JOURNAL OF APPLIED PHYSICS 99, 053702 共2006兲

Positional disorder enhancement of exciton dissociation

at donor/acceptor interface
M. Koehlera兲
Departamento de Engenharia Elétrica, Universidade Federal do Paraná, 81531-990 Curitiba, Paraná,
Brazil and Departamento de Física, Universidade Federal do Paraná, 81531-990 Curitiba, Paraná, Brazil
M. C. Santos and M. G. E. da Luzb兲
Departamento de Física, Universidade Federal do Paraná, 81531-990 Curitiba, Paraná, Brazil
共Received 19 August 2005; accepted 13 January 2006; published online 1 March 2006兲
We investigate the dissociation of a Coulomb bounded electron-hole geminate pair at a disordered
donor/acceptor 共D-A兲 heterojunction by extending a previous proposal in the literature 关Arkhipov et
al., Appl. Phys. Lett. 82, 4605 共2003兲兴 and using Monte Carlo simulations. We show that the
presence of a layer of randomly distributed dipoles at the D-A interface creates both a potential well
that confines the hole and a repulsive barrier that prevents the geminate pair recombination, even
when the effective mass of the hole is around the electron rest mass. Our calculations depend
strongly on the heterojunction morphology. However, contrary to what is generally believed, we find
that the disorder in the position of the dipoles along the D-A interface axis enhances the pair
dissociation. Inhomogeneities in the acceptor concentration at the heterojunction can then create
highly efficient centers for exciton dissociation. The model explains recent experimental results for
organic D-A heterojunctions and has important consequences on the design of organic photovoltaic
devices. © 2006 American Institute of Physics. 关DOI: 10.1063/1.2174118兴

I. INTRODUCTION available for carriers hopping in a rigid cubic heterojunction

The electron-hole pair separation at semiconductor het-
erojunctions is a key factor underlying the physics of photo-
voltaic devices.1–3 For instance, one of the possible strategies
to enhance device efficiency is to engineer the heterojunction
morphology on molecular scales to control the charge trans-
fer 共CT兲.4–6 For so, it is necessary to better understand the
exact mechanisms involved in such process, which is what
recently has motivated many theoretical works as in Refs. 2
and 7–9, just to cite a few.
The above observations are particularly true for
polymer/electron-acceptor systems, which allow the fabrica-
tion of low-cost efficient organic devices,10 reaching external
quantum efficiencies as high as 75%.11 However, among
other factors further optimization depends on determining
the role played by structural disorder at the polymer/acceptor
interface to the CT. This is a question still waiting for a
definitive answer.
In the first step of the CT, a short geminate pair of car-
riers is formed, with the electron trapped at the acceptor
共e.g., fullerene兲 and the hole localized in an adjacent donor
共e.g., a conjugated segment兲.9,12 Considering the low dielec-
tric constant of materials such as conjugated polymers, the
electrostatic attraction between the two carriers must be
strong with a binding energy considerably larger than kT.
Nevertheless, the pair separation probability into free charges
is approximately 100%.11,13 Different studies have addressed
this surprisingly high carrier separation efficiency at organic
donor/acceptor 共D-A兲 junctions.9,14–16 For instance, it was
shown that a random distribution of energy of localized sites
a兲
Electronic mail: koehler@fisica.ufpr.br
b兲
Electronic mail: luz@fisica.ufpr.br
could assist the pair dissociation.8 However, generally the
models in the literature do not properly consider the impor-
tant aspect of the heterojunction positional disorder on exci-
ton dissociation.
A sound proposal suggests that the efficient charge sepa-
ration at the D-A interface is due to a repulsive potential
barrier, which separates the electron and hole.9,14 The prox-
imity of a trapped electron in a nearby acceptor molecule and
partial positive charges of dark dipoles at the D-A interface
can produce a potential well that confines the on-chain hole.
The cage effect would then increase the hole’s ground state
energy, decreasing the energy required to escape from the
Coulomb attraction. The idea of a dipolar layer at the
polymer/acceptor interface is confirmed by experimental re-
sults 共see Ref. 9 and references therein兲. Also, their existence
in molecularly doped polymers is supported by some univer-
sal properties of charge mobility.17
Such model, however, has two basic approximations: 共i兲
it considers the contribution of only two dark dipoles regu-
larly spaced at each side of the short geminate pair to the
potential energy and 共ii兲 it assumes alignment of the polymer
chain to the heterojunction. From these assumptions, a repul-
sive potential barrier that prevents geminate recombination
and stabilizes the geminate pair is established only when the
effective mass of the hole along the donor chain is meff
Ⰶ me,15 with me the rest mass of the electron. A so small
effective mass is rather unlikely given the narrow bandwidth
characteristic of disordered organic materials.15
In this contribution we calculate, from Monte Carlo
simulations, the potential barrier produced by an array of
many dipole moments randomly distributed around average
positions at each side of the short geminate pair. In contrast

