A Decade of Organic Polymeric Photovoltaic Research

REVIEW
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25th Anniversary Article: A Decade of Organic/Polymeric

Photovoltaic Research
Letian Dou, Jingbi You, Ziruo Hong, Zheng Xu, Gang Li,* Robert A. Street,* and Yang Yang*
to their synthetic variability, low-temperature processing, and the possibility
of producing lightweight, flexible, easily
manufactured, and inexpensive solar
cells.[38] Organic electronic devices,
such as organic light-emitting diodes
(OLEDs), organic field effect transistors
(OFETs), and organic memory devices,
have attracted considerable attention
as well.[914] Among them, OLEDs have
been successfully commercialized.
Unlike inorganic semiconductors, in
which atoms are covalent-bonded in threedimentions, organic conjugated molecules
or polymers are individual molecular
semiconductors.[1517] Within a molecule,
the pz atomic orbitals of the carbon atom
(also for the nitrogen, oxygen, sulfur
atoms, etc.) overlap to form conjugation molecular orbitals and the electrons
are delocalized within the conjugated backbone. Inter-molecular interactions are formed through Van der Waals and aromatic interactions, which play important roles in the solid
state.[16,17] The energy difference between the highest occupied
molecular orbital (HOMO) and lowest unoccupied molecular
orbital (LUMO) levels determines the bandgap of the material. The organic semiconductors can be p-doped or n-doped
by removing electrons from the HOMO level or adding electrons to the LUMO level, respectively. Typically, materials with
relatively high HOMO level can be easily p-doped and transport
holes and are thus called p-type (or electron donor), while materials with relatively low LUMO level can be easily n-doped and
transport electrons and are called n-type (or electron acceptor).
Electrically, there are two major distinctions between organic
and inorganic semiconductors. First, the charge carriers move
freely in the conjugated backbone, but the inter-molecular
charge transport is much more difficult for organic materials.
Hopping from one molecule to the adjacent molecule limits
macroscopic charge transport. As a result, the charge mobility
of organic materials is significantly lower than the mobility
of inorganic materials, such as crystalline Si (103 versus
103 cm2V1s1).[11,12,18] However, the high absorption coefficient
of organic chromophores allows organic semiconductors to capture most of the photons (within the absorption range) using a
very thin layer (100200 nm) and avoid severe charge recombination. Second, tightly bound Frenkel excitons (electronhole
pairs) in organic materials are observed, resulting from their
low dielectric constant (r 24). The binding energy of the
Frenkel exciton is in the range of 0.31 eV, whereas the binding
energy of the Wannier exciton (free electron hole pairs at room
temperature) in the inorganic semiconductors is comparable to
Organic photovoltaic (OPV) technology has been developed and improved

from a fancy concept with less than 1% power conversion efficiency (PCE)
to over 10% PCE, particularly through the efforts in the last decade. The
significant progress is the result of multidisciplinary research ranging from
chemistry, material science, physics, and engineering. These efforts include
the design and synthesis of novel compounds, understanding and controlling the film morphology, elucidating the device mechanisms, developing
new device architectures, and improving large-scale manufacture. All of these
achievements catalyzed the rapid growth of the OPV technology. This review
article takes a retrospective look at the research and development of OPV,
and focuses on recent advances of solution-processed materials and devices
during the last decade, particular the polymer version of the materials and
devices. The work in this field is exciting and OPV technology is a promising
candidate for future thin film solar cells.
1. Introduction
Photovoltaic (PV) technology, which generates electricity
directly from sunlight, is a promising solution to the energy
crisis. Intensive research is searching for high efficiency solar
cells with low-cost fabrication. Currently, various inorganic
materials (for example, silicon (Si), III-V group semiconductors, CdTe, CIGS) based PV devices are the dominating
technologies in the market.[1] However, partially due to the
high production cost and related environmental issues, conventional PV technology hasnt successfully replaced gridelectricity. At the current stage, electricity generated from
the PV accounts less than 0.1% of total US energy generation, and similarly, worldwide.[2] In recent years, there has
been growing interest in organic-based PV (OPV) technology. Organic semiconductors show great promise owing
L. Dou, Dr. J. You, Dr. Z. Hong, Dr. Z. Xu, Dr. G. Li,

Prof. Y. Yang
Department of Materials Science and Engineering
University of California, Los Angeles
Los Angeles, CA 90095, USA
E-mail: gangl@ucla.edu; yangy@ucla.edu
L. Dou, Prof. Y. Yang
California Nano Systems Institute
University of California, Los Angeles
Los Angeles, CA 90095, USA
Dr. R. A. Street
Palo Alto Research Center
Palo Alto, CA 94304, USA
E-mail: street@parc.com
DOI: 10.1002/adma.201302563
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2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Adv. Mater. 2013, 25, 66426671
Yang Yang received his

M.S. and Ph.D. in Physics
and Applied Physics from the
University of Massachusetts,
Lowell in 1988 and 1992,
respectively. Before he joined
UCLA in 1997, he served as
the reseasrch staff in UNIAX
(now DuPont Display) from
1992 to 1996. Yang is now the
Carol and Lawrence E. Tannas
Jr. Endowed Chair Professor
of Materials Science at UCLA. He is an expertise in the
fields of organic electronics, such as photovoltaic cells,
OLEDs, and memory devices.
REVIEW
thermal energy at room temperature 26 meV.[19,20] Therefore,

to separate the tightly bound exciton effectively, an organic hetero-junction that consists of two distinct materials (n- and ptype, respectively) with sufficient energy band offset is needed.
Due to these characteristics of organic semiconductors, very
different device architectures and processing techniques for the
organic solar cell are employed to achieve high power conversion efficiency (PCE).
Three important parameters determine the PCE of a solar
cell: the open-circuit voltage (VOC), short-circuit current density (JSC), and fill factor (FF). The PCE is equal to the product
of these three parameters divided by the input power.[21] The
simplified working principle of an OPV device is comprised of
four steps: (1) photon absorption and exciton generation, (2)
exciton diffusion, (3) charge separation, and (4) charge collection.[38] The external quantum efficiency (EQE) is defined as
the numerical ratio of the collected photo-generated charges
and the incident photons at certain wavelength, and it is determined by the efficiency of the above four steps. The JSC of a
solar cell is also equal to the integral of the product of cell
responsivity (or EQE as a function of wavelength) and incident
solar spectral irradiance.[21] It is worth pointing out that other
important phenomena can influence the PCE, such as ultrafast
charge transfer, hot excitons, etc.
The fundamental knowledge of organic semiconductors and
photovoltaic devices was obtained through a long journey of
research. The first successful OPV device was reported as early
as 1986 by Tang et al. using a bi-layer structure.[22] Between two
electrodes (indium tin oxide and silver), thin layers of p-type
small molecules (copper phthalocyanine) and n-type molecules
(perylene diimide derivative) were thermally evaporated (vacuum-processed). The charge separation at the donor-acceptor
interface was found to be very efficient and an impressive
PCE of 1% and high FF of 65% were demonstrated.[22] In the
early 1990s, Heeger, Sariciftci et al.[23a] first discovered electron
transfer from polymer to fullerene, and Yoshino et al. reported
photoconductivity enhancement when polythiophene is
blended with C60 buckeyball.[23b] Heeger reported ultrafast photoinduced electron transfer (50fs) from a conjugated polymer
(MEH-PPV, synthesized by Wudl et al.) to fullerene (C60), which
opened the possibility of using conjugated polymers as the
donor and fullerenes as the acceptor in the OPV devices.[23a]
The devices using the bi-layer structure demonstrated low
efficiency,[24] because the lifetime of the exciton is very short
and its diffusion length is only 10 nm.[25,26] This means the
active layer must be very thin to avoid exciton recombination.
However, such a thin film (20 nm) is insufficient for effective optical absorption. To overcome this problem, the bulk
heterojunction (BHJ) structure made from a solution of p- and
n-type materials was invented by Sariciftci and Heeger in a
1992 patent,[27a] followed by two important papers by Heeger
et al. and Friend et al., respectively.[27b,c] The nano-scale phase
separation of the donor and acceptor materials in the bulk creates interfaces for exciton dissociation throughout the film.[27]
Encouragingly, much efficiency improvement was achieved
by using the BHJ structure. Since then, BHJ has become the
standard device structure in OPV research.
Over the past decade (2003 2013), substantial progress has
been made in understanding the working mechanism of the
OPV devices,[2830] design and synthesis of new materials,[3134]

morphology control and characterization,[3538] developing
new device architectures and interface engineering,[3942] and
improving the device stability.[43] As a result, high efficiencies of
9% for single junction devices and 11% for tandem devices
have been published with fairly good stability.[4446] Heliatek Co.
in Germany recently demonstrated certified 12% PCE of a vacuum-processed small molecule organic triple junction tandem
solar cell with an active area of >1 cm2.[47] These are significant
milestones in OPV research. This review article focuses on
recent advances in the aforementioned aspects. Six main topics,
including mechanism, new materials, morphology, interface
engineering & inverted device structure, tandem devices, and
manufacture & stability, are discussed. Future perspectives are
given with emphasis on new directions derived from current
research and novel applications of OPV technology. Both solution and vacuum processing are important methods for the fabrication of OPV devices. Thermally evaporated small molecule
BHJ solar cells have achieved 67% in single junction[4850]
and beyond 10% in tandem devices.[47,51,52] Impressive work
has been published by Forrest, Leo, Wong, Buerle, and others
on different material systems.[4852] In this review, due to the
limitation of space, our focus is on the solution processed OPV
materials and devices.
2. Mechanisms
2.1. Basic Structure and Operation of Cell
The typical binary BHJ solar cell is a blend of an electron donor
and an electron acceptor. As the solution-coated film dries it phase
separates into a nanoscale domain morphology that is the key to
the solar cell properties.[38] (The details of Morphology is discussed in the Section-4 of this manuscript.) The basic geometry
and energy band configuration are illustrated in Figure 1a1c.
As indicated in the Introduction part, the optically excited excitons in the organic semiconductor are too tightly bound to dissociate into free electrons and holes by thermal excitation,[53]
but the exciton can dissociate at the interface due to the energy
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Figure 1. Basic geometry and electronic stricture of the BHJ cell. (a) The nanoscale phase-separated domain morphology showing exciton absorption
leading to the charge transfer state that separates into mobile electrons and holes. (b) The same process illustrated in an energy diagram showing the
band offset between the donor and acceptor materials. (c) Schematic of solar cell current flow at voltage bias V. (d) Example of cell current-voltage characteristics (points) and the same result obtained by separately adding the dark and photocurrent (solid line). The dashed line illustrates the expected
cell current in the absence of significant recombination. (e) Examples of dark forward bias current for various organic cells.
loss associated with the band offset (see Figure 1b). The interface band gap EGI is defined as the energy difference between
the valence band (or HOMO) of the donor and the conduction
band (or LUMO) of the acceptor. Provided that EGI is less than
the exciton energy, it is energetically favorable for the exciton to
separate at the interface into a hole in the donor and an electron
in the acceptor. This is known as the charge transfer (CT) state
and mobile free electrons and holes are formed from this state.
An important unresolved question is how small an energy
difference between the exciton energy and EGI can maintain
efficient charge separation, since the energy difference represents a significant loss of cell efficiency.[54] Also unclear is
whether the excitons reach the interface by diffusion or by
energy transfer but, in either case, their range is only a few 10 s
of nanometers.[55] Hence, the BHJ structure must have a comparable nanoscale structure to be an effective solar cell. Fortunately, phase separation with domain size about 20 nm occurs
spontaneously in a range of materials. The exciton reaches the
BHJ interface within 1 ps,[56] and the exciton radiative recombination is almost completely suppressed.
An efficient organic solar cell therefore requires strong
absorption of light to form excitons, followed by efficient
transfer of the excitons to the CT state at the interface, dissociation of the CT state into mobile free electrons and holes, and
finally a high probability of charge collection at the contacts.
The formation and dissociation of the CT state is perhaps the
most complex and controversial process, and this is discussed
after some other concepts are introduced.
As in other solar cells, the BHJ cell is constructed with a
built-in potential VBI so that the electrons and holes separate
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in the internal field which has opposite polarity to the external

voltage, allowing power generation. The usual configuration has
a glass substrate, a transparent metal electrode such as indium
tin oxide (ITO), a hole contact layer, the BHJ active layer and
an electron contact.[57] The inverted device structure swaps
the electron and hole contacts, and provides many advantages.
The built-in potential is created by the effective Fermi energy
(or work function) of the conducting materials in contact with
the active layer. The hole contact is usually the p-type doped
polymer PEDOT:PSS or a metal oxide such as MoOX or ITO.
Cells that use the metal electrode for the electron contact layer
need to have a low work function such as Ca/Al. However a
separate electron contact layer such as TiOX, can provide the
low work function contact. (In Section-5 of this manuscript,
the interface and inverted device architecture are extensively
discussed.)
The solar cell current comprises of electrons flowing in the
acceptor material and the holes in the donor, which is a unique
feature of the BHJ cell. The carrier mobility and the diffusion
length are both small and current flow is primarily by drift in
the internal field of the built-in potential VBI. The cell thickness
is typically only 100 nm, and the internal space charge created
by the carriers or by residual doping is not enough to give a
large band bending effect, so that the internal electric field
extends through the active layer.
The PCE of a solar cell efficiency obeys the well-known relation, PCE = VOC JSC FF/Pin, where Pin is the input power.
The current in the solar cell at any voltage is most readily
understood as the sum of the dark current JD(V) and the photocurrent JP(V),
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J(V) = JD (V) + JP (V)
(1)
In the solar cell operating voltage range, the dark current and
photocurrent have opposite signs. A typical cell current-voltage
J(V) characteristic is illustrated in Figure 1d and confirms the
validity of Equation (1). VOC is the voltage at which JD(VOC)
and JP(VOC) are equal and opposite. The photocurrent changes
sign when the applied voltage exceeds the built-in potential,
and hence VOC < VBI. By definition, no current flows at VOC,
and therefore the carrier excitation rate is balanced by an equal
carrier recombination rate. The excitation rate G under 1-sun
illumination in a typical organic cell is about 1022 cm3, and
the recombination lifetime is about 106 sec, from which the
carrier concentration of both electrons and holes, NC = G is
about 1016 cm3.[58] At short circuit, for a material with mobility
103 cm2/Vs and cell current 10 mA/cm2, the carrier concentration is about 1015 cm3. These approximations give the order
of magnitude of carrier concentration, which increases towards
VOC as the internal field decreases.
The carrier concentration also determines the electron and
hole quasi-Fermi energies EqFE, EqFH through,
NC = N0 exp[(E C E q F E ,H )/kT ]
(2)
where N0 is the effective density of states at the band edge.

