10.1515 - Oph 2015 0007

Org. Photonics Photovolt.
2015; 3:71–100
Review Article Open Access
Nagesh B. Kolhe, Shekhar Shinde, B. Saibal, and S. K. Asha*
Novel Approaches in the Design of Donor-Acceptor

Oligomeric and Polymeric Materials for
Photovoltaic Applications: D/A Blend versus
Self-assembly of D/A by Covalent or Non-Covalent
Interaction
DOI 10.1515/oph-2015-0007 ules have kept the field ongoing [10–13]. The basic OPV
Received October 14, 2014; accepted May 12, 2015 device architecture consists of a photo-active layer of or-
ganic /polymeric semiconductor sandwiched between in-
dium tin oxide (ITO) electrode (anode) and metal elec-
trode (cathode) [3]. Tang implemented modifications in-
1 Introduction volving a bilayer heterojunction OPV device comprising of
p-type donor and n-type acceptor as active layer, which im-
Organic semiconducting materials involving small π- proved the device performance [1, 9]. The working princi-
conjugated molecules as well as polymers are fast grow- ple of such device involves the light absorption by active
ing members in the family of potential materials for har- layer which lead to creation of electron-hole pair i.e. ex-
vesting non-conventional source of energy like the solar citon. The next step is the dissociation of excitons; which
radiation [1–8]. Organic photovoltaic cells (OPVs) are a recombined by emitting photon or non-radioactive recom-
revolutionary technology which converts the solar radia- bination if eventual separation to its component electron
tions into electrical energy using organic/polymeric semi- and hole did not occur within the short exciton diffusion
conducting material (active layer). The technology has lenght [1, 3, 6–8]. Once the charges are separated into elec-
become very promising due to its low fabrication cost, trons and hole, they move towards the respective electrode
lightweight, large area and mechanical flexibility. The ma- and finally charge collection leads to electric current. The
jor breakthrough in OPV was created by Tang et al. who charge extraction is driven by internal electric field in cell
reported the first hetero junction organic solar cell with caused by different work function of electrodes. It is widely
power conversion efficiency (PCE) ~1% [1, 9]. Although in- accepted that the exciton diffusion at D/A interface is the
tensely researched for more than two decades, the effi- most important step that depends upon how the donor and
ciency of organic solar cell remains lower compared to ef- acceptor are arranged in the nanoscopic length scale of
ficiency based on inorganic crystalline silicon which has about 10–20 nm which is critical to the exciton life time.
reached up to ~25%. However, promising breakthroughs in Generally, the life time of exciton is very short with diffu-
terms of better device performance efficiencies, device de- sion length limited to 5–20 nm after which they will recom-
signs as well as longer outdoor performance of test mod- bine and fail to generate free charges [3, 6, 8]. The exci-
ton diffusion is considered to be the most important aspect
during design of active layer of solar cell. Therefore, mor-
*Corresponding Author: S. K. Asha: Polymer Science and En- phology of the active layer component (donor-acceptor)
gineering Division, CSIR-National Chemical Laboratory, Dr Homi
plays a vital role in the device efficiency of solar cells [14].
Bhabha Road, Pune 411008, India; Academy of Scientific and Inno-
vative Research, New Delhi, India; CSIR-Network Institutes of Solar
For instance, the bilayer solar cell (Figure 1a) comprising
Energy, New Delhi, India; Email: sk.asha@ncl.res.in; Fax: 0091-20- of individual donor and acceptor layer forms large scale
25902615 interface that fail to dissociate sufficient exciton and ends
Nagesh B. Kolhe, Shekhar Shinde, B. Saibal: Polymer Science up with lower solar cell efficiency [15]. This limitation was
and Engineering Division, CSIR-National Chemical Laboratory, Dr overcome to a certain extent by using the "bulk heterojunc-
Homi Bhabha Road, Pune 411008, India; Academy of Scientific and
tion (BHJ)" device architecture (Figure 1b) where the donor
Innovative Research, New Delhi, India; CSIR-Network Institutes of
Solar Energy, New Delhi, India and acceptor materials were intimately blended together
© 2015 S. K. Asha et al., licensee De Gruyter Open.

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivs 3.0 License.
72 | S. K. Asha et al.
beneficial to improve the efficiency of BHJ solar cell de-

