Review

Received: 8 June 2011 Revised: 10 October 2011 Accepted: 10 October 2011 Published online in Wiley Online Library: 5 January 2012

(wileyonlinelibrary.com) DOI 10.1002/pi.3233

Organic solar cell materials and active layer designs improvements with carbon nanotubes: a review
Bernard Ratier,a Jean-Michel Nunzi,b Matt Aldissi,a Thomas M Krafta,b and Erwin Buncelb
Abstract
Organic solar cells offer an opportunity to diversify renewable energy sources owing to their low technological cost. They are amenable to large surfaces and can easily be integrated into buildings. It is necessary, however, to improve their energy efciency and durability for the development of a sustainable technology. In these devices, photovoltaic conversion is based on the separation of photogenerated charges at an interface between electron donor and acceptor materials, which imposes some constraints on the photoactive layer of the cells. In this paper, which includes some of our studies, we address optimization of the active layer: absorption and exciton dissociation steps, the open-circuit voltage and the active layer morphology. A promising direction proposed to improve the active layer morphology and cell efciency is the incorporation of highly anisotropic nanoparticles such as carbon nanotubes, which may facilitate charge transport to the electrodes. Dispersion and orientation of the nanotubes in the organic matrix are discussed and we suggest an ideal model polymer solar cell which will maximize performance of the cells by using carbon nanotubes in the active layer. c 2012 Society of Chemical Industry Keywords: organic solar cell; polymer solar cell; bulk heterojunction; carbon nanotube; carbon nanotube functionalization; electric eld orientation; interpenetrating network morphology

INTRODUCTION
Electronic devices based on conjugated organic materials are being developed at a fast pace due to the unique electrical and optical properties exhibited by such materials in addition to their low cost and processing advantages. For example, n- and p-type materials can be achieved, and low-cost deposition processes such as printing can be used with the expectation of low energy pay-back time. Because organic electronic devices are based on thin lms, exibility, light weight, semitransparency and large-area applications, they present an attractive alternative to their inorganic counterparts. The worldwide demand for low cost and clean energy sources has never been greater. With a desire to reduce the negative environmental impact that fossil fuel consumption has on earth, we must seek methods to harvest energy from alternative sources. These sources need to be abundant and available worldwide. Our omnipresent energy source is the sun. Conversion of sunlight to electricity is achieved by the photovoltaic process. The majority of solar cells currently available on the market are rather expensive and relatively rigid compared with polymer solar cells (PSCs). PSCs represent a photovoltaic technology which should be able to deliver lowcost, exible, large-area solar modules worldwide. For this reason, the use of PSCs is expected to increase rather rapidly in niche markets, such as energy sources for use in remote areas, and on a longer term in organic photovoltaic modules which should be easily integrated into buildings (i.e. on roofs and semitransparent windows).1 Many recent and relevant efforts have been published in the last few years on the design and synthesis of active layer

polymeric materials,2 their electronic and optical properties,3 polymerfullerene bulk heterojunction (BHJ) solar cells,4 6 smallmolecule organic solar cells7,8 and their electronic doping.9 One major drawback of organic solar cells is their low overall power conversion efciency, although great improvements have been obtained throughout the last decade, from less than 1%10 to more than 8%11 established by the main leading companies in the domain: Solarmer (8.13%) and Konarka (8.3%) with PSCs, and Heliatek (8.3%) with small-molecule organic solar cells. There have been tremendous efforts aiming to increase the efciency of PSCs by modifying various components of the cell. One such modication is the incorporation of carbon nanotubes (CNTs), which is the subject of this short review. The rst part focuses on recent progress and insights relative to light absorption, charge separation and active layer morphology of the PSCs. The second part is a discussion of the inclusion of

Correspondence to: Bernard Ratier, XLIM UMR 6172, Universit e de Limoges/CNRS, 123 av. Albert Thomas, Limoges, France. E-mail: bernardratier@unilimfr Jean-Michel Nunzi, Department of Chemistry, Chernoff Hall, Queens University, Kingston, ON K7L, 3N6, Canada. E-mail: nunzijm@queensuca

a XLIM UMR 6172, Universit e de Limoges/CNRS, 123 av. Albert Thomas, Limoges, France b Department of Chemistry, Chernoff Hall, Queens University, Kingston, ON K7L 3N6, Canada

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www.soci.org CNTs in the PSCs active layer. Because of their high anisotropy, such nanoparticles are expected to show unique properties that may improve the quality of the interfaces and the transport of photogenerated charges to the electrodes.

Erwin Buncel, Professor Emeritus at Queens University, is a physical organic chemist with strong interests in the cognate disciplines of bioorganic, environmental, and materials science. Major interests include photochromic materials, the reactivity of heteroaromatic superelectrophiles, and carbanion chemistry. Buncel is the author/coauthor of over 300 research papers in these areas, as well as a number of chapters, review articles and monographs. Dr. Matt Aldissi received his M.S. degree and Ph.D. in polymer science from the University of Montpellier, France. Successively postdoc at the Univ. of Pennsylvania, staff member at Los Alamos National Laboratory, vice president for Advanced Technology at Champlain Cable Corp., Business Development Mgr at Foster-Miller Inc., senior staff scientist at Cape Cod Research. He is now President of Fractal Systems Inc., a company he founded in 1997. He spent 2-year sabbatical at the University of Limoges, France, in organic optoelectronics (2008/09 and 2010/11). Bernard Ratier is a full professor of Physics at Limoges University, France, where he received also his Ph.D. degree (1990). He works on optoelectronic properties of -conjugated materials and currently he is the head of the Plastic Optoelectronics group at XLIM Research Institute where organic devices and mainly solar cells are developed (8 grants with EC, ANR, DGA,CNRS and Disasolar). Jean Michel Nunzi is T1 Canada Research Chair, member of the NSERC Photovoltaic innovation Network in Canada, Chairman of the SPIE Conference Large-Scale Organic Device Fabrication. He was the chairman of the rst successfully granted EC project on Organic Solar Cells (EUROSCI) in 1996. He built in Angers the rst team dedicated entirely to the technology of Plastic Solar Cells in 2000. Thomas M. Kraft is a PhD candidate in the department of chemistry at Queens University (Canada) and the XLIM research institute at the University of Limoges (France). He received his MSc in chemistry from Queens University (2011) studying polymer : carbon nanotube organic photovoltaics. Thomas specializes in polymer solar cell research and is currently investigating their large-area fabrication via inkjet printing.

