A fullerene silirane derivative to improve the open circuit voltage in a polymer–fullerene solar cell: a theoretical study

In this letter quantum chemical calculations are performed on fullerene derivatives with varying reduction potentials, successfully used as electron acceptor in bulk heterojunction solar cells with the aim to investigate the energy levels of the frontier orbitals. We have successfully correlated the theoretical lowest unoccupied molecular orbital (LUMO) levels of different fullerenes with the open circuit voltage of the photovoltaic device based on the polymer–fullerene blend. We have also proposed a new fullerene silirane derivative with a raised LUMO level useful to increase the open circuit voltage of a polymer solar cell. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Inverse relation between photocurrent and absorption layer thickness in polymer solar cells

Organic solar cells based on polymer–fullerene bulk heterojunctions were optimised with respect to the short circuit photocurrent by means of optical modelling. Due to interference effects present in the thin film multilayer device, an inverse relation between active layer thickness and photocurrent was predicted and experimentally verified. Optimised photovoltaic devices yield power conversion efficiencies of 4%. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fabrication and characterization of fullerene/porphyrin bulk heterojunction solar cells

Fullerene/porphyrin bulk heterojunction solar cells were fabricated and, the electronic and optical properties were investigated. Effects of exciton-diffusion blocking layer of perylene derivative on the solar cells between active layer and metal layer were also investigated. Optimized structures with the exciton-diffusion blocking layer improved conversion efficiencies. Energy levels of the molecules were calculated and discussed. Nanostructures of the solar cells were investigated by X-ray and electron diffraction, which indicated formation of fullerene/porphyrin mixed crystals. Electronic structures of the molecules were investigated by molecular orbital calculation, and energy levels of the solar cells were discussed.     

Simulation study of the losses and influences of geminate and bimolecular recombination on the performances of bulk heterojunction organic solar cells

We use the method of device simulation to study the losses and influences of geminate and bimolecular recombinations on the performances and properties of the bulk heterojunction organic solar cells. We find that a fraction of electrons(holes)in the device are collected by anode(cathode). The direction of the corresponding current is opposite to the direction of photocurrent. And the current density increases with the bias increasing but decreases as bimolecular recombination(BR)or geminate recombination(GR) intensity increases. The maximum power, short circuit current, and fill factor display a stronger dependence on GR than on BR. While the influences of GR and BR on open circuit voltage are about the same.Our studies shed a new light on the loss mechanism and may provide a new way of improving the efficiency of bulk heterojunction organic solar cells.     

Effect of Ultraviolet Light on Hybrid Zinc Oxide Polymer Bulk Heterojunction Solar Cells

Compared to conjugated polymer poly[2-methoxy-5-（3＇ ,7＇-dimethyloctyloxy）-l,4-phenylenevinylene] （MDMO-PPV） solar cells, bulk heterojunction solar cells composed of zinc oxide （ZnO） nanocrystals and MDMO-PPV have a better energy conversion efficiency. However, ultraviolet （UV） light deteriorates the performance of solar cells composed of ZnO and MDMO-PPV. We propose a model to explain the effect of UV illumination on these ZnO：MDMO-PPV solar cells. According to this model, the degradation from UV illumination is due to a decrease of exciton dissociation efficiency. Our model is based on the experimentM results such as the measurements of current density versus voltage, photoluminescence, and photocurrent.     

胆甾液晶掺杂活性层对有机太阳能电池性能的影响

以poly(3-hexylthiophene)(P3HT)为电子给体,indene-C60bisadduct(ICBA)为电子受体,通过掺杂不同浓度胆甾液晶氯化胆甾醇制备了有机体异质结太阳能电池.结果表明,适当浓度掺杂使器件的开路电压提高到了0.78 V,但短路电流密度却有所降低,填充因子几乎不变,能量转换效率提高了10%.利用X射线、光致发光、原子力显微镜及紫外-可见吸收光谱进行表征,发现液晶掺杂对活性层的结晶度、分子内部排列情况、薄膜表面形貌和光吸收特性等都有明显影响.     

