Temperature dependence of polymer/fullerene organic solar cells

The temperature dependence of bulk heterojunction organic solar cells fabricated from poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) was studied in detail. Individual materials as well as blends and solar cell devices were examined. Light absorption, photoluminescence, quantum efficiency, total efficiency, and current-voltage characteristics were studied from temperatures −10 to 140 °C. A method and apparatus for testing these parameters at various temperatures is described. Parameters were measured for both unannealed and annealed samples to give insight into the annealing process. It was found that absorption and photoluminescence of devices shift both position and intensity with varying temperatures. Quantum efficiency and total efficiency were monitored as they increased with annealing. Once annealed, device efficiency peaked at temperatures from 10 to 60 °C because of competing temperature dependent effects of the materials. The temperature dependence study provides valuable information on device properties and thermal annealing.     

Improved high temperature stability of organic solar cells using a phosphine oxide type cathode modification layer

The high temperature stability of the organic solar cells (OSCs) was improved using a phosphine oxide based organic cathode modification layer instead of LiF. The OSC modified with the phosphine oxide cathode modification layer showed constant device performances after a thermal treatment at 90 °C, while the LiF based OSC exhibited degraded device performance after the thermal treatment. The use of the phosphine oxide based interlayer was effective to improve the high temperature stability of the OSC.     

Effect of solvent on fabrication of active layers in organic solar cells based on poly(3-hexylthiophene) and fullerene derivatives

Investigating the effect of solvent on the fabrication of photo-active layers in bulk heterojunction organic solar cells based on poly(3-hexylthiophene) and [6,6]-phenyl C₆₁-butyric acid methyl ester, we found the short-circuit current density (J_SC) and fill factor (FF) of a cell with a photo-active layer made using materials dissolved in a mixture of o-dichlorobenzene with chloroform to be slightly higher than those of a cell made using the same materials dissolved only in chlorobenzene. Evaluating the absorption spectra, surface morphology, charge mobility, and solubility of photo-active films made using different solvents, we concluded that the higher J_SC and FF were due to a larger interfacial area between the photo-active materials in the layer.     

Light-induced degradation of the P3HT-based solar cells active layer

We report on the effects of long-term artificial accelerated ageing on the active layer of organic solar cells in the absence of oxygen. The samples were composed of a bulk heterojunction formed by poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) deposited on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). First, a set of experiments was performed to study the modifications resulting from prolonged exposure to UV-vis light. A gradual decrease in absorbance was recorded, and TEM results clearly indicated that the initial morphology was unstable upon long irradiation times. Second, we revealed that the annealing temperature of PEDOT:PSS strongly influenced the degradation of the active layer. Indeed, an increase in the PEDOT:PSS annealing temperature resulted in an important improvement in stability. Third, a comparison was made between different active layers obtained by changing the P3HT type, polymer:fullerene weight ratio and solvent nature. As expected, the polymer:fullerene weight ratio was shown to significantly impact the degradation kinetics. The ageing effects on the photovoltaic properties were then explored, and extrapolation of the data to outdoor exposure is also discussed.     

Vacuum-free processed transparent inverted organic solar cells with spray-coated PEDOT:PSS anode

Spray coating is a high throughput coating technique that is scalable and adaptable for organic photovoltaic manufacturing. To ensure uniform coating of the organic layers, the wettability, surface tension and boiling points of the solvents have to be optimized. Here, we used microscopic videos to understand the dynamics of the spray coating process. By optimizing the wettability and drying time of the PEDOT:PSS suspension on a hydrophobic surface, we attained a spray coated transparent anode without compromising on device performance. We further applied this vacuum-free process to a near infrared absorber to achieve a transparent organic solar cell with close to 60% transparency.     

Modeling the short-circuit current density of polymer solar cells based on P3HT:PCBM blend

We have investigated the short-circuit current density of organic solar cells based on poly (3-hexylthiophene)(P3HT)/6,6-phenyl C61-butyric acid methyl ester (PCBM) blend. In order to model charge collection efficiencies with respect to short circuit density in such blends, a full optical modeling of the cell is performed. From the distribution of the electromagnetic field, we compute the rate of exciton generation. This exciton generation rate is used as input in the transport equations of holes and electrons. Charge densities at steady state are obtained as solutions are used for computing short-circuit current densities generated in the cell. The dependence of short-circuit current densities versus the thickness of the blend is analyzed and compared with our experimental data and with data extracted from the literature.     

