still
determine mobility. In fact, comparing the results of different
lower fields. Although saturation is not reached in the field
averagings we have found that, for both large diagonal and
region shown for some values of r, it is clear that the satu-
off-diagonal disorder, the scatter of the data is considerable.
rated v does not vary monotonically with r.
Many more realizations would be needed to get statistically
We now compare these results with those obtained from
reliable data in such cases. However, the trends in the mo-
the off-diagonal (aD) disorder based on a Gaussian with
bility data have been easily discerned.
variance I attached to each site, which we may call "site
The calculated results for f-L and the drift velocity v = f-LE
specific aD disorder." Numerical results for f-L vs E1I2 for
are plotted in terms of the parameter F=eEalk. Here e is
0'=0 and different values of I from Fig. 6 of Ref. 8 may be
the charge of the electron and a the distance between nearest
compared with our results of Fig. 2. In Fig. 6 of Ref. 8 it is
neighbor sites. For the calculations a was chosen as 9 A. The
found that f-L also decreases monotonically with increasing E.
field E=10 5 V/cm then corresponds to F=10 2 K 106 V/cm
However, the changes in f-L with increasing I are very much
to F=10 3 K, etc. Because of the form of Eq. (2), '
Vij and
larger, particularly at the lower fields, than the changes found
therefore f-L and v are functions of the scaled, dimensionless
with increasing r. For example, a change in I from 0 to 3.25
variable FIT. We have therefore plotted our results vs FIT. It
increases the low field f-L by almost two orders of magnitude,
is also convenient to use the dimensionless variable 0-=0'1
whereas a similar change in r increases f-L by less than a
kT. When the Monte Carlo results are plotted in the scaled
units we find a coincidence for plots obtained originally at
different temperatures. The units for mobility and drift veloc-
ity have been chosen arbitrarily, but they are the same
throughout the paper.
10.00

III. SIMULATION RESULTS AND DISCUSSION

The results of incorporating off-diagonal disorder ac-
<?
• ..
~ 1.00 f- ~ '"
cording to Eq. (7), for various values of r, and no diagonal 'c '" ~
disorder, are shown in Figs. 1 and 2. For r=O where there is
OJ

.e
0
Cl .0.
0
Q
..
+
+
..
<>• <> + +
also no off-diagonal disorder, it is seen in Fig. 1 that the drift ~ 8
velocity rises initially with field and comes to a constant .
I-
::t. 0.10 l - .
0 r=O
r= 3.5
Q Q
0<><>
.0. 00
.0.
value, unity in the units chosen, at high fields. The high-field + r=5 .0.
<> r= 8
saturation is the result of taking Vij from Eq. (2), according r=10
to which downhill hops are not accelerated by the electric '"
field. Thus velocity saturation must occur at high enough E 0.01
0 2 3 4
whatever the disorder. It is clear, however, from Eq. (2) that (Frr)1/2
the ~aturation value of v will depend on Wij' thus on the
details of the off-diagonal disorder. FIG. 2. J-LT vs (FIT)l!2 for different degrees of off-diagonal disorder taken
In the saturation region f-L must decrease with field as from Eq. (7) with no diagonal disorder. For a =9 A, F= 102 K corresponds
E- l • At low fields, where Ohm's law is obeyed, f-L is inde- to E=105 V/cm.

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 9178 Yu. N. Gartstein and E. M. Conwell: High-field hopping mobility

1.000 0
is similar to what was seen for (T=O in Figs. 1 and 2. In
0
0 contrast, at the highest fields shown v and f.L decrease mono-

