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FEATURE ARTICLE View Journal | View Issue

Arising applications of ferroelectric materials in

photovoltaic devices
Cite this: J. Mater. Chem. A, 2014, 2,
6027
Yongbo Yuan,† Zhengguo Xiao,† Bin Yang† and Jinsong Huang†*

The ferroelectric-photovoltaic (FE-PV) device, in which a homogeneous ferroelectric material is used as a

light absorbing layer, has been investigated during the past several decades with numerous ferroelectric
oxides. The FE-PV effect is distinctly different from the typical photovoltaic (PV) effect in semiconductor
p–n junctions in that the polarization electric field is the driving force for the photocurrent in FE-PV
devices. In addition, the anomalous photovoltaic effect, in which the voltage output along the
polarization direction can be significantly larger than the bandgap of the ferroelectric materials, has been
frequently observed in FE-PV devices. However, a big challenge faced by the FE-PV devices is the very
low photocurrent output. The research interest in FE-PV devices has been re-spurred by the recent
discovery of above-bandgap photovoltage in materials with ferroelectric domain walls, electric
switchable diodes and photovoltaic effects, tip-enhanced photovoltaic effects at the nanoscale, and new
Received 18th October 2013
Accepted 13th November 2013
low-bandgap ferroelectric materials and device design. In this feature article, we reviewed the advance
in understanding the mechanisms of the ferroelectric photovoltaic effects and recent progress in
DOI: 10.1039/c3ta14188h
improving the photovoltaic device performance, including the emerging approaches of integrating the
www.rsc.org/MaterialsA ferroelectric materials into organic heterojunction photovoltaic devices for very high efficiency PV devices.

energy by converting the incident photons into owing free

1. Introduction to ferroelectric charge carriers and thus produce electricity. The photovoltaic
photovoltaic devices technologies have advanced for more than a century aer the
discovery of the photoelectric effect by Einstein.3,4 However,
Clean and sustainable solar energy is regarded as one of the
aer decades of development, the commercialized crystalline
most reliable and abundant energy sources to replace fossil
silicon solar panels are still too expensive to compete with fossil
fuels.1,2 The photovoltaic effect is used to directly harvest solar
energy.5 In order to reduce the energy harvesting cost, the
second and third generation photovoltaic cells, such as thin
Department of Mechanical and Materials Engineering, Nebraska Center for Materials lm amorphous silicon solar cells,6 copper indium gallium
and Nanoscience, University of Nebraska, Lincoln, Nebraska 68588-0656, USA. E-mail:
selenide solar cells,7 dye-sensitized solar cells,8 cadmium
[email protected]
telluride solar cells,9 quantum dot solar cells,10 organic solar
† All authors contributed equally.

Yongbo Yuan received his PhD Zhengguo Xiao obtained his B.S.
degree in condensed matter at Shandong University of
physics from Sun Yat-sen Science and Technology in 2008,
University (China) in 2009, and M.S. at the Chinese
during which his research Academy of Science in 2011.
focused on organic light-emit- Thereaer, he joined Prof. Jin-
ting devices. He is currently a song Huang's research group in
postdoctoral fellow in Prof. Jin- the Department of Mechanical
song Huang's research group at and Materials Engineering at
the University of Nebraska- the University of Nebraska-
Lincoln. His research interests Lincoln at 2011 as a PhD
include organic optoelectronics student. His current research
such as solar cells, thin lm focuses on organic electronic
transistors and photodetectors. devices including OPVs, OLED,
OFETs, etc.

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Journal of Materials Chemistry A Feature Article

cells,11 perovskite solar cells,12–14 etc. are under intense study experimentally observed that the output photovoltage is
because of their potential to dramatically reduce the cost by the proportional to the magnitude of electric polarization and
lower-cost materials and fabrication. The power conversion electrode spacing.17,18,30 As a result, a unique and important
efficiency (PCE, h) of a solar cell, dened by the electric energy characteristic of the FE-PV devices is the anomalous photovol-
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output (Pout) divided by the solar energy (Pin) it absorbs, is taic (APV) effect, i.e. the output Voc can be a few orders of
expressed as: magnitude larger than the bandgap of the FE mate-
rials.20,21,30,33,34 The photovoltage is as large as over 104 volts in
h ¼ Pout/Pin ¼ JscVocFF/Pin (1) some cases, e.g. in LiNbO3 bulk crystals.33 This unique FE-PV
device working mechanism provides another viable route to
where Jsc is the short circuit current density, Voc is the open convert light into electric energy.
circuit voltage, and FF is the ll factor which is the ratio of However, long aer its discovery, the FE-PV effect has
maximum obtainable power to the product of the Voc and Jsc. remained an academic curiosity rather than having any realistic
The ferroelectric photovoltaic effect was discovered about application because of the very low energy conversion efficiency
half a century ago in a variety of ferroelectric materials without achieved in regular FE-PV devices. The PCE of FE-PV devices
central symmetry in which a steady photovoltaic response based on the pure APV effect had not exceeded 0.1% under 1
(photovoltage and photocurrent) can be generated along the sun illumination over half a century, mainly due to very small
polarization direction.15,16 Generally, the ferroelectric photo- output photocurrent densities in the order of nA cm2.29,35–37
voltaic effect originates from the spontaneous electric polari- The situation has not changed until recent advance in much
zation in ferroelectric materials.17,18 An unique characteristic of better engineered ferroelectric materials,30,36 new photocurrent
FE-PV devices is that the photocurrent direction can be extraction techniques,35,38,39 and particularly the hybridization
switched by changing the spontaneous polarization direction of of FE-PV devices with traditional p–n junction photovoltaics
a FE material with the electric eld. To date, the photovoltaic which have yielded comparable or superior device perfor-
effect has been studied in the lithium niobate (LiNbO3) mances to regular p–n junction devices.40,41
family,19–24 barium titanate (BaTiO3 or referred to as BTO),20 lead In this feature article, we rst review the advance in
zirconate titanate (Pb(ZrTi)O3 or PZT) family,25–28 and bismuth understanding the mechanism of FE-PV devices, especially
ferrite (BiFeO3 or BFO) family.29–32 the origin of the abnormally large photovoltage, as well as the
Among the next generation photovoltaic technologies, the factors that determine the photocurrent. Then, the recent
ferroelectric photovoltaic effect is completely different from the progress in enhancing the efficiency of FE-PV devices is dis-
traditional p–n junction photovoltaic effect as shown in Fig. 1a cussed which addresses the issues of the absent and/or weak
and b. In traditional p–n junction solar cells (Fig. 1a), the visible light absorption and low conductivity of common
absorbed photons can pump the electrons from the valence ferroelectric materials. And nally, the most recent advance
band of a light absorbing semiconductor material to its in the application of ferroelectric materials in high efficiency
conduction band, with holes le in the valence band. The organic photovoltaic (OPV) devices is highlighted. In addi-
photogenerated electrons and holes are quickly separated by tion to photovoltaic devices, large bandgap ferroelectric
the built-in electric eld inside the p–n junction and collected semiconductors (e.g. PZT and BaTiO3) have also been used to
by the respective electrodes.3 Theoretically, the magnitude of separate the photogenerated charge pairs in other solar
Voc in p–n junction solar cells is determined by the quasi-Fermi energy conversion devices, such as photoelectrochemical
energy difference of photogenerated electrons and holes which cells, which can be found in review papers by Tiwari et al. and
is limited by the bandgap of the light absorbing semi- will not be reviewed here.42–45
conductors.3 Nevertheless, for the FE-PV devices (Fig. 1b), it is

Bin Yang has been a PhD Jinsong Huang received his PhD
student in Prof. Jinsong Huang's degree in Material Science and
research group in the Depart- Engineering from the University
ment of Mechanical and Mate- of California-Los Angeles in
rials Engineering at the 2007. Aer working in Agiltron
University of Nebraska-Lincoln Inc. as a research scientist for
since 2010. He obtained a two years, he joined the Univer-
B.S. in 2007 and a M.S. in sity of Nebraska-Lincoln (UNL)
2010 at Hunan University as an assistant professor in
(China). His current research the Department of Mechanical
focuses on organic optoelec- Engineering and Nebraska
tronic electronics. Center for Materials and Nano-
science. His current research
interests include solution processed electronic materials for
applications in sensing, energy and consumer electronics.

