Polymer Journal (2017) 49, 85–111

& 2017 The Society of Polymer Science, Japan (SPSJ) All rights reserved 0032-3896/17
www.nature.com/pj

REVIEW

Liquid crystals in photovoltaics: a new generation

of organic photovoltaics
Manish Kumar and Sandeep Kumar

This article presents an overview of the developments in the field of organic photovoltaics (PVs) with liquid crystals (LCs).
A brief introduction to the PV and LC fields is given first, followed by application of various LCs in organic PVs. Details of LCs
used in bilayer solar cells, bulk heterojunction solar cells and dye-sensitized solar cells have been given. All the liquid crystalline
materials used in PVs are structured and the efficiency of solar cells is tabulated. Finally, an outlook into the future of this newly
emerging, fascinating and exciting field of self-organizing supramolecular LC PV research is provided.
Polymer Journal (2017) 49, 85–111; doi:10.1038/pj.2016.109; published online 9 November 2016

INTRODUCTION important process for the conversion of light to electrical or chemical

For the sustainable growth of the global economy, availability of cheap energy, includes the light-induced exciton (electron–hole pair) gen-
energy is essential. Our energy demand is increasing continuously to eration, separation and migration of electrons and holes in outer
improve our lifestyle. At present, fossil energy sources are the primary circuit. Inorganic semiconductors, such as Si, GaAs, CdSe and so on,
sources for most of the world’s current energy requirements and only have often been used owing to their high charge-carrier mobility and
a little is provided by hydropower, nuclear energy and biomass. stability. High cost of these electronic-grade materials and processa-
The exponential growth of carbon dioxide level in the atmosphere bility are the main concerns in utilizing inorganic semiconductors.
owing to the burning of fossil fuels is leading to the threat of a Therefore, recently organic semiconductors have attracted much
universal climate change. Moreover, there will be limited availability of attention for solar cell materials owing to their low cost processing,
conventional energy sources in the long term. Future energy fabrication on both hard and flexible substrates, large-area application
demand cannot be met with conventional sources of energy. Nuclear and the availability of unlimited variety of organic molecules with
energy sources are one of the promising energy sources, but owing to different opto-electronic properties.
their associated hazardousness and cost effectiveness, these energy Organic semiconducting materials is a field of intense scientific
sources does not appear to be socially acceptable universally. activity because of their potential application in electronic and
Moreover, nuclear fuel is also limited to tackle gigantic demand of opto-electronic devices, such as field effect transistors, light-emitting
energy. Despite several efforts, the problem of energy provision diodes, sensors and PV cells.1–6 During the past decade, organic solar
around the world remains unsolved, and there is a great need cells have attracted considerable attention owing to their outstanding
of finding alternative clean energy sources. To solve the energy crisis of characteristics, such as potential low-cost fabrication, utilize high
the globe, exploitation of solar energy is undoubtedly the best answer. throughput, light weight, flexibility and easy processability with
It is the most abundant inexhaustible source of regenerative energy. efficiency upto 10%.7–11 Organic PVs (OPVs) has been the subject
It is known since the evolution of life on the Earth that Mother Nature of enormous scientific interest and therefore has been covered in many
generates chemical energy from solar energy via photosynthesis. reviews, special issues and books.12–22 Significant attention has been
The supply of energy by Sun on Earth in an hour is more than that given to overcome technological and materials problems in order to
we use in a year. Therefore, only a fraction of solar energy is required develop these OPV devices, which can perform better than inorganic
to overcome our all energy requirements, if it can be converted to PV devices. In recent years, several researches are conducted to
electric energy efficiently. The device that is developed to convert solar improve the efficiency of organic solar cells and thereby realized
energy into electrical energy is known as photovoltaic (PV) solar cell. applications, such as lightweight or flexible power sources.8
During the past 60 years, PV energy has been used as a promising Organic solar cells have better potential than conventional solar cells
candidate for energy devices because it is abundant, inexhaustible, owing to their easy fabrication with the common vacuum evaporation
cheap, straight to production ability and pollution-free that does technique, spin-coating, inkjet printing, doctor-blading, drop-casting,
not raise the green-house gases. The PV effect involves the generation screen printing and roll-to-roll printing. In addition to that, they
of a photocurrent and photovoltage on absorption of light photons can be readily processed on flexible substrates and devices could
in a semiconductor. The three-step process, which is an be translucent.

Soft Condensed Matter Group, Raman Research Institute, Bengaluru, India

Correspondence: Professor S Kumar, Raman Research Institute, C.V. Raman Avenue, Sadashivanagar, Bengaluru 560 080, India.
E-mail: skumar@rri.res.in
Received 6 July 2016; revised 27 September 2016; accepted 28 September 2016; published online 9 November 2016
 Liquid crystals in photovoltaics
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86

The operation mechanism of light conversion in OPV cells is based favorable when
on charge generation at the interface between two different organic
semiconductors, followed by their separation and migration toward EHOMO ðDÞ 2 ELUMO ðAÞoEex
opposite electrodes. These cells are known as heterojunction solar Many different types of organic materials have been used in OPVs,
cells.9 In these heterojunction solar cells, the transportation of the for example, small molecules, polymers, oligomers, dendrimers,
holes and electrons is conducted through organic p-type and n-type organic dyes and liquid crystals (LCs). Owing to the paucity of space,
semiconductors and the spontaneous charge flow produces electricity. it is not possible to cover the developments happened in all types of
The concept of heterojunction was first introduced using bilayer OPV cells; therefore, this article deals only with the use of LCs
structures5 where a layer stacking of donor and acceptor molecules in OPVs.
with a planar interface (Figure 1) is realized. This provides a spatially
uninterrupted pathway for the photogenerated charge carriers to the A BRIEF OVERVIEW OF LCS
respective electrodes.23 However, creating an organic bilayer structure LCs, also referred to as mesophases, are materials that have the
is not easy and economical, and therefore the concept of bulk properties of both crystals and liquids. These materials show order and
heterojunction (BHJ) is realized. Figure 1 represents the device mobility at molecular, supramolecular and macroscopic levels. LCs are
structures of bilayer heterojunction (a), BHJ (b) and the fundamental accepted as the fourth state of matter after the three classical states of
steps occurring in donor–acceptor heterojunction solar cells with the matter: solid, liquid, and gas. LCs are ubiquitous in everyday life in the
highest occupied molecular orbital/lowest unoccupied molecular form of LC display devices, thermal sensors and so on. They are not
orbital (HOMO/LUMO) electronic band gap structure (c). In a bilayer only important in materials science but also in living systems and in
heterojunction solar cell, both donor and acceptor materials are biology.24 Several bio-molecules, such as DNA, lipids and proteins,
separately layered with cathode and anode while in BHJ a nanoscale form various liquid crystalline phases under appropriate conditions.24
blend of both donor (D) and acceptor (A) is used as active layer. The appearance of mesomorphism in DNA fragments (nano DNAs)
The nanometer domain sizes of this blend allowing the excitons with has been related to the significant role of LCs in the evolution of life in
short lifetimes to reach at an interface and dissociate owing to the large the prebiotic world.25
donor–acceptor interfacial area. An energy-level diagram and the LCs are classified in various ways, such as: depending on the molar
conversion process are given in Figure 1c to illustrate the principle of mass of the constituent molecules, low molar mass (monomeric and
operation of the conversion of energy. The ionization potential oligomeric) and high molar mass (polymeric) LCs; depending on
of the D is low and has high EHOMO, whereas the A has a high the process by which the liquid crystalline phase is obtained, whether
electron affinity (EA) and low ELUMO. When the light incidents by adding solvent (lyotropic) or by changing the temperature
on the surface, excitons (electron–hole pair) are formed in the (thermotropic); depending on the nature of the constituent molecules
material (1), these photogenerated excitons diffuse to the interface (organic, inorganic, ionic, organometallic); depending on the
(2), electrons and holes are separated; electrons migrate to acceptor (3) geometrical shape of the molecules (rod-like, disc-like); and
and holes migrate toward anode (4). Charge separation is energetically depending on the arrangement of the molecules in the liquid

Figure 1 Device structure of (a) bilayer heterojunction, (b) bulk heterojunction, (c) device working principle with electronic HOMO/LUMO structure
and (d) schematic illustration of charge separation at donor–acceptor interface ((1) exciton formation, (2) diffusion of exciton to interface, (3) dissociation and
(4) charge transport in the active layer of organic photovoltaic solar cell). A full color version of this figure is available at the Polymer Journal online.

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crystalline phase (nematic, smectic, columnar, helical, B phases core (intracolumnar) is generally of the order of 0.35 nm while the
and so on). The most common class of LCs commonly known as separation between neighboring columns (intercolumnar) is in
calamitic LCs are derived from rod-like molecules.26 They have the range of 2–4 nm. This assembly of molecules gives more
primarily been exploited for their applications in LC displays.27 interaction between neighboring molecules within the same column
Calamitic LCs were discovered more than a century ago in 1888 when compared with the neighboring column. In this columnar
Reinitzer28 noticed an unusual double melting behavior of cholesterol arrangement of aromatic cores, each column acts as a molecular wire
benzoate. For about 90 years, it was believed that only rod-like where the electrons or holes migrate efficiently along the columns in
(calamitic) molecules can form LCs when Chandrasekhar et al.29 quasi one dimension (Figure 3). Owing to this unidirectional
synthesized and realized the LC phases of disk-like molecules. These arrangement, the electrical conductivity along the columns have been
are now commonly referred to as discotic LCs (DLCs). Both calamitic observed to be many orders of magnitude greater than that in
and discotic mesogens exhibit nematic (having only long-range orienta- perpendicular direction.35 Because of this behavior, DLCs could be
tional order) or higher order smectic and columnar phases (Figure 2). used in opto-electronic devices, such as PV solar cells, light-emitting
Another variety of LCs in which usually two calamitic molecules are diodes and gas sensors. Owing to the technological applications and
joined via a central bent unit is classified as banana or bent-core LCs.30 fundamental importance of DLCs, they have received much attention
Though they were known in literature as calamitic LCs since 1929,31 of the scientists around the globe thtat has been reviewed in several
their ferroelectric properties owing to the formation of chiral articles.33,34,36–51
mesophase are realized only in 1996.32 Although bent-core LCs
have not been much studied for PV properties, both calamitic
and DLCs are explored to fabricate PV solar cells. As the story
of LC PVs started with DLCs, we begin our discussion with
these systems.

DISCOTIC LCS
The self-organization of disc-like or plate-like molecules leads to the
formation of DLCs. A majority of DLCs are composed of
polycyclic aromatic cores, such as triphenylene (TP), anthraquinone,
phthalocyanine (Pc) and so on, surrounded by plural number of
flexible aliphatic chains.33,34 The strong π–π interactions between
aromatic cores favor columnar stacking of the molecules. The
columnar mesophase is formed owing to the self-assembly of rigid
disc-shaped aromatic cores, which consists usually 6–8 peripheral
molten aliphatic chains with mobility. The separation between core– Figure 3 One-dimensional charge migration in DLCs.

Figure 2 Schematic representations of nematic-, smectic- and columnar-phase formation by calamitic and discotic mesogens.