From the estimates for NC at VOC, the quasi-Fermi energies
are about 0.25 eV from the band edges. VOC cannot exceed EGIEqFE-EqFH, otherwise current will flow in the forward direction.
Hence VOC is set by whichever is smaller of the built-in potential or the quasi-Fermi energies and for the latter case, VOC
expected to be about 0.5 V less than EGI, which is confirmed by
measurement.[59] Equation (2) applies to a semiconductor with
a sharp band edge and should be generalized when there is a
band tail of localized states. However, the estimate of the quasiFermi energy is not changed much for the band tail in typical
organic cells.
Figure 1e shows examples of the dark forward current in
some solar cells, which obey the well-known diode equation,

V RS J D
e(V RS J D )
1 +
J D (V ) = J 0 exp
(3)
nkT
RP
where n is the ideality factor, RP is the parallel shunt resistance and RS is the series resistance. The pre-factor J0 is
related to the barrier height and decreases with larger VBI.
The shunt resistance is highly variable in different devices
and its precise origin is unclear. The series resistance can
arise from the specific contacts or from within the BHJ active
layer. Large series resistance significantly degrades the cell
J(V) characteristics.
The ideality factor is typically in the range 1.5-2 in good
organic cells. Classic semiconductor theory shows that n = 1 is
associated with band-to-band recombination while n = 2 is associated with recombination through states in the middle of the band
gap by the Shockley-Read-Hall mechanism. Modeling shows that
the intermediate values of n which are observed in other disordered semiconductors, arise from recombination through band
tails states, possibly in combination with deeper states.[60] The
dashed line in Figure 1d illustrates the expected cell J(V) when
the dark current has an ideality factor of 1.5 and the photocurrent
Adv. Mater. 2013, 25, 66426671
Figure 2. (a) Optical absorption of some BHJ cell component materials, PC61BM and two different polymers with the indicated structure.
(b) Photocurrent spectral response from PCDTBT:PC61BM showing the
weak absorption from the CT state and from deep traps.
is constant up to VBI, representing an approximation to an ideal

cell, with fill factor is 0.8. The lower fill factor in real cells results
from recombination of electrons and holes before they reach the
contacts and is discussed in section 2.5.
2.2. Electronic Excitations in BHJ Cells
The different electronic states represented by excitons, the CT
state, the mobile transport states and the localized trap states
each play a crucial role in the operation of an organic solar
cell. These states have characteristic optical absorption spectra
which are illustrated in Figure 2a.[61] The excitonic absorption
is strong with a series of absorption bands that are sensitive
to the underlying order of the material.[62] The absorption is
characterized by strong electron-phonon coupling that gives
rise to phonon sidebands that are often obvious in the spectra
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and are split by about 0.18 eV, the energy of

vibrational modes of the conjugated ring.
A more ordered (i.e. semicrystalline) material morphology tends to have narrower
optical absorption bands shifted to a lower
energy than a more disordered form. The
excitations are essentially molecular, being
primarily confined to a single polymer molecule. The low dielectric constant leads to a
large Coulomb binding energy that tightly
confines the electron and hole.
The CT state comprises an electron and
hole on either side of the BHJ interface
and therefore has an intermediate character
between the exciton and the free carriers,
because the electron and hole separation
reduces the Coulomb interaction.[63] The
CT optical absorption is weak because it
only occurs at the interfaces, but it can be
observed by various sensitive techniques,
like the photocurrent spectral response
(PSR) which is shown in Figure 2b.[64] The
CT absorption is a broad featureless band
extending below the exciton absorption
bands with no sign of phonon sidebands.
The CT state is an excitation across the interface band gap (see Figure 1) and so provides
a measure of EGI. Street et al. have proposed
that the shape of the CT absorption reflects
the joint density of states of the polymer
valence band and the fullerene conduction
band, while Vandewal et al. propose that the
broadening is primarily due to an electronFigure 3. (a) Illustration of the expected density of states in a disordered semiconductor with
phonon interaction.[65]
The CT state dissociates easily into mobile band-like states, localized band tails and deep traps. (b) Multiple trapping of carriers in a band
free carriers in the higher efficiency organic tail/mobility edge model. (c) transient photocurrent data for PCDTBT:PC61BM showing dispersive transport characteristic of the band tail/mobility edge model. (d) Photocurrent spectral
solar cells. The reason for the high disso- response measurements showing the increase in low energy absorption as a result of illuminaciation probability has been much discussed tion in PCDTBT:PC61BM and P3HT:PC61BM. (e) Atomic model of polythiophene illustrating
and the explanations fall into three general the hydrogen vacancy and CH2 model of defect formation. (c) Reproduced with permission
categories. One explanation is ionization of from.[74] (d,e) Reproduced with permission from.[77] Copyright 2012 American Physical Society.
the CT state by the internal electric field, a
well-known process described by the Braunthis is not the case at least in P3HT:PC61BM cells.[68] A more
Onsager model.[66] This mechanism not only explains the crearecent model of assisted ionization comes from the evidence
tion of mobile carriers but also how the geminate recombinafor some intermixing of the fullerene into the polymer.[69] The
tion of the CT state at low internal field can account for the
idea is that intermixing creates an interface zone where it is
reduced FF of the cell. However, although this mechanism
energetically favorable for the electron and hole to separate furdoes occur in some cell materials, it is insignificant in at least
ther, leading to efficient ionization.
some of the higher efficiency cells.[67] A second explanation is
that the binding energy of the CT state is sufficiently small so
that thermal ionization occurs with high probability even at low
2.3. Mobile States, Localized Band Tail States and Dispersive
internal field. This mechanism is estimated to occur when the
Transport
binding energy is less than about 0.25 eV, which is roughly the
expected binding energy of the CT state.[58]
The third explanation is assisted thermal ionization, which
Electrons and holes that are ionized from the CT state move
invokes an additional mechanism to push the CT state further
in the internal field to the cell contacts. The cell materials
apart and make complete ionization easier. An early suggestion
are disordered which is known to introduce a band tail of
of this type was that the excess kinetic energy of the separating
localized states extending into the band gap, as illustrated in
electron and hole pushes the carriers apart so that they never
Figure 3a3c, and polaron behavior adds to the tendency of carreach the CT ground state. However, measurements show that
riers to localize. The mobility edge model describes a situation
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where conduction occurs in the region of higher density of

states but not in the deeper localized states.[70] The dividing
line between localized states and mobile states may be at a welldefined energy or more gradual, but does not greatly affect the
model. This mobility edge model accounts well for the properties of organic thin film transistors.[71]
The band tail/mobility edge model is characterized by low
average mobility because carriers are repeatedly trapped in
localized states and excited to the mobile states (Figure 3d) so
that the effective mobility is expressed as Equation (4),[70]
: = :0
tF
t F + tT
(4)
where 0 is the free carrier mobility and tF and tT are the relative time that the carrier is free or trapped, respectively. An
exponential band tail has the property that as time progresses,
carriers are increasingly likely to be trapped in rare deep band
tail states and take much longer to be thermally excited. Hence
the mobility of an excited carrier decreases with time, a property known as dispersive transport.[72] Transient photoconductivity in which a short pulse of laser illumination excites
carriers which move across the sample is the classic experiment to observe the effect. The data in Figure 3c confirm the
power law decreases in the current which reflects the time
dependent mobility, t1, and which changes to a steeper
power law after the transit time. This result is characteristic of
dispersive transport from an exponential band tail, described by
a density of states, NBT(E) = N0exp((E-E0)/EB), and the slope
of the exponential is EB = kT/.[73] These measurements find
EB = 35 meV and 45 meV for the polymer in P3HT:PC61BM
and PCDTBT:PC61BM respectively,[74] and the same exponential
slopes are observed in PSR data as in Figure 1e.
The trap-limited mobility of the polymer in a typical organic
solar cell is 103104 cm2/Vs. It is not easy to deduce the
mobility of the free carriers but it is probably 1 cm2/Vs or
larger. Solution cast organic thin film transistors have mobility
up to 110 cm2/Vs and single crystal organic have mobility
>10 cm2/Vs. Mobile electron and hole states are evidently significantly delocalized, and there is further evidence for delocalization in BHJ cells.[75] Excitons and mobile carriers apparently
have different characteristics, the former being highly molecular and the latter being relatively delocalized. The contribution
of the electron-phonon coupling to the exciton energy is clear,
but the magnitude of phonon coupling in the mobile carrier
states is less obvious, and is probably a strong function of the
structural disorder.
Figure 4. Illustration of the main recombination mechanisms

expected in BHJ organic cells; (a) geminate recombination; (b) mobile
carrier recombination; (c) deep state recombination; (d) reverse diffusion.
illumination, as measured by the low energy absorption band

in a PSR measurement, and are implicated in the loss of efficiency of some solar cells exposed to prolonged sunlight.[77]
Recent evidence suggests that the light-induced deep states
arise from the breaking of C-H bonds and the migration
of the hydrogen to other sites on the polymer or possibly on
the fullerene.[77] The site vacated by H and a site with excess
hydrogen are illustrated in Figure 3e and are defects capable
of forming a trap, as has been shown by first principle calculations. The states formed by illumination by white light, UV light
or soft x-rays are reversible by annealing at about 100 C and
with an activation energy of 11.2 eV.[77] Again, theory shows
that the migration of hydrogen within the polymer occurs with
an energy of 1.21.4 eV, consistent with the annealing data and
providing further evidence for the hydrogen bond breaking
model of these deep states.
2.5. Recombination Mechanisms
2.4. Deep Localized States

Almost every type of solar cell is limited by deep localized states
that act as traps and recombination centers and organic solar
cells are no different. In crystalline silicon it is surface states,
in amorphous silicon it is dangling bonds and in polycrystalline materials it is usually grain boundaries. A small density of traps, of order 101516 cm3, is sufficient to impact the
efficiency of a cell. Localized states in organic BHJ cells have
been observed by a variety of measurement techniques.[76]
Figure 3d shows that the deep states can be enhanced by strong
Adv. Mater. 2013, 25, 66426671
Recombination of the electron and hole competes with collection of the charge at the electrode and is one of the primary
reasons for low solar cell efficiency. Carrier recombination
increases as VOC is approached because the internal electric field decreases and hence the rate of charge collection
decreases. The four main recombination mechanisms that are
anticipated in organic solar cells are illustrated in Figure 4.
Recombination mechanisms are characterized by their recombination order. First order mechanisms are proportional to the
free carrier concentration, while second order recombination
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is proportional to the square of the free carrier concentration.

First order recombination results in a cell FF that changes little
with illumination intensity, while second order recombination results in a FF that decreases as the illumination intensity
increases.
Geminate recombination (Figure 4a) is a first order mechanism which occurs when the CT state recombines before
the electron and hole dissociate.[66] As discussed in 2.2, field
dependent dissociation competes with recombination and can
explain J(V) in some cells but is absent in others. Mobile free
carrier (Langevin) recombination (Figure 4b) is the recombination of mobile electrons and holes,[78] and is a second-order
process that can be identified and quantified from the lightintensity dependence. Recombination occurs through the CT
state and so is closely related to geminate recombination. This
mechanism usually dominates at sufficiently high light intensity and hence the primary question is its relative strength at
solar intensities compared to other mechanisms. Localized
state recombination (Figure 4c), for example between a mobile
hole and a trapped electron,[79] is an important mechanism best
identified by correlating the deep state density to the recombination. For example, deep states introduced by prolonged
illumination are correlated to a corresponding increase in
recombination.[77] Reverse diffusion to the contact (Figure 4d)
occurs when an exciton splits close to one of the electrodes, and
the wrong carrier diffuses against the internal field to reach
the contact and recombine.[80] This is usually a small contribution to recombination but can become significant if other
mechanisms are suppressed.
The starting point for any model is the density of states

distribution, which as we have shown comprises of mobile
states at the band edges, localized band tail states that limit
carrier mobility and deep localized states that can act as
recombination centers. An example of the DOS is shown
in Figure 5a for PCDTBT:PC61BM, and is based on theoretical calculations of the density of states in the bands,
measurements of the band tail slopes and estimates of the
defect density, along with some interpolation, where there
is incomplete data.[74] The model combines the HOMO
states of PCDTBT and the LUMO states of PC61BM which
are the relevant states for the cell. Although small in total
number, the majority of carriers occupy the band tail states
(see Figure 5a) and relatively few are mobile. Recombination
is probably dominated by mobile carriers which can move
to a recombination center, rather than by localized band tail
states which can only tunnel a very short distance. The DOS
along with the specific recombination mechanisms and the
built-in potential and other parameters, allows a numerical
solution of the drift-diffusion equations. An important role
of modeling is to predict how the performance of cell can
be improved. For example, Figure 5b shows a result of an
empirical model to estimate how the solar cell efficiency
depends on the band offset energy, and shows that if the
band offset could be almost eliminated, then cells that are
now about 12% efficient, can increase to above 20%. The
result motivates the search for materials with low band
offset.
2.6. Modeling of Cell Properties
3. New Materials
Although simple in concept, solar cells are complex in detail

and in a disordered material typically requiring numerical
modeling to fully analyze.[81] A caution is that cell models
often ignore the effects of cell contact resistance, which significantly changes the J(V) characteristics.[82] There is plenty
of evidence for a series contact resistance in organic cells, and
also for contact degradation when some cells are exposed to the
ambient.
There has been intense research on developing novel organic

semi-conducting materials, including polymers and small
molecules (SM), for BHJ photovoltaic devices during the
last decade. Here, some representative p-type and n-type
materials featuring several important design rules will be
reviewed. Their chemical structures are shown in Figure 6
(p-type) and Figure 7 (n-type). For the p-type materials discussed here, the corresponding n-type material is PC61BM or
PC71BM.
3.1. P-type Materials: Polymers
Figure 5. (a) Density of states distribution for PCDTBT:PC61BM showing mobile and localized
band tail states. The occupancy under 1-sun illumination is shown. (b) Empirical model of the
cell efficiency as a function of the interface band gap and the band offset. Reproduced with
permission from.[74] Copyright 2011 American Physical Society.
6648
Conjugated polymer based electron donor materials are the best-studied materials to date for
the OPV. Among them, poly(3-hexylthiophene)
(P3HT) is the most commonly used material
due to the advantages of easy synthesis, high
charge carrier mobility, good processability, etc.
Highly regioregular P3HT can be obtained via
McCullough, Rieke or GRIM methods.[8385]
Efficiencies of 4 5% based on the regioregular P3HT have been achieved about ten years
ago.[8688] Since then, numerous groups have
been trying to increase the performances by
modifying the morphology, the device architecture, and the electron acceptor. As a result,
efficiencies can now go up to 7% with external
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REVIEW
One of the successful examples at the