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053702-2 Koehler, Santos, and da Luz J. Appl. Phys. 99, 053702 共2006兲

the dn’s are, in fact, given by truncated Gaussians of Lx = a

− d, see Fig. 1. At the same token, the ␦n’s cannot be larger
than the width c separating the first and second donor chains,
i.e., outside the heterojunction region. Thus, they are also
given by truncated Gaussians, for which we set Ly = 2 / 3
⫻ 2c.
The presence of the dipoles restricts the geminate pair
motion along the x direction. The potential energy of the
on-chain short geminate hole, E p共x兲, results from the electro-
static interactions with the trapped electron at the acceptor
and with the dipoles of partial charge q␣, so E p共x兲
= 共q2 / 4␲⑀⑀0兲关−共x2 + b2兲−1/2 + ␣兺nFn共x兲兴, with
1 1
Fn = − . 共1兲
冑共dn − x兲 2
+ ␦2n 冑共dn − x兲 2
+ 共b − ␦n兲2
E p共x兲 is a potential well for the geminate pair hole, as one
FIG. 1. Schematic illustration of the 共a兲 optical excitation, 共b兲 interface
can find from the second order expansion E p共x兲
⬇ 共q2 / 4␲⑀⑀0兲共l1x2 + l2x + l3兲, for 关f n共u兲 ⬅ 1 / 冑d2n + 共␦n − u兲2兴,
electron-hole dissociation, and 共c兲 free electron 共hole兲 at the acceptor 共do-
nor兲 layer in a donor/acceptor system. In detail the short geminate pair at the
donor/acceptor heterojunction. The dipole random positions are drawn from
1 ␣
Gaussians of truncated width L and variance ␴2. l1 = + 兺 3d2n关f 5n共0兲 − f 5n共b兲兴 + f 3n共b兲 − f 3n共0兲,
2b3 2 n
to what was previously believed, we show that structural
disorder along the heterojunction can be an important factor l2 = ␣ 兺 dn关f 3n共0兲 − f 3n共b兲兴,
to help the short geminate pair dissociation. Under certain n
conditions, this kind of structural disorder can favor pair sta-
bilization even for meff ⬇ me. Further, the model explains 1
l3 = − + ␣ 兺 f n共0兲 − f n共b兲. 共2兲
why the short circuit current observed in some D-A photo- b n
voltaic devices with a disordered donor layer is higher when
compared to the short circuit current measured in similar Using the coordinate transformation z = x + l2 / 共2l1兲, the
devices but with an ordered donor layer of the same potential energy 共2兲 is cast as the harmonic potential E p
polymer.18 ⬇ 共q2 / 4␲⑀⑀0兲l1兵z2 + 关l3 / l1 − l22 / 共4l21兲兴其. The hole ground state
energy at chain 1, E共1兲, is the sum of the kinetic and mini-
mum potential energies of zero-point oscillations,9 which
II. MODELING THE PROBLEM
from the previous expression reads
The problem we discuss is schematically depicted in Fig.
1. After the optical excitation of the donor, Fig. 1共a兲, an
exciton can diffuse toward the heterojunction, forming there
E共1兲 =
q2
4␲⑀⑀0
冉 l2
l3 − 2 +
4l1
ប
2
冊 冑 q2
4␲⑀⑀0meff
l1 , 共3兲

a short geminate pair of charge carriers, Fig. 1共b兲. Then, with meff the on-chain carrier effective mass. Following simi-
energetic balance favors the pair dissociation, resulting in a lar calculations, the ground state energy for the hole at chain
free electron 共hole兲 at the acceptor 共donor兲 material, Fig. 2 is