vices [18–21]. On the other hand, control over morphology
has been achieved using novel approaches such as D-A
self-assembly by covalent or non-covalent route. Several
reviews have appeared highlighting the merits of the self-
assembly or bottom-up approach for assembling the active
Figure 1: Schematic representation a) bilayer b) bulk-heterojunction
components [22–26]. Similarly, there are reviews project-
(BHJ) and c) ideal BHJ OPV device.
ing the high device efficiency values achieved using D-A
blend of small organic molecules as well as main chain
semiconducting polymers [1, 2, 4]. A review comparing the
two approaches self-assembly by covalent or non-covalent
versus D/A blend, especially in terms of the device effi-
ciency numbers is highly forthcoming. Mainly two aspects
of device performance are targeted in this combination
of donor (D) and acceptor (A) for photovoltaic applica-
tions. The first aspect is the fine-tuning of the energy lev-
els (LUMO and HOMO) and bandgap by the direct cova-
lent linkage of D and A in a single structure [27, 28]. For in-
stance, using this approach polymer with bandgap lower
than 1.6 eV has been reported [29, 30]. Another aspect aims
for the D-A microphase separation to get efficient exciton
Figure 2: A typical current density-voltage (J-V) curves under dark dissociation and charge separation at interface. Both the
(blue) and under illumination (red) for polymer solar cell. Essen- covalent or non-covalent approach could be utilized for
tial parameters determining power conversion eflciency (PCE) are combining D-A to achieve a better microphase separation
shown: J sc , V oc , FF, J max , V max . in active layer. Where the covalent linking becomes syn-
thetically challenging, there a non-covalent self-assembly
to form a composite, which was then deposited as the ac- approach helps to bring the donor and acceptor in close
tive layer [16]. proximity for efficient charge separation to occur in the
In this way donor and acceptor eventually form sev- micro-phase separated domains. The self-assembly or bot-
eral interfaces within the blend at smaller length scale. tom up approach to assemble the organic semiconducting
A major improvement was observed in the efficiency of materials was a prominent or enthusiastically pursued one
solar cell using BHJ device and today it serves as the right from the early 2000s when the potential of the or-
state-of-art concept for polymer based solar cells exhibit- ganic semiconducting materials were recognized for pho-
ing best efficiency of 9.48% [12]. However, the BHJ archi- tovoltaic applications. Even though the self-assembly ap-
tecture also has a drawback that over a period of time proach received such wide publicity, when it came to ac-
or at elevated temperatures, phase separation occurs be- tual device performance it fell way short of expectations.
tween donor and acceptor in the blend creating morpho- On the other hand, the D-A blend approach dominated
logical instability [17]. To overcome this problem the con- the area with the best power conversion efficiencies (PCEs)
cept of ideal bulk heterojunction OPV device (Figure 1c) reported in organic solar cells [31–33]. Poor morphology
was proposed, where donor-acceptor were held together has sometimes been cited as the culprit that prevented
by strong covalent or non-covalent interaction to form the self-assembly approach from attaining its full potential
periodic nano-morphology. In the ideal BHJ device, the as a simple and easy approach towards large scale active
donor and acceptor are expected to form well organized area device fabrication. This is despite the fact that some
microphase separation at length scale (10–20 nm) almost of the most beautiful hierarchical organization of donor
equal to exciton diffusion length which consequently re- and acceptor materials has been achieved through the self-
duce the loss by recombination via better charge sep- assembly route. This contradictory phenomenon makes
aration at D-A interface. Research in terms of the mor- one wonder if the self-assembly route has still not been
phology development of donor-acceptor (D-A) active layer exploited with enough rigor. This review aims to address
has been progressing very fast, the use of additives and this very important question of which approach has been
compatibilizers along with D-A blend were found to be more successful in this D-A blend versus self-assembly by
covalent or non-covalent design for organic photovoltaic
Novel Approaches in the Design of Materials for Photovoltaic Applications. . . | 73
application in the last two decades. The comparison is whereas the fullerene and its derivative such as PC61 BM or
a little difficult since there are not many reports on ac- PC71 BM are extensively investigated as acceptor material
tual device numbers in the case of the self-assembly ap- in donor-acceptor composite solar cell due to several rea-
proach; those available mostly give the charge carrier mo- sons including reversible electrochemical reduction, fa-
bility values only. Photovoltaic performance efficiency of vorable LUMO energy level, excellent electron transport
self-assembled organic semiconducting materials is rare properties and anisotropic charge transport [34–36]. How-
and not very promising. The review covers the traditional ever, recent developments in the synthesis of D-A polymers
D-A blend approach to donor-acceptor (D-A) oligomers and with high electron affinity, improved electron transport
polymers and compares it with the supramolecular ap- and solution processability has made it possible to use this
proach towards D-A assemblies. Before starting further D-A polymer as the acceptor material in all-polymer so-
discussion on the topic, some of the important parameters lar cells [37–40]. Furthermore, increased absorption up to
that are used to describe solar cell efficiency are mentioned visible region with high molar extinction coefficient com-
here. Figure 2 shows a typical current density -voltage (J- pared to fullerene makes them very attractive as alter-
V) curve of organic photovoltaic device in dark and under natives to fullerene based acceptors. Although the donor
illumination. In dark there is no current flow in circuit and polymer are considered to be as more responsible for the
J − V curves passes through the origin. When the cell is il- light absorption and exciton formation, the acceptor can
luminated, the J − V curves are shifted down in the fourth also absorb the photon to create exciton, after dissocia-
quadrant of the graph from which lot of valuable parame- tion of which the hole is transferred to the HOMO of donor
ters can be extracted such as short circuit current density to realize charge separation at D-A interface [28]. There-
(J sc ), open circuit voltage (V oc ), fill factor (FF) and power fore, light absorbing low band gap D-A polymers were
conversion efficiency (PCE or η). found to be beneficial for better photon harvesting and
J max and V max are the value of maximum current den- thereby increase the photocurrent in solar cell [7, 41, 42].
sity and voltage respectively on the J-V curve which is used Some of the well-studied alternative systems from the fam-
to calculate the fill factor. The PCE in solar cell is defined ily of conjugated D-A polymers include those based on
as the amount of power produced by cell relative to the perylenediimide, naphthalenediimide, diketopyrrolopyr-
power available in incident solar radiations (P in ). Pin is role, isoindigo etc. There are several ways in which the
sum over all wavelengths and generally fixed at intensity donor-acceptor conjugated polymers can be linked like D-
100 W/cm2 . The equation to calculate PCE is given in Fig- A alternative polymer, donor-block-acceptor or randomly;
ure 2 which shows that PCE is proportional to the J sc , V oc all of which require different synthetic strategies to ac-
and FF. The value J sc depends upon the photon harvest- complish the polymer architecture. Conjugated polymers
ing capability of active layer, charge separation at D/A in- are generally synthesized by the step-growth polymeriza-
terface, charge transport and collection at electrodes. V oc tion mechanism and are not amenable to the controlled
is dictated by energy gap between LUMO of acceptor and polymerization methodologies that produce block poly-
HOMO of donor. Therefore the following factor has to be mers following the chain-growth kinetics. However, recent
taken into account while designing the material for OPV advances in synthetic methodology have enabled the pre-
application. 1) Broad and strong absorption in visible and cise construction of fully conjugated D-A polymers in var-
near IR region to match with solar spectrum 2) Suitable ious architectures like block, random or alternating. Com-
LUMO and HOMO energy level to maintain V oc as well bination of different polymerization strategies can also
as energy offset for exciton dissociation at D-A interface be used to obtain the desired D-A permutations. Main
3) High charge carrier mobility (hole mobility for donor chain conjugated polymeric structures are formed by C-C
and electron mobility for acceptor) to enhance the charge bond formation reactions like Suzuki [43], Stille [44], Ya-
transport 4) Optimum morphology of D-A with nanoscale mamoto [45], Heck [46], Wittig-Horner [47–49] etc. Con-
phase separation within active layer which influences J sc , trolled polymerization methods like the Grignard Metathe-
V oc and FF. sis (GRIM) polymerization also has proved successful in
developing regioregular polymers as well as multiblock
polymers with narrow size distribution based on a variety
of different donors and acceptors [50, 51]. Block copoly-
2 All-Polymer Solar Cells mers based on donor blocks with acceptor units as pen-
dants from acrylic or vinylic backbones also were reported
Presently, poly (3-alkylthiophene) and its several ana-
to form lamellar or cylindrical morphologies [52]. The ran-
logues are majorly used as p-type (donor) material
dom donor-acceptor systems mostly involved post modifi-
Chart 1: Chemical structures of some p-type donor polymer used in the solar cells.
cation of donor blocks with pendant acceptor units, based molecules as well as polymers. There are several very good
on fullerene or perylenediimide (PDI). The covalent D- review articles on small molecule based D-A assemblies
A linkage has been adapted successfully to both small applied in photovoltaic applications [1–3]. Therefore, only
Chart 2: Chemical structures of perylenediimide (PDI) based D-A polymers used in all-polymer solar cells and OFETs.
the oligomeric and polymeric designs involving covalent intramolecular charge transfer (ICT) band in their absorp-
linkage of donor and acceptor- randomly, alternatively or tion spectrum which is accounted for by the photoinduced
as block will be presented here. Among the various donors intramolecular charge transfer from donor to acceptor. The
and acceptors, the choices for suitable donors are far more decrease in the band gap reduction is strongly dictated by
than for acceptors. For the sake of simplicity, the D-A poly- the strength of donor and acceptor units present in the
mers have been classified as those based on fullerene ac- conjugated backbone. Therefore, proper selection of D-A
ceptor and those based on other than fullerenes. segments is very important which would allow the fine
tuning of energy level and band gap of final polymer. Com-
pared to the D-A block polymer synthesis, where it is very
2.1 D-A Polymer/Polymer Blend Solar Cell difficult to purify and separate any unwanted homopoly-
mer block, the D-A alternating copolymers are easier to
2.1.1 Alternate D-A Linkage develop and purify. The number of reports on covalently
linked D-A polymers with broad absorption is continu-
The alternate D-A linkage or the "push-pull" approach in- ously increasing in the literature. They are successfully im-
volved in the synthesis of polymer was introduced in the plemented as acceptor materials in combination with vari-
1990s and is known to result in low band-gap conjugated ous known donor polymers (Chart 1) in all-polymer BHJ so-
polymers. They are spectroscopically well identified by the
lar cells. Recently the highest power conversion efficiency tuted polythiophene (PT1) as a donor exhibited power con-
(PCE) of 6.71% was achieved by using naphthalenedi- version efficiency around 1%. They further modified the
imide based D-A copolymer as acceptor in an inverted so- polymer structures by adding two dithienothiophene moi-
lar cell structure [53]. The all-polymer solar cell devices eties in the polymer backbone [56] by which the PCE of the
are typically fabricated in two ways - the first is the con- device was increased after changing the donor/acceptor
ventional (normal) structure with ITO/PEDOT:PSS/active weight ratios. The optimized device gave PCE of 1.48%,