The inverted solar cells with the polymer:fullerene blend film possessing a stratified composition profile

The inverted polymer:fullerene solar cells with structure of ITO/TiO₂/P3HT:PCBM/MoO₃/Al have been fabricated, where P3HT and PCBM stand for poly (3-hexylthiophene) and [6,6]-phenyl C₆₁-butyric acid methyl ester, respectively. It is discovered that the P3HT:PCBM blend film manipulated into the improved stratification structure, characterized as P3HT crystallite-rich zone close to the top surface and PCBM constituent-rich zone adjacent to the bottom surface, can offer nearly the same power conversion efficiency of solar cell, compared to the one grown into the bulk heterojunction structure, characterized as the bicontinuous interpenetrating network of P3HT and PCBM. We provide an alternative insight to the morphology control of inverted polymer:fullerene solar cells.     

阴极缓冲层对于不同惰性气氛气压退火处理的 P3HT∶PCBM光伏性能的影响

制备了基于聚(3-己基噻吩)(P3HT)与可溶性富勒烯衍生物(PCBM)共混体系的太阳能电池。通过改变活性层退火处理时惰性气氛环境的压强,在一定程度上实现对共混物相分离以及聚合物结晶度的控制,研究了LiF作为阴极缓冲层对不同压强下退火处理的器件性能的影响。实验发现,LiF层的关键作用在于稳定开路电压以及提升短路电流,从而带动转化效率整体提升。结果表明,LiF层可以改善器件活性层与金属电极接触的界面形态,而器件的最终性能则由活性层的微观形貌与电极界面形态共同决定。     

Influence of charge carrier mobility on the performance of organic solar cells

The power conversion efficiency of organic solar cells based on donor–acceptor blends is governed by an interplay of polaron pair dissociation and bimolecular polaron recombination. Both processes are strongly dependent on the charge carrier mobility, the dissociation increasing with faster charge transport, with raised recombination losses at the same time. Using a macroscopic effective medium simulation, we calculate the optimum charge carrier mobility for the highest power conversion efficiency, for the first time accounting for injection barriers and a reduced Langevin‐type recombination. An enhancement of the charge carrier mobility from 10^–8 m²/V s for state of the art polymer–fullerene solar cells to about 10^–6 m²/V s, which yields the maximum efficiency, corresponds to an improvement of only about 20% for the given parameter set. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of morphology of PCDTBT:PC71BM on the performance of solar cells

Because of the restriction of low energy difference between the highest occupied molecular orbital of P3HT and the lowest unoccupied molecular orbital of PCBM, the obtained power conversion efficiency of P3HT:PCBM solar cells is merely half the ideal value. In this paper, we have fabricated bulk heterojunction solar cells based on PCDTBT and PC71BM (structure: ITO/PEDOT:PSS/PCDTBT:PC71BM/LiF (0.8 nm)/Al (80 nm)). In order to optimize the performance of the cells, the weight ratio of PCDTBT to PC71BM, the thickness of the active layer and thermal annealing are investigated. When the weight ratio of PCDTBT to PC71BM is 1:2 and the thickness of the active layer is 73 nm, a short circuit current density of 10.36 mA/cm², an open-circuit voltage of 0.91 V, a fill factor of 55.06 % and a power conversion efficiency of 5.19 % can be achieved. Moreover, we probe the influence of annealing temperature on the performance of organic solar cells, and find that the thermal treatment methodology (apart from the removal of trapped casting solvent) is of limited benefit.     

Minimizing optical losses in bulk heterojunction polymer solar cells

The efficiency that a solar cell can reach is ultimately limited by the number of photons absorbed in its active layer. Bulk heterojunction polymer solar cells are fabricated from a stack of thin film layers, each of which is thinner than a single wavelength from an incident photon within its absorption band. One consequence of this thin film layer stack is a strong optical interference between the various layers that can change the quantity of light dissipated in the active layer by 50%. Here we use optical modeling to quantitatively calculate the dissipation in each of the various layers as functions of wavelength and layer thickness. Using this information the loss free short circuit current density can be calculated (J_scmax). Optimization of J_scmax leads to direct improvements in the efficiency of the solar cell through improved light dissipation in the active layer. The optical properties for a P3HT:PCBM active layer and a model Lorentzian low band gap spectrum are optimized and ideal fabrication conditions are reported for these materials. PACS 72.40.+w; 72.80.Le     

The effect of post-annealing on the interface between the aluminum electrode and the active layer in polymer/fullerene solar cells

The post-annealing effects on the performance of poly (3-hexylthiophene) (P3HT)/(6,6)-phenyl C₆₁ butyric acid methyl ester (PCBM) solar cells with conventional bulk heterojunction (CBHJ) and layer-evolved bulk