冉 冊 冑
1共c兲. We shall address the transfer mechanisms in step 共b兲.
For so, we follow closely Ref. 9 and show that a potential q2 p2 ប q2
E共2兲 = p3 − 2 + p1 , 共4兲
barrier separating the electron and hole at the donor/acceptor 4␲⑀⑀0 4p1 2 4␲⑀⑀0meff
interface is mediated by the dipole layer at the D-A hetero-
where p1, p2, and p3 are written in the same way than, re-
junction, see Fig. 1.
spectively, l1, l2, and l3, by making the substitution b → b
For the locations of the dipoles and the geminate pair we
+ c and f n共0兲 → f n共c兲.
take as reference the positive charges. The distance between
the donor’s first 共1兲 and second 共2兲 chains is c. The short
III. RESULTS AND DISCUSSION
geminate pair is on the origin of the xy plane. b is the sepa-
ration between the charges of each dipole and also of the An important quantity is ⌬E = E共1兲 − E共2兲, the difference
electron-hole geminate pair. Along the x axis 共y axis兲 the of the chains 共1兲 and 共2兲 hole energies. For each specific set
dipole labeled n = ± 1 , ± 2 , ¼ , ± N is located at dn共␦n兲. Fur- of positions for the dark dipoles at the donor/acceptor inter-
thermore, due to structural disorder of the donor chain, we face, we have a certain value for E共1兲 − E共2兲, resulting from
assume that dn 共␦n兲 is a random variable obtained from a Eqs. 共3兲 and 共4兲. Using Monte Carlo simulations, we calcu-
Gaussian distribution centered at x = na 共y = 0兲 and of stan- late an effective ⌬E, obtained from averaging over many
dard deviation ␴x 共␴y兲. Adjacent dipoles feel an electrostatic disordered configurations for the dipole locations. Then, we
repulsion when very close to each other. To model it in a analyze when ⌬E ⬎ 0, which favors the pair dissociation
simple way we just assume a forbidden region of width d since it indicates the presence of a repulsive potential barrier
between successive dipoles 关situation in 共b兲 of Fig. 1兴. So, helping the hole diffusion to the second chain 关chain 共2兲 in

