Fullerene based Organic Solar Cells

L˘ cr˘ mioara Mihaela Popescu a a

Zernike Institute PhD thesis series 2008-17 ISSN 1570-1530

The work described in this thesis was performed in the research group Molecular Electronics of the Zernike Institute for Advanced Materials at the University of Groningen, the Netherlands.

P RINTED BY: Drukkerij van Denderen B.V., Groningen, the Netherlands

RIJKSUNIVERSITEIT GRONINGEN

Fullerene based Organic Solar Cells

Proefschrift
ter verkrijging van het doctoraat in de Wiskunde en Natuurwetenschappen aan de Rijksuniversiteit Groningen op gezag van de Rector Magnificus, dr. F. Zwarts, in het openbaar te verdedigen op vrijdag 3 oktober 2008 om 16:15 uur

door

L˘ cr˘ mioara Mihaela Popescu a a
geboren op 23 april 1978 te Timisoara, Roemeni¨ e ,

P. C. W. Janssen Prof. ir. R. dr. J. A.Promotor: Copromotor: Beoordelingscommissie: Prof. H. Jonkman Prof. T. ir. Ingan¨ s a Prof. Hummelen Dr. J. O. dr. M. dr. dr. Blom ISBN 978-90-367-3482-0 .

Familiei mele. sprijinul si incurajarea constanta ¸ de-a lungul aniilor . pentru iubirea.

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. . . . . . . . . . . . .3. . . . . . . . Morphology and optical properties . . . . . . . . . . . . . . . .3. . . References and notes . . . . . . . . . . . . . . . . . . . . . . . .1 1. . . . . . . . References and notes . .1 3. . . . . . . . Preparation of various device structures used . . . . . . .1 2. . . . . .1 1. . . . . . . . . . . . . . . . . Organic solar cells . . . . .3 Introduction . . . . . . . . . . . . . .3 2. Device characterization . . . . 1 1 5 8 8 10 11 13 19 20 20 20 23 26 28 31 33 34 35 37 37 39 43 45 Motivation and outline of the thesis . . . . 3 A thienyl analogue of PCBM for bulk heterojunction solar cells 3. . . . . . . . . . . . . . . . . . .2 1. .1 2.1 3. . . . . . . . 3. . . . . . .2. . . . Characterization under illumination . . . . . . . . . .4 [60]ThCBM and MDMO-PPV blends . . . . . . . . . . . . . . .2 2.3 Photovoltaics: A historical perspective . . . . . . . . . . . . .3. . vii . . . . [60]ThCBM and P3HT blends . . . . . . . . .2 Introduction . . . . . . .2 3. . . . . . . . . Conclusion . . . . . . .2 3. References and notes . 1. . . . . . . . . . .2 1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4 Determining the charge carrier mobility . . . . . . . . . . . . . . .3. . . . . . . . . Characterization of organic solar cells . . . 2 Materials and experimental techniques 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Electron transport in pristine [60]ThCBM . . . . . . . . . . .4 Materials and solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . Device preparation . .Contents 1 Introduction 1. . . . . . . . . . . . . . . . Bulk heterojunction solar cells using [60]ThCBM as acceptor . . . . . . . . . . . . 2. . . . . . . . . . . . . . . . . .2.

. . . . . . . . .5 Conclusion . . . . . . 6 Efficient PV blends comprising more than two semiconductors 6. . . . . . . . . References and notes . . . . . . . . . . References and notes . . . .2 Solar cells parameters . 5. . 5. . . . . . . 5. . . . . . . . . . . . . . . . . . . . .4 Solar cells characterization . . . 5. . . . . . . . . . . . . . . . . . . . . . .3 Improving open-circuit voltage using bis-adducts fullerenes 6. . 49 50 51 54 55 58 61 63 64 65 66 67 68 71 73 75 77 78 81 84 85 88 89 91 95 4. . . . 4. . . . . . . . . . . . . 5 Stability tests of P3HT:methanofullerence solar cells 5. . . . . . . . . . . . . . . . . . . . .viii 4 CONTENTS Effect of the P3HT:ThCBM growth rate on solar cell performance 4. . .2 Morphology . . Summary Samenvatting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6. References and notes . .3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6. . . . . . . . . . . .1 Introduction . . . . . . . . . . . 4. . . . . 6. . . . . . 4. . . . . . . . .5 Conclusion .4 Effect of impurities in the fullerenes on cell efficiency . . .3 External quantum efficiency (EQE) . . . . . . . . . . . . . . . . . . . . . .1 Introduction . . . . . . . . . . . . . . . . . . . . . . 5. . . . . . . . . . . . . . . .3 Effect of ageing on the device performance . . .1 Charge carrier transport . . . . . . . . . . .3.4 Conclusion .2 Accurate efficiency measurements . . . .2 Mixture of two n-type semiconductors in the active layer . . . . . . . . . . . . . . . . . . . . . . . . . . 5. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 Hole transport . . . . . . . . . . . . . . . .3. . . .1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1 Photovoltaics: A historical perspective Photovoltaics literally means light-electricity: photo comes from the Greek phos. Later. clean. Smith and Adams were the first to report on experiments with selenium [2. but the photoconductivity. who reported a photocurrent when a silver coated platinum electrode was illuminated in aqueous solution [1]. This technology has many advantages: it is modular. Forty years later. meaning light. The electricity produced can be used directly. and in 1913 Volmer [5]. In 1906 Pochettino [4]. The scientific interest as well as the commercial potential led to increased research into photoconductivity and related subjects. discovered photoconductivity in anthracene. these dyes 1 . it was not the photovoltaic properties of materials. and volt from the Italian scientist Alessandro Volta.1 Introduction 1. in 1873 and 1876. and can be installed almost anywhere to suit the needs of the user. By that time the first solid state photovoltaic devices were constructed. In the late 1950s and 1960s the potential use of organic materials as photoreceptors in imaging systems was recognized [6]. respectively. In the early 1960s it was discovered that many common dyes. stored locally or fed into an existing electricity grid. as methylene blue. 3]. a pioneer in the study of electricity. The discovery of the photovoltaic effect is ascribed to the French physicist Edmund Becquerel in 1839. had semiconducting properties [7]. easy to maintain. However. like selenium which excited researchers.

benefited greatly from the high standard of silicon technology developed originally for transistors and lately for integrated circuits. Wafer-based crystalline silicon has dominated the photovoltaic industry since the dawn of the solar PV area [13. and the structurally related phtalocyanines. GaAs. The highest solar cell efficiency has been demonstrated using III-V semiconductors [51]. GaAs cells have been developed primarily for use in space applications where the priority is to reduce the cell weight. 14]. Fuller and Pearson in 1954 at Bell Laboratories [10]. The technology used to make most of the silicon solar cells fabricated so far. It is melted and solidified using a variety of techniques to produce ingots or ribbons with different degrees of crystal perfection.1. Over the years the efficiency of crystalline silicon cells has reached more than 24% in a laboratory setting [11]. six times higher than the best previous attempt. in part thanks to its use in the half-century-old microelectronics industry. Most of the earlier understanding of the photovoltaic effect in organic photocells comes from the study of devices fabricated from many biological molecules like carotenes. which is close to the theoretical upper limit of 31% [12. An overview of the current PV technologies and the efficiencies reached are presented in Table 1. For the past few years the availability of polysilicon feedstock has been a critical issue for the rapidly growing PV industry. The attractive features of GaAs are its high absorbtion coefficient (devices only few µm thick absorb most of the light) and its high temperature coefficient compared with silicon (GaAs solar cells performs better in situations where the cells operates at high temperature and in space).2 Chapter 1: Introduction were among the first organic materials to exhibit the photovoltaic effect [8. The ingots are shaped into bricks and sliced into thin wafers. which converted sunlight into electric current with an efficiency of 6%. However. a range of photovoltaic (PV) technologies are commercially available or are under development in the research laboratories. The first fabricated inorganic solar cell was reported by Chapin. 9]. InP and their alloys have been used in single-junction and multi-junction configurations. has a convincing track-record in reliability and its physical characteristics are well understood. 13]. It was a crystalline silicon solar cell. Today. Wafers are processed into solar cells and interconnected in weather-proof packages designed to last for at least 25 years. Purified silicon (polysilicon) is the basic ingredient of the silicon modules. The tight supply has caused very high polysilicon spot market prices and has limited production expansion for part of the industry [15]. GaAs cells are used in ter- . It is widely available. chlorophylls and other porphyrins.

10.4% commercial module efficiency [22] 16.4% laboratory efficiency [27] Theoretical efficiency limits are 5060% [28.5% (a-Si) [18]. minimize series resistance and substrates costs (yet depositing GaAs on GaAs substrates is prohibitively expensive). 40.9% laboratory efficiency [21]. 13. Nanoparticle inclusion in host semiconductor Up-down converters Novel PV technologies: Boosting the structure at the periphery of the device > 10% efficiency improvement relative to baseline should be demonstrated in the coming decade > 10% efficiency improvement relative to baseline should be demonstrated in the coming decade Laboratory efficiencies: 26. 29] Galium arsenide (GaAs) Thin-film silicon (TFSi) Thin-film technologies Cu(In. Ga)(S.8% @ 96 suns (Si cells) [30]. Se)2 and related I-III-VI compounds (CIGS) Cadmium telluride (CdTe) GaAs Organic-based solar cells Bulk-heterojunction cells Dye-Sensitized cells (Graetzel cell) Novel PV technologies: Novel active layers Quantum wells. 13% (triple junction using SiGe alloys) [20].1% laboratory efficiency [51] 9. Thin-film solar cell active layer materials are deposited directly on large area substrates. Technology Monocrystalline solar cells Photovoltaic device Silicon solar cells Conversion efficiencies and notes 24. Photovoltaics: A historical perspective 3 Table 1. Quantum dots.1.7% laboratory efficiency [11].5% [52] solar 6.7% commercial module efficiency [24] 24. Quantum wires. III-V multi-junction cells Concentrator photovoltaic technologies (CPV) restrial applications for power generation under concentrated light.7% @ 240 suns (III-V cells) [31] Exploitation of plasmonic effects Si concentrator cells.5% laboratory efficiency [26] 10. 12% (tandem aSi/µc-Si) [19].1. The main challenges for GaAs solar cells relate to minimize front surface and junction recombination. 20.5% laboratory efficiency [23]. All these are laboratory efficiencies 19. such as glass panels (square meter-sized and larger) or foils (several hundred meters long). Thin-film PV has an inherent low-cost potential because its manufacture requires only a small amount of active (high cost) materials (film thickness is typically 1 µm) and is suited for fully integrated processing and .1: Current photovoltaic technologies and their efficiencies.1% commercial module efficiency [17] 25.

Because of its highly ionic nature. and Cu(In. There are three major inorganic thin-film technologies: amorphous/microcrystalline silicon (TFSi). Another problematic issue is that the available resources of indium are very limited. two technology branches exist. One is the hybrid approach in which organic solar cells retain an inorganic component (for example the Graetzel cell [27]). Within this category. Ga)(S. Se)2 (CIGS). even though very small amounts are used in the modules. lowcost substrates. 33]. The attractive features of CdTe are its chemical simplicity and stability. Tailoring the incoming solar spectrum for maximum conversion efficiency in the active semiconductor layer . The CIGS technology currently exhibits the highest cell and module efficiencies of all inorganic thin film technologies [22]. Its ionic nature also means that absorbed photons do not damage its stability. the polycrystalline semiconductors CdTe. Another advantage is the possibility of printing active layers . Ga) should be replaced. Within ”organic solar cells”. low energy input and easy upscaling. The main concern with this technology is the toxicity of the materials involved. CdTe’s favorable thermo-physical properties and chemical robustness make the CdTe cells easy and cheap to manufacture. the temperature at which the layers are deposited and the substrate on which they are deposited.4 Chapter 1: Introduction high throughputs [14]. Organic solar cells offer the prospect of low cost active layer material. stability improvement and the development of a technology adapted for these materials. using a variety of deposition methods. The efficiency of CdTe cells depends on how the CdTe layers are grown. More details about organic solar cells will follow in the next section. The other is the full organic approach (for example bulk-heterojunction solar cells [26]). and tolerance impurity in the materials should be increased. The novel PV technologies can be characterized as high-efficiency approaches. a distinction is made between approaches that tailor the properties of the active layer to better match the solar spectrum and approaches that modify the incoming solar spectrum without fundamentally modifying the active layer properties. the surfaces and grain boundaries tend to passivate and do not contain significant defects. A main challenge specially facing CIGS thin-film technology is the reduction of the material costs: high cost materials (In. By introducing quantum wells or quantum dots consisting of a low-band gap semiconductor within a host semiconductor with a wider band gap. active layer thicknesses should be reduced. thereby boosting production throughputs typically by a factor of 10 to 100 compared to other thin-film technologies. the current might be increased while retaining (part of) the higher output voltage of the host semiconductor [32. The main challenges for both approaches relate to the increase of efficiency.

and increases their efficiency. molecular semiconductors.2. An additional feature of an organic semiconductor is that they are less expensive compared with inorganic semiconductors like Si. Concentrating the sunlight by optical devices like lenses or mirrors reduces the area of solar cells and/or of the modules that house them. or.1. Specifically.and down-conversion layers and plasmonic effects [34–36]. but the fact that they can be ”bolted-on” to conventional solar technologies (crystalline silicon. which is as old as the science of photovoltaics itself. which can be processed over large areas at relatively low temperatures. is partly compensated by longer exposure of the cells to sunlight during the day. Compared with Si.and down-convertors or the exploitation of plasmonic effects should be demonstrated in the coming decade. requiring new materials. or a PV system price of 2. An improvement of at least 10% (relative) of the performance of existing solar cells technologies thanks to up. The application of such effects in PV is definitely still at a very early stage. The challenges in developing organic semiconductors for use in photovoltaic applications are considerable. further development of PV technology is crucial to enable PV to become a major source of electricity. high optical absorption coefficients are possible with these materials.15 euro/kWh. 1. this means reaching PV generation costs of 0. which can not be achieved by single-junction 1-sun (non concentrating) photovoltaic technology.2 Organic solar cells An alternative approach for inorganic semiconductor photovoltaic devices is the use of organic. . which allows production of thin solar cells with many advantages and opportunities as a result. The concentrator technologies (CPV) are based on the idea of concentrating sunlight to generate photovoltaic electricity. by processing from solution of film-forming materials such as polymers. Currently the research is primarily aimed at reducing the generation cost of PV electricity which at present may vary from 4 to 8 euro/watt peak [15]. Organic solar cells 5 relies on up.5 euro/watt peak. thin films) may reduce their time-to-market considerably. The most important benefit of this technology is the possibility to reach system efficiencies beyond 30%. preferably. either by vacuum sublimation of molecular materials. Considering the present development rate the cost of PV electricity is expected to be competitive with consumer electricity (grid parity) in Southern Europe by 2015. CPV’s reliance on beam irradiation and the necessity to track the sun’s motion across the sky by moving the system. Although PV systems are commercially available and widely developed.

Due to this low dielectric constant strongly bound excitons are formed upon light absorption. new substrates. The energy gap between the HOMO and the LUMO ranges from 1 to 4 eV which makes most semiconducting polymers ideally suited for applications in optoelectronic devices operating in the visible light range. One of the electrodes must be (semi-)transparent since the cell will be exposed to light. new device architecture. due to the work function difference between the electrodes. This means that the bonds between carbon atoms in the framework of the polymer are alternating single or double (called conjugation). or a mixture of two (or more) semiconductors. Therefore the electric field in PV device. (d) dissociation and separation of the carrier pair. by that delocalizing π electrons along the entire conjugated path. The novel electronic properties of both molecular and polymeric semiconductors arise from their conjugated chemical structure. In conjugated materials three sp2 hybrid orbitals form covalent bonds: one with each of the carbon atoms next to it. that initiated an exciting and rapidly expanding field of research into these materials. and the third with a hydrogen atom or other group. that the conductivity of the conjugated polymer polyacetylene can be increased by several orders of magnitude upon doping with iodine [37]. (b) exciton diffusion. a bi-layer. 39]. (f) collection of charges by the electrodes. An organic solar cell consists of a photoactive layer sandwiched between two different electrodes. Until the seventies. The underlying principle of a light-harvesting organic PV cell consists of six distinct processes: (a) absorption of a photon creating an exciton (bound electron-hole pair).1%. (e) charge carrier transport to the corresponding electrodes. PV devices based on dyes or polymers yield limited power conversion efficiencies. and encapsulation materials. mainly because of the low relative dielectric constant of organic materials.6 Chapter 1: Introduction new methods of manufacture. The highest filled π orbital is named the highest occupied molecular orbital (HOMO) and the empty lowest π ∗ orbital is named the lowest unoccupied molecular orbital (LUMO). Tang et al. is much too weak to dissociate the excitons. demonstrated . The mutual overlap of pz orbitals creates π bonds along the conjugated backbone. The remaining electron occupies a pz orbital. carbon-based molecules and polymers have been considered to be insulating materials. This discovery was followed by the observation of electroluminescence in poly(p-phenylene vinylene)(PPV) in 1990 [38. (c) charge transfer at donor/acceptor interface. A step forward for the molecular electronic materials was the discovery in 1977 by Heeger et al. typically well below 0. The photoactive layer is based on a single. and as such have been exploited as electrical insulators in many applications.

This favors exciton dissociation at the interface: the electron is accepted by the semiconductor with the larger electron affinity and the hole by the material with the lower ionization potential. for most organic semiconductors the film thickness should be more than 100 nm in order to absorb most of the light. Organic solar cells 7 that bringing a donor and an acceptor together in one cell dramatically increases the power conversion efficiency to 1% [40]. It is clear that exciton dissociation is most effective at the interface in the planar heterojunction cells. In 1992 Sariciftci et al. In this device the excitons should be generated in the close proximity to the D/A interface. Therefore the interfacial area is greatly increased and the distance excitons have to travel in order to reach the interface is reduced. reported from field-effect measurements on thin films of evaporated C60 . Otherwise. The sixty electrons from the pz orbitals give rise to a delocalized π system similar to that in conjugated polymers. Since typically diffusion lengths are only 5-7 nm [54.08 cm2 V−1 s−1 [51]. The electron mobility of 0. within the exciton diffusion length. thus the exciton should be formed within its diffusion length from the interface. This problem was solved by Yu et al. 44–46]. this limits the effective light-harvesting layer. This device structure is called bulk heterojunction. Further experiments performed by Shaheen et al. One of the most used acceptors in planar heterojunction solar cells is the football-shaped fullerene molecule C60 . planar organic semiconductor cells [40. In the planar heterojunction (bi-layer device) charge separation is much more efficient at the donor/acceptor (D/A) interface than at the electrode interface in the single layer device. and has been extensively used since 1995. One of the inherent problems with bulk heterojunction is that of solid-state miscibility. showed that the solvent used plays an important role on the film quality. and bulk heterojunction solar cells [47–50].2. [49] who intimately mixed the donor and acceptor. and mobilities of 0. strengthened the fact that the solid . measured by time-of-flight experiments [52] for C60 single-crystals grown from the vapor phase. 55]. Therefore thick film layers increase light absorption but only a small fraction of the excitons will reach the interface and dissociate. and implicitly on the performance of the bulk heterojunction solar cell. report the photoinduced electron transfer from a semiconducting polymer onto C60 [53]. Yu et al.5 cm2 V−1 s−1 .1. However. the excitons decay instead of to contribute to the photocurrent. The idea behind a heterojunction is to use two semiconductors with different electron affinities and ionization potentials. makes it ideal for use as an electron acceptor in organic PV cells. This concept of the heterojunction has since been widely exploited in a number of donor-acceptor cells: dye sensitized solar cells [41–43].

while they are bulkdependent in the high voltage/high current regime (Figure 1. assuming that the injecting contact is Ohmic. 58]: µ = µ0 exp γ V L (1. yielding to a power conversion efficiency of 2. In 2000 [56] they obtained the first truly promising results for bulk heterojunction solar cells when mixing MDMO-PPV and [60]PCBM (1:4 by weight) and optimizing the nanoscale morphology of the film.2) is the dielectric constant of material. so that the injected carrier will form a space charge. In the latter case. The SCL dark conduction occurs when the contacting electrodes are capable of injecting either electrons into the conduction band or holes into the valence band of a semiconductor or an insulator. For a trap free semiconductor. Therefore the SCL current is bulk limited.1).8 Chapter 1: Introduction state morphology has an important effect on the power conversion efficiency of solar cells. V is the internal voltage of the . The mobility µ of carriers in molecularly doped polymers is empirically described by a stretched exponential dependence [57. electrical characteristics are essentially interface-dependent in the low voltage/low current regime. γ the field activation factor. Generally. the SCL current density is given by the Mott-Gurney equation: [59] JDark = where 9 V2 µ 8 L3 (1.1) where µ0 is the zero-field electron mobility. when the applied voltage (Vbias ) exceeds the built-in voltage (Vbi ) the dark current density scales quadratically with de voltage indicative of a spacecharge limited (SCL) transport. Nowadays the power conversion efficiency of polymer/fullerene bulk heterojunction solar cells approaches 6% [26]. and V /L is the applied electric field.3 1. limiting the current flow.3. 1.5%.1 Characterization of organic solar cells Determining the charge carrier mobility The current density-voltage characteristics in the dark are the result of the bulk charge carrier transport properties and the electrical properties of the organic-electrode interface. One of the frequently used tools to determine the charge carrier mobilities is to examine the space charge limited conduction in the dark from current-voltage measurements. and when the initial rate of such carrier injection is higher than the rate of recombination or extraction.

that the charge carrier density in solar cells is fairly modest [64] and the density dependence of charge carrier mobility is negligible.1 to describe the electric field dependence of the charge carrier mobility in low mobility media is not fully correct due to the fact that the density dependence of charge carrier mobility has been neglected [61–63]. The VRS is the voltage drop across the series resistance of the substrate.1.0 Voltage Figure 1. This can be achieved if the work function of one of the electrodes is close to the .4) where the built-in voltage (Vbi ) is the voltage at which the J − V characteristic become quadratic. Recent developments shown that the application of Equation 1.89γ 8 V L V2 L3 (1.3. In the foregoing discussion. however. Characterization of organic solar cells 9 Dark current density 2 3 J V /L Space-charge limited current J exp (qV/kT) Diffusion current J V/L leakage current) (local 0. Thus the SCLC is given by: [60] JDark = 9 µ0 exp 0.3) Here V is related to the applied voltage (Vbias ) as: V = Vbias − Vbi − VRS (1. µ is the charge carrier mobility and L is the thickness of the active layer. thereby enabling to selectively determine the charge carrier mobility of either electrons or holes. It should be noted.1: The J − V characteristic in the dark with the three different domains. device. only the dependance of the charge carrier mobility on the electric field was taken into account. One can choose the electrodes materials in such a way that the injection of either electrons or holes can be suppressed or enhanced.