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In comparison to other organic semiconducting materials such as produce thin films with vertically segregated perylene and
single crystals and conducting polymers, DLCs possess many hexabenzocoronene with large interfacial surface area.
advantages. Both p-type and n-type DLCs can be easily designed Power-conversion efficiency (PCE) upto 2% was achieved with a
and synthesized, their optical and electronic properties can be tuned small incident irradiance o1 mW cm − 2. However, it degrades at
via proper chemical modifications, they can be easily obtained in very higher intensities and reaches to 0.22% under 1 Sun illumination at
high purity, they can be aligned parallel to the electrode surface AM 1.5G.79 Simple solution-processing steps are used to fabricate
(homeotropic alignment) for better one-dimensional charge migration these OPV devices. Intermolecular and macroscopic ordering was
(Figure 3), they display self-healing of structural defects owing to their reported to be responsible for the high performance of fabricated
fluid nature, they are soluble in common organic solvents and possess devices. For compound HBC-PhC12, the calculated HOMO level was
low melting point and therefore can be economically processed.52 5.25 eV and LUMO level was 2.64 eV, with a large band gap of
Long exciton diffusion length and high charge-carrier mobility are 2.61 eV. Similarly, HOMO and LUMO energies for perylene were 5.32
the key factors to realize efficient OPV solar cells. Some DLCs exhibit and 3.29 eV, respectively. From HBC-PhC12 to perylene, which has a
very good exciton diffusion length (~70 nm) and very high high electron affinity as a result of the electron-withdrawing diimide
charge-carrier mobility (~1 cm2 V− 1 s − 1).53 The simulated bridges, there is 0.65 eV LUMO step and 0.07 eV HOMO step. The
defect-free DLC assembly was reported to have the mobility in excess devices showed high external quantum efficiencies (EQEs; Figure 6),
of 10 cm2 V − 1 s − 1.54 The charge-carrier mobility in organic materials which is due to the large interfacial area within the bilayer structure,
may be correlated with the molecular structure and packing of and possibly owing to the high exciton diffusion ranges in the
constituting molecules. In DLCs, the charge-carrier mobility is separated HBC-PhC12 and perylene regions. The short circuit current
expected to improve upon the close stacking of the columns, and (JSC) and open circuit voltage (VOC) were − 33.5 μA cm − 2 and 0.69 V,
the molecular order could be enhanced by enlarging the size of respectively, and the fill factor (FF) was 40% (Figure 6). Later, they
polycyclic aromatic core as a result of intense π–π interactions. tried several other HBC-based DLCs (Figure 4) to prepare PV solar
A speculative relationship between charge mobility and core size has cells.80,81 However, none of these devices could cross the PCE of the
been proposed,55 Several large polycyclic aromatic hydrocarbon cores, above-mentioned first device. PCE of some of the HBC-based
defined as ‘nano-graphenes’ have been explored by Müllen and DLCs used in PV solar cells are presented in Table 1. In all
co-workers to build various DLCs.39,45,56 The dispersion of large-size tables, Cr = crystals; LC = liquid crystal; Colh = columnar hexagonal;
discotics in archetypal DLCs is reported to improve physical properties Colp = columnar plastic; N = nematic and SmA = smectic A.
of the system significantly owing to complimentary polytopic Device prepared using chiral HBC derivative 1b (Figure 4) and
interactions.57 In another innovative approach, we realized that the perylene derivative 2a (Figure 5) exhibits ISC, 3.3 μA cm − 2,
conductivity of DLCs can be enhanced by several orders of magnitude VOC 0.46 V, FF 32.5% and PCE of 0.1% at 490 nm. Compared with
by dispersing a very small amount of metallic, semiconducting or the above-mentioned HBC-PhC12/perylene device, it gives very poor
carbon nanoparticles.58–67 results. This has been attributed to different film-forming properties
Since the discovery of DLCs, there has been tremendous interest in and film morphologies of HBC derivative 1b.80 In this case, vertical
utilizing these materials as one-dimensional semiconductors. segregation of HBC and perylene layer was not observed in the
Conducting and photoconducting properties of DLCs have been spin-coated blends. A combination of 1a or achiral 1b with perylene
studied extensively.50,68 Owing to their excellent charge-transport acceptor 2a gives very poor PCE.81 Efforts have also been made to
property, DLCs have been applied to prepare bilayer and BHJ solar attach perylene dye covalently to HBC discotic as shown in structure
cells.6 They have also been used as additives in solar cells69–72 and also 1n to realize phase-segregated donor–acceptor structure. However,
as electrolyte in dye-sensitized solar cell (DSSC).73 DLCs derived from this device exhibits very poor PCE.82 Replacing the perylene dye 2a by
porphyrin, Pc, TP, hexabenzocoronene and decacyclene have been other perylene dyes such as 2b–2d (Figure 5) also did not improve the
used as hole-transporting layer while crystalline and liquid crystalline efficiency.81,82
perylene derivatives and C60 derivatives have commonly been used as Jung et al.83 added a photoconducting carbazole-based polymer in
electron-transporting materials. the HBC/perylene solar cell to improve its efficiency. It was observed
Gregg et al.74 and Petritsch et al.75 were the first ones to that the PCE of the device is dependent on the morphology of film. An
demonstrate the PV effect in porphyrin- and Pc-based DLCs. addition of the photoconducting polymer improves the device
However, the seminal work of Schmidt-Mende et al.6 on performance, albeit only for experiments performed in vacuum.
well-defined discotic PV solar cell prepared from a hexa-peri- The PV properties of three HBC derivatives were investigated with
hexabenzocoronene (HBC)-based DLC, reported in 2001, generated respect to the influence of the alkyl side chains (Figure 4, structure 1d,
tremendous interest in this field. Therefore, we open this section with 1f and 1g) by Li et al.84 For the devices fabricated from 1d compound,
HBC-based DLCs in PVs. the VOC is 0.52 V and the PCE is 1.5% with EQE values of 12%, which
is much higher than the EQE of 6% and 4% in 1f and 1g, respectively.
HEXABENZOCORONENE DLCS IN PVS This is due to the shielding effects of the alkyl chains, which reduces
HBC is one of the largest and highly symmetrical all-benzenoid the HOMO level on increasing side chain length. HBC derivative 1c
polycyclic aromatic hydrocarbons that has recently been realized to with normal dodecyl peripheral chains exhibits EQE of 29.5%.85
function as a core fragment for generating DLCs by Müllen and The effect of chemical structure and self-assembly of HBC discotics
co-workers.76 HBC-based DLCs show columnar phases with were studied by Hesse and co-workers.79,86 Various phenyl-substituted
remarkably high mesophase breadth and charge-carrier HBCs (Figure 4, structure 1h, 1i, 1j, 1k and 1l) as electron donor
mobilities.77,78 They act as donor materials (p-type, blended with PDI, 2a were studied. They investigated the effect on the
hole-transporting semiconductors) in electronic devices. Schmidt- device performance by means of different parameters, such as different
Mende et al.6 prepared an OPV device using a HBC-based DLC, alkyl chain lengths (6, 8, 12 and 16) of carbon atoms, introduction of a
HBC-PhC12, 1a (Figure 4) in combination with an organic soluble triple bond linker between HBC core and residual phenyl group and a
electron-accepting perylenediimide (PDI) dye, 2a (Figure 5) to swallow-tailed dialkylphenyl chain. It was also observed that by

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Figure 4 Chemical structure of HBC DLCs used in OPV.

increasing the side chain length of the HBC molecule the layered 1p, 1q, 1r and 1s). Formation of columnar structures is reported in
structure is disrupted, which results to disordered structure. PCE up to these materials by X-ray diffraction studies. BHJ solar cells with
0.24% was realized in these devices.79,86 the structure ITO/PEDOT:PSS/FHBC/PC61BM (1:2 w/w)/TiOx/Al
Wong et al.87,88 prepared a number of fluorenyl-substituted HBC were fabricated and PCE up to 2.5% was observed in these
(FHBC) and their thiophene dendrimers (Figure 4, structure 1m, 1o, devices (Table 1).87,88 In these devices, [6,6]-phenyl-C61-butric acid

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Figure 5 Chemical structure of perylene-based electron acceptors used in OPV.

methyl ester (PC61BM) and [6,6]-phenyl-C71-butric acid methyl ester devices were fabricated with the cell structure of ITO/PEDOT:
(PC71BM) have been used as electron acceptor. Addition of PSS/DLC/PC61BM/Ca-Al. An active layer of 80-nm porphyrin was
HBC-based amphiphilic interface modifier improves the PCE of the spin-coated from its chlorobenzene solution and a 30-nm-thick
device made of compound 1o and PC61BM by 20%.89 PC60BM layer was thermally deposited under vacuum to construct
Kang et al.90 demonstrated the self-assembled molecular structure bilayer solar cells. On the other hand, BHJ devices were prepared from
of p–n junction of HBC discotic 12-c-HBC, 1t (Figure 4) and a blend of porphyrin and PC60BM (1:1 w/w, 230–250-nm thick). It
PC70BM. The PCE is increased up to 2.41% upon addition of 10% has been observed that thermal annealing of these devices induced
donor material with 10:90 wt% of 21:PC70BM. The solution-processed alignment of discotic molecules in the photoactive layers, leading to a
fabricated device showed the VOC 1 V and JSC 6.37 mA cm − 2.90 The factor of 4–5 higher PCE. PV parameters of these devices are tabulated
enhancement to the PCE is due to the formation of ball-and-socket in Table 2 along with Pc discotics.
packing nest structure of 12-c-HBC molecules into PC70BM, which Although porphyrin DLCs exhibit many attractive features, such as
results in the formation of well-defined molecular p–n junctions. broad absorption spectrum, low gap between HOMO and LUMO
energy levels, facile homeotropic alignment, high charge-carrier
PORPHYRIN DLCS IN PVS mobility and resemblance with natural photosynthetic antenna,
Porphyrins are considered as ‘pigments of life’ owing to their surprisingly, out of 4200 DLCs derived from porphyrin nucleus only
biochemical involvement in various vital processes in the living 2 DLCs have been so far used to fabricate real solar cell. Therefore, it
systems.91 Porphyrin derivatives, such as hemes, chlorophylls, would be quite interesting to further explore these interesting
cytochromes, peroxidases, myoglobins, catalases and so on, are some intriguing materials.
important biological representatives. They are the primary
light-harvesting molecules in natural photosynthesis.92,93 Porphyrin PC DLCS IN PVS
derivatives absorb light up to the red region of the visible spectrum Pcs are closely related to porphyrins and are also known as tetrabenzo
with high extinction coefficients. A number of porphyrin derivatives tetraazaporphyrins. Pcs are macrocyclic compounds with an
have been successfully used in DSSCs, bilayer and BHJ solar cells.94–97 alternative carbon atom–nitrogen atom ring structure, which acts as
The use of DLC porphyrin in OPV was first realized by Gregg a tetradentate ligand. They have found applications in bio and
et al.98 who prepared an unusual PV cell using a DLC porphyrin, zinc electronic industries.101 Pcs can act both as p-type and n-type
octakis(8-octyloxyethy1)porphyrin 3a (Figure 7), sandwiched semiconductors depending on peripheral substitutions.102 Piechocki
in between two symmetrical indium tin oxide (ITO) electrodes in et al.103 discovered columnar mesophase properties of Pc LCs in 1982,
1990. It was proposed that ‘the illuminated electrode interface and since then, about 400 Pc-based DLCs have appeared in the
possesses much higher concentration of excitons than at the counter literature.34 Pc-based DLCs have been extensively studied for their
electrode owing to strong absorption of incident light by the conducting and photoconducting properties and charge-carrier
porphyrin. The exciton dissociation at the porphyrin/ITO interface mobility up to 0.71 cm2 V − 1 s − 1 has been realized.49 Several
was inherently asymmetric, and this leads to a significant and Pc-based DLCs have been used to fabricate solar cells. Chemical
persistent PV effect’.98 structures of these DLCs are presented in Figure 8 and their PV
BHJ solar cells incorporating porphyrin discotic molecules 3b and parameters are tabulated in Table 2.
3c (Figure 7) with PC61BM electron acceptor were prepared by Li and Petristch et al.104 utilized discotic liquid crystalline Pc in organic
co-workers that showed PCE upto 0.222%.99,100 These porphyrin have solar cells in 1999. They investigated a double-layer PV device
high absorption range over solar spectrum and align homeotropically comprising a discotic Pc derivative 4a (Figure 8) as electron donor
for efficient charge transport. Both bilayer heterojunction and BHJ and a perylene derivative 2e (Figure 5) as electron-acceptor material.