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053702-3 Koehler, Santos, and da Luz
FIG. 2. ⌬E as functions of 共a兲 the number of dipoles N at each side of the
short geminate pair and 共b兲 the forbidden region width d.
Fig. 1兴 of the donor layer and preventing the pair recombi-
nation 关the hole returning to chain 共1兲兴. We should observe
that ⌬E can be associated with the average pair dissociation
probability through the hopping rate of the hole from chains
共1兲 and 共2兲 and from chain 共1兲 to the donor layer 共recombi-
nation兲. These rates obey the detailed balance and may be
calculated from the energy using the Miller-Abrahams rela-
tion or a polaronic rate. However, such analysis is outside the
scope of the present work.
We set a = 0.5 nm, b = c = 0.6 nm, ␣ = 0.4, and make av-
erages over 104 ⫻ 104 configurations of the positions dn and
␦n. Always, unless otherwise explicitly mentioned, we as-
sume meff / me = 0.5, d = 0.1a, and N = 10 共this value for N
guarantees, in all the examples, saturation of the dipoles con-
tribution, see below兲.
For ␴x = 2␴y = 0.2 nm we show in Fig. 2 ⌬E as a function
of the number of dipoles N and of the forbidden width d.
From Fig. 2共a兲 we see that larger N’s lower the hole confin-
ing potential well, decreasing ⌬E. However, the interaction
of these additional charges with the on-chain hole decreases
fast with the distance from the geminate pair. Thus, ⌬E starts
to saturate for N ⬇ 5. Considering a ⬇ 0.5 nm, the conjuga-
tion segment in which the hole is located must have a mini-
mum length around 1 nm, which is compatible with the di-
ameter of small conjugated molecules used as donors in
photovoltaic devices.19 Hence, the results in Fig. 2共a兲 suggest
that the zero-point oscillations of the hole can explain the
high collecting efficiency observed in some D-A junctions
consisting of small weight molecules once a dipole layer is
formed at the interface.20 We should mention that the inabil-
ity to explain such high efficiency was pointed out15 as a
great weakness of the original model of Ref. 9. Regarding
Fig. 2共b兲, we observe that a larger d represents a stronger
repulsion between adjacent dark dipoles and a smaller range
of variation around the dipole mean positions. Therefore, the
effect of increasing d is the same as decreasing ␴x, i.e., the
barrier for the geminate pair recombination lowers with d.
From Fig. 2 one sees that ⌬E saturates very fast with N
compared to a more slow variation with respect to d. Due to
the larger number of dipoles occupying the same volume of
space in the vicinities of the short geminate pair for increas-
ing concentration of electron acceptors, d becomes smaller.
So, the potential barrier preventing the electron-hole recom-
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J. Appl. Phys. 99, 053702 共2006兲
FIG. 3. The dependence of ⌬E on the disorder ␴x in the x direction for some
␴y’s.
bination becomes stronger for higher acceptor concentra-
tions. This result confirms recent measurements showing that
the yield of charge carrier photogeneration increases dra-
matically with the acceptor concentration.9,21 Also, it indi-
cates that the leading factors for the geminate pair separation
change at lower and higher electron acceptor
concentrations.12
In Fig. 3 we plot ⌬E as a function of the disorder pa-
rameter in the x direction, ␴x, for different values of ␴y. ⌬E
increases with increasing disorder in the x direction but de-
creases with increasing disorder in the y direction. Since the
parameter ␴y is related to the microscopical degree of rough-
ness of the interface, one concludes that the pair dissociation
is less efficient in rough heterojunctions, as expected. When
␴x Ⰷ a − d, the truncated Gaussian distribution tends to a
square distribution. Then, ⌬E becomes independent on ␴x
and saturates.
The above results can be easily understood by noticing
that any displacement of the dipoles in the y direction de-
creases the potential well in which the on-chain hole is con-
fined, diminishing the cage effect. On the other hand, dis-
placements in the x direction can either increase or decrease
the potential well. If the dipole is displaced towards the ger-
minate pair, the potential energy of the hole increases dra-
matically, intensifying the cage effect. Those configurations
in which this kind of displacement occurs overweight, pro-
ducing a higher energy for the hole in chain 共1兲 compared to
a completely ordered system.
Our findings demonstrate that the morphology of the in-
terface separating the donor and the electron acceptor has
indeed a strong influence on exciton separation. But it is not
true that any disorder at the interface is counterproductive.
Two important consequences for device optimization are 共i兲
the smoothness of the donor/acceptor interface is crucial for
a higher efficiency and 共ii兲 inhomogeneities on the acceptor
distribution near the heterojunction will increase the zero-
point oscillations and can create highly efficient exciton dis-
sociation centers.
Figure 3 explains recent measurements performed in
poly共3-4⬘-共1⬙ , 4⬙ , 7⬙-trioxaoctyl兲phenyl兲thiophene 共PEOPT兲
upon addition of 关6,6兴-phenyl C61 butyric acid metyl ester
共PCBM兲, an acceptor molecule. PEOPT is a conjugated poly-
mer that exhibits two different phases with well-defined
order/disorder character on one-and-the-same material.18 It
was observed that the lifetime of photoexcited charge carrier
in ordered PEOPT/PCBM is considerably shorter than that in