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Fig. 1 The working principle of (a) p–n junction solar cells and (b) FE-PV devices.

2. Advance in the understanding of under illumination is related to the noncentrosymmetric nature

of the ferroelectric crystal.1–5,8 In the noncentrosymmetric
the ferroelectric photovoltaic crystal, the transition probability of an electron jump from the
mechanism and enhanced state with a momentum of k to the state with a momentum of k0
performance may be different with the corresponding probability of the
reverse process, which causes an asymmetric momentum
2.1 Origin of the large photovoltage in FE-PV devices distribution of the photogenerated charge carriers and thus a
It has been controversial on the origin of the APV effect in the steady photocurrent.17 The total current through the ferroelec-
ferroelectric materials. The typical FE-PV devices with vertical or tric materials ( J) can be described as:
lateral congurations are illustrated in Fig. 2. The photovoltage
has been shown to be dependent on many factors such as the J ¼ Js + (sd + sph)E (2)
distance between the two opposite electrodes,28,46 light inten-
sity,47 electrical conductivity33 remnant polarization of the where sd and sph are the dark conductivity and photoconduc-
ferroelectric crystals/lms,48 crystallographic orientation,49 tivity of the ferroelectric materials, respectively, and E ¼ V/d is
dimension/size of the crystals,46,50 domain walls30 and the the internal electric eld, depending on the applied voltage (V)
and the distance (d) between two electrodes. The FE-PV devices
ferroelectric/electrode interface.37 In order to explain the ultra-
high photovoltage output, several models have been proposed can be deemed as the current source due to the very low dark
in early years, including the shi current model and the conductivity and photoconductivity50 of most ferroelectric
nonlinear dielectric model.51 The common characteristic of materials and the large distance between the electrodes.28 The
these theories is that the photovoltage is generated in the bulk Voc, corresponding to the condition of J ¼ 0, can be described as:
of the ferroelectric crystals, hence named as the bulk photo- Js
Voc ¼ Ed ¼ d (3)
voltage effect. A recent theory gives an alternative explanation sd þ sph
on the origin of the APV effect using a series of domain walls in
tandem with each other outputting a small photovoltage.30 The shi current model predicts a larger Voc under stronger
Other effects related to the ferroelectric/electrode interface, e.g. light intensity Iop because it gives a large Js. Voc is expected to
Schottky effect and screening effect,52–55 are also believed to increase linearly with Iop (or Js) if the total conductivity (sd + sph)
generate or inuence the photovoltage output in ferroelectric is insensitive to light intensity. This occurs in a situation where
thin lms. These theories are related to the domain wall inter- sph is signicantly lower than sd in the studied light intensity
face or the FE/electrode interface. range. A good example for this case is the FE-PV effect in the
2.1.1 Bulk photovoltaic effect. According to the frequently LiNbO3 : Fe crystal, in which the Voc increased linearly to 103 to
cited shi current model, the ferroelectric materials act as a sort 104 V with the light intensity in a range of 0.01–1 W cm2.33 On
of “current-source”.21,33,34,56 The formation of a steady current ( Js) the other hand, if the sph is much larger than sd in the studied
light intensity range, a constant Voc is expected since both Js and
photoconductivity sph are correlated with light intensity. An
example for this case is that a saturated photovoltage was
observed in the iron-doped potassium niobate (KNbO3 : Fe)
crystal. Since KNbO3 : Fe and LiNbO3 : Fe have a similar crystal
structure, the difference in the magnitude of sph is related to the
much longer lifetime of the photogenerated charges in
KNbO3 : Fe.22,33
In the nonlinear dielectric model, the large observed pho-
tovoltage output is caused by the nonlinear response of the
Fig. 2 FE-PV device architectures: (a) vertical and (b) lateral, in which a polarization density to the electric eld of the incident light,
large photovoltage proportional to the electrode spacing can be which led to an effective DC electric eld throughout the
measured along the polarization direction (P). ferroelectric materials.51

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2.1.2 Domain wall theory. Recently, Yang et al. studied the of the domains. Later the lifetime of photogenerated charges in
APV effect on the BFO lm with ordered domain strips and bulk BFO was measured to be as long as 75 ms which is
lateral device conguration (Fig. 3). They observed that the comparable with that near the domain wall.58
photovoltage in the BiFeO3 lm increased linearly with the total There are other facts that cannot be explained solely by the
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number of domain walls along the net polarization direction domain wall theory and that bulk photovoltaic effect theory
(perpendicular to the domain walls, Fig. 3a and c).30 The cannot be excluded. According to the domain wall model, the
photovoltaic effect vanished along the direction perpendicular photocurrent should be independent of the light polarization
to the net polarization direction (Fig. 3b and d). The intrinsic directions due to the intrinsic potential drop at the domain wall
potential drop at domain walls (10 mV), arising from the induced by the polarization charges. However, the dependence
component of the polarization perpendicular to the domain of the photovoltaic current on the polarization direction of the
wall, induces a huge electric eld of 5  106 V m1 in the incident light in BFO has been frequently observed,29,31 indi-
narrow domain wall, which was suggested to be the driving cating that the origin of the photovoltaic effect in ferroelectrics
force for the dissociation of the photogenerated exciton. The is more complex than expected. A rst-principle calculation
illuminated domain walls act as nanoscale photovoltage based on the bulk photovoltaic effect tried to reconcile the
generators connected in series, wherein the generated photo- contradictory observations in the BFO devices.59 It was
current is continuous and the photogenerated voltage accu- explained that the vanished photocurrent along the direction
mulates along the net polarization direction. This proposed parallel to the striped domain wall in Yang's experiment is
mechanism is analogous to the concept of tandem solar cells, mainly attributed to the unique geometry of the striped
where the output voltage is the sum of the photovoltage of each domains, where the bulk photovoltaic effect in each domain
sub-cell. Nevertheless, it was noticed in another publication was cancelled by the adjacent domains. It was also pointed out
that the domain wall is also considered as a current source, and that the large observed photovoltage in Yang's experiment
the total Voc was determined by the Jsc, the conductivity of the FE should be attributed to the domain wall effect because it formed
lm under illumination and the distance between the elec- a photocurrent in the opposite direction with that of the bulk
trodes (eqn (3)).57 This explanation attributed the APV effect to effect. This study also indicates that the photocurrent due to the
the exciton generated inside the domain wall and suggested domain wall effect was partially cancelled by the bulk effect. An
that the bulk photovoltaic effect was ignorable due to a quick enhanced PCE is hence expected if the photovoltaic currents
recombination of excitons generated outside the domain wall, caused by the bulk photovoltaic effect and domain wall effect
which is apparently different from those previously repor- can be designed to be in a same direction.59
ted.21,33,34,51,56 In contrast, it was suggested by Alexe et al. that the 2.1.3 Schottky-junction effect. When the ferroelectric
recombination of the excitons in the bulk of the BFO domain is semiconductors form Schottky contacts with metal electrodes,
not as quick as expected.38 The authors investigated the BFO there is photocurrent under illumination driven by the local
single crystal with a photoelectric atomic force microscopy electrical eld which is caused by the band bending near the
(Ph-AFM) system combining with piezoresponse atomic force electrodes. The generated photocurrent is largely determined by
microscopy (PFM), where both the polarization direction and the Schottky barrier height and the depletion region depth.60
photocurrent can be mapped with the same scanning The magnitude of the photovoltage caused by the Schottky
conducting tip. A similar large photocurrent in the regions contact is still limited to the bandgap of the ferroelectric
inside or outside the domain wall was observed, indicating a semiconductor materials. The photovoltage caused by the
weak recombination of the photogenerated carriers in the bulk Schottky-junction effect was ignored in the early stage of studies