POLYMER SOLAR CELLS, A BRIEF REVIEW

Device description Nowadays, the most studied organic solar cells are donoracceptor BHJs where the photoactive layer is made of an electron donor D and an electron acceptor A. These devices function by a mechanism (see Fig. 1) that is controlled by interfacial processes: charge carriers are photogenerated and subsequently separated at the donoracceptor interface by exciton dissociation.12 14 Photons pass through the transparent electrode (often a thin lm of indium tin oxide, ITO) and are absorbed by the polymer. The energy stimulates a coulombically bound electronhole pair, known as the exciton, from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). This is followed by exciton dissociation that occurs due to electron transfer from the LUMO of the donor to the LUMO of the acceptor. Charge transport of the hole (from the donor) to the anode and the electron (from the acceptor) to the cathode enables these charge carriers to ow through the external circuit and create electricity as illustrated in Fig. 2. To summarize, the successive steps that must be optimized are (a) polymer photon absorption, which should match well with the solar spectrum, (b) exciton generation and diffusion to the DA interface, (c) exciton separation into free charges at this interface, (d) charge transport to the electrodes and (e) charge collection at the electrodes. The interface is of paramount importance in such devices. Due to their short lifetime and low mobility, the diffusion length of excitons in organic semiconductors is limited to ca 10 nm, which means that the distance to the interface from the point of exciton generation anywhere in the active layer should be of the order of its diffusion length.15 In the case of planar heterojunctions, thinning the active layers in order for each photogenerated exciton to reach the DA interface and to be separated into free charges has the benet of reducing the series resistance of the cell, but the drawback is a drastically reduced light absorption. The polymer-based BHJ solar cell (see Fig. 2) is generally considered thus far as the most promising architecture in

Figure 1. HOMO and LUMO energy levels of the photoinduced charge transfer within BHJ solar cells.

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Figure 2. Interpenetrating network of the donor and acceptor active layer in a BHJ cell (left) and general PSC composition (right).

(a)

(b)

(c)

(d)

Figure 3. Some of the most studied materials used in PSCs. Donor conjugated polymers: (a) poly(2-methoxy-5-((3 , 7 -dimethyloctyl)oxy)-1,4phenylenevinylene) (MDMO-PPV); (b) poly(3-hexylthiophene) (P3HT). Acceptor fullerene derivative: (c)6,6 -phenyl-C61-butyric acid methyl ester (PCBM). Hole injection layer: (d) poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) (PEDOT : PSS).

comparison with other organic solar cell congurations currently under study. The conceptual advantage of such a device is that the interface area is signicantly enhanced relative to other types of heterojunction and that a thicker photoactive layer, optimized for light absorption, can be implemented in the devices.16,17 Another signicant advantage of the concept is its robustness which can be implemented with many different polymers.18 The challenge here is to manipulate the donor and acceptor components such that the interface is maximized.19,20 Enhancing charge carrier transport in organic and polymer materials can be achieved by increasing their crystallinity. Hence, a nanoscale interpenetrating network (IPN) of both components with crystalline order seems to be a preferable architecture for the active layer. In polymer solar cells, this IPN is obtained by blending a donor (conjugated polymer) and an acceptor (buckminsterfullerene derivative), sandwiched between two electrodes. The most common buckminsterfullerene derivative is [6,6]-phenyl-C61butyric acid methyl ester ([C60 ]PCBM or PCBM) which is miscible with conjugated polymers, a highly efcient electron acceptor with a relatively high electron mobility. Many electron donor conjugated polymers are used in PSC studies, the most common

being poly(phenylene vinylene)s, polyuorenes, polycarbazoles and polythiophenes (Fig. 3).2 Most commonly, charge extraction is achieved using ITO, which has a high work function, as the positive electrode (anode) and aluminium, which is a low work function metal, as the negative electrode (cathode). The positive electrode (ITO) extracts holes from the active layer through a hole transport layer (e.g. poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) (PEDOT : PSS)), while simultaneously the negative electrode (Al) extracts the electrons. One of the most prominent concerns for polymer photovoltaics is their lifetime performance (longevity in air).21,22 Problems can arise from both excessive sunlight and also from the use of a low work function back electrode (e.g. Al) that can be easily oxidized in the presence of oxygen.23 Not only can sunlight alter the morphology of the layers within the cell but it can also induce interfacial degradation over the cells lifetime. Potentially, the cells can be made more durable by including polymers in the BHJ layer that are designed to have an increased Tg (glass transition temperature) or by crosslinking of the polymers.24 Oxidation of the electrode can be minimized by either encapsulating the low work function metal (e.g. capping with a less reactive metal) or by
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www.soci.org with VOC being the open-circuit voltage, ISC the short-circuit current, FF = Im Vm /(VOC ISC ) the ll factor of the cell, in the incident light energy ux and Ein = in A1 the incident light illumination (with A being the cell surface). EQE is the ratio of collected charge carriers (electrons) [Isc ()/A]e = JSC ()/e = ne () per incident photon ( in /A)/(hc/) = Ein /(hc/) = nph () at a specic wavelength (Eqn (2)), with expressed in nanometres. This value takes into account all the physical phenomena involved during the photovoltaic process.

Figure 4. Reverse BHJ solar cell with high work function back electrode (Ag).

EQE = EQE() =

dark light Iph Vm 1/rp slope VOC i ip rp Vj 1/rs slope (b) V RC rs I I

ISC () hc JCC () hc ne () = = nph () in () e Ein () e JCC () = 1240 Ein ()

(2)

Im ISC

Figure 5. Current versus voltage curve for a photovoltaic cell in the dark and under illumination and the equivalent electrical circuit.

using a metal electrode that has a higher work function.25 When a high work function metal (e.g. Ag) is used, the charge extraction within the cell must be inverted. This implies that the ITO will be used to extract electrons and that the silver back electrode will collect holes (Fig. 4). To ensure that this process works efciently, a hole blocking layer must be added between ITO and the BHJ layer to ensure that only electrons reach the negative electrode (ITO). Shaheen and coworkers deposited a zinc acetate lm (via spin coating) and subsequently performed a thermal conversion to form a zinc oxide (ZnO) hole blocking layer.23 A silver oxide (Agx O) layer on the silver electrode forms between the organic layer and the metal electrode. The silver oxide is a p-type semiconductor with a high work function that can effectively extract holes from the cell, whose efciency can be further increased by the introduction of a hole transport layer (PEDOT : PSS) between the silver electrode and BHJ layer. Solar cell characterization Several parameters (VOC , ISC , FF and Pmax ) need to be measured to quantify the overall efciency of PSCs (power conversion efciency, PCE) or external quantum efciency (EQE).26 Fig. 5 provides a visual illustration of the parameters on a solar cells I V characterization curve. The PCE (Eqn (1)) provides the efciency of the cell under illumination by the standard light source, air mass (AM) 1.5. AM 1.5 is 100 mW cm2 white light illumination matching the spectral intensity distribution on the earths surface when it is tilted at an angle of 48.2 with respect to the normal direction. maximal power produced per surface unit total incident light power per surface unit Pm Vm J m Vm Im FF.ISC VOC = = = = Ein in in in