layer/LiF/Al and the other is the inverted type structure the devices were optimized at a blend ratio of 3:1 (D: A,
with ITO/ZnO/active layer/MoO3 /Ag configuration. Small w/w). This was one of the earliest reports of bay substi-
modifications in cathode (Al or Ag), buffer layer (LiF or Ca) tuted rylenediimides with donor groups linked in conju-
or electron transporting and hole transporting layer are gation at the bay position. These early reports initiated a
also sometimes used in the basic device architecture. flurry of research activity on this bay substituted rylenedi-
Throughout the review, such minor modifications will not imide family of perylene and naphthalenediimides. Alter-
be specified; the device configuration should be consid- nating donor-acceptor copolymers (structure PDI-3) based
ered as the conventional (normal) structure unless specifi- on PDI and oligothiophene (n=2, 3) linked at the bay posi-
cally mentioned as inverted solar cell device configuration. tion was reported by Kozma et al. [57] The polymer showed
The milestones in all-polymer solar cells comprising cova- ambipolar charge transport characteristics with wide ab-
lently linked D-A alternate copolymer as acceptor layer in sorption range. All-polymer solar cells were constructed
a blend with donor polymer is discussed in the following using this polymer as the acceptor material and poly-3-
section. The list of donor (p-type) polymers which are com- hexylthiophene (P3HT) as the donor polymer, which ex-
monly used along with D-A polymers (n-type) in blend and hibited power conversion efficiencies of 0.8% and 0.4% for
discussed throughout the review is given in Chart 1. oligothiophene with n=2 and 3 respectively. Tajima’s and
Hashimoto’s group compared the device efficiency of a se-
ries of perylenediimide linked at the bay position (struc-
(A) Perylenediimide Based D-A Polymer ture PDI-4) to various donor moieties including vinylene,
thiophene, dithieno[3,2-b :2’, 3-d]pyrrole, fluorene, diben-
The chemical structures of perylenediimide (PDI) based D- zosilole, and carbazole in all-polymer solar cells where
A polymers discussed in this section are shown in Chart 2. two polythiophene derivatives (P3HT and PT1) were used
One of the early examples of photovoltaic device using as the donor polymers [58]. The highest power conversion
the alternating D-A polymer structure was the one based efficiency of 2.23% was obtained for polymer PDI-4 (PC-
on OPV as the donor and PDI as the acceptor PDI-1 re- PDI) having carbazole as co-monomer after spin-coating
ported by the group of Mikroyannidis et al. [54] They re- from a solvent mixture of toluene/chloroform 9:1. The ef-
ported a high electron mobility of 0.85×10−2 cm2 /V s ob- ficiency was quite high compared to that reported for all-
tained using space charge limited current (SCLC) mea- polymer based solar cells reported until then. Pai’s group
surements for the polymer. This D-A polymer was used reported two polymers (structure PDI-5, PDI-6), having
in combination with poly(3-phenyl hydrazone thiophene) difference in attachment of dithiophene donor at position
(PPHT) as the donor polymer in solar cell where a power of 1, 7 (rPDI-diTh) and mixed 1,7 and 1,6 (iPDI-diTh) of
conversion efficiency of 1.67% to 2.3% was observed. The perylenediimide along with a bulky, branched alkyl chain
PDI based donor-acceptor combination has also been re- at the imide position, thereby suppressing the π–π inter-
ported with PDI linked through the bay (core) position. actions between perylenediimide units [59]. The blend of
Their synthesis is easily achieved using any of the C-C regioregular rPDI-diTh with P3HT showed PCE of 2.17% in
bond forming reactions between suitably functionalized inverted solar cell device configuration, whereas the iPDI-
donor and acceptor co-monomers. Core-substituted alter- diTh exhibited PCE of 1.55% with similar blending ratio
nating perylenediimide and dithienothiophene polymer 1:1.5.
PDI-2 was developed by Marder’s group [55] and used as Very recently, good solar cell performance was re-
an electron transport polymer with electron mobilities in ported for all-polymer solar cells using polymer structure
the range of 1.3×10−2 cm2 /V s. The increased conjugation PDI-2 as the acceptor and PBDTTT-CT as donor polymer by
afforded by the direct linkage of the perylenediimide aro- Cheng and co-workers [31]. They used a molecule having
matic core to the dithienothiophene resulted in absorption similar structure as the repeat unit of the acceptor poly-
covering the visible region and extending into the near-IR. mer as non-volatile additive along with 1,8-diiodooctane
The 1:1 blend of all-polymer solar cells fabricated using this (DIO) as a solvent additive. The additives not only facili-
polymer as acceptor and a bi(thienylenevinylene) substi- tated improved mixing with the donor polymer, it also fa-
Chart 3: Chemical structures of naphthalenediimide (NDI) based D-A polymers used in all-polymer solar cells and OFETs.
cilitated aggregation and crystallization resulting in a high in all polymer solar cell along with PBDTTT-CT as donor
PCE of 3.45%, which was one of the highest reported value polymer. All polymers except the PDI parent, showed PCE
for all-polymer solar cells based on perylenediimides. Ge of ~0.2% irrespective of NDI/PDI composition in polymer
et al. reported 2,1,3-benzothiadiazole (BT) containing PDI backbone whereas the parent PDI polymer exhibited PCE
polymers PDI-7 and PDI-8. PDI-8 had additional acety- of 0.57%. This result showed that PCE was not NDI/PDI
lene linkage between PDI and BT unit which gave it more composition dependent, but rather solely dependent on
planar backbone compared to PDI-7 [60]. However, all- the presence of NDI unit.
polymer solar cell based on PDI-7 as acceptor and P3HT as
donor polymer showed much better performance with PCE
of 0.15% than those based on PDI-8 with PCE of 0.07%. (B) Naphthalenediimide Based D-A Polymer
Kozycz et al. reported random copolymers PDI-9 having
different composition of two acceptors PDI and NDI (25:75, The bay substituted naphthalenediimide (NDI) based
50:50, 72:25) with one donor 2,7 carbazole [61]. Also parent copolymers cover a wide family of alternate D-A polymers
copolymers containing carbazole donor and PDI or NDI ac- and chemical structures of naphthalenediimide (NDI)
ceptor were synthesized and used as acceptor component based D-A polymers discussed in this section are shown
in Chart 3. The synthesis of the NDI monomer is easily donor to acceptor using chloroform as the solvent. Fur-
carried out using alkylation of 2,6-dibromo naphthalene- thermore, the addition of additive 1,8-diiodooctane (DIO)
1,4,5,8-tetracarboxylic dianhydride (NDI-Br2) at the imide was found to be very effective in improving the PCE, where
position [62]. The research on the bay substituted naph- the increased PCE was attributed to improved face-on π–π
thalenediimide linked donor acceptor polymers was ini- stacking of the all-polymer blends which facilitated charge
tiated by the group of Fachetti with the synthesis and transport from active layer to electrode. Recently, Jen and
later commercialization of P(NDI2OD-T2, NDI-10); as Poly- coworkers reported fluoro-substituted NDI polymer NDI-
eraActivInk N2200 (Bay substituted naphthalenediimide 11, where they modified the structure of NDI-10 through
with a bithiophene alternating comonomer), which has substitution of thiophene unit with electron withdrawing
shown very high electron mobilities up to ~0.85 cm2 /V s fluorine atom as well as side chain engineering [53]. A
in organic field effect transistors (OFETS ).63 P3HT/NDI-10 maximum PCE of 6.3% was achieved using PTB7-Th/NDI-
blends have shown ambipolar FET characteristic with bal- 11b blend which further increased to 6.7% after side
anced electron and hole mobilities of 4×10−3 cm2 /V s and chain engineering in PTB7-Th/NDI-11c blend; these val-
2×10−3 cm2 /V s respectively [64]. The initial reports of so- ues were significantly higher than PCE of 5.28% obtained
lar cell device performance of the bay substituted naph- for the non-fluorinated analogue NDI-10, also the value
thalenediimide polymer NDI-10 independently by Loi’s was among the best PCEs reported so far all-polymer so-
and Sirringhaus’s groups were not very promising [65, 66]. lar cells. The blend of fluorine substituted NDI polymer
A maximum PCE of 0.2% was obtained using solvents like with donor PTB7-Th showed higher thin-film crystallinity
chlorobenzene (CB), p-xylene, dichlorobenzene (DCB), or with preferential face on orientation which facilitated the
chloroform for device fabrication. Further improvement vertical charge transport in devices to give in higher FF
in PCE to 1.4% was reported by Neher and coworkers us- and J sc . Moreover, they exhibited slightly higher LUMO
ing P3HT as donor and NDI-10 as acceptor material us- value and wide band gap which lead to high V oc com-
ing a 1:1 solvent mixture of p-xylene and chloronapthalene pare to NDI-10. The groups of Fachetti and Marks reported
(CN) [67]. This dramatic effect of the solvent was attributed the photovoltaic properties of newly synthesized NDI co-
to aggregation of the polymer in solvents like chloroben- polymerized with alkoxy-functionalized thienyl-vinylene
zene, p-xylene, dichlorobenzene, or chloroform, whereas (TVTOEt) building-block (NDI-12). The all-polymer solar
the polymer aggregation was completely suppressed in cell fabricated from the blend of PTB7: NDI-12 showed PCE
the 1:1 solvent mixture of p-xylene: chloronaphthalene. of 1.7% [70].
The group of Fachetti and Marks recently reported the In general, the bay substituted NDI-donor structure
performance of BHJ solar cells fabricated using NDI-10 has been widely explored in all-polymer solar cells in com-
and PTB7 as donor polymer [68]. Using systematic film bination with various donor polymers. Several aromatic
morphology optimization, PTB7: NDI-10 all-polymer so- and heteroaromatic moieties have been used as donor in
lar cell were fabricated using chlorobenzene, xylene, and the bay substituted NDI- donor structure. The recent re-
chloroform as processing solvents, which exhibited PCE view by Sommer gives a very good overview of the bay sub-
of 1.35%, 2.7% and 1.78% respectively. They observed that stituted naphthalenediimide polymers, their synthesis as
the morphology, microstructure, charge transport, and well as a wide array of the aromatic co-monomer "donor"
photovoltaic response of all-polymer solar cells were very that has been used in an alternate D-A combination in
sensitive to film processing parameters. A high PCE ex- photovoltaic devices [71]. Some of the best PCE’s for the
ceeding 4% was recently reported by the group of Ben- D-A alternating polymers based on bay substituted NDI-
ten and Ito using a structure NDI-10 as the acceptor and donor has been reported from Jenekhe’s group. In fact,
poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl- alt - the last two years have seen a huge jump in the reports of
thiophene-2,5-diyl] (PTQ1) as the donor polymer [69]. Sev- new structures based on bay substituted naphthalenedi-
eral blending ratios of the donor and acceptor were tested imide. As a structural modification, Jenekhe and coworker
for the all- polymer solar cell, among which a 70:30 wt% replaced bithiophene donor by biselenophene group in
combination of PTQ1: NDI-10 showed short-circuit current structure NDI-10 to achieve structure NDI-13 (PNDIBS).
density of 8.85 mA/cm2 , a fill factor of 0.55, and open cir- This newly synthesized crystalline copolymer acceptor ex-
cuit voltage of 0.84 V resulting in PCE exceeding 4% [41]. hibited high electron mobility of 0.07 cm2 /V s and PCE of
Kim’s group demonstrated the PCE of 4.6% in all-polymer 0.9% in all-polymer solar cell comprised of NDI-13 as an
solar cells by using NDI-10 as acceptor and PTB7-Th as the acceptor and P3HT as donor [72]. Later on they reported
donor polymer [32]. The inverted type solar cell device was all-polymer inverted solar cells based on bay substituted
fabricated by using optimized blend ratio of 1.3:1 (w/w) naphthalenediimide-selenophene copolymer (PNDIS-HD;
structure NDI-14a) as the acceptor and a thiazolothiazole performance in solar cell [75]. They synthesized a series
copolymer (PSEHTT) as the donor, which exhibited power of napthalediimide-thiophene polymer (NDI-15) with dif-
conversion efficiency of 3.3% [73]. The device which had ferent alkyl side chains and used them as acceptor in in-
a short circuit current density of 7.78 mA/cm2 was com- verted solar cell along with donor PTB7-Th polymer. The
parable to the best solar cells based on PC61 BM and PSE- polymer with shorter chain 2-hexyldecyl side chain NDI-
HTT. The thiophene based NDI polymer PNDIT (structure 15a exhibited highest PCE of 6%. Takimiya and coworkers
NDI-15c) under identical conditions gave device efficiency added a new D-A copolymer naphthodithiophenediimide