10 Chapter 1: Introduction J Current density Dark FF = 0. The operating regime of a solar cell is the range of bias from 0 to VOC in which the cell delivers power. while a high barrier for injection of the other carrier type into the material exists.2 shows the typical J − V curve of a solar cell in the dark (empty symbols) and under illumination (full symbols). The photocurrent drawn when the terminals are connected together is the short-circuit current (JSC ). as well as its electrical behavior. The maximum of the obtained electrical power Pmax is located in the fourth quadrant where the product of current density J and voltage V reaches its maximum . The cell power density is given by: P =J ×V (1. 1. Figure 1. An energy diagram for such an electron-only and hole-only device will follow in Chapter 2. current density-voltage (J − V ) measurements in the dark and under illumination are performed.2: Typical J − V curves of an organic bulk heterojunction solar cell in the dark (empty symbols) and illumination (full symbols) conditions.2 Characterization under illumination In order to determine the performance of a solar cell device.0 V OC J max x V max J Light Maximum J SC power point 0. The short-circuit current density (JSC ) and open-circuit voltage (VOC ) are shown. energy level of the transport band under investigation.3.0 Voltage Figure 1. The photovoltage developed when the terminals are isolated is called the open circuit voltage (VOC ).5) P reaches a maximum at the cell’s operating point or maximum power point. The maximum output power is given by the rectangle Jmax × Vmax .

All these photovoltaic parameters should be defined for particular illumination conditions. the intensity of radiation (1000 W/m2 ). If its costs can be lowered. which is the spectrum of sunlight that has been filtered by passing through 1. VOC . F F and η are the key performance characteristic parameters of a solar cell. The power conversion efficiency η of a solar cell is related to these three quantities by: η= JSC × VOC × F F Plight (1.5 or AM 1. Although a lot of progress has been made with organic bulk heterojunction solar cells. These four quantities JSC . the power .8) where Plight is the power of the incident light. EQE depends upon the absorption coefficient of the solar cell material. and the spectral distribution of the light (air mass 1.1. 1. (1. Motivation and outline of the thesis 11 value : Pmax = Jmax × Vmax (1. which were briefly discussed in the previous sections. and it is therefore a key quantity describing solar cell performance under different conditions. The Standard Test Conditions (STC) include a constant temperature of the PV cells (25 o C). photovoltaic electricity could become a competitive source of energy. The EQE is the ratio between the photocurrent and incident photon flux at one particular wavelength. The photocurrent generated by a solar cell under illumination at short circuit is dependent on the incident light intensity. the efficiency of charge separation and the efficiency of charge collection in the device.7) JSC × VOC which is the ratio between the Pmax that can be drawn from the device and the product of JSC and VOC .5 global.6) The fill factor (F F ) measures the quality of the shape of the J − V curve and is defined as: Jmax × Vmax FF = . The relation between the photocurrent density and the incident spectrum is defined as the cell’s external quantum efficiency (EQE).5 thickness of the earth atmosphere). It would help to combat the global threat of climate change and improve the security of energy supply. The EQE does not depend on the incident spectrum.4.4 Motivation and outline of the thesis Photovoltaic technology converts the sun’s rays directly into electricity without moving parts or emitting pollutants.

So far [60]PCBM remains the best performing soluble fullerene derivative used in polymer:fullerene blends. In Chapter 3. Chapter 6 describes the solar cells performance in blends of P3HT and a mixture of two n-type semiconductors with approximately the same electron accepting ability (as measured by the reduction potential) such as C60 and C70 fullerene derivatives. Chapter 2 presents an overview of the materials used in the active layer of bulk heterojunction solar cells. [60]ThCBM was designed with the aim of improving miscibility with polythiophene donors. Electrical and optical properties of these devices have been monitored for a test period of 1000 hours of continuous illumination. This thesis addresses the possibility of using new fullerene derivatives in organic bulk heterojunction photovoltaic devices since one of the challenges for organic solar cells relates to developing of new materials. The benefit of a well balanced and enhanced charge carrier transport for slow growing films makes it possible to fabricate thicker films maximizing the light absorption in these blends. The use of two or more different n-type semiconductors concomitantly in the same device is essentially unheard of in the field of organic electronics.12 Chapter 1: Introduction conversion efficiency needs to be improved further if these cells are to be commercialized. . always using the same fullerene derivative ([60]PCBM). The influence of film organization on the performance of the P3HT:[60]ThCBM bulk heterojunction photovoltaic cells is discussed in Chapter 4. experimental studies of the morphology. Furthermore. The photovoltaic performance of the fast drying and subsequent annealing of the active layer is compared with the one of the cells with a slow growth photoactive layer. the effect that certain impurities in the n-type semiconductor composition (such as pure C60 or higher fullerenes than C70 ) have on the electrical properties of the solar cell devices is quantified. charge transport and solar cell performance in blends of P3HT and a newly developed analogue of [60]PCBM ([60]ThCBM) are presented. let alone solar cells. Since 2000 the bulk heterojunction solar cells are prepared from conjugated polymers and. Finally. and the protocols that we developed for reproducible device preparation and characterization. Chapter 5 addresses the electrical stability of P3HT:Methanofullerene bulk heterojunction solar cell devices which has been investigated under standard condition of illumination and temperature. especially (regioregular) P3HT. with only few exceptions.

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For this purpose we performed our experiments in a glove-box system equipped with preparation facilities such as a spin-coater. and electrical characterization set-up. The operational characteristics of devices based on organic semiconductors are very sensitive with respect to the exposure to oxygen and water. a vacuum deposition system.2 Materials and experimental techniques A short overview of the materials used and the protocols that we developed for reproducible device preparation and characterization will be presented. Therefore the preparation and characterization of such devices should be carried out in a controlled atmosphere. 19 .

Finally. the electron-donating material (the donor. the experimental setup for the study of the degradation of the cells upon light exposure is described. This finds its origins in the weak van der Waals type intermolecular forces in organic materials that localize the excitons within molecules. As a result. This illustrates the importance of controlled environment during the preparation and characterization of the organic-based devices. p-type semiconductor). which have quasi-particle sizes smaller than the ones produced in inorganic solar cells. We present the protocols that were developed for reproducible preparation and characterization of solar cell devices.2. the transport properties of a semiconductor change in time by exposure to air or moisture and this limits the performance of the solar cell devices. and soft lithography techniques have been developed for these flexible materials. By replacing MDMO-PPV with P3HT higher solar cell efficiencies were obtained.1). Different device structures. modifying the chemical nature of the molecules. as will be demonstrated in Chapters 3 and 4. Regioregular P3HT. In all of these cases.7’-dimethyloctyloxy)-1. doping agent.2 2.1 Device preparation Materials and solutions Absorption of light in organic materials results in the production of strongly bound electron-hole pairs (Frenkel type excitons). or quenching sites [2–5]. One of the organic semiconductors used. screen printing. acting as traps. . reacting with the employed electrodes.4phenylene vinylene) (MDMO-PPV) and regioregular poly(3-hexylthiophene) (P3HT) (See Figure 2. ink-jet printing. used for the experimental evaluation of the transport properties. is a conjugated polymer. The conjugated polymers used through this thesis are: poly(2-methoxy-5-(3’. MDMOPPV was purchased from Covion and used here as received. special measures need to be taken during the preparation and characterization of the devices. 2. For instance water and oxygen molecules can easily penetrate in the organic films. such as electron and hole mobilities are described. In general two semiconductors with different electron affinities are needed to dissociate these excitons in free charge carriers in organic solar cells.20 Chapter 2: Materials and experimental techniques 2.1 Introduction Since 1977 when the field of electronics based on conjugated polymers started [1] a number of a new processing technologies such as spin-coating.

6]-phenylC61 butyric acid methyl ester ([60]PCBM).) was further purified by Bert de Boer in our laboratory [6]. and non-methanofullerene derivatives called fulleropyrrolidines such as: 2-(4-Butyloxyphenyl)N-methyl[60]fulleropyrrolidine ([60]BPMF) and 2-(4-Butyloxyphenyl)N-methyl[70]fulleropyrrolidine ([70]BPMF) were used as n-type semiconductors.2. while maintaining much of the desirable electronic properties of the native fullerene.6]phenylC71 butyric acid methyl ester) was used as acceptor in the photoactive layer of the solar cells.1: Chemical formulae of the conjugated polymers used in this thesis. which is in our study a methanofullerene. The most commonly used methanofullerene is [6. and their chemical formulae are presented in Figure 2. Methanofullerenes possess many benefits compared to the native (un-derivatized) fullerene in organic electronics. All the n-type semiconductors used throughout this thesis were obtained from Solenne B. purchased from Rieke Metals Inc.6]-thienylC61 butyric acid methyl ester([60]ThCBM) (used in the Chapter 3 and Chapter 4 of this thesis). In the last chapter a new library of methanofullerenes such as: [70]ThCBM ([6.2.5 %. The op- . electronic grade ( regioregularity more than 98. Device preparation 21 Figure 2. The typical average molecular weight. [60]ThCBMbis adducts and [70]ThCBM-bis adducts.000 g/mol. To study the device performance.V. When the MDMO-PPV was the donor material. suggested by SEC (size exclusion chromatography). One benefit is their increased processability (increased solubility in aromatic solvents) compared to native fullerenes. was ≈ 50.2. n-type semiconductor). blend solutions of polymer:methanofullerene were prepared.6]-thienylC71 butyric acid methyl ester). Another methanofullerene derivative is [6. The other semiconductor used in the active layer of these solar cells is an electron-accepting material (the acceptor. In Chapter 5 a higher methanofullerene analog of [60]PCBM such as [70]PCBM ([6. the solvents used were chlorobenzene (CB) or ortho-dichlorobenzene (ODCB).

.22 Chapter 2: Materials and experimental techniques OCH3 O S O OCH3 [60]PCBM [60]ThCBM OCH3 O S O OCH3 [70]PCBM [70]ThCBM S OCH3 O S O OCH3 S O H3CO [60]ThCBM-bis adducts O H3CO S [70]ThCBM -bis adducts OC4H9 N N OC4H9 [60]BPMF [70]BPMF Figure 2.2: The chemical structures of the methanofullerenes used in this thesis.

2 Preparation of various device structures used A plastic solar cell typically consists of a photoactive layer sandwiched between a glass substrate covered with a patterned layer of indium tin oxide (ITO)(from Philips Research Laboratories) and a top electrode (as shown in Figure 2. The solutions were prepared in a N2 atmosphere and rigorously stirred for more than 12 hours on a hot plate maintained at 50 o C.2. Furthermore. the solvents used were either chloroform. timum weight ratio of MDMO-PPV:methanofullerene ([60]ThCBM or [60]PCBM) was in this case 1:4 [7.2. 8]. followed by ultrasonic treatment in isopropanol for 5 minutes. methylthiophene. surface treatments were used to remove the contaminants and to reduce the roughness of the ITO layer. One substrate contains four devices with different active areas.2. Device preparation 23 Figure 2. Subsequently. rinsing with de-mineralized water. and finally 20 minutes of plasma treatment. When the donor material was P3HT. These cleaning steps consist of: rubbing the ITO glass substrates with soap and water. Prior to the spin-coating of the photoactive layer on ITO. the substrates were immersed in cascade water (running water with nitrogen bubbling through) for 5 minutes. all solutions prepared for the experiments which are presented in Chapters 5 and 6 were made from a mixture of P3HT:methanofullerene of 1:1 in ODCB. Next. a 60 nm transparent layer of poly(3.3).3: Sandwich structure of a solar cell (left) and the layout of a photovoltaic cell (right).4ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) (Baytron P VP Al 4083 grade ) was spin coated from an aqueous dispersion under ambient condi- . followed by ultrasonic treatment in acetone (for 5 minutes) in order to remove the organics (soap) from the surface. 2. or ODCB with an optimum weight ratio of P3HT:metanofullerene of 1:1 [9]. except for the solutions in chloroform which were stirred at room temperature.

The spin-coating process was divided in three steps: in the first step the solution is spread over the surface when the substrate was accelerated to its final rotation speed.4: The Karl Suss spin coater that we used in all our experiments. Subsequently. in order to improve device performance and stability. the active layer is drying while the substrate is spinning at a constant lower rate and the solvent evaporation rate dominates the thinning behavior. Thermal annealing was performed on complete P3HT:ThCBM devices in a nitrogen (N2 ) atmosphere on a hot plate at 150 o C for 4 minutes. in ambient atmosphere. the substrate was spinning at a constant rate where viscous forces dominate the thinning behavior of the active layer. This last spin-coating step was not performed for slow growth active layers (as will be discussed in the next paragraph). The fast grown P3HT:[60]ThCBM layer thicknesses varied from 85 to 262 nm. This annealing temperature and duration was found to give optimum perfor- .4). The thicknesses of the MDMOPPV:methanofullerene ([60]PCBM or [60]ThCBM) blend film was typically 100 nm. in the second step. In this second step the film is gradually formed and it is often possible to see color change in the reflected light. After spin coating the layer was baked at 200 o C.24 Chapter 2: Materials and experimental techniques Figure 2. In the third step. tions.1 ppm. that can cause degradation of the device. The photoactive layer was spin-coated on top of the PEDOT:PSS layer using a Karl Suss spin coater (see Figure 2. The thickness of PEDOT:PSS layer was typically 60 nm. for 5 minutes in order to remove the remaining water from the PEDOT:PSS layer. The spin-coating of the organic layer was performed inside a nitrogen glove box with O2 and H2 O levels below 0. We refer to layers obtained by the process above as fast growth active layers.

For all the solar cell devices presented throughout this thesis.02) cm2 . (0. The sample holder. Device preparation 25 Figure 2. Boats made of a refractory metal (tungsten or tantalum) were used as deposition sources. The sample holder which could accommodate nine samples is located above the sources.378 ± 0.047 ± 0. All the film thicknesses were determined with a Dektak 6M Stylus profiler (Veeco).5: The metal evaporation system with two sources for simultaneous deposition. Subsequently.002). the wet films were dried overnight at room temperature. Chapter 3 addresses the variation of the photovoltaic parameters of P3HT:[60]ThCBM solar cell devices as a function of the . The metal deposition system (see Figure 2. which could accommodate nine substrates with the typical size of 3×3 cm2 each. the top contact was either LiF (1 nm)/Al (100 nm) or Sm (5 nm)/Al (100 nm). The top electrode was deposited by thermal evaporation through a shadow mask at a base pressure of 10−7 mbar.172 ± 0. Each substrate consisted of four independently addressable devices with different active areas: (0. was positioned above the two sources. The active layer thicknesses ranged for these devices from 150 to 500 nm.096 ± 0. The evaporation rate can be controlled by the applied electrical power.2. mance for the solar cells fabricated using chloroform as solvent [10]. in a closed Petri dish [11]. (0. All the top electrode materials used in this thesis were obtained from Sigma Aldrich.2. These areas were measured at Energy research Centre of the Netherlands (ECN) using an optical microscope. The slow growth P3HT:methanofullerene films were spun from either 2-methylthiophene or ODCB solution on top of the PEDOT:PSS layer.5) includes two resistive heating evaporation sources located at the bottom of the evaporating chamber. inside a N2 glove box.001). and (1.001).

used to investigate the electron transport in the pristine [60]ThCBM films. Consequently.6 left) devices.6 right) [14]. The hole-only devices were fabricated with the following structure: ITO/ PEDOT:PSS/Polymer (MDMO-PPV or P3HT):[60]ThCBM/Pd. which leads to a large mismatch with the LUMO level of [60]ThCBM [15] and therefore it prevents injection of the electrons into [60]ThCBM [16](or other methanofullerene with similar LUMO level). The work function of PEDOT:PSS is about 5. The work function of PEDOT:PSS (5. resulting in a hole-only device (see Figure 2.6: Schematic representation of an electron-only device (left) and of a hole-only device (right). 2. annealing temperature for these two different top contacts (Sm/Al and LiF/Al). therefore in the dark only the electron current is measured [13]. the electron current through the [60]ThCBM (or other methanofullerene) phase has to be blocked. For such a device it is expected that LiF/Al will form an Ohmic contact for electron injection into [60]ThCBM. were fabricated in the same way as was presented above. PEDOT:PSS serves as an Ohmic contact for hole injection into the HOMO level of the polymer (MDMO-PPV or P3HT).3 Morphology and optical properties Atomic Force Microscopy (AFM) probes the topography of a surface.12 eV.1 eV).2 eV) does not match the HOMO level of [60]ThCBM (≈ 6. Hence. The operation of an AFM is based on the measurement of the force between the sample .2 eV. only the electrons are expected to flow into [60]ThCBM under forward bias conditions. The work function of Pd is about 5. thus the hole injection current from PEDOT:PSS into [60]ThCBM can be neglected.26 Chapter 2: Materials and experimental techniques Figure 2. In order to investigate the hole transport through the polymer phase (MDMOPPV or P3HT) in a blend with [60]ThCBM. The electron-only (see Figure 2. This can be achieved by choosing proper electrodes which suppress the injection of electrons into the device.

non-contact and tapping mode. At the right is a solar cell (with the four active areas) during illumination from the halogen lamp.2. Morphology and optical properties 27 Figure 2. In this mode the cantilever oscillates at the resonance frequency of the quartz crystal it is mounted on. The (AFM) height and phase images of polymer:methanofullerene films were taken using a DI NanoScope IV scanning probe microscope operating in a tapping mode with a silicon cantilever. In this mode there is only a intermediate contact between tip and the sample. The magnitude of the deflection is measured with high precision by the reflection of a laser beam from the back side of the cantilever on a photodiode detector. scanning soft samples (like polymers) in contact mode may cause damage to the sample. Depending on the distance between the tip and surface.3. which is a semi-contact mode. surface and a sharp tip located at the free end of a flexible cantilever. It is preferable in this case to use the tapping mode. Absorption spectra of the active layers were collected using a Perkin-Elmer . although the resolution that can be achieved with AFM is lower compared with Scanning Tunneling Microscope (STM). One of the main advantages of AFM is that any type of sample can be scanned. under ambient conditions. the interaction between the tip and the surface causes the cantilever to deflect. However.7: Solar cell set-up (left) that consist of a light source (1). and electrical connectors (2). sample table. three main AFM operation modes can be distinguished: contact. While the tip is scanned with respect to the sample.