Another interesting value is the internal quantum efciency IQE, with EQE = A IQE, where A is the absorption efciency of the cell. Regardless of the absorption efciency of the materials, IQE is a relevant indicator of cell quality and provides a qualitative assessment of its ability to separate excitons into free charges and collect them at the electrodes. From the PCE expression, it can be clearly understood that maximizing the performance of the solar cells consists of maximizing the values of VOC , ISC and FF. The FF parameter is greatly dependent on the cell technology and on the active layer morphology. As can be seen in Fig. 5, the I(V ) curves under illumination will show an ideal characteristic if the series resistance of the device rs is close to 0 and the shunt resistance rp approaches an innite value.27 The series resistance is attributed to both material resistivity and contact resistance of the cell. The higher charge carrier losses are, the lower is the shunt resistance. Charge carrier losses are due to cell imperfections which can result in short-circuit pathways. They could also be due to charge or mobility imbalance in the device inducing carrier recombination. The latter parameter is signicant and is dependent on the IPNs ability to separate and carry charges to the electrodes. The shunt resistance is largely dependent on charge carrier losses due to short-circuit pathways and carrier recombination. As we shall see in the next section, enhancing the ISC is equivalent to harvesting more photons. Most of the conjugated polymers used in solar cells do not absorb the red part of the solar spectrum. Shifting the absorption edge of the polymer from 550 nm (MDMO-PPV : PCBM solar cells) (MDMO-PPV is poly[2methoxy-5-((3 , 7 -dimethyloctyl)oxy)-1,4-phenylenevinylene]) to 1 m would imply an enhancement of the harvested photons from 25% to 90%.28 The VOC is directly linked to the respective energy levels of the donor and acceptor materials, so that ne-tuning this parameter will be linked to material pairing and tuning of the absorption and may inuence the exciton dissociation efciency. Optimizing the open-circuit voltage In a rst simple approach, exciton separation into free charges at the DA interface of an organic solar cell can be understood as a charge transfer of the electron from the LUMO of the donor to the LUMO of the acceptor. The gain in energy ( LUMO ) gives rise to the driving force necessary for charge separation (Fig. 6(b)). The separated charges will reach the LUMO of the acceptor (electron afnity A ) and the HOMO of the donor (ionization potential ID )

PCE =

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(a)
PEDOT:PSS 3.0 P3HT 3.7 PCBM Al 4.2

(b)

Energy S1 LUMOdon T1 CT T1 LUMOacc

Eex

D A

ID - A
Eg don

ITO 4.7

5.2

4.9

6.1
Figure 6. (a) Energy band diagram of a P3HT : PCBM solar cell. (b) Charge transfer mechanism between donor and acceptor materials. Blue arrows indicate the right way to improve the VOC or the polymer absorption, red arrows the way to improve absorption which is detrimental to the VOC .

S0
Figure 7. Exciton dissociation scheme at the DA interface including the inuence of the geminate pair state. Two cases are described: the blue arrows represent efcient dissociation when the triplet state energy is located above the CT state, and the red arrows represent the geminate pair recombination when the triplet state energy is located below the CT state.

for electrons and holes respectively. More precisely, the exciton binding energy Eex is somewhat lower than the donor band gap, so that the separation condition will be Eex > ID A . In the case of poly(3-hexylthiophene) (P3HT):PCBM solar cells ( LUMO = 0.7 eV), the exciton separation efciency is assumed to approach 1 (Fig. 6(a)). Considering electrodes with ohmic contact, acceptor donor | |ELUMO |) V 29 VOC can be expressed as VOC = (1/e) (|EHOMO where 0.2 V < V < 0.5 eV depending on the nature of the polaron states in the material.30 From Fig. 6(b), one can conclude that it is possible to improve performance of the solar cells in two ways: the rst is to decrease the material band gap in order to increase the absorption, which will give rise to an increase of the photogenerated charges, and the second is to enhance VOC by lowering the ionization potential ID of the donor material or to enhance the electron afnity of the acceptor A . However, it is also possible to enhance both VOC and the absorption by decreasing together the ionization potential and the electron afnity of the polymer (with a larger decrease of the electron afnity in order to lower the band gap). Several models have been developed following these design rules. Scharber and coworkers29 have tuned the energy level of the polymer with respect to PCBM as the acceptor material and with a driving force LUMO higher than 0.3 eV, while Koster and coworkers31 have studied the combined inuence of the driving force LUMO (maintained at >0.5 eV), the polymer band gap and the energy levels of the acceptor. Both studies yield predicted efciencies around 10% for a single polymer cell. Other efciency predictions have been made in the case of tandem solar cells.5,32 These devices consist of two (or more) superimposed cells, with the front cell absorbing the blue part of the solar spectrum while the back cell absorption is efcient in the red part of the solar spectrum. The cells are generally connected in series by an intermediate electrode recombining the electron current of the front cell with the hole current of the back cell. The resulting efciency is increased by the absorption broadening and by the addition of the VOC of the two cells. This device architecture is one of the most promising ways to improve the efciency and is intensively studied by many groups.33 Modelling tandem solar cells has been investigated with optimization of each cell, including the absorption domain of each cell according to Scharbers rules. The modelling effort suggests that, with a 1.7 eV band gap polymer in the rst cell and a 1.1 eV band gap polymer in the second, optimized efciencies higher than 15% can be obtained. However, these design rules have been established with a very simple description of the charge separation mechanism by photoinduced charge transfer from the donor to the acceptor material. One has to take into account the fact that, upon exciton