Bulk and contact resistance in P3HT:PCBM heterojunction solar cells

In this paper, the series resistance of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) bulk heterojunction (BHJ) organic solar cells (OSC) has been studied. The series resistance of thermal annealed and un-annealed devices with different active layer thicknesses was measured. The series resistance of the organic solar cells consists of the bulk resistance of the active layer itself and the specific contact resistance between the active layer and the electrode. The bulk resistance and contact resistance were extracted from the measured series resistance using the vertical transmission line model (TLM) method. By fabricating solar cell devices with different active layer thicknesses, a relationship of the series resistance with thickness was established from which bulk and contact resistances were derived. We have also found that thermal annealing helps reduce both contact resistance and bulk resistance significantly; the contact resistance dropped by a factor of 2, while the bulk resistance decreased by a factor of 8. Results have shown that for an annealed P3HT:PCBM device that has an active layer thickness of 85 nm (optimum thickness for high efficiency), 17% of the total series resistance was due to the contact resistance, and bulk resistance contributed the rest 83%. The bulk resistance value for thermal annealed organic solar cell device with an active area of 0.1 cm² was found to be 150 Ω, and the measured specific contact resistance was 3.1 Ω cm². The measured bulk and contact resistance values are much higher as compared to the high efficiency silicon solar cells. Bulk resistance and contact resistance need to be further decreased in order to achieve higher organic solar cell efficiency.     

A computational study on optimal design for organic tandem solar cells

A new model is developed by combining the optical model and the drift-diffusion model to optimize the thicknesses of active layers of individual sub-cells for high performance of organic tandem solar cell. When the photovoltaic properties of tandem organic solar cells based on poly(2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta (2,1-b;3,4-b′) dithiophene)-alt-4,7-(2,1,3-benzo-thiadiazole))/(6,6)-phenyl C71-butyric acid methyl ester and poly(3-hexylthiophene)/(6,6)-phenyl C61-butyric acid methyl ester are calculated as functions of thicknesses of individual sub-cells using the new model, it is found that the optimum thickness pair of active layers is 150 and 120 nm for the front and back sub-cell, respectively. Comparison of simulation with experiment reveals that the simulated results are very consistent with experimental ones.     

Morphological and electrical effect of an ultrathin iridium oxide hole extraction layer on P3HT:PCBM bulk-heterojunction solar cells

An ultrathin iridium layer was treated with O₂-plasma to form an iridium oxide (IrO_x), employed as a hole extraction layer in order to replace poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) in organic photovoltaic (OPV) cells with poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PCBM). The IrO_x layer affects the self-organization of the P3HT:PCBM photo-active layer due to its hydrophobic nature, inducing a well-organized intraplane structure with lamellae oriented normal to the substrate. Synchrotron radiation photoelectron spectroscopy results showed that the work function increased by 0.57 eV as the Ir layer on ITO changed to IrO_x by the O₂-plasma treatment. The OPV cell with IrO_x (2.0 nm) exhibits increased power conversion efficiency as high as 3.5% under 100 mW cm⁻² illumination with an air mass (AM 1.5G) condition, higher than that of 3.3% with PEDOT:PSS.     

Flexible organic P3HT:PCBM bulk-heterojunction modules with more than 1 year outdoor lifetime

Flexible organic solar cells and modules based on P3ht:PCBM bulk-heterojunctions were fabricated and their lifetime was investigated under laboratory and outdoor conditions. In the laboratory cells were exposed to 1 sun illumination at 65 °C in order to accelerate the degradation. The outdoor behavior of modules was investigated at the Konarka rooftop testing setup in Lowell, MA (USA). We show that these flexible polymer solar cells have a good light stability, passing 1000 h under accelerated light soaking conditions in the laboratory, and that flexible modules survived over 1 year of outdoor exposure without performance losses.     