The devices were illuminated by a white light halogen lamp with an output power of 100 mW/cm2 . Cooling of the cells was ensured by ventilation by electrical fans in order to maintain the temperature at the surface of the samples constant at approximately room temperature. with a light spectrum that approximates the AM1. a solar simulator class A was used.5 global (AM1.5 or AM1. The detailed procedure of the STC measurements is described elsewhere [12]. and the cells were either kept under open circuit operation (without any bias) or under maximum power point conditions.4 Device characterization The electric characterization of the devices was performed under a dry nitrogen atmosphere (inside glove box). performed at ECN. The typical emission spectrum of this halogen lamp is shown in Figure 2. the cooling was switched off and the degradation tests were performed at an elevated temperature (≈ 50 o C). Sm/Al or Al) as the negatively biased electrode. Herein the anode (ITO) was taken as the positively biased electrode and the cathode (LiF/Al. was used as a reference cell in order to set the light intensity of the solar simulator. In all these measurements the mismatch factor correction for the solar simulator was taken into account. At the RuG laboratory the degradation tests were performed at a temperature of ≈ 50 o C.5G. with O2 and H2 O levels below 0. The output power of these lamps was typically 100 mW/cm2 as controlled by a calibrated silicon diode. which is the spectrum of sunlight that has been filtered by passing through 1. In some tests.5 G) spectrum (air mass 1. Four halogen lamps were used for the stability tests at the ECN facility. which was initially calibrated at ISE Callab (Freiburg.5 thickness of the earth atmosphere). calibrated with a silicon diode received from ECN (see the experimental set-up in Figure 2. During the ageing test the cells were kept at maximum power point operation (≈ 0. These tests were carried out in two different locations: at ECN and in our laboratory (RuG). The characteristic spectrum of the halogen lamps used .7). However. Germany). 2.1 ppm. All films were measured in the transmission mode on glass/ITO/PEDOT:PSS substrates and subsequently corrected for substrate absorption.8. A single halogen lamp was used for these tests.4 V forward bias). which is similar to the operational conditions of the normal outdoor solar cell. The stability tests of polymer:methanofullerene solar cells (as investigated in Chapter 5) were carried out inside a N2 glove box. for accurate photovoltaic measurements.28 Chapter 2: Materials and experimental techniques Lambda 900 UV-VIS/NIR spectrometer. A monocrystalline Silicon diode. however.

10 sec.4 0.2 0. sweeping in steps of 0.0 400 600 800 1000 1200 1400 1600 1800 Wavelength [nm] Figure 2. Device characterization 29 1.0 Photon flux [arb.5G solar spectrum.05 V with a delay of 0.8: Typical emission spectrum of the halogen lamp used in our experiments together with the AM 1. Current-voltage measurements were performed using a computer-controlled Keithley 2400 Source Meter. in both laboratories is shown in Figure 2.8.5 Global Halogen lamp 0.4.2. .units] AM 1.8 0. in the dark or under illumination.6 0.

.

Steiger. [11] G. B. J. Emery. L. Forrest. K. L. 864. T. K. van’t Hof. [2] A. Thin Solid Films 403-404 (2002). 1098. de Boer. Sieval. D. V. V. Meng. A. Parisi. W. M. Huang. J. C. Y. Louis. Charge transport and photocurrent generation in poly(3-hexylthiophene):methanofullerene bulkheterojunction Ssolar cells. J. Dyakonov. J. Li. S. H. E. 223. Synthetic Metals 122 (2001). J. Sun. Park. Hummelen. Hor. D. Blom. K. Advanced Functional Materials 15 (2005). V. W. S. Koster. Mihailetchi. R. [4] J. J. Influence of nanomorphology on the photovoltaic action of polymer-fullerene composites. [3] M. 699. [10] L. Yang. Barbara. Thienyl analog of 1-(3-methoxycarbonyl)propyl-1-phenyl. Heeger. S. Jonkman. M. Nature Matererials 4 (2005). Papadimitrakopoulos. J. Y. M. H. C. Physical review. Advanced Functional Materials 16 (2006). M. J. MacDiarmid. High-efficiency solution processable polymer photovoltaic cells by self-organization of polymer blends. Hamed. C. Journal of Applied Physics 90 (2001). F. Popescu. English. Shrotriya. Applied Physics Letters 89 (2006). Mihailetchi.[6. M. H.REFERENCES AND NOTES 31 References and notes [1] C. de Boer. Hummelen.5% efficient organic plastic solar cells. J. S. W. H. 3242. R. A. Compositional dependence of the performance of poly(p-phenylene vinylene):methanofullerene bulk-heterojunction solar cells. R. A. J. 795. Accurate efficiency determination and stability studies of conjugated polymer/fullerene solar cells. Rothberg. P. T. Chiang. Y. Sariciftci. T. P. J. Effects of oxygen and illumination on the in situ conductivity of C60 thin films. [12] J. van Duren. Electrical Conductivity in Doped Polyacetylene. J. Brabec. Hummelen. 49. 2. [8] V. Blom. 744. Aging induced traps in organic semiconductors. Direct observation of structural changes in organic light emitting devices during degradation. [9] D. Defect Quenching of Conjugated Polymer Luminescence. Galvin. E. Shirakawa. N. A. [6] V. Physical Review Letters 39 (1977). M. Thompson. Bulovic. E. Y. M. P. . S. Applied Physics Letters 78 (2001). C. Xie. Fincher. B. Kolosov. P. B. E. Wienk. A. von Seggern. R. 213507. 841. W. C. Miller. P. Melzer. G. H. R. L. M. C. J. Karg. Kroon. F. J. Physical Review Letters 73 (1994). Koster. D. Gau. Janssen. Shaheen. J. M. C. Moriarty. K. Tao. L. A. Chirvase. [7] S. Verhees. Y. H. Y. [5] D. Schmechel. B. 1317. 10873.6]-methanofullerene for bulk heterojunction photovoltaic devices in combination with polythiophenes. Yan. Solid state 47 (1993). Nanotechnology 15 (2004). Yao.

Verhees. E. J. M. M. Rispens. Rispens. Advanced Functional Materials 13 (2003). W. P. P. D. G. J.32 Chapter 2: Materials and experimental techniques [13] V. [16] V. Hole transport in poly(phenylene vinylene)/methanofullerene bulk-heterojunction solar cells. Melzer. C. D. Al-Ibrahim. Blom. J. J. Koop. van Duren. Solar Energy Materials&Solar Cells 85 (2005). Mihailetchi. Hummelen. 865. [15] M. M. Mihailetchi. H. Hummelen. U. M. H. J. R. 43. P. Mihailetchi. . Janssen. M. K. W. Blom. J. W. Journal of Applied Physics 94 (2003). S. D. K. V. Cathode dependence of the open-circuit voltage of polymer:fullerene bulk heterojunction solar cells. A. Kroon. Advanced Functional Materials 14 (2004). Blom. [14] C. T. M. J. Zhokhavets. 13. Sensfuss. Wienk. M. Flexible large area polymer solar cells based on poly(3-hexylthiophene)/fullerene. 6849. C. M. T. J. Gobsch. W. Electron transport in a methanofullerene. Roth.

Harry T. charge transport and solar cell performance in blends of P3HT: [60]ThCBM are reported.6]-thienylC61 butyric acid methyl ester ([60]ThCBM). experimental studies of the morphology. Jonkman. ∗ The main results of this Chapter have been published as: Lacramioara M. Hummelen. 213507. resulting in a compound named [6. Alexander B.6]-phenylC61 butyric acid methyl ester ([60]PCBM) was designed with the aim of improving miscibility with polythiophene donors. especially poly(3-hexylthiophene) (P3HT). In the title compound the phenyl group of [60]PCBM is replaced by a thienyl group. In this chapter. Popescu. [60]ThCBM is a first example of more tailored fullerene acceptor materials. Applied Physics Letters 89 (2006).3 A thienyl analogue of PCBM for bulk heterojunction solar cells∗ An analogue of [6. Sieval. and Jan C. which may optimize the morphology of bulk heterojunction photovoltaic devices with respect to their transport properties in combination with a specific kind of donor polymer. 33 . Patrick van’t Hof.

the highest reported hole mobility in a diode configuration amounts to 10−4 cm2 V−1 s−1 [5]. A step forward towards higher efficiency was reached by replacing MDMO-PPV with a high-mobility polymer as the light absorber and the electron donating material. P3HT has the advantage of an enhanced photostability and an improved optical absorption in the visible region which results in a better overlap with the solar emission spectrum compared to MDMO-PPV.7’-dimethyloctyloxy)-1. resulting in [60]PCBM analogues with altered substitution patterns on the solubilizing phenyl ring or by replacement of the methano bridge present in both [60]PCBM and many other derivatives [10–14].4-phenylene vinylene] (MDMO-PPV) and [60]PCBM reached a power conversion efficiency of 2.34 Chapter 3: A thienyl analogue of PCBM for bulk heterojunction solar cells 3. and. The synthesis of this compound was done using procedures as described . For pristine regioregular P3HT. and charge carrier transport.1 Introduction Organic photovoltaic devices consisting of three dimensional interpenetrating networks of conjugated polymers and a C60 derivative represent a challenging alternative for renewable sources of electrical energy [1]. 1). Herein. Attempts have been made to develop new fullerenoids for bulk heterojunction solar cells by attaching solubilizing groups to C60 . Subtle as this modification may seem. In the last few years. the morphology of the spin coated films. an analogue of [60]PCBM was designed with the aim of improving miscibility with polythiophenes donors. The efficiency of solar cells based on P3HT and [60]PCBM was shown to depend strongly on the processing conditions.5% [2]. In this compound the phenyl group from [60]PCBM is replaced by a thienyl group. resulting in [60]ThCBM (the chemical structure shown in Figure 3. whereas the hole mobility of pristine MDMOPPV is 5×10−7 cm2 V−1 s−1 [6–8]. we have previously observed that even slight modifications of the [60]PCBM structure may lead to significant changes in its solubility. in particularly. especially P3HT. Bulk-heterojunction solar cells made from poly [2-methoxy-5(3’. Up till now [60]PCBM is the remains the best performing soluble fullerene derivative in combination with regioregular P3HT. 36]. it shows an improvement when the devices are thermally annealed [9. One major improvement to this device structure was obtained by optimizing the morphology of the blend by casting the polymer and [60]PCBM from a solvent that prevents large scale phase separation and enhances the polymer chain packing. Moreover. several efforts to improve the efficiencies of these devices were undertaken [2– 4]. The most promising polymer solar cells developed at the start of this investigation in terms of efficiency and stability was based on a combination of P3HT as donor and [60]PCBM as acceptor [9].

3.2. Electron transport in pristine [60]ThCBM

35

for [60]PCBM [15]. Cyclic voltametry measurements of [60]ThCBM show that the energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are identical to those of [60]PCBM. In this chapter we report experimental studies of the morphology, charge transport and solar cell performance in blends of MDMO-PPV:[60]ThCBM and P3HT:[60]ThCBM. The results indicate that [60]ThCBM provides the same charge carrier mobility as [60]PCBM and that a highly functional bulk heterojunction morphology with P3HT can be obtained.

3.2 Electron transport in pristine [60]ThCBM
Prior to investigating solar cells made with this methanofullerene as active layer component, it is important to determine its electron transport properties, since this is a relevant parameter which strongly influences the solar cell performance [16]. For films of pristine [60]PCBM, spin coated from a chlorobenzene (CB) solution, an electron mobility of 2×10−3 cm2 V−1 s−1 has been observed [17]. [60]ThCBM is not as soluble as [60]PCBM in CB but it dissolves readily in orthodichlorobenzene (ODCB). Hence, for a better comparison, the electron mobilities of [60]PCBM and [60]ThCBM were determined in films spun from ODCB solution. Among the various methods to determine the charge carrier mobility we regard as the most appropriate one, the analysis of the space-charge limited current (SCLC) by investigating the (J-V ) characteristics in the dark. For a trapfree semiconductor, assuming that the injecting contact is Ohmic, the SCLC is given by the Mott-Gurney[26] equation: J ∝ µV 2 L−3 , where µ is the charge carrier mobility, V is the applied voltage, and L is the thickness of the active layer. Only the dependence of the charge carrier mobility on the electric field was taken into account here. Thus, the SCLC is given by Eq. (1):[27] JDark = 9 8
0 r µe

exp 0.89γ

V L

V2 , L3

(3.1)

where µe is the zero-field electron mobility, 0 is the vacuum permittivity, r is the relative dielectric constant, γ the field activation factor, and V /L is the applied electric field (E). Recent developments shown that the application of Equation 3.1 to describe the electric field dependence of the charge carrier mobility in low mobility media is not fully correct due to the fact that the density dependence of charge carrier mobility has been neglected [28–30]. It should be noted, however, that the charge carrier density in solar cells is fairly modest

36

Chapter 3: A thienyl analogue of PCBM for bulk heterojunction solar cells

4

10

[A/m ]

2

3

10
[A/m ]
2

10 10 10 10 10 10 10 10

4 3 2 1 0

J

10

J

D

S O

Dark

OCH3

2

-1 -2 -3

1

-1

0
V

1
bias

2
[V]

3

4

10

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

[60]ThCBM

V
bias

-V

-V
RS

[V]

bi

Figure 3.1: Chemical structure of [60]ThCBM (left). Experimental (symbols) and calculated (solid line) JDark -V characteristics for ITO/PEDOT:PSS/[60]ThCBM/LiF/Al electron-only device with a thickness L=102 nm (right). JDark is plotted against the applied voltage (Vbias ) corrected for the built-in voltage (Vbi ) and the voltage drop over the ITO/PEDOT:PSS layers (VRS ; RS=18 Ω). The inset shows the experimental data without any voltage corrections.

[31] and the density dependence of charge carrier mobility is negligible. The r for [60]ThCBM as well as for [60]PCBM (≈3.9) [17] was determined from impedance spectroscopy measurements. Hence, the only unknown parameter in Eq. (1) is the charge carrier mobility. The JDark -V characteristic of an electron-only pristine [60]ThCBM device, measured at room temperature is depicted in Figure 3. 1. The active area was 0.1 cm2 . Based on the work function of ITO/PEDOT:PSS (≈5.2 eV) and LiF/Al (≤3.7 eV), compared with the HOMO (6.1 eV) and LUMO (3.7 eV) levels of [60]ThCBM, one can assume that the current through the device is dominated by the electrons, since only electrons are injected from LiF/Al electrode in forward bias (when ITO is positively biased). The value of µe was extracted by fitting Eq. (1) to the experimental data, as shown in Fig. 3. 1. [60]ThCBM shows a µe of 1.8(±0.8)×10−3 cm2 V−1 s−1 at room temperature. For [60]PCBM films, spin coated from ODCB solution, a µe of 1.4(±0.5)×10−3 cm2 V−1 s−1 was obtained accordingly. These values of µe are similar to those observed previously for [60]PCBM films spun from chlorobenzene [17]. Moreover, both methanofullerenes have the same electron mobility, which indicates that the electron transport properties of [60]PCBM are not altered upon replacing the phenyl group by a thienyl moiety.

3.3. Bulk heterojunction solar cells using [60]ThCBM as acceptor

37

Figure 3.2: The 1.0×1.0 µm AFM height and simultaneously taken phase images of MDMO-PPV:[60]ThCBM (1:4 w/w) films spin cast from: a CB solution (a) and an ODCB solution (b).

3.3 Bulk heterojunction solar cells using [60]ThCBM as acceptor
3.3.1 [60]ThCBM and MDMO-PPV blends It has been shown in literature that different solvents can result in different efficiencies for MDMO-PPV:methanofullerene bulk heterojunction solar cells, as a result of a changed morphology [2, 18, 19]. Tapping mode atomic force microscopy (AFM) was employed, to gain insight in the molecular packing of the compounds. For the MDMO-PPV:[60]ThCBM (1:4 w/w) blends processed from CB solutions the height images reveal a rough surface with domain sizes of approximately 50-200 nm and a surface roughness (root-mean-square [rms]) of ≈3 nm for a 1.0 µm scan size. Contrary, the samples fabricated from ODCB show a smooth surface with a roughness of ≈ 0.7 nm, and domain sizes of approximately 10 nm (as seen in Figure 3. 2). Because the exciton diffusion length in

as a result of an enhanced charge carrier generation rate due to an increased donor/acceptor interface area. 4 shows the experimental JDark -V of an ITO/PEDOT:PSS/MDMOPPV:[60]ThCBM (1:4 w/w)/Pd hole-only device with a thickness of 260 nm.0 V 0. which facilitates exciton dissociation. spin coated from CB (full symbols) and ODCB solutions (empty symbols). calibrated using a reference silicon diode.38 Chapter 3: A thienyl analogue of PCBM for bulk heterojunction solar cells 20 [60]PCBM [60]ThCBM [A/m ] 0 2 J Light -20 -40 -60 -0. The short-circuit current density (Jsc) is increasing for cells with MDMO-PPV:[60]ThCBM spin coated from ODCB solution.0 [V] Figure 3. 5-7 nm [20–22]. To compare the role of [60]ThCBM on the photovoltaic device performance. organic materials is typically small. The solar cell devices were illuminated with a halogen lamp. The solar cells were made by sandwiching the MDMO-PPV:[60]ThCBM (1:4 w/w) blend between an ITO/PEDOT:PSS bottom electrode and a LiF/Al top electrode. Similar power conversion efficiencies were obtained for solar cells with a photoactive layer of MDMO-PPV:[60]PCBM spin-coated from the same solvent. Figure 3.2 0. calibrated to an intensity of approximately 1 sun with a Si diode. Figure 3.4 -0. resulting in a overall power conversion efficiency (η) of approximately 1.6 %. The active layer thickness is ≈100 nm. The open-circuit voltage (V oc) of 0.6 0. 3 shows the J-V characteristics of the solar cell devices under illumination.4 0. All the devices were illuminated by halogen lamp with intensity of 100 mW/cm2 . The large differences in morphology induced by the solvent are also reflected by the photovoltaic behavior of the MDMO-PPV:[60]ThCBM devices.8 1. reference devices of MDMO-PPV:[60]PCBM (1:4 w/w) were made and characterized in the same manner. the latter morphology favors exciton dissociation and subsequently yields a higher photocurrent.2 bias 0.3: JLight -V characteristics of ITO/PEDOT:PSS/MDMO-PPV:[60]Fullerene (1:4 w/w))/ LiF/Al devices.75 V and a fill factor (F F ) of 52 % are somewhat lower. at .

1 V -V bi 1 -V RS 10 [V] 10 -5 bias -1 0 1 V 2 [V] 3 4 5 bias Figure 3.0)×10−5 cm2 V−1 s−1 . In contrast to MDMO-PPV:[60]PCBM blends. at a temperature T = 298 K.5(±1. 4. in the order of 2. when holes are injected from PEDOT:PSS.3. In the forward bias.3. shown in the inset of Figure 3. A reason for the poor overall performance of the solar cell might be the presence of a large mobility mismatch between the electrons and holes in MDMO-PPV:[60]ThCBM blend. however. the injection of holes from Pd is suppressed due to the offset between its work function and the HOMO level of the polymer [24]. From the fit of the SCLC to the experimental data (solid line) we have extracted a hole mobility of MDMO-PPV phase.2 [60]ThCBM and P3HT blends Next we studied the solar cell performance of devices with a P3HT:[60]ThCBM photoactive layer and the influence of the thermal annealing on the power con- . indicates that JDark depends quadratically on the voltage.3. In reverse bias.4: JDark -V characteristics of ITO/PEDOT:PSS/MDMO-PPV:[60]ThCBM (1:4 w/w)/Pd hole-only device with a thickness of 260 nm. room temperature. This is a characteristic for a space-charge limited current [23]. the slope of the log(JDark ) versus log(Vbias − Vbi − VRS ) plot. the hole mobility of MDMO-PPV is not as strongly enhanced when blended with [60]ThCBM [25]. corrected for the built-in voltage (Vbi ) and the voltage drop over the ITO/PEDOT:PSS layers (VRS . 3. Bulk heterojunction solar cells using [60]ThCBM as acceptor 39 10 10 10 10 Dark 3 2 1 3 [A/m ] 2 0 10 10 [A/m ] 2 2 10 10 10 10 -1 10 10 10 10 10 1 J Dark -2 0 -3 J -1 -2 -4 -3 0. The inset shows the JD plotted against the applied voltage (Vbias ). RS=18 Ω) in a double logarithmic scale.

version efficiencies. The active layer thicknesses is ≈ 100 nm.58 0. and also the F F is increased when Sm/Al is used as top contacts.5: Device performance of P3HT:[60]ThCBM (1:1 w/w) blends. followed by evaporation of the top contacts Sm (5 nm) or LiF (1 nm) and Al (100 nm). under illumination from a halogen lamp. on a hotplate for 5 minutes. The annealing was performed on a complete device in N2 atmosphere. Figure 3.6 0.0 20 40 60 80 100 120 140 o 160 180 Annealing temperature [ C] Figure 3.56 72 FF [%] V 60 48 36 3. as a function of annealing temperature and for different top contacts (see the legend). The devices consist of P3HT:[60]ThCBM (1:1 w/w) blend films.62 [V] OC 0. 5 shows the variation of the principal photovoltaic parameters as a function of the annealing temperature.40 Chapter 3: A thienyl analogue of PCBM for bulk heterojunction solar cells 100 [A/m ] 2 80 60 SC Sm/Al LiF/Al J 40 20 0. which is an . The thicknesses of all P3HT:[60]ThCBM devices are ≈100nm.8 0.60 0. The V oc for the cells with Sm/Al as top contact is ≈ 30 mV higher compared with the V oc of the cells with LiF/Al as top contact.4 1.2 [%] 2. spin coated from chloroform solution on an ITO/PEDOT:PSS layer.