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Figure 6 (a) EQE action spectra for a 40:60 HBC-PhC12:perylene diimide blend (solid line) and the fraction of absorbed light in an HBC-PhC12 film
(dashed line), a perylene film (dotted line) and a 40:60 blend film (dash-dotted line). (b) Current–voltage characteristics for this device in the dark and under
illumination at 490 nm. The JSC and VOC under illumination are − 33.5 μA cm − 2 and 0.69 V, respectively, and the FF is 40%. The diode has a rectification
ratio of 8.3 × 102 at 2 V. (c,d) Normalized EQE action spectra taken under illumination through the ITO and Al electrodes, respectively, corrected for the
absorption of the contacts and glass. Reproduced with permission from Schmidt-Mende et al.6 Copyright 2001 American Association for Advancement of
Science.

Compound 4a was heated to its isotropic temperature (292 °C) and partially opened pores cannot provide a sufficiently dense filling of
cooled slowly to room temperature. Then a thin layer of perylene as CuPc molecules to form a conductive wire for hole transport to the
electron acceptor and Al as top contact electrode were deposited. anode. This is consistent with the theoretical model, which indicates
The device exhibits EQE of 1%. They also prepared a blended OPV that the I–V curve degradation occurs as a result of a decrease of the
device based on Pc 4a as donor and perylene derivative 2a as hopping coefficient; poor filling leads to isolation of the CuPc
acceptor105 that shows EQE upto 1% with VOC of 0.1 mV and aggregates making them insulated from each other’.106
25% FF. Fujii and co-workers extensively studied various Pc DLCs in
Levitsky et al.106 demonstrated a solar cell based on n-type PVs.69,70,107–113 They prepared an OPV device based on Pc derivative
nanoporous Si (PSi) filled with copper Pc (CuPc) and its discotic 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH2) 4d (Figure 8)
derivatives 4b (Figure 8). The fabricated device shows the PCE upto as donor and the fullerene derivative PC61BM as acceptor in 2010.107
2%. Such organic filled nanoporous inorganic matrices may lead to High EQE of 470% in the Q-band absorption region of C6PcH2 and
the fabrication of hybrid PV systems with efficient photoinduced a high energy-conversion efficiency of 3.1% were achieved with
charge transfer and charge migration. Both CuPc and PSi contribute different compositions of both donor and acceptor materials. The
to the photocarrier generation, but the CuPc discotic derivative shows values of VOC is 0.81 V, ISC of 9.6 mA cm − 2 and FF of 40% were
the property of increasing the hole mobility along the quasi-one- observed for the solar cell with the C6PcH2:PC61BM composite layer
dimensional columns. The device was fabricated as ITO/PSi–CuPc/Al at a weight ratio of 2:1. To improve the FF of the above device, they
architecture followed by the plasma etching of nanoporous Si to studied the optimization of the active layer thickness and insertion of
ensure the opening of the all pores. PSi was filled by dropping a buffer layer.108 The optimized active layer thickness was determined to
solution (10 − 2 M) of CuPc. The I–V curves of Psi samples that were be 120 nm. By inserting a hole-transporting MoO3 buffer layer
not treated by plasma etching to open all pores exhibited a ‘kink’ between cathode and active layer, the PCE was enhanced to 3.2%.
behavior leading to a decrease of the VOC and ISC values. The authors Working on the same DLC 4d, they studied the effect of additional
suggested that ‘samples with a poorly developed pore structure or with additives on the surface morphology.109 By using processing additive

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Table 1 Photovoltaic parameters of some best-performing HBC DLC-based solar cells

Donor Acceptor VOC (V) JSC (mA cm − 2) FF (%) EQE (%) PCE (%) Illumination source (mW cm − 2)/nm Phase Reference

1a 2a 0.69 0.033 40 34 1.95 490 nm Colh 6

1b chiral 2a 0.46 0.033 32.5 34 0.1 490 nm Cr 80

1b achiral 2a 0.82 0.039 31 — — 490 nm Cr 81

1c 2a 0.70 — — 29.5 — 460 nm Cr 85

1d 2a 0.52 — — 12 1.5 470 nm Cr 84

1e 2a 0.6 — 34.6 14 — 490 nm LC 72

1f 2a 0.56 — — 6 — 470 nm Colp 84

1g 2a 0.56 — — 4 — 470 nm Colp 84

1h 2a 0.64 1.03 33.4 — 0.22 100 mW cm − 2 Cr 79

1i 2a 0.665 1.065 34.3 — 0.24 100 mW cm − 2 Cr 79

1j 2a 0.59 0.34 39.2 — 0.08 100 mW cm − 2 LC 79

1k 2a 0.69 0.81 39.3 — 0.22 100 mW cm − 2 LC 79

1l 2a 0.54 0.3 44.5 — 0.07 100 mW cm − 2 Cr 79

1m PCBM 0.61 0.17 32 2 0.03 100 mW cm − 2 LC 87

1n 2a 0.78 — 22.6 0.1 — 490 nm LC 82

1o PCBM 0.91 2.68 61 39 1.46 100 mW cm − 2 LC 87

1p PCBM 0.9 2.73 44 — 1.1 100 mW cm − 2 Colh 88

1q PCBM 1 2.91 42 — 1.2 100 mW cm − 2 Colh 88

1r PCBM 1 6.37 38 — 2.5 100 mW cm − 2 Colh 88

1s PCBM 0.87 2.03 60 27 1.06 100 mW cm − 2 LC 87

1t PCBM 1 6.37 38 — 2.41 100 mW cm − 2 Cr 90

Abbreviations: Cr, crystalline; Colh, columnar hexagonal; Colp, columnar plastic; DLC, discotic liquid crystal; EQE, external quantum efficiency; FF, fill factor; HBC, hexa-peri-hexabenzocoronene;
JSC, short circuit current; LC, liquid crystalline; PCBM, [6,6]-phenyl-C61-butyric acid methyl ester; PCE, power-conversion efficiency; VOC, open circuit voltage.

Figure 7 Chemical structure of porphyrin DLCs used in photovoltaics.

1,8-diiodooctane (0.2% v/v) in various organic solvents, such as Solar cells with homologous series of 1,4,8,11,15,18,22,25-octahex-
toluene, trichloroethylene and chloroform, the performance of BHJ ylphthalocyanine (Figure 8, structure 4c, 4d, 4e, 4f and 4g) were
solar cells was markedly improved. The values of VOC of 0.78 V, ISC of prepared by Dao et al.112 to understand the effects of alkyl chain length
9.1 mA cm − 2, FF of 58% and the PCE 4.1% were recorded. on PV parameters. They observed that, ‘by shortening the alkyl
Other additives such as 1,8-dichlorooctane and 1,8-dibromooctane substituents length, the columnar structure of the Pc discotic altered
also exhibit similar effect. However, increasing the amount of additives from 2D rectangular lattices to pseudohexagonal structures and
decreases the PCE.110 The marked improvement in the PCE has Davydov splitting at the Q-band of CnPcH2 absorbance spectra
been attributed to distinctly different surface morphology (Figure 9) decreases, which results in the higher hole mobility and the deeper
of the active layer where processing additive separated the HOMO energy levels. As a result, the PCE of CnPcH2-based BHJ solar
donor–acceptor phases.110 cell is improved from 0.3% to 3.7% by changing the alky substituent
The stability and the degradation mechanism of the solar cell length’.112 In this series, the highest PCE was observed in the Pc 4d
have also been studied.111 Solar cells based on Pc show higher with hexyl alkyl chain.
stability than the cells fabricated with the conventional donor Very recently, Dao et al. utilized various Pc–tetrabenzoporphyrin
material poly(3-hexylthiophene) (P3HT) in the same environment hybrid macrocycles 4i–4m to prepare solar cells.113 These compounds
(45 °C temperature and 1 Sun). It was observed that the irradiation of were prepared by replacing azo links of Pc 4d by methane groups.
a solar simulator degrade the C6PcH2 molecule by breaking chemical Thus non-peripherally substituted octahexyl tetrabenzoporphyrin
bonds of two pyrrole aza nitrogens as well as the four meso-bridging (C6TBPH2, 4i), tetrabenzomonoazaporphyrin (C6TBMAPH2, 4j)
aza nitrogens with neighboring carbons and this affected the device tetrabenzodiazaporphyrins 4k and 4l (C6TBDAPH2, a mixture of
lifetime. Deposition of various buffer layers between the active layer cis and trans compounds) and tetrabenzotriazaporphyrin (C6TBTAPH2,
and counter electrode improve the stability.114,115 4m) were prepared. These hybrid molecules were reported to exhibit

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Table 2 Photovoltaic parameters of some best-performing porphyrin and phthalocyanine DLC-based solar cells

Donor Acceptor VOC (V) JSC (mA cm − 2) FF (%) EQE (%) PCE (%) Illumination source (mW cm − 2) Phase Reference

3b PCBM 0.51 5.03 — — 0.775 100 mW cm − 2 Colh 99

3c PCBM 0.51 3.99 — — 0.712 100 mW cm − 2 Colh 100

4a 2a 0.11 — 25 1 — 0.25 mW cm − 2 Cr 105

4b p-Si 0.015 0.6 — — 2 30 mW cm − 2 Cr 106

4d PCBM 0.81 9.6 40 70 3.1 100 mW cm − 2 Cr 107

4d PCBM 1.27 8.1 50 50 3.2 100 mW cm − 2 Cr 108

4d PCBM 0.78 9.1 58 54 4.1 100 mW cm − 2 Cr 109

4c PCBM 0.77 9.5 48 — 3.5 100 mW cm − 2 Cr 112

4e PCBM 0.69 7.8 42 — 2.6 100 mW cm − 2 Cr 112

4f PCBM 0.67 4.1 35 — 1 100 mW cm − 2 Cr 112

4g PCBM 0.65 1.4 28 — 0.3 100 mW cm − 2 Cr 112

4h PCBM 0.30 1.49 35 — 0.15 100 mW cm − 2 LC 116

4i PCBM 0.51 5 54 — 1.5 100 mW cm − 2 Cr 113

4j PCBM 0.67 6.6 57 — 2.5 100 mW cm − 2 Cr 113

4k PCBM 0.69 8.4 50 — 2.9 100 mW cm − 2 Cr 113

4m PCBM 0.73 10.8 59 — 4.7 100 mW cm − 2 Cr 113

Abbreviations: Cr, crystalline; Colh, columnar hexagonal; DLC, discotic liquid crystal; EQE, external quantum efficiency; FF, fill factor; JSC, short circuit current; LC, liquid crystalline; PCBM, [6,6]-
phenyl-C61-butyric acid methyl ester; PCE, power-conversion efficiency; VOC, open circuit voltage.