Fig. 3 Schematics of the FE-OPV device with (a) a perpendicular domain wall and (b) a parallel domain wall as demonstrated by Yang et al.30 The
corresponding photocurrent–voltage curves for the devices in (a) and (b) are shown in (c) and (d), respectively.

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because it is much less than the anomalous photovoltage in ferroelectrics lead to a larger depolarization eld than metal
bulk ferroelectric crystals. This effect becomes more evident in because of a weaker screening effect caused by their lower free
thin lm FE-PV devices because of the small photovoltage charge densities and larger dielectric constants.
output in these devices.52,53 Generally, this additional photo- Recently, Dong et al. used aluminum-doped zinc oxide
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current contribution is absent in the FE-PV devices with the (Al : ZnO) as an electrode material, in which a larger photo-
same electrode contacts, because the photovoltage from the two voltage by about 0.25 V was found as compared to that of
Schottky-junctions possess opposite polarization and thus devices with the Au electrode. A larger depolarization electric
cancel each other. However, this component may play an eld was suggested as one of the reasons for the increased
important role in the FE-PV device with a vertical structure photovoltage.74 Chen et al. studied the FE-PV effect of a 400 nm-
where different electrodes are easier to be implemented.37,61–65 thick PZT lm sandwiched between two transparent indium tin
The Schottky-junction effect is independent of the polarization oxide (ITO) layers. The ITO lms were used as electrodes
directions of the ferroelectric materials, which was used to because a large depolarization eld was expected. They
distinguish the contributions of the Schottky barrier and bulk observed a gradually decreased photovoltage output from 0.4 V
photovoltaic effects.66 However, there are situations where the to 0.1 V and attributed it to a reduced depolarization eld in the
photovoltage of the Schottky-junction FE-PV devices switch PZT lm caused by different remnant polarizations.73,74 The
together with the ip of spontaneous polarization by the tunable screening effect provides opportunities to verify if the
applied electric bias, which oen originates from some artifact depolarization eld has a critical contribution to the APV.
effects. For example, in reported ferroelectric diodes with a However, the relationship of the depolarization eld and the
vertical structure of gold (Au)/BFO/Au, a rectied dark current photovoltage output in the previous reports were not clearly
and photovoltage with good switch capability (between about +1 revealed due to the presence of some other mechanism such as
V and 1 V) were observed.29,62 It was originally thought that the different built-in potential or changed remnant polarization.73,74
switchable photovoltage was caused by the bulk photovoltaic On the other hand, it has been observed that the inuence of
effect in the BFO lm, but a continued study by the same group the depolarization eld on the photocurrent is stronger than on
revealed that the BFO/Au contacts switched between Schottky- the photovoltage, where tens of times improvement in the
contact and Ohmic-contact during the poling process due to the photocurrent was reported experimentally and computation-
electromigration of the oxygen vacancies, whereas the photo- ally, as will be discussed below.35,72
voltaic effect was not switched when the oxygen vacancy Since the depolarization eld is inversely proportional to the
migration was frozen at cryogenic-temperature.62 distance between the two electrodes, the depolarization eld
2.1.4 Depolarization eld model. In polarized ferroelectric can play a role in the photovoltaic response only when the
lms, there are high densities of polarization charges on the ferroelectric lms are thin (<100 nm) but it will be too low to
surface, which can induce a huge electric eld inside the account for the photovoltaic effect in bulk ferroelectric crystals
ferroelectric layer if they are not screened. For the BFO with a (>100 mm).46,68–70
remnant polarization of 26 mC cm2, the induced electric eld
by the unscreened polarization charges can be as large as 3 
104 V mm1.67 When ferroelectric thin lms are in contact with 2.2 Factors determining the photocurrent in FE-PV devices
metal or semiconductors, the surface charge caused by the In contrast to the huge photovoltage output, the photocurrents
remnant polarization will be imperfectly screened by the free of the FE-PV device are quite low, usually in the order of nA
charges in the metal or semiconductors. Usually the screening cm2.17 The photocurrent of the FE-PV device is determined by
of the surface charge is incomplete because the center of gravity the light absorption process, dissociation efficiency of the
of the polarization charge and the free compensation charge are excitons, lifetime of the photogenerated nonequilibrium
not coincident, which results in an electrical eld throughout charges and the charge carrier mobility. The photocurrent
the ferroelectric lm named as the depolarization eld.68–70 This under a certain wavelength light illumination was described by
depolarization eld can be large, e.g. the depolarization eld in an empirical equation called Glass law: Js ¼ akIop, where a is the
the 10–30 nm BTO lm sandwiched between SrRuO3 electrodes absorption coefficient, k is the Glass coefficient which is related
was estimated to be 25–50 V mm1.71 It is suggested that the to the charge generation and collection efficiency and Iop is the
depolarization eld may be the dominating driving force for the light intensity as mentioned above.21
separation of photogenerated charge carrier-pairs. It was also 2.2.1 Optical bandgap and absorption coefficient. Similar
suggested that the anomalous photovoltage should be closely to any type of photovoltaic device, the ferroelectric materials
related to the degree of screening of the spontaneous polari- should be able to absorb as much sun light as possible to have a
zation.35,72–74 The screening charge distribution depends on reasonably large photocurrent, which requires the ferroelectric
both the properties of ferroelectric materials and the metal or materials to have a low bandgap and large absorption coeffi-
semiconductor, such as the remnant polarization, the free cient. Most of the commonly used ferroelectric materials, such
charge density and the dielectric constant. Meanwhile the as LiNbO3, BaTiO3, and PZT crystal, have a bandgap larger than 3
impact of the incomplete screening on the depolarization eld eV, thus can only harvest sunlight in the UV range. However, the
depends on the thickness of the ferroelectric layer: a smaller total energy of the light with a wavelength less than 400 nm
thickness of the ferroelectric layer results in a larger depolar- constitutes only about 3.5% of solar energy. Hence it is crucial to
ization eld.46,68–70 In general, semiconductors in contact with develop ferroelectric materials with a reduced bandgap. Recently