0 -6 -1 0 1 V bias 2 [V] 3 4 5 Figure 3. the electron current through the [60]ThCBM phase has to be blocked. as will be demonstrated in the following. The J-V characteristics of the solar cell devices.35 A/m2 . 6. After thermal annealing the Jsc increased to 83.8 1.5%.6: J-V characteristics of ITO/PEDOT:PSS/P3HT:[60]ThCBM (1:1 w/w)/Sm/Al devices as cast (circles) and after thermal annealing (squares) is shown in a semilogarithmic plot.3. the overall polymer crystallinity has improved and the hole mobility is increased. indication that Sm/Al is a better top contact compared to LiF/Al. A substantial increase in the current is observed upon annealing.65 A/m2 . as cast and after thermal annealing are represented in Figure 3.6% to 61. The devices under illumination were measured by a halogen lamp with intensity of 100 mW/cm2 .0 V bias 0.6 0.4 -0. V oc = 0.2 0.59 V. resulting in a hole-only device. The devices show an increase in F F from 36. Due to annealing.31%. and η = 0. Herein the hole-only devices were fabricated with the following structure: . Bulk heterojunction solar cells using [60]ThCBM as acceptor 41 10 10 10 10 10 10 10 6 as cast 4 annealed 2 J [A/m ] 2 20 0 [A/m ] 2 0 -20 -40 Light -2 -60 -80 J -4 -100 -120 -0.4% upon thermal annealing. in the dark and under illumination.03%. calibrated using a reference silicon diode. F F = 36.3. reflecting a higher overall mobility. This can be done by choosing proper electrodes which suppress the injection of electrons into the device. The devices were measured at room temperature (295 K) in the dark (full symbols) and under illumination (empty symbols) through the transparent ITO electrode.4 0.2 [V] 0. In order to investigate the hole transport through the P3HT phase in a blend with [60]ThCBM. This suggests an increase in carrier transport and it results in η of 3. The inset shows the J-V characteristics under illumination in a linear scale. For the as cast devices the performance characteristics were: Jsc = 14.

the transport of holes through the P3HT is limited by the space-charge that accumulates. the JDark -V measurements provide information on the zero field hole mobility (µh ) of the P3HT phase in a blend. (1).5 V−0. which leads to a large mismatch with the LUMO of [60]ThCBM [24] and this prevents injection of the electrons into [60]ThCBM. The AFM images of the P3HT:[60]ThCBM films for as cast and after thermal annealing. 8. PEDOT:PSS serves as an Ohmic contact for hole injection into HOMO of P3HT (≈4. are shown in Figure 3. as cast and after thermal annealing (see legend). In pristine P3HT.5×10−4 m0.42 Chapter 3: A thienyl analogue of PCBM for bulk heterojunction solar cells 10 4 [A/m ] 10 2 2 Dark 10 J 0 as cast annealed SCLC fit 10 -2 0 1 V 2 -V 3 -V RS 4 [V] 5 bias bi Figure 3.12 eV. Upon thermal annealing of P3HT:[60]ThCBM films an enhancement of the hole mobility by a factor of 100 was observed (µh ≈2×10−4 cm2 V−1 s−1 ). The experimental JDark of P3HT:[60]ThCBM blends that were measured in hole-only device configuration.2 eV. ITO/PEDOT:PSS/P3HT:[60]ThCBM (1:1 w/w)/Pd. The work function of Pd is about 5.7: Experimental (symbols) and calculated (solid lines) JDark -V for an ITO/PEDOT:PSS/ P3HT:[60]ThCBM (1:1 w/w)/Pd hole-only device. 7. and consequently the current is described by Eq. Assuming that the device is hole dominated. Hence. The active layer thickness is L=145 nm. as cast and after thermal annealing. this predominantly polycrystalline film may be formed already during the coating process and the thermal . When the applied voltage exceeds the built-in voltage (Vbi ) in this hole-only device. It has been shown that a whisker morphology is present in P3HT [33–35]. The work function of PEDOT:PSS is about 5. the µh in blend of P3HT:[60]ThCBM (1:1 w/w) is approximately 2×10−6 cm2 V−1 s−1 and the field activation factor γ is 1.9 eV [32]). are shown in Figure 3.5 . For as cast films.

In a blend film the presence of another molecule. A phase AFM image of a P3HT:[60]ThCBM (1:1 w/w) spin coated film as cast [see Figure 3. as cast (a) and after thermal annealing (b). 8(b)]. more structures can be seen in the spin-coated layer [see Figure 3.3.8: The 500×500 nm AFM height and simultaneously taken phase images of P3HT:[60]ThCBM (1:1 w/w) films. in this case [60]ThCBM.8(a)] reveals an amorphous structure. we have investigated a new methanofullerene for application as an acceptor material in bulk heterojunction solar cells. annealing does not further improve the crystallinity. 3. and the crystallinity of the P3HT is enhanced [36]. At this point many researchers are tempted to believe that the resulting interpenetrating network provides continuous pathways in the entire photoactive layer for efficient charge carrier transport. The electrical characterization of pristine [60]ThCBM films reveals that its electron transport properties . might prevent crystallization of P3HT. demixing of the two components is increased. Upon thermal annealing. Conclusion 43 Figure 3.4 Conclusion In conclusion.4.

In contrast. the overall power conversion efficiencies was increasing only to 1. In the next Chapter more detailed studies of the morphology and electrical properties of photovoltaic devices consisting of blends of P3HT:[60]ThCBM will be presented. spin coating the mixture from ODCB solvent gave smooth films and an increase in the current output which makes it similar to the MDMOPPV:[60]PCBM current. The diminished solubility of [60]ThCBM resulted in undesirable morphologies of the active layer when the MDMO-PPV:[60]ThCBM (1:4 w/w) mixture was spun from CB. However. The increase of efficiency is due to the increasing crystallinity of P3HT and hence the enhancement of the hole mobility in the P3HT phase of the blend by two orders of magnitude relative to as cast devices. the improved morphology.6%. using [60]ThCBM in combination with P3HT as the donor counterpart.0%. after thermal annealing and the optimized absorber composition. which indicates that the electron transport properties are not altered upon replacing the phenyl group by a thienyl moiety. leads to a power conversion efficiency up to 3. slightly lower compared to the F F of the MDMO-PPV:[60]PCBM devices. But as result of a low V oc of the devices.44 Chapter 3: A thienyl analogue of PCBM for bulk heterojunction solar cells equal those of [60]PCBM. The F F of 52%. is in accordance to the fact that the hole mobility of MDMO-PPV phase in a blend is not enhanced by [60]ThCBM. .

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49 . making it possible to optimize light absorption in these blends. In this way we control the growth rate of the films. it is shown experimentally that optimum device performance. Additionally. for the slow growth procedure.4 Effect of the P3HT:ThCBM growth rate on solar cell performance We present a study of the morphology and electrical properties of photovoltaic devices consisting of blends of regioregular poly(3-hexylthiophene) (P3HT) as electron donor and [6.4% (absolute) increase in power conversion efficiency. as well as a well-defined fibrilar and crystalline structure for slowly grown films.6]-thienylC61 butyric acid methyl ester([60]ThCBM) as an electron acceptor. The solar cells were fabricated by depositing the photoactive layer from solvents with different boiling points. is obtained at film thicknesses of approximately 300 nm. Electrical characterization of the solar cell devices indicates a clear advantage of the slow growth procedure. As a consequence of a more balanced transport of electrons and holes in the blend and an 0. This results in an order of magnitude enhancement in the hole mobility through the P3HT phase. Atomic force microscopy analysis reveals a more granular structure in case of fast grown films.

have recently reported plastic solar cells based on a rr-P3HT:PCBM mixture with a power conversion efficiency up to 4%. an improved film morphology. shown in Chapter 3. indicate that [60]ThCBM gives the same charge carrier mobility as [60]PCBM and that a highly functional bulk heterojunction morphology can be readily obtained with rr-P3HT [6] as donor counterpart. An efficient acceptor-type fullerene that can be used in solar cells based on rr-P3HT and other donor-type materials was synthesized in our group [6]. Previous results. In the solar cell devices. . we study the influence of processing conditions by investigating the effect of the boiling point of the casting solvent on the morphology and transport properties of P3HT:[60]ThCBM photoactive layer. This enhancement of the power conversion efficiency (η) has been attributed to: an increase of the hole transport in the blend due to crystallization of P3HT. As is demonstrated in the following. For these cells it was demonstrated that a thermal annealing process of the complete devices resulted in an enhancement of the solar cell performance [1]. resulting in [60]ThCBM. the charge transport properties. and a red shift of the absorption spectrum that results in a better overlap with the solar spectrum [2–4]. high electron and hole mobility is desired to obtain good fill factors and high conversion efficiencies. Additionally the thickness dependence of the solar cell performance was analyzed in detail. Up to now the ’state of the art’ polymer solar cells are based on a combination of regioregular P3HT and [60]PCBM. this study provides insight in the relation between the microscopic morphology of the organic photoactive layer. Li et al.50 Chapter 4: Effect of the P3HT:ThCBM growth rate on solar cell performance 4. This fullerene derivative was designed to improve the compatibility with polythiophene donors by replacing the phenyl group of [60]PCBM with a thienyl one. Previously it was demonstrated that high hole mobility can be obtained in field effect transistors with P3HT by using high boiling point solvents in the film casting process [7]. In this chapter.1 Introduction Solar cells based on blends of conjugated polymers and methanofullerene derivatives continue to be of interest as promising candidates for low cost and large area photovoltaic devices. The microstructure of such devices was found to be highly crystalline. with a needle-like morphology. which was realized by controlling the growth rate of the photoactive layer [5]. and the performance of the bulk heterojunction solar cells.

8]. Figure 4. The domain sizes are small. Morphology 51 4. due to rapid evaporation of the solvent during the spin-coating process. For films spin cast from methylthiophene. Hence the interchain interactions. in a closed Petri dish in nitrogen glove box. Compared with the fast grown film. approximately 10 nm. The most common and practical tool to investigate the morphology of the organic films is AFM. Spin coating the photoactive layer from 2methylthiophene and ODCB results in wet films. 2) is much more pronounced for the slowly grown films.2.4. 1 shows the AFM images of the P3HT:[60]ThCBM blend films cast from three solvents with different boiling points: chloroform (bp 61 o C). which were dried overnight at room temperature. the degree of crystallization remains limited by the time available for chain alignment. and ODCB (bp 173 o C). however. Here AFM was used to investigate the morphology of the active layer of regioregular P3HT:[60]ThCBM blends that were grown at different rates by using solvents having different boiling points. the P3HT chains are lying normal to the long axis of the . and consequently the device performance. Such well organized whisker-like structures are present over the whole surface and we attribute them. 1(b)] that well-defined whisker-like structures with a width of approximately 15 nm and a length of more than 600 nm are formed during drying. one can see [Figure 4. A red shift of approximately 37 meV appears in the better ordered films due to a better interchain π system overlap.2 Morphology The morphology of the active layer film is a key parameter in understanding the device performance of the organic bulk heterojunction solar cells. the absorption shifts a little to the red in the slowly grown film. 1(a)] indicate that these films are less crystalline and have a granular surface topography without apparent whisker-like structures. The vibronic structure of the absorbtion peaks (see Figure 4. indicating a higher degree of ordering [9]. The films spin coated from chloroform solution were named fast growth active layers. We refer to the layers obtained by the later method as slow growth active layers (more details can be found in Chapter 2). Even though thermal annealing of the fast grown P3HT:methanofullerene films was found to enhance the P3HT crystallinity to some extent [4]. 2-methylthiophene (bp 113 o C). The tapping mode AFM images of the fast grown films [see Figure 4. in agreement with literature. and the domains consist of small crystalline P3HT chain like structures together with either pure [60]ThCBM or mixed P3HT:[60]ThCBM domains. It was previously shown that in a P3HT whisker morphology. to crystalline P3HT domains [4. are not optimal for fast grown films.

10. and slow grown spun from ODCB (c). and 300 nm active layer thickness of the slow grown films. This is in a good agreement with the topographical measurements shown in Figure 4. as inset the schematic representation for the whisker formation (b).1: The 1 × 1µm AFM height and simultaneously taken phase images of P3HT:[60]ThCBM blend films after the following treatment: fast grown spun from CHCl3 (a). This pictures are taken for 200 nm active layer thickness of the fast grown film. slow grown spun from methylthiophene. 11]. Moreover. whisker and are folded with a period of approximately 15 nm [8. the films prepared from an ODCB solution have a different .52 Chapter 4: Effect of the P3HT:ThCBM growth rate on solar cell performance Figure 4. 1(b).

The P3HT whiskers form a matrix.0 0.9 0.7 0. morphology compared to those prepared from methylthiophene.8 Normalised 0. ODCB). slower solvent evaporation facilitates the growth of highly crystalline films. which can be seen in the AFM image in Figure 4.7 3.e. as will be shown in the following section.4 0.5 0. 1(b) and 4. 1(c). 1(c). even though they were both grown under slow drying conditions. However.2: Normalized absorbtion coefficient (α) for fast and slow grown P3HT:[60]ThCBM blend films. ODCB has a higher boiling point (173 o C) than methylthiophene (113 o C). more pronounced [60]ThCBM crystallites are observed at the surface. The drying time for films spin coated from ODCB solution is substantially longer under the same (atmospheric) conditions. which is clearly visible in the phase images of Figures 4.3 0.2 0.4.4 2.1 2. It is known that [60]PCBM tends to crystallize in the pristine form and even crystallizes in blends with MDMO-PPV or P3HT [12.6 0. This is also the case for [60]ThCBM when blended with P3HT and spun from ODCB solution. 13].. are between 20-30 nm in size and are presumed to represent the [60]ThCBM crystallites.3 fast grown (CHCl ) 3 slow grown (ODCB) Energy [eV] Figure 4. Morphology 53 1. This indicates that the boiling point of the solvent is a critical factor in the polymer crystallization process as well as for finding the optimum film morphology in order to realize the best device performance [7].2. and a phase separation into relatively large domains occurs.8 2. which enhances polymer interchain interactions and thus improves the hole mobility significantly.1 0. The [60]ThCBM molecules diffuse out of the matrix and form large crystalline clusters for slow grown films from higher boiling point solvents (i. In case of films spun from ODCB.5 1.0 1.0 3. The round shaped structures. this may have a negative effect . Consequently.

2 eV and therefore the PEDOT:PSS serves as an Ohmic contact for hole injection .54 Chapter 4: Effect of the P3HT:ThCBM growth rate on solar cell performance 10 [A/m ] 2 3 10 Dark 2 10 10 1 slow grown (Methylthiophene) slow grown (ODCB) J 0 fast grown (CHCl ) 3 SCLC fit 0 1 V 2 -V bi 3 -V [V] RS 4 5 bias Figure 4. JDark is plotted against the applied voltage (Vbias ). whereas the thickness of the fast grown film is 160 nm.3: Experimental (symbols) and calculated (solid lines) JDark -V characteristics for ITO/PEDOT:PSS/P3HT:[60]ThCBM/Pd hole-only devices. and the analysis of the space-charge limited current (SCLC) [14] by investigating current densityvoltage (J-V ) characteristics in the dark. 3 shows the experimental dark current densities (JDark ) of a hole-only device for fast growth as well as for slow growth of the active layer. is evaluated. The work function of PEDOT:PSS is 5. slow drying of the P3HT:[60]ThCBM films using high boiling point solvents results in an enhanced crystallization of the P3HT phase. 4. the charge carrier mobility in the blends. on the photocurrent of solar cells since phase separation into large domains will reduce charge generation as a result of the short exciton diffusion lengths. Figure 4. prepared with different growth rates. The thicknesses of the slow grown films are 270 nm.3 Hole transport In organic bulk heterojunction solar cells charge carrier mobility in the active layer is determining the power conversion efficiency. Electron and hole mobility values are determined experimentally using various techniques including time-of-flight measurements [5]. field-effect transistor measurements [7]. corrected for the built-in voltage (Vbi ) and the voltage drop over the ITO/PEDOT:PSS layers (VRS ). As shown in the previous section. Before discussing the solar cell performance of P3HT:[60]ThCBM blends. as compared with a fast drying procedure. characteristic for conjugated polymers.

12 eV. 3. All devices were . and L is the active layer thickness. For disordered semiconductors the electric field dependence of the µ must be considered: µ ∝ µ0 exp(γ V ). and amounts to µh =2×10−3 cm2 V−1 s−1 . at zero electric field. the work function of palladium is 5.where 0 r is permittivity of the polymer. and therefore the charge transport in the P3HT phase is increased. Solar cells characterization 55 into the HOMO of P3HT (4. further increasing the drying time of the blend films mainly results in the formation of more crystalline [60]ThCBM domains. indicative of space-charge limited (SCL) transport: JDark ∝ 0 r µV 2 /L3 .4. When the applied voltage exceeds the built-in voltage (Vbi ). µ charge carrier mobility. 1(b) and 4. the P3HT has more time for reaching thermodynamic equilibrium. Most likely. We conclude that during slow drying of the films. we determined a hole mobility of P3HT phase of 2×10−4 cm2 V−1 s−1 . the hole mobility in the P3HT phase increases one order of magnitude with respect to the thermally annealed films.9 eV [15]). On the other hand. since an electron mobility of ≈2×10−3 cm2 V−1 s−1 has been reported in P3HT:[60]PCBM blends for similar casting conditions [2. 20]. 1(c). and it prevents injection of electrons into [60]ThCBM. applying slow drying. despite of a difference in film morphology shown in Figures 4. was extracted by fitting the SCL dark current density (using the above equations) to the experimental data.This leads to a more balanced transport of electrons and holes in the device. The hole mobility of P3HT in a blend with [60]ThCBM turned out to be the same for the films prepared by the slow growth method from methylthiophene and ODCB solution. For the fast dried and thermally annealed P3HT:[60]ThCBM blend films. JDark scales quadratically with the voltage V . The combined equations provide for a direct determination of the charge carrier mobility [17–19]. The fact that the hole mobility is identical in both slow grown films. γ is the field activation parameter which depends on the energetic and positional disorder of localized transport states.4 Solar cells characterization After a study of the morphology and charge transport we proceeded with the analysis of the performance of the solar cell with photoactive P3HT:[60]ThCBM blend layers prepared under fast and slow growing conditions. which leads to a large mismatch with the LUMO level of [60]ThCBM [16].4. The value of the hole mobility (µh ). is an indication that maximum crystallinity of P3HT is reached already at moderate growing times (moderate boiling point solvents). as shown in Figure 4. L where µ0 is the zero-field mobility. and the films have a high degree of ordering as can be seen from the absorption spectra. Hence. 4.

indicating an efficient charge generation in these devices.56 Chapter 4: Effect of the P3HT:ThCBM growth rate on solar cell performance 60 40 [A/m ] fast grown (CHCl ) 3 20 0 -20 Light slow grown (Methylthiophene) slow grown (ODCB) 2 -40 -60 -80 -100 -120 -0.8 A/m2 . V oc = 0.4: JLight -V characteristics of ITO/PEDOT:PSS/P3HT:[60]ThCBM/Sm /Al devices with an active layer fast and slow grown. prepared as described in the experimental section. The best device prepared from 2-methylthiophene showed a similar efficiency of η = (3.2 0.5 A/m2 . or by slow drying. compared to the thermally annealed fast grown ones. In order to improve the device performance we also studied the influence of the thickness of the active layer on the solar cells performance.2)%.0 V bias J 0. The slow grown films are 300 nm thick. and the fast grown film is 200 nm thick.59 V.6 Figure 4. most probably originates from an improved morphology and the subsequent enhancement of the hole mobility through the crystalline P3HT phase in the blend.3)%.5±0.2)%. For the slowly dried films the best performance is obtained using an ODCB solution.2 [V] 0.3%. a short-circuit current density Jsc = 90. 5 shows the variation of the photovoltaic parameters as a function of active layer thickness.4 -0. an open-circuit voltage V oc = 0. Figure 4. and a fill factor F F = 59. The devices fabricated by the slow drying method were all spun from ODCB. Jsc = 99. The best device prepared by a fast drying procedure had a power conversion efficiency η = (3. with values of η = (3.4±0. This is in agreement with previous results which showed that for . The Jsc is increasing rapidly with the active layer thicknesses for both slow and fast growth films until approximately 200-230 nm. 4 shows the photocurrent (JLight ) of the solar cells in which the active layers were prepared by either fast drying and subsequent annealing. At a P3HT:[60]ThCBM film thickness of 200-230 nm. Figure 4.1±0. most of the incoming photons are absorbed by the active layer.4 0.55 V and F F = 63%. The better performance of the slowly grown devices.