of 1.3%. Compared to the thiophene based NDI polymers, and bithiophene (PNDTI-BT-DT; structure NDI-18), to the
the selenophane based NDI polymers have slightly smaller library of NDI based copolymer that absorbed strongly in
band gap, enabling better near IR light harvesting. Aver- the near IR region [76]. A PCE of 2.6% was obtained in
age charge carrier mobility of the donor-acceptor blend all-polymer solar cells fabricated using this copolymer as
measured using both OFET and SCLC devices showed bal- acceptor along with PTB7 as donor. The copolymer ex-
anced electron and hole transport for NDI-14a: PSEHTT hibited higher NIR response up to 900 nm compared to
blend as the active layer. Jenekhe’s group achieved so- other reported acceptors and showed external quantum ef-
lar cells with PCE 4.4% and short circuit current density ficiency (EQE) of 25% at 800 nm. Although heteroaromatic
of 10.4 mA/cm2 using naphthalenediimide-selenophene groups like thiophene and thiophene based derivatives
copolymer (PNDIS-x-BO; structure NDI-16) as the acceptor have dominated as the bay-position linked co monomers,
and PSEHTT as donor in an inverted solar cell device [33]. reports citing other donor moieties like those contain-
Compared to the PCE value of 2.62% for the combination ing only aromatic units like OPV oligo (phenyleneviny-
PSEHTT/NDI-14b, a high PCE of 3.61% was obtained for lene) have also emerged. Our research group reported NDI
the combination PSEHTT/NDI-16 (random incorporation based alternating D-A polymers with OPV as the donor
of NDI with butyl octyl (BO) side chain; x=30%) demon- moiety linked at the bay position of NDI (structure NDI-
strating the influence of side chain engineering of the alkyl 19) [77]. Balanced ambipolar charge transport was ob-
substituent. Higher incorporation of the short BO alkyl served for this polymer with electron and hole mobilities
substituted NDI increased the crystallinity and electron 3.09×10−3 cm2 /V s and 2.1×10−3 cm2 /V s respectively. Ne-
mobility thereby enhancing the photocurrent. PCE of 4.4% her and coworkers synthesized one new NDI based accep-
was obtained for the combination PSEHTT/NDI-16 after tor polymer by using dithienothiophene (CPDT) as donor
ZnO surface modification and device optimization. The moiety P (NDI-TCPDTT) NDI-20 [67]. The solar cell de-
same group also reported mixed NDI and PDI containing vice fabricated using P3HT as donor showed PCE of 1.1%
(NDI-17) copolymer which was synthesized using differ- and FF of up to 0.70 using tetralin as solvent. Higher
ent random incorporation of ethyl hexyl containing PDI J sc was obtained using tetralin as solvent compared to
monomer (x=10%, 20%, 30%, 50%) into 2-hexydecyl con- other solvents such as p-xylene, chloroform and 1:1 mix-
taining NDI monomer along with selenophene as common ture of p-xylene and chloronaphthalene. Tajima and co-
co-monomer [74]. The random copolymer NDI-17 having workers [78] synthesized NDI based polymer acceptor NDI-
30% incorporation of PDI as the acceptor and PBDTTT- 21 by incorporating fluorene as donor moiety by Suzuki
CT as donor in an inverted solar cell device showed coupling. Bulk heterojuction solar cells were fabricated us-
good performance with the PCE of 5.1% which was fur- ing NDI-21 polymer along with two polythiophene deriva-
ther increased up to 6.3% after ZnO surface modifica- tives, P3HT and PT2, as donors. Almost similar photo-
tion. On the other hand, NDI-14a without incorporating voltaic performance of P3HT: NDI-21 and PT2: NDI-21 was
of PDI unit showed maximum PCE of 1.23%. Further- observed (PCE 0.64–0.78%), when spin-coated from three
more, PBDTTT-CT/NDI-17 also exhibited higher V oc and different solvents, namely, chlorobenzene (CB), ortho-
higher current density of (J sc ) of 18.55 mA/cm2 compared dichlorobenzene (DCB), and xylene. By adding DIO as a
to best performing PC71 BM: PBDTTT-CT solar cell de- solvent additive to optimize the mixing morphology of the
vice which showed maximum current density J sc of 15.5– P3HT: NDI-21 combination, the PCE and fill factor (FF)
17.7 mA/cm2 . This dramatic increase in the current den- reached values of 1.63% and 0.66, respectively. Apartfrom
sity and PCE is accounted for by the optimum bulk crys- this, several other NDI based donor-acceptor alternating
tallinity of NDI-17 (30% PDI) that facilitated the compat- polymers incorporating a variety of donors have been re-
ibility in blend with given donor polymer (PBDTTT-CT). ported and implemented in solar cell devices; however
Kim and coworkers demonstrated the use of side chain their power conversion efficiencies were not very encour-
engineering in NDI based polymer to get optimum crys- ageable [79–82]. Zheng and co-workers reported three new
tallinity and blend morphology which lead to improved building blocks of angular shaped NDI polymers as an
Chart 4: Chemical structures of D-A polymers (other than rylenediimide and fullerene) used in all-polymer solar cells.
acceptor with increasing number of thiophene as donor in Chart 4. One of the earliest reports of all-polymer
units (1–3) structure NDI-22. These polymers exhibited solar cells was from the groups of Friend and Heeger
high open circuit voltage up to 0.94 V in case of P3 due to independently, which were based on poly(phenylene
relatively high-lying LUMO as compared to linear-shaped vinylene) [84, 85]. Cyano PPV was used as the accep-
NDI containing polymers (<0.6 V). The all-polymer solar tor in combination with MEH-PPV as the donor, where
cells fabricated by blending these polymers with P3HT re- Heeger’s group reported a blend OPV device with PCE
sulted in PCE of 0.32% using P1 as the acceptor [83]. The of ~0.9%. Polythiophene based donor polymers have
potential of the bay substituted PDI and NDI based poly- also been used in combination with cyano PPV poly-
mer for all-polymer solar cell application looks very bright mers in all-polymer blend solar cells. The initial re-
based on these recent reports of good performance effi- ports of blend of POPT with acceptor MEH-CN-PPV have
ciencies of devices using this polymer in combination with shown PCE around 1.9% [7]. Using regioregular POPT
a host of donor polymers. A few acceptor polymers other prepared by GRIM polymerization method, bilayer de-
than that based on perylene or naphthalenediimides also vices of MEH-CN-PPV with GRIM POPT exhibited PCE
have shown promise in all-polymer solar cell application. ~2.0% [15, 86, 87]. A bulk heterojunction all-polymer solar
Some of the examples of D-A alternating polymers based cell based on poly 2-methoxy-5-3,7-dimethyloctyloxy-1,4-
on other than rylene bisimides are discussed below. phenylenevinylene (MDMO-PPV) as the electron donor
and a red emitting alternating poly 9,9-dioctylfluorene-
2,7-diyl-alt-1,4-bis 2- 5-thienyl -1-cyanovinyl-2-methoxy-5-
(C) D-A Polymer Based on Other Chromophores 3,7-dimethyl-octyloxy benzene copolymer (PF1CVTP; AC-
21) as the acceptor showed promise with a power con-
The chemical structures of D-A polymers based on version efficiency of 1.5% [88]. An alternating donor-
other chromophores discussed in this section are shown acceptor copolymer poly((9,9-dioctylfluorene)-2,7-diyl-
Chart 5: Chemical structures of PDI based alternating D-A polymers used in single component all-polymer solar cells.
alt-[4,7-bis(3-hexylthiophen-5-yl)-2,1,3-benzothiadiazole]- BTD) [93]. These n type polymers were blended with donor
2’,2”-diyl) (F8TBT; AC-22) was blended with P3HT in an polymer-P3HT in all-polymer solar cells, where efficiency
all-polymer solar cell [89] and annealed samples exhib- of 0.5% was observed. Janssen and co-workers reported
ited a PCE of 1.4%. Although the F8TBT had only been three novel diketopyrrolopyrrole (DPP) based D-A poly-
used as electron donor until then, with this work the au- mers incorporating 2,1,3-benzothiadiazole, thiophene and
thors demonstrated the efficient performance of F8TBT fluorene moiety respectively as donor AC-26 a, b, c. These
as an electron acceptor/electron transporter in blends novel polymers were incorporated in BHJ solar cell with
with P3HT. A similar D-A alternating polymer based on P3HT as donor in a 1:1 ratio. Despite the almost similar V oc
9,9-didodecylfluorene and benzothiadiazole, but lacking and FF values for all polymers, the P3HT: AC-26 (c) exhib-
the alkyl substitution on the thiophene ring (AC-23) was ited higher PCE of 0.37% compared to P3HT:AC-26 (a) and
used as the acceptor polymer; in combination with poly(3- P3HT: NDI-AC-26 (b) exhibiting PCE of 0.14% and 0.11%
hexylthiophene) [90] in an all-polymer blend solar cell by respectively. They concluded that the lower electron mo-
the research group of Benten and Ito. They observed PCE bility and inefficient generation of long-lived free charge
of 2% for thermally annealed devices fabricated from chlo- carriers limited the device performance [94, 95]. Recently,
roform. They attributed the improved device efficiency to they reported both donor and acceptor polymers based on
phase separation on a nano scale, which was dependent DPP, by linking thiophene (PDPP5T see in Chart 1) and
both on the solvent used for fabricating the device as well thiazole (PDPP2TzT) units respectively AC-27, along the
as the thermal annealing process. polymer chain with DPP. Blends of the donor and acceptor
Zhan and co-workers reported n-type copolymer polymer based on DPP was used as the active layer in an in-
based on dithienocoronenediimide AC-24 with different verted solar cell device configuration and PCE of 2.9% was
number of thiophene units attached to it. The polymers ex- observed after optimization with processing additives [96].
hibited almost similar LUMO energy level irrespective of
the number of thiophene units. However the HOMO en-
ergy levels shifted up on increasing the number of thio- 2.2 D-A Single Component Solar Cell.
phene groups (6.0 to 5.7 eV). All-polymer solar cell fab-
ricted by using PT5TPA as donor showed steady improve- 2.2.1 Covalent Approaches
ment in PCE as the number of thiophene units increased;
the best power conversion efficiency of 2.14% was achieved There are only very few references of single layer solar cell
with AC-24- P3 [91]. The group of Reynolds reported the devices using the donor-acceptor (D-A) alternating poly-
use of Isoindigo as acceptor for solar cell application [92]. mer as the active layer of the solar cell; probably as they
They were the first to develop polyisoindigo AC-25– a are not very efficient. For instance, Neutboom et al. re-
fully electron deficient polymer compared to the D-A struc- ported the D-A polymers PDI-23 and PDI-24 (Chart 5) based
ture usually adopted for developing n type polymers. on perylenediimide (PDI) as the acceptor and oligo p-
They also developed a copolymer of isoindigo with 2,1,3- phenylene vinylene (OPV) as the donor [97], which was
benzothiadiazole alternating in the repeat unit, Poly(iI- one of the first reports of photovoltaic application of PDI
Chart 6: Chemical structures D-A block copolymers used in all-polymer solar cell.
containing D-A alternating polymers. In the all-polymer ductor with improved micro-phase separation on thin-
solar cell devices using either PDI-23 or PDI-24 as the film devices. Although D-A block copolymers have some
active layer material, it was observed that the short cir- outstanding properties like micro-phase separation (10–
cuit current was not very high. In another report N-alkyl 20 nm) and broad absorption etc, their availability is still
perylenediimide was linked to OPV through ether linkage limited due to synthetic difficulties. Some examples of
from the 1 and 7 bay position to form the alternate D-A poly- D-A block copolymers which have been used as active
mer PDI-25 (Chart 5) [98]. The device performance of all- layer in all-polymer BHJ solar cell is discussed here and
polymer solar cells in single layer based on PDI-4 showed their chemical structures are shown in Chart 6. The syn-
power conversion efficiency of 0.07% under illumination thesis of D-A block copolymer can be achieved by two
at an intensity of 75 mW/cm2 . different approaches, one where the acceptor possess
polymerizable units and serves as monomer and the
other where the acceptor unit can be attached to one
(A) D-A Block Copolymers of the blocks by post modification [26]. Thelakkat and
coworkers reported probably for the first time the syn-
Donor-acceptor block copolymers comprising of conduct- thesis of poly (bisphenyl-4-vinylphenylamine)-block-poly
ing polymer blocks is another emerging class of conju- (perylenediimide acrylate), (PvTPA21 -block-PPer-Acr79
gated polymers which can be successfully utilized to 1a) through nitroxide-mediated polymerization (NMP).
control the structural ordering of polymeric semicon- The self-assembly of block-copolymer was characterized
lakkat and coworkers reported a set of crystalline–

