6 January 1999

. Chemical Physics Letters 299 1999 115119

Charge injection and recombination at the metalorganic
interface
J. Campbell Scott
)
, George G. Malliaras
( ) IBM Research Diision, Almaden Research Center and Center on Polymer Interfaces and Macromolecular Assemblies CPIMA , 650 Harry
Road, San Jose, CA 95120, USA
Received 11 September 1998; in final form 28 October 1998
Abstract
We consider the mechanism of charge injection from metals into amorphous organic semiconductors. By first treating
charge recombination at the interface as a hopping process in the image potential, we obtain an expression for the surface
recombination rate. The principle of detailed balance is then used to determine the injection current. This simple approach
yields the effective Richardson constant for injection from metal to organic, and provides a means to derive the electric field
dependence of thermionic injection. The result for the net current, injected minus recombination, is in agreement with a
more exact treatment of the driftdiffusion equation. q1999 Elsevier Science B.V. All rights reserved.
The process of charge transfer at the contact
.
between a metal and an organic or polymeric semi-
conductor plays an important role in many areas of
technology. For example, in organic light emitting
w x
diodes 1 , which are being developed for use in flat
panel displays, metal electrodes inject electrons and
holes into opposite sides of the emissive organic
. w x
layer s . In the organic photoconductors 2 used in
laser printers and photocopiers, photogenerated
charge must be extracted from the bottom of the
w x
polymer film. Organic semiconductors 3 are being
considered for use in the logic circuitry of inexpen-
sive smart cards. Yet some of the fundamental
aspects of the charge injection process are not under-
stood in any real detail. It is the purpose of this
Letter to propose a simple approach to the basic
)
Corresponding author. E-mail: jcscott@almaden.ibm.com
science of metalorganic injection that can be re-
lated to bulk properties of the materials involved and
therefore makes predictions that are amenable to
experimental test.
The history of the study of charge injection from
a metal to an insulator can be traced back to the
w x.
RichardsonDushman equation see, e.g., Ref. 4
which was first applied to thermionic emission from
a metal cathode into vacuum and later modified by
w x
Bethe, Schottky and others 5 for charge injection at
.
the interface between a crystalline, inorganic semi-
conductor and a metal. The calculation is predicated
on the assumption that electrons in the semiconduc-
tor are freely propagating in the conduction band of
the semiconductor with a thermal distribution of
kinetic energies. There are two contributions to the
current, flowing from the semiconductor to the metal
and vice versa. At zero voltage they are equal and
w x
opposite; the net current is zero. Later work 6
extended the early formalism to include diffusive
0009-2614r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
. PII: S0009- 2614 98 01277- 9
( ) J.C. Scott, G.G. MalliarasrChemical Physics Letters 299 1999 115119 116
contributions to the current, but still within the
framework of electron velocities and mean-free-
paths.
The difficulty in extending the calculational pro-
cedures from crystalline to highly amorphous semi-
conductors arises because charge transport in the
latter is no longer free propagation in extended states,
but rather hopping between localized states. This
w x
problem was treated by Emtage and ODwyer 7
who solved the driftdiffusion equation in a poten-
tial which included the attraction of each charge to
its image in the electrode. Their result, which gives a
current proportional to carrier mobility, involves the
determination of an integral which can only be ap-
proximated analytically at high and low electric field.
In recent simulations of injection from metal to
w x
polymer, Abkowitz et al. 8 and Gartstein and Con-
w x
well 9 used a transfer rate that depends on the
distance of the target site from the interface. This
rate was taken to be similar to that for site-to-site
hopping, as previously used in the bulk transport
w x
simulations of Bassler et al. 10 . It can therefore be
obtained, in principle, by comparison with experi-
mental mobility data or by quantum-mechanical cal-
culations of molecule-to-molecule charge transfer
w x
matrix elements. Davids et al. 11 have modeled the
injection from metal into conjugated polymers using
a phenomenological surface recombination velocity,
which by detailed balance is proportional to the
Richardson constant, but they take no account of
how the electronic structure of the polymer might
modify the injection rate.
The purpose of this Letter is to derive expressions
.
for the injection metal to organic and recombina-
.
tion organic to metal currents which involve exper-
imentally determined properties of the organic mate-
rial. Our approach is based on the premise that
surface recombination is a field-enhanced diffusion
process, entirely analogous to Langevin bimolecular
w x
recombination in amorphous semiconductors 12,13 .
We then use detailed balance to find the injection
current, and obtain the effective Richardson constant
for the metalorganic interface. We emphasize that
this approach is quite general and independent of the
microscopic details of the injection process.
In the Langevin theory, applicable in the case
where random, diffusive motion of charges is domi-
nant and drift can be viewed as a small bias in the

time-averaged displacement for a review, see Ref.