A small decrease in Jsc for fast drying films for thicknesses above 200 nm can be attributed to the limitation imposed on Jsc by space-charge effects and/or charge recombination.5: Device performance of the P3HT:[60]ThCBM blends.62 0. a P3HT film of 240 nm more than 95% of the incoming photons are absorbed by the active layer within its spectral range [21]. The active layer was casted in two different ways: fast grown spun form CHCl3 plus a subsequent thermal annealing step (empty circles).54 0.0 100 200 300 400 500 [%] FF [%] Voc [V] Jsc [A/m ] 2 3.4.52 120 100 80 60 40 0 100 200 300 400 500 Active layer thickness [nm] Figure 4. under illumination from a halogen lamp.58 0. These effects are a con- .60 0.5 3. The full lines are a guide to the eye. as a function of the active layer thickness. Solar cells characterization 57 0 4.4.56 0.0 2. and slow grown spun from ODCB (full circles). Above 200 nm film thickness only a small fraction of photons from the solar spectrum remains to be absorbed and therefore the Jsc saturates.5 70 65 60 55 50 45 0.

The difference in power conversion efficiency between slow and fast grown films is mainly determined by the difference in the fill factor and open- . we have shown that slow growing of the active layer films in P3HT:[60]ThCBM blends. This leads to a well balanced charge carrier transport in the blend. Consequently. 4. with a larger voltage produced by the fast dried and annealed devices. facilitates growing of highly crystalline films. The reduction of the optical gap of P3HT is a consequence of the decrease in ionization potential (HOMO level) by an enhancement of the intermolecular overlap. The FF is decreasing linearly with the layer thicknesses for both. compared to the fast growth films. It appears to be in agreement with a simple model calculations which confirm the reduction of the band gap and find that about 3 of 4 the shift occurs in the valence band [24]. Since the V oc of donor:acceptor bulk heterojunction solar cells is linearly related to the HOM Odonor -LU M Oacceptor energy difference [16]. fast and slow growth methods. due to increasing recombination of charge carriers by increase of the mean distance they need to travel before they are extracted at the electrodes. and improves the hole transport in the blend by an order of magnitude. Although the V oc is lower for slow growth films its superior fill factors well compensate the loss in V oc and therefore result in a better overall cell performance. The benefit of an improved charge carrier mobility for slow growing films together with a better balanced electron and hole transport makes it possible to manufacture thicker active layers without significant loss in F F . as a result of a better and more balanced transport of electrons and holes in the device (see previous section). 23]. Consequently the V oc is lowered in slow grown films. Moreover the FF for the slow growth films is in average 10% higher for the same film thickness. by using solvents with a high boiling point. the difference in conversion efficiency between slow and fast growing films is mainly determined by the difference in F F and V oc for the same film thickness. the V oc is lowered when the ionization potential of the donor is decreased. This difference in voltage of approximately 40 mV is fully accounted by the red shift in absorbtion spectra (37 meV) as a result of the enhanced crystallinity of P3HT in the slow grown films (see Figure 4. This enhances the interchain interactions in the P3HT phase. and therefore it allows to maximize charge generation in these blends.5 Conclusion In conclusion. 2).58 Chapter 4: Effect of the P3HT:ThCBM growth rate on solar cell performance sequence of an unbalanced electron and hole transport which is present in the blend and is caused by a lower hole mobility of P3HT phase [22. The V oc is relatively constant as a function of active layer thickness.

In the next Chapter a study of the lifetime of the bulk heterojunction photovoltaic devices. with a slow growth P3HT:methanofullerene photoactive layer. .5. Although the open circuit voltage tends to be lowered (with approximately 40 mV) in devices with active layers with a higher degree of molecular organization. and therefore it allows for maximizing light absorption in these blends.4. will be presented. The benefit of better charge transport for slow growing films makes it possible to fabricate thicker films without significant loss in fill factor. it is the significant increase in the fill factor (up to 70%) which gives much higher (13% relative) power conversion efficiencies. Conclusion 59 circuit voltage of the cells.

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I. J. N. G. X. [12] X. A. F. van Duren. Blom. Emery. Heeger. Journal of polymer science. Angewandte Chemie. Nano Letters 5 (2005).6]-methanofullerene for bulk heterojunction photovoltaic devices in combination with polythiophenes. Yang. van’t Hof. B. Stafstrom.REFERENCES AND NOTES 61 References and notes [1] F. Advanced Functional Materials 13 (2003). K. W. L. Yang. S. 4772. C. B. Kroon. Janssen. Breiby. Yang. H. Y. [4] X. Meyer. Nandi. J.[6. T. Part B. J. R. W. S. A. C. M. V. 1617. O. J. Rispens. M. Verhees. Polymer physics 31 (1993). Langeveld-Voss. A. Huang. Lee. Veenstra. Sun. H. Yang. [8] J. J. W. Nature Matererials 4 (2005). Chemistry of materials 16 (2004). J. 435. J. Thienyl analog of 1-(3-methoxycarbonyl)propyl-1-phenyl. Ma. Chang. Shrotriya. Xie. R. Loos. Padinger. Part B. W. M. Journal of polymer science. Sieval. ¨ ¨ [9] M. A. M. I. Sariciftci. Ingan¨ s. J. J. 85. B. A. Whiskers of poly(3-Alkylthiophene)s. M. Charge transport and photocurrent generation in poly(3-hexylthiophene):methanofullerene bulkheterojunction Ssolar cells. B. J. Moriarty. Sirringhaus. Giles. Two-dimensional crystals of poly(3-alkylthiophene)s: direct visualization of a polymer folds in submolecular resolution. [2] V. Thermally Stable. B. Advanced Functional Materials 16 (2006). J. M. M. Solling. [10] S. J. Janssen. Gustafsson. E. M. de Boer. Polymer physics 40 (2002). D. H. 699. McCulloch. S. Solid State Communications 71 (1989). Crystalline organization of a methanofullerene as used for plastic solar-cell applications. Li. S. J. W. Smith. Enhanced mobility of poly(3-hexylthiophene) transistors by spin-coating from high-boiling-point solvents. Mena-Osteritz. T. K. K. Nielsen. A. B¨ uerle. Efficient Polymer solar cells with nanoscale control of the interpenetrating network morphology. Michels. A. P. Janssen. Wienk. Y. [11] E. C. 2073. Yao. R. Meijer. Ihn. P. A. Rittberger. T. R. Applied Physics Letters 89 (2006). Jonkman. M. 735. Sundberg. International edition 39 (2000). Nanoscale morphology of high-performance polymer solar cells. A. [6] L. K. Koster. 579. J. Popescu. J. P. 802. 2679. Effects of postproduction treatment on plastic solar cells. 864. P. D. Malik. Hummelen. J. Optical absorption a of poly(3-alkylthiophenes) at low temperatures. [3] W. C. M. Michels. Moulton. Advanced Functional Materials 15 (2005). J. Advanced Materials 16 (2004). Gong. Hummelen. [5] G. Crystallization mechanism of regioregular poly(3-alkyl thiophene)s. High-efficiency solution processable polymer photovoltaic cells by self-organization of polymer blends. Sjogren. 213507. Mihailetchi. M. Loss. T. H. . ¨ [7] J. M. A.

J. E. V. Cathode dependence of the open-circuit voltage of polymer:fullerene bulk heterojunction solar cells. [15] Y. Mihailetchi. applied physics 3 (1970). Yao. de Boer. N. Dyakonov. Journal of Applied Physics 94 (2003). van Duren. 063502-1. Compositional dependence of the performance of poly(p-phenylene vinylene):methanofullerene bulk-heterojunction solar cells. Applied Physics Letters 87 (2005). Blom. R. D. H. Janssen. P. Street. Choulis. Theory of Space-Charge-Limited Current Enhanced by Frenkel Effect. [16] V. B. Transport in polycrystalline polymer thin-film transistors. C. J. 4533. Durrant. [18] V. Popescu. D. Hole transport in poly(phenylene vinylene)/methanofullerene bulk-heterojunction solar cells. Li. [22] L. Hummelen. Physical Review B 71 (2005) 165202. [19] P. J. J. M. 012107. P. S. 151.62 Chapter 4: Effect of the P3HT:ThCBM growth rate on solar cell performance [13] D. M. Northrup. A. Koop. [20] V. A. Xie. [17] C. J. Chemistry of materials 16 (2004). Melzer. M. Applied Physics Letters 86 (2005). J. Device annealing effect in organic solar cells with blends of regioregular poly(3-hexylthiophene) and soluble fullerene. D. Hummelen. McGehee. 126602. P. Mihailetchi. de Boer. Mihailetchi. Origin of the light intensity dependence of the short-circuit current of polymer/fullerene solar cells. W. W. 063503. L. D. V. Nelson. Space-Charge Limited Photocurrent. J. 795. Influence of nanomorphology on the photovoltaic action of polymer-fullerene composites. W. J. D. D. . D. A. Blom. 6849. B. J. Mihailetchi. A. [24] R. R. T. P.6]-phenyl C61-butyric acid methyl ester solar cells upon slow drying of the active layer. Wildeman. Blom. Koster. P. V. M. C. Murgatroyd. Mihailetchi. Advanced Functional Materials 14 (2004). D. J. Rispens. Journal of physics. G. M. Degradation mechanism of organic light-emitting device investigated by scanning photoelectron microscopy coupled with peel-off technique. P. D. L. W. Salleo. Nanotechnology 15 (2004). S. K. Origin of the enhanced performance in poly(3-hexylthiophene): [6. Applied Physics Letters 89 (2006). Applied Physics Letters 89 (2006). M. Blom. M. [14] V. 203502. Koster. Yang. Hummelen. Chirvase. Shrotriya. D. A. H. Mihailetchi. Bradley. M. Coakley. [21] K. [23] V. Cook. J. C. A. C. Xie. Parisi. Kim. J. W. Physical Review Letters 94 (2005). M. J. J. Y. Conjugated polymer photovoltaic cells. W. Melzer. Advanced Functional Materials 15 (2005). M. 865. Y. E. Blom. 1317. Blom.

5 Stability tests of P3HT:methanofullerence solar cells In spite of the high potential of polymer photovoltaic cells. as acceptor. show a faster degradation compared to [70]PCBM and [60]PCBM solar cell devices. 63 . the main challenge remains the improvement of their stability under operational conditions. Electrical and optical properties of these devices were monitored for a test period up to 1000 hours under continuous illumination. External quantum efficiencies and absorption spectra indicate that the fullerene degradation is more prominent than that of the polymer. The results indicate that solar cells with [60]ThCBM. The stability of P3HT:methanofullerene solar cell devices was investigated in this chapter. therefore the hole mobility is not the cause for the degradation observed in the solar cell devices. The hole transport through the blend (P3HT phase) remains unaffected during the stability test.

. careful design and material engineering can substantially improve device lifetimes. In the last couple of years organic photovoltaics based on conjugated polymers and methanofullerenes have been suggested as a low cost alternative to the inorganic semiconductors due to their advantages of light weight and low-cost plastic-based technologies. etc) of donor:acceptor bulk heterojunction solar cells. the nanomorphology and the stability of the contact between metal conductors and organic semiconductors. layer materials. high hole mobility. including its self organization. measured under a solar simulator class A with a light spectrum that approximates the AM1. Germany).64 Chapter 5: Stability tests of P3HT:methanofullerence solar cells 5. which was initially calibrated at ISE Callab (Freiburg. The power conversion efficiency [1] and the lifetime of organic photovoltaic devices still do not warrant commercialization. Device degradation arises from changes in morphology. In all these measurements the mismatch factor correction for the solar simulator was taken into account. for blends of regioregular P3HT and various methanofullerenes. loss of interfacial adhesion. Most promising devices to date are blends of polythiophenes [such as regioregular P3HT] as donors and metanofullerene [such as [60]PCBM] as acceptors [1–5]. some approaches have been used to improve the efficiency. including thermal annealing with simultaneously applied external voltage [6]. The term ”stability” used here deals with the intrinsic stability of the organic materials used in the active layer.5 global spectrum. Thus. was used as a reference cell in order to set the light intensity of the solar simulator. For this type of blends. A monocrystalline Silicon diode. postproduction annealing at high temperatures [2]. as well as chemical decomposition under operational conditions.1 Introduction A key issue faced by the organic electronics community in general is the stability of the devices. Further we present experimental studies on the stability under continuous illumination of the solar cells fabricated by slow drying of the active layer of P3HT:methanofullerene. P3HT possesses some unique properties compared to other polymers. and controlling the growth rate of the photoactive layer in the device preparation [1]. Many efforts made in the past decade were focussed on optimizing the device parameters (film thickness. and interdiffusion of components. and extended absorption in the red region. In this chapter we report on the power conversion efficiency values. whereas only limited research exist on their stability and the degradation of the electrical characteristics [7–17].

2 Accurate efficiency measurements Prior to the investigation of the stability of the various P3HT:methanofullerene solar cell devices.1. From the data it can be concluded that the difference in the power conversion efficiency (η) between the investigated solar cells finds its origin in the variation of the fill factor (F F ) and where [60]ThCBM shows a slightly increased performance.7 63. These thicknesses have been found to be the optimum for these type of blends (as shown in Chapter 4).8 5. In figure 5. To complete the devices Sm (5nm)/Al (100 nm) or only Al (100 nm) top electrode was deposited by thermal evaporation. The slow grown P3HT:methanofullerene blend films were spin cast from an orthodichlorobenzene (ODCB) solution on top of a 60 nm thick PEDOT:PSS layer. but there is no contribution present in the EQE at the same wavelength range.6 3. Here L is the active layer thickness. an accurate efficiency determination is necessary.1 VOC (mV) 563 573 566 FF (%) 60.2 10. A small shoulder that is present at 480 nm in the absorption of P3HT:[70]PCBM solar cell (as shown in the top part of Figure 5. 19]. Table 5.0018) cm2 . which will be elaborated more in the next chapter. Subsequently.1 lists the photovoltaic parameters of the best fabricated P3HT: methanofullerene solar cells. .1: Photovoltaic parameters of the best P3HT:methanofullerene solar cells with an active area of 0. Nevertheless up to 70% of the incoming photons are converted to current at the maximum absorption range in these blends. measured at ECN.5.7 3. The device fabrication procedure is described in detail in Chapter 2 of this thesis.1) is a result of the fullerene contribution [18]. The short-circuit current density (JSC ) varies less than 4% for these solar cells and no significant improvement is observed with respect to the [70]PCBM [18. the wet films were dried overnight inside a closed Petri dish at room temperature in a N2 glove box. This absorption seems not to contribute to the EQE in the relevant wavelength range. although this may be caused by the lesser sensitivity of the EQE measurements.3 65.1 (bottom) we compare the external quantum efficiencies (EQE) of the solar cells listed in Table 5.0958(±0.5 10.9 η (%) 3. Accurate efficiency measurements 65 Table 5. The active layer thicknesses is approximately 300 nm for [60]PCBM and [60]ThCBM cells and 250 nm for [70]PCBM cell.2. Methanofullerene [60]PCBM [70]PCBM [60]ThCBM L (nm) 300 250 300 JSC (mA/cm2 ) 10.

cooling was not applied and the stability tests were performed at an elevated temperature (around 50 o C). Four halogen lamps were used for the stability tests at the ECN facility. The total output power of these lamps was typically 100 mW/cm2 (one sun) as controlled by a calibrated Si diode. . however.3 Effect of ageing on the device performance After the initial current-voltage characterization of the P3HT:methanofullerene solar cells presented in the previous section.1 ppm in two different locations: at ECN and in our laboratory (RUG). with O2 and H2 O levels below 0. In this section the investigation was focused on the charge carrier mobility and on the solar cell performance. Cooling of the cells was ensured using ventilation by electrical fans in order to maintain the temperature at the surface of the samples around room temperature. 5. For some tests. These tests were carried out inside a N2 glove box.66 Chapter 5: Stability tests of P3HT:methanofullerence solar cells 4 5x10 [cm ] 4x10 3x10 2x10 1x10 4 [60]PCBM [70]PCBM [60]ThCBM -1 4 4 4 0 EQE [%] 60 40 20 0 [60]PCBM [70]PCBM [60]ThCBM 420 480 540 600 660 720 780 Wavelength [nm] Figure 5.1: Absorption coefficient α (top) and the external quantum efficiency EQE (bottom) of ITO/PEDOT:PSS/P3HT:Methanofullerene/Sm/Al devices. stability test were carried out in order to investigate their useful lifetime under continuous illumination.

Effect of ageing on the device performance 67 5. for about 200 hours at 50 o C. Experimental trials using a thin and transparent Sm low work function electrode have failed to succeed due to a large increase in leakage current of such a electron-only device upon illumination. the dark current of the hole-only device after 200 hours of continuous illumination is slightly higher compared to the dark current before degradation test. This increase in the hole-mobility after 200 hours of continuous illumination could be due to a more favorable morphology for hole transport in the blend. This type of device is difficult to realize and it is less likely to remain stable during illumination. Subsequently the illumination was switched off and dark J − V characteristics of the devices were measured. No significant degradation occurs in the dark current of the devices due to illumination and the rise in temperature.3. This result indicates that the hole mobility is not the cause for the degradation observed in the solar cell device. Figure 5. Here hole-only devices were fabricated by depositing an electron blocking contact on an otherwise normal P3HT:[60]PCBM solar cell device (see Chapter 2 for details). It has been shown in various papers that one of the most reliable ways to obtain information about the hole transport in a polymer:fullerene blend is the investigation of the current-voltage characteristics of a hole-only device in the dark [20–23]. electron transport is difficult to be measured independently during degradation due to the fact that an electrononly device will require a low work function transparent metal electrode (in order to block hole injection). However.3 × 10−3 cm2 V−1 s−1 ).1 Charge carrier transport One of the most important parameters that determines the performance of a bulk heterojunction solar cell is the charge carrier mobility of electrons and holes after dissociation of the excitons at the donor/acceptor interface.3. The typical hole mobility of the P3HT phase in the blend before degradation test (t = 0 hours) is ≈ 2 × 10−3 cm2 V−1 s−1 and after 200 hours of continuous illumination the hole mobility is slightly higher (≈ 3. The other important parameter that could affect current transport through the solar cells is the electron mobility. in a nitrogen glove box by a halogen lamp adjusted to a power of 100 mW/cm2 . This hole-only device was then illuminated (at RUG). 2 shows the J − V characteristics of the hole-only devices (open symbols) before and after 200 hours of constant illumination. Therefore in this section aging tests were carried out to investigate the changes that may occur in the charge carrier transport properties of the solar cells. Moreover. This is consistently observed for all devices investigated. A successful method exists to fabricate an electron-only device using a bottom electrode consisting of a self assembled monolayer (SAM) on top of a .5.

we have investigated the dark current of the solar cell (before and after continuous illumination) where both charge carriers are injected from the respective electrodes. as an alternative.2. 5.0 1.3 shows the parameters of the P3HT:methanofullerene solar cells measured under maximum power point operation during 1000 hours of constant illumination at 25 o C.68 Chapter 5: Stability tests of P3HT:methanofullerence solar cells 4 10 [A/m ] 2 3 10 2 Dark 10 J solar cell (t = 0 hrs) 1 10 solar cell (t = 200 hrs) hole-only (t = 0 hrs) hole-only (t = 200 hrs) 0 10 0. The decay of the photovoltaic parameters after 2 hours of illumination.5 2. this method can not be used here to measure degradation of the devices under illumination since a (semi) transparent electrode is required for photocurrent generation.0 2. The applied voltage (Vbias ) is corrected for the built-in voltage (Vbi ). In the more prolonged tests. and [70]PCBM.5 3. in a nitrogen atmosphere. is in the same range for all three types of solar cells. The methanofullerenes used are [60]PCBM.0 V bias -V bi [V] Figure 5.5 1. [60]ThCBM. However.3.2 Solar cells parameters Figure 5. The results are represented by full symbols in Figure 5. The performance is well above 95% of the initial values. Since the hole current through the solar cell is slightly higher after 200 hours of light exposure it is intuitively anticipated that the decline of the dark current of the solar cell is a result of a change in the electron transport properties and/or in the recombination rates of electrons and holes in the solar cell device since both charges are injected from the electrodes [25]. Thus.0 0.2: Dark J-V characteristics of the P3HT:[60]PCBM bulk heterojunction solar cells (see legend)and of the P3HT:[60]PCBM hole-only devices measured at 0 and after 200 hours of continuous illumination under V oc condition. there is a clear difference in the photovoltaic parame- . thick (> 50 nm) Ag layer [24].