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BFO has attracted intensive research interest for optoelectronics by only several angstroms before they decay, explaining the very
application because of its lower bandgap.29,31,36,55,62,74–80 The small photocurrent in FE-PV devices.33 From this point of view, it
bandgaps of its rhombohedral single crystal, rhombohedral is necessary to increase the noncentrosymmetry of the crystal by
polycrystalline,75,76 and pseudocubic perovskite structure29 are developing new ferroelectric materials for improved photocur-
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2.2 eV, 2.31–2.63 eV and 2.7 eV, respectively. So theoretically it rents.24,59,89,90 It is known that changing the chemical composi-
can absorb visible light up to 560 nm, allowing about 25% of the tion of ferroelectric materials can signicantly change their
solar energy to be absorbed. The optical absorption spectrum crystal structures and thus the degree of noncentrosymmetry,
can also be adjusted by manipulating the ferroelectric material which can affect the photovoltaic response.91–93 For example, in
compositions through chemical doping or alloying. For the PZT ceramics, when the Zr/Ti atomic ratio varies from 48/53
example, in the LiNbO3 or KNbO3 crystals, Fe-doping extends the to 54/46, the crystal structure changes from tetragonal to
absorption edge to the region of 400–500 nm, corresponding to rhombohedral, where the latter shows stronger crystallographic
the excitation of electrons from Fe2+ ions to the conduction band asymmetry. Therefore in the lanthanum-doped PZT (PLZT)
of the crystals.81 In BaTiO3, Fe-doping can extend the absorption ceramics, the photocurrent was observed to increase by six times
edge to around 647 nm.82 Recently, ferroelectric bismuth titanate when the dopant loading was reduced from 6% to 4%.91
Bi4Ti3O12 (BiT) with a wide bandgap tenability of 1 eV has been 2.2.3 Charge collection efficiency. The next step aer
demonstrated by alloying it with Mott insulator LaCoO3 (LCO). A exciton dissociation is the collection of free charges. The
unique unit cell structure, featured by an alternating arrange- charge collection efficiency is determined by the carrier life-
ment of the BiT and LCO layers, has been demonstrated to time, the carrier mobility and the electric eld. The lifetime of
systematically tune the optical bandgap of BiT from 3.6 eV to the photogenerated nonthermalized charges in ferroelectric
2.7 eV with its strong ferroelectric property uninuenced.83 In materials was thought to be in the picosecond scale,17 while
addition, one general type of defects in ferroelectric oxide is the the recombination lifetime was measured to be sub-micro-
oxygen vacancy which can broaden the absorption spectrum if seconds to tens of microseconds.58,94 Reducing the thickness
there is a large density. For example, the oxygen vacancies in the of the low conductive ferroelectric lm can lead to increased
BFO lm can extend the absorption spectrum to 560–650 nm.77 charge collection efficiencies, e.g. Ichiki et al. compared the
The density of the oxygen vacancies can be controlled by thermal photovoltaic effects of the PLZT bulk crystal (with a thickness
annealing, while the spatial distribution of the oxygen vacancies of 2.4 mm) and PLZT thin lm (with a thickness of 4 mm) and
can be shied by electrical pulses.62,84–86 Interestingly, the light found an improvement of over 100 times in the photocur-
absorption was also reported to be enhanced by utilizing the rent.28 However, the photovoltage was observed to decrease
internal photoelectric effect at the metal electrode, where the simultaneously when the thickness was reduced. Another
electrons excited from the metal electrode to the PZT lm apparent method to increase the charge collection efficiency is
require photons with energy less than the bandgap of PZT. This to increase the collecting electric eld. For example, in the
component was also found to contribute to the measured BFO based device, Zang et al. replaced the ITO electrode with
photocurrent.60 nitric acid (HNO3) treated graphene and observed a much
In addition to the large optical bandgap, the small absorption increased photocurrent of 2.8 mA cm2, which was attributed
coefficient of the ferroelectric materials is another issue limiting
the photocurrent. A strong absorption allows a thinner lm to be
used which is benecial for charge collection. Most oxides have
very low absorption coefficients in the visible range. The
absorption coefficient of PZT and BFO families (104 to 105 cm1
at around 400 nm) is about three to four magnitudes higher than
that of LiNbO3 and BaTiO3 materials (10–100 cm1 at around
400 nm),80,84,87,88 which enables a high light absorption in PZT
and BFO lms with a thickness of hundreds of nanometers. The
optimized sample thickness for a maximized photocurrent is a
tradeoff between light absorption and charge collection.
2.2.2 Exciton dissociation efficiency. The electron–hole
pairs (or excitons) generated by incident photons with energy
above the bandgap need to be dissociated efficiently to generate
photocurrent. The binding energy of the excitons is inversely
proportional to the dielectric constant of an active material.
Fortunately, the dielectric constant of most ferroelectric mate-
rials (102 to 103) is much larger than that of organic and inor-
ganic semiconductors (3–13), hence a small binding energy
Fig. 4 Ultra-high efficient charge collection on the BFO crystal ach-
between holes and electrons is expected. According to the Glass
ieved by a conducting AFM tip demonstrated by Alexe et al.,38 where
model, the separation of the electrons and holes is driven by the the upper left image is the measurement setup, the lower inset shows
noncentrosymmetric potential well in the unit cells.11,22 The the locations of the silver (Ag) electrode (yellow arrows) and the illu-
excited electrons generally shi along the polarization direction minated area on the BFO crystal.

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to the extended depletion region throughout the entire ferro- interface and lm thickness,46,68–71 an increased exciton
electric layer by the formation of metal–intrinsic semi- dissociation as well as charge collection is expected by
conductor–metal (MIM) structure.78 It should be noticed that reducing the screening of the spontaneous polarization and
recently Alexe et al. observed a tip-enhanced photovoltaic the lm thickness. Qin et al. did a theoretical calculation
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effect in the BFO lm, where the photogenerated carriers in which suggested that the photocurrent in PLZT could be
the bulk of the BFO lm were collected very efficiently by the increased by tens of times by (1) replacing the metal electrode
AFM tips (Fig. 4).38 The nonuniform local electric eld due to a with semiconductors (reduced screening effect) and (2)
particular geometry of the tip contributed to the very high reducing the PLZT thickness.35 The maximum internal power
photocurrent density of 10–100 A cm2 which is eight orders of conversion efficiency was calculated to be as high as 18.7%
magnitude higher than that in devices with parallel electrodes. for an 8 nm thick PLZT lm. However, when an ultra-thin FE
This result might enable promising large-area ferroelectric layer is used, one accompanying problem is that the light
photovoltaic devices with much improved photocurrent by absorption will be severely reduced. In the experimental part,
using nano-tip arrays as the electrodes. Chen et al. studied the anomalous photovoltaic effect in the
There has been an interesting idea on utilization of the device with a structure of Au/polycrystalline BFO/Au and
increased depolarization eld for enhanced charge collection found that the photocurrent output was increased 24 times
efficiency. Since the depolarizing eld is strongly inuenced when the Au electrode was replaced by ITO, which was
by the screening condition at the ferroelectric/electrode attributed to the increased depolarizing eld.72

Table 1 Summary of the performance of the reported ferroelectric photovoltaic devicesa

Photovoltage Photocurrent

Light Light Efficiency Dominating FE-lm

Isc intensity wavelength (Pout/Pin) working fabrication
Device structure Voc (V) L (mm) (mA cm2) (mW cm2) (nm) (%) mechanism methods