dissociation at the DA interface, there is an intermediate state where electrons and holes are separated but are not released from coulombic attraction. This intermediate state is often called a geminate pair, where the electron is energetically located at a charge transfer (CT) energy state below the acceptor LUMO level (Fig. 7), depending on the donoracceptor interaction.6,34,35 The energy level of this CT state is of prime importance with respect to the triplet states T1 of both donor and acceptor materials. If the triplet state energy level is located below the CT state (red case in Fig. 7), energy transfer by intersystem crossing from the CT to the T1 states is favourable, recombining the geminate pair into a triplet exciton and followed by decay to the ground state. This process may be responsible for a signicant decrease of the charge separation efciency. In MDMO-PPV : PCBM solar cells, only 60% of geminate pairs can be separated into free carriers in the best case when the polymerfullerene ratio is 1 : 4. Reducing the PCBM amount provokes a decrease of this efciency to 40%.36 The PCBM concentration increase will enhance the dielectric permittivity of the blend, lowering the coulombic attraction of the geminate pair. Consequently, the absorption of the cell is signicantly decreased by this high PCBM concentration. If the triplet state is located above the CT state (blue case in Fig. 7), the charge separation is of course efcient, as in the case of the P3HT-PCBM blend where the exciton dissociation efciency is assumed to be near 90%.37 Taking into account the charge separation efciency introduces a new constraint to the design rule of the polymers. For example, new materials with very low energy difference between singlet and triplet states need to be synthesized. However, another way to circumvent geminate pair recombination will be to increase the dielectric permittivity of the materials in order to diminish the electronhole coulombic interaction. The above mentioned expression of the open-circuit voltage 29 has to be considered as the upper limit given by the intrinsic VOC electronic properties of the materials. Beside these properties, one has to take into account that the VOC value will be given by the respective quasi-Fermi levels of the electrons in the acceptor material and of the holes in the donor material, which depend themselves on the charge carrier densities. Thus so far these carrier densities will depend on generation/recombination rates and charge trapping, the latter parameters being greatly affected by temperature, light intensity and morphology. In the open-circuit regime and for high light intensities, photogenerated charge carrier densities increase due to the absence of drift mobility, and the bimolecular recombination process is prevalent. With
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Organic solar cell materials and active layer designs such assumptions the open-circuit voltage will decrease linearly with temperature and logarithmically with light intensities, so that the temperature effect is prevalent.38 At lower light intensities, corresponding to lower VOC , monomolecular recombinations governed by the traps have to be taken into account. It has been evidenced by controlling the amount of impurity in the BHJ that trap recombinations are also responsible for a decrease of the open-circuit voltage.39 The transition between monomolecular and bimolecular regime has been experimentally observed by transient voltage decay measurement, increasing light intensity and temperature.40 Designing new polymers and fullerenes in light of model predictions During the past few years, signicant progress has been made in the development of new low band gap electron donor polymers with absorption spectra extending to larger wavelengths of the solar spectrum. Their HOMO and LUMO levels have been engineered for a better spectral match than those of P3HT when blended with PCBM for a higher VOC . According to Scharbers rule,29 the decrease in the optical gap should be done by lowering the energy of the donor materials LUMO and if possible maintaining or reducing as much as possible the HOMO to promote high values of VOC . The synthesis of these materials, combined with band modelling, with PCBM as the acceptor, has been initiated by groups led by Leclerc (University of Laval),41 Yang (University of California at Los Angeles, UCLA)42 and Yu (University of Chicago).43 These new polymers are based on DA monomer units resulting in alternative copolymers. The objective is to lower the materials electron afnity by adding electron-decient units (acceptor) to electron-rich units (donor), resulting in an intramolecular charge transfer. The reduced band gap is thus formed by the CT states resulting from the donoracceptor unit interaction.2 However, precautions must be taken, so that the HOMO is maintained at a relatively lower energy level than the oxidation threshold of oxygen (around 5.3 eV) to obtain stable materials.41 The rst achievements with devices showing a signicant increase of cell efciency have been made by Heeger, University of California, the Gwangju Institute of Technology (South Korea) and the University of Laval, with a National Renewable Energy Laboratory (NREL) certied PCE of 6%.44 Solar cells made by Heegers group were fabricated with poly[N-900-hepta-decanyl-2,7-carbazole-alt-5,5-(40,70-di-2thienyl-20,10,30-benzothiadiazole)] (PCDTBT), a copolymer of carbazole derivative (HOMO energy 5.45 eV), giving a VOC around 0.9 V. The performance of their devices (20 cells out of 100 made) is due to (i) solvent optimization (dichlorobenzene), which provides a nanostructure for efcient diffusion of excitons to the DA interface; (ii) optimization of polymerPC70 BM mass ratio 1 : 4, which ensures the IPN formation; and (iii) the use of a TiOx optical spacer at the cathode, which allows for eld connement into the active layer. Their average cell performance consisted of a PCE = 6.1% under AM 1.5 illumination for fresh cells without heat treatment, an NREL certied PCE of 5.96% on the same aged cell and a VOC = 0.88 V which is close to the theoretical maximum. In addition, the internal quantum efciency value, as deduced from measurements of the external quantum efciency and the absorption spectrum, was found to be close to 100% over the whole absorption wavelength range. This shows that the cell operates at its optimum, probably due to a nearly ideal nanostructure. However, the cell exhibited a low absorption due to a high concentration of PC70 BM (80 wt%) in the active layer, resulting in a
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www.soci.org short-circuit current density of only 10.6 mA cm2 . New records followed, established by the group of Yang (UCLA) in collaboration with the spinoff company Solarmer, using the University of Chicagos materials, the rst with an NREL certied PCE of 6.77%45 and, a few months later, an NREL certied PCE of 7.9%.46 As with the above effort by Heegers group, the cells use a low band gap alternating copolymer, poly[4,8-bis-substituted-benzo[1,2-b:4,5b ] dithiophene-2,6-diyl-alt-4-substituted-thieno[3,4b] thiophene -2,6-diyl] (PBDTTT)47 whose monomer unit consists of a thienothiophene and a benzodithiophene. This polymer mixed with PC70 BM had previously shown excellent performance:47 PCE = 5.7% with short-circuit current density exceeding 15 mA cm2 , but only with a VOC of 0.56 V. Improvements have been obtained subsequently by an overall lowering of the polymers HOMO and LUMO levels by replacing in three different polymers the alkyloxy side groups by alkyl groups, and reinforcing the electron accepting character of thienothiophene (the acceptor moiety of the comonomer) by grafting a uorine. The maximum theoretical VOC should be in this case about 0.9 V. It should be noted that the polymerPCBM weight ratio does not exceed 1 : 1.5 for the best polymer, which is much more favourable to a good absorption by the active layer. This results in large photogenerated current densities of 1315 mA cm2 for the three types of cell. As might be expected, the gradual lowering of the HOMO level for the three different polymers helps to increase VOC up to 0.76 V. It follows that the average PCE values (as determined by characterization of 75 cells of each type of material) obtained with fresh devices are quite exceptional, around 7.4% for PBCTTT-CF (with a maximum of 7.73%) and an NREL certied PCE of 6.77% (probably for the aged cell). The authors concluded that further improvements are undoubtedly possible by lowering the HOMO level of the polymer, since the maximum VOC has not yet been attained. A study of the morphology of the blends reported an active layer relatively nonstructured and unorganized compared with that usually observed in the most efcient P3HT-PCBM blends. This may indicate that the optimization of new polymers does not necessarily follow all the rules established for P3HT. Adding a small quantity of diiodoctane to the solvent (dichlorobenzene) resulted in diminishing phase separation in the blend, leading to a better dened nanomorphology of the active layer. This solvent-assisted manipulation of the morphology resulted in a signicant enhancement of the ll factor and 7.4% efciency.48 It should be noted that following the publication of this work Solarmer has set new records that have been documented this time by the Newport Technology and Applications Centers Photovoltaic Lab with 7.6% for a cell and 3.9% for a module, and more recently (2 December 2009) 7.9% by NREL. However, the certication was based on cells of 0.1 cm2 area through an aperture of 0.047 cm2 , which is far from the recommended area of 1 cm2 . Recently, benzodithiophene derivatives have been investigated as high performance polymers49 with high efciencies measured on large-area cells (5.5% on 1 cm2 ) in open air. Solvent mixing with diiodoctane seems to produce remarkable effects on the nanomorphology, giving rise to higher ll factors and current densities.50 Comparatively fewer studies have been dedicated to acceptor optimization with the same objective. Better absorption has been obtained with PC70 BM44,48,49,51 due to its asymmetrical structure which hinders the forbidden transition encountered with the highly symmetrical C60 molecule, but no noteworthy results were achieved with respect to energy matching with the donor polymer. A rst study concerns a by-product of PCBM