crystalline donor–acceptor block copolymers poly (3-
hexylthiophene)- block-poly(perylenediimide acrylate)
(P3HT-block-PPerAcr 4), which was prepared via nitrox-
ide mediated polymerization [101]. The P3HT contain-
ing micro-initiator was prepared in the first step which
was then copolymerized with perylenediimide acrylate
to obtain a series of block copolymers with different seg-
ment lengths. Solar cells were fabricated using the device
structure indium tinoxide/PEDOT:PSS/active layer/Al, the
block copolymer (P3HT-block-PPerAcr 4) with a molec-
ular weight of 29.5 kg/mol which showed a maximum
power conversion efficiency of 0.2% [102]. Zhang et al.
reported similar block copolymer with little modification
in structure (P3HT-block-PPerAcr 5); vinyl-terminated rr-
P3HT was synthesized by Grignard metathesis polymer-
ization and converted to an alkoxyamine macroinitiator.
Figure 3: (a) SFM phase image and (b) TEM image of block copoly- This polythiophene macroinitiator was used in the con-
mer P3HT-block-PPerAcr5 (Chart 6) thin film (from a 1 wt% toluene trolled free radical polymerization with a perylenediimide-
solution at 2500 rpm) after annealing for 2 h in toluene/chloroform containing acrylate.
vapor. (c) SFM phase image and (d) TEM image of drop-cast block The spin coated thin-film of block copolymer showed
copolymer film from 0.1 wt% toluene solution on Si substrate each
fibrillar morphology after solvent annealing using the
scale bar (100 nm). Reprinted with permission from ref [103]. Copy-
right 2014 American Chemical Society. solvent mixture toluene/chloroform (50:50). The same
morphology was also obtained from thin films which
were solution-cast from toluene and subsequently evap-
by tapping-mode AFM topography images which sug- orated for 1 day. The corresponding SFM and TEM
gested that the characteristic width of the microdomain images are given in Figure 3. Solvent annealed de-
structure (10–50 nm) was of the same order as the exci- vices of solar cell fabricated with the architecture:
ton diffusion length. Single-layer solar cell devices fabri- ITO/PEDOT:PSS/copolymer1/LiF/Al showed PCE of 0.49%
cated from the block copolymer exhibited PCE of 0.07% which was higher than that obtained for pristine thin
which was one order of magnitude higher than the PCE film of PCE 0.1% [103]. Block copolymers containing
of (0.007%) devices fabricated from the blend of the two naphthalenediimide as acceptor block is not very com-
individual homopolymers [99]. Subsequently, they synthe- mon and their photovoltaic properties are rarely re-
sized two other block copolymers by slight modification ported in literature. A unique example was reported
in the donor block while keeping the acceptor block in- by Nakabayashi and co-workers. They synthesized two
tact [100]. The first block representing the donor was made fully conjugated D-A BCPs (P3HT-NBI-P3HT 6) com-
up of either substituted triphenylamines-(poly(bis(4- posed of poly (naphthalenediimide) (PNDI)-as acceptor
methoxyphenyl)-4′ -vinyl-phenylamine), (PvDMTPA- and regioregular P3HT as donor segments [104]. The
b-PPerAcr, 2a, 2b) or substituted tetraphenylben- synthesis of BCPs was achieved in two steps, in the
zidines (poly(N,N′ -bis(4-methoxyphenyl)-N-phenyl-N′ -4- first step two monobromo-terminated regioregular poly(3-
vinylphenyl-(1,1′ -biphenyl)-4,4′ -diamine), (PvDMTPD-b- hexylthiophene)s P3HT1and P3HT2 with different molec-
PPerAcr, 3). All block copolymers showed micro-phase ular weights 9400 and 6300 (Mn) respectively were
separation in the form of worm or worm-like structure as synthesized using the quasi-living Grignard Metathe-
evidenced by TEM images. sis method. In the second step, D-A block copolymers
Single-active-layer organic solar cells of PvDMTPD- P3HT1-PNBI-P3HT1 and P3HT2-PNBI-P3HT2 were synthe-
b-PPerAcr 3 showed four times improvement in power sized from P3HT and N,N′ -bis(2-decyl-1-tetradecyl)-2,6-
conversion efficiency (PCE=0.26%) and PvDMTPA-b- b is (5′-bromo-4′ -hexylthiophenyl) naphthalene-1,4,5,8-
PPerAcr, 2a showed a five times increased efficiency tetracarboxylic acid diimide by Yamamoto coupling re-
(PCE=0.32%) compared to the unsubstituted analogue action. The all-polymer solar cell of BCPs were fab-
PvTPA-b-PPerAcr 1b (PCE=0.065%). Continuing the work ricated using P3HT as donor in the device architec-
on block copolymer for photovoltaic application, The- ture ITO/PEDOT:PSS/P3HT:P3HT-PNBI-P3HTs/Ca/Al. The
Chart 7: Chemical structures of fullerene containing D-A alternating and block polymers used in all-polymer solar cells.
highest PCE of 1.28% was observed in P3HT2-PNBI-P3HT2 (B) Fullerene Containing D-A Alternating and Block
device after thermal annealing at 200∘ C for 15 min; the Copolymers
as-cast device showed PCE of 0.37%. Guo et al. demon-
strated the effect of self-assembly and thereby micro- Fullerene incorporated D-A alternating and block copoly-
phase separation on photovoltaic performance of poly(3- mers are synthetically very challenging due to their low
hexylthiophene) -block - poly-(( 9,9-dioctylfluorene) -2,7- solubility in common organic solvents which make the pu-
diyl-alt-[4,7- bis(thiophen-5-yl )-2,1, 3-benzothiadiazole]-2′ , rification of monomer and polymers very difficult. Some-
2”-diyl) (P3HT- b –PFTBT 7) block copolymers. The BCP times, these polymers are termed as "double cable poly-
strongly self-assembled in to lamellar morphologies with mer". The Chemical structures of some fullerene contain-
alternating electron donor and acceptor domains and also ing D-A alternating and block copolymers explained in
showed dominant face-on orientation in the crystalline this section are shown in Chart 7 (F1-F4). There are only
P3HT block as proved by conventional X-ray diffraction few reports available in literature; for instance, Janssen
(XRD) and grazing incident wide-angle X-ray scattering et al. reported methano-fullerenes containing covalently
(GIXRD) studies. The solar cell device fabricated of P3HT- linked novel D-A polymer F-1 via palladium-catalyzed
b-PFTBT as single active layer was compared with blend cross-coupling reaction. This polymer exhibited photo-
of two individual homo-polymers, which were not able induced electron transfer reaction and was used as ac-
to form self-assembled domains. The block copolymer tive layer of photovoltaic cell. Although the exact value
showed best overall PCE of 3.1%, whereas the blend of two of PCE was not available, a short circuit current of (Isc)
homo-polymers exhibited PCE of 1.1% [105]. 0.42 mA/cm2 , an open circuit voltage of (V oc ) 0.83 V, and
Figure 4: Co-operative hydrogen bonding of OPV-PBI-OPV and AFM topographic images of self-assembled 1b-2-1b (A) and 1a-2-1a complex
(D) after spin-coating from MCH B) Locally enlarged picture (scale bar 100 nm). (C) Enlarged picture of the location around the upper arrow
(scale bar 50 nm). Reprinted with permission from ref [115] and ref [116]. Copyright 2014 American Chemical Society.
a fill factor of 0.29 appeared promising for further de- C60 MS). The block copolymer showed improved perfor-
velopment of fullerene based polymeric materials [106]. mance of solar cell parameters V oc (0.52), J sc (5.8), FF
Zhang and co-workers reported oxidative polymerization (0.23) as compared to the blend with V oc (0.40), J sc (0.15)
of thiophene by slow addition of a slurry of FeCl3 in and FF (0.28) [108]. In 2010, Tajima and Hashimoto’s group
CHCl3 to a solution containing monomers to obtain thio- demonstrated for the first time high power conversion ef-
phene functionalized with different percentage incorpo- ficiency of 1.70% in a single component solar cell using
ration of fullerene side groups F-2 [107]. Even up to donor-acceptor diblock copolymer [109]. They synthesized
14% side chain functionalization of fullerene did not dis- fullerene containing D-A diblock polymer F-4 by using Ni-
rupt the ordering of the polythiophene. It was observed catalyzed quasi-living polymerization. A random copoly-
that chloroform vapor annealing enhanced the absorp- mer was also synthesized by using the mixed monomers.
tion at long wavelength to 700 nm. Photodiodes were The photovoltaic performance of single component solar
prepared from copolymer by spin coating chloroform so- cell showed higher PCE for D-A diblock copolymer (PCE
lution on PEDOT:PSS/ITO electrodes and illuminated by 1.70%) as compared to random copolymer (PCE 0.48%).
monochromatic light of intensity 0.1 mW/cm2 at 505 nm. Later on in 2012, the same group reported improved PCE
A PCE of 0.6% was obtained with fill factor 0.25 under by slightly altering the structure of existing diblock copoly-
these low intensity monochromatic illumination condi- mer. This time they synthesized three D-A block copoly-
tions. Enhancement of EQE at long wavelengths was ob- mer (D1, D2 and D3 F-4) by varying the length of the P3HT
served with chloroform vapor treatment. Hadziioannou’s block. The photovoltaic performance of single component
group reported a novel diblock-copolymer, where one solar cell of D-A copolymer once again showed higher PCE
block was poly (p-phenylene vinylene) while the other of 2.46% compared to the random copolymer [110]. Most of
was fullerene functionalized polystyrene. Initially statis- the reports on D-A block copolymers employ them as com-
tical copolymer of styrene and chloro-methyl styrene was patibilizer rather than as the active layer component of so-
obtained from PPV based microinitiator, which upon func- lar cell, where they are used in small amounts along with
tionalization with C60 gave PPV-block-poly(S-stat- C60 MS) P3HT: PC61 BM blend [111–113]. Although covalent linkage
F-3. For comparison two solar cell devices were fabri- of the fullerene with donor polymer blocks did not yield
cated on ITO/PEDO:PSS glass substrate-one with 1:1 ratio high device efficiencies compared to the blend, latest re-
of a blend of PPV homopolymer and poly(S-stat- C60 MS) search in this area highlighted the vital role of the D-A
and the other with block copolymer PPV-block-poly(S-stat- block copolymers in improving the thermal stability of
P3HT: PC61 BM blend solar cell devices by reducing interfa- motivation behind incorporating self-assembling func-
cial energy between donor (P3HT) and acceptor (PC61 BM) tionalities on the donor and acceptor molecules was to en-
which ultimately reduced their phase separation. sure close association among the D-A pairs; however it has
also been pointed out that homo-stacks of the donor or
acceptor formed among themselves leading to unwanted
aggregation and phase separation. In fact, there are as
3 Non-Covalent Approaches many reports citing the negative or unwanted influence of
hydrogen bonding interaction on device performance in
3.1 Hydrogen Bonded Oligomeric D-A small molecule based donor-acceptor assemblies as there
Assemblies are those vouching for their advantages [114]. Most of these
studies employ analogous systems with and without hy-
Non-covalent approaches adopted for photovoltaic mate- drogen bondable moieties to effectively compare the good
rial design mainly included incorporating self-assembly and bad influence of directed self-assembly. The Chart 8
kits like complimentary hydrogen bonding units at the shows chemical structures of some small molecules and
terminal of small molecules or oligomers of donor and oligomers with and without hydrogen bondable moieties.
acceptor molecules. These upon interaction in appropri- Since fullerene is the most well-studied n-type material in
ate solvent medium and further assisted by π–π stack- photovoltaic applications, functionalization of fullerene
ing of the aromatic core, formed heteroaggregates of D-A to incorporate hydrogen bonding moieties like amide or
units in the domain range (5–10 nm) required for the effi- barbituric acid adduct linkage were also pursued [118].
cient charge separation. The initial research in this area in- Notable among these was the study conducted by Bas-
volved incorporation of simple units like the amide or urea sani and coworkers to understand the influence of hy-
groups in organic semiconductors, which helped them drogen bonding in fullerenes on their electronic interac-
stack into long polymeric fibers. Such fibrillar organization and charge carrier mobility [119]. They designed HB-
tions led to tremendous improvement in their charge car- C60 , (shown in Chart 8) a C60 derivative with a barbi-
rier mobilites [114]. Realizing the potential of such non- turate adduct functionalization, which could be grown
covalent interactions in assisting better charge separation, into single crystals by diffusion of chloroform into its so-
the concept was further extended to donor-acceptor as- lution in ortho dichlorobenzene (ODCB) containing 10%
semblies. DMSO. Data collected using synchrotron radiation sug-