Abnormally high photocurrent of a degraded organic solar cell under chopped light

Photocurrent of an organic solar cell under chopped monochromatic light was studied at different stages, i.e. just after fabrication (without degradation) and after serious degradation. A large photocurrent under chopped light was observed for a seriously degraded device, unexpected from intuitionistic reckoning. This work demonstrates that both light bias and chopper frequency affect the photocurrent measurement of an organic solar cell, especially for a degraded device. The influence of light bias and chopper frequency is explained as the result of traps produced during the degradation of an organic solar cell. Thus measuring photocurrent under one sun light bias at low chopper frequency is suggested to more accurately determine the external quantum efficiency.     

Stability/degradation of polymer solar cells

Polymer and organic solar cells degrade during illumination and in the dark. This is in contrast to photovoltaics based on inorganic semiconductors such as silicon. Long operational lifetimes of solar cell devices are required in real-life application and the understanding and alleviation of the degradation phenomena are a prerequisite for successful application of this new and promising technology. In this review, the current understanding of stability/degradation in organic and polymer solar cell devices is presented and the methods for studying and elucidating degradation are discussed. Methods for enhancing the stability through the choice of better active materials, encapsulation, application of getter materials and UV-filters are also discussed.     

Monochromatic versus solar efficiencies of organic solar cells

The photovoltaic behavior in a perylene/phthalocyanine hetero-p/n-junction solar cell was investigated using intensity-dependent I/V-characteristics and short circuit photocurrent spectroscopy. It is concluded that the charge carrier generation occurs only in a very thin active region at the contact. By optimizing the light trapping, a maximum solar AM 1.5 efficiency of about 2% can be obtained. A further increase requires better material properties or new cell structures.     

Progress in stability of organic solar cells exposed to air

In this paper, the stability of small-molecule organic solar cells based on copper phthalocyanine (CuPc) and fullerene (C₆₀) is investigated. The use of silver instead of aluminum as the metal electrode in these solar cells, with smaller grain size and grain boundaries as well as with more uniform grain size distribution in the film, results in significant improvement in the lifetime of the devices. The substantial role of silver in the protection of the cells against permeation of oxygen and/or water molecules into the organic thin films is confirmed. Substitution of a thin buffer layer (70 Å) of bathophenanthroline (Bphen) for bathocuproine (BCP), sandwiched between C₆₀ and the cathode, makes considerable progress in the lifetime of the device.     

Oxide/polymer interfaces for hybrid and organic solar cells: Anatase vs. Rutile TiO2

In this work, we study the effect of the transparent conducting oxide (TCO) and the polymer applied (MEH-PPV or P3HT) on the photovoltaic properties of TCO/TiO₂/polymer/Ag bi-layer solar cells. The solar cells were analyzed under inert atmosphere conditions resembling an encapsulated or sealed device. We demonstrate that the substrate applied, ITO or FTO, modifies the crystalline structure of the TiO₂: on an ITO substrate, TiO₂ is present in its anatase phase, on an FTO, the rutile phase predominates. Devices fabricated on an FTO, where the rutile phase is present, show better stability under inert atmospheres than devices fabricated on an ITO, anatase phase. With respect to the polymer, devices based on MEH-PPV show higher Voc (as high as 1 V), while the application of P3HT results in lower Voc, but higher J_sc and longer device stability. These observations have been associated to (a), the crystalline structure of TiO₂ and (b) to the form the polymer is bonded to the TiO₂ surface. In-situ IPCE analyses of P3HT-based solar cells show a red shift on the peak corresponding to TiO₂, which is not present on the MEH-PPV-based solar cells. The latter suggest that P3HT can be linked to the TiO₂ though the S-end atom, which results in devices with lower Voc. All these observations are also valid for devices, where the bare TiO₂ is replaced by an Nb-TiO₂. The application of an Nb-TiO₂ with rutile structure in these polymer/oxide solar cells is the reason for their higher stability under inert atmospheres. We conclude that the application of TiO₂ in its rutile phase is beneficial for long-term stability devices. Moreover there is an interplay between low Voc and J_sc in devices applying P3HT, since power conversion efficiency can be partially canceled by their lower Voc in comparison with MEH-PPV. These findings are important for polymer/oxide solar cells, but also for organic solar cells, where a layer of semiconductor oxides are in direct contact with a polymer, like in an inverted or tandem organic solar cells.     