rectangular columnar mesophases. Photovolatiac solar cells were of ITO increases while it decreases on argon plasma treatment.
prepared using various Pc–tetrabenzoporphyrin hybrid macrocycles The VOC depends both on the organic–organic interface as well as
mixed with PC70BM in ITO/MoOx/BHJ/Al structures and solar cell on the electrode–organic interface. The UV–ozone treatment of ITO
performance was measured under AM 1.5G illumination at an decreases VOC, whereas it increases on the argon plasma treatment.121
intensity of 100 mW cm − 2. PV parameters of these devices are In 2010, Jeong et al.71 used TP discotics as an additive to
presented in Table 2. The best PCE of 4.7% with VOC of 0.73 V, JSC well-established P3HT:PC61BM BHJ OPV device to realize the effect
of 10.8 mA cm − 2 and FF of 59% was achieved for the devices on PCE. The devices configured with P3HT:PC61BM (1:1.2 w-w) layer
prepared from C6TBTAPH2 mixed with PC70BM. doped with 2,3,6,7,10,11-hexaacetoxytriphenylene (3 wt%) exhibit an
Fujii and co-workers also used Pc DLCs 4d and 4e as additives average PCE of 3.97% after thermal annealing. In comparison, the
in classical BHJ thin-film solar cells based on P3HT and reference cells display only 3.03% PCE. Two derivatives of TP,
[6,6]-phenyl-C61-butyric acid methyl ester (PCBM).69,70 The PV namely, 2,3,6,7,10,11-hexaacetoxytriphenylene 5b and 2,3,6,7,10,11-
devices show EQEs of 74, 66 and 47% at a wavelength of 540 nm hexamethoxytriphenylene 5c were used to fabricate OPV devices.
without CnPcH2, with C6PcH2 and with C7PcH2, respectively. The However, it may be noted that both these compounds do not show
PCE of the solar cell without CnPcH2 was 2.3% with ISC of any thermotropic mesomorphism.
8.6 mA cm − 2, VOC of 0.57 V and FF of 48% that improves to 3.0% A year later, Zheng et al.122 reported the use of a well-known DLC,
with ISC of 12.1 mA cm − 2, VOC of 0.56 V and FF of 44% with namely, 2,3,6,7,10,11-hexabutoxytriphenylene (HAT4) 5d (Figure 10)
C6PcH2. However, the addition of C7PcH2 does not show much as an additive to improve the PCE of P3HT:PC61BM-based solar cells.
improvement in PCE. The TP discotics (HAT4) disperse in the active layer to form a
Jurow et al.116 synthesized a mixture of various thioalkyl-substituted more efficient pathway for charge carriers. The influence of
Pc derivatives 4h. Number of thioalkyl-substitution was estimated in charge-carrier mobility with annealing and insertion of HAT4
between 3 and 10. Some of these mixtures were reported to be discotic discotic were studied. The hole and electron mobilities of the pristine
liquid crystalline. Solar cells prepared from these materials exhibit PCE P3HT:PC61BM blended system devices were recorded as 7.86 × 10 − 6
in between 0.06% and 0.15%. and 5.35 × 10 − 5 cm2 V − 1 s − 1, respectively, after thermal annealing.
On dispersion of HAT4, hole and electron mobilities increase to
TP DISCOTICS IN PVS 4.50 × 10 − 5 and 2.32 × 10 − 4 cm2 V − 1 s − 1, respectively. They
TP-based DLCs are the most rigorously studied materials. More than demonstrated that both JSC and FF were increased without changing
1000 TP DLCs have been prepared and studied for various physical the VOC. PCEs up to 3.5% were realized in these devices. The
properties.117–119 Because of their good photoconducting and improvement in JSC and FF was attributed owing to efficient
charge-carrier mobility behavior, it was obvious to look for their use photoinduced charge transfer in BJH solar cells by inserting HAT4.
in PV solar cells.50 Chemical structures of TP DLCs used in PVs are The AFM (atomic-force microscopy) images of HAT4 film surface
presented in Figure 10. PV parameters of some best-performing before and after annealing are shown in Figures 11a and b. The
devices are tabulated in Table 3. The first report appeared in 2005 sectional morphology of the device after thermal annealing is shown in
when Oukachmih et al.120 prepared two-layered devices using TP Figures 11c and d.
ether 5a (Figure 10) as a hole-transporting material and perylene We further explored the use of HAT4 as an additive in classical
derivatives 2d, 2f and 2g (Figure 5) as electron-transporting materials. OPV cells.72 A conventional device was fabricated with cell structure of
These devices showed EQE of around 3%. They studied the effect ITO/PEDOT:PSS/HAT4-PCBM:P3HT/Al and its PV parameters were
of UV–ozone and argon plasma treatment of ITO on the solar cell compared with the device without HAT4. The PCE was improved
efficiency of these devices. On UV–ozone treatment, the work function 63% after addition of the DLC. A significant improvement in JSC from

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Figure 8 Chemical structure of phthalocyanine-based DLCs used in photovoltaics.

Figure 9 AFM images of surface of C6PcH2:PCBM composite thin films: (a) without DIO, (b) with 0.2% v/v of DIO, and (c) with 0.8% v/v of DIO.
Reproduced with permission from Dao et al.110 Copyright 2013 Elsevier B.V. A full color version of this figure is available at the Polymer Journal online.

7.4 to 10.3 mA cm − 2 was observed. This enhancement could be due decreases JSC and PCE. On increasing thickness beyond a certain
to the increased charge-separation efficiency in active layer owing to length, traps are created owing to the dislocation of columns.
HAT4. Thickness of DLC layer have important role in the device. Annealing of the device is also crucial for getting high PCE. On
When the thickness of the layer was 10–20 nm, the maximum value of annealing, traps get healed resulting in improved JSC and efficiency of
JSC and PCE was achieved. Further enhancement in the layer thickness the devices with DLC increased to 12.9 mA cm − 2 and 2.27%,

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Figure 10 Chemical structure of triphenylene-based DLCs used in photovoltaics.

Table 3 Photovoltaic parameters of some best-performing TP DLC-based solar cells

Donor Acceptor VOC (V) JSC (mA cm − 2) FF (%) PCE (%) Illumination source (mW cm − 2) Phase Reference

5a 2d 0.7 0.04 40 — 5.4 Cr 120

5b PCBM 0.67 9.15 64.9 3.97 100 Cr 71

5c PCBM 0.65 9.30 63.6 3.9 100 Cr 71

5d/P3HT PCBM 0.62 10.6 56 3.5 100 Cr 122

5d/P3HT PCBM 0.54 12.90 34 2.27 100 Cr 72

5d/PCDTBT PCBM 0.85 10.40 58 5.14 100 Cr 124

5f PCBM 0.60 6.51 39 1.54 100 Cr 125

5g PCBM 0.60 10.36 64.9 4.03 100 Cr 126

5h/ZnO@N719 PCBM 0.73 16.4 65 8 100 Cr 127

P3HT/TP-S@ZnO — 0.60 4.52 35 0.95 100 Cr 128

Abbreviations: Cr, crystalline; DLC, discotic liquid crystal; FF, fill factor; JSC, short circuit current; N719, ditetrabutylammonium cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato) ruthenium
(II); PCBM, [6,6]-phenyl-C61-butyric acid methyl ester; PCDTBT, poly [N-9′′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)]; PCE, power-conversion efficiency;
P3HT, poly(3-hexylthiophene); TP, triphenylene; TP-S, dithiol-functionalized TP; VOC, open circuit voltage.

respectively. The device without DLC in it did not affect the PCE on having a TP liquid crystalline pendant. The copolymers form an
annealing. Insertion of molybdenum oxide as a buffer layer between extremely well-defined highly ordered nanowires owing to the presence
ITO and active layer also gives similar results.123 of LCs that enhance the charge transport. Diblock copolymers of
We also developed BHJ solar cells based on composites P3HT/P3TPT with molar ratios of 3:1, 6:1 and 9:1 termed H3P1, H6P1
of copolymer poly [N-90-heptadecanyl-2,7-carbazole-alt-5,5- and H9P1 were synthesized. The thin films were solution coated on
(40,70-di-2-thienyl-20,10,30-benzothiadiazole)] (PCDTBT) and the ITO substrate and annealed. The morphology change to the thin film
fullerene derivative PC71BM with an inserted layer of HAT4.124 structures and self-assembly was studied by AFM. Different treatments
Two different materials, poly (3,4 ethylenedioxythiophene)-poly were given to the thin films, such as as-cast, slow film growth (SA),
(styrenesulfonate) (PEDOT: PSS) and molybdenum trioxide (MoO3) thermal annealing (TA) and ortho-dichlorobenzene (o-DCB) vapor
were used as buffer layers between ITO and DLC layers. All the devices annealing followed by thermal annealing (SA+TA). The OPV device
with inserted DLC layer exhibited better performance compared with based on the SA+TA-treated H9P1/PC61BM blend exhibits the best
reference cells. PV solar cells containing 30-nm thick HAT4 layer performance with a PCE of 1.54%, JSC of 6.51 mA cm − 2, VOC of
display 5.14% PCE under 1 Sun condition. This is a significant 0.601 V and FF of 39.4%, whereas the device based on its analogous
improvement in the PCE compared with earlier reports. block copolymers H6P1 and H3P1 only shows PCE values of 0.99%
TP DLCs as a moiety to form self-assembly with diblock poly- and 0.24%, respectively. The improved PCE results from the interaction
thiophene on side chains were used by Chen et al.125 They synthesized between the TP moieties. The SA+TA treatment can easily drive
diblock copolymers P3HT-block-poly[3-(10-(2,3,6,7,10-pentakis(hexy- interchain π–π interactions to develop the fine formation of crystalline
loxy)triphenylene)decyloxy)thiophene] (P3HT-b-P3TPT) 5f (Figure 10) lamellar aggregation favoring an optimized morphology of the active

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Figure 11 Tapping-mode AFM surface image of HAT4 film, (a) before annealing and (b) after annealing; the inset shows a simplified diagram of the π–π
stacking configuration in HAT4. (c, d) SEM images of the sectional morphology of the device with HAT4. Reproduced with permission from Zheng et al.122
Copyright 2011 Elsevier B.V. A full color version of this figure is available at the Polymer Journal online.

Figure 12 Chemical structure of perylene-based DLCs used in photovoltaics.