early stage is the carbazole and benzothiadiazole (BT) based polymer (PCDTBT) reported
by Leclerc et al.[93] The optical bandgap of
this polymer is 1.88 eV with a low-lying
HOMO energy level of 5.50 eV. Initial
results of the photovoltaic devices showed
a high VOC of 0.89 V, a JSC of 6.92 mA/cm2,
a FF of 63%, and a PCE value of 3.6%.
Later, Heeger et al. introduced a solution
processed TiOx as the electron transport
layer and optical spacer in the device and
achieved a certified PCE of 6.1% with higher
JSC over 10 mA/cm2 and high FF of 66%.[94]
Recently, a PCE of 7% has been achieved
by device engineering, demonstrating the
great potential of the carbazole based polymers.[95] However, the bandgap of PCDTBT
is still too large to harvest photons in the
NIR region. To further lower the bandgap,
cyclopenta[2,1-b;3,4-b]dithiophene (CPDT)
and dithieno[3,2-b:2,3-d]silole (DTS) units
with stronger electron-donating properties
were independently synthesized by Yang
et al. and Brabec et al., respectively.[96,97]
The polymers PCPDTBT and PSBTBT show
small bandgaps of 1.5 eV due to the strong
intra-molecular donor-acceptor interactions.
Interestingly, the performance of PCPDTBT
based devices can be enhanced significantly
by adding 3% 1,8-diiodooctane (DIO) as a
processing additive to tune the morphology,
whereas PSBTBT does not.[98] Both of them
show PCE 5% in a single junction device
with photo-response up to 850 nm for PCPDTBT and 820 nm for PSBTBT. The major
difference is that the C-Si bond is longer
Figure 6. Chemical structures of some high performance p-type materials including conjugated than the C-C bond. Consequently, less steric
polymers and small molecules.
hindrance is created in the DTS core by the
side chains, leading to a better stacking
and enhanced crystallinity.[99] Another important building
quantum efficiencies around 70%.[8992] However, the main issue
block is diketopyrrolopyrrole (DPP), which was first used in
with P3HT is its quite large bandgap (1.9 eV) and high HOMO
OPV in 2008 by Janssen et al.[100] The electron-withdrawing
level, which lead to insufficient NIR photon absorption and low
effect of the lactam units causes the chromophore to have
open circuit voltage of the corresponding devices. To harvest a
a high electron affinity and thus, it can be used as a strong
greater part of the solar spectrum and provide as much VOC as poselectron-withdrawing unit. When polymerized with a thiosible, narrowing the bandgap and down-shifting the HOMO level
phene unit via Suzuki cross-coupling, a low bandgap polymer
of the p-type materials (or up-shifting the LUMO level of the n-type
PDPP3T was reported by Janssen et al. in early 2009.[101] The
materials) have become important topics for materials scientists.
polymer shows bandgap as low as 1.31 eV and deep HOMO
To realize these goals, several synthetic strategies have been
level of 5.17 eV. This low bandgap polymer showed a photodeveloped and proven to be very effective: (1) construct the
response up to 930 nm when combined with PC71BM, and
backbone using alternating electron-rich (donor) and electronEQE was around 35%. Good photovoltaic performance of 4.7%
deficient (acceptor) units to form the D-A co-polymers; (2) staPCE with VOC = 0.65 V, JSC = 11.7 mA/cm2, and FF = 0.60 was
bilize the quinoid resonance structure; (3) incorporate strong
achieved. Very recently, by increasing the molecular weight of
electron withdrawing substitutes such as carbonyl group or fluPDPP3T and improving the thin film morphology, PCEs over
orine atoms; (4) attach conjugated side chains on the polymer
6% have been achieved.[102,103] These three polymers represent
main chains. The details can be found in recent reviews on the
an important family of photovoltaic materials due to their relchemistry of the materials.[3134] By using or combining these
atively small optical bandgaps, which are useful in a tandem
approaches, numerous new compounds have been designed
solar cell device.
and synthesized for OPV applications.
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Figure 7. Chemical structures of some high performance n-type materials including fullerene and non-fullerenes derivatives.
A breakthrough in new material and high efficiency single

junction OPV device was achieved by joint efforts between Yu
(U. of Chicago) and Li (Solarmer Energy Inc.). Yu first reported
the thieno[3,4-b]thiophene (TT) building block, which can stabilize the quinoid structure to reduce the bandgap.[104] Yang
et al. reported the application of the benzo[1,2-b;4,5-b]dithiophene (BDT) unit in OPV materials.[105] When combining these
two units together and adding a fluorine atom on the TT unit
to lower the HOMO level, from 2009 to 2010, Yu, Li and Hou
et al. reported several high performing polymers, such as PTB7
and PBDT-TT-CF.[106,107] They have similar bandgap of around
1.6 eV and HOMO level of around 5.2 eV. The initial results
were reported as 7.4% and 7.7% PCEs in single junction devices
for PTB7 and PBDT-TT-CF, respectively. Recently, Hou et al.
reported several modification on this family (PBDTTT-C-T and
PBDTTT-S-T) with with conjugated thiophene side chains on
BDT unit.[108] Note worthy, this series of polymers set the milestones of 7%, 8%, and even 9% PCEs, respectively (details will
be discussed in the interface section), which greatly boosted the
momentum in OPV field. These polymers are still among the
6650
leading figures in single junction devices up to date.[45] Despite

the high efficiency of the BDT-TT based polymer, the tedious
synthesis of the fluorinated TT monomers does not make the
cost very low. Later, another easily-synthesized strong electron
acceptor unit, thieno[3,4-c]pyrrole-4,6-dione (TPD), was reported
by a number of groups. The first polymer, PBDT-TPD, was published in 2010 by the Leclerc, Frechet, and Jen groups independently.[109111] The polymer shows a bandgap of 1.81 eV and
very deep HOMO level of 5.57 eV. The initial device results
differ from each group. The best one by Frechet et al. gave a
JSC of 11.5 mA/cm2, a VOC of 0.85 V, a FF of 0.68 and a PCE of
6.8%. To lower the bandgap of the TPD based polymers, Tao et
al. copolymerized it with the DTS unit and obtained a polymer
PDTS-TPD with bandgap of 1.73 eV and deep HOMO level.[112]
Higher PCE of 7.3% was achieved mainly due to a higher JSC
compared to the PBDT-TPD based devices. Further optimization on this structure was reported by Reynolds et al., who
replaced the silicon atom in the DTS unit with a germanium
atom to form the dithienogermole (DTG) unit.[113] The new
polymer PDTG-TPD shows slightly lower bandgap of 1.69 eV,
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and Yoshinura et al. reported a new family of low bandgap polymers using an asymmetric electron rich dithieno[3,2-b:2,3-d]
pyran (DTP) unit.[128] The electron-donating property of the DTP
unit was found to be the strongest among the most frequently
used donor units, such as BDT, DTS or CPDT. When the DTP
unit was polymerized with the strongly electron-deficient DFBT
unit, a regiorandom polymer (PDTP-DFBT, bandgap = 1.38 eV)
was obtained. It was found that the DTP based polymer PDTPDFBT shows significantly improved solubility and processability compared to the BDT or CPDT based polymers with same
alkyl side chains. Consequently, very high molecular weight
and soluble PDTP-DFBT can be obtained with less bulky side
chains. PDTP-DFBT shows excellent performance in bulkheterojunction solar cells with power conversion efficiencies
reaching 8.0% (VOC = 0.69 V, JSC = 18.0 mA/cm2, FF = 0.64),
with EQE over 60% in the NIR region.[46,128] As a result, tandem
polymer solar cells fabricated with P3HT and PDTP-DFBT
achieved 10.6% efficiency as certified by NREL.[46,128]
As we can see, through smart materials design, different
families of polymers with higher and higher PCEs can be
obtained. Aside from the new structure design, it is very important to note that polymer purity, molecular weight, the polydispersity index, and the choice of solubilizing side chain are
also essential for determining performance. It is obvious that
higher purity will lead to less defects and thus better charge
transport in the bulk. Although the purity-performance dependence of a polymer solar cell is not as high as a silicon solar cell,
it is still important to keep the impurity level as low as possible (at least < 1%).[129] The molecular weight has significant
impact as indicated by a number of studies of different polymer
systems.[128,130,131] Generally, the larger molecular weight,
the better as long as the polymer is still soluble. The high
molecular weight polymers are believed to show better charge
transport properties and more favorable thin film morphology
when blended with PC61BM /PC71BM.[128,130,131] The effects of
the polydispersity index of polymers on their performance are
relatively less investigated and only a few studies report that
polymers purified by preparative gel permeation chromatography (GPC) show lower polydispersity index (low molecular
weight part was removed) and better performance.[132] The
choice of side chains on the polymer backbone is an important and complicated issue. Shorter and less bulky ones should
enhance the molecular packing and charge transport, however,
they may limit the solubility and obtainable molecular weight
significantly (high molecular polymers will precipitate out
during polymerization and cannot be dissolved anymore). The
side chains can also help on the supra-molecular self-assembly
between different polymer chains to enhance structural order
as well as modulate the interaction between polymers and
PC61BM/PC71BM (affect morphology).[106,111] Until now, there
is no simple way to predict which kind of side chain is the best
for a specific polymer system and thus side chain engineering
must be done to locate the one with optimized performance.
REVIEW
higher HOMO of 5.65 eV and similar performance of 7.3%.

By using an inverted device structure and modified ZnO electron transport layer, So and Reynolds et al. demonstrated the
PDTG-TPD based device with 8.1% PCE (certified 7.4%) with a
JSC of 14.0 mA/cm2, a VOC of 0.86 V, a FF of 0.67.[114] In 2011,
another strong electron deficient unit, difluorobenzothiadiazole
(DFBT), was first reported by You et al., inspired by Yus previous work on the fluorinated TT unit.[115] An alkyl group was
attached to the BDT unit instead of an alkoxyl group to weaken
the electron donating property of the BDT moiety to maintain a
deep HOMO level. The new polymer, PBDT-DTffBT, showed a
bandgap of 1.7 eV and a HOMO level of 5.54 eV. Compared to
the polymer without the fluorine atoms on the BT unit, the new
polymer showed simultaneously enhanced VOC (from 0.87 to
0.91 V), JSC (from 10.0 to 12.9 mA/cm2) and FF (from 57% to
61%), and thus the PCE increased from 5.0% to 7.2%. Later on,
several more polymers with fluorinated BT unit were reported
with enhanced VOC and efficiencies.[116120]
With the aim of absorbing more photons in the NIR region,
the Yang group recently carried out a systematic investigation on the BDT and DPP based low bandgap polymers. A
polymer reported by Yang et al. is PBDTT-DPP, which shows
small bandgap of 1.46 eV, deep HOMO level, and high charge
carrier mobility.[45,121] The material design was inspired by a
previous published polymer (PBDT-DPP).[122] By replacing
the oxygen atoms attached to the BDT unit with thiophene
moieties to form the thienylbenzodithiophene (BDTT) unit,
the HOMO level of PBDTT-DPP is shifted deeper (5.30 v.s.
5.16 eV) to increase VOC. Bulkier 2-ethylhexyl side chains
on BDTT and 2-butyloctyl side chains on DPP are used to
increase the solubility of the resulting polymers and thus,
obtain much higher molecular weights (40.7 kDa v.s. 8.5 kDa).
Compared to PBDT-DPP, the new polymer shows improved
solubility, higher molecular weight, and higher carrier mobility
(3.1 104 v.s. 6.6 105 cm2V1s1). Power conversion efficiencies around 6.5% were achieved in single junction devices
with both a regular and an inverted structure (VOC = 0.74 V,
JSC = 13.7 mA/cm2, FF = 64%), which were the highest for a
polymer with a bandgap less than 1.5 eV at that time. The EQE
of the PBDTT-DPP based device has a peak value around 50%
in the region from 350 to 850 nm. When combined with the
highly efficient front cell based on P3HT:ICBA in an inverted
tandem device configuration, a NREL certified record efficiency
of 8.62% for the tandem polymer solar cell was achieved.[45]
To further improve this polymer and inspired by Heeneys
work on the selenium based polymers for field effect transistors,[123] Yang and Dou et al. showed that the reduction of the
bandgap and the enhancement of the charge transport properties of PBDTT-DPP can be accomplished by substituting the
sulfur atoms on the DPP unit with selenium atoms.[124] The
new polymer PBDTT-SeDPP (Eg 1.38 eV) demonstrated excellent photovoltaic performance in single junction devices with
PCEs of 7.2% (VOC = 0.69 V, JSC = 16.8 mA/cm2, FF = 0.62). The
high JSC can be attributed to higher EQE of 53% and broader
photo-response (up to 900 nm) of the PBDTT-SeDPP based
device. When applied into the tandem device, a PCE of 9.5%
was achieved with improved JSC.[124] Later, more and more DPP
based low bandgap polymers with high efficiencies of 6 7% in
single junction devices were reported.[125127] Very recently, Dou
3.2. P-type Materials: Small Molecules

As an alternative to the polymer, solution-processed conjugated
small molecule based solar cells have attracted much attention
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6652
in the last few years.[133135] Compared to the polymeric counterpart, small molecules are expected to have higher molecular
precision relative to the statistically determined nature of synthetic polymers and less batch to batch variations. Therefore,
more advantages, such as reproducible fabrication protocols and
a better understanding of structure property relationships, are
anticipated.[136138] While a library of oligothiophenes has been
built and explored over the past two decades, donor-acceptor
type small molecules appended with solubilizing substituents
are now being systematically studied as more promising candidates for OPV application. So far, a variety of structures have
been reported, such as subphthalocyanine, merocyanine, squaraine, diketopyrrolopyrroles, borondipyrromethene, isoindigo,
perylene diimides, fused acenes, oligothiophenes, and triphenylamine derivatives.[136138] Several kinds of molecular shape
and arrangements, like linear molecules with D-A, D-A-D or
A-D-A structures and three-arms, X-shape or star-shape molecules, have been reported.[133138]
Early efforts on solution process small molecule OPV
showed that the efficiency was limited by the low photo-current
and fill factor and the initial PCEs were only 13%. An encouraging discovery was reported by Nguyen et al. in 2009. They
showed that a DPP based SM, DPP(TBFu)2, can give up to 4.4%
PCE in a BHJ device.[139] It was found that when DPP(TBFu)2 is
blended with PC71BM, very little phase separation was apparent
in the as-cast film. Interestingly, thermal annealing of the film
led to suitable phase separation so that favorable BHJ morphology was obtained. The degree of phase separation can be
controlled by adjusting annealing temperature; it was found
that 110 C annealing yielded optimum device properties with a
JSC of 10 mA/cm2, a VOC of 0.9 V, and a FF of 0.48.[139] Encouraged by this work, more and more recent efforts have been
devoted to the development of new small molecular materials
for OPV application. Chen and coworkers designed and synthesized a series of oligothiophenes end-capped with electronwithdrawing alkyl cyanoacetate groups.[140] The alkyl cyanoacetate end group can reduce the HOMO level of the molecule
and improve the film quality significantly. The best performing
molecule, DCAO7T, exhibited a bandgap of 1.8 eV and PCE of
5.08%, with a JSC of 10.7 mA/cm2, VOC of 0.86 V, and a FF of
0.55 as reported in 2011.[140] Recently, the cyanoacetate group
was replaced with a 3-ethylrhodanine moiety as the end acceptor
to narrow the bandgap and further reduce the HOMO level of
the SM; the thiophene unit in the middle of the molecule was
replaced by a co-planar BDT unit to enhance the packing. A new
molecule, DR3TBDT (bandgap 1.7 eV), was published with a
high PCE of 7.4% with a JSC of 12.2 mA/cm2, VOC of 0.93 V, and
a FF of 0.65.[141] All the parameters are higher than DCAO7T
based devices due to the smaller bandgap, deeper HOMO level,
and better thin film morphology. Another important family of
SM was innovated by Bazan and Heeger et al., which has a D-AD-A-D structure. The most studied molecule, DTS(PTTh2)2,
consists of an electron donating DTS unit as the middle core,
two strong electron withdrawing [1,2,5]thiadiazolo[3,4-c]pyridine (PT) units, and two alkylated bithiophenes as the end
group.[142] The material exhibited strong optical absorption
from 600 to 800 nm and a high hole mobility of 0.1 cm2V1s1
measured by organic field-effect transistor. Under AM1.5 irradiation (100 mW/cm2), a record SM based BHJ device PCE of
6.7% in 2011 was achieved using DTS(PTTh2)2:PC71BM blend.