en Ifl
.
0
+
<> <> <> <>
tonically as r increases. The latter behavior is opposite to
that found for site specific OD disorder, Eqs. (3) and (4)
'§
OJ
0.100 ~ <>
" " '" where f.L is seen to increase monotonically as ! increases
.e " both at low and high fields. I ,8 It is apparent that there are
~ strong differences between our Fig. 4 and the corresponding
.?;o ?
'0
o
o ,0 r= 0 plots of f.L vs E 112 as a function of !, Figure 7 of Ref. 8 or
~ 0.010 * r= 3.5 Fig. 10 of ReL 1. To understand the monotonic decrease of f.L
+ + r=5
t.
o <> r= 8 with r at high fields in our case, note that the fact that the
r=10
" hopping paths become less twisted at high fields suggests
thdi they may be thought of as one dimensional. At large
o 2 4 6 8 10 enough (T the dwell time of a charge carrier on a given site at
FIT
high fields is then determined mainly by hops in the field
direction because perpendicular hops are not affected by the
FIG. 3. Drift velocity vs FIT for different degrees of off-diagonal disorder field. For a one-dimensional case with forward hops the av-
taken from Eq. (7) with diagonal disorder characterized by u=3kT. erage dwell time T obtained from Eq. (2) with Wij given by
Eq. (7) is found to be
factor 2. This difference can be understood as follows. An T oc sinh(r)lr. (10)
increase in either r or ! allows larger values of exp(gij) or Because v and f.L are inversely proportional to the dwell
smaller values of r, respectively, increasing the overlap for time, they then decrease as r increases, as is observed in
some pairs, i.e., strengthening some bonds. For the bond dis- Figs. 3 and 4. Note, however, that this argument cannot hold
order case, Eq. (7), only random bonds are strengthened,
for very large r, where hops perpendicular to the field direc-
whereas in the site specific OD disorder case, all of the bonds tion become essential. Note also that the velocity begins to
around some particular sites are strengthened. It is apparent saturate at different FIT values for different degrees of dis-
that the latter situation increases opportunity to find new fa- order. Below saturation it is seen in Fig. 4 that, despite the
vorable paths. The effect of increasing ! is not small. For difference in detailed behavior of v and f.L as functions of the
instance, at !=3.25 both r l and r 2 have still considerable amount of disorder, introduction of off-diagonal disorder ac-
probability of being reduced to ya -!= 1.75. In that case the cording to Eq. (7) results in a range of fields over which In f.L
hopping rate to a site 3a away is almost as large as the rate might be considered proportional to EI12.
to the nearest neighbor site in the absence of off-diagonal
To investigate how the dependence of v and f.L on E is
disorder! This seems unrealistic. Of course, in disordered changed for off-diagonal disorder different from that of Eq.
systems the probability of longer hops can be and frequently (7) we have done calculations for bond disorder given by
is larger than that of shorter ones but the magnitude of the
Eq. (8). In Fig. 5 are shown the results for g;j taken as a
corresponding rate should be properly scaled.
random variable, uniformly distributed between exp( -3) and
Consider now the results of introducing only diagonal
exp( +3), while gjj is again allowed to vary between -r and
disorder, specifically a Gaussian distribution of site energies
r. This form of Wij retains the large range of available bonds
with variance (T. In the ohmic and near-ohmic regions it is
but leads to a more uniform distribution of the probability of
found that obtaining a bond Wij than P(Wij)oc1IWij that results from
~v--~ ~
characteristic of a Gaussian density of states. I ,16 Although
the low field mobility decreases with increasing diagonal dis- 0.100 . - - - - - - - - - - - - - - - : :0 - - - - 1
.
.• .
order, as expected because the barriers to hopping increase, 0
0

in the high field limit kF~(T the same saturated velocity, 1.0 0
+ +
in our units, is obtained whatever the 0- value. I This result Q +
follows from Eq. (2) and is independent of the dimensional- <>
.. i .
0 +
+

."
:§' <> <> <> <> <> <> <>
ity of the system. It is seen in the plot of Fig. 3 for 0-=3 and '2 "+ i!I " "
" """
OJ
0
r=O. It may be verified that the ratio of drift velocity for the .e 0.010
~
0
lowest field shown in this figure to that shown in Fig. 1 is
close to exp[ - (20-13f], as expected for the ohmic region. I ,8
.
l-
.
0 r= 0
r= 3.5
With diagonal disorder only, for large enough a: mobility in + r= 5
<> r= 8
the field region of interest increases with increasing E be- r=10
cause larger E overcomes more barriers. This behavior of f.L "
is in contrast to that of Fig. 2. o 2 3 4
When off-diagonal disorder, according to Eq. (7), is in- (F/T)1/2
troduced in addition to diagonal disorder, at low fields v and
f.L both increase for a range of r and then decrease with FIG. 4. fLT vs (FIT) 112 for different degrees of off-diagonal disorder taken
further increase in r. This behavior, shown in Figs. 3 and 4, from Eq. (7) with diagonal disorder characterized by u=3kT.