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www.soci.org synthesis, bisPCBM, which presents a LUMO 0.1 eV higher than that of PCBM. Considering that the resulting VOC is proportional to acceptor donor | |ELUMO |, this higher LUMO level is assumed to increase |EHOMO the devices VOC , what was experimentally measured as an increase of 0.15 V of the VOC and a 20% increased efciency compared with cells made of PCBM.52 A new C60 derivative molecule, indene-C60 bisadduct (ICBA), can be easily obtained from a heated solution of C60 and indene in trichlorobenzene.53 Moreover, its solubility in the most used solvents is slightly better than that of PCBM. Although its absorption in the UV-visible exhibits a far lower level than that of PCBM in the 200300 nm range, it is higher in the 300500 nm range, which is useful with respect to the action spectra of the organic solar cells. In addition, the LUMO level derived from cyclic voltammetry is 0.17 eV higher than that of PCBM. Solar cells with active layers made of P3HT-ICBA and P3HT-PCBM blends with a 1 : 1 donoracceptor ratio have been achieved and their photovoltaic performances compared. The devices were made with an average active layer thickness of 200 nm, using the solvent annealing method. The results indicate a better performance with the cells made of P3HT-ICBA blend: a better power conversion efciency of 5.44% (compared with 3.88% with PCBM), better ll factor (0.67 compared with 0.62) and, as predicted, a remarkably high VOC = 0.84 V (compared with 0.58 V in the case of PCBM). The increase in VOC which can be clearly correlated to the higher LUMO level of the molecule shows that cell optimization is also possible by ne-tuning the acceptor energy levels and matching with those of the donor polymer. Morphology of the active layer As has been emphasized above, the IPN morphology of the active layer plays a key role in building efcient devices. The ideal IPN should meet the following criteria: (i) a maximum interfacial area to favour exciton dissociation; (ii) a domain size of the order of magnitude of the exciton diffusion length; (iii) effective crystallization of the two compounds of the IPN so as to favour high mobility charge transport and charge balance between holes and electrons and to limit the charge recombination; and (iv) a bicontinuous IPN, which means that the different domains of the two materials have to be linked to create percolation pathways to the electrodes. The absence of some or all of the above properties can seriously affect the cells ll factor. Processing conditions inuencing the morphology are the solvent used in the blend formulation and thermal annealing. The effect of the solvent has been clearly established in the case of MDMO-PPV : PCBM PSCs where toluene was replaced by dichlorobenzene, doubling the device efciency.54 As observed by SEM and AFM experiments, the improved efciency is attributed to the different morphologies obtained in the two cases, where the use of toluene results in a large domain size and non-bicontinuous IPN, while dichlorobenzene allows a 10-fold decrease of the domain size.55 Nanobres of P3HT prepared in p-xylene56 were found to signicantly improve the P3HT-PCBM blend morphology when added at high concentrations to amorphous P3HT. The resulting absorption is remarkably enhanced in the 500650 nm range, with a highly structured spectrum. Another fruitful strategy consists of adding a high boiling point selective solvent (i.e. only PCBM is soluble in it) in the solution.57 In this case, P3HT crystallization occurs more rapidly, and a PCBM liquid phase can more easily interpenetrate the P3HT. The resulting morphology is improved where more interconnected and crystallized fullerene domains in the IPN are observed, improving electron transport in

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the cell. This strategy seems to be efcient in the case of the new low band gap generation polymers.45,50,58,59 In all cases, the resulting IPN morphology originates from the non-miscible nature of the polymer and the fullerene. This is where the deposition process (from solution formulation to the annealed active layer formation) has a great inuence: spin coating at various speeds and durations will yield different morphologies. The solvent annealing process, which leads to phase segregation after deposition of the solution under a saturated solvent atmosphere, affects the spinodal decomposition in the liquid phase and can yield efcient devices.60 Consequently, it may be possible to control the phase separation kinetics by changing the materials concentration.61,62 It was shown by the Plastic Optoelectronics Group (Limoges University, France) that, at very high material concentrations in the liquid phase, the free space limitation between moieties will slow down molecular rearrangement giving a smaller segregated domain size.62 The high efciency solar cells thus obtained have been observed by ultrahigh vacuum near eld investigation (Kelvin probe force microscopy), performed by the CEA (Grenoble, France), and have given the best resolved surface potential images of a P3HT-PCBM active layer blend to date,63 with an IPN domain size around 15 nm. However, thermal annealing remains the last step of the phase separation process where the molecular weight, regioregularity and dispersity have an important role to play, which means that the appropriate annealing parameters are polymer-dependent. It has been shown that in the case of P3HT and poly 3-butylthiophene (P3BT) cells,64 a polymer with high dispersity and high molecular weight generally results in the best performance but with no clear correlation between material properties and annealing temperature. Not surprisingly, different optimized annealing temperatures and times can be found in the literature, varying in most cases from 100 C to 150 C.62,65 68 The most commonly agreed upon mechanism occurring during thermal annealing is (i) enhancement of the polymer crystallization into larger grains, (ii) PCBM diffusion between P3HT crystallites forming needles and (iii) formation of the IPN. An opposing view of the concept of the phase separation mechanism does exist and has been reported by Hein and coworkers, rst in the case of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4phenylene-vinylene] (MEH-PPV):C60 cells (PPV, poly(m-phenylene vinylene))69 71 and then in the case of P3OT : PCBM cells (P3OT, poly(3-octylthiophene)).72 The authors have studied interdiffusion during thermal annealing of the polymer and the fullerene from bilayer devices achieved by successive spin coating and annealing steps of MEH-PPV, followed by C60 sublimation, or by successive spin coating and annealing steps of P3OT and PCBM respectively in orthogonal solvents. Diffusion of the fullerene into the whole polymer layer is effective after annealing at a temperature around 150 C for 2030 min. The best PCE, around 1%, was obtained in the case of P3OT : PCBM cells, where the resulting morphology consists of opposite gradient concentrations of the two materials in the bulk of the active layer. Very recently, the inter-diffusion of PCBM and P3HT has been studied by Treat et al. with the same bilayer device structure.73 Evidence for very efcient diffusion of PCBM into the P3HT layer has been established by SEM, dynamic secondary ion mass spectroscopy (DSIMS) (Fig. 8) and two-dimensional X ray diffraction, even at a very low temperature (50 C). The conclusion from the above efforts is that the nal blend composition is a three-phase structure: crystallized phase of pure P3HT, amorphous phase of pure PCBM and an amorphous mixture of P3HT and PCBM.
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(a)

(b)

(c)

(d)

Figure 8. Cross-sectional SEM images of a P3HTd-PCBM (deuterium substituted PCBM for SIMS detection) bilayer on a silicon wafer annealed at (a) 70 C, (b) 110 C and (c) 150 C for 5 min. The scale bar represents a distance of 200 nm. (d) DSIMS proles of 2 H in bilayer samples of P3HT and d-PCBM annealed for 5 min at different temperatures. Reprinted with permission from reference73 . Copyright Wiley-VCH Verlag GmbH & Co. KGaA.