Notably, this high effciency was obtained by adding remarkably
low percentage of solvent additive (0.25% v/v of DIO) during
the film-forming process, which led to decreased domain sizes
in the BHJ layer.[142] Bazan et al. carried out a detailed study
on this series of molecules and found that the shape, bending
angle, and dipole moment (the position of the nitrogen atom
on the PT unit) of the molecules affect their performance dramatically.[143] Recently, Gupta and Heeger et al. reported a new
material, DTS(FBTTh2)2, by replacing the PT unit with a fluorinated BT unit to lower the HOMO level and enhance the VOC of
the devices.[144] Together with a polyethylenimine (80% ethoxylated) (PEIE) modified ZnO electron transporting layer in the
inverted device, an amazing PCE of 7.88% was achieved with a
JSC of 15.2 mA/cm2, VOC of 0.77 V and a FF of 0.67. In addition,
the devices based on DTS(FBTTh2)2 show high stability when
stored in air.[144] This rapid progress in the solution processed
SM BHJ solar cells has significant influence in the OPV field
and therefore, more exciting improvements in the near future
can be anticipated.
3.3. N-type Materials
The n-type semi-conductor plays an equally important role as
the p-type material in a solar cell.[145,146] In 1995, Heeger et al.
invented the BHJ structure for the polymer solar cells incorporating a soluble C60 derivative PC61BM (synthesized by Wudl
et al.) as an acceptor blended with conjugated polymer donor.[27]
Since then, PC61BM and its corresponding C70 derivative
PC71BM (first reported by Janssen et al.),[147] which possesses
stronger visible absorption than PC61BM, are widely used in
the fabrication of BHJ OPV devices. Although great efforts
have been made in developing new n-type materials in the last
decade, including fullerene derivatives and non-fullerenes, it is
quite interesting that PC61BM/PC71BM is still the best choice
for most of the high performance polymers.
So far, most of the work on fullerene derivatives is aiming at
up-shifting the LUMO level of the acceptor to enhance the VOC
of the solar cell device. An example are the trimetallic nitride
endohedral fullerenes, which were discovered in 1999 by Stevenson and coworkers.[148] Theoretical and experimental studies
suggest that the LUMO energy levels of this type of fullerenes
are much higher than those of their corresponding empty-cage
fullerenes. Recently, Drees et al. synthesized a series of soluble
PC61BM-like Lu3N@C80 derivatives. Among them, Lu3N@
C80-PCBH shows similar solubility and miscibility to PC61BM.
The LUMO energy level of Lu3N@C80-PCBH was found to be
0.28 eV higher than that of PC61BM. The electron mobility of
Lu3N@C80-PCBH was measured to be 4.0 104 cm2V1s1
compared to 1.4 103 cm2V1s1 for PC61BM. The solar cell
devices based on P3HT:Lu3N@C80-PCBH displayed VOC of
0.89 V, which is 0.26 V higher than that of the PSC based on
P3HT:PC61BM and similar JSC and FF values as those of the
PSCs based on P3HT:PC61BM. The maximum PCE of the
devices based on P3HT:Lu3N@C80-PCBH reached 4.2%.[148]
However, the high synthetic cost of this series materials may
limit their real application in commercial products. Another
approach to lift the LUMO level of the fullerenes is to make
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0.76 V and 1.86%, respectively.[157] More recently, by changing

the thiophene unit on the FFI-1 to a 2-methylbenzene group,
higher VOC and JSC were observed in P3HT based devices and
an impressive PCE of 2.9% was achieved.[158] Polymer based
electron acceptors have also been explored for several years.
Relatively well studied examples are F8TBT, CN-PPV and
PDI-DTT.[159161] F8TBT and PDI-DTT were used in BHJ solar
cells blended with P3HT and CN-PPV was used in a bi-layer
device structure. PCE 2% for F8TBT, CN-PPV and PDI-DTT
based devices were reported by McNeill et a., Friend et al., and
Zhan et al., respectively. Although the VOC was higher than the
PC61BM based devices, the substantially low JSC and FF limited the efficiency greatly.[159161] The electron mobility does not
seem to be a problem. Therefore, a better understanding of the
profound interactions between acceptor and donor materials,
especially in blend systems, will undoubtedly play a critical
role in improving the performance of OPV devices using nonfullerene acceptors.
REVIEW
a bisadduct on it. Indeed, a number of fullerene bisadducts

based on PC61BM (Bis-PC61BM) and related structures were
synthesized and higher VOC and PCE were obtained for P3HT
based devices.[149,150] In 2009, Li et al. reported a new fullerene
bisadduct, indene-C60 bisadduct (IC60BA), via a simple onepot reaction of indene and C60.[151] The product is a mixture of
unreacted fullerene, indenefullerene monoadduct, indene
fullerene bisadduct and indenefullerene mutiadduct. Each
component can then be separated and purified by silica gel
chromatography. Surprisingly, when IC60BA was blended with
P3HT and applied into solar cell devices, PCEs of 6.5% were
achieved with a JSC of 10.6 mA/cm2, a high VOC of 0.84 V, and
a FF of 0.72, which is the highest value for a P3HT based solar
cell device.[152] Except for the higher LUMO level of IC60BA,
the beauty of this molecule is that it does not affect the charge
transport when blended with P3HT. IC60BA was then blended
with other low bandgap polymers; nevertheless, the attempts
were not very successful.[153] Lower JSC and FF were obtained
in most cases, probably due to insufficient LUMO-LUMO
offset between donor and acceptor materials for efficient charge
separation or due to poor thin film morphology. To make the
indene-fullerene adduct more compatible with low bandgap
polymers, Yang et al. designed and synthesized indene-C70
monoadduct with an ester group on the indene unit (the synthesis of bisadduct was not successful). The new fullerene
derivative, H120, was tested using PBDT-TT and PBDTT-DPP
as the donor material. Slightly higher VOC and similar PCE
compared to PC61BM based devices were obtained.[154] Another
interesting fullerene acceptor is SIMEF, which was synthesized
by Nakamura et al. in 2009.[155] It was reported that SIMEF has
0.1 eV higher LUMO level than that of PC61BM. The same
authors fabricated the solution processed pin photovoltaic
devices based on a tetrabenzoporphyin derivative as the donor
and SIMEF as the acceptor. After device optimization, the VOC,
JSC and PCE of the device reached 0.75 V, 10.5 mA/cm2 and
5.2%, respectively, while the VOC, JSC and PCE of the device
using PC61BM as acceptor were only 0.55 V, 7.6 mA/cm2 and
2.0%, respectively.[155]
Although fullerene derivatives show very promising properties for OPV application, their relatively high cost is a concern.
The pursuit of high performance, non-fullerene acceptors have
drawn great attention in recent years.[146] Both small molecules
and polymers with high electron affinity have been investigated to find an alternative for PC61BM/PC71BM. Besides the
lower cost, an important feature for the non-fullerene acceptors is that the high absorption coefficient in the visible region
could be achieved and thus, they can compensate the absorption range of low bandgap polymers.[146] For example, Wudl
et al. synthesized 9,9-bifluorenylidene (9,9-BF) as a scaffold for
small molecule acceptors.[156] The 9,9-BF structure experiences
torsional strain in the ground state due to repulsive interaction
between H1H1 and H8H8 protons, but the strain can be
relieved when the molecule receives an extra electron and
gains aromaticity. Initial characterization of BHJ solar cells
with P3HT has revealed a particularly high VOC = 1.1 eV and
a respectable FF = 40%, yielding PCEs as high as 2%.[156] Pei
et al. reported a series of fluoranthene-fused imide (FFI) derivatives. The first molecule, FFI-1, when used as the acceptor
material for P3HT, the VOC and PCE of the devices reached
4. Morphology
In BHJ solar cells, the morphology of the PV active film is critical for the achieving high efficiency. In organic/polymer materials, while the atoms are well organized within the molecules,
the weak Van der Waals force between molecules results in a
relatively disordered arrangement. As discussed in Section-2,
the excitons in organic/polymer materials are strongly localized
Frenkel excitons. In the simplified photophysics model, upon
photogeneration of excitons, the large exciton binding energy
(>>kT at room temperature) prohibits excitons to be dissociated
thermally and under normal electric field, and this task needs
to be accomplished at the donor/acceptor interface. The much
lower carrier and exciton mobility in the organic materials prevents the planar junction structure used in inorganic solar cell
to be applied to the OPV devices. The preferred morphology of
BHJs is a bi-continuous interpenetration network. Both donor
and acceptor domains should have the sizes of twice the exciton
diffusion length (10 nm), so that excitons can diffuse to the
D-A interface to achieve high exciton diffusion and dissociation
(charge separation) efficiency to generate charge. After charge
separation at the D-A interface, holes and electrons need to
travel to positive and negative electrodes through donor and
acceptor networks, respectively.
4.1. Thin Film Morphology Investigated via AFM, SEM and TEM
The understanding of polymer solar cell morphology has
gone a long way and is strongly related to materials systems.
One of the early successful polymers for solar cells is poly(2methoxy-5-(3,7-dimethyloctyloxy)-p-phenylene
vinylene),
MDMO-PPV. In 2001, Shaheen et al. showed that in a MDMOPPV:PC61BM system, the organic solvent selection plays important role.[162] Using chlorobenzene (CB) as the solvent led to a
much smoother polymer blend film than that using toluene
solvent. Figure 8a, 8b show the AFM images of the MDMOPPV:PC61BM films cast from toluene and CB, respectively.
The device performance exhibits a significant improvement,
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more efforts are needed to replace them with

environmental friendly solvents such as nonhalogenated solvents.
Regioregular (RR) P3AT has high regioregularity and enabled high crystallinity and
high mobility (0.1 cm2/v-s),[165] which in turn
led to intensive interest in organic electronics
society on organic transistors and OPV. With
high mobility and much improved absorption comparing to earlier generation PPV
polymers, RR-P3AT (particularly RR-P3HT)
should easily lead to higher efficiency. However, this did not happen until several effective approaches were developed in the early
2000s, and the importance of morphology
control was soon realized to be a key component in OPV, which is far beyond what we
know from PPV system. Although P3HT is
not the highest efficiency OPV polymer any
more, it provides an excellent model systems
and the morphology study techniques started
on P3HT:PCBM system have long lasting
impacts.
Figure 8. (a) AFM images of the MDMO-PPV:PCBM films cast from toluene and (b) CB. (c) SEM
Thermal annealing approach was shown
cross-section views of the MDMO-PPV:PC61BM films casted from toluene and (d) from CB.
by Friend et al. in early 2000 in OPV using
(e) AFM phase image of high crystalline P3HT:PC61BM films achieved using solvent annealing
and (f) additive approaches. (g) BF-TEM images of PTB-7:PC61BM film casted using CB as P3HT as donor and a small molecule
major solvent with and (h) without DIO as additive. (i) BF-TEM and (j) defocussed phase acceptor, but the efficiency was low (peak
contrast TEM images of multiply polymer (blend) layers. (a,b,c,d) Reproduced with permis- EQE 11%).[166] Camaioni et al. observed that
sion from.[162] Copyright 2001 American Institute of Physics. (e,f) Reproduced with permission a very mild annealing at 55 C can improve
from.[36] Copyright 2007 Wiley VCH. (g,h) Reproduced with permission from.[107a] Copyright
the P3HT:fulleropyrrolidine solar cell from
2010 Wiley VCH. (i,j) Reproduced with permission from.[173] Copyright 2012 Wiley VCH. (k)
0.1 to 0.6% PCE.[167] Padinger, Sariciftci et al.
[
175
]
Reproduced with permission from.
Copyright 2009 American Chemical Society. (l) Reprofurther improved approach by introducing
duced with permission from.[176] Copyright 2009 American Chemical Society.
post (electrode deposition) annealing (and
also anneal under bias) in a P3HT:PC61BM
from 0.9% in Toluene case to 2.5% in CB case, with excellent
system.[168] The 3.5% efficiency achieved is beyond MDMOexternal quantum efficiency above 50% achieved. The higher
PPV system and thus has high impact. Imperial College,[169]
solubility of PC61BM in CB was proposed to be responsible for
UCLA,[170] UCSB,[87] Wake Forrest[171] groups also conducted
better morphology and thus device efficiency. This is a good
influential work on the thermal annealing approach. It is
example of solvent selection in the controlling of polymer morrealized that although P3HT itself has excellent absorption
phology. Figure 8c,8d show the SEM cross-section views of the
up to 650 nm, the long wavelength section (correlated to
MDMO-PPV:PC61BM system casted from chlorobenzene and
stacking of polymer chains) is severely suppressed with the pretoluene, respectively. A 2040 nm thick skin layer (identified
sent of acceptor PC61BM. The thermal annealing approach can
as polymer nanospheres) was observed in the toluene-casted
partially recover the polymer ordering and absorption. Another
film, which covers PC61BM nanocrystallites. However, for
approach solvent annealing was then reported by Li et al.[35]
most chlorobenzene-casted films, the polymer nanospheres are
In this approach, the slower solvent evaporation rate allows
homogeneously distributed. The morphology difference in verpolymer RR-P3HT to self-organize and restore its high degree
tical direction may be linked to exciton dissociation and charge
of order even in the polymer:PC61BM blend.[36] The enhanced
transport.
absorption and transport enabled the high efficiency OPV.
Later studies further showed that the solubility of the
In addition to thermal and solvent annealings, a mixturefullerene could affect the solvent selection strongly. Large
solvent approach represents another promising method to
fullerenes tend to be less soluble; different solvents have been
modify solar cell morphology and improve light-harvesting
used for optimal processing conditions. For example, MDMOefficiency. Zhang et al. found a significant enhancement in
PPV:PCBM solar cells were typically spun from CB solution
photocurrent density in polyfluorene copolymer/fullerene
for easier smooth film formation, and for higher efficiency,
blends when introducing a small amount of chlorobenzene
PC71BM, was introduced for MDMO-PPV system. A record
into chloroform solvent.[172] Time-resolved spectroscopy on the
3.5% efficiency OPV was reported 1,2-diclorobenzene (DCB) as
picosecond time scale shows that charge mobility was influsolvent.[147,163,164] CB and DCB are now the most popular solenced by the mixing solvents. Bazan et al. reported that when
vents used for OPV research. It needs to be pointed out that
working with an amorphous low band-gap polymer PCPDTBT,
these solvents are not good solvents for manufacturing, and
incorporating a few volume percent of alkanedithiols into the
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PCPDTBT/PC71BM polymer blend solution can double the PCE