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 Yu. N. Gartstein and E. M. Conwell: High-field hopping mobility 9179

1.000 . - - - - - - - - - - - - - - - - - - - , impression is gotten from data of Bassler and co-workers.

Thus, the functional dependence In fLCJ:.E1I2 is rather invoked
by experimental data than following clearly from Monte
<>
Carlo simulations.
:§' 0.100
'1: i However, if this functional dependence is chosen as a fit
::::J
to Monte Carlo data for some range of fields, one can readily
.e
~
0"00
see how Eq. (5) follows not only from Bassler's simulations
DO
I-
o 0 0 but could result from different types of disorder for fL being
;. 0.010 , 0 D o n o off-diagonal disorder
• r= 2 an increasing function of E. Assume that the system is char-
+ r=S.5 acterized by appreciable amount of diagonal disorder and
<> r = 5 moderate off-diagonal disorder, such as that seen in Figs. 3
0.001 L -_ _ _- ' -_ _ _---''---_ _ _--'-_ _ _- '
and 4 for r:s;;5. For such samples the ohmic and near-ohmic
o 2 3 4
mobility, which, as seen in Fig. 3, occurs in the range F < T,
(FfT)1/2
is increased by off-diagonal disorder. Instead of Eq. (9) we
FIG. 5. p,T vs (FIT)lfl for off-diagonal disorder taken from Eq. (8) with
may then write for this range
g/j in the range exp( -3) to exp( +3), gij in the range -r to r, and diagonal In v(F$T)~rl-(;.z, (11)
disorder characterized by u=3kT.
where rl is a constant depending on the degree of off-
diagonal disorder. As is seen in Fig. 3 saturation begins at
Eq. (7). It is seen in Fig. 5 that incorporating this form of kFIa=2 or 3. We may therefore write for the near-saturation
g;j leads to a milder field dependence than is seen in Fig. 4. and saturation region
As an example of a distribution with more weight on unfa-
vorable bonds we have also studied the case of a concentra- In v(F;::::;alk)~r2' (12)
tion of 20% of broken bonds. This was obtained by allowing where r2 is a constant, also depending on off-diagonal disor-
gfj in Eq. (8) to take on in random fashion the values zero or der. For the parameters of Fig. 3, r2<0. According to Eq.
unity. The results are shown in Fig. 6. (The lowest F point (10), when the disorder is given by Eq. (7), r2 is approxi-
for r=6 is uncertain because of computational difficulties.) mately equal to -r. For the models we have investigated
Note that saturation of velocity begins at lower fields than r2<rl' If one wanted to interpolate between the near-ohmic
for previous cases. ··
and near-saturatIOn ·th
regIOns WI a C~orm In fL varymg
. as E1I2 ,
The two types of mobility variation with field common one would obtain, using Eqs. (11) and (12)
to all samples, regardless of disorder, that have the jump rate
given by Eq. (2) are (i) fL independent of E in the ohmic p,(T<F<alk»)
In ( fL(F$T) ~[a-2-(rl-r2)](kFla)1I2 (13)
region and (ii) Wx:E- 1 in the saturation region. The position
of these regions and dependence of p, on E in the transition because for moderate off-diagonal disorder saturation is
between them is quite sensitive to the type and degree of reached for kF;::::;a. It is seen that, if rl - r2 is identified as
disorder. According to Monte Carlo simulations only some ~?, Eq. (13) is the same as Eq. (5). This can explain the
small parts of the data look like straight lines on plots of In p, success of Eq. (5) in giving a good fit to some experimental
vs E 1I2·, although it must be said that they often look like data;I,8 it does not require the particular form of off-diagonal
straight lines on plots of In fL vs E as well. The same visual disorder used in the Monte Carlo simulations that originally
led to this equation. Moreover, with reasonable values of
alk~103 K and a~lO A, Eq. (13) implies the constant in Eq.
(5) C=1O- 3 (cmN) 112, not far from the value obtained in
0.1000 . - - - - - - - - - - - - - - - - - - - , Ref. 8.
The temperature dependence of v in Eqs. (9) and (11) is
characteristic of a Gaussian density of states. If instead one
had activated behavior, because of a different energy distri-
Cil 0.0100 o
:e bution of the density of states,16 the type of argument leading
::::J
to Eq. (13) (with. a replaced by the activation energy Llo)
.e
~ leads to the mobility dependence in the transition region de-
I-
;. 0.0010 f- scribed by Gill's formula, Eq. (1). Estimates using Llo=0.5
<> o no off-diagonal disorder 'eV lead to f3 values comparable with experiment. The
• r= 0
intersection temperature To is then related to off-diagonal
+ r= 3
<> r = 6 disorder.
0.0001 1..-_ _ _--'-_ _ _---1_ _ _ _- ' -_ _ _- '