8 0. and F F is more stable for [70]PCBM-based solar cells (a decrease . The decay of the fill factor for all three types of solar cells roughly follows the same pattern as the decay in open-circuit voltage and could be due to modification in contact resistance. increased recombination/trapping rates or poorer charge carrier mobility.8 [60]PCBM [70]PCBM 0. 1000 hours of continuous illumination resulted in a decrease to 85% respectively 80% of the initial short-circuit current. The short-circuit current of the [70]PCBM solar cells shows the smallest decrease in the ageing tests.0 0.6 [60]ThCBM FF (t)/FF (t=0) (t=0) (t)/ 1. VOC .8 0. These results suggest that the overall efficiency. with its value staying above 90% of the initial value after 1000 hours of continuous illumination. at room temperature in a nitrogen atmosphere.8 0. under maximum power point conditions. For the [60]PCBM and [60]ThCBM solar cells.0 0.6 1.3: Normalized operational parameters for the P3HT:Methanofullerene bulk heterojunction solar cells (see legend) measured during 1000 hours of constant illumination. Effect of ageing on the device performance 69 Jsc (t)/Jsc (t=0) Voc (t)/Voc (t=0) 1.3.5.0 0.6 0 200 400 600 800 1000 Time [hours] Figure 5. being proportional to the JSC . The degradation of the open-circuit voltage lies in the same range for all three types of solar cell devices and their final value amounts approximately 90% of the initial values. ters for the three different methanofullerene used.6 1.0 0.

4 shows that there is no significant difference for the solar cell parameters of the cells kept under open-circuit or at maximum power point conditions during the tests. therefore this kind of degradation of cell performance as a result of a phase separation with this higher fullerene derivative in the active layer is very likely reduced.7 0.6 0.0 0. by simultaneous illumination of both devices with one halogen lamp. at a temperature of 50 o C. which could result in a decrease of the electron mobility in the blend as a consequence of an interrupted percolation path. The decrease in efficiency for solar cells containing [70]PCBM. In both cases the degradation was significantly more pronounced compared to cells exposed to light at room temperature (see Figure 5.5 0.9 0. [60]PCBM. indicating that the kinetics of the degradation are not influenced by the applied bias (≈ 0. The data in the left figure shows the solar cells aged at maximum power point condition whereas the right figure shows the results of cell aged at open-circuit condition. These tests were carried out at the RUG laboratories in nitrogen glove box. Next we studied the degradation of devices under different operational conditions: maximum power point and open-circuit. to ≈ 90% after 1000 hours of continuous illumination) compared to [60]PCBM and [60]ThCBM solar cells (a decrease to 80% respectively 75% after 1000 hours of continuous illumination).6 0.7 0. The [70]PCBM (which is an isomeric mixture) has less tendency to crystallize compared to [60]PCBM and [60]ThCBM.4 V forward bias).3). and [60]ThCBM can be explained by the fact that during illumination also fullerenes crystallize and form larger crystallites in time.4 0 200 400 600 800 1000 J SC 1.9 0.4: Normalized parameters of the P3HT:[60]PCBM bulk heterojunction solar cells (see legend) measured during 1000 hours of constant illumination at a temperature of 50 o C in nitrogen atmosphere.8 0.8 0. Figure 5.4 0 200 400 600 800 1000 J SC Open circuit operation V OC V OC FF FF Time [hours] Time [hours] Figure 5. It was observed that most of the degradation occurs directly after . One can conclude that the crystallization of the methanofullerene phase is an important factor in the stability of the devices under continuous illumination.70 Chapter 5: Stability tests of P3HT:methanofullerence solar cells Normalized parameters Maximum power point operation Normalized parameters 1.5 0.0 0.

we studied solar cells with different top electrodes. This initial degradation is attributed to the morphology changes at the elevated temperature of the cells. and F F ) of P3HT:[60]PCBM solar cells having either Sm/Al or only an Al as top electrode. 5 shows the decay of the photovoltaic parameters (JSC . 5.8 Al Sm/Al J SC 0. and all cell parameters are affected.3 External quantum efficiency (EQE) In order to gain an additional understanding of the origin of solar cell degradation upon illumination. the illumination was switched on and consequently during the rise in temperature. we investigated the EQE of the P3HT:methanofullerene . Effect of ageing on the device performance 71 Normalized solar cell parameters 1. and it is not observed for the degradation carried out at room temperature (as seen in Figure 5.0 0. Empty symbols are solar cells with Al top contact and full symbols are solar cells with Sm/Al top contact. as seen in this specific study. at open-circuit conditions.7 V OC FF 0 60 120 180 240 300 360 Time [hours] Figure 5.5.3.5: Normalized parameters for the P3HT:[60]PCBM bulk heterojunction solar cells (see legend) measured during 360 hours of constant illumination.3. Therefore most probably the degradation in cell parameters. Another issue is the effect of the top electrode on the degradation process. VOC . Figure 5.3). after 360 hours of continuous illumination at 50 o C. These results indicate that the top electrodes used in our devices do not significantly affect the stability of these devices under illumination. Since the contact resistance between the active layer and metal electrode could be affected by light exposure. at a temperature of 50 o C in nitrogen atmosphere. In both cases the same degradation was observed for all cell parameters.9 0. might be caused by the changes that occur in the active layer of the solar cells.

Figure 5. The full symbols represent the initial EQE measurements (taken at t=0 hours).6: Influence of the ageing on the EQE of the P3HT:methanofullerene solar cells (see legend).6 shows the EQE as a function of the incident wavelength for solar cells measured before and after 1000 hours of illumination at room temperature for blends of P3HT and the three methanofullerenes used in this 1.7: Normalized absorption coefficients of a pristine [60]PCBM. P3HT films and of a P3HT:[60]PCBM (1:1 w/w) blend film.72 Chapter 5: Stability tests of P3HT:methanofullerence solar cells 70 60 EQE [%] 50 40 30 20 10 0 EQE (t=1000)/EQE (t=0) 1.8 Normalized 0.0 [60]PCBM P3HT P3HT:[60]PCBM (1:1 w/w) 0.4 0.2 0.6 0. whereas the empty symbols indicate the EQE measured after 1000 hours of illumination at room temperature and in nitrogen atmosphere. solar cells.8 0.4 0.0 0.2 [60]ThCBM 400 450 500 550 600 650 700 750 800 Wavelength [nm] Figure 5.6 [60]PCBM [70]PCBM 0. .0 300 400 500 600 700 800 Wavelength [nm] Figure 5.

most of the degradation occurred directly after the illumination was switched on and thus during the rise in temperature. with a power conversion efficiency decreasing to about 82% of initial performance. The P3HT:[70]PCBM cell was found to be the most stable one.4. after 1000 hours of operation under continuous illumination at room temperature. under specific test conditions used in this study. is caused by the changes that occur in the active layer . mostly due to its superior fill factor. Additional results presented in this chapter indicate that the top electrodes used do not significantly affect the stability of P3HT:methanofullerene devices under continuous illumination. This could be an indication that after illumination less excitons generated in the fullerene domain are able to dissociate into free charge carriers as a result of a more unfavorable morphology created during illumination. and this affected all cell parameters.7) and the subsequent hole transfer at donor:acceptor interface.4 Conclusion The experimental results reported in this chapter show that the highest power conversion efficiency (3.5. the hole mobility through the P3HT phase in the blend is slightly higher after 200 hours of continuous illumination. 5.6 shows that a much stronger degradation occurs for wavelengths below 500 nm irrespective of the fullerene used. The [70]PCBM is a mixture of isomers and has less tendency to crystallize compared to [60]PCBM and [60]ThCBM therefore this kind of degradation of cell performance as a result of phase separation with this higher fullerene derivative in the active layer is very likely reduced.8%) for the slow growth P3HT:methanofullerene films is obtained for P3HT:[60]ThCBM solar cells. The changes in morphology could favor hole transport and in the same time be unfavorable for the electron transport leading to an unbalanced charge carrier mobility in the devices after the stability test. This is another indication that the degradation in the cell parameters. Conclusion 73 investigation. compared with the hole mobility before degradation test. The lower part of the Figure 5. Furthermore. These measurements were performed at ECN laboratories. For these short wavelengths the EQE of the solar cells is very likely dominated by the response of fullerene absorption (as can be seen from Figure 5. for the case when degradation tests were performed at higher temperatures. Moreover. This means that the crystallization of the methanofullerene phase might play an important factor in the stability of devices under continuous illumination. This initial degradation might be attributed to morphology changes in the photoactive layer at the elevated temperature of the cells.

In the last Chapter experimental studies of the bulk heterojunction solar cells containing two different types of n-type semiconductors [60]PCBM and [70]PCBM (of which one as a mixture of isomers) in combination with rr-P3HT as a p-type semiconductor will be presented.74 Chapter 5: Stability tests of P3HT:methanofullerence solar cells of the solar cells. .

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Blom. Bradley. W. B. S. J. P. Mihailetchi.4-phenylenevinylene] Journal of polymer science. W. [24] V. Katz. Advanced Functional Materials 16 (2006). A. Moons. 052104. Y. P. D. D. Firon. R. J. L. [23] V. Bertho. Degradation mechanism of organic light-emitting device investigated by scanning photoelectron microscopy coupled with peel-off technique. D. V. L. A. Wienk. 385. Part A. C. Out-door testing and long-term stability of plastic solar cells. D. [16] S. Yao. G. Popescu. A. Applied Physics Letters 89 (2006). Manca. Orynbayev. A. [19] M. Lutsen. J. J. Q. Bonfiglio. Y. [21] S. Hole transport in poly(phenylene vinylene)/methanofullerene bulk-heterojunction solar cells. [18] Y. J. M. M. 3493. E. Origin of the enhanced performance in poly(3-hexylthiophene): [6. M. L. V. B. Li. M. van Hal. Hummelen. D. C. Polymer chemistry 45 (2007). L. C. C. 394. Yao. A. Solar Energy Materials&Solar Cells 91 (2007). Blom. Janssen. Ambipolar charge transport in films of methanofullerene and poly(phenylenevinylene)/methanofullerene blends. . A. Aging of a donor conjugated polymer: photochemical studies of the degradation of poly[2-methoxy-5-(3’. D. Applied Physics Letters 89 (2006). P. J. Durrant. J. Effects of C70 derivative in low band gap polymer photovoltaic devices: spectral complementation and morphology optimization. de Boer. Choulis. J. M. G. A. W. H. Verhees. [20] C. Gardette. F. M. M. Yang. Advanced Functional Materials 14 (2004). -L. M. D. W. [22] V. 865. Martens. J. Tuladhar. Shrotriya. 012107. J. Yang. T. M. 307. Blom. [15] E. W. C. Vanderzande.7’dimethyloctyloxy)-1. Influence of thermal ageing on the stability of polymer bulk heterojunction solar cells. de Boer. [17] S. P.76 Chapter 5: Stability tests of P3HT:methanofullerence solar cells MDMO-PPV:PCBM blends. Melzer. H. Nelson. Efficient Methano[70]fullerene/MDMO-PPV bulk heterojunction photovoltaic cells. A. European physical journal. 153507. Koop. 699. P. Shrotriya. Mihailetchi. Blom. Li. 1171. I. Chambon. Mihailetchi. Swinnen. Applied Physics Letters 88 (2006). Koster. Haeldermans. Kroon. Bimolecular recombination in polymer/fullerene bulk heterojunction solar cells. S. Pei. Lutsen. Koster. Rivaton. Angewandte Chemie 115 (2003). R. W. J. Poplavskyy. Krebs. Mihailetchi. Applied Physics Letters 89 (2006). [25] L. Knol. Xie. Charge transport and photocurrent generation in poly(3-hexylthiophene):methanofullerene bulkheterojunction Ssolar cells. Applied physics 36 (2007). A. V. S. Shi. J. Solar Energy Materials&Solar Cells 91 (2007). 063503. Gevorgyan. J. H. Senes.6]-phenyl C61-butyric acid methyl ester solar cells upon slow drying of the active layer. Y. D. A. Advanced Functional Materials 15 (2005). M. 317. Xie. Hummelen.

concomitantly in the same device. Replacing the n-type with the [60]PCBM/[70]PCBM mixture with no change in processing conditions results in identical device performance within experimental error. we show that this concept generalizes to other fullerene derivative types. two different types of n-type semiconductors [60]PCBM and [70]PCBM (of which one as a mixture of isomers. used as n-type semiconductors in combination with rr-P3HT. in this case) in combination with a p-type semiconductor. the effect that certain impurities in the n-type semiconductor composition (such as pure C60 or PCBM derivatives of fullerenes higher than C70 ) have on the electrical properties of the solar cell devices is quantified. The fullerene bis-adducts. Next. are promising candidates for increasing power conversion efficiency of the solar cells because they show a clear enhancement in the VOC compared with the ”state of the art” P3HT:[60]PCBM solar cells. Furthermore. 77 .6 Efficient PV blends comprising more than two semiconductors In this chapter we present experimental studies of the bulk heterojunction solar cells containing. here rr-P3HT.

Isolation and purification of C60 (by far the most abundant fullerene) or C70 (the second in abundance) from mixed fullerenes remains a costly procedure. sensors. photodetectors [9]. like its classical counterpart silicon. One benefit is their increased processability compared to native fullerenes. it is quite hard to make a good assessment of the cost aspect of the donors. This does not seem to be the case of the acceptor component. is readily available. Further reduction of the materials prices is therefore needed and fortunately possible. and many other ”higher” fullerenes. Another methanofullerene derivative is [60]ThCBM [11]. The basic atom ingredient carbon. The cost of production of the two components of the PV active layer. The increase in processability is related to an approximately ten-fold increase in solubility in aromatic solvents. 84. but it is more feasible to separate these two fullerenes from the higher ones. but very little research seems to indicate (at least up to now) that acceptors outside the fullerene realm are true competitors. In the cost analysis of the fullerene derivatives commonly used in organic solar cells. Some alternative fullerene acceptors have been described more recently. The two main forces that drive this upcoming technology is the promise of low cost and possibility of mass production. which is a methanofullerene. 70. should definitely be relatively low compared to the total cost of the device. Hence it is of great importance for the field to investigate and optimize the cost and availability aspects of fullerenes and their derivatives. the fullerene raw material is at present the largest . the donor and acceptor materials. and to assure that even up to a terawatt/year production this technology would indeed be feasible from the materials point of view. Independent of the production method. 76.78 Chapter 6: Efficient PV blends comprising more than two semiconductors 6. transistors [6–8]. such as [60]PCBM. Since new and improved donor materials are being developed steadily. at the moment. Very limited research exists on the potential of the cost aspect of future mass production of plastic PV devices. while maintaining much of the desirable electronic properties of the native fullerene. Many of these devices utilize solution-processable semiconductors based on fullerene derivatives in pure form. Methanofullerenes possess many benefits compared to the native (underivatized) fullerene in organic electronics applications. fullerenes are always formed as a mixture of carbon cages Cn with n = 60. The most commonly used fullerene derivative is [60]PCBM [10]. such as solar cells [1–5].1 Introduction Significant progress has been made in the development of thin-film organicbased electronic devices. i. as used in Chapter 3.e. 78. and other devices for commercial application.

the potential of improving power conversion efficiency of the bulk heterojunction solar cells using [60]ThCBM bis-adducts and/or [70]ThCBM bisadducts is investigated with respect to their superior VOC . The chemical formulae of . the use of two or more different n-type semiconductors concomitantly in the same device is essentially unheard of in the field of organic solar cells let alone in the field of classical inorganic electronics. The high price of single component fullerenes C60 and C70 is due to the high price of separation and purification. Furthermore. which were dried overnight at room temperature. Further.6. which is clearly seen by comparing the cost of pure fullerene grades to the asproduced ”raw” fullerene grades. which are mixtures primarily of C60 and C70 . In the end. [60]ThCBM bis-adducts. Hence. [60]ThCBM bis-adducts/[70]ThCBM bisadducts mixture. The acceptors comprise of [60]PCBM. Particulary here the solvent used for spin coating the active layers was ortho-dichlorobenzene (ODCB) and the weight to weight ratio of P3HT:acceptor was always 1:1. both the HOMOs and LUMOs of these molecular semiconductors are (close to) identical. So far all these solar cells utilize a single n-type (acceptor) semiconductor. Introduction 79 driver of final cost of the derivative. and a [60]BPMF/[70]BPMF mixture. In this chapter experimental studies of the solar cells performance of blends of rr-P3HT and a mixture of two n-type semiconductors [60]PCBM and [70]PCBM (of which one as a mixture of isomers) are presented. [70]ThCBM bis-adducts. Since the composition of the active layer is typically at least half fullerene derivative for this type of organic solar cells. the effect that certain impurities in the n-type semiconductor composition (such as pure C60 or PCBM derivatives of fullerenes higher than C70 ) have on the electrical properties of the solar cell devices is quantified. [70]ThCBM. [70]PCBM. Spin coating the photoactive layer from ODCB results in wet films. The photoactive layer of organic bulk heterojunction solar cells is based on a blend of an electron donating material (p-type semiconductor) and an electron accepting material (n-type semiconductor) forming nanostructured bicontinuous interpenetrating network. [60]ThCBM. The detailed fabrication procedure and the electrical characterization of the devices are described in detail in Chapter 2. there is a large incentive in final device cost-savings to minimize fullerene purification as much as possible. in a closed Petri dish in nitrogen glove box. We refer to the layers obtained by this method as slow growth active layers. It should be noted that [60]PCBM and [70]PCBM have a close to identical first reduction potential and the onset of their optical absorption is also identical (≈ 695 nm). [60PCBM/[70]PCBM mixture. [60]ThCBM/[70]ThCBM mixture.1.

1. The design of the experiments and the analysis of the obtained data throughout this chapter was done using a confidence-interval and hypothesis-testing procedure for single factor experiments [12].80 Chapter 6: Efficient PV blends comprising more than two semiconductors OCH3 OCH3 O O [60]PCBM [70]PCBM S S O OCH3 OCH3 O [60]ThCBM [70]ThCBM S OCH3 O S O OCH3 S O H3CO [60]ThCBM-bis adducts O H3CO S [70]ThCBM -bis adducts OC4H9 N N OC4H9 [60]BPMF [70]BPMF Figure 6. all these fullerenes used here are shown in Figure 6. The experimental factor chosen here was the acceptor mixture of methanofullerenes while the response variable was solar cell parameters .1: The chemical formulae of the methanofullerenes used in this chapter.