Table 4 Photovoltaic performance of perylene, decacylene and other DLCs

Donor Acceptor VOC (V) JSC (mA cm − 2) FF (%) PCE (%) Illumination source (mW cm − 2) Phase Reference

Zinc Pc 6a 0.6 1.6 40 — 100 Cr 129

6b 2a 0.04 0.01 48 — — Cr 130

MEH-PVV 7 1.3 0.03 32 0.30 0.73 Cr 132

9/P3HT 2a 0.60 5.18 51 1.60 100 Cr 134

Abbreviations: Cr, crystalline; DLC, discotic liquid crystal; FF, fill factor; JSC, short circuit current; MEH-PVV, [2-methoxy-5-(20 -ethylhexyloxy)-1,4-phenylenevinylene]; PCE, power-conversion
efficiency; P3HT, poly(3-hexylthiophene); VOC, open circuit voltage.

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layer. Similarly, a DLC block poly(2,3,6,7,10-pentakis(hexyloxy)-11- mesophases and the use of these liquid crystalline materials in PVs
(oct-7-en-1-yloxy)triphenylene) (P3HT-b-PTP) 5g (Figure 10) was is presented here. Kim and Bard129 prepared an organic donor/
used to configure PV device structure of P3HT-b-PTP):PCBM)/LiF/ acceptor heterojunction PV devices based on a non-LC zinc Pc (ZnPc)
Al.126 The highest PCE of 4.03% is achieved when the concentration of as donor and a liquid crystalline perylene diimide, N,N-diheptyl-
P3HT-b-PTP is 5%, with a JSC of 10.36 mA cm − 2 and an FF of 64.91%. 3,4,9,10-perylenebiscarboximide (PTCDI) 6a (Figure 12) as acceptor
They further prepared dye-sensitized nanoarrays (NAs) with DLC with the cell configuration ITO/ZnPc/PTCDI/Ga:In. The device with
interlayer for high-efficiency inverted polymer solar cells. Inverted D and A thickness of 100 nm generated FF of 22%, with a JSC value of
polymer solar cells were fabricated with well-aligned and highly 0.40 mA cm − 2 and VOC of 0.60 V. The FF was improved by 40% with
uniform one-dimensional ZnO nanoparticles with organic ditetrabu- a JSC value of 1.58 mA cm − 2 and VOC of 0.60 V (Table 4) by lowering
tylammonium cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarbox- the donor and acceptor thickness to 25 nm. The better performance
ylato) ruthenium(II) (N719) dye and 3,6,7,10,11-pentakis(hexyloxy)- of thin active layer device was attributed to the efficient separation of
2-hydroxytriphenylene 5e (Figure 10).127 The N719 shell and N719/ excitons and facile transport of free charges in thin layer.
LC double-shells were introduced to modify the interface between the In another study, Archambeau et al.130 used a benzoperylene LC 6b
active organic layer and ZnO NAs. The self-organization of DLC as an electron donor in conjunction with another perylene-based
facilitate the active layer components to rearrange, leading to a more acceptor 2f (Figure 2). Compound 6b is actually a mixture of four
orderly nanomorphology of active layer and consequently reduces the
regioisomers, which exhibit a columnar mesophase at ambient
probability of electron/hole recombination at the interface donor/
temperature and clears at 180 °C. The device exhibits an FF value of
acceptor materials. The best PCE of the device with only dye-coated
48% with low VOC of 0.4 V.
NAs was 7.3%, which increases to 8% when the NAs were coated with
dye and DLC.
Chen et al.128 extended their work by synthesizing DLC ligands
DECACYCLENE DLCS IN PVS
dithiol-functionalized TP (TP-S) 5h modified ZnO nanoparticles
1,7,13-Trialkanoyloxydecacyclene DLCs exhibit very interesting
(TP-S@ZnO). Hybrid solar cells based on a blend of P3HT and
physicochemical properties and can be prepared easily by direct
TP-S@ZnO were prepared and characterized. They reported that
Friedel–Crafts acylation of parent hyderocarbon.131 Owing to the
‘DLC ligands improve the compatibility between P3HT polymer and
presence of keto groups, they act as electron-deficient
ZnO nanoparticles, which is beneficial for enhanced charge separation
molecules. Hirota et al.132 utilized discotic liquid crystalline
and transfer efficiency. DLC molecular interface modification can
1,7,13-heptanoyldecacyclene (C7DC) 7 (Figure 13) as an electron-
provide a viable and interesting method to promote the compatibility
and a large interfacial area between polymers and nanocrystals, which accepting layer in a [2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylene-
improve the performance of the device. The self-assembly of TP-S vinylene] (MEH-PVV)-based solar cell. The PV device with ITO|
ligands tends to provide a better pathway for electrons and holes for PEDOT:PSS|MEH-PVV|C7DC|LiF/Al structure was prepared by spin-
transporting in the active layer’.128 Solar cells with a conventional coating PEDOT:PSS and MEH-PVV/C7DC on ITO/glass substrate
device configuration ‘ITOPEDOT:PSS/active layer/LiFAl’ were followed by vacuum deposition of LiF/Al. Crystal-like C7DC domains
prepared. The BHJ devices based on P3HT/ZnO film showed a PCE buried in MEH-PVV were observed in AFM images of active layer.
of 0.46%, which improves to 0.51% on directly grafting the ligand Poor miscibility of C7DC and MEH-PVV resulted in distinct phase
TP-S onto ZnO NPs and annealing the sample at 130 °C. The device separation between MEH-PVV and C7DC. The PV cell showed JSC of
based on TP-S@ZnO/P3HT showed an improvement with a PCE of 3.6 μA.cm2, VOC of 1.3 V and FF was 32% with PCE of 0.14%, which
0.70%, which further improves to 0.95% on annealing the sample at increased to 0.30% upon annealing the device at 100 °C.
130 °C.

PERYLENE DLCS IN PVS

Perylene tetracarboxylic acid bisimides commonly known as
perylenebisimides are among the best n-type organic semiconductors
known to date. Many non-LC perylenebisimide derivatives have been
used as electron acceptor in PV solar cells. Upon appropriate
peripheral substitution, perylene derivatives exhibit columnar

Figure 14 Chemical structure of benzo[o]ditriphenyleno[2,1,12,11-efghi:

Figure 13 Chemical structure of 1,7,13-heptanoyldecacyclene. 11′,12′,1′,2′-uvabc]ovalene DLCs.

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BENZO[O]DITRIPHENYLENO[2,1,12,11-EFGHI:11′,12′,1′,2′- DIBENZO[A,C]PHENAZINE DLCS IN PVS

UVABC]OVALENE DLCS IN PVS Lee et al.134 attached a 2,3,6,7-tetra-6-hexyloxydibenzo[a,c]
Müllen and co-workers explored the ‘bottom-up’ approach to build phenazine-11-carboxylic acid discotic monomer to polyacrylamide.
DLCs derived from large polycyclic aromatic hydrocarbon cores, The resultant polymer (DLC-PAM) 9 (Figure 15) exhibits a hexagonal
defined as ‘nano-graphene’ structures formed by π–π stacking. columnar mesophase. It was used to prepare a conventional
With appropriate flexible alkyl chains, these larger aromatic cores P3HT/PCBM cell with an active layer of DLC-PAM. The optimized
lead to DLCs with enhanced columnar stability and supramolecular thickness of the PAM-DLC layer was 90 nm to enhance the charge
order with improved charge-carrier transport owing to the transport. The JSC and VOC values of 5.18 mA cm − 2, and 0.60 V,
more extended p-orbital overlap.133 DLCs with three swallow-tailed respectively, with 51% FF and 1.60% PCE were achieved in this device.
alkyl substituted (benzo[o]bistriphenyleno[ 2,1,12,11-efghi:2′,1′,12′,
11′-uvabc] ovalene, 8 (Figure 14), were prepared and utilized to CALAMITIC LCS IN PVS
fabricate solar cells. Crystalline PDI 2a (Figure 2) was used as an Calamitic or rod-like LCs have primarily been explored in display
electron acceptor. Scanning electron microscopic investigations devices and conducting impurities are considered as ‘black sheep’ in
revealed homogeneous bicontinuous phase across the thickness with these materials. However, as the dark conductivity and photo-
PDI crystals evenly dispersed in the liquid crystalline matrix. This conductivities of nematic, smectic and cholesteric materials were
morphology could be favorable for hole and electron migration in measured in 1969,135 calamitic LCs also became interesting materials
donor and acceptor domains. PV devices with ITO/DLC-PDI/Ag for semiconducting applications.135 Kamei et al.136 studied the PV
structure were fabricated by spin-coating from a chloroform solution effect in the nematic LC (NLC) in 1972 and observed the maximum
of a mixture of donor and acceptor materials. The highest device VOC of 0.5 V. Kelly and co-workers, in a series of papers,137–140
efficiency was observed for blends with donor and acceptor ratio of 4:6. reported the preparation of real PV devices from various calamitic
EQE up to 19% was achieved at 490 nm for these graphene discotics. LCs. PV parameters of some best-performing calamitic LC-based solar
cells are presented in Table 5. Nematic gel template is formed from a
mixture of polymerizable mesogen 10a and non-polymerizable
mesogen 10b (Figure 16), which contains phase-separated droplets
of LC in crosslinked polymer. Compound 10a with terminal double
bonds is a reactive mesogen that forms a nematic glass at room
temperature on cooling. Compound 10b exhibits a monotropic
nematic phase stable down to room temperature. These materials
have an ionization potential of 5.31 eV, so that they are suitable for use
as an electron-donating species in the gel. Compound 11a is an
electron-withdrawing perylene derivative having fluorene groups. In
Figure 15 Chemical structure of polymer DLC-PAM. the thin film of compound 11a, rapid quenching introduces a glassy

Table 5 Photovoltaic parameters of some best-performing calamitic LC-based solar cells

Donor Acceptor VOC (V) JSC (mA cm − 2) FF (%) PCE (%) Illumination source (mW cm − 2) Phase Reference

10a:10b 11a 1.37 — 25 0.6 45 N 137

10c 11a 1.2 — 26 0.9 24 N 138

10d 11a 1.31 — — 0.8 0.28 N 139

10d 11a 1.2 0.50 36 0.93 24 Cr 140

10e PCBM 0.67 9.55 53 3.4 100 Cr 142

12 PCBM 0.59 10.7 50 3.2 100 Cr 143

13 PCBM 0.41 1.23 24 0.12 100 Cr 144

14 ZnO 0.83 2.10 35 0.61 100 Cr 145

15 ZnO 0.81 4.71 52 1.98 100 Cr 146

17 PCBM 0.57 7.84 57 2.57 100 Cr 147

18/ZnO — 0.64 3.77 51 1.23 100 Cr 148

19/ZnO — 0.63 2.98 47.5 0.89 100 Cr 149

12/CdS — 0.60 4.32 46.9 1.23 — Cr 150

20 PCBM 0.54 4.42 23.6 0.56 100 Cr 126

21/22/PBDTTT-C-T PCBM 0.77 16.4 58.7 7.49 — Cr 152

23 PCBM 0.72 16.03 64.9 7.6 100 Cr 152

25a PCBM 0.93 8.27 55 4.3 100 Cr 153

26 PCBM 0.90 13.90 77 9.3 100 Cr 154

27a PCBM 0.56 11.2 47 2.9 100 Cr 155

27b PCBM 0.2 3.68 37 0.27 100 Cr 156

28a PCBM 0.60 8.86 61.1 3.27 100 Cr 157

28b PCBM 0.60 9.64 63.9 3.72 100 Cr 157

28c PCBM 0.63 10.08 54.9 3.5 100 Cr 158

Abbreviations: Cr, crystalline; FF, fill factor; JSC, short circuit current; LC, liquid crystal; PBDTTT-C-T, poly(4,8-bis(5-(2-ethylhexyl)thiophene-2-yl)-benzo[l,2-b:4,5-b′]dithiophene-alt-alkylcarbonyl-
thieno[3,4-b]thiophene); PCBM, [6,6]-phenyl-C61-butyric acid methyl ester; PCE, power-conversion efficiency; VOC, open circuit voltage.