Pt/PZT(52/48)/Pt or Ni102 0.8 0.2 0.03 0.05 300–390 — SC Sol–gel

Pt/PLZT(3/52/48)/ITO28 0.86 4 1700 150 — — BPV MOD
496 2400 16.8
Au/PLWZT(3/52/48)/Au65 7.0 25 — 1.11 365 — BPV Solution
coating
Au/PLWZT(3/52/48)/Au61 0.6 0.706 — 0.74 365 — SC Sol–gel
Nb : SrTiO3/PLZT 0.7 0.068 0.8 0.059 — 0.28 DF Sputtering,
(3/52/48)/LSM35 epitaxial
Pt/PZT(20/80)/Pt66 — 0.36 8 10 350–450 — SC & BPV Sputtering
SrRuO3/BFO/ITO36 0.8–0.9 0.2 1500 285 Sunlight 10 (EQE) SC MOCVD
Au/BFO/Au29 0.08 80 8.219 <20 532 — SC Mix-ux
technique
SrRuO3/BFO/Au37 0.286 0.17 0.4 750 435 — SC Sputtering,
epitaxial
Pt/BFO/Pt30 16 200 120 285 W-light 103 (IQE) DW MOCVD
Pt/BFO/Pt57 0.014 One DW 50 100 W-light 10 (IQE) DW MOCVD
Pt : Pd/BFO/Pt : Pd38 6–30 50–300 107–108 40 000 405 40 (IQE) TE & BPV Mix-ux
technique
Pt/Poly-BFO/Au and ITO72 0.1 0.3 1 450 340 — SC & DF Sol–gel
Graphene/Poly-BFO/Pt78 0.20 0.3 2800 100 Sunlight — MIM–SC Sol–gel
ZnO : Al/BFO/LSC54 0.22 0.35 5 1 W-light — — PLD
Au/BFO/Au62 0.7 60 1.58 20 532 1.5 (EQE) SC Mix-ux
technique
Nb-doped SrTiO3/BFO/Au79 0.15 0.1 6000 285 W-light 0.03 SC PLD
Pt/Bi2FECrO6/Nb–SrTiO332 0.74 0.125 990 1.5 635 6.5 BPV PLD, epitaxial
ITO/PZT/Cu2O/Pt39 0.6 270 4800 100 Sunlight 0.57 SC Sol–gel
ITO/PZT(53/47)/ITO73 0.45 0.4 0.006 0.45 — 0.6 SC & BPV PLD
Ag/Pr-doped BFO NTs/Ag89 0.21 — — 10 Sunlight 0.5 — Chemical
template
Mg/PLZT(3/53/48)/ITO60 8.34 300 3.25 100 Sunlight — PE & BPV HPC
FTO/Poly-BFO/AZO74 0.63 — 130 100 Sunlight 7 (EQE) BI & DF CSD
Fe/BFO/LSM/SrTiO3100 0.21 — 48 20 W-light — SC & BPV PLD, epitaxial
a
PZT(a/b) ¼ PbZra%Tib%O3; PLZT(a/b/c) ¼ Pb1a%Laa%Zrb%Tic%O3; LSM ¼ LaSrMnO3; LSC ¼ LaSrCoO3; IQE ¼ internal quantum efficiency; EQE ¼
external quantum efficiency; DF ¼ depolarization eld effect; BPV ¼ bulk photovoltaic effect; DW ¼ domain wall effect; SC ¼ Schottky contact effect;
MIM ¼ metal/insulate/metal junction, PE ¼ photoelectric effect; BI ¼ built-in potential due to asymmetric electrodes; TE ¼ tip enhancement effect;
MOD ¼ metal–organic decomposition; MOVCD ¼ metal–organic vapor phase epitaxial; PLD ¼ pulsed laser deposition; HPC ¼ hot-pressing
calcinations; CSD ¼ chemical solution deposition.

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2.3 Other characteristics of FE-PV devices

Another unique property of the FE-PV devices is that their
photovoltaic output is switchable with the polarization.
Generally, the photovoltages in the opposite poling
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direction should be symmetric, i.e. |V+poling| ¼ |Vpoling|, but

the symmetry can be lost due to other effects such as an
additional built-in electric eld coming from the work function
difference of the electrodes and graded composition in FE
lms.36,37,61,62,66 On the other hand, the magnitude of the pho-
Fig. 5(a) The device structure of a typical BHJ-OPV; (b) process of the
tovoltage aer multiple switching tends to systematically conversion of incident light into electricity in OPVs. The electrons on
decrease due to ferroelectric fatigue. The ferroelectric fatigue is the acceptor are still bound to holes on the donor right after the
a common behavior in ferroelectric materials which can result charge transfer, as illustrated by the ellipse in the figure.
from (1) charge trapping at the domain wall or near the elec-
trode which screens the polarization eld;61,95–98 (2) the
formation of defects, such as oxygen vacancies, at the FE/
electrode interface which pins the domain boundaries and substrates like glass or exible polymer substrates and a metal
hinders their movements under an applied electric eld;98 (3) cathode of Al, as shown in Fig. 5a. The organic layer is generally
the formation of cracks or de-adhesion of the lm from the as thin as 80–200 nm because of the large absorption
substrate from due to the residual tensile or compressive coefficient (105 cm1) and relatively low carrier mobility
stress.99 Recently, Guo et al. demonstrated a novel non-volatile (104 to 101 cm2 V1 s1) of many organic molecules. Due to
the high binding energy (0.4–1.0 eV) of Frenkel-excitons in
memory array based on the photovoltaic effect in BFO, where
organic semiconductors, photo-generated excitons cannot be
the photovoltaic output (Voc or Jsc) was used as the read-out
dissociated by the weak built-in electric eld provided by the
signal. The photovoltage output can be robustly switched
between 0.11 V and 0.23 V for up to 108 cycles.100 electrode work function difference.103 A donor–acceptor type
In ferroelectric materials, the rising time of the photocurrent heterojunction is generally formed in OPVs to dissociate
was reported to be about 105 s.58 The response speed of the excitons.104,105 The photoactive layer can be either a blend or a
photovoltage is pretty slow. The saturation of the photovoltage layered structure. Studies of OPVs reveal that the light to
output under a continuous illumination takes tens to hundreds electricity conversion involves four steps, which are labeled in
Fig. 5b: (1) light absorption to generate an exciton; (2) exciton
of seconds,94 which is several orders of magnitude slower than
diffusion; (3) charge transfer between the donor and acceptor
that in the conventional PV effect. The slow response time is
(aer this step the electrons and holes locate in different
thought to be related to the very small photoconductivity.81,101 In
general, larger photocurrents lead to faster photovoltaic materials, but are still electrically bound together due to the
response. Hence it is not surprising that the response time is low dielectric constant of organic material and proximity
also dependent on the light intensity and wavelength.102 between them – these are referred to as charge transfer excitons
To date, numerous inorganic FE-PV devices have been (CTEs),106–110 to distinguish them from Frenkel-excitons); and
studied. The device structures, photovoltaic performance and (4) separation of the CTEs into free charges and extraction of
the free charges to electrodes.111
the dominating working mechanisms of the related devices are
The inefficient charge extraction issue remains a grand
summarised in Table 1.
challenge for bulk-heterojunction (BHJ)-OPVs. The inefficient
charge extraction is caused by the low carrier mobility of the
3. Recent progress in the integration existing polymer semiconductors,112 which yields strong
of ferroelectric materials in organic recombination of both bound electron–hole pairs and free
charges. As illustrated in Fig. 5, the recombination of electron–
photovoltaic devices hole pairs occurs in multiple paths: (1) Frenkel-exciton recom-
Although there is no demonstration of efficient photovoltaic bination before the photo-induced electron transfer, (2) CTE
devices based on the FE-PV effect yet, there has been signicant recombination (or geminate recombination) of the bound
progress recently in the integration of ferroelectric materials in electron–hole pair aer the photo-induced electron transfer, (3)
traditional p–n junction photovoltaic devices to overcome the Schottky–Read–Hall (SRH) recombination at the interfacial
challenges in these traditional devices. Here the working prin- traps, dead-ends, and in the disordered band-tails, and (4)
ciples and challenges in organic photovoltaic devices are bimolecular recombination of the free charges. The charge
introduced and approaches to address them are reviewed. recombination mechanism in OPVs varies from material
systems, material morphology, electric eld, etc. In optimized
BHJ devices, the Frenkel-exciton recombination and SRH
3.1 Introduction to organic solar cells and the challenge in recombination constitute only a small portion of the total
efficiency enhancement recombination loss because the photo-induced electron trans-
A typical OPV device consists of one or more layers of organic fer efficiency was shown to be almost 100% efficient.113 The
materials located between a transparent electrode coated on major charge recombination in most optimized OPVs falls into