Here the acceptor is a blend of [60]PCBM and [70]PCBM. Mixture of two n-type semiconductors in the active layer 81 (JSC .15 500 V OC 3.2 Mixture of two n-type semiconductors in the active layer Figure 6. 13]. It is known by now that significant optimization 580 4.30 3.90 560 3.6.75 [mV] 3. such as Tukey’s honestly significant difference (HSD) procedure [12. and η). since these compounds may act as electron traps and diminish performance (see section 6. there is sufficient evidence to conclude that the means of all solar cell parameters (see Table 6. [60]PCBM and [70]PCBM do have very different solubilities and precipitation behaviors as pure components.60 .2 are based on Tukey’s HSD multiple comparison procedure [12. F F .2: Mean VOC and η values of the P3HT:acceptor (1:1 w/w) solar cells as a function of the weight percentage of [70]PCBM in the acceptor mixture (given by [60]PCBM:[70]PCBM). Statistical models were used to describe the responses from experiments. Based on this statistical analysis of the experimental data. Fullerenes higher in molecular weight than C70 and fullerene derivatives higher in molecular weight than [70]PCBM were removed. VOC . 6.00 480 2. but blends of the two surprisingly do not seem to affect morphology or complicate the processing conditions for devices.05 3. each of 99% pure or higher. 13].2 shows the mean values for VOC and η of the P3HT:acceptor (1:1 w/w) blend devices fabricated under identical processing conditions where the only difference was in the composition of the acceptor.2. The intervals around each averaged value in Figure 6.85 0 20 40 60 80 100 Weight percentage of [70]PCBM Figure 6.1) are not significantly different across various compositions of [60] and [70]PCBM in the acceptor mixture.4).45 OC V 520 3. [%] 540 3. The 95% Tukey HSD confidence intervals are shown for all averaged.

82 Chapter 6: Efficient PV blends comprising more than two semiconductors Table 6.13) 3.4 (±0.13) efforts are often required because small changes in processing conditions and materials can cause significant changes in device performance.0 (±0.54) 9.53) 8.4 (±0.5 (±0.46) 6.58) VOC (mV) 553 (±3.46) 10.4 (±0.46) 11. [70]PCBM (%) 0 20 30 50 70 80 90 100 Counts (-) 6 6 6 6 6 6 6 6 JSC (mA/cm2 ) 9.3 (±0.54) VOC (mV) 563 (±5.4 (±0.1) 562 (±7.4 (±0.13) 3.2 (±0.2: Mean values and 95 percent Tukey HSD intervals of the photovoltaic parameters of P3HT:acceptor (1:1 w/w) solar cells.46) 4.54) 9.8 (±0.4) 635 (±3.46) 6.20) 2.30) 2. The acceptor here is a mixture of [60]PCBM and [70]PCBM in the weight percentage of [70]PCBM indicated in the first column.22) 2.13) 3.7) 561 (±5.4 65.50) 6.5) 558 (±5.4 (±0.5 (±0.5 (±0.1 (±0.5) 564 (±5.1 (±0.13) 1.5) 556 (±5.9 (±0.1 62.4 (±0.7 (±0.22) 3.0 (±0.8 (±0.2 40.3 (±0.22) 3.9 (±0.0 (±0.55) 9.3 65.13) The results shown in Figure 6.53) 9.2) 557 (±3.3 (±0.7 (±0.58) 6.14) 3.2 64.13) 3.5 62.5 65.2) 559 (±3.2 59.57) 9.5 62.22) 0. The active layer thickness of all devices ranges from 180 to 300 nm.4 (±0. acceptor [60]ThCBM [70]ThCBM [60]:[70]ThCBM [60]ThCBM bisadducts [70]ThCBM bisadducts [60]:[70]ThCBM bis-adducts [60]:[70]BPMF (4:1) [60]:[70]BPMF (3:2) Counts (-) 6 6 5 6 6 6 6 6 JSC (mA/cm2 ) 9.3 63.8 (±0.9) 556 (±5.2) 628 (±3.54) 9.5) 558 (±5. Table 6.13) 3.4 (±0.4 (±0.5 26.13) 3.1) FF (%) 62.9 (±0.5) FF (%) 66.2) 627 (±3.2 indicate that by replacing the n-type with the [60]PCBM/[70]PCBM mixture with no change in processing conditions or device parameters results in identical device performance within experimental error.1 65.2) 515 (±7.1 (±0.9 η (%) 3.8 64.2 η (%) 3.0 65. . The acceptor composition is either a methanofullerene or a mixture of methanofullerenes (3:1 w/w of [60]:[70] unless otherwise indicated in the table).5) 555 (±5.1: Mean values and 95% Tukey HSD intervals of the P3HT:acceptor (1:1 w/w) solar cells parameters.4 (±0.

2 0. that [60]PCBM and [70]PCBM have in common is their electron accepting ability (as determined by the reduction potential) or. especially for VOC .2.2 shows statistically different results.2 [V] 0. Very similar J − V characteristics are observed for ThCBM’s but also for ThCBM bis-adducts.3 shows the J − V characteristics of the P3HT:acceptor solar cell devices under illumination.2 with PCBM.1. in other words. because the solar cells were not fully optimized with 8 6 4 [mA/cm ] 2 [60]ThCBM [70]ThCBM [60]ThCBM:[70]ThCBM (3:1) [60]ThCBM bis-adducts [70]ThCBM bis-adducts 2 0 -2 Light [60]ThCBM:[70]ThCBM (3:1) bis-adducts -4 -6 -8 -10 -12 -0. Mixture of two n-type semiconductors in the active layer 83 One important thing.0 V bias J 0. For donor/acceptor blends. Figure 6. see Figure 6. new fullerenes with the same LUMO levels (such as [60]ThCBM and [70]ThCBM.4 -0.8 Figure 6. As can be seen from the table.4 0. In order to verify the general applicability of the mixtures of fullerene derivatives in the acceptor. The acceptor composition here is either [60]ThCBM and [70]ThCBM or a mixture of them. The weight to weight mixture of the C60 fullerene derivatives to C70 fullerene derivatives in the active layer is 3:1. the LUMO level of the acceptor determines the upper limit of the VOC [14].2. in terms of device operation. [60]BPMF and [70]BPMF) were tested. their lowest unoccupied molecular orbital (LUMO) level. This further strengthens the results obtained in Figure 6. [60]ThCBM bis-adducts and [70]ThCBM bis-adducts. .3: J-V characteristics under illumination of the best ITO/PEDOT:PSS/P3HT:acceptor (1:1 w/w)/Sm/Al devices. and [60]ThCBM bis-adducts and [70]ThCBM bis-adducts or a mixture of them (in the weight ratios indicated in the legend).6. The statistical analysis of the solar cells parameters are listed in Table 6. there is no statistical difference between [60] and [70]ThCBM and their mixtures or between [60] and [70]ThCBM bis-adducts and their mixture. It should be noted that the [60]BPMF and [70]BPMF mixtures indicated in Table 6.6 0.

However. meaning that the work function of the positive electrode matches the HOMO level of the donor and the negative electrode matches that of the LUMO level of the acceptor.. [60]ThCBM bis-adducts. All parameters of the solar cells are shown in Table 6.2. the VOC can be increased by either lowering the HOMO level of the polymer (the donor) or raising the LUMO level of the fullerene (the acceptor) until remaining sufficient offset between the LUMOs of the donor and the acceptor necessary for charge transfer [18] . a lot of effort has been put to influence the LUMO level of [60]PCBM by placing electron donating and electron withdrawing substituents on the phenyl ring. [70]ThCBM.84 Chapter 6: Efficient PV blends comprising more than two semiconductors respect to the solubility and film crystallinity. It should be . Therefore these bis-adducts of fullerene derivatives could be a real candidates for further improving the power conversion efficiencies of bulk heterojunction solar cells when blended with rr-P3HT (Lenes et al. The [60]ThCBM bis-adducts (see molecular structure depicted in Figure 6.1) have the first reduction potentials (as measured with cyclic voltametry) ≈ 100 mV more negative compared to [60]PCBM. As seen in Figure 6. Advanced Materials in print). 6. [70]ThCBM bis-adducts. This parameter received much attention in the last couple of years [10. The device structure is ITO/PEDOT: PSS/P3HT:methanofullerene (1:1 w/w)/Sm/Al. 14–17]. allowing further optimization of the VOC of polymer:fullerene organic solar cells [19]. [60]ThCBM/[70]ThCBM mixture. Consequently. the solar cells fabricated using ThCBM bis-adducts do not exhibit superior cell efficiencies (solely because of much lower JSC ) as compared with ThCBM.4 shows the VOC values of a series of six photovoltaic devices fabricated under the same processing conditions and containing rr-P3HT as the electron donor and different methanofullerenes as the electron acceptor.3 Improving open-circuit voltage using bis-adducts fullerenes One of the basic photovoltaic parameters that limits the overall performance of the P3HT:[60]PCBM bulk heterojunction photovoltaic devices is the VOC .4. Figure 6. In our laboratory. The methanofullerenes comprise [60]ThCBM. the VOC is governed by the HOMOLUMO difference of the donor and the acceptor [14]. In case of ohmic contacts. all devices fabricated using bis-adducts fullerenes show a clear enhancement in the VOC of the cells by an average of 75 mV (in close agreement with the expectation from their reduction potentials). in spite of the enhancement in VOC . and [60]ThCBM bisadducts/[70]ThCBM bis-adducts mixture.

As the JSC of the bulk heterojunction solar cells is strongly related to the solid-state morphology of the photoactive layer.4 Effect of impurities in the fullerenes on cell efficiency The impact that impurities present in the fullerene acceptors can have on device performance is linked.4. The methanofullerenes used and their 3:1 w/w mixtures are shown in the legend. Therefore it is important to understand and predict the behavior of the solar cells upon the presents of impurities in fullerene mixture. since the reduction potentials of fullerenes are not the same. the electronic properties. the optimization of the process condition is required in order to maximize the efficiency for these new molecules. Effect of impurities in the fullerenes on cell efficiency 640 635 630 [mV] 85 625 OC 620 570 565 560 555 550 A = [60]ThCBM B = [70]ThCBM C = [60]ThCBM bis-adducts D = [70]ThCBM bis-adducts V A C A:B C:D B D Methanofullerenes Figure 6. at least in part. Each data point is an average of 6 devices. noted that the solar cells using ThCBM bis-adducts were fabricated using the process conditions optimized for [60]ThCBM. Advanced Materials in print). For example trace amounts of higher fullerenes in the [60] or [70]PCBM may alter significantly the VOC of the device. to the degree of energetic disorder (or lack of crystallinity) that influences the electron mobility [20. . Impurities may affect the morphology. The recently obtained results with PCBM bis-adducts were obtained after substantial optimization efforts (Lenes et al.6.. 6.4: Mean VOC values of the ITO/PEDOT:PSS/P3HT:Methanofullerene (1:1 w/w)/Sm/Al solar cell devices. 21]. and almost certain the film morphology may vary significantly from that with ThCBM bis-adducts (which are bigger molecules). and device performance of a solar cell device in an unpredictable manner.

86

Chapter 6: Efficient PV blends comprising more than two semiconductors

8
[60]PCBM:[70]PCBM

6
[mA/cm ]
2

[60]PCBM:[70]PCBM + C
60

(13%) (39%)

[60]PCBM:[70]PCBM + C

4 2 0
Light

60

[60]PCBM:[70]PCBM + [C ]PCBM (4%)
n

-2 -4 -6 -8 -10 -0.4 -0.2 0.0
V
bias

J

0.2
[V]

0.4

0.6

0.8

Figure 6.5: JLight -V characteristics of the best ITO/PEDOT:PSS/P3HT:acceptor (1:1 w/w)/Sm/Al solar cell devices. Here the acceptor is a [60]PCBM/[70]PCBM mixture (3:1 w/w) which is contaminated with molar percentage of C60 (see the legend).[Cn ]PCBM describes all the PCBM derivatives of fullerenes higher than C70 .

Herein we have investigated the device performance of P3HT:fullerene (1:1 w/w) blends by intentionally contaminating the fullerenes acceptors with various amounts of pure C60 or other fullerenes with higher molecular weight. The acceptors used here are [60]PCBM, [70]PCBM or [60]PCBM/[70]PCBM mixture with a purity of about 99% or higher. Including C60 up to 2.5% (molar) in the P3HT:[60]PCBM (1:1 w/w) active layer does not degrade the photovoltaic performance even if the VOC is decreasing with ≈ 17 mV. The decrease of the VOC

Table 6.3: Mean values and 95 percent Tukey HSD intervals of the photovoltaic parameters of P3HT:acceptor (1:1 w/w) solar cells. The acceptor composition is either [60]PCBM (denoted as A) or a 3:1 w/w mixture of [60]PCBM and [70]PCBM (denoted as B). All the methanofullerenes used here are intentionally contaminated with various (molar) percentages of C60 . [Cn ]PCBM describes all PCBM derivatives of fullerenes higher than C70 .

acceptor A A + 2.5 % C60 B B + 13% C60 B + 39% C60 B + 4% [Cn ]PCBM

Counts (-) 3 6 5 6 6 9

JSC (mA/cm2 ) 9.6 (±1.66) 9.5 (±1.17) 8.3 (±1.28) 8.1 (±1.17) 6.3 (±1.17) 1.0 (±0.18)

VOC (mV) 582 (±4.2) 566 (±3.0) 550 (±3.3) 504 (±3.0) 479 (±3.0) 289 (±2.7)

FF (%) 58.7 62.4 62.5 60.7 56.9 42.1

η (%) 3.3 (±0.45) 3.3 (±0.32) 2.8 (±0.35) 2.5 (±0.32) 1.7 (±0.32) 0.12 (±0.09)

6.4. Effect of impurities in the fullerenes on cell efficiency

87

590 580 570 560 550 540 530 520 510 500 490 480

A = [60]PCBM B = [60]PCBM:[70]PCBM

V
OC

J
SC

B

B+13% B+39%

A
60

A+2.5%

14 12 10 8 6 4 2

[mV]

[mA/cm ] J
SC

V

OC

Molar percentage of C

Figure 6.6: Operational parameters for the ITO/PEDOT:PSS/P3HT:acceptor (1:1 w/w)/Sm/Al solar cell devices as a function of the molar percentage of C60 in the acceptor. Here the acceptor is either [60]PCBM (denoted as A) or [60]PCBM/[70]PCBM mixture (3:1 w/w) (denoted as B). The circles represent the VOC and the triangles represent the JSC (see the legend).

is compensated by the increase in the F F , and in this way the solar cell efficiency (η) stays the same as compared with the bulk heterojunction solar cells with an active layer without contamination with C60 (see Table 6.3). The influence of pure C60 that is added to an acceptor mixture of [60]PCBM:[70]PCBM (3:1 w/w) was further investigated. Figure 6.5 shows the photocurrent (JLight ) of these solar cells for different levels of pure C60 in the acceptor mixture. From Figure 6.5 and Table 6.3 it can be seen that 39% molar of pure C60 in the active layer leads to a decrease of 1.1% (absolute) of the power conversion efficiency as compared with uncontaminated cells (our reference cells, denoted as B in the Table 6.3). Nevertheless, the introduction of up to 39% molar of pure C60 in the acceptor mixture did not completely degrade the device performance. On the other hand, however, the addition of only 4% (molar) of PCBM derivatives greater than C70 (which are deep traps), resulted in a strong decrease in the cell efficiency. This is understood to be due to a combined effect of a decrease in VOC , as a result of lower lying LUMO level for higher fullerenes, but also by a decrease in JSC as a result of deep traps introduced in the active layer [21]. Figure 6.6 shows the variation of the VOC and JSC as a function of the molar percentage of C60 added in the active layer. The VOC (represented by the circles) is decreasing rapidly with the amount of C60 introduced in the active layer indicating that traps lower the quasifermilevel therefore the LUMO level of the

2

88

Chapter 6: Efficient PV blends comprising more than two semiconductors

resulted acceptor is altered. Furthermore, the JSC (represented by the triangles) is staying constant till C60 reached a concentration of 39 %. The fact that the JSC is staying constant at low concentrations of C60 in the active layer confirms that we do not introduce electron traps by introducing C60 . We simply obtain the VOC of P3HT:C60 cell, but of one in which morphology is influenced by the presence of the methanofullerene. At 39 % (molar) of C60 in the active layer one may expect percolation in the C60 phase and the JSC starts to decrease.

6.5

Conclusion

In conclusion, we have shown that blends of [60]PCBM and [70]PCBM can be used as n-type semiconductor in combination with rr-P3HT for bulk heterojunction solar cells. By replacing the n-type semiconductor with a [60]PCBM/ [70]PCBM mixture, without any optimization in the processing conditions, device performance of these type of solar cells shows very little or no sensitivity to the blend composition. The use of a mixture of a C60 fullerene derivative and a C70 fullerene derivative as the semiconductor composition in photovoltaic devices is advantageous because it is much less expensive to prepare a mixture of a C60 fullerene derivative and a C70 fullerene derivative compared to a pure C60 or C70 fullerene derivative. Preparation of a pure C60 or C70 fullerene derivative necessarily requires expensive purification processes at some stage in the synthesis. This purification is necessary because known processes for producing native fullerene feedstocks produce mixtures of fullerenes. The fullerenes bis-adducts, used as a n-type semiconductors in combination with rr-P3HT, are real candidates for increasing the power conversion efficiency of the bulk heterojunction solar cells because they show a clear enhancement in VOC (with approximately 80 mV) compared with P3HT:[60]ThCBM solar cell devices. Finally, we demonstrate that by introducing some trace amounts of pure C60 in a given fullerene derivative n-type semiconductor does not strongly reduce the VOC of the solar cells. Furthermore, by including in the n-type semiconductor trace amounts of PCBM derivatives of fullerenes higher than C70 ([Cn ]PCBM , where n>70), which are deep traps, the device performance is drastically altered due to the significant decrease of the VOC as a result of a lower lying LUMO level for these PCBM derivatives.

Emery. Tanase. P. E. J. Li. D. J. Perisutti. F. J. [12] D. 2. Brabec.5% efficient organic plastic solar cells. 34-43. S. 6th ed. Applied Physics Letters 78 (2001). Sariciftci. 58. K. deMello. J. M. Dante. Blom. Barrett. de Leeuw. C. -Q. M. Wang. M. 213507. P. C. Carroll. T. Huang. Applied Physics Letters 89 (2006). Muhlbacher. M. D. P. Yao. Thienyl analog of 1-(3-methoxycarbonyl)propyl-1-phenyl. Heeger. Hummelen. Science 317. Nguyen. C. Hauch. J. S. A. 864. J. E. Anthopoulos. M. Gunst. Setayesh. 2005). M. Lee. K. S. A. C. Tanase.. Jonkman. J. Applied Physics Letters 85 (2004). Padinger. [2] F. Hummelen. E. Effects of postproduction treatment on plastic solar cells. J. B. J. T. [8] C. (John Wiley & Sons. G. Coates. [11] L. Advanced Materials 16 (2004). D. V. P. Inc. C. N. Design and Analysis of Experiments. Lab on a chip 7 (2007). Scharber. C. A. Fromherz. Shaheen. [7] T. 841.[6. J. J. L. [3] G. Denk. Mason. 85. 789. D. Kim. M. Blom. Sieval. [5] J. C. Sariciftci. Kim. New York. Applied Physics Letters 90 (2007). D. Bradley. Schillinsky. J. Efficient tandem polymer solar cells fabricated by all-solution processing. [9] H. J. D. Das. Meijer. Waldauf. C. Heeger. S. ¨ [10] M. C. 2084. Meijer. O. J. Moses. Yang. Advanced Materials 18 (2006). 2174. C. Cantatore. Ambipolar organic field-effect transistors based on a solution-processed methanofullerene. Brabec. Setayesh. E. C. Hofmann. deMello. Brabec.6]-methanofullerene for bulk heterojunction photovoltaic devices in combination with polythiophenes. M. A. Moriarty. Namboothiry. van’t Hof. [4] K. E. 163511. Solution-processed organic n-type thin-film transistors. M. C. T. R. D. Popescu. Roles of donor and acceptor nanodomains in 6% efficient thermally annealed polymer photovoltaics. Advanced Functional Materials 13 (2003). Anthopoulos. 222. Y. Advanced Materials 15 (2003). J. E. 4205. Design rules for donors in bulk-heterojunction solar cells towards 10% energyconversion efficiency. Hummelen. H. de Leeuw. D. Integrated thin-film polymer/fullerene photodetectors for on-chip microfluidic chemiluminescence detection. C. L. Statistical Design and Analysis of Experiments with . Koppe. Padinger. High-efficiency solution processable polymer photovoltaic cells by self-organization of polymer blends. Hess. Shrotriya. Organic complementary-like inverters employing methanofullerene-based ambipolar field-effect transistors. T. A. Nature Matererials 4 (2005). J. [13] R. Liu. N. Hummelen. Rittberger. Waldauf. F. L. W. Y. N. J. C. M. Y. [6] T. S. R.REFERENCES AND NOTES 89 References and notes [1] S. W. P. R. (2007). Montgomery. D.