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Figure 16 Chemical structure of fluorene-thiophene donors and perylene-based acceptors.

state. It has a high EA of 3.94 eV and therefore can be used as an In another study, they prepared organic bilayer PV cell with an
electron-accepting material. From ionization potential and EA data, it insoluble electron-donating layer formed by crosslinking a nematic
is clear that charge separation at the interface is thermodynamically reactive mesogen.140 In a nematic reactive mesogens, a planar align-
favorable in these donor–acceptor couples. A mixture of 10a and 10b ment with the long molecular axis aligned on the substrate plane can be
in the ratio 1:2 forms a gel, which displays a nematic phase that achieved upon crosslinking.141 The performance of the device is limited
remained stable at room temperature for a long period. A PV device by the charge-carrier mobility of the acceptor material, which can be
with cell structure of ITO/PEDOT:PSS/LC gel/LiF/Al was fabricated enhanced by the electron-donating layer formation by mesogens.
that exhibits EQE of 5.3% and PCE of 0.6%. A number of PDI-based crystalline and liquid crystalline acceptors
They extended their work by taking four different perylene-based having fluorine or carbazole moieties were prepared (Figure 16).
electron acceptors having similar EAs but different thermotropic Bilayer solar cells prepared from crosslinkable donor 10d and
phases and two fluorene–thiophene LCs 10c and 10d (Figure 16). 138 acceptors 11a, 11c, 11e and 11f exhibit PCEs in between 0.42% and
Best results are obtained when the nematic donor is mixed with an 0.93%. It was observed that crosslinking of the monomer 10d by
amorphous acceptor to give a super-cooled nematic glass at room irradiation with UV light to obtain an insoluble layer does not degrade
temperature. AFM reveals phase separation on a nanometer scale with device performance
a broad distribution of domain sizes. PV device with a blend of donor Kekuda et al.142 demonstrated the effect of donor–acceptor interface
10c and acceptor 11a showed the best PCE of 0.9%.138,139 on the performance of BHJ device. They reported performance of a

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Figure 17 Chemical structure of calamitic LCs used in photovoltaics.

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Figure 18 (a) A schematic representation of the device configuration (up) of a bulk heterojunction solar cell based on PBTTT:PCBM (1:3 wt %) and the
associated energy level diagram (bottom). (b) J–V characteristics of the ITO/PEDOT/PBTTT:PCBM (1:3 wt %)/Al solar cells at different substrate temperatures.
The inset shows the PCE values as a function of the substrate temperature. (c) J–V characteristics of the ITO/PEDOT/PBTTT:PCBM/Al solar cells with
different weight ratios of PBTTT to PCBM at the substrate temperature of 50 °C. The inset shows the JSC and PCE values of the devices as a function of
the PBTTT:PCBM weight ratio. (d) Topographical (up) and phase (bottom) AFM images of pure PBTTT films and PBTTT:PCBM (1:3 wt %) films on the
ITO/PEDOT substrate. Reproduced with permission from Sun et al.143. Copyright 2009, American Chemical Society. A full color version of this figure is
available at the Polymer Journal online.

device based on a commercially available liquid crystalline polymer cynaobiphenyloxy)-hexyl) thiophene](P3HbpT) 14 (Figure 17) having
poly(9,9′-dioctylfluorene-cobithiophene) (F8T2) 10e (Figure 16). The well-known LC cyanobiphenyl was prepared by attaching 4’-hydro-
conventional device configuration ITO/PEDOT:PSS/F8T2/C70/Al xycyanobipheny to 3-(6-bromohexyl)thiophene followed by nuclear
showed a PCE of 3.4% after annealing the polymer LC films at 200 °C. bromination of thiophene ring and its polymerization. It shows liquid
Sun et al.143 used liquid crystalline poly(2,5-bis(3-alkylthiophen-2-yl) crystalline property with order morphology and microstructure.145
thieno[3,2-b]thiophene) (PBTTT) 12 (Figure 17) to fabricate a ZnO nanoparticles were dispersed in it and a hybrid BHJ device
bilayer device (Figure 18) composed of the active layer of PBTTT: was prepared with the active layer of P3HbpT/ZnO. PCE of 0.61% was
PCBM (1:2)/MDMO-PPV:PC70BM (1:4) and compared the results achieved.
with single layer (PBTTT:PCBM or MDMO-PPV:PC70BM) devices. The work was extended by the synthesis of a new donor–acceptor-
The exact nature of the mesophase has not been revealed in this paper. type liquid crystalline copolymer, poly[3-(6-(cyanobiphenyoxy)thio-
The bilayer device exhibited a VOC of 0.59 V, JSC values of phene)-alt-4,7-(benzothiadiazole)] (P3HbpT-BTD) 15 (Figure 17).146
10.1–10.7 mA cm − 2, FF of 50% and PCE values of 3.0–3.2%, which This liquid crystalline copolymer was reported to have good optical
were significantly (by a factor of 2) higher than single-layer devices. absorption abilities and spontaneous organizational properties on
Hindson et al.144 used liquid crystalline triphenylamine-based poly thermal annealing. The devices based on P3HbpT-BTD and ZnO
(azomethine)s as hole-transport materials in typical ITO/PEDOT:PSS/ nanoparticles show the PCE of 1.98% after annealing the composites
TPA/PCBM/Al devices. 4,4′-Diaminotriphenylamine (TPA) was poly- at 180 °C. The reason to the better performance could be ascribed
merized with either terephthalaldehyde (TPA-14Ta), 2,5-thiophene- owing to the self-assembly of mesogens, which induce the ZnO
dicarboxaldehyde (TPA-25Th) or 1,3-isophthalaldehyde (TPA-13Iso) nanoparticles to form a well-dispersed and highly orientated region
to yield various polymers. Structure of one of these polymers 13 is that resulted in better hole and electron transport.
shown in Figure 17. The HOMO and LUMO energy levels of these In continuation to their work on thiophene-based LC donors, they
polymers were in the range of 5.0–5.3 and 2.4–3.3 eV. PV devices prepared novel copolymer systems PBbTTT-T 16 and PBbTTT-TT 17
show the best PCE value of 0.12%, with VOC of 0.41 V, JSC of with high crystallinity and photocrosslinkable building blocks for
1.23 mA cm − 2and FF of 24% after annealing the composite at 200 °C. p–p intermolecular interactions by copolymerization of 2,5-bis
Chen and co-workers used various calamitic LCs to prepare PV (3- bromododecylthiophen-2-yl)thieno[3,2-b]thiophene (BbTTT) mono-
solar cells.126,145–152 An electron-donor material poly[3-(6-(4- mer with thiophene and thieno[3,2-b]thiophene.147 The solar cell

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device that consist of PBbTTT-TT:PC71BM in 1:3.5 ratio shows the Liquid crystalline calamitic molecules DPBT-S 19 and PBTTT 12
PCE of 2.57%. This could be ascribed owing to the high order and were also used to prepare CdS nanocrystals for PV solar cells.150
crystallinity of the LC material and also to the enhanced stability A solution of LC and CdS precursor in chlorobenzene was spin-casted
owing to the photocrosslinkable bromine-functionalized unit. and annealed at different temperatures to decompose the CdS
In another study, they demonstrated the OPV device based on precursor to generate CdS nanoparticles embedded in LC matrix.
P3HT/ZnO hybrid system by employment of liquid crystalline The efficient charge transfer in the LC/CdS nanocomposites makes
ligands 4-(5-(1,2-dithiolan-3-yl)pentanoate)-4′-(hexyloxy)-terphenyl these materials suitable to be used as an active layer in PV solar cells.
18 (HTph-S) at interface to induce the compatibility, charge PV devices with inverted architecture (glass/ITO/ZnO/CdS interface
separation and transfer efficiency enhancement and optimized layer/active layer/MoOx/Ag) were fabricated and the best PCE of 1.2%
micro-morphology.148 The device configuration was ITO/PEDOT: was realized.
PSS/HTph-S@ZnO/P3HT. The effect of modification of active layer They also synthesized P3HT-based liquid crystalline rod-coil block
and annealing of layer was demonstrated. The unmodified ZnO/P3HT copolymers, that is, rod-like LC block poly(4-(dodecyloxy)-4′′-(oct-7-
showed a JSC of 2.01 mA cm − 2, VOC of 0.57 V and an FF of 41% en-1-yloxy)-1,10:4′,1′′-terphenyl), 20 (P3HT-b-Pterph).126 The
with low 0.47% PCE, but the device containing active layer of configured device architecture ITO/PEDOT:PSS/P3HT-b-Pterp exhibit
HTph-S@ZnO/P3HT gives the JSC of 3.77 mA cm − 2, VOC of 0.64 V PCE of 0.34–0.44%, which improve to 0.56% for P3HT-b-Pterph after
and an FF of 51%, resulting in PCE of approximately 1.23%. Similarly, annealing at 200 °C. Corresponding PV devices with DLC block poly
ZnO nanoparticles passivated by a layer of 4,7-diphenyl-2,1,3-ben- (2,3,6,7,10-pentakis(hexyloxy)-11-(oct-7-en-1-yloxy)triphenylene),
zothiadiazole-based LC molecules 19 were prepared149 and used in (P3HT-b-PTP) show better performance than those based on P3HT:
P3HT/ZnO hybrid PV devices. The LC-ZnO layer acts as an PCBM:P3HT-b-Pterph. It has been attributed that ‘the DLC block in
electron-acceptor layer in hybrid solar cells and also enhances the P3HT-b-PTP is more favorable in interpenetrating networks and also
order and crystallinity of P3HT chains. Moreover, the order of more compatible with the fullerene acceptors. This is because liquid
the P3HT/LC-ZnO blend morphology is significantly enhanced after crystalline state annealing promotes the orientation of mesogens to
thermal annealing at 160 °C, which improves PCE by 1.8-fold induce polythiophene backbone packing with higher ordering, which
compared with the device based on P3HT/ZnO. PCE up to 0.89% further enhances the charge-carrier mobility and improves the JSC’.126
was realized in these devices. Chen et al.151 also demonstrated that ionic LCs (ILCs) can be self-
assembled with conjugated polymer as an interlayer to achieve high
PCE via rapid LC-induced dipole orientation in polymer-based solar
cell. The ILCs 3-((2′-(4″-cyanobiphenyl-4-yloxy)ethyl)dimethylam-
monio)propanesulfonate 21 (CbpNSO) with zwitterionic charges
were blended with cationic conjugated polyelectrolyte (CPE) poly
[3-(6-trimethylammoniumhexyl)-thiophene] 22 (PTNBr) to afford a
novel CPE − ILC complex. It has been pointed out that ‘the
spontaneous orientation of LC favors more ordered structural
arrangement in CPE − ILC complexes. LC-assisted electrostatic
assembly can improve the orientation of dipole moments at
cathode interface, which significantly reduces the work function of
ITO. Compared with pure PTNBr CPE as electron transport layer
(ETL), CPE − ILC complex increases the efficiency of P3HT:PCBM
cell by 37%. Solar cell prepared with donor poly(4,8-bis(5-(2-
ethylhexyl)thiophene-2-yl)-benzo[l,2-b:4,5-b′]dithiophene-alt-alkyl-
Figure 19 Chemical structure of DPP-TP6 and DPP-TP12. carbonyl-thieno[3,4-b]thiophene) (PBDTTT-C-T) and acceptor

Figure 20 (a) J − V characteristics under 1 sun illumination (inset: dark J − V curves) and (b) IPCE spectra for BHJ solar cells based on DPP-TP6:PC71BM
(1:1, w/w) blend as-cast and after thermal annealing at 140 °C for 10 min. Reproduced with permission from Shin et al.153 Copyright 2013, American
Chemical Society. A full color version of this figure is available at the Polymer Journal online.