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two categories:112,114 geminate recombination113,115–118 and A similar bulk photovoltaic effect has been observed in
bimolecular recombination,117,119–123 although the dominating polymer lms based on PVDF and its derivatives, where a Voc of
charge recombination mechanism is presently under intense 50 V and a power conversion efficiency of 0.25% under UV
debate.106,109,112,124 illumination has been reported.135 The polymer FE-PV devices
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Another grand challenge of OPV device efficiency enhance- possess good exibility as compared to those in-organic FE-PV
ment is the signicant energy loss during the charge transfer devices.
from the donor to the acceptor.41 It is generally accepted that the 3.2.2 Ferroelectric P(VDF–TrFE) layer at the semi-
LUMO level offset between the donor and acceptor should be conductor/electrode interface to induce an electric eld. As
larger than the exciton binding energy (0.3–0.5 eV) in order to introduced above, the internal electric eld generated by the
get an efficient charge transfer. However, a smaller LUMO offset work function difference between two electrodes is insufficient
of 0.12 eV has been reported recently which could also result in so that not all of the electron–hole pairs can be dissociated
efficient charge transfer.125 Until now, most high efficiency under short-circuit conditions in many polymer material
polymer:fullerene-derivative systems have a very large LUMO systems. Although the charge recombination processes in BHJ
offset around 1 eV between the donor and acceptor, which OPVs are complicated, a straightforward approach to enhance
results in signicant energy loss. the charge collection efficiency is to apply a large electric eld
The existing bottlenecks of the FE-PV and organic solar cell (or reverse bias), which is evident in the application of the
devices indicate that the modication on either type of devices to photodetectors. However it is not feasible to apply an external
enhance the device performance is shown to be inefficient. To electric eld in a solar cell device.
tackle this issue, an effective way is to integrate the functionality To tackle this issue, Yuan et al. incorporated a thin layer of
of two types of materials into one cell to take advantage of their ferroelectric P(VDF–TrFE) at the organic/electrode interface to
complementary properties. The ferroelectric materials can generate an extra electric eld in the active layer. The ferro-
generate a huge permanent electric eld, which is essential to electric layer was deposited on poly(3-hexylthiophene):phenyl-
assist the separation of electron–hole pairs and extraction of free C61-butyric acid methyl ester (P3HT:PCBM) surface by the LB
charge carriers in the organic solar cells. Organic semiconductors method, followed by a thermal annealing process to convert it
have very strong absorption in the visible and near infrared range. into the ferroelectric phase.40 Aer poling under negative bias,
The ferroelectric materials can be used as the interfacial layer the dipoles in the FE layer are aligned with their positive
between the active layers and electrodes,40 between the donor and polarization charges close to the P3HT:PCBM layer and the
acceptor layers,41 or be blended in the bulk lms, which will be negative polarization charges close to the Al layer, as illustrated
discussed in detail in the following part of this review. in Fig. 6a. The negative polarization charges are neutralized by
the electrode due to the large density of free charges in metal.

3.2 Increasing the efficiency of organic photovoltaic devices

by a ferroelectric polymer
3.2.1 Ferroelectric polymer polyvinylidene uoride and its
copolymer with triuoroethylene. Polyvinylidene uoride
(PVDF) and its copolymers with TrFE, P(VDF–TrFE), are widely
used room temperature ferroelectric materials because of their
large polarization charge density and low fabrication cost.
There is a large dipole moment of 6.4  1030 C m pointing
from uorine to hydrogen atoms,126 and the spontaneous
polarization reaches 0.1 C m2 for some co-polymers aer the
dipoles are aligned. The PVDF polymers usually have mixed
crystalline and amorphous phases. It has been reported that
pure PVDF only has a degree of crystallinity of 50%, while
P(VDF–TrFE) can reach almost 100% crystallinity.127 There are
four phases for the P(VDF–TrFE) copolymer, i.e. the paraelectric
a phase, ferroelectric b, d and g phases.128 More details of the
organic ferroelectronics and P(VDF–TrFE) can be found in other
references.126,129
Ferroelectric polymers, such as P(VDF–TrFE), can be depos-
ited by various methods including spin coating,130 electro-
spinning,131 nano-imprinting,40,132,133 and Langmuir–Blodgett
(LB) deposition.70,75 The spin coating from a low boiling point Fig. 6 (a) Schematics of FE-OPV and working principle with the
ferroelectric polymer at the interface; (b) photocurrent curves of a
solvent usually leads to an amorphous lm, which can be
poly(4,4-dioctyldithieno(3,2-b:20 ,30 -d)silole)-2,6-diyl-alt-(2,1,3-benzo-
thermally annealed to increase its ferroelectric phase at a thiadiazole)-4,7-diyl (PSBTBT):phenyl-C71-butyric-acid-methyl ester
temperature higher than its Curie point. The LB method has (PC70BM) device without an FE layer (magenta line), with an FE layer
been used to deposit high quality P(VDF–TrFE) monolayers.134 before poling (black square line) and after poling (red squares).40

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Journal of Materials Chemistry A Feature Article