from 2.8% to 5.5%.[37] The doubled performance was a result
of the enhanced interactions between the polymer chains and/
or between the polymer and fullerene phases upon alkanedithiols addition, which was evidenced by the absorption data. The
additive approach is also useful for P3HT system.
Characterization of the polymer morphology involves
multiple technologies. Microscopic techniques provide a direct
view of polymer morphology. Atomic force microscopy (AFM)
in tapping mode is suitable for soft PSC films and can provide
high-resolution surface topography and surface D-A distribution on the nanoscale. Figure 8e and 8f show the phase image
of high-crystalline P3HT:PC61BM films achieved using solvent
annealing and additive approaches, respectively.[36] The polymer
nanofibrillar structure is consistent with that in pure P3HT
film. P3HT nanofibrillar width is 2030 nm, consistent with
the morphology model.
Another powerful imaging technique is transmission electron microscopy (TEM). A P3HT:PCBM film was studied using
bright field TEM (BF-TEM) technique shown in Figure 8g.[173]
The specific density difference of P3HT and PC61BM (1.1 vs.
1.5 mg/cm3) enables the mapping of polymer and fullerene
rich regions, providing information on the dimensions of
the P3HT nanostructure. Loos et al. thus showed in the thermally annealed P3HT:PC61BM film, fibril structured P3HT
is clearly seen, and PC61BM is showed as darker region in
the TEM image. One of the major breakthroughs in the field
beyond P3HT is the BDT-TT based polymer. Yu and Li et al.
showed 78% PCE can be achieved using the new polymer.
Figure 8g and 8h shows the BF-TEM images of PTB-7:PC61BM
film casted using CB as major solvent with and without DIO as
additive.[107] Large domains (about 100200 nm in diameter) in
the blend film were observed in CB case, which is expected to
diminish exciton migration to the donor/acceptor interface and
thus is not favorable for charge separation. The morphology of
blend film prepared from CB/DIO is much more uniform with
no large phase separation. However, fibril polymer structures
are clearly seen, showing good miscibility between PTB-7 and
PC71BM and the formation of interpenetrating networks. The
DIO additive indeed leads to much improved performance with
the fine-tuned morphology.
Cross-section TEM provides another critical piece of morphological information. Heeger et al. showed cross-section
TEM images of a P3HT:PC61BM solar cell, where bicontinuous
interpenetrating polymer and fullerene domains were elucidated.[172] In Figure 8i and 8j, UCSB group further showed the
difference in conventional BF-TEM and defocussed phase contrast TEM images of multiply polymer (blend) layers, including
P3HT:PCBM, PCDTBT and PCDTBT:PCBM bulk heterojunction.[173] The combination of surface topological and cross section imaging tools provide strong evidence for the morphology
of quasi-optimized polymer:PC61BM solar cells. One has to
keep in mind that the valuable polymer/PC61BM morphology
information needs very careful defocused phase contrast TEM,
which otherwise may easily have artifacts.
Originally developed in life science, electron tomography
is used to reconstruct 3-D objects from a series of 2-D images
through sequential tilting of the sample about a single axis (tilt
series). It has also been applied to polymer blends using BF-TEM
Figure 9. (a) EELS results of pristine P3HT and PC61BM films. (b) EF-TEM
images filtered at 0V (conventional BF-TEM), (c) 19 eV (4 eV) and
(d) 30 eV (4 eV) of P3HT:PC61BM film. Reproduced with permission
from.[178] Copyright 2011 American Chemical Society.
as a nano-scale 3-D imaging tool recently.[174] Andersson et al.

showed 3-D nanostructure of a APFO-3:PC61BM solar cell using
electron tomography (Figure 8k).[175] The electron scattering
from the film of pure phase of PC61BM and polymer is observed
to be considerably different (by a ratio of 3). This allows the use
of the differing content of PC61BM to show 3-D nanostructure.
In the reconstruction of the 3-D image of the blend materials in
Figure 8k, the highlighted (scattering) domains are PC61BM rich
volumes with APFO-3 rich volumes as surrounding materials.
Loos et al. studied 3-D morphology in MEH-PPV:PC61BM and
P3HT:PC61BM systems.[176] The contrast between crystallized
polymer nanostructures with PCBM (Figure 8l) enables the estimation of P3HT crystallinity (60%). The volume percentage
of crystalline P3HT nanorods varies in the vertical direction,
indicating a more delicate 3-D morphology.
A further improvement of TEM contrast is enabled by using
energy-filtered TEM (EF-TEM).[177] The contrast is based on the
local material electronic signature via electron energy loss spectrum and the EF-TEM images were collected using electrons
within a specified energy loss window. Indeed, polymers and
fullerenes turn to have different plasmon energy loss windows.
This provides an effective way to get detailed morphology in the
subtle BHJ films. Figure 9a shows the electron energy loss spectroscopy (EELS) result of pristine P3HT and PC61BM films.[178]
Based on EELS result, Figure 9b, 9c and 9d show the EF-TEM
images filtered at 0V (conventional BF-TEM), 19 eV (4 eV) and
30 eV (4 eV) of P3HT:PC61BM film. Bright regions in Figure 9c
correspond to P3HT-rich region while the bright regions in
Figure 9d are PC61BM-rich. Fibular features P3HT domain are
clearly visible in all figures, and 9c and 9d are basically inverted.
Very recently, Yang et al showed EF-TEM in a more amorphous
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PDTP-DFBT:PC61BM blend film, where the

contrast of polymer and fullerene is not as
high as in the P3HT:PCBM system.[46]
4.2. Vertical Phase Separation in Donor/

Acceptor Blend Fims
Although the polymer blend film is casted
from uniformly distributed donor/acceptor
solution, vertical phase separation has
also been reported in a variety of semiconducting polymer blend systems. Bjrstrm
et al. observed a multilayer formation after
spin-coating APFO-3 blended with PC61BM
in chloroform by dynamic secondary ion
mass spectroscopy (SIMS).[179] The vertical
structure exhibited a four-fold multilayer
morphology with APFO-3 enriched at the
top surface, followed by a PC61BM-enriched
layer underneath, then a APFO-3-enriched
layer in the middle, and a PC61BM-enriched
(APFO-3-depleted) adjacent to the silicon
substrate.
Campoy-Quiles et al. used variableangle spectroscopic ellipsometry (VASE)
to model the vertical composition profile
of P3HT:PC61BM thin films casted from Figure 10. (a) GIXRD data of as-cast and thermally annealed P3HT:PCBM. (b) GIWAXS results
various preparation methods, and reported of conventional non-annealed and thermal annealed P3HT (95% RR):PC61BM. (c) GIWAXS
a common vertically-and laterally-phase results of solvent annealed P3HT:PCBM film. (d) GIXRD results of BDT-TPD copolymers with
61BM films casted
separated morphology, independent of the different side chains. (e) GIWAXS images of pure PTB-7 film, and PTB-7:PC[184
from CB and CB + DIO, respectively. (a) Reproduced with permission from. ] Copyright 2005
preparation techniques. A concentration
Wiley VCH. (b,c) Reproduced with permission from.[36] Copyright 2007 Wiley VCH. (d) Reprogradient varying from PC61BM-rich near the duced with permission from.[111] Copyright 2010 American Chemical Society. (e) Reproduced
PEDOT:PSS side to P3HT-rich adjacent to the with permission from.[186b] Copyright 2011 American Chemical Society.
free (air) surface was consistently observed.
Another way is using XPS measurement
on the top and bottom surfaces of the active
4.3. Molecular Level Structural Order in BHJ Thin Films
layer to determine the polymer/fullerene composition. Yang
et al. used the floating off method in water to peel off the film
and put it on a TEM grid. The results of peak area ratios of the
Grazing-incidence X-ray diffraction (GIXRD) is able to detect the
S(2p) (signature of polymer) and C(1s) (total content of P3HT
details of crystallinity structure in thin films. Figure 10a shows
and PC61BM) peaks for the top and bottom surfaces were comthe GIXRD data of as-cast and thermally annealed P3HT:PCBM
pared. It is found that fast coated P3HT:PC61BM has a homofilm by Erb et al., where it can clearly see the enhancement
geneous distribution of P3HT in the vertical direction. Howof polymer crytallinity after thermal annealing.[184] However,
ever when add OT additive, the top surface is P3HT rich. Yang
the weak polymer crystallinity requires a synchrotron beamet al. further improved the accuracy of this approach by using
line with high X-ray photon flux and collimation for accurate
F-PC61BM to replace PC61BM, and using F-atom signature to
structure information.[185] Figure 10b shows the synchrotron
[
180
]
trace the fullerene distribution.
This further strengthened
GIWAXS results of conventional non-annealed and thermal
the conclusion in P3HT:PC61BM device.
annealed P3HT (95% RR):PC61BM. A clear improvement in
In addition to the P3HT rich region on the top surface, a nearcrystallinity is clearly seen. Solvent annealed P3HT:PC61BM
edge X-ray absorption fine structure spectroscopy (NEXAFS)
film, which showed much higher vibronic stacking peaks
study by DeLongchamp et al. showed that P3HT concentrain absorption, was also examined using Synchrotron X-ray
tion at the buried interface depends strongly on the substrate
source (Figure 10c).[36] The prominent (n00) diffraction peaks
surface energy.[181] Similar results were also obtained in recent
indicates high crystallinity with dominantly edge-on chain orineutron reflectometry (NR) studies.[182] Chu et al. applied conentation. The high resolution GIWAXS signal also enabled the
focal optical microscopy combined with a fluorescence module
elucidation of polymer inter-chain distance spacing reduction
to study the exciton lifetime in thick P3HT:PC61BM films
in solvent annealing approach (from 16.9 in fast grown film
(2 um), which provides certain 3-D morphology information
to 16.3 in solvent annealed film), which can be translated into
for OPV.[183]
improved carrier transport in OPV device.
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5. Interface Engineering & Inverted Device

Structure
After the electrons and holes are separated at the BHJ interface,
the collecting electrode should effectively drain the charges and
move them to the external circuit. The organic/metal contacts
of an OPV device play critical role for determining the device
performance. An electrical contact of barrier height of few
tens of meV can result in significant charge accumulation and
thus inferior photovoltaic performance. Therefore, it is necessary to establish ohmic contacts on both sides of the anode
and cathode contacts for efficient charge extraction with high
selectivity. In this section, we will discuss the interface engineering of the anode and cathode contacts; and the formation
of inverted device architecture.
In the typical OPV structure, or the rigid band metalsemiconductor-metal model, the difference in work function
between the anode and cathode provides the driving force for
the charge transport and extraction process. (See Sction 2 of
this manuscript.) Tremendous efforts have been devoted to
modify interfaces between organic materials and metals for
improving efficiency, device stability, and simple fabrication.
This is often done by inserting of organic (such as conducting
polymer or poly-electrolyte) or inorganic (such as metal oxides)
layers between the metal and organic materails. In addition,
the insertion of interfacial layers offers an effective approach to
finely tune the optical properties in the multi-layer devices, so
as to position the photoactive layer to maximize the optical field
strength or to change the exciton distribution to be favorable
for charge extraction.[191]
In this section, we will introduce the principles that dominate the electrical processes at interfaces and summarize the
progress in interface engineering. The interface engineering
has led to the invention of inverted device architecture, which
has shown promising engineering advantages in industrial
scale fabrication.
REVIEW
Wei et al. further studied the P3HT:PC61BM system with

and without annealing using a combination of GIWAXS and
GISAXS, which provides both the lattice spacing parameters
and statistically averaged morphology information such as
grain sizes.[186a] They showed there is a correlation between
device performance with the sizes of PC61BM cluster (from
GISAXS) and P3HT crystallites (from GIWAXS). It is proposed that PC61BM cluster radius of gyration (Rg) need to
be larger than 20 nm, and P3HT crystallites greater than
16 nm give high efficiency in thermally annealed
P3HT:PC61BM devices.
The GIXRD technique is also applied to new high-efficiency
low bandgap copolymer systems. In some BDT-containing
polymer:PC61BM systems, face-on orientation is clearly seen.
Figure 10d shows the GIXRD results of BDT-TPD copolymers
with different side chains.[111] Large planar BDT unit prefers
face-on orientation in film formation. This indicates different
polymers need different orientations for high performance,
which requires customization in film processing. In Figure 10e,
Chen et al. shows the GIWAXS images of pure PTB-7 film, and
PTB-7:PC61BM films casted from CB and CB + DIO, respectively. They showed that the polymer packing is dominantly
face-on in both pristine polymer and polymer blend. Using
various scattering techniques, including GIWAXS, resonance
soft x-ray scattering (RSoXS), specular X-ray reflectivity (XRR)
etc., the authors proposed a multi-length scale morphology
model of a PTB-7:PC61BM solar cell. This includes (1) PTB7
crysatllites of a few nm surrounded by polymer and fullerene
intermixture; (2) PTB-7 crystallite of tens of nm, amorphous
polymer-fullerene surrounded by polymer rich regions of
200 nm.[186b]
X-ray diffraction techniques have also been used to provide
insight of polymer-fullenerne interactions inside the film. One
example is from McGehee et al. They showed that poly-(2,5bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene (PBTTT) and
PC71BM forms a bimolecular crystal, and the PC71BM molecules intercalate between the PBTTT side chains.[187] The
conformation of the polymer is significantly disrupted by the
incorporation of the fullerene molecules, which introduce
twists and bends along the polymer backbone and fullerene
channels. The existence of mixed phase is correlated to reduced
cell efficiency due to poor carrier transport.[188]
Recently there have been a few interesting in situ X-ray investigation of polymer blend film formation process. SchmidtHansberg et al.[189] reported an in situ real-time GIWAX study
on the composition dependence during the drying of doctorbladed P3HT:PC61BM film. They found that during the blend
film formation, when a large amount of PC61BM is present
(P3HT:PCBM = 1:2), it impedes the P3HT crysatlization, and
an interesting diffraction signal with 12.6A spacing is observed.
This is attributed to a new disordered phase of intimate mixed
P3HT:PC61BM. Amassian et al. conducted time-resolved
GISAXS and GIWAXS together with in situ spectral reflectometery to study the P3HT:PC61BM thin film formation during a
much faster spin-coating process. Both polymer crystallization
and phase separation information can be derived.[190] These insitu efforts are expected to be very valuable for the development
of OPV technology, as they can be used to closely related to the
real-world device/module fabrication process.
5.1. Energy Level Alignment at Interface