Although morphology of the active layer is a key parameter and has prompted many studies, there is still lack of a clear relationship between physical and chemical properties of the materials and how exactly the morphology is inuenced by the device fabrication process. Predictive relations between properties, process and device efciency are an important milestone that has yet to be achieved for a large-scale organic solar cell technology to be viable.

Waals). These modications are performed to increase the CNTs solubility in various solvents, for their incorporation in a matrix (polymer, ceramic, metal). Nucleic acids have also been used for both non-covalent and covalent functionalization of CNTs.81 83 The interest in functionalization has recently grown enormously in an effort to explore and utilize the unique electronic and physical properties of CNTs. Covalent functionalization The tips and sidewalls of CNTs can be functionalized through covalent bonding, with the ends of the tubes being the most reactive. Acids (such as HNO3 , HNO3 + H2 SO4 , H2 SO4 in conjunction with KMnO4 ) that are often used for the purication and end opening of CNTs can also be used to functionalize the tips and defects of tubes with carboxyl (COOH) and alcohol (OH) groups. Oxidation of the tubes surface can allow for their electrostatically stabilized colloidal dispersion in water and ethanol.84 Further functionalization of the tubes with organic or inorganic materials can be achieved by reacting with the OH and COOH groups. Functionalization of the nanotube can serve to achieve enhanced solubility, self-assembly or also chemical sensing. There are numerous examples of nanotube functionalization schemes such as attaching long aliphatic amines to tube ends and attaching CNTs to each other forming macromolecules. In 1998, Smalley and coworkers connected nanotubes together in sequence by attaching NH2 (CH2 )11 SH groups via an amide linkage to the tips of SWNTs.85 Not only is it possible to add functional groups to the tube ends, but sidewall functionalization can also be achieved. When highly reactive reagents are used, it is possible to covalently

CARBON NANOTUBES IN POLYMER SOLAR CELLS

Carbon nanotubes (CNTs) have been incorporated into various components of organic solar cells to improve their efciency and enhance their reproducibility. Replacement of the ITO transparent anode with a thin single-walled carbon nanotube (SWNT) layer has been investigated by several groups.74 76 SWNTs functionalized with phthalocyanine-pyrene conjugates have also been utilized by Guldi and coworkers in dye-sensitized solar cells.77 Two different approaches published by us of this paper, discussed further, show that the use of SWNTs improves the photovoltaic properties of efcient polymer solar cells by structuring the BHJ active layer.78,79 However, the use of CNTs in organic photovoltaics is not limited to SWNTs as demonstrated by the incorporation of PCBM-functionalized multi-walled carbon nanotubes (MWNTs) in PSCs.80 For optimal efciency, CNTs may not be incorporated outright in PCSs. Various functionalization techniques have been developed in that respect. Functionalization of CNTs The physical and electrical properties of CNTs can be exploited through covalent bonding or non-covalent interactions (van der
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www.soci.org modify the tube walls. The reactivity of the tubes sidewall is increased as the diameter of the tube is decreased because the curvature increases. The sidewalls can be functionalized in many different ways which include uorination, formation of carbenes and nitrenes, alkylation and arylation, 1,3-dipolar cycloaddition of azomethine ylides, solution phase ozonolysis, addition of radicals, silylation, electrochemical reactions, and grafting of polymers. Polymer grafting can be accomplished via amide linkages when the carboxyl group on the nanotube is reacted with an aminopolymer (i.e poly[propinylethyleneimine-co-(vinyl alcohol)]). In a similar fashion, highly soluble linear polymers can also be attached via ester linkages, which can be accomplished with poly[(vinyl acetate)-co-(vinyl alcohol)] (PVA-VA). The latter method can increase the solubility of the nanotubes in many different solvents. Polymers can also be grafted to improve the nanotubes bonding in CNT/polymer composites. Ajayan and collaborators treated SWNTs with sec-butyllithium to create an initiator for the anionic polymerization of styrene.86 This resulted in polystyrenegrafted SWNTs in a single step. Even though the covalent modications of nanotubes mentioned above provide a means to incorporate these unique carbon structures into various applications, one drawback is that covalent bond formation disrupts the native electronic structure of the tube. However, covalent functionalization of SWNTs was also identied as a means to signicantly deplete the concentration of metallic tubes in the as-grown mixture which naturally contains a third of metallic SWNTs.87 Non-covalent functionalization To modify CNTs while retaining the original electronic structure, non-covalent functionalization can be used. Non-covalent modications are particularly important when pursuing applications that exploit the unique electronic properties of CNTs. This electronically mild functionalization normally occurs via van der Waals forces between the tubes and surfactants, planar aromatics (such as pyrene) or by helical wrapping by polymers around the tube.88 Surfactants (anionic, cationic or non-ionic) and diblock copolymers (hydrophilic : hydrophobic) are often used to solubilize both SWNTs and MWNTs in water.84 A commonly used ionic surfactant is sodium dodecyl sulfate (SDS) which coats the tubes, transfers charge to their surface and disperses the CNTs in water by electrostatic forces. This dispersion can be performed by addition of 1% SDS to an aqueous suspension of CNTs followed by ultrasonication. Other surfactants used to solubilize CNTs include the use of Triton-X-100 with sodium dodecyl benzene sulfonate (SDBS) and a poly(acrylic acid)-CTAB (hexadecyltrimethylammonium bromide) complex to form a lamellar structure on the surface of MWNTs.89 Polyelectrolytes can also be used to disperse the CNTs in water.90 Small molecules have been used to bind non-covalently to the surface of nanotubes. One of the rst research groups to try this was that of Dai in 2001. Dais group used a pyrene derivative to form interactions between the -orbitals of the planar pyrene and those of the CNT sidewall.91 Other groups have used various heterocyclic polyaromatic molecules, such as porphyrins and phthalocyanines, to modify the tube surface through van der Waals interactions. Another method to functionalize CNTs without covalent bonding is by polymer wrapping.92 Polymers are used to helically wrap around the nanotube surface to aid in the tubes possible application. In 2001, Smalleys group used poly(vinyl pyrrolidone) and poly(styrene sulfonate) to solubilize SWNTs.93 This work was published in the same year as research performed by Stoddart