053702-4 Koehler, Santos, and da Luz
FIG. 4. ⌬E as a function of the effective mass of the on-chain hole for the
parameters.
disordered PEOPT/PCBM composites. Therefore, charge
carrier recombination is easier in the ordered system. Fur-
ther, measurements performed on photovoltaic devices
showed that the short circuit current of disordered PEOPT/
PCBM devices is higher compared to devices using ordered
PEOPT/PCBM junctions. This result is surprising since the
ordered PEOPT has a higher charge carrier mobility. The
better performance of the disordered device can be attributed
to a higher potential barrier at the polymer/acceptor interface
that increases the charge separation efficiency and compen-
sates its poor transport properties. As a last comment it is
worth to mention that as suggested in Ref. 8, energetic dis-
order assisted separation of geminate pairs can also play an
important role in the higher values of the photogeneration
yield at disordered PEOPT/PCBM compared to ordered
PEOPT/PCBM junctions.
The dependence of ⌬E on the effective mass of the on-
chain hole is shown in Fig. 4 for different values of ␴x and
␴y = 0.1 nm. ⌬E is positive for a large range of values of meff.
One sees that disorder in the dipole positions creates a repul-
sive barrier for charge separation even when the hole effec-
tive mass is approximately 60% of the rest mass of the elec-
tron.
IV. CONCLUSION
In conclusion, from Monte Carlo simulations we have
investigated the role of positional disorder on exciton disso-
ciation at an interface between a donor such as a conjugated
polymer and an electron acceptor. We have shown that inho-
mogeneities in the acceptor distribution at the D-A interface
can create highly efficient exciton dissociation centers by
enhancing the energy barrier for the hole on the chain nearest
to the heterojunction, even for meff ⬇ me. Since the zero-point
oscillations of an on-chain hole is damped by the interface’s
roughness, we have also demonstrated quantitatively that
smoothness of the interface is a crucial feature to improve
exciton dissociation. The theory can explain recent experi-
mental results: 共i兲 the longer lifetime of photoexcited charge
carrier in disordered PEOPT/PCBM when compared to com-
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J. Appl. Phys. 99, 053702 共2006兲
posites fabricated from an ordered phase of the same poly-
mer, 共ii兲 the higher short circuit current in photovoltaic de-
vices fabricated with disordered PEOPT/PCBM junctions
compared to devices using ordered PEOPT/PCBM junctions,
and 共iii兲 the increase of the exciton dissociation yield with
the acceptor concentration.
Finally, we mention that variations in the interactions of
the chain ␲ orbitals with the random environment may also
create further energy differences between chains 共1兲 and 共2兲,
a factor not considered in the present calculations. This effect
can influence the average pair dissociation probability and
will be addressed in a future work.
ACKNOWLEDGMENTS
We acknowledge the research fellowships from CNPq
and grants from Finepe/CT-Infra, CNPq/CT-Energ, CNPq/
Edital Universal, and Fundação Araucária.
1
D. M. Adams, J. Kerimo, E. J. C. Olson, A. Zaban, B. A. Gregg, and P. F.
Barbara, J. Am. Chem. Soc. 119, 10608 共1997兲; M. Theander, A. Yartsev,
D. Zigmantas, V. Sundstrým, W. Mammo, M. R. Andersson, and O. Inga-
nýs, Phys. Rev. B 61, 12957 共2000兲.
2
M. R. Singh and J. Desforges, Physica E 共Amsterdam兲 12, 327 共2002兲; M.
O. D. Camara, A. Mauger, and I. Devos, Phys. Rev. B 65, 205308 共2002兲.
3
A. C. Morteari, P. Sreearunothai, L. M. Herz, R. H. Friend, and C. Silva,
Phys. Rev. Lett. 92, 247402 共2004兲; A. S. Dhoot, J. A. Hogan, A. C.
Morteani, and N. C. Greenham, Appl. Phys. Lett. 85, 2256 共2004兲.
4
S. Alem, R. de Bettignies, J. Nunzi, and M. Cariou, Appl. Phys. Lett. 84,
2178 共2004兲.
5
B. Pradhan, A. Bandyopadhyay, and A. J. Pai, Appl. Phys. Lett. 85, 663
共2004兲.
6
D. Chirvase, J. Parisi, J. C. Hummelen, and V. Dyakorov, Nanotechnology
15, 1317 共2004兲.
7
J. Nelson, J. Kirkpatrick, and P. Ravirajan, Phys. Rev. B 69, 035337
共2004兲; I. Kamohara, M. Townsend, and B. Cottle, J. Appl. Phys. 97,
014501 共2005兲.
8
T. Offermans, S. C. J. Meskers, and R. A. J. Janssen, Chem. Phys. 308,
125 共2005兲.
9
V. I. Arkhipov, P. Heremans, and H. Bässler, Appl. Phys. Lett. 82, 4605
共2003兲.
10
N. S. Sariciftci, L. Smilowitz, A. J. Heeger, and F. Wuld, Science 258,
1474 共1992兲.
11
P. Schilinsky, C. Waldauf, and C. J. Brabec, Appl. Phys. Lett. 81, 3885
共2002兲.
12
M. C. Scharber, N. A. Schultz, N. S. Sariciftci, and C. J. Brabec, Phys.
Rev. B 67, 085202 共2003兲.
13
C. J. Brabec, G. Zerza, G. Cerullo, S. D. Silvestri, S. Luzzati, J. C. Hum-
melen, and S. Sariciftci, Chem. Phys. Lett. 340, 232 共2001兲.
14
V. I. Arkhipov and H. Bässler, Phys. Status Solidi A 201, 1152 共2004兲.
15
P. Peumans and S. R. Forrest, Chem. Phys. Lett. 398, 27 共2004兲.
16
V. D. Mihailetchi, L. J. A. Koster, J. C. Hummelen, and P. W. M. Blom,
Phys. Rev. Lett. 93, 216601 共2004兲.
17
D. H. Dunlap, P. E. Parris, and V. M. Kenkre, Phys. Rev. Lett. 77, 542
共1996兲.
18
C. J. Brabec, C. Winder, M. C. Scharber, N. S. Sariciftci, J. C. Hummelen,
M. Svensson, and M. R. Andersson, J. Chem. Phys. 115, 7235 共2001兲.
19
P. Peumans, A. Yakimov, and S. R. Forrest, J. Appl. Phys. 93, 85 共2003兲.
20
H. Vázquez, W. Gao, F. Flores, and A. Kahn, Phys. Rev. B 71, 041306共R兲
共2005兲.
21
D. M. Russel, A. C. Arias, R. H. Friend, C. Silva, C. Ego, A. C. Grims-
dale, and K. Müllen, Appl. Phys. Lett. 80, 2204 共2002兲.