o 2 3 4 IV. CONCLUSIONS
(FfT)1/2
We have demonstrated that the high-field hopping mo-
FIG. 6. p,T vs (FIT)w, for off-diagonal disorder taken from Eq. (8) with
bility is quite sensitive to the details of the model of off-
g/j chosen to give 20% broken bonds, gij in the range -r to r, and diagonal diagonal disorder. This sensitivity is well known for ohmic
disorder characterized by u=3kT. conductivity far from the percolation threshold. 9 ,IO Compar-

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12 Feb 2016 00:27:25
 9180 Yu. N. Gartstein and E. M. Conwell: High-field hopping mobility
ing the results obtained with our bond-disorder. models and
the site-specific OD disorder model studied by Bassler
et al.,I,7,8 one sees that they can differ by orders of magni-
tude. In our view; their model exaggerates the contribution
from longer hops owing to off-diagonal disorder, reSUlting in
large mobility increase at relatively low fields. (The main
reason is transfer of disorder effects into random decay
rates.) Different models can also differ in the predicted
trends of mobility with increasing field. As we have been
discussing, the site specific OD disorder model lacks some
features that are desirable for describing positional and ori-
entational disorder. In our bond-disorder model we have tried
to keep these features. However, we do not know the actual
distributions of the random variable g and were forced to use
some trial distributions for demonstration. Also, in obtaining
the field dependence of mobility at large disorder, it is nec-
essary to take other than nearest neighbor hops into account,
which we have neglected to do in this study. In particular,
non-nearest neighbor hops must be important for off-
diagonal disorder large enough that critical percolation paths
determine the mobility. Including non-nearest-neighbor hops
should increase JL and also decrease the sensitivity to field
because they allow percolation paths to be less twisted, and
indeed make the percolation picture less relevant. I7
We have seen that some features are weakly model de-
pendent, notably the decreasing slope with increasing off-
diagonal disorder of In JL vs E in the region where the fit
with E 112 dependence is made. The magnitude and details of
this effect are, however, model dependent. The functional
dependence In JL<xE 1I2 cannot be considered to clearly follow
from Monte Carlo data. If this dependence is assumed, how-
ever, formula (5) follows, reflecting disorder effects phenom-
enologically for some range of fields and disorders. Our re-
sults imply that the absolute magnitude of the mobility is
strongly model dependent and in this respect Eqs. (5) and (6)
cannot be regarded as reliable. To make better predictions for
the high-field mobility on the basis of the disorder model it
J. Chern. Phys., Vol. 100, No. 12, 15 June 1994
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Feb 2016 00:27:25
would be desirable to have realistic distributions for off-
diagonal disorder. The relevant data for orientation-
dependent overlaps are, with the exception of Ref. 11, prac-
tically nonexistent.
ACKNOWLEDGMENTS
We greatly appreciate stimulating discussions with Dr.
R. Young, Dr. S. Jeyadev, Dr. D. Pai, and Dr. P. Gomes da
Costa. Dr. Gomes da Costa was most helpful in the initial
phases of the work. Y. G. was supported by the National
Research Council through a CAST grant. He is also grateful
to the NSF Center for Photoinduced Charge Transfer at the
University of Rochester and the Xerox Webster Research
Center for their hospitality.
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4N. F. Mott and E. A. Davis, Electronic Processes in Non-Crystalline Ma-
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6 A. Miller and E. Abrahams, Phys. Rev. 120,745 (1960).
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