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and Heath from UCLA in which polymer wrapping was performed with PPV with octyloxy sidechains to achieve soluble nanotube complexes.94 Polymer wrapping can be improved by the introduction of large planar aromatic groups into the polymer backbone to enable stacking between the polymer and the CNT. A pyrene-containing co-oligomer (n = 3) and SWNT fragment was theoretically investigated at Queens University to determine the optimized geometry of this interaction (Fig. 9).95 The geometry optimizations were performed semi-empirically using the Austin model 1 method (AM1)96 which illustrated the stacking attraction between the pyrene moiety and the CNT. CNT orientation by an electric eld Orientation of organic chromophores in a PSC has been used to improve photovoltaic efciency.97 In the case of CNTs orientation can originate from the strong anisotropy of the polarizability. The interaction of electromagnetic waves with conducting tubular molecules has been studied for a long time since the introduction of these materials in dielectric matrices can lead to a very high dielectric permittivity.98 Electric eld tends to orient the nanotubes parallel to it since the induced polarizabilities in parallel and perpendicular directions to the axis of the nanotubes have their relative values such that the dipole moment is mainly directed along the tube axis.99 CNT orientation is generally achieved and observed by biasing planar interdigitated structures where a drop of CNT solution is deposited. Dipoleelectric eld coupling is carried out under DC or AC elds. The effect of an AC eld reinforces the CNT alignment in solution as the induced agitation can generate free space around the nanotubes, which helps their orientation.100 Moreover, superimposing a DC offset to a low frequency signal (a few hundred hertz) leads to an aggregation of the nanotubes near one of the electrodes, cathode or anode, depending on the positive or negative charge sign of defects in the nanotubes.101,102 Double-wall (DW) CNTs have also been oriented in a P3HT polymer matrix by application of the electric eld in the liquid phase during the deposition of the composite.103 The nature of the solvent can signicantly inuence the type of CNT charged defect, and opposite migrations toward the electrode have been noticed in the case of chloroform and dichlorobenzene. Polymer/CNT composites Research to develop high performance functional materials has been conducted for over 10 years using composites of CNTs and polymers. The CNTs can be incorporated with or without prior functionalization. The pristine, functionalized or polymer grafted nanotubes can be dispersed in polymer matrices through various methods that include melt processing (disperses CNTs in melted thermoplastic polymer), solution processing or in situ polymerization. CNT composites have been prepared with thermosetting resins and polymers that are solvent-processable, semicrystalline, amorphous, liquid crystalline and -conjugated. It has been shown that the CNTs can enhance many different properties of the materials. Properties such as strength, stiffness, thermal stability, solvent resistance, glass transition temperature (Tg ), crystallization time, crystallinity, electrical conductivity, reduced thermal shrinkage and optical anisotropy can be enhanced by the presence of CNTs. The improved qualities provided by the incorporation of CNTs in different materials can be exploited in numerous applications. These applications include chemical and physical
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Figure 9. Interaction between an SWNT fragment and a quaterthiophene-pyrene co-oligomer.95 .

sensors, probe tips for AFM, electrically and thermally conducting bre functional textiles, nanowires, quantum wires, nanoscopic levers, components in molecular motors and other molecular devices. CNT composites in the biomedical eld can be used as scaffolds for tissue growth, substrates for neuron growth, actuators, and novel microporous and mesoporous carbon structures for ltration. In the electronics eld, these CNTenabled materials can be used in eld emission display devices, packaging materials for thermal management, supercapacitors for charge storage devices, electromagnetic interference shielding, and photovoltaic cells. In 2000, Ago and his fellow researchers were the rst to investigate the electronic properties of a conjugated polymer/CNT composite made of PPV and MWNTs.104 They demonstrated that there was a strong interaction (energy transfer) between the photoexcited conducting polymer and the MWNTs. The main electronic interaction was found to be nonradiative energy transfer of singlet excitons from the polymer to the nanotube. Since this initial work, research efforts have been performed to investigate -conjugated polymer/CNT composites in BHJ solar cells. Polymer/CNT composites for photovoltaic cells Numerous efforts have been made to take advantage of the electronic and structural CNT properties in PSCs. The acceptor, which must have greater electron afnity than the polymer, can be replaced by single-walled, double-walled or multi-walled nanotubes. CNTs have a high surface area which provides an ideal morphological architecture for exciton dissociation. The nanotubes high aspect ratio (>1000) allows for the creation of percolation pathways at low doping levels and this provides a means for high carrier mobility and efcient charge transfer to the appropriate electrodes. SWNTs were rst used as the acceptor in the PSCs BHJ by Kymakis and Amaratunga who blended P3OT with 1 wt% CNTs.105 The performance of the solar cells was increased with respect to VOC and ISC . The addition of SWNTs introduced internal polymernanotube junctions, which allowed for exciton dissociation and a continuous path for electron transport to the cathode. The semiconducting SWNT has an n-type character106 and the ability to promote charge separation and electron transport. Low efciencies of SWNT-based solar cells can be associated with a few factors such as the presence of metallic
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SWNTs that short circuit the cell (reducing the shunt resistance), impurities (mostly metal catalyst residue), SWNT aggregation, and low charge carrier mobility in the polymer matrix. Ab initio calculations have been used to evaluate the electron charge transfer ability in such polymerCNT heterojunctions.107 It was found that only semiconducting SWNTs can favour the electron charge transfer. It is clearly possible to predict VOC from the heterojunction energy band diagram deduced from this study which has shown that it remains very low (0.3 V) even in the most favourable conguration (polymer chain parallel to the CNT). This result is compatible with the experimentally measured VOC for such P3HTCNT heterojunctions.105 Conversely, high charge transfer ability has been experimentally evidenced on nanoplanar heterojunction structures consisting of highly oriented and isolated SWNTs grown by chemical vapour deposition parallel to the substrate on which was deposited a P3HT layer.108 A heterojunction based on one SWNT and P3HT was estimated to yield a 3% efciency with a surprisingly high VOC of 0.5 V. This higher VOC was obtained with an n-type SWNT doped by a prior coating of polyethylene imine, shifting the Fermi level close to the LUMO level. The authors attributed their nanodevice performance, 50100 times higher than those obtained in P3HTCNT blends, to the fact that no CNT aggregation was present to create CNTCNT junctions which hinder the effect of the isolated CNTP3HT junction. Thus a perfect CNT dispersion in the polymer matrix seems to be mandatory for efcient devices. Nogueira and colleagues tried to mitigate some of these potential problems by the covalent functionalization of SWNT ends and defects with thiophene moieties.109 The thiophene pendent groups were used to increase the dispersion of the tubes in a P3OT matrix. It is critical that the nanotubes are dispersed homogeneously throughout the polymer matrix to achieve an optimized interfacial area for charge transfer. Hummelgen and colleagues also used a P3OT/SWNT composite to prepare a solar cell that yielded power conversion efciencies of 1.48% under 15.5 W m2 light.110 The solar cell had a CNT composite layer deposited on a polybithiophene layer between the two electrodes. Pal and coworkers also used two layers within their photovoltaic devices.111 The solar cells produced by their group had a C60 layer vacuum evaporated on a spin coated MWNT/P3HT composite. The nanotubes were used to aid in exciton dissociation and extract charges toward the ITO electrode. Fullerenes were also