A study of stabilization of P3HT/PCBM organic solar cells by photochemical active TiOx layer

We describe a study of the stabilization behavior of P3HT/PCBM organic solar cells under air and UV irradiation using a 20 nm thin TiO_x protection layer made by partial hydrolysis of a Ti-alkoxide and spin coating in air. Data on the degradation of solar cell performance under air and under UV exposure are presented indicating that significant improvements are observed with TiO_x layer protection. The protection mechanism has been investigated by transmission IR and UV spectroscopy and by ESR spectroscopy. The results of this study suggest how sol-gel derived TiO_x films containing organic functionalities serve as effective passivation films for protection from oxygen when excited by photons, where the photooxidation of the bound organic moieties causes oxygen gas scavenging.     

The importance of post-annealing process in the device performance of poly(3-hexylthiophene): Methanofullerene polymer solar cell

We investigated the effect of annealing sequence on the performance of polymer solar cell with the composite of poly(3-hexylthiophene) (P3HT) and a C₆₀ derivative. The post-annealing under the existence of Al metal cap induced a substantial increase in the interfacial area between the active layer and Al cathode and in crystallization of P3HT molecules, resulting in reduction of series resistance and the enhanced photocurrent in the device. Furthermore, the post-annealing brought about the increase of light harvest in active layer and hindered the formation of shunt paths in the donor (D)/acceptor (A) bulk-heterojunction structure compared to the pre-annealing.     

Effects of a perfluorinated compound as an additive on the power conversion efficiencies of polymer solar cells

A perfluorinated compound, 4-amino-2-(trifluoromethyl)benzonitrile (ATMB), was applied as an additive to polymer solar cells (PSCs) with P3HT [poly(3-hexylthiophene)]:PCBM [[6,6]-phenyl-C₆₁-butyric acid methyl ester] blend films. The addition of 6 wt% ATMB to a P3HT:PCBM layer led to an increased power conversion efficiency of 5.03% due to the enhanced short circuit current and fill factor when compared with that of the reference cell without an additive. On the other hand, the devices with 4-aminobenzonitrile as an additive, not containing fluorine atoms in the molecule, displayed lower PCEs than that of the reference cell. The UV-visible absorption spectra, X-ray measurements and carrier mobility studies revealed that ATMB facilitated ordering of the P3HT chains, resulting in higher absorbance, larger crystal size of P3HT and enhanced hole mobility. XPS depth profiling measurements also showed that the additive molecules were predominantly positioned in the range of 25 nm under the surface of the P3HT:PCBM film, leading to improved fill factor.     

Effect of strong base addition to hole-collecting buffer layer in polymer solar cells

We report a brief study on the effect of strong base addition to the hole-collecting buffer layer [poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)] on the performance of polymer solar cells made using blend films of poly(3-hexylthiophene) and soluble fullerene. A concentrated aqueous solution of sodium hydroxide (NaOH) was added to the PEDOT:PSS solution to decrease its acidity. The optical absorption spectra of modified buffer layers were measured to investigate the influence of NaOH addition on the spectral shape, while the surface of modified buffer layers was examined using atomic force microscopy. Results showed that the acidity of PEDOT:PSS solutions was remarkably reduced by adding the NaOH solution. However, the performance of solar cells was slightly degraded, which has been attributed to the decreased charge transportability as evidenced from the dark current-voltage characteristics.     

Metal cluster enhanced organic solar cells

An enhancement of the photovoltaic conversion efficiency of an organic solar cell by incorporation of small metal clusters has been reported recently [1]. The enhancement is explained in terms of resonant light absorption in the metal cluster which is accompanied by a strengthened electric field in the vicinity of the particle. It is therefore assumed to be based on an enhanced absorption of the organic dye film. In contrast we will show here that an excited plasmon in a metal cluster is also capable to emit an electron directly in a preferential direction if the particles are placed inside an oriented electrical field like the one existing in the depletion layer of a Schottky junction. Thereby a primary photocurrent is observed in a spectral region without any direct absorption in the organic film. We will present results obtained at a Schottky junction formed at the interface of ITO and zinc phthalocyanine. In order to study the influence of the metal particles we evaporated a thin silver film on top of the ITO substrate and tempered the system in a vacuum, thereby forming small separated silver clusters. We investigated the influence of the silver clusters on the optical extinction spectra and on the short circuit photocurrent spectra of such constructed organic solar cells. The experimental data will be discussed using a qualitative energy diagram.