R. 6849. [15] K. A. A. D. Blom. J. B. Enhanced opencircuit voltage in subphthalocyanine/C60 organic photovoltaic cells. Janssen. Friend. Organic Letters 9 (2007). Melzer. Hummelen. R. Rispens. Compositional dependence of the performance of poly(p-phenylene vinylene):methanofullerene bulk-heterojunction solar cells. M. de Boer. Increasing the open circuit voltage of the bulk-heterojunction solar cells by raising the LUMO level of the acceptor. Knol. Ingan¨ s. Applied Physics Letters 88 (2006). Svensson. Journal of the American Chemical Society 128 (2006). (John Wiley & Sons. Blom. Kooistra. Arias. W. I. Gadisa. Barker. J.90 Chapter 6: Efficient PV blends comprising more than two semiconductors Application to Engineering and Science. C. Kastenberg. Advanced Functional Materials 15 (2005). R. L. M. Hummelen. Popescu. B. Blom. C. [20] V. N. C. 1609. B. Mandoc. [14] V. Forrest. B. van Duren. L. B. J. H. M. M. 2003). P. P. Mutolo. 263505. Mihailetchi. J. W. J. A. Inc. [17] C. M. Koster. Anderson. Applied Physics Letters 84 (2004). Koster. O. S. C. MacKenzie. P. Ramsdale. Journal of Applied Physics 92 (2002). Blom. [19] F. A. Greenham. E. Cathode dependence of the open-circuit voltage of polymer:fullerene bulk heterojunction solar cells. H. M. J. The origin of the open-circuit voltage in polyfluorene-based photovoltaic devices. M. 4266. K. D. D. Journal of Applied Physics 94 (2003). C. New Jersey. Maio. Hummelen. [21] M. R. M. J. J. D. M. Mihailetchi. A. Rand. Mihailetchi. Correlation between oxidaa tion potential and open-circuit voltage of composite solar cells based on blends of polythiophenes/fullerene derivative. V. . 795. P. Verhees. M.. P. C. Effect of traps on the performance of bulk heterojunction organic solar cells. [16] A. 551. J. 8108. E. Applied Physics Letters 91 (2007). W. 2nd ed. F. Kroon. Ultimate efficiency of polymer/fullerene bulk heterojunction solar cells. W. M. [18] L. L. T. 093511. Kooistra. F. J. M. J. J. Thompson. de Boer. J. W.

if the cell is to be exposed to light. at least one of the electrodes must be (semi-)transparent. Clearly. A typical bulk heterojunction solar cell (see Figure 1) consists of a photoactive layer sandwiched between two different electrodes. this material combination has been extensively studied in organic solar cells leading to a power conversion efficiency approaching 6% nowadays. Figure 1: Device configuration of a bulk heterojunction solar cell with a photoactive layer consisting of a blend of rr-P3HT (the donor) and methanofullerene (the acceptor). 91 . Since the discovery of photo induced charge transfer from a conjugated polymer to C60 . collection of charges by the electrodes.Summary The direct conversion of the sunlight into electricity is the most elegant process to generate environmentally-friendly renewable energy. Plastic solar cells offer the prospect of flexible. lower cost of manufacturing. followed by introduction of the bulk heterojunction concept. exciton diffusion. The photoactive layer is based on a blend of an electron donating material (p-type semiconductor) and an electron accepting material (n-type semiconductor) forming nanostructured bicontinuous interpenetrating networks. charge carrier transport to the corresponding electrodes. charge transfer at donor/acceptor interface. and hopefully an efficient way to produce electricity from sunlight. lightweight. The fundamental steps in molecular solar power conversion are: absorption of a photon creating an exciton (bound electron-hole pair). dissociation and separation of the carrier pair.

the current efficiency of these solar cells does not guarantee (large scale) commercialization. which indicates that the electron transport properties are not altered upon replacing the phenyl with a thienyl group.92 Summary Although significant progress has been made for bulk heterojunction photovoltaic devices.0%. The increase of efficiency. and discusses the preparation. and more insight in the operation of these devices. The preparation of an analogue of [60]PCBM with the aim of improving miscibility with polythiophenes donors. Up till now [60]PCBM remains the best performing soluble fullerene derivative in combination with rr-P3HT. the improved morphology. especially rr-P3HT is described in Chapter 3. and the morphological and electrical characterization of devices made from rr-P3HT and a library of new methanofullerenes. after thermal annealing. The most commonly used n-type semiconductor in the bulk heterojunction solar cells is [60]PCBM. when using [60]ThCBM in combination with P3HT (1:1 w/w) as the donor counterpart. When [60]ThCBM was blended with MDMO-PPV (1:4 w/w) the power conversion efficiency was lower compared to that of the MDMO-PPV:[60]PCBM solar cells. due to an unbalanced charge transport (the hole mobility of MDMO-PPV is not strongly enhanced upon blending with [60]ThCBM). the experimental set-up used to study the device characteristics of bulk heterojunction solar cells based on different n-type semiconductors is outlined. leads to a power conversion efficiency up to 3. It is shown that slow growing of the active layer films in P3HT:[60]ThCBM (1:1 w/w ) blends. A short overview of the materials used and the protocols that we developed for reproducible device preparation and characterization is presented. resulting in [60]ThCBM (see Figure 1). The solar cells were fabricated by depositing the photoactive layer from solvents with different boiling points. In contrast. In Chapter 2. after thermal annealing and the optimized absorber composition. is due to the increasing crystallinity of P3HT and hence the enhancement of the hole mobility in the P3HT phase of the blend by two orders of magnitude relative to as cast devices. Improving the performance and lifetime of bulk heterojunction solar cells requires careful design and material engineering. The electrical characterization of pristine [60]ThCBM films reveals that its electron transport properties equal those of [60]PCBM. This thesis addresses the possibility of using new fullerene derivatives in organic bulk heterojunction photovoltaic devices. In Chapter 4 we present a more detailed study of the morphology and electrical properties of photovoltaic devices consisting of blends of rr-P3HT as electron donor and [60]ThCBM as an electron acceptor. by . In this way the growth rate of the films was controlled. In this compound the phenyl group from [60]PCBM is replaced by a thienyl group.

in Chapter 5 the stability of the slow growth P3HT:methanofullerene solar cells devices has been investigated. it is the significant increase in the fill factor (up to 70%) which gives much higher (13% relative) power conversion efficiencies. The same degradation for photovoltaic parameters. The benefit of better charge transport for slow growing films makes it possible to fabricate thicker films (≈ 300 nm) without significant loss in fill factor. Electrical and optical properties of these devices were monitored for a test period up to 1000 hours under continuous illumination. which could result in a decrease of the electron mobility in the blend as a consequence of interrupted percolation paths. was observed upon using Al as top electrode instead of Sm/Al. The difference in power conversion efficiency between slow and fast grown films is mainly determined by the difference in the fill factor and open-circuit voltage of the cells. The decrease in efficiency for solar cells containing [70]PCBM. facilitates the formation of highly crystalline films. after 1000 hours of operation under continuous illumination at room temperature. Additional results presented in this chapter indicate that the top electrodes used do not significantly affect the stability of P3HT:methanofullerene devices under continuous illumination. Although the open circuit voltage tends to be lowered (with approximately 40 mV) in devices with active layers with a higher degree of molecular organization. after 360 hours of continuous illumination. a major challenge remains the improvement of their stability under operational conditions. The experimental results reported in this chapter show that the P3HT:[70]PCBM cell was found to be the most stable one. This leads to a well balanced charge carrier transport in the blend. The [70]PCBM (as a mixture of isomers) has less tendency to crystallize compared to [60]PCBM and [60]ThCBM. In spite of the high potential of polymer photovoltaic cells. and therefore it allows for maximizing light absorption in these blends. therefore the hole mobility is not the cause for the degradation observed in the solar cell devices. The hole transport through the blend (P3HT phase) remains unaffected during the stability test. and [60]ThCBM can be explained by the fact that during illumination also fullerenes crystallize and form larger crystallites in time. Therefore. [60]PCBM. [60]ThCBM . and improves the hole transport in the blend by an order of magnitude. This enhances the interchain interactions in the P3HT phase. This is . with a power conversion efficiency decreasing to about 82% of initial performance. The methanofullerenes used in this chapter are [60]PCBM. therefore this kind of degradation of cell performance as a result of phase separation with this higher fullerene derivative in the active layer is very likely reduced.93 using solvents with a high boiling point. and [70]PCBM (see Figure 1).

might be caused by the changes that occur mainly within the active layer of the solar cells during continuous illumination. Next.94 Summary another indication that the degradation in the cell parameters. two different types of n-type semiconductors [60]PCBM and [70]PCBM (of which one as a mixture of isomers. By including in the n-type semiconductor trace amounts of PCBM derivatives of fullerenes higher than C70 the device performance is drastically influenced because they act as deep electron traps. are promising candidates for increasing power conversion efficiency of the solar cells because they show a clear enhancement in the VOC compared with the ”state of the art” P3HT:[60]PCBM solar cells. It should be noted that both the HOMOs and LUMOs of [60]PCBM and [70]PCBM are (close to) identical. . in this case) in combination with a donor material. Simply replacing the n-type with the [60]PCBM/[70]PCBM mixture with no change in processing conditions or device parameters results in identical device performance within experimental error. as seen in this specific study. The fullerene bis-adducts. used as n-type semiconductors in combination with rr-P3HT. the effect that certain impurities in the n-type semiconductor composition (such as pure C60 or PCBM derivatives of fullerenes higher than C70 ) have on the electrical properties of the solar cell devices is quantified. Finally. concomitantly in the same device. These two molecular semiconductors do have very different solubilities and precipitation behaviors as pure components. here rr-P3HT. but using blends of the two surprisingly does not seem to affect morphology and does not complicate the processing conditions for devices. In Chapter 6 we present experimental studies of the bulk heterojunction solar cells containing. we show that this concept generalizes to other fullerene derivative types.

heeft geleid tot uitvoerige studies van deze combinatie van materialen in organische (plastic) zonnecellen. waarvan er een licht moet kunnen doorlaten. Een plastic zonnecel volgens het principe van de bulkheterojunctie is afgebeeld in Figuur 1.Samenvatting De directe omzetting van zonlicht in elektriciteit met behulp van zonnecellen is het elegantste proces voor de productie van duurzame energie. De fotoactieve laag zelf bestaat uit een mengsel van een elektrondonerend materiaal (p-type halfgeleider) en een elektronaccepterend materiaal (n-type halfgeleider) die samen een driedimensionaal netwerk vormen waarin de beide materialen tot op nanometerschaal met elkaar gemengd zijn. 95 . en kunnen in de toekomst hopelijk met voldoende effici¨ ntie licht omzetten in eleke triciteit. Figure 1: Structuur van een zonnecel volgens het principe van de bulkheterojunctie. De ontdekking van ladingsoverdracht van een geleidend polymeer naar C60 onder invloed van licht. met een fotoactieve laag die bestaat uit rr-P3HT (de donor) en een methanofullereen (de acceptor). licht en goedkoop zijn. Momenteel worden rendementen tot 6% gehaald voor de omzetting van het invallende lichtvermogen in elektrisch vermogen. Zonnecellen gemaakt van plastics kunnen in principe flexibel. Gewoonlijk bestaat deze uit een fotoactieve laag tussen twee verschillende elektroden. gevolgd door de introductie van het concept van de bulkheterojunctie.

van de meettechnieken en van de methoden die zijn ontwikkeld om de assemblage van de zonnecellen reproduceerbaar te maken. Alhoewel behoorlijke vooruitgang is geboekt voor de fotovolta¨sche systeı men gebaseerd op bulkheterojuncties is het succesvol commercialiseren ervan momenteel nog niet goed mogelijk doordat het rendement van de cellen nog niet hoog genoeg is. waardoor [60]ThCBM ontstaat (Zie Figuur 1). In deze variant is de benzeenring in [60]PCBM vervangen door een thiofeengroep. dus dat de elektrontransporterende eigenschappen niet veranderen door het vervangen van de benzeengroep door een thiofeenring. een positieve lading).96 Samenvatting De fundamentele stappen in het moleculaire proces dat in deze cel leidt tot de omzetting van licht in elektrische stroom zijn: absorptie van een foton in een van beide materialen genereert een exciton (een koppel van een elektron en een gat. worden onderzocht. In dit e proefschrift worden diverse nieuwe fullereenderivaten getest in de organische zonnecellen gebaseerd op de combinatie rr-P3HT/methanofullereen. De meest gebruikte n-type halfgeleider in de bulkheterojunctiezonnecellen is [60]PCBM. ladingsoverdracht bij het donor/acceptor grensvlak. Een mengsel van [60]ThCBM met MDMOPPV in een gewichtsverhouding van 1:4 gaf zonnecellen met een lager rendement dan die met [60]PCBM. zoals rr-P3HT. met daarin de diverse n-type halfgeleiders. omdat er een te groot verschil was in het transport . en diverse relevante eigenschappen van deze cellen. De elektrische metingen aan films van [60]ThCBM laten zien dat het elektronengeleidende vermogen van beide verbindingen gelijk is. diffusie van het exciton naar een grensvlak tussen de beide materialen. Tevens wordt een kort overzicht gegeven van de gebruikte materialen. zoals morfologie en geleiding van de actieve laag. omdat dit tot op heden het fullereenderivaat is dat voldoende oplosbaar is en in combinatie met rr-P3HT de beste resultaten geeft. naar de juiste elektrode. Hoofdstuk 3 beschrijft de ontwikkeling van een variant van [60]PCBM met als doel het verbeteren van de menging van het methanofullereen met polythiopheen donoren. ieder door een van beide materialen. transport van de beide ladingen. in combinatie met gedetailleerde studie van de werking van het systeem. De experimentele opstelling die gebruikt is om de eigenschappen van de bulkheterojunctie zonnecellen. verzamelen van de ladingen door de elektrodes. Het verder verbeteren van de levensduur en het rendement van de bulkheterojunctiezonnecellen vereist. een systematische aanpak voor wat betreft het onderzoek aan en het vari¨ ren van de gebruikte materialen in de fotoactieve laag. dissociatie en scheiding van de beide ladingen. te onderzoeken wordt besproken in Hoofdstuk 2.

Hierdoor treedt een stijging van twee ordes van grootte op van de gatengeleiding in de P3HT fase ten opzichte van die in onbehandelde actieve lagen.In dergelijke films is er een betere interactie tussen de polymeerketens in de P3HT fase. De open klemspanning daalt gewoonlijk met ongeveer 40 mV in films die meer moleculair geordend zijn. zoals de hier beschreven zonnecellen. De stabiliteit van de zonnecellen met langzaam gevormde P3HT:methanofullereen lagen is bestudeerd . Een meer gedetailleerde studie van de morfologie en de elektrische eigenschappen van fotovoltaische systemen bestaande uit mengsels van het elektrondonerende rr-P3HT en de electronacceptor [60]ThCBM wordt beschreven in Hoofdstuk 4. Het verschil in rendement tussen films die langzaam of snel gegroeid zijn wordt voornamelijk bepaald door het verschil in ”fill factor” en open klemspanning tussen de beide soorten films. De huidige resultaten die worden verkregen met de plastic fotovolta¨sche ı cellen. maar gaan voorbij aan de noodzaak om ook de stabiliteit van de zonnecellen over een langere operationele periode te verbeteren. Het transport van gaten in de MDMO-PPV fase bleek niet substantieel te stijgen na menging met [60]ThCBM.0% na optimalisatie van de samenstelling van de actieve laag en het verkrijgen van een verbeterde morfologie na verwarmen van deze laag.97 van de beide ladingen. Deze films worden verkregen als een oplosmiddel met een hoog kookpunt wordt gebruikt. De resultaten toonden aan dat in het geval van P3HT:[60]ThCBM mengsels (in een 1:1 gewichtsverhouding) het langzaam laten groeien van de actieve laag de vorming van meer kristallijne films bevordert. dit in tegenstelling tot wat gebeurt in mengsels met [60]PCBM. waardoor het gatentransport in het mengsel met een orde van grootte verbetert en een goede balans wordt verkregen in het transport van de beide ladingen. De combinatie van [60]ThCBM met de donor P3HT (gewichtsverhouding 1:1) gaf echter zonnecellen met een rendement van 3. maar deze daling wordt gecompenseerd door een significante stijging van de fill factor. zodat de lichtabsorptie in de films kan worden geoptimaliseerd. Het verbeterde ladingstransport in de actieve lagen die langzaam gevormd worden maakt het ook mogelijk om dikkere films (300 nm) te maken zonder dat de fill factor al te veel kleiner wordt. Oplossingen van de organische materialen in een aantal oplosmiddelen met verschillende kookpunten werden gebruikt voor het maken van de actieve laag van de zonnecellen. zijn weliswaar veelbelovend. De stijging van het rendement na verwarmen is het gevolg het meer kristallijn zijn van de P3HT fase. waardoor een netto toename van ongeveer 13% (relatief) in rendement wordt bereikt. Dit maakt het mogelijk om de groeisnelheid van de film te controleren.

met een daling van het rendement naar 82% van de beginwaarde. Opmerkelijk genoeg blijkt at het gebruik van mengsels van beide stoffen in de actieve laag niet leidt tot veranderingen in de morfologie noch problemen geeft bij het fabriceren van de films. In vergelijking met [60]PCBM en [60]ThCBM heeft [70]PCBM.98 Samenvatting in Hoofdstuk 5. zodat deze degradatieroute als gevolg van fasescheiding in het geval van actieve lagen met dit methanofullereen veel minder aanwezig is. zoals gevonden in deze studie. voornamelijk het gevolg is van veranderingen in de actieve laag. wat betekent dat verandering in de mobiliteit van de gaten niet de oorzaak kan zijn van de verslechtering van de werking van de zonnecel. Het gatentransport in de P3HT fase bleef stabiel gedurende de testperiode. De elektrische en optische eigenschappen van de cellen werden gevolgd gedurende een periode van maximaal ongeveer 1000 uur. In Hoofdstuk 6 worden experimenten beschreven aan bulkheterojunctiezonnecellen waarvan de actieve laag naast het donormateriaal P3HT twee verschillende soorten n-type halfgeleiders bevat. waarbij de cellen continu belicht werden. De positie van zowel de HOMO als de LUMO van deze twee verbindingen is nagenoeg gelijk aan elkaar. Dit is opnieuw een aanwijzing dat de verslechtering van de eigenschappen van de zonnecellen. Hierdoor kan de elektronmobiliteit in het mengsel dalen doordat een deel van de aanwezige transportwegen wordt onderbroken. Verdere resultaten in dit hoofdstuk tonen aan dat de topelektroden geen belangrijke invloed hebben op de stabiliteit van de P3HT/methanofullereen zonnecellen. namelijk [60]PCBM en [70]PCBM (waarbij de laatste uiteraard als mengsel van isomeren aanwezig is). Na 360 uur continue belichting bleken de diverse parameters van de zonnecellen in het geval van een Sm/Al elektrode dezelfde daling te geven als bij een Al elektrode. veel minder de neiging om kristallen te vormen. De resultaten laten zien dat in dit geval de P3HT[70]PCBM zonnecel de stabielste is. Deze twee moleculaire halfgeleiders hebben ieder afzonderlijk echter behoorlijk verschillende oplosbaarheidseigenschappen en een verschillende tendens tot precipiteren. De rendementsdaling van de zonnecellen kan wel worden verklaard door langzame kristallisatie van een deel van de aanwezige fullereenmoleculen. na 1000 uur werkzaam te zijn onder continue belichting. [60]ThCBM en [70]PCBM (zie Figuur 1). dat een mengsel van isomeren is. De gebruikte methanofullerenen zijn [60]PCBM. Het eenvoudigweg vervangen van de zuivere n-type halfgeleider door een mengsel van [60]PCBM en [70]PCBM zonder verdere wijziging van de procescondities of andere parameters levert cellen op die binnen de experimentele foutenmarge een gelijk rendement geven. Verdere experimenten tonen aan dat dit principe alge- .

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