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www.soci.org used by Mitra and coworkers to functionalize SWNTs for their incorporation into a P3HT composite to be used as the active layer in a BHJ solar cell.112 There was improvement in both the ISC and FF by taking advantage of the acceptor nature of fullerene and the charge transport capability of SWNTs. PSCs that used CNT/P3HT composites were studied by Arranz-Andr es and Blau who used SWNTs, DWNTs and MWNTs.113 It was found that the CNTs induced local order of the polymer chains and that there was an increase in the PCE, VOC , ISC and FF compared with cells without CNTs. CNTs within the cell should ease exciton dissociation and charge extraction. Multi-component composites of CNT/P3HT/PCBM were used as the active layer in BHJ cells prepared by Berson and coworkers.114 They prepared dilute solutions of SWNTs and MWNTs which they added to solutions of P3HT/PCBM. This threecomponent mixture, dissolved in chlorobenzene, was spin coated to prepare the thin lm active layer in various photovoltaic devices. A power conversion efciency of 2.0% was achieved with a 1 : 1 P3HT/PCBM solution with 0.1 wt% MWNTs. It was found that thermal treatment of the DA layer was necessary to ensure high current density. The thermal annealing of the BHJ active layer produces a nanostructured morphology that reduces charge carrier recombination which can occur in the polymer composite (due to the proximity of the donor and acceptor). The polymer/CNT solutions used to prepare the BHJ thin lm must be stable and free of CNT aggregates. This is successfully achieved with conjugated polymers whose chains interact with the nanotubes via stacking. When SWNTs are used as the acceptor in the BHJ, internal polymernanotube junctions are present which allow for the photoinduced electron transfer from the polymer to the SWNT. Kymakis and colleagues who used SWNTs as an acceptor with P3OT found that the solar cell had an increased photoresponse and that the photocurrent increased by more than two orders of magnitude.115,116 The introduction of SWNTs ensured that a bicontinuous network was present for the electrons and holes to travel to their respective electrodes. The internal electric eld created within the BHJ causes the excitons to dissociate into electrons and holes which travel in opposite directions. The free holes travel through the polymer to the anode and the free electrons travel to the cathode through the nanotubes. The nanotubes presence within the BHJ layer is critical to achieve an ordered phase separation and self-organization of the bicontinuous internal pathway. The Plastic Solar Cells Group at the University of Angers, France, incorporated a few per cent of metallic depleted ester-functionalized SWNTs (about one ester per 50 carbon atoms) into the P3HTPCBM BHJ active layer. This resulted in an increased ISC of the solar cells owing to improved ordering of the material.117 Moreover, VOC was also increased, thus breaking down the currently admitted necessary reduction V of VOC related to interface polarons or built-in eld. Signicant improvement of the ISC of P3HT : PCBM solar cells has been obtained by the Plastic Optoelectronics Group of Limoges University, adding a small amount (0.1 wt%) of SWNTs in the solution and performing their orientation during the annealing process.79 The initial average cell efciencies before annealing, around 2.5%, have been enhanced to 4.4% with 10 MHz electric eld application. The improvement was attributed to the orientation of the CNTs perpendicularly to the electrodes, previously observed with the same electric eld conditions on planar interdigitated structures by SEM,103 favouring the charge transport to the electrodes. Moreover it was found that the small

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h
anode
eh+ h+

C60 CNTn
ee-

CNTp P3HT
cathode

Figure 10. An ideal composite P3HTPCBMCNT solar cell.

amount of CNTs incorporated into the polymer matrix increased the composite absorption in the solid phase. Considering the ability of CNTs to provide percolation pathways for the photogenerated charges in PSCs, there remains an important question about what type of charge will be carried by these nanoparticles. It has been established for example that SWNTs carry holes in the case reported by Berson et al.114 . Very recently, doping the CNTs with boron and nitrogen was shown to improve hole and electron transport respectively when the CNTs were incorporated into P3HT : PCBM BHJ solar cells.118 Thus, the authors were able to balance the electron and hole mobility with Bdoped CNTs, resulting in increased VOC and JSC and improvement of PCE from 3% to 4.1%. Doping CNTs with C60 by chemical or microwave119 grafting methods to enhance electron transport was also successfully demonstrated. In summary, by incorporating CNTs in BHJs, one can improve the polymer organization,120 charge transport and mobility balance by providing selective hole or electron pathways. Additionally, electric eld orientation and migration of the CNTs can be achieved to reinforce the above effects. Thus, an ideal polymerPCBMCNT layer, as proposed in Fig. 10, would consist of electric eld aligned and well dispersed functionalized SWNTs which provide an interdigitized structure perpendicular to the electrodes. The polymer is organized by CNT incorporation as well. Excitons photogenerated in the polymer are separated into electronhole pairs at the PCBMpolymer interface. Electron and holes are driven respectively by selectively doped CNTs (CNTn and CNTp are functionalized to drive electrons and holes respectively). A DC eld migration of the electron-carrying CNTs to the cathode and of the hole-carrying CNTs to the anode will improve charge collection by forming ohmic contacts with the electrodes. Such a device still remains to be fabricated and tested.

CONCLUSION
Numerous advances have been made at all levels of development of polymer solar cells, particularly in the areas of materials and device architecture with current cell efciencies exceeding 8%. Although this is not a comprehensive review of organic photovoltaics, the wealth of information summarized here and elsewhere indicates that there is room for signicant improvements towards low cost, efcient, stable and reproducible organic photovoltaics. As we have witnessed in the latest materials
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Organic solar cell materials and active layer designs development efforts, engineering the active layer is of particular importance. Although efcient materials are combined for the makeup of efcient devices, active layer morphology and charge transport to the electrodes remain as major weak points. With proper incorporation of CNTs, we have been able to demonstrate that further improvements can be made particularly if the nanotubes are well dispersed in the medium and preferably oriented for straightforward charge transport capability to the electrodes. Due to their abundance and stability, CNTs can improve crystallinity and ordering of the BHJ active layer if processed properly towards enhancing cell performance for viability of organic photovoltaic technology.

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