The positive polarization charges can generate an electric eld or/and PCBM domains. This thermal treatment can be avoided
penetrating through the organic active layer. This additional if ferroelectric P(VDF–TrFE) can be directly deposited on the
electric eld can facilitate the dissociation of the bound polymer:PCBM surface. For this purpose, a simple solvent
electron–hole pairs and charge collection, leading to increased chemistry method for the synthesis of ferroelectric phase
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Jsc, FF and Voc. The typical photocurrents of the devices before P(VDF–TrFE) nano-crystals was developed by Xiao et al.130
and aer poling are shown in Fig. 7b. The PCEs of poled FE-OPV The amorphous P(VDF–TrFE) nanoparticles with a diameter of
devices were about twice larger compared to the devices without 60–100 nm were rstly synthesized using acetone as a good
FE layers for many types of polymer systems tested. The solvent and methanol : water blend as a bad solvent. The
efficiencies of these devices are higher than the optimized ones hydrophobic interaction between water and uorine atoms in
with other methods. From the enhanced photocurrent in the P(VDF–TrFE) leads to the aggregation of P(VDF–TrFE) chains
FE-OPV devices, the additional electric eld induced by the and formation of amorphous ball like NPs. The size of the NPs
ferroelectric layers was estimated to be about 12 V mm1, which can be controlled by tuning the volume blend ratio of meth-
is much larger than the built-in electric eld (4 V mm1) anol : water from 300–500 nm (1 : 0 v/v) to 60–100 nm (10 : 1 v/
caused by the work function difference between the anode and v). Then the amorphous P(VDF–TrFE) NPs were converted into
cathode. The induced electric eld was actually limited by the the ferroelectric phase by reuxing them in liquid. The
incomplete coverage of the P(VDF–TrFE) on the P3HT:PCBM preformed ferroelectric nano-crystals enable the fabrication of
surface. There is still much space for the improvement because FE-OPV devices without annealing the PCDTBT:PC70BM layer,
the electric eld induced by 3 monolayers of P(VDF–TrFE) was resulting in a high efficiency of 6.7% which is 20% higher than
calculated to be as large as 50 V mm1. that of the optimized device using low work function metal
One issue in applying this method to the recently developed calcium as the electrode.
low bandgap polymer for efficiency enhancement is that the LB This approach has been shown to be universal and is
deposition used to fabricate monolayers of P(VDF–TrFE) lms is followed by several other groups. It has been shown that the
not compatible with the process of these polymers due to the ferroelectric layer is not necessarily located at the cathode
high temperature thermal annealing around 130  C needed to electrode side. For example, by inserting the P(VDF–TrFE) into
convert the P(VDF–TrFE) LB lm into the ferroelectric phase. For the interface between the PEDOT:PSS layer and organic active
example, many state-of-the-art low bandgap polymers, such as layer, Rastogi also obtained an improved photocurrent from
poly[N-90 -hepta-decanyl-2,7-carbazole-alt-5,5-(40 ,70 -di-2-thienyl- 5.2 mA cm2 to 9 mA cm2.136 It was observed that the
20 ,10 ,30 -enzothiadiazole)] (PCDTBT), poly[4,8-bis-(2-ethyl-hexyl- photocurrent systematically increased with the magnitude of
thiophene-5-yl)-benzo[1,2-b:4,5-b0 ]dithiophene-2,6-diyl]-alt-[2- the poling voltages, demonstrating the key role of the electric
(20 -ethyl-hexanoyl)-thieno[3,4-b]thiophen-4,6-diyl (PBDTTT-C- eld introduced by the aligned ferroelectric layer which facili-
T)] and poly[thieno[3,4-b]thiophene/benzodithiophene] (PTB7), ties the charge extraction.136
cannot be thermally annealed at temperatures above 70  C It was also proposed that ferroelectric materials such as
which otherwise results in the formation of oversized polymers BaTiO3 or PZT can be used at the front/rare surface of inorganic
photovoltaic devices, wherein the surface charge caused by the
polarized ferroelectric materials can induce an electric eld
inside the semiconductor layer to prevent the electron–hole
recombination occurring around the front/rare surface.137 An
increased power conversion efficiency and Voc was hence
expected. Similarly, the ferroelectric polymer P(VDF–TrFE) was
also suggested to be used in inorganic photovoltaics. The surface
charge at the interface between P(VDF–TrFE) and the inorganic
semiconductor could lead to the formation of an inversion layer
which helps to separate the electron–hole pairs.138
3.2.3 Ferroelectric P(VDF–TrFE) layer at the p/n interface to
shi the relative energy levels. Another attracting application of
incorporating the P(VDF–TrFE) in OPV devices for efficiency
enhancement is to tune the relative energy level of donor and
acceptor for maximizing the Voc output.41 The concept is illustrated
in Fig. 7a and b. A smaller energy offset of the donor and acceptor
is highly desired to reduce the energy loss during the charge
transfer process. This concept can be realized by designing new
materials with substituted functional groups.139,140 For example,
Zhong et al. synthesized uoroalkylated P3HT and PCBM to shi
Fig. 7 The energy level diagram of the semiconductor hetero-
the energy level of the donor and acceptor and applied them in a
structure without (a) and with (b) a dipole layer inserted at the D/A
interface. (c) Photocurrent curves for the as-made device (black balls), bilayer device. The uoroalkyl groups on P3HT or/and PCBM
after poling the P(VDF–TrFE) layer with reverse bias (red triangles) and spontaneously form a surface-segregated monolayer on the spin
forward bias pulses (blue squares).41 coated lm due to their low surface energy, which induced aligned

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dipoles at the D/A interface.140 Alternatively, tuning the D/A energy which is around 50–70 V mm1. The higher exciton dissociation
offset with aligned ferroelectric dipoles can avoid changing the rate in the device with the blended ferroelectric polymer was
polymer chemical structures. Many polymers show promising supported by a shorter photoluminescence lifetime in the
properties in many other aspects, such as bandgap, absorption P(VDF–TrFE) mixed P3HT:PCBM lm (73 ps) than that in the
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coefficient, solubility, and charge mobilities, but a too large LUMO controlled lm without the ferroelectric polymer (100 ps),
offset. Therefore, using a ferroelectric interfacial layer is a general implying an increased exciton dissociation rate caused by the
approach applicable to all polymer systems and it should have local electrical eld.
minimal inuence on other properties of the semiconducting
polymers. Yang et al. demonstrated an increased Voc in the P3HT/ 3.3 Switchable property of FE-OPV devices
PCBM bilayer device by inserting a monolayer of P(VDF–TrFE) LB
One unique property of inorganic FE-PV and FE-OPV devices is
lm between P3HT and PCBM.41 The energy level shi, DE, caused
their switchable photocurrents and dark currents controlled by
by the dipole layer can be estimated by: DE ¼ dsPq/303FE, where d is
the polarization direction of the ferroelectric layer. For the FE-
the thickness of the ferroelectric layer, sP is the polarization charge
OPV device with P(VDF–TrFE) at the organic/electrode interface,
density, q is the elemental charge, 30 and 3FE are the dielectric
the generated electric eld is expected to be switched parallel or
constant of the vacuum and relative dielectric constant ferroelec-
antiparallel with the built-in eld, resulting in better and worse
tric layer, respectively. Theoretically, an 0.6 nm thick P(VDF–TrFE)
device performance.40,130,136 This was clearly demonstrated by
layer between the donor and acceptor can lead to an energy level
Yuan et al. as shown in Fig. 8a. By inserting the P(VDF–TrFE) at
shi by 0.8 eV which is enough for all these applications. Inter-
both anode and cathode sides as interfacial layers, the diode
estingly, the insertion of the ferroelectric dipole layer between the
polarity of the OPV device based on P3HT:PCBM was switched
donor and acceptor layer did not inhibit the charge transfer from
under different poling directions, as shown in Fig. 8b.40,132 This
the donor to the acceptor. A strong charge transfer was found aer
is the rst time both the switchable diode and photovoltaic
aligning the ferroelectric dipoles in a preferred direction, which
effect was demonstrated in FE-PV devices. For the device with
was evidenced by the stronger photoluminescence quench in the
P(VDF–TrFE) mixed in the P3HT:PCBM bulk lm, the Jsc, Voc
D/FE/A trilayer lm than in the D/A bilayer lm. According to the
and FF also showed switchable variation under different poling
Marcus theory, it has been observed that the charge transfer rate
directions.142 For the device with P(VDF–TrFE) inserted at the
can be signicantly altered by changing the LUMO offset because
donor and acceptor interface, the LUMO offset between the
of the changed electron cloud coupling between the donor and
donor and acceptor can be tuned as well by the different dipole
acceptor.141 Using a ferroelectric interfacial layer hence provides an
directions of the ferroelectric layer, which results in a switch-
effective approach for the optimization of the charge transfer rate.
able Voc between 0.55 V and 0.67 V.41
As shown in Fig. 7c, the Voc was increased from 0.55 V to 0.67 V
It should be noted that only the ferroelectric phase of P(VDF–
aer aligning the dipoles of the ferroelectric layer with a negative
TrFE) has aligned dipoles aer external applied bias. The
external bias, exceeding all other observed Voc values in either bulk
amorphous P(VDF–TrFE) lm, e.g. formed by spin coating from
or bilayer devices for the P3HT:PCBM system. However, the
a low boiling point solvent, only works as a dielectric layer, so
coverage of the P(VDF–TrFE) layer on the P3HT surface deposited
that OPV devices with P(VDF–TrFE) spin-coated from acetone
by the LB method was only around 20%, which causes a large
did not show switchable performance.132,143
portion of P3HT to directly contact with PCBM materials, thus
limiting a potential increase in Voc. For this concern, great effort is
being made to increase the coverage of the ferroelectric layer by 3.4 Stability of the polarization of a ferroelectric layer in FE-
better controlling the ferroelectric layer processing technique. OPV devices
Furthermore, the morphology and uniformity of ferroelectric lm In order to apply the FE-PV or FE-OPV devices for solar energy
also need to be improved for better device performance. A pros- harvesting, the polarization of the ferroelectric polymer should
pect of this work is that the Voc can be enhanced to about 1.0–1.5 V be very stable both in the dark and under illumination. It is still
if 100% coverage of ferroelectric lm is achieved. under debate about the polarization stability of the ferroelectric
3.2.4 Mixing P(VDF–TrFE) into bulk heterojunction lms. material at the metal/semiconductor interface. Naber et al.
Mixing the photoactive materials with the ferroelectric mate- claimed that the polarization of P(VDF–TrFE) in the metal/
rials is another approach to utilize the large local electric eld of P(VDF–TrFE)/semiconductor (P3HT) (MIS) structure was not
ferroelectric molecules for efficiency enhancement in OPV stable due to a lack of minority electrons to compensate the
devices. By mixing a small amount of P(VDF–TrFE) polymer into spontaneous polarization charges.144 However, many other
the bulk P3HT:PCBM lms, Nalwa et al. enhanced the charge results showed that the polarization of a ferroelectric material
collection efficiency and achieved a very high internal quantum can be stable on a semiconductor and even on an insulator.
efficiency of 100%.142 According to a classic dipole-electric eld Kalbitz et al. showed that the polarization of P(VDF–TrFE) in the
model: E ¼ 4psf/303FE, where s is the surface charge density and MIS structure was very stable at either direction, demonstrated
f is the volume fraction of the dipoles, the electric eld gener- by the full ferroelectric polarization hysteretic loop. The trapped
ated by the P(VDF–TrFE) was estimated to be as large as 240 V electrons at the interface between the poled P(VDF–TrFE) crys-
mm1 when the volume fraction of P(VDF–TrFE) was 3%. tallites and the p-type semiconductor were sufficient to
The local electric eld induced by the ferroelectric dipoles is compensate the spontaneous polarization charges.145 In the
much larger than the electric eld needed to dissociate CTEs case of P(VDF–TrFE) inserted between a metal electrode and