w x.
14 , the average electronhole pair that approach
each other within a distance such that their Coulom-
bic binding energy exceeds kT will ultimately re-
combine. The demarcation distance should of course
be understood in a statistical sense. It is known as
the Coulomb radius
r se
2
r4p kT . 1 .
C 0
The Langevin mechanism is justified in the present
case by considering the attractive image potential
.
acting on a charge carrier electron in the organic

material as it approaches the metal surface see inset

. w x
of Fig. 1 5
f x sf yeExye
2
r16p x , 2 . .
B 0

where f is the Schottky barrier height the differ-

B
ence between the workfunction of the metal and the
.
electron affinity of the semiconductor , E is the

applied electric field assumed to be constant over

.
the distance range of interest and is the permit-
0
tivity of the organic material. First consider the
Fig. 1. Net injected current density as a function of electric field at
the interface. Solid line shows the results of the analysis presented
.. here Eq. 12 . The current is normalized by the factor J s
0
. . . N mkTrr exp yf rkT ; the field according to Eq. 8 . The
0 C B
dashed and dotted lines show the asymptotic results of Emtage
w x and ODwyer 7 for low and high field, respectively. Inset
electron potential energy vs. position near the interface of a metal
. . left and semiconductor right . f is the Schottky barrier height.
B
. Dashed line a shows the image potential in the absence of an
applied electric field. The energy is lower by an amount kT at a
. distance x from the interface. Curve b is the potential due to a
C
uniform applied field. When both image and applied field are
included one obtains the potential given by the full solid line
which illustrates the reduction in barrier height.
( ) J.C. Scott, G.G. MalliarasrChemical Physics Letters 299 1999 115119 117
zero-field case; the electronimage binding energy is
equal to kT at a distance x sr r4. At room tem-
C C
perature and for typical values of the dielectric con-
.
stant s3.5 , x f4.0 nm, which is ;10 times
C
larger than an intermolecular distance. Therefore, the
assumption of diffusive transport holds, namely that

the mean-free-path of the carrier in this case, the

.
mean hopping distance is shorter than the Coulomb
capture distance. We therefore proceed in the same
spirit; the average charge that approaches the inter-
face within x inevitably recombines. Thus the re-
C
combination current is that at the plane xsx ,
C
2
2
J sn emE x s16p kT n mre , 3 . . .
rec 0 C 0 0
where n is the charge density at the interface
0
.
strictly at x and m is the the electron mobility.
C
The recombination process at a semiconductor inter-
face is frequently parameterized in terms of a surface
recombination velocity, SsJ rn e. Thus, the zero
rec 0
field value is
2
3
S 0 s16p kT mre . 4 . . .
0

In order to determine the injection current from

.
metal to polymer we invoke detailed balance. With-
out an applied electric field, the thermionically in-
jected current, is equal to, but opposite in direction
to the surface recombination current. Write J s
inj
.
C exp yf rkT where C is a constant to be deter-
B
mined. The density n is given by a Boltzmann
0
factor, then
J yJ sC exp yf rkT yn rN s0 , 5 . .
inj rec B 0 0
where N is the density of chargeable sites in the
0
polymer. Hence
Cs16p k
2
N mT
2
re
2
sA
)
T
2
. 6 .
0 0
A
)
is the effective Richardson constant, in analogy
with the metalvacuum and metalsemiconductor
cases.
. ..
Note that the expressions Eqs. 4 and 6 for S
and A
)
contain only properties of the organic mate-
rial, namely the dielectric constant, the site density
and the mobility. Unlike the case of crystalline semi-
conductors, the effective mass and Plancks constant
.
related to the density of states do not enter here.
Nevertheless, the injection current has the same tem-

2
perature dependence T in the pre-exponential fac-
.
tor as the ballistic electron case, but contains the
mobility and density of states in the form reminis-
w x
cent of Schottky diffusion 5 . The proportionality to
mobility justifies the assumption by Gartstein and
w x
Conwell 8 discussed above concerning the metal-
to-organic hopping rate.
To estimate the surface recombination velocity in
materials of interest, take a mobility, at room tem-
perature, of 10
y5
cm
2
V
y1
s
y1
; then one obtains
.
y1
S 0 s0.6 cm s . As expected this is considerably