The most studied complimentary hydrogen bonding gested formation of infinite linear hydrogen bonded tapes
moieties were the imide and ureido pyrimidinone (UPI) with anisotropic distribution of fullerene cages in crystals
pair introduced by Meijer et al., which was introduced into of HB-C60 , which stacked along the b − c direction. In
donor-acceptor pairs like perylenediimide (acceptor) and contrast, the fullerene in pristine C60 has a highly sym-
oligo(p-pheylene vinylene) (OPV donor) as shown in Fig- metric FCC lattice structure. The anisotropic distribution
ure 4 (OPV-PBI-OPV) along with their thin film morphol- of fullerene in HB-C60 suggested efficient charge transport
ogy [115, 116]. Although the ureido pyrimidinone function- along the a axis with a 9.95 Å center-to-center distance,
alized OPV formed columnar stacks and hierarchical as- while charge transport along the b or c axis with a 15.88 Å
semblies with perylenediimide (PDI), the device perfor- separation would require tunnelling through a barrier. The
mance in field effect transistors (FET) as well as solar cells anisotropy was proven by fluorescence polarization stud-
were poor [117]. A non-ideal lateral organization of the co- ies, which showed strongly polarized fluorescence origi-
aggregated aromatic units on the substrate surface was nating from fullerene excimer-like emitting states in single
assumed to be the cause of the poor device performance crystals of HB-C60 . On the other hand, the highly symmet-
of the otherwise highly organized donor-acceptor as- ric FCC lattice of C60 exhibited no polarization under sim-
semblies. Other well-studied self-assembling complimen- ilar conditions. The bulk charge carrier mobility in OFET
tary units are the melamine-barbiturate/cyanurate and devices prepared using HB-C60 gave values which were
diaminopyrimidine-thymine pairs. The association con- about 2 orders of magnitude lower compared to that mea-
stant for these complimentary hydrogen bonding are very sured for C60 (1.2×10−4 cm2 /V s vs. 1.2×10−2 cm2 /V s) which
high and the self-assembly could be visualized from mi- was attributed to the reduced dimensionality of HB-C60 as
croscopy images like AFM, TEM and SEM. Improved charge a wire-like semiconductor.
carrier mobilities compared to non-hydrogen bonded Not only for fullerene derivatives but the direction-
bench mark molecules has been reported in many cases; ality of the hydrogen bonding interaction was shown to
however the solar cell performance were not very high. The be restrictive compared to the freedom in charge trans-
Chart 8: Chemical structures of some small molecules and oligomers with and without hydrogen bondable moieties.
port pathways offered by the three dimensional crys- ganization of the non-hydrogen bonding ester based NDI
talline organization in small molecules based on naph- derivative (2×10−2 cm2 /V s) compared to the restricted
thalenediimides. Research from our own group had also directional hydrogen bonding interaction that existed
pointed towards the unwanted effects of directional hydro- in the amide (9.5×10−3 cm2 /V s) derivatives. Hydrogen
gen bonding in small molecule based on naphthalenedi- bonding interaction in donor-acceptor systems also have
imide having either an ester (NDI-E) or amide (NDI-A) link- been found to exhibit mostly deleterious effect barring
age [120]. Organic field effect transistor (OFET) device mea- a few exceptions. Wong et al designed small molecules
surements clearly demonstrated that the n-type charge based on dithieno[3,2-b;29,39-d]thiophene (DTT) having
transport was better for three-dimensional crystalline or- either octyl cyanoacetate (M1) or octyl cyanoacetamide
(M2) as non-hydrogen bonding and hydrogen bond- ter with PCBM as electron acceptor produced a bi con-
ing terminal functionalities respectively [121]. BHJ solar tinuous BHJ morphology with well-defined interface in
cells were constructed for both the molecules in com- the domain scale of 20–30 nm resulting in an optimized
bination with a fullerene derivative functionalized with PCE exceeding 4.3%. On the other hand, the correspond-
an amide group ([6,6]-phenyl-C61 -N-methyl butyramide; ing amide derivatives, namely, C8 and C10 amide pro-
PC61 MBA,) or the regular [6,6]-phenyl-C61-butyric acid duced PCE of 3.2 and 3.7% respectively with PCBM. The
methyl ester (PC61 BM) (shown in Chart 7). While the non- hole mobilities determined using OFET showed that the
hydrogen bonding M1-PC61 BM combination exhibited a C8 and C10 ester molecules exhibited high hole mobili-
device efficiency of PCE=0.65%, the hydrogen bondable ties of 1.37×10−2 cm2 /V s and 2.82×10−2 cm2 /V s, respec-
counterpart, M2-PC61 MBA performed very poorly with tively, whereas the mobility of the amide derivatives C8
a PCE of 0.004%. This drastic reduction in device per- and C10 amides were lower by an order of magnitude
formance was attributed to unfavorable morphology in- (2.18×10−3 cm2 /V s and 2.99×10−3 cm2 /V s respectively).
duced by intermolecular hydrogen bonding, which re- Grazing Incidence X-ray Scattering (GIXS) studies showed
sulted in large scale phase separation and aggregation. that the ester derivatives formed well-ordered, "edge-on"
The amide hydrogen bonding in M2 disrupted the close molecular orientations with distinct (010) inplane reflec-
π stacking of the central DTT conjugated building block, tion indicating 3D conduction channels. Compared to the
while the hydrogen bonding in PC61 MBA resulted in un- ester derivatives the amide derivatives formed ill-defined
wanted self-aggregation as well. Similar results were re- molecular orientation brought about by the strong hydro-
ported by Siram et al. where they studied phase separa- gen bonding interaction in the active layer. In contrast,
tion in a donor /acceptor blend via supramolecular chem- Lam et al. compared two quarterthiophene derivatives -
istry approach [122]. They synthesized two oligomers (TTB one end-functionalized with carboxylic acid (QT-DA) and
and NMeTTB) by coupling donor-acceptor-donor (D-A-D) the other terminated with its diester analogue (QT-ES) and
through a vinylene spacer. TTB was functionalized with showed that the caryboxylic acid terminated system exhib-
barbiturate which underwent self-assembly by hydrogen ited a two fold increase in BHJ solar cell device efficien-
bonding, whereas self-assembly was disrupted by intro- cies compared to the latter [124]. The QT-DA: PC61 BM blend
ducing a methyl group in NMeTTB. Morphological stud- showed an un-annealed PCE of 0.91%, while the annealed
ies carried out using AFM showed smooth and uniform PCE of QT-ES: PC61 BM blend was around 0.4%. While an-
film for NMeTTB whereas a thin film of TTB obtained un- nealing resulted in improved device performance in the
der similar conditions showed well-ordered nanoribbons QT-ES: PC61 BM blend due to the improved crystallization
due to self-assembly. Upon mixing the molecules with of QT-ES, it resulted in large domain aggregation in the
PC61 BM in 1:1 ratio, a smooth bicontinuous network was QT-DA: PC61 BM blend resulting in decrease in device ef-
observed for NMeTTB. However, self-assembly of TTB re- ficiency. It was concluded that hydrogen bonding afforded
sulted in phase separation between the TTB nanoribbon optimum phase separation in the QT-DA: PC61 BM blend
and PC61 BM. The Bulk heterojuction solar cell device of in the as-cast spin coated films, which was also proved
NMeTTB: PC61 BM showed PCE 1.8% which was an or- by better hole mobility measured using space charge lim-
der of magnitude higher than that of TTB: PC61 BM de- ited current (SCLC) measurements. The SCLC mobility val-
vice (0.1%). The low efficiency for TTB based devices was ues of QT-DA and QT-ES were 2.83×10−5 cm2 /V s and
attributed to various factors including low charge carrier 6.91×10−6 cm2 /V s respectively.
mobility (~10−7 cm2 /V s) for TTB as compared to NmeTTB
(~10−4 cm2 /V s for), phase separation between TTB nano-
ribbons, and PC61 BM with large grain boundaries. An- 3.2 Hydrogen Bonded Polymeric D-A
other example was reported by Kim et al. where they Assemblies
investigated the effects of intermolecular interactions of
electron-donating small molecules on their performance There are not many reports extending the complimentary
in (OFETs) and organic photovoltaics (OPVs) [123]. A se- hydrogen bonding interaction to fully polymeric donor-
ries of dithienosilole (DTS) based small molecule donors acceptor systems. Therefore, the discussion also cov-
were synthesized having either ester (DTS-E) or amide ers complimentarily functionalized polymer and small
(DTS-A) terminated alkyl terminal chains. Compared to molecule combinations also. The few reports available on
the systems with ester terminal groups, those with amide polymeric donors are based on polythiophene, where suit-
terminal groups exhibited strong intermolecular interac- able functionalities were introduced in the side chain for
tion by hydrogen bonding. Blend films of C8 and C10 es- hydrogen bonding interaction with complimentarily func-
Chart 9: Chemical structures of some donor polymers showing co-operative hydrogen bonding with C60 (PCBM) derivatives.
tionalized PC61 BM as the acceptors. The chemical struc- ester groups of PC61 BM was attributed as the cause of the
ture of some donor polymers exhibiting co-operative hy- reduced domain size and finer nanoscale morphology of
drogen bonding with C60 (PCBM) derivatives are shown P3HT-b-P3AcidHT:PC61 BM. This was an example of suc-
in Chart 9. cessful hydrogen bonding interaction. Qin et al. reported
Yasser et al. developed random as well as diblock three-point complimentary hydrogen bonding involving
copolymers of poly (3-alkylthiophene)s (NC-1) bearing po- in (NC-2) isoorotic acid on the side chain of a diblock
lar COOH group on the side chain by the GRIM poly- polythiophene and diaminopyridine moieties located on
merization route involving the protected acid function- fullerene derivative (PCBP) respectively [126]. Although
ality [125]. The block copolymer, P3HT-b-P3AcidHT had the PCE of 2.65% obtained for solar cells made from a (NC-
a short 95:5 acid component to overcome the reduced 2)/PCBP (10/8, w/w) was lower compared to the 3.56% ob-
solubility of the rigid polyelectrolyte in organic solvents. tained for a reference P3HT/PC61 BM (10/8, w/w) combi-
Photovoltaic properties of copolymers were investigated nation, the triple hydrogen bonded block polymer system
in bulk heterojunction devices with PC61 BM as acceptor. fared better in thermal ageing studies compared to the ref-
The block copolymer P3HT-b-P3AcidHT showed the best erence. The hydrogen bonded polymer donor-acceptor so-
performance with a PCE of 4.2%, an open-circuit volt- lar cell exhibited hitherto unobserved long range ordered
age (V oc ) of 0.60 V, a short-circuit current density (J sc ) nanostructures with only 20% PCE reduction after aging
of 13.0 mA cm−2 , and a fill factor (FF) of 0.60. Atomic Force tests. A combination of cooperative effects of block copoly-
Microscopy (AFM) analyses indicated well-defined inter- mer self-assembly and complimentary hydrogen bonding
faces for P3HT-b-P3AcidHT:PC61 BM with an average do- was credited with the good device performance in the
main size of about 11 nm, which was close to the exci- bulk heterojunction solar cells. Later they improved the
ton diffusion length. The hydrogen bonding interaction be- performance of devices fabricated from the isoorotic acid
tween the carboxyl groups on P3HT-b-P3AcidHT and the functionalized polythiophene (NC-3 or P1) by replacing
Figure 5: TEM images of (A) P1 or NC-3 (Chart 9) nano fibers (NFs); (B) preformed P1NFs with the addition of PCBM (40 w%); (C) NFs in situ
formed from the P1/PCBM (10/4, wt./wt.) mixture solution; (D) P3HT NFs; (E) preformed P3HT NFs with the addition of PCBM (40 wt%); and
(F) NFs in situ formed from the P3HT/PCBM (10/4, wt./wt.) mixture solution. Top left inserts: distributions of fiber widths sampled from
100 individual NFs. Bottom right inserts: magnified images. Scale bars in all: 200 nm. Reprinted with permission from ref [127]. Copyright
2014 American Chemical Society.
Figure 6: Co-operative hydrogen bonding of P3HTM: PCBA (a, b) TEM images of P3HTM: PCBA (1:0.8 w/w) films using the chlorobenzene
(CB) as solution under different treatments (a) as-cast and (b) after annealing at 130∘ C; and (c, d) P3HTM:PCBA (1:0.8 w/w) films using
the CB:MeOH (49:1) as solution under different treatments (c) as-cast and (d) after annealing at 130∘ C. The insets in (d) show the zoom-
in image of the annealed sample with the corresponding SAED pattern. Reprinted with permission from ref [128]. Copyright 2012 American
Chemical Society.