Polymer-fullerene blend films are generally formed onto a substrate surface from the solution phase, and it inevitably causes
contamination of hydrocarbons and/or native oxides. The contaminated films physically and electronically decouple the
polymer film from the continuum of the electronic states in
bulk metal layers. Consequently, vacuum level alignment, i.e.
SchottkyMott limit, holds at the polymer/electrode interface and
the barrier for electron injection equals the difference between
work function of the substrate and the LUMO of the polymer.
Vacuum level shift occurs after the polymer film is deposited on
the conductive substrate, which is explained using the integer
charge transfer (ICT) model as shown in Figure 11.[192]
Although the contamination layer decouples the polymer
layer from the substrate, charge transfer can still occur via tunneling as long as the contamination layer is sufficiently thin.
Since the conjugated polymers are electronically soft materials, adding or withdrawing charges induces substantial electronic and geometric relaxation effects, leading to self-localized
polaronic (single charge) or bipolaronic (double charge) states.
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the ORG/SUB in this case is also independent

of SUB. Thus, when the work function
of the conductive substrates spans a sufficiently large range, there is a clear dependence between SUB and the work function of
the organic-on-substrate interface ORG/SUB
with sharp transitions between the vacuum
alignment (Shottky-Mott limit, EICT < SUB
< EICT+ with ORG/SUB = SUB) and Fermi
level pinning (SUB < EICT or SUB > EICT+
with constant ORG/SUB) regimes.
The ICT model gives reasonable explanations to most of the experimental phenomena
related to the formation of metal/organic
interfaces, and also provides a general guide
for the selection of interfacial materials.
5.2. P- and n-type Interface Materials
The interfacial materials between the semiconducting organic films and conductive
electrodes are critical in several aspects. Sufficient work function difference between two
metal electrodes is the basic requirement for
the efficient and selective charge collection
Figure 11. Schematic illustration of the evolution of the energy-level alignment when
a -conjugated polymer comes to form a contact with a substrate surface when (a) by the respective electrodes in the sandwich
EICT < SUB < EICT+: vacuum level alignment, (b) SUB > EICT+: Fermi-level pinning to a positive
structure. To realize such a scenario in thin
integer charge-transfer state, and (c) SUB < EICT: Fermi-level pinning to a negative integer film devices, direct contact between active
charge-transfer state. represent the charge-transfer-induced shift in vacuum level, where
materials and metallic electrodes is normally
applicable. Reproduced with permission from.[192] Copyright 2009 Wiley VCH.
not the ideal case in terms of charge collection, since metallic surfaces have a high density of defects causing surface recombination and/or they can
Such states are located within the band gap, which is normally
induce strong surface dipoles at metal/organic interfaces that
forbidden, of the neutral molecule or conjugated units. Here
are eventually harmful for selective charge extraction. In spite
we define the energy required to take away one electron from
of having an enormous library from previous publications,
the polymer as the positive integer charge transfer state, EICT+,
we only pick a small number of them as examples. For more
which results in a fully relaxed state. Similarly, the energy of the
details, see recent review articles by Jen et al. and So et al.[193]
negative integer transfer state, EICT-, is the gained energy when
For anode contacts, PEDOT:PSS has been commonly used.
adding one electron to the conjugated chains, which produces
However, its acidic nature etches the ITO and imposes potena fully relaxed state. According to the ICT model, the energy
tial instability on the device lifetime.[194] A number of transilevel alignment of an organic/conductive substrate system with
tion metal oxides (MoO3, V2O5, NiO, and WO3) with high
very weak interfacial interaction can be determined by the work
transparency and moderate conductivity have been successfully
function of the substrate (SUB) and the energy of the charge
employed to modify the anode interface. Both thermal evaporatransfer states of the organic material. When SUB lies between
tion and solution process can be used to deposit these metal
the EICT+ and the EICT as illustrated in Figure 11a, no spontaoxide layers.[89,195197] Yang et al. reported using V2O5 and MoO3
neous charge transfer occurs at the substrate/organic interface.
to replace PEDOT:PSS in conventional structure P3HT:PC61BM
In this case, vacuum level alignment holds, and the work funcsolar cell and achieved comparable performance. MoO3 is
tion of the substrate coated with polymer, ORG/SUB, equals the
commonly used so far as reported in a number of high peroriginal SUB.
formance devices. Yang et al. recently demonstrated a solution
If SUB is larger than EICT+ in Figure 11b, electrons shall be
processed MoO3 interfacial layer in P3HT based devices.[197]
transferred from the polymer layer to the substrate, creating an
Later, several record high efficiency devices were fabricated
interfacial dipole that pushes the vacuum level downward. Such
using MoO3 as a hole transporting layer, showing its great
electronic structures form until the interface dipole equals
importance for OPV devices.[44,114] Interestingly, it was found
EP+ SUB. The Fermi level is then pinned to the P+ state at the
that the work function of MoO3 varies greatly (from 5.3 eV [195]
interface. Under this condition, the ORG/SUB remains invarto 6.86 eV [198] depending on the processing environments and
iant while the interface dipole changes with SUB. Figure 11c
thus, special care is needed during processing. Gao et al.[198b]
shows that SUB is smaller than EICT- in the equilibrium state.
was able to show a gradual surface work function change from
An interface dipole, which equals ECT- SUB, is formed and the
6.8 eV (fresh thermal evaporated film) to 5.3 eV upon oxygen
Fermi level is pinned to the CT state at the interface. Note that
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in inverted device were observed and the high PCE was benefitted from the hydrophobic surface and the suitable electronic
energy levels of TIPD. Some polar materials with small thicknesses or even mono-layers are able to induce a surface dipole
at the metal/polymer interfaces and shift the work function
of metals to a desirable level. Some of those have been found
to outperform the traditionally used materials. For example,
Huang, Wu, Cao, Jen and Bazan et al. demonstrated that a
very thin layer of conjugated polyelectrolyte (such as PFN) can
enhance the electron extraction significantly in OPV devices
compared to the those without it.[42,44,201,202] Recently, graphene
and graphene oxide have also been applied in BHJ solar cells as
both hole and electron transporting layers due to their proper
work function, high optical transmittance, and high electrical
conductivity.[203208] It is encouraging that reasonable performance has been achieved and future work should be able to
further enhance the efficiency.
5.3. Inverted Device Configuration
Figure 12. (a) Device structure of the inverted cells using different electron transporting materials. (b) Device efficiency and stability based on
different electron transporting materials. (c) Schematic of the invertedtype polymer photovoltaic cells, in which the photoactive layer is sandwiched between a PFN-modified ITO cathode and an Al,Ag-based top
anode and chemical structures of PTB7 and PFN. (a, b) Reproduced with
permission from.[200] Copyright 2012 Wiley VCH. (c) Reproduced with permission from.[44] Copyright 2012 Nature Publishing Group.
exposure. The good news is that even a 5.3 eV workfunction

is enough for a majority of new polymers. This makes it effective in OPV application. Doping MoO3 with aluminum has also
been shown to be effective in finely tuning the work function so
as to fit various purposes.[198c]
In contrast to anode contact layers, which have high work
functions and relatively good stability against ambient exposure, the cathode contact buffer consisting of low work function metals is rather sensitive to oxygen and moisture and thus
should be avoided. Alternatively, n-type metal-oxides, such as
ZnO and TiOx, have been widely adopted due to their superior
stability in terms of both film morphology and electronic properties. Heeger et al. using TiOx as the electron collection layer
and the cathode buffer improved photovoltaic efficiency to 6%
PCE for PCDTBT based devices.[94] Later, the same group demonstrated sol-gel processed ZnO as the electron collection layer
for high performance OPV device based on the same polymer.
PCEs approaching 7% were obtained due to the efficient charge
collection of the ZnO layer.[199a] Yang and Li introduced anatase
TiOx nano-particles as an electron buffer material, and found
that mixing TiOx with Cs2CO3 leads to Cs-doping of TiOx, and
this results in a more reliable electron buffer material for OPV
and OLED devices.[200a] Yang and Li et al. further did a thorough
comparison of different n-type metal oxide based interface
layers and found that ZnO is the best due to better performance,
repeatability, and stability of the devices (Figure 12a,12b).[200b]
Recently, titanium chelate TIPD as cathode buffer material was
reported by Li et al.[200c] Significant JSC and PCE enhancement
Adv. Mater. 2013, 25, 66426671
In principle, the electrical polarity of polymer photovoltaic cell

can be determined by the interfacial layer of the electrode. For
the conventional device, a p-type buffer layer is deposited on
the transparent anode (glass/ITO, high work function), followed by the active layer, then an n-type buffer layer, and finally
the cathode (metal electrode). For the inverted device, an n-type
beffer layer is deposited on the transparent cathode (glass/
ITO), followed by the active layer, then a p-type buffer layer, and
finally the anode (metal electrode). Yang and Li et al. in 2006[209]
first demonstrated the concept of using a low workfunction
interficial layer (Cs2CO3) to lower ITO work function, and
transition metal oxides (e.g. V2O5, MoO3, WO3)[195a] as a hole
buffer in OPV device to form inverted polymer solar cell. White
et al. at NREL shortly after showed ZnO can be used to form
inverted polymer solar cells.[210] ITO/ZnO/active layer/MoO3/
Metal is now the standard inverted structure. Nowadays,
the inverted structure has become equally important as the
conventional structure owing to the flexible structural design,
materials selection, and a powerful approach to achieve high
photovoltaic performance, including efficiency, stability, etc. For
example, So et al. showed that a modification on ZnO surface
by PVP can enhance the electron extraction efficiency greatly.
It was interesting to find that the use of PVP as an organic
capping molecule and polymeric matrix for ZnO can produce
electron-transporting nanocomposite films with excellent filmforming characteristics.[114] When a high performance germole-based polymer was used as the active layer, photovoltaic
efficiency over 8% was reached (certified by Newport Inc. PCE
= 7.4%). More recently, Wu and Cao et al. demonstrated that
when using a thin layer of polyelectrolyte (PFN) as a cathode
buffer, the PCE was dramatically enhanced to 9.2% based on
PTB7:PC71BM system (VOC = 0.754 V, JSC = 17.5 mA/cm2, FF
= 70.0%) with EQE approaching 80%.[44] The device structure
is shown in Figure 12c. The work function of the ITO was
reduced from 4.7 eV to 4.1 eV, and the authors suggested that
the orientation of PFN on ITO with a permanent dipole was the
major cause. The simultaneous enhancements of VOC, JSC, and
FF can be attributed to this interfacial dipole. It is worth noting
that the authors predicted that a further increase of 10% in JSC
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could be obtained if the optical constants of the interlayer were

matched with those of the stacks of other layers.[44]
6. Tandem OPV Devices

Currently, the PCE for a single junction cell has been
pushed to 89% with the introduction of state-of-the-art
cells.[44,107,108,114,128] Although technically impressive, it is not
sufficient for mainstream applications. Several groups have
predicted that the power conversion efficiency (PCE) limitation
of single junction organic solar cells is 1012%, through optimization of materials with appropriate band gap, energy levels,
and carrier mobility.[211,212] To achieve high PCE, a balanced
consideration of photocurrent, photovoltage and fill factor
needs to be implemented. Large photocurrent requires a lower
band gap material for more solar radiation harvesting, but this
also means lower photovoltage. The limitations of single junction photovoltaic devices can be overcome using tandem or
multi-junction solar cells, in which two or more single cells
that absorb complementary wavelength ranges are stacked
together.[213215] By doing so, the photon utilization efficiency
can be significantly improved and thermalization losses can be
lowered due to the use of materials having different band gaps.
Brabec et al. predicted that 15% efficiency polymer tandem solar
cells can be achieved in a two cell tandem configuration.[216]
In reality, it is beneficial in the tandem approach to have two
sub-cells with less overlap in absorption, as this can simplify
the optimization process of the tandem structure. Yang et al.
and Brabec et al. have published excellent review articles on
organic tandem solar cells. Comprehensive reviews of the different device structures and tandem cell working mechanisms
have been discussed.[213,215] The focus of this reviews tandem
polymer solar cell section is on the latest materials issues: both
active layer materials and interfacial materials for sub-cell interconnection. It consists of three parts: regular tandem structure,
inverted tandem structure and finally, a most recent high efficiency homogeneous tandem solar cell.
6.1. Tandem Cells with Regular Structure
The first polymer tandem solar cell consisting of two sub-cells
with different materials was demonstrated in 2006 by Boer and
Janssen et al.[217] The tandem device structure and absorption
spectra are shown in Figure 13. Even though the tandem solar
cell efficiency was only about 0.57%, the efficiency was clearly
Figure 13. (a) Device structure of the tandem cell reported by Janssen
et al. (b) absorption spectra of corresponding materials used in the tandem
cell. Reproduced with permission from.[217] Copyright 2006 Wiley VCH.
6660
higher than that of each sub-cell. In 2007, Kim et al. used the
solution processed TiO2(n-type)/PEDOT:PSS(p-type) interconnecting layer to bridge two higher performance single cells to
realize a tandem structure.[40] The front cell active layer is a
low bandgap PCPDTBT and PC61BM blend, and the rear cell
is made of P3HT and PC71BM. With the front and rear cell
of 3.0% and 4.7% efficiency, respectively, a 6.5% efficiency of
tandem solar cell was achieved. The low band gap polymer
PCPDTBT cell showed lower quantum efficiency and FF than
the P3HT:PC61BM cell and this limited the performance of the
tandem device. Later on, Yang et al. and Janssen et al. have done
much work on tandem solar cells, especially with new polymer
design, interconnecting layer design, optical modeling, and
device optimization to push forward the power conversion efficiency. For example, Yang et al. reported a tandem device using
a new low band gap polymer PSBTBT as the rear cell combined
with a metal oxide (MoO3) as an interconnecting layer. High
PCE of 6% was achieved.[218] Later on, they introduced ICBA
as a new acceptor for P3HT to improve the VOC of the front
cell and developed a mechanically robust modified-PEDOT:PSS
layer as the interconnecting layer. A PCE of 7% for the tandem
solar cells was achieved in 2011.[219] Janssen et al. introduced
solution processed ZnO(n-type)/PEDOT:PSS(p-type) as an
interconnecting layer for regular tandem solar cells, and they
introduced pH-neutral PEDOT:PSS to avoid the reaction
between ZnO and PEDOT:PSS layers. With the development
of the low bandgap polymers (PDPP3T and its derivatives) and
device optimizations, Janssen et al. reported the power conversion efficiency from 2% to about 9%.[220222]
6.2. Tandem Cells with Inverted Structure