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Fig. 8 Switching property of the P3HT:PCBM device. (a) Device with P(VDF–TrFE) at the cathode interface, (b) device with P(VDF–TrFE) at both
cathode and anode interfaces.40

insulator, Horie et al. also observed a full ferroelectric polari- 4. Summary and outlook for future
zation hysteretic loop for the device with a structure of metal/
VDF/aluminium oxide (Al2O3)/Al. The polarization could be development of FE-PV devices
repeated more than 10 000 times.146 The research into FE-PV devices is still increasing with contri-
The polarization of the ferroelectric polymer was shown to be butions from better material engineering and new approaches to
very stable even without a top electrode. For example, Hu et al. utilizing the ferroelectric dipoles. One major direction in pure
used the nano-imprinting process to fabricate nano-arrays of FE-PV device development could be reduction of the bandgap of
P(VDF–TrFE) on top of high doped silicon substrates with a the ferroelectric materials and increase of the carrier lifetime so
thickness of around 50 nm. A PFM tip was used to switch the that more free charges can be generated by sunlight and
dipoles. It was found that the polarization could be switched up extracted out of the devices. The electronic structures and the
or down. The polarization was found to be very stable aer one
electrical properties of the semiconductor materials are highly
day even without a top electrode.133 Sharma et al. deposited an sensitive to the unit cell structure and chemical substitution. A
ultrathin ferroelectric P(VDF–TrFE) layer on a highly doped Si recent example is from the studies of the halide perovskite
substrate using the LB method and used the PFM to measure its photovoltaic device, where the electron–hole diffusion length in
ferroelectric switching. A quite symmetric hysteresis loop with a solution-processed CH3NH3PbI3 was found to be increased by
symmetry coercive eld was observed for the nanomesa of the about ten times when some of the iodine ions in the perovskite
P(VDF–TrFE) and the polarization was very stable without a top structure were replaced by chloride ions.149,150 From this point of
electrode.147 Most strikingly, it was demonstrated that the view, it is crucial to develop new ferroelectric materials or
epitaxial BaTiO3 (with thickness varying from 1.6 nm to 40 nm)
functional microscopic structures with the guidance of rst-
showed stable and switchable polarization on insulating silicon principles calculation. FE-PV devices based on ferroelectric
oxides without a top electrode.148 nanomaterials such as nanowires or nanoparticles might be
In the OPV devices with P(VDF–TrFE) inserted at the cathode another possible direction, where the unit cell and its corre-
interface, Yuan et al. reported that the polarization was very sponding ferroelectric/piezoelectric properties are supposed to
stable for more than two weeks, supported by the non-degraded be signicantly inuenced by the surface effect.134,151–155 Besides,
performance of the device.132 In the device with the P(VDF– the distribution of the depolarization eld in the ferroelectric
TrFE) layer inserted at the anode side between the PEDOT:PSS nanomaterials should be very different from that in thin lm
and P3HT:PCBM layer, Rastogi et al. observed a full ferroelectric
structures because of the different screening effect in nano-
polarization hysteresis loop. By inserting the P(VDF–TrFE) layer structured materials.156–158 It is also believed that ferroelectric
between two semiconducting P3HT:PCBM layers, a full hyster- materials will nd more applications in traditional p–n junction
esis loop was also observed, indicating that the polarization on photovoltaic devices. The semiconductor materials used in
both directions was stable.136 traditional p–n junction photovoltaic devices have advantages in
All the above reported results suggest that the polarization charge transport and light absorption. On the other hand, the
of the ferroelectric P(VDF–TrFE) layer with one semicon- polarization charges caused by the remnant polarization can
ducting electrode in the SIM structure, or sandwiched play a role in the separation of the photogenerated charge
between two organic semiconducting layers, or even with
carrier-pairs and the transportation of the carriers by intro-
only one electrode is stable. One reason may be that the ducing an extrinsic electrical eld in the active layers; meanwhile
trapped charges at the P(VDF–TrFE)/semiconductor interface the aligned dipoles in the ferroelectric materials provide a
are sufficient to compensate the polarization charges of the promising way to control the barrier height, interfacial energy
ferroelectric layer.145

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Feature Article Journal of Materials Chemistry A

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27 M. Ichiki, Y. Morikawa, K. Nonaka, T. Nakada, C. Endo and

We thank the nancial support by the National Science Foun- R. Maeda, in Photovoltaic effect of PLZT in a layered lm
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