the hydrogen bondable diaminopyridine functionalized glass/ MoO3 (10 nm)/active layer (100 nm)/Al (100 nm) ex-
PC61 BM with the regular phenyl-C61 -butyric acid methyl hibited PCE of 4.17%, which was one of the highest values
ester (PC61 BM [127]. Under optimized conditions like us- reported for single junction P3HT/PCBM based active layer
ing a mixed solvent system of acetone/chlorobenzene at devices. Compared with simple blend based BHJ devices
a 1/5 volume ratio and a 12 h aging time they could obtain prepared under similar conditions, the performance effi-
pre-assembled nanofibers (NFs) with average fiber width ciency of the composite NF films was better with higher
of 20 nm which is shownin Figure 5. OPV devices fabri- PCE originating from higher short circuit current (J sc ). The
cated from preformed polymer (NC-3)/PC61 BM nanofibers increased J sc was attributed to controlled and favorable
(weight ratio 10:4 wt/wt) with the device structure: ITO confinement of the P3HT domains via NF formation in
Figure 7: Tapping mode AFM phase images of thin films of (a) P3HT-b-P3TODT, (b) P3HT- b-P3TODT/bis-PCBA (8/2), and (c) P3HT-b -
P3TODT/bis-PCBA (6/4), after thermal annealing at 150∘ C for 30 min; Reprinted with permission from ref [129]. Copyright 2012 American
Chemical Society.
length scale suitable for exciton diffusion. Although reg- absorption spectrum was observed. Thermal annealing
ular P3HT (without isoorotic acid functionalization) also also did not adversely affect the morphology by selective
formed NFs with similar fiber width, the J sc was higher crystallization of the polythiophene; in fact the hydrogen
for the isoorotic acid functionalized P3HT/PCBM devices bonding interaction between PCBA and P3HTM prevented
due to more efficient charge dissociation at the polymer macrophase separation. BHJ solar cells fabricated using
nanofiber/PCBM interfaces. the D-A blend processed from a solvent mixture of CB and
Even when weak hydrogen bonding interactions methanol after annealing exhibited PCE of 3.2%.
were present, like that between imidazole side chains Yet another photovoltaic device making use of the self-
on polythiophene and COOH groups located on fullerene assembly route involving COOH functionalized fullerene
as shown in Figure 6, stable nanophase structures and polythiophene reported by Watkins and cowork-
were obtained with PCE of 3.2% in BHJ solar cells. ers [129]. As shown in Figure 7, they developed di-
Higher device performance efficiencies were obtained block copolymers comprised of poly(3-hexylthiophene)
for the thiophene-PCBM donor-acceptor combina- and poly[3-(2,5,8,11-tetraoxadodecane) thiophene (P3HT-
tion via the self-assembly approach by using a re- b-P3TODT) and blended them with bis-[6,6]-phenyl-C61-
gioregular poly[3-(60-bromohexyl)thiophene]-co-[3-(60- butyric acid (bis-PCBA) to form BHJs which exhibited pho-
(1-imidazole) hexyl)thiophene] (P3HTM) with PCBA toconversion efficiency of 2.04%. Various characterization
(the hydrolyzed acid) [128]. The regioregular poly(3- techniques like GISAXS, TEM and SEM imaging proved the
bromohexylthiophene) (P3HTBr) was synthesized via the existence of nanostructured D/A interpenetrating lamel-
Grignard metathesis route and post functionalized with lar network in the 10–20 nm domain range. The hydrogen
imidazole (P3HTM) so as to interact with the carboxyl bonded D/A system remained thermally stable for long pe-
group of PCBA through intermolecular O-H. . . N hydrogen riods of time (~6 h) under annealing conditions of 150 ∘ C
bonds. In films of the P3HTM:PCBA blend prepared from without fullerene phase separation or crystallization and
solvents like chlorobenzene (CB), there was not much only a 0.95% reduction in its PCE.
evidence of interaction between the two species; how- Under similar extended periods of annealing condi-
ever upon addition of appropriate amounts of polar sol- tions, the bench mark device comprising of P3HT:PCBM
vents like methanol, self-assembly leading to red shifted blend as the active layer degraded to 0.4% of its original
Figure 8: Schematic representation of the photovoltaic cell structure showing the alternating donor (D) and acceptor (A) layers, forming the
active material. Reprinted with permission from ref [130]. Copyright 2014 American Chemical Society.
PCE of 3.08%. There are also of suitably functionalized obtained in P1/S3 complex [131]. As shown in Chart 10,
PCBM with complimentarily functionalized donor systems Lin and coworker designed a supramolecular polymer net-
other reports of self-assembly than those based on poly- work containing multiple functionalized melamine pen-
thiophene that have been utilized as active layer in photo- dants and complementary H-bonded uracil motifs using
voltaic devices. The group’s of Schanze and Reynolds re- DTP, bithiazole, and thiophene units as the backbone
ported photovoltaic cells using a layer by layer (LBL) self- of a conjugated main-chain polymer PBTH, where the
assembly of anionic conjugated polyelectrolyte based on melamine pendants could be H-bonded with complemen-
poly(phenylene-ethynylene) with water-soluble cationic tary uracil-based conjugated crosslinkers containing car-
fullerene C60 derivatives as acceptors schematic of which bazole (C) or fluorene (F) units [132]. These supramolec-
is shown in Figure 8 [130]. The power conversion efficien- ular polymer networks were used in combination with
cies were around 0.01–0.04% for devices fabricated us- PC70 BM in a 1:1 weight ratio as the active layer in BHJ so-
ing 50 bilayers. This was one of the better device perfor- lar cells. PCE values of 0.97 and 0.68% were obtained for
mance values for photovoltaic devices constructed based the PBTH/C and PBTH/F supramolecular combination re-
on donor acceptor assembly through the LBL approach. spectively, which was higher than that of PBTH alone.
Liang et al. reported supramolecular side chain electron Better PCE values of 1.56% with short circuit cur-
donor polymer by complexing low band gap organic dyes rent densities (J sc ) of 7.16 mA/cm2 , open circuit volt-
to them. As shown in Chart 10, they synthesized two side ages (V oc ) of 0.60 V, and fill factor (FF) of 0.36 could
chain polymers (P1 and P2) incorporating varying percent- be attained at an optimized weight ratio of PBTH/C
age of proton accepting pyridyl unit by free radical poly- as polymer:PC70 BM=1:2 w/w. Improved light harvesting,
merization. lower HOMO energy levels, higher crystallinities were
The low band gap dyes S1-S4 having electron donat- attributed to the enhancement of V oc , J sc values and
ing tri-phenylamine or carbazole at one terminal and elec- overall PCE in the supramolecular polymer network
tron accepting cynoacrylic acid at another terminal was compared to the pristine polymer PBTH. Our research
bridged through various numbers of fluorine bithiazole group also has reported nanostructured donor-acceptor
and thiophene units. These dyes were then complexed supramolecular self-assembly of complimentarily func-
with the side chain polymers in a 1:1 molar ratio of acceptor tionalized perylenediimide (PDI) and oligo(p-phenylene
pyridyl to the donor carboxylic acid group by dissolving in vinylene) that exhibited higher bulk mobility estimate
THF and slow evaporation of solvent to form supramolec- measured by space charge limited current (SCLC) [133]. We
ular complexes P1/S1–P1/S4 and P2/S1–P2/S4. The for- designed donor and acceptor small molecules with built-
mation of hydrogen bonding in supramolecular polymer in capabilities for self-assembly as well as functionalities
was confirmed by FT-IR spectroscopy and their optical which could be polymerized so as to translate the self-
studies showed broad absorption peaks in the range of assembly of the small molecules to polymers.
440–462 nm with optical band-gaps of 2.11–2.25 eV. These Thus, as shown in Figure 9, the donor OPV molecule
supramolecular polymer complexes were incorporated in was functionalized with hydrogen bondable hydroxyl moi-
bulk heterojuction solar cell with PCBM as acceptor in 1:1 ety at one end and polymerizable methacrylamide units
ratio and the PCE in the range of 0.06% to 0.50% was at the other termini (OPVM OH), while the acceptor
obtained in various complexes with highest PCE of 0.5% PDI molecule (UPBI-py) was complementarily function-
Chart 10: Chemical structures of some p-type (donor) and n-type (acceptor) polymers showing co-operative hydrogen bonding.
alized with pyridine units at one terminus and solubiliz- which could be attributed to facile photoinduced charge
ing branched alkyl chains at the other termini. The 1:1 generation and separation prevailing in the D-A system.
donor-acceptor complex between (UPBI-py:OPVM OH) One reason for the less number of reports on polymeric
was further subjected to photopolymerization. Both the donor-acceptor self-assembly could be the difficulty in
1:1 D-A molecular complex as well as the supramolec- synthesizing suitable polymeric donors or acceptors in-
ular polymer complex showed uniform lamellar struc- corporating functionalities suitable for hydrogen bond-
tures in the domain range <10 nm which is shown in Fig- ing interaction in the side chain, so that every repeat
ure 7. The pristine structure UPBI-Py exhibited an SCLC unit has a site for D-A interaction. Recently increasing re-
bulk mobility estimate of ~10−4 cm2 /V s while the 1:1 ports are available where P4VP has been used as a tem-
D-A complex exhibited a mobility estimate that was an plate to assemble complimentarily functionalized donors
order higher ~10−3 cm2 /V s. The intensity dependence or acceptors. For instance, this rod-coil block copoly-
of the photocurrent response was determined which re- mer self-assembly concept was made use of to assemble
vealed an interesting trend of superlinear response for donor based on polythiophene as one block with accep-
both D-A complex and supramolecular polymer complex, tor based on PCBM which was self-assembled to the sec-
Figure 9: TEM images (samples drop cast from DMF solution at 2mg/ml concentration) of (a-c) 1:1 complex [UPBI-Py (OPVM-OH)] 1.0 and (d-
f) supramolecular polymer complex [UPBI-Py Poly(OPVM-OH)] 1.0 at different length scale, recorded at room temperature. Reprinted with
permission from ref [133]. Copyright 2014 American Chemical Society.
ond block made up of P4VP by the group of Mezzenga molecule alone [137, 138]. Compared to the scenario of the
et al. [134] Photovoltaic devices with inverted device con- self-assembled small molecular donor-acceptor systems,
figuration glass/ITO/TiOx/active layer/HTL/Al were fabri- the future of the polymeric counterparts looks promis-
cated with varying ratios of P3HT-P4VP (NC-4 chart 9): ing with better morphologies, good device efficiencies and
PCBM blend. PCE of 1.2% could be achieved with relatively overall better device performance being reported. In gen-
large fullerene content (~36 vol%) with better thermal sta- eral, it has definitely been observed that the morpholog-
bility compared to the standard P3HT: PCBM blends. This ical stability can be improved by usage of appropriate
is one of the very good device performance reported so solvents for processing while adopting the self-assembly
far for self-assembled active layer materials. Xu et al. used approach for the active device materials. Thermal an-
P4VP to assemble hydroxyl-functionalized oligothiophene nealing sometimes leads to preferential crystallization in
(P4VP-b-PS 4T) which is shown in Chart 10 [135]. They case of devices fabricated using P3HT as the donor ma-
could produce solution processable nanostructured semi- terial, which results in macrophase separation and poor
conductor composites with good charge carrier mobilities. device performance. In almost all examples where self-
The hydrogen bonding interaction between the oligothio- assembling tools were introduced for specific interaction
phene and P4VP in the block copolymer P4VP-b-PS re- between donor and acceptor, the macrophase separation
sulted in potentially useful morphologies like nanoscopic during annealing could be prevented, besides being able
network of oligothiophene and nanoscopic crystalline to load higher amounts of the PCBM based acceptor in the
lamellae [136]. Our group has also contributed to this donor: acceptor blend. Processing conditions have been
area by self-assembling hydroxyl functionalized "n" type proved to be very critical for self-assembled active layer
perylene and naphthalenediimides (PDI/NDI) with P4VP devices. The choice of right solvent and pretreatment can
which is shown in Chart 10. In both instances, lamel- make or break device performance [139].
lar structures 5–10 nm in size were produced which had
higher conductance compared to the pristine PDI/NDI
be improved by optimizing physical parameters like sol-