The inverted structure has been considered as better architecture due in part to the higher stability.[223] Jen and co-workers[224]
reported the first solution-processed inverted tandem polymer
solar cell using a PEDOT:PSS/ZnO recombination contact
between two P3HT:PC61BM photoactive layers. They demonstrated that efficiencies can be improved by using a fullerene
self-assembled (C60-SAM) to modify the interface between the
ZnO and the P3HT:PC61BM layers. The highest efficiency of
2.9% was reported, which was lower than the best single-junction cell (PCE = 4.1%) presented in the same study. Yang et al.
demonstrated a 5.1% PCE inverted tandem structure by using
metal oxide interconnecting layer MoO3 and ZnO. Additionally,
a thin Al layer was inserted to reduce the resistance between
MoO3 and ZnO.[225] However, the interconnecting layer was not
robust enough and could not resist solvent penetration when
using a chlorinated solvent with high boiling point. As a result,
chloroform with a very low boiling point was used. The problem
is that for most of the polymers, good performance in CF is hard
to achieve (empirically, most polymers can work well in ODCB
or CB). Later, Yang et al. developed a robust thick PEDOT:PSS
layer with higher conductivity and was used to replace the thin
PEDOT:PSS or MoO3. No additional layer was needed between
the PEDOT:PSS and n-type buffer layer.[219] TiO2:Cs was initially used as an n-type buffer layer[226] and then ZnO NPs
were used in the tandem solar cell.[45] A significant improvement in tandem cell performance was achieved by combining
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REVIEW
Recently, impressive work on designing

new interconnecting layers for inverted
tandem cells has also been reported by
Brabec et al. and Kippelen et al.[228,229] Brabec
et al. used aluminum-doped ZnO and lowconductivity PEDOT:PSS as the interconnecting layer and found that the thicknesses
of the interconnecting layer could range from
50 to > 60 nm to fit the optical interference
maximum in organic multi-junction solar
cells and meet the thickness requirement
of large-scale production.[228] Kippelen et al.
applied a non-conjugated polyelectrolyte, ethoxylated polyethylenimine (PEIE), as the electron transporting material in the interconnecting layer. Interestingly, a higher FF of the
tandem cell compared to both of the single
junction sub-cells was obtained and high
PCEs of 7 8% were achieved using inverted
device structure.[229]
In 2012, for the first time a tandem
polymer solar cell with a 10.6% PCE was
achieved by incorporating improved materials and processing.[46] Specifically, a new
low band gap polymer PDTP-DFBT with a
band gap of 1.38 eV was designed. The EQE
of single junction PDTP-DFBT:fullerene
Figure 14. (a) Device structure of the tandem cells reported by Yang et al. (b) Orignal I-V curve photovoltaic cells reached over 60% in the
certified by NREL for PBDTT-DPP:PC71BM based tandem device. (c) Orignal I-V curve certified
infrared region.[128] Moreover, when blended
by NREL for PDTP-DFBT:PC61BM based tandem device. (d) EQE spectra of two sub-cells based
with PC71BM and PC61BM, the PCEs
on P3HT: PC61BM and PDTP-DFBT:PC61BM in the tandem device. (a, b) Reproduced with per[
45
]
mission from. Copyright 2012 Nature Publishing Group. (c, d) Reproduced with permission reached impressive values of 8% and 7%,
respectively. The tandem architecture confrom.[46] Copyright 2013 Nature Publishing Group.
sists of a PDTP-DFBT:PC61BM rear sub-cell
and P3HT:ICBA front sub-cell. Since the
absorption bands of PDTP-DFBT and P3HT are well sepathe progress of interconnection layers and the development of
rated, the rear sub-cell is responsible for the near-infrared light
the high performance low band gap polymer. In 2011, Yang et
in the 650 nm to 900 nm spectrum and P3HT covers the phoal. designed a low band gap polymer PBDTT-DPP with a band
tons from the near-ultraviolet to 650 nm spectrum. For the rear
gap of 1.46 eV, which has narrow absorption and can provide
cell, PC61BM (instead of PC71BM) was used to optimize the
complementary absorption with wide band gap polymers, such
current balance. As a result, a high short-circuit current can
as P3HT. Both regular and inverted structure single junction
be attained in the tandem cell, and a certificated power converdevices showed 67% efficiency with fill factor close to 70%.
sion efficiency of 10.6% has thus been achieved.[46] The certiThis forms an excellent combination with the P3HT:ICBA subfied IV from NREL is shown in Figure 14c and the quantum
cell. As a result, a record-high efficiency of 8.62% was certified
efficiency of the corresponding device is shown in Figure 14d.
by NREL in 2011 a breakthrough in polymer tandem solar
This breakthrough progress sets a new record efficiency in the
cells research.[45] The device structure and the certified results
OPV field.[46]
are shown in Figure 14a and 14b. In addition to high efficiency,
the device also showed very good stability. After that, a new
polymer PBDTT-SeDPP, which owns a lower bandgap (50 nm
6.3. Homogeneous Tandem Solar Cells
redshift) and higher mobility than PBDTT-DPP, was developed,
and 9.5% power conversion efficiency tandem solar cells have
In addition to the conventional tandem device including polybeen achieved by combining with P3HT:ICBA.[124] Janssen
mers with complementary absorption, there are also some
et al. also showed a similar device structure, where they used
attempts to make a tandem solar cell using the same mateP3HT:ICBA as the front cells active materials, PEODT:PSS/
rials (or sub-cells), i.e., a homogeneous tandem solar cell.
ZnO as the interconnecting layer, and PDPP5T:PC61BM layer
This type of tandem solar cell is intended to improve the net
as the rear cell active materials. A tandemcell with a 5.8% PCE
absorption and thus enhance the power conversion efficiency.
was reported.[227] These results indicate that, at least for the
The study of homogenous tandem solar cells started from
tandem structure where polymer P3HT was used as front cells,
the early stage of tandem solar cell research, probably due
PEDOT:PSS/ZnO is a near-perfect interconnecting layer for the
to lack of proper materials. Previously, several groups have
inverted polymer tandem solar cells.
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tried to make the polymer tandem solar cells by stacking the

same sub-cells of wide bandgap polymer-fullerene system,
such as P3HT:PC61BM,[230232] PCDTBT:PC61BM,[233] and
poly[9,9-didecanefluorene-alt-(bis-thienylene) benzothiadiazole]
(PF10TBT): PC61BM.[234] However, the efficiency improvement is limited due to the large bandgap of the polymers or
the optical/electrical loss in the interconnecting layer which
joins the two subcells together. In accordance with materials
and interconnecting layer progress, a high-performance low
bandgap polymer, such as PDTP-DFBT, was also used to form
a new homogeneous tandem structure, which contains two
identical PDTP-DFBT:PC71BM sub-cells.[235] The homogeneous
tandem solar cell also provides a solution to resolve the low
carrier mobility of organic compounds. It enhances the optical
absorption via stacking two or more layers of thin active layer
while maintaining the charge transport and collection. In principle, the homogeneous tandem cell works differently than
hetero-tandem cell, as it does not reduce the thermal loss by
stacking active layer with complementary absorption. The PCE
of the identical sub-cell-based tandem cells is still limited by
the Shockley-Queisser theory. Yet, considering the low carrier
mobility in polymer-fullerene blend films, the homogeneous
tandem cell architecture has a higher chance to enhance both
the IQE and the EQE of the PSCs. Very recently, Janssen et al.
developed a homogeneous tandem solar cell and applied it into
a triple junction device. Specifically, the first junction is a wide
band polymer and the other two junctions consist of two identical low bandgap PMDPP3T:PC71BM based sub-cells. Interestingly, they achieved 9.64% efficiency in the triple junction solar
cells.[222]
In parallel to the polymer version of tandem solar cell,
small molecule tandem solar cells, which are mainly based on
vacuum process, also have made significant progress. In 2005,
Forrest et al. achieved 5.7% efficiency in small molecule tandem
solar cells.[48] In April of 2012, Heliatek GmbH, a company
located in Dresden, Germany, announced a PCE of 10.7% from
dual- junction tandem cells based on small molecules. Recently,
they have achieved a 12% PCE based on triple junction OPV
cells.[47] Currently, these achievements in small molecule
tandem cells are all based on thermal evaporation technology.
At the current stage, 8% efficiency for single junction from
solution processed small molecules has been achieved by several groups.[141,142] It is anticipated the development of solutionprocessed small molecule tandem solar cells will follow soon.
7. Manufacture & Stability

With the continuous improvement of lab cell efficiency, the
interest of commercialization of OPV technology has been
growing larger. To move this technology from research laboratory to volume industrial production, many aspects have to
be optimized and overcome. In this section we will give a brief
review on roll-to-roll compatible materials systems and large
area wet coating technologies. Additionally, device stability will
be discussed at the end of this section. A more complete discussion about different OPV manufacturing technologies can
be found in a review paper by F. C. Krebs et al. (Ris National
Laboratory, Denmark).[236]
6662
Figure 15. Side view a OPV module with series connected strip cells.
In order to provide a desired voltage output, large area

OPV panels are usually designed as series connected stripes
(monolithic integration) as shown in Figure 15. Laser scribing
or chemical etching can be used to form a desired pattern of
cathode on the substrate, while the pattern can then be simply
formed during coating/printing process for each layer.[236]
7.1. Materials and Inks
In manufacturing, flexible transparent plastic films are more
attractive because of their low-cost and roll-to-roll processability.
The lightweight and flexible substrates also give OPV panels
some special advantages in comparison with their inorganic
counterparts. Several plastic substrate candidates are: polyethylene terephthalate (PET), polyethylene naphthalate (PEN),
polycarbonate (PC), polyethersulfone (PES), polyarylate (PAT)
and polyimide (PI). MacDonald et al. compared the key properties of these materials as substrates for flexible electronic
devices and showed that heat stabilized PET and PEN films
have an excellent balance of the key properties required for
flexible electronics.[237] Because of its low cost, PET is a more
preferred material for OPV production. It is worth noting that
Corning recently demonstrated flexible glass, which may be
another promising candidate for OPV panels.[238]
For the transparent electrode (cathode) used in high performance OPV devices, both good electrical conductivity and
optical transparency are required. Indium-Tin-Oxide (ITO)
is the most commonly used transparent conductive material.
However, it requires high temperature processing, which is
incompatible with the plastic substrates such as PET. In addition, the brittle ceramic ITO film can crack at very low tensile
strains. Moreover, due to the scarcity of indium, the cost of
the ITO is also a concern. For these reasons, various flexible
electrodes, such as silver nanowires (AgNW),[239241] thin metal
films,[242] conductive polymers with metal grid,[243,244] carbon
nanotubes (CNTs),[245] and graphene,[246249] have been suggested as alternatives to flexible ITO electrodes. Among them,
highly flexible silver nanowire film can achieve the highest
optical and electrical performance (improved transmission and
lower sheet resistance) compared to ITO-coated films, which
makes it a very promising candidate as a transparent conductor.
For the non-transparent back electrode, solution-processable
conductive inks are desirable to simplify the manufacturing
process. Highly viscous silver inks (paste) with relatively large
silver particles are chosen because of their good conductivity
and stability. Krebs et al, compared 10 commercially available
silver pastes which can either be cured thermally or with UV
light.[249] The solvents in the conductive inks are undesirable,
since they may dissolve and damage the pre-coated layers.
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7.2. Roll to Roll Production

One advantage of polymer solar cells is that they can be easily
printed or coated in ambient conditions with high throughput.
For wet printing or coating, a large number of well-established
techniques can be used. The choice is mainly based on following factors: 1. rheology of the inks; 2. layer thickness,
feature resolution and uniformity; 3. coating/printing size
and speed. Galagan et al. did a throughput study comparing
different deposition techniques.[254]
Spin coating is the most widely used method in OPV device
fabrication. However, it is hard to scale up and cannot be used
in a roll-to-roll process. The low materials utilization also
makes it an unfavorable choice for manufacturing. As a result
of easy operation and roll-to-roll compatibility, blade coating
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REVIEW
In this study, the authors found that the silver inks that generally performed well were those with a high silver content
(8086% wt/wt) and those that did not perform as well generally had lower silver contents and consequently more solvent.
Additionally, the high-silver-content inks generally had a higher
viscosity resulting in slower diffusion of solvents out of the ink.
Thus, the panels based on solvent free UV curing paste show
the best results. To reduce the cost of silver, Ag grids combined
with conductive polymers such as PEDOT:PSS were used as
semi-transparent electrodes.[249]
Thermally deposited aluminum is another choice for the
back electrode (anode). For large volume production, the high
cost of vacuum equipment can be offset by the inexpensive
raw material aluminum. More importantly, the dry deposition process provides more flexibility in materials selection and
device design, which can be applied to different polymer systems and enables higher performance panels. The approach,
however, does break the continuous web process in fabrication,
and thus additional processes need to be implemented in order
to improve the output.
With respect to the processing solvent of the active layers,
o-dichlorobenzene and chlorobenzene are widely used to reach
good solubility and stability and ultimately high device efficiencies. However, chlorinated aromatic solvents cannot be
used in mass-production due to health and environmental reasons. Several more environment-friendly, non-chlorinated solvent systems have been used for the deposition of the active
layer.[250252] Green et al. prepared P3HT:PC61BM devices with
airbrush spray deposition from a variety of common organic
solvents, including toluene and p-xylene.[250] The devices made
from p-xylene show over 2% PCE. Waldauf et al. used o-xylene
as a solvent and demonstrated over 3% PCE on P3HT: PC61BM
based devices.[251] Over 4% P3HT: PC61BM devices made from
a xylene-based solvent were reported by Schilinsky et al.[252]
Recently, some promising results have been demonstrated on
water based processing methods with PCE as high as 0.7%.[253]
Between the photoactive layer and electrodes, interfacial layers are used to enhance charge collection. ZnO and
PEDOT:PSS are widely used n-type and p-type interfacial layers
in roll-to-roll processes. The PEDOT:PSS layer can also be used
to protect the photoactive layer from the damage caused by
organic solvent in silver inks.
Figure 16. (a) Illustrations of the principles of gravure printing. (b) Schematic illustration of slot-die coating. (c) OE-A demonstrators with solt
die coated electron transport layer, active layer and hole transport layer.
(d) Illustrations of the principles of flat-bed screen printing. (e) Principles
of roll to roll screen printing. (a, b, d, e) Reproduced with permission
from.[236] Copyright 2012 Elsevier Ltd. (c) Reproduced with permission
from.[268] Copyright 2011 Royal Society of Chemistry.
was employed as an intermediate step towards real roll-to-roll