smaller than that for crystalline semiconductors of

4 y1
w x.
order G10 cm s 5 or for crystalline an-
y1
w x
thracene at 100 cm s 15 . However, it is of the
same order as the few available values for glassy
y1
w x
organic dyes at ;0.1 cm s 16 . We know of no
cases where the recombination velocity and mobility
have been measured in the same material, so this
prediction of the theory cannot yet be tested. The
corresponding Richardson constant, assuming a value
of the site density of 10
22
cm
y3
, is A
)
s10
y2
A
cm
y2
K
y2
compared to the free-electron value of
120 A cm
y2
K
y2
.
Admittedly there are several approximations made
in the derivation of these equations. Most notable is
w x
the neglect of the disorder-induced broadening 2,9
in the energy density of states in the organic, typi-
cally 0.1 eV. Thus the simple relations probably will
only hold for barrier heights somewhat larger than
this. Nevertheless the equations should describe many
cases of practical interest. Space charge effects have
also been neglected. This is not a severe limitation
however, since the carrier density at which interac-
tions between electrons becomes comparable to the
electronimage attraction is x
y3
f1.6=10
19
cm
y3
,
C
high compared to most cases of experimental inter-
est. In real material combinations there is the possi-
bility of an additional interfacial barrier layer, for
example a native oxide. If such a layer is thinner

than the Coulomb capture distance taking into ac-

.
count its dielectric constant then it should not signif-
icantly affect the recombination process. Charges
will still be attracted to and bound by their own
images, and although there may be slower final
recombination across the barrier, the dipolar field
produced by the recombining pair will have a rela-
tively small effect on the motion of other charges.
Surface states are known to modify the recombina-
( ) J.C. Scott, G.G. MalliarasrChemical Physics Letters 299 1999 115119 118
tion process at inorganic semiconductor interfaces. It
is generally believed, and has recently been shown
w x
17 in some prototypical organic systems, that an
insignificant number of interface states are formed
when an organic material is deposited on a metal
surface. The converse, metal on organic, may not be
so ideal. We have considered only electrons in the
above discussion; clearly the same analysis will ap-
ply to hole injection at the anode, with appropriate
identification of the density of states and mobility.
Lastly we consider the electric field dependence
of the injection and recombination currents, which is,
after all, the experimentally relevant behavior. The
primary effect of the field is to lower the energy
barrier by an amount proportional to the square root

of the applied field the Schottky effect see Fig. 1,

.
inset . The resulting exponential increase in the in-
jection current dominates the voltage dependence.
The surface recombination velocity is also field de-
pendent. Now taking the Coulomb capture distance
as that at which the energy is kT below the field-de-
pendent maximum, one finds
S E sS 0 1rc
2
yf r4 , 7 . . . .
where the reduced electric field is
f seEr rkT 8 .
C
and
1r2
y1 y1r2 y1 1r2
c f sf qf yf 1q2 f . 9 . . .
The field dependence of S is considerably weaker
than that due to barrier height reduction. Since the
effective Richardson constant is not expected to de-
pend explicitly on field, the net current is
JsA
)
T
2
exp yf rkT exp f
1r2
yn eS E . . .
B 0
10 .
In many organic materials the carrier mobility m is
w x
electric field dependent 2,9 , in which case it may
be more accurate to use, in the expressions for A
)
. .
and S E , the mobility at field E x . By equating
C
.
the net surface current, Eq. 10 , to the bulk current
leaving the interface, Jsn emE, we obtain an ex-
0
pression for the field dependence of the surface
charge density
n s4c
2
N exp yf rkT exp f
1r2
11 . .
0 0 B
which, rather surprisingly, is independent of the
mobility. The net current is then
Js4c
2
N emE exp yf rkT exp f
1r2
. 12 . .
0 B
This result, plotted in Fig. 1, is in exact agreement
w x
with the asymptotic result of EO 7 at low electric
.
fields f <1 and shows similar behavior at high
fields, although it increasingly underestimates the
current. Note that a simple approximation to include

2
.
barrier lowering i.e., without the factor 4c overes-
timates the current, indicating that surface recom-
bination continues to play a role at high field.
Note that the mechanism described in this Letter
relates only to the interface, not the bulk, of organic
semiconductor devices. In particular, there is no
assumption made regarding bulk vs. injection limited
currents and the ensuing effects of space charge.
Additional calculations are needed to determine,
self-consistently, the interfacial charge density, n ,
0
and the corresponding electric field there. The ex-
pressions given here do however permit an estimate
of the maximum injection current which may help to
determine into which regime a particular device falls
at a given temperature and voltage. Nor have we
discussed tunneling injection which will add an addi-
tional component to the current at high electric fields
and may become dominant for large values of elec-
tric field andror low temperature.
In summary, we have used Langevin theory in
conjunction with the concept of image potential at a
metal interface and the principle of detailed balance
to derive the surface recombination velocity and
effective Richardson constant describing charge in-
jection at the interface between an amorphous semi-
conductor and a metal. It will be interesting to make
experimental tests of the predictions contained in the
derived expressions. The simple picture leads to an
expression for the net current that is in substantial
agreement with, and interpolates between, the two
limits of a more exact calculation.
Acknowledgements
This work was supported in part by the NSF
Materials Research Science and Engineering Center
Grant DMR-9400354 for CPIMA.
( ) J.C. Scott, G.G. MalliarasrChemical Physics Letters 299 1999 115119 119
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