4 Conclusion vent annealing, thermal annealing, using mixture of sol-
vent, etc. For example, the self-assembled block copoly-
Overall, comparing the various approaches for Donor-
mer bearing complimentary hydrogen bonding function-
Acceptor structure design based on actual device perfor-
ality on one of the blocks exhibited good micro-phase sep-
mances in solar cells, the D-A alternate covalently linked
aration and their cooperative self-assembly with molecu-
polymers blended with various donor polymers seems to
lar acceptors retained the morphology so that higher ef-
have a slight upper hand compared to the self-assembled
ficiency was observed in solar cells compared to a phys-
D-A systems. For instance, while maximum PCE of 6.7%
ical blend of non-hydrogen bonding donor polymer and
has been attained for the bay substituted naphthalenedi-
acceptor. Furthermore, in lieu of the molecular-wire effect
imide with fluorinated bithiophene alternating structure
in semiconductor based fluorescence sensing, the multiple
(NDI-11) in combination with various donor polymers,
self-assembly sites along the polymer backbone ensures
PCE of 4.17% was achieved for the three–point hydro-
that good nanoscale D-A interaction is afforded with not
gen bonded system of diblock copolymer of isoorotic acid
so strongly interacting functionalities also.
functionalized polythiophene and diaminopyridine func-
Compared to the large number of articles using cova-
tionalized fullerene [126]. The scenario for self-assembled
lently linked donor-acceptor systems as the active layer
small molecule D-A systems does not look very promising
material, there are only limited numbers of articles provid-
from the photovoltaic application point of view but their
ing device values for self-assembled active layer material
polymeric counterparts seem to hold better promise. By
design. However, the values for the non-covalent based
way of their polymeric nature, their processability is better
approaches are comparable with the best solar cells based
compared to the small molecule counterparts. However,
on the covalent linked ones. It is time that the percep-
looking at the structures of the non-covalent D-A systems
tion that the self-assembly approach is not so successful
that have shown promise, it is clear that one can no longer
as a design strategy should be changed. More and more
claim that their synthesis is easily achieved compared to
such systems should be developed and tested so that a li-
the covalent D-A designs. Almost equal synthetic as well
brary is created and comparison would become more reli-
as purification efforts is required for both the successful
able. Unfortunately, the best results of the covalent or non-
covalent and non-covalent routes.
covalent D-A systems also have not so far matched the ef-
Among the covalent D-A design, the alternate D-A ap-
ficiencies exhibited by the donor polymer/small molecule
proach, which is much simpler compared to the block
(PCBM) state-of-art blend solar cells, which have reached
copolymer in terms of synthetic effort, seems to be good
PCE >9% [12].
performers, based on the literature reports available so far.
Although block copolymers have definitely proved more
Acknowledgement: N.B.K., S.S. and B.S thank CSIR-New
successful compared to the random analogues; probably
Delhi for SRF fellowship.
simpler synthetic strategies need to be evolved to make
them appear less daunting so that more of them are devel-
oped and studied in actual devices. It was quite surprising
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Org. Photonics Photovolt.

Review Article Open Access

Nagesh B. Kolhe, Shekhar Shinde, B. Saibal, and S. K. Asha*

Novel Approaches in the Design of Donor-Acceptor

© 2015 S. K. Asha et al., licensee De Gruyter Open.

beneficial to improve the efficiency of BHJ solar cell de-

lakkat and coworkers reported a set of crystalline–

be improved by optimizing physical parameters like sol-

Adv. Funct. Mater. 17, 2007, 1493. 10252.

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