processing.[252,255] Ink jet printing can easily generate various
2-dimensional patterns with high resolution. The challenge
of this technique is to improve its processing speed and formulate inks to provide uniform coating with desired morphology. Ink jet printing has been used to deposit PEDOT:PSS
and P3HT:PC61BM layers.[256,257] The best device (9 mm2) has
shown a PCE of 3.71%.[257] However, roll-to-roll processed large
area devices have not been demonstrated yet. As an efficient
deposition method with less demand in terms of ink formulation, spray coating can be used for the deposition of the electron
transport layer, active layer, hole transport layer and even the
silver back electrode.[250,258261] Lewis et al. demonstrated semitransparent OPV devices with a spray coated electron transport
layer, active layer and hole transport layer and achieved 1.80%
PCE.[258] However, it is hard to control layer homogeneity
in spray coating. Lack of easy-to-use patterning strategies is
another drawback of this technique. Although a shadow mask
can be used in generating desired patterns, applying it to a rollto-roll process would not be that attractive.
Gravure is known for its high throughput, high-quality
printing. Gravure-printed products include magazines, catalogues and packaging used in our everyday lives. Figure 16a
shows a diagram of the Gravure process. Gravure-printed OPV
devices have been reported by several research groups.[262264] A
PCE of 2.8% has been reported for small area (19 mm2) flexible
devices with Gravure printed PEDOT:PSS hole transport layer
and P3HT:PC61BM active layers.[262] A 1.68% PCE has also been
achieved on flexible panels with the same devices structure.[263]
Voigt et al, for the first time, prepared inverted solar cells with
Gravure-printed TiOx, P3HT:PC61BM and PEDOT:PSS layers
and reached 0.6% PCE.[264]
In slot-die coating, the ink is forced out of a reservoir through
a slot by pressure and transferred to a moving substrate
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(Figure 16b). As a result, the wet thickness thus can be accurately controlled by adjusting either the speed of the web, the
ink supply, or both. This technique can be used for coating all
three layers (electron transport layer, active layer, hole transport
layer) in the OPV panel. Moreover, unlike most of the other
coating techniques, by partially blocking the coating flow in the
slot with an inserted shim, 1-dimentional stripe patterns can
be coated. As a result of all these advantages, slot die coating
has been used by many research groups and companies in
OPV panel fabrication.[249,265268] Furthermore, this method has
already been applied for small scale manufacturing. Krebs et al.
fabricated more than 10000 pieces of OPV modules and subsequently integrated them into the Organic Electronics Association (OE-A) demonstrator in 2011 and presented it as a small
credit card sized lamp with a flat outline (Figure 16c).[268]
For the deposition of high viscosity materials like silver
paste, screen-printing can be used. There are two types of
screen-printing techniques as shown in Figure 16d. The
mesh on the screen defines the printing patterns. During the
printing process, the squeegee moves relative to the screen and
squeezes the ink through the opening of the mesh. Screenprinting allows deposition of thick films, which is very helpful
in forming high conductive electrodes. The screen-printing
method has also been used for other layers.[269,270]
After deposition of the solar cell stack, the device needs
to be laminated with protective films. The lamination or
encapsulation provides mechanical protection to the delicate
layers. It also protects the device from oxygen and moistures
in ambient environments. To achieve this, a transparent barrier film with a good oxygen transmission rate (OTR) and
water vapor transmission rate (WVTR) is needed. It is generally accepted that to achieve above 10000 h lifetime for
OLED devices, a WVTR and OTR of about 106g /m2/day and
103-105cm3/m2/day, respectively, are required. It is believed
that slightly less advanced encapsulation solutions (e.g., OTR
of about 104 g/m2/day) should work for OPV.[271] However,
unlike OLED, UV and heat damage need to be considered
when choosing barrier films, since the devices will be directly
exposed under sunlight. UV blocking coating is a mature process in coating industry. Some interface buffer layers such as
TiOx need UV activation to provide enough density of state
to function well. ZnO and Cs-dopped TiOx was found to not
need UV acitivation,[235] and thus have their advantages. The
selection of adhesive is also important. It not only requires
good adhesion, optical transparency, and flexibility, but also
low WVTR and OTR to avoid lateral ingress of the oxygen
and moisture from the edge of the encapsulation. A detailed
description of the encapsulation process can be found in the
literature.[237,248]
7.3. Device Stability
Despite significant efforts, the degradation of OPV devices is
still far from being fully understood. Nevertheless, several main
mechanisms have been identified. The degradation of the low
work function metal under the presence of oxygen and moisture is a well-known phenomenon. Complex chemical reactions of organic semiconductors with oxygen and moisture
6664
were observed especially when the device is illuminated.[271274]

The interface is another source of degradation.[275] The diffusion of the electrode materials into the active layer could
potentially alter the semiconducting properties of the active
layer.[273] The acidity of PEDOT:PSS layer and the moisture
adsorbed in it may also induce potential damage of the electrode and the active layer. The change of the morphology is
another reason for device degradation. For many polymer solar
cells, the optimal morphology of the bulk heterojunction is not
at thermodynamic equilibrium and when devices are heated,
a change of phase may occur and inferior device performance
will result. A more detailed discussion on OPV degradation
mechanism can be found in ref. [276] and ref. [277].
Extrinsic instabilities that arise from oxygen and moisture
in air can be significantly reduced by appropriated encapsulation. Long-term stability has been demonstrated in encapsulated OPV devices. Tipins et al. evaluated the lifetimes of rigid
P3HT/PC61BM OPV panels (233 cm 2).[278] A linear fit to the
life time data gives a decay rate of 9.82% per 1000 h, based
on which the lifetime of the module was estimated to be 5000
h. Hauch et al. compared outdoor lifetimes with temperatureaccelerated indoor lifetimes of flexible P3HT:PC61BM OPV
devices.[279] The rooftop testing setup even showed a slight
increase in device performance after 14 months of outdoor
testing. A rough correlation indicates that some 600800 h
of accelerated light soaking under 1 sun at 65 C are approximately equivalent to 1 year of outdoor exposure at 42 lateral
altitude. J. Hauch et al. reported accelerated lifetime testing
results on flexible P3HT/PC61BM devices encapsulated with
food-quality packaging barrier film with 0.2 g/m2/day.[280] A
lifetime over 1250 h has been achieved at 65 C/85% relative
humidity. In a more recent presentation, Konarka Technology
Inc. reported a lifetime over 4000 h at 65 C/85% relative
humidity on OPV modules encapsulated with high quality barrier films.[281] Solarmer Energy, Inc reported 96% remaining
PCE after a 3600 h 85 C/85% relative humidity acceleration
test.[282] Heliatek reported extrapolated lifetime of over 20 years
based on the light soaking test on their rigid tandem small
molecule OPV cells.[283] McGehee et al. recently reported 7
years lifetime for PCDTBT:PCBM solar cells (rigid).[284] It is
worth to mention all the lifetimes mentioned above are T80
lifetimes. Although exciting lifetime data have been released,
it is still hard to obtain a trustworthy estimation of real lifetime
based on these acceleration tests. Considering the number of
different materials systems used in OPV manufacturing and
how rapidly the technology is developing, it is very challenging
to find acceleration test methods that can give a reliable real
lifetime evaluation at this point. Setting up a standard lifetime
testing procedure and evaluation method is important for comparison results from different sources. Some efforts have been
initiated by an international OPV community and a summit
named the International Summit on OPV Stability (ISOS) has
been held 4 times to discuss related issues.
8. Future Perspectives
Forrest et al. recently reported that the thermodynamic limit
of PCE in OPV is 2227%, depending on the exciton dissociation energy.[285] Janssen and Nelson also suggested that limits
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Acknowledgements
This article is part of an ongoing series celebrating the 25th anniversary
of Advanced Materials. This work is supported by Air Force Office of
Scientific Research (AFOSR, Grant No. FA955012-10074), Office of
Naval Research (ONR, Grant No. N00014-11-1-0250), and National
Science Foundation (NSF, Grant No. DMR-1210893, ECCS-1202231,
Adv. Mater. 2013, 25, 66426671
CHE-1230598). Gang Li would like to thank the UCLA Henry Samueli

School of Engineering and Applied Science for financial support. We
thank Mr. Eric Richard, Mr. Bryan Luong and Mr. Christopher Matthew
Knapp at UCLA for the English editing and proof-reading of this article.
Received: June 4, 2013
Revised: July 19, 2013
Published online: September 18, 2013
REVIEW
of 2024% PCE are reachable in single junctions.[286] Thee

OPV limits are under the same ideal assumptions as Shockley
and Quaisser (S-Q) did in their landmark paper.[287] In a more
down-to-earth estimation, the efficiency limit of OPV is a
moving target following the progress in the field. While in the
initial widely-cited Scharber model the assumption was that FF
and EQE are both 65% (a good estimation for P3HT:PC61BM
cell), both parameters are now believed to be much higher. An
EQE peak value of over 80% has been reported,[288] and the FF
is also close to 80% in cells.[289]
Another key parameter is the Voc. In inorganic PV technology, the bandgap-Voc offset (or so called WOC = Eg/e VOC)
is typically around 0.4 to 0.5 V.[290] The lowest Woc value is 0.3V,
not surprisingly from an almost perfect GaAs solar cell which
is close to the S-Q limit efficiency. In OPV, the existence of
the driving force for exciton dissociation (D/A LUMO difference) leads to larger Woc. Various experimental results showed
the limit of Woc in OPV is 0.6 0.7 V. The lowest Woc in an
OPV system with over 60% EQE is now 0.7 V.[46,128] Based on
the device parameter of a recent 10.6% tandem polymer solar
cell (keeping the bandgaps of the two polymers of 1.9 eV and
1.38 eV, respectively), assuming WOC of 0.6 V for both subells and FF of 80%, the achievable PCE will be 2125%. Triple
junction is also a possible way to further advance the polymer
solar cell efficiency. This will need material innovation on
much lower bandgap polymers (1 eV) with high NIR spectral
response and low Woc to realize this goal.
Polymer solar cells have many unqiue properties such as
flexibility, light weight, high transparency etc. The success of
the technology must utilize the uniqueness of polymer solar
cells. A good example is the transparent solar cell, particularly visibly transparent solar cell. The low bandgap polymers
absorption window in the infrared range enables the efficient
solar cells to have high transparency.[290] The potential applications can be anything from power windows to built-in chargers
for the portable electronic gadgets. Highly flexible, stretchable
and wearable power source applications are also attractive for
the future. Its worth mentioning that polymer solar cells have
been shown to be able to sustain considerable X-ray radiation
dose, and a self-healing phenomenon was also observed.[291,292]
The advantagese in radiation hardness, light weight and flexibility indicate polymer solar cell could be a viable technology
for space application.
In summary, in the last decade the field of organic solar cells
has gone through tremendous progress. The device efficiency
was improved from below 3% to the current 12% certified
PCE. The lifetime of the solar cell also improved from hours to
years. Its a technology with great opportunities and also great
challenges. This amazing progress should encourage more
researchers and industrial companies to make viable solar cell
technology in the near future.
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Adv. Mater. 2013, 25, 66426671
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DOI: 10.1002/aenm.201200377
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E. J. Kramer, C. J. Hawker, M. L. Chabinyc
All-Solid-State Lithium-Ion Microbatteries: A Review

of Various Three-Dimensional Concepts
J. F. M. Oudenhoven, L. Baggetto, P. H. L. Notten
http://onlinelibrary.wiley.com/doi/10.1002/
aenm.201000002/full
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GrapheneCellulose Paper Flexible Supercapacitors
Zhe Weng, Yang Su, Da-Wei Wang, Feng Li,
Jinhong Du, Hui-Ming Cheng*
aenm.201100312/full
Recent Progress in the Development of Anode
Materials for Solid Oxide Fuel Cells
P. I. Cowin, C. T. G. Petit, R. Lan, J. T. S. Irvine,
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Beyond 11% Efficiency: Characteristics of State-ofthe-Art Cu2ZnSn(S,Se)4 Solar Cells

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W.-S. Liu, Q. Zhang, Y. Lan, S. Chen, X. Yan,
Q. Zhang, H. Wang, D. Wang, G. Chen, Z. Ren

A Decade of Organic Polymeric Photovoltaic Research

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A Decade of Organic Polymeric Photovoltaic Research

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REVIEW

25th Anniversary Article: A Decade of Organic/Polymeric

Organic photovoltaic (OPV) technology has been developed and improved

L. Dou, Dr. J. You, Dr. Z. Hong, Dr. Z. Xu, Dr. G. Li,

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2013, 25, 66426671

Adv. Mater. 2013, 25, 66426671

Yang Yang received his

thermal energy at room temperature 26 meV.[19,20] Therefore,

OPV devices,[2830] design and synthesis of new materials,[3134]

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

in the internal field which has opposite polarity to the external

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2013, 25, 66426671

J(V) = JD (V) + JP (V)

where N0 is the effective density of states at the band edge.

Adv. Mater. 2013, 25, 66426671

is constant up to VBI, representing an approximation to an ideal

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

and are split by about 0.18 eV, the energy of

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2013, 25, 66426671

where conduction occurs in the region of higher density of

Figure 4. Illustration of the main recombination mechanisms

illumination, as measured by the low energy absorption band

2.4. Deep Localized States

Adv. Mater. 2013, 25, 66426671

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

is proportional to the square of the free carrier concentration.

The starting point for any model is the density of states

2.6. Modeling of Cell Properties

Although simple in concept, solar cells are complex in detail

There has been intense research on developing novel organic

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2013, 25, 66426671

Adv. Mater. 2013, 25, 66426671

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

One of the successful examples at the

A breakthrough in new material and high efficiency single

leading figures in single junction devices up to date.[45] Despite

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2013, 25, 66426671

Adv. Mater. 2013, 25, 66426671

higher HOMO of 5.65 eV and similar performance of 7.3%.

3.2. P-type Materials: Small Molecules

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

6.7% in 2011 was achieved using DTS(PTTh2)2:PC71BM blend.

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2013, 25, 66426671

Adv. Mater. 2013, 25, 66426671

0.76 V and 1.86%, respectively.[157] More recently, by changing

a bisadduct on it. Indeed, a number of fullerene bisadducts

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

more efforts are needed to replace them with

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2013, 25, 66426671

Adv. Mater. 2013, 25, 66426671

PCPDTBT/PC71BM polymer blend solution can double the PCE

as a nano-scale 3-D imaging tool recently.[174] Andersson et al.

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PDTP-DFBT:PC61BM blend film, where the

4.2. Vertical Phase Separation in Donor/

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2013, 25, 66426671