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PC70BM in the presence of PTNBr-CbpNSO exhibits PCE of (S)-5-octyloxy-2-[{4-(2-methylbuthoxy)-phenylimino}-methyl]-phe-

7.49%’.151 nol 27a (Figure 23) in a P3HT/PCBM BHJ organic solar cell. The
Recently, they also synthesized LC-conjugated polyelectrolytes poly charge-carrier mobility of the composites increased on addition of the
[9,9-bis[6-(4-cyanobiphenyloxy)-hexyl] − fluorene − alt-9,9-bis(6- LC material. The addition of LC in P3HT:PCBM solar cells increases
(N,N-diethylamino)-hexyl)-fluorene] 23 (PF6Ncbp) and poly[9,9-bis JSC from 4.1 to 11.2 mA cm − 2 and result in substantial improvement
[6-(4-cyanobiphenyloxy)-hexyl] − fluorene − alt-9,9-bis(6-(N-methylimi of PCE from 1.1% to 2.9%. The LC forms a nanomorphology between
dazole)-hexyl]-fluorene] 24 (PF6lmicbp) (Figure 17) by covalently donor and acceptor phases owing to the higher degree of order of
linking cyanobiphenyl mesogen with conjugated polyelectrolytes.152 films, which leads to the improved photocurrent, larger IPCE values
It has been pointed out that ‘after deposition of a layer of and higher PCE. They extended their work on another smectic
LC-conjugated polyelectrolytes on ZnO interlayer, the spontaneous LC, namely, 5-(10-undecenyloxy)-2-[[[4-hexylphenyl]imino]methyl]
orientation of LC groups can induce a rearrangement of dipole phenol 27b (Figure 23).156 The addition of LC improves the
moments at the interface, which leads to the better energy-level crystallinity of the P3HT layer, the JSC from 0.53 to 3.68 mA cm − 2
alignment’. The orientation of dipoles can be successfully improved and PCE from 0.008% to 0.27%.
without interference and can also induce the upper active layer to Jeoung et al.157 incorporated classical NLCs 4-cyano-4’-pentylbi-
form better crystallization morphology, which facilitate the electron phenyl 28a (5CB) and 4-cyano-4’-octylbiphenyl 28b (8CB) in a typical
extraction and transportation. Significant PCE of 7.6% can be P3HT:PC61BM solar cells. They reported that ‘the incorporation of
achieved by deposition of LC polyelectrolytes PF6Ncbp and PF6lmicbp NLC additives led to a higher absorbance in blend thin film, a higher
on ZnO as ETL. crystallinity of P3HT, closer P3HT chains, larger PC61BM domains
Shin et al.153 observed PV properties of diketopyrrolopyrrole (DPP)- and enhanced hole/electron mobilities even without postthermal
based mesomorphic small-molecules, 3,6-bis{5-(4-alkylphenyl)thio- annealing’. The non-annealed cell with 4 wt% 8CB additives showed
phen-2-yl}-2,5-di(2-ethylhexyl)-pyrrolo[3,4-c]-pyrrole-1,4-diones 25 an increase in all parameters, resulting in PCE of 3.72% compared
(DPP-TP6 and DPP-TP12, Figure 19). DPP-TP6 with hexyl terminal with 2.14% of the reference device without NLC additives. The JSC is
chains exhibits LC properties while the higher homolog DPP-TP12 strongly dependent on the absorption intensity derived from the
was found to be non-mesomorphic. BHJ PV solar cells were fabricated crystallinity of P3HT and the charge-transport properties of networks
using DPP-TP6 and DPP-TP12 as an electron donor and PC71BM as in PV blend films, hence the blending of the LC in blend enhance the
an acceptor with a typical device structure; ITO/PEDOT:PSS/donor: absorption peak improving the spectral overlap with solar emission at
PC71BM blend/LiF/Al. Solar cells with DPP-TP6:PC71BM films show a 603 nm for the P3HT and this further leads to closer π–π stacking of
PCE as high as 4.3% with a VOC of 0.93 V and an FF of 55%, the P3HT and lower to the band energy.
while only 1.2% PCE could be realized for DPP-TP12 (Figure 20). Shi et al.158 used 4-octyloxy-4’-cyanobiphenyl 28c (8OCB), another
This clearly demonstrates that molecular organization induces the classical NLC to evaluate the performance of P3HT:PCBM solar cell.
self-assembly, which is auspicious to fabricating high-performance Pristine P3HT:PCBM device and the devices with the LC weight
solution-processable solar cells. ratios of 3, 6 and 10 wt% exhibited a JSC of 8.11, 9.10, 10.08 and
Recently, Sun et al.154 synthesized a new molecular donor NLC 6.36 mA cm − 2, respectively. The device performance depends on
benzodithiophene terthiophene rhodanine 26 (Figure 21) and doping percentage of NLC, too much additives led to a lower JSC
fabricated a device (Figure 22), which shows the promising PCE of because of the decreased crystallinity and the phase separation in large
9.3% with FF of 77%, which is rare in OPV devices. They attributed scale, which were unfavorable for charge transport. The performance
that the donor phase in OPV is well ordered, which favors the exciton was better after mixing 6% 8OCB and annealed at 70 °C, which gives
diffusion length for efficient charge separation. Interestingly, thick the JSC of 10.08 mA cm − 2 and high FF of 54.9%. The annealing
solar cells with active layer of thicknesses up to 400 nm also exhibits temperature of 70 °C in liquid crystalline transitions facilitated the
high FF of ~ 70% and high PCE of ~ 8%. formation of an optimized phase separation in P3HT:PCBM:8OCB
system (Figure 24). PCE up to 3.5% was realized.
CALAMITIC LCS AS ADDITIVES IN PVS
Similar to DLCs, the effect of doping calamitic LCs on the PV LCS IN DSSCS
performance of classical solar cells have been studied.155–158 DSSCs are highly promising candidates for the next-generation PVs
Canli et al.155 investigated the effect of a chiral smectic LC namely owing to their low fabrication cost and good PCE. After the pioneering

Figure 21 Chemical structure of BTR.

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Figure 22 Device architecture and photovoltaic performances. (a) Schematic diagram of a normal cell architecture used in this study. (b) J–V characteristics
of BTR:PC71BM BHJ solar cells with or without THF solvent vapor annealing tested in air under 98 mW cm − 2 AM 1.5G illumination. Inset: dark current
plotted in a semi-log scale of the two solar cells. (c) EQE spectra of optimized BTR-based solar cells with or without THF SVA treatment. (d) J–V curve of the
most efficient BTR:PC71BM BHJ solar cell after 15 s of THF SVA measured by an independent research institute in nitrogen atmosphere under an
illumination of 100 mW cm − 2. Reproduced with permission from Sun et al.154 Copyright 2015, Nature Publishing Group. A full color version of this figure is
available at the Polymer Journal online.

Figure 23 Chemical structure of calamitic LCs used as additives in photovoltaics.

work of O’Regan and Grätzel,159 huge interest has been developed in oxidized dye receives electrons from I− ion redox, and the iodide is
these PV devices and PCE values up to 13% has been achieved.160 oxidized into I3−. The process continues and the circuit is completed.
A schematic structure of a DSSC is shown in Figure 25. DSSC differs As ionic conductivity is quite important in DSSC, early efforts have
from both BHT and bilayer solar cell by its basic construction and been made to use ILCs in these devices.161,162 Yamanaka et al.161
operational process. A DSSC basically consists of a sandwich structure synthesized a new ILC, 1-dodecyl-3-methylimidazolium iodide
of nanocrystalline TiO2/dye-electrolyte between transparent anode and 29 (C12MImI, Figure 26), and used in DSSC cells as a hole transport
counter cathode. As shown in Figure 25, the light photons are layer to enhance the JSC and PCE. The bilayer structure of inter-
absorbed by the dye adsorbed over TiO2 nanocrystals that provides digitated alkyl chains of the imidazolium cations in ILC with the
larger surface area for absorption. In this process, the dye molecules smectic A phase localized the I− and I3− between the smectic A layers.
absorb the photons and excited electrons flow into TiO2 and become The exchange reaction can be promoted by the presence of localized
oxidized. Electrons travel to anode, external load and finally to the high concentration of I− and I3− ions. The higher conductivity of the
cathode, where it transferred to electrolyte usually containing I −/I3. LC-conjugated electrolyte leads to high value of JSC compared
The electrolyte works as brokers between cathode and TiO2. The with non-liquid crystalline ionic liquid electrolyte.161 The higher

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Figure 24 AFM images of P3HT:PCBM:8OCB films with 8OCB weight ratio of 3 wt% (a), 6 wt% (b) and 10 wt% (c) after annealing at 70 °C for 20 min, and
the films with 8OCB weight ratio of 6 wt% without (d) or with annealing (e) at 130 °C for 10 min, respectively. Reproduced with permission from
Shi et al.158 Copyright 2014, Springer-Verlag Berlin Heidelberg. A full color version of this figure is available at the Polymer Journal online.

redox species in the quasi-solid-state DSSCs. Kim et al.163 mixed the

classical LC mixture E7 in a polymer electrolyte and demonstrated the
effect of the function of the concentration rate of the LC on the PCE
and the FF of the DSSC. The polymer electrolyte consists of ethylene
carbonate, propylene carbonate, acetonitrile, tetrabutylammonium
iodide, iodine, 1-propyl-3-methylimidazolium iodide and
polyacrylonitrile (PAN). The quasi-solid-state DSSCs with optimized
concentration of LC as 10 wt% exhibit the best PCE of 4.52%
(Table 6).
They further studied the effects of LC E7 or ML-0249 addition in
PAN-based electrolyte composed of I −/I3− redox species.164 The high
order and molecular arrangement of the LC incarcerated in polymeric
electrolyte molecules creates the transport pathway of redox species.
This high mobility and transportation of carriers improved the
photocurrent density and also the PV performance. The devices based
Figure 25 Schematic representation of a typical DSSC. A full color version on ML-0249:PAN (1:1) was fabricated and showed a VOC of 0.703 V,
of this figure is available at the Polymer Journal online. JSC of 13.57 mA cm− 2, FF of 66.8% and PCE of 6.29% and E7:PAN
(3:1) device showed a VOC of 0.719 V, JSC of 13.27 mA cm − 2, FF of
conductivity of ILC is attributed to the enhancement of the exchange 65.1% and PCE of 6.21% at 1 Sun. It has been revealed that ‘the
reaction between iodide species, which was supported by the large higher ionic conductivity of the LC embedded in polymeric electro-
exchange reaction-based diffusion coefficients.162 They utilized these lytes leads to enhancement in both JSC and FF of the quasi-solid-state
ILCs to prepare a quasi-solid-state DSSC by incarcerating a low DSSCs, which significantly improved the PV performance’.164
molecular weight gelator. Furthermore, improvement to the PCE Karim et al.165 prepared solar cells with device configuration of
could be achieved on addition of 5.0 g l− 1 gelator to ILC, which also SnO2:F|TiO2|N719|polymer LC electrolyte|pt where the polymer
increase JSC owing to the enhancement of the conductivity of the electrolyte was composed of iodine, tetrabutylammoniumiodide,
liquid crystalline gel electrolyte.162 The device exhibits JSC value of 1-propyl-3-methylimidazolium iodide, ethylene carbonate/propylene
7.7 mA cm − 2. Full characterization of these devices has not been carbonate (EC/PC, 3/1 as weight ratio), PAN or click polymers as a
revealed. polymer matrix, LC (ML-0249) as a plasticizer and acetonitrile.
Similar to LC additives in BHJ solar cells, efforts have also been Click polymers (Figure 26) were prepared from 2,7-diazido-9,
made to evaluate the performance of DSSC by adding LCs. The 9-dioctylfluorene and 2,7-diethynyl-9,9-dioctylfluorene, respectively,
embedded LC induced a diffusing pathway, which may increase the using CuI-catalyzed (P1) and non-CuI-catalyzed (P2) click polymer-
ordering strength in the electrolyte and enhance the transportation of ization. The liquid electrolyte was trapped in the polymer matrix to

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Figure 26 Chemical structure of LCs used in DSSCs.

Table 6 Photovoltaic performance of quasi-solid state DSSCs with liquid crystals

LC Dye VOC (V) JSC (mA cm − 2) FF (%) PCE (%) Illumination source (mW cm − 2) Phase Reference

E7 N719 — — 63 4.52 — Cr 163

ML-0249 N719 0.703 13.57 66 6.29 100 Cr 164

30/ML-0249 N719 0.65 10.73 68.5 4.78 100 Cr 165

7CB/PVDF C106 0.685 17.20 68 8.01 100 Cr 166

E7 N719 0.72 14.62 64.8 6.82 100 Cr 167

HHTT N719 0.95 0.534 88.2 0.45 100 Cr 73

33 N719 0.46 8.3 — 1.5 100 Cr 168

34 D205 0.67 14.6 60 5.8 100 SmA@30 °C 169

35 D205 0.67 5.9 40 1.6 100 Cr@30 °C 169

35 D205 0.55 10.1 43 2.4 100 SmA@90 °C 169

36 D205 0.54 1.0 31 0.2 100 SmA@30 °C 169

36 D205 0.55 10.9 35 2.1 100 SmA@90 °C 169

Abbreviations: Cr, crystalline; DSSC, dye-sensitized solar cell; FF, fill factor; HHTT, hexahexylthiotriphenylene; JSC, short circuit current; LC, liquid crystal; PCE, power-conversion efficiency;
PVDF, poly(vinylidenefluoride-co-hexafluoropropylene); VOC, open circuit voltage.

ML-0249 (1:3) system showed the highest PV performance with a

PCE of 4.78%. It has been described that ‘by using LC, the viscosity of
the electrolyte became low, which provided high diffusion properties
of the I3 − ion. As a result, the performance of the DSSC was
improved’.165
Wang et al.166 used the classical NLC, 4-cyano-4’-n-heptyloxybi-
phenyl (7CB), into the poly(vinylidenefluoride-co-hexafluoropropy-
lene) (PVDF)-based polymeric gel electrolyte for quasi-solid-state
Figure 27 The geometry of DSSC with discotic electrolytes. A full color DSSC. The device architect FTO|TiO2|C106|LC-PVDF|Pt were fabri-
version of this figure is available at the Polymer Journal online. cated, DSSC with the PVDF electrolyte shows a JSC of 14.89 mA cm − 2,
VOC of 685 mV, FF of 74% and an PCE of 7.54% upon adding of the
generate polymer electrolyte. The DSSCs without ML-0249 (LC) LC was into the PVDF-based polymeric gel electrolyte, no change in
showed a PCE of 3.53% for PAN-based electrolyte. The highest PCE the VOC, a decrease in FF and a remarkable increase (from 14.89 to
of 4.70% and 4.78% were resulted for the DSSCs devices for P1: 17.20 mA cm − 2) in the JSC were obtained with higher PCE of 8.01%.
ML-0249 (1:3) and PAN:ML-0249 (1:3), respectively. The PAN: This change is attributed to ‘the light trapping scheme formed by the

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Figure 28 The schematic illustration of the assembly of LC electrolytes into layered smectic A phases and an LC-based dye-sensitized solar cell. Blue areas
represent insulating parts, and red areas show ion conductive parts. FTO, fluoride-doped tin oxide. Reproduced with permission from Högberg et al.169
Copyright 2016, American Chemical Society. A full color version of this figure is available at the Polymer Journal online.

addition of LC, the optical path of incident light is enhanced and Very recently, Kato et al.169 developed nanostructures of liquid
consequently the light harvesting efficiency, which benefit the crystalline electrolytes 34-36 (Figure 26) to prepare DSSCs. They
generation of photoelectron. Therefore, the electron diffusion demonstrated two types of electrolyte assemblies, first as non-covalent
coefficients and diffusion length of the DSSC were enlarged as well assemblies of two-component mixtures consisting of I2-doped
as photocurrent density, which offsets the lower FF and results in imidazolium ionic liquids and carbonate-terminated mesogenic
higher PCE’.166 compounds and second as single-component mesogenic compounds
Ahn et al.167 developed DSSCs composed of LC-embedded covalently bonded with an imidazolium moiety doped with I2
electrospun polymer gel electrolyte. Two types of solar cells (Figure 28). The fabricated device with components 34 shows PCEs
having electrospun poly(vinylidene fluoride-co-hexafluoropropylene) of 5.8 ± 0.2%, with VOC of 0.65 V, JSC of 14.6 mA cm − 2 and FF of
(e-PVdF-co-HFP) polymer gel electrolyte were fabricated; first with 60% in the liquid crystalline smectic phase at 30 °C. The PCE
doping of E7 LC and, in another device, without doping with the LC decreases to 0.9 ± 0.1% in the isotropic phase at 120 °C. DSSC
E7 and with a liquid electrolyte. DCCS containing the E7-embedded prepared from 35 exhibits PCE of 2.4% in the smectic phase at 90 °C.
e-PVdF-co-HFP polymer gel electrolyte show a much higher The efficiency decreases both in the crystalline phase at 30 °C to 1.6%
PCE of 6.82% than that of an e-PVdF-co-HFP nanofiber as well as in the isotropic phase at 120 °C to 1.4%. However, in the
covalent-type electrolyte 36, the PCE increases with temperature in the
(6.35%) with VOC of 0.72 V, JSC of 14.62 mA cm − 2 and FF of
smectic phase. It shows PCE of 0.2% at 30 °C in the SmA phase, which
64.8% values.
increases to 2.4% at 120 °C in the same LC phase. These liquid
In DSSC, the use of iodine solution is highly problematic owing to
crystalline DSSCs have been reported to exhibit excellent stability over
its corrosive nature. Recently, we demonstrated the use of discotic
1000 h.
mesogenic molecules, hexahexylthiotriphenylene 31 (HHTT) and
hexahexyloxytriphenylene 32 (HAT6) as iodine-free redox electrolyte
SUMMARY AND OUTLOOK
in DSSCs (Figure 27).73 The cell shows VOC of 0.95 V, JSC of Past few years have witnessed tremendous development in the field of
0.534 mA cm − 2, FF of 88.24% and overall PCE of 0.45% in a typical OPVs owing to the predicted limited availability of fossil fuels and
fluorine-doped tin oxide/TiO2/N719/HHTT/Pt DSSC configuration. the impact of burning of these hydrocarbons on environment.
The discotic material acts as charge carrier and mediator in these The potential inexpensive fabrication, lightweight, flexible,
solar cells. semitransparency and so on of solar cells made of organic materials
Guldi et al.168 demonstrated the effect of LC phases in solid-state make them one of the most promising candidates for environmentally
DSSCs. They synthesized novel imidazolium-based ILCs, which shows acceptable and commercially viable energy devices. A number of
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dye and hole transport is accumulated by the presence of liquid in OPVs is currently a subject of great importance. In this paper, we
crystalline phase, which gives rise to the stability of the device. have given an overview of the development of liquid crystalline

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Manish Kumar was born in Jerathi, India in 1989. He is a PhD student at Soft-condensed matter Group (SCM), Raman Research
Institute, Bengaluru, India under the supervision of Professor Sandeep Kumar. He received his MTech in Nanotechnology from Amity
University, Noida, India in 2014. His major interests are the synthesis and characterization of novel functional liquid crystalline
nanocomposites, fabrication of organic solar cell, OLEDs and nanomaterial synthesis. His research currently focuses on the synthesis of
functionalized metallic and semiconducting nanostructures materials and their self-assembly in discotic liquid crystals.

Sandeep Kumar obtained his PhD in Chemistry-Medicinal Chemistry from Banaras Hindu University, Varanasi in 1986. He was a
Postdoctoral Research Fellow at the Hebrew University of Jerusalem, Jerusalem, Israel; Technion, Israel Institute of Technology, Haifa,
Israel; the Scripps Research Institute, La Jolla, CA, USA and the University of Mainz, Mainz, Germany during 1988–1995. He joined the
Centre for Liquid Crystal Research, Bengaluru, India to start a new Chemistry laboratory in 1995. In 2002, he moved to the Raman
Research Institute, Bengaluru, India. He was a visiting Research Professor at the Naval Research Laboratory, Washington DC, USA
during 1999–2000 and the National Dong Hwa University, Hualien, Taiwan during 2008 and E.T.S. Walton Visiting Professor at the
Trinity College, Dublin during 2012–2013. He has published 220 research papers in peer reviewed international journals. He also
authored a book entitled ‘Chemistry of Discotic Liquid Crystals: from monomers to polymers and several book chapters. He is also
having many patents in his credit. He was awarded the inaugural LG Philips Display Mid-Career Award by the International Liquid
Crystal Society in 2008. His current research interests include design, synthesis and applications of liquid crystals, green chemistry and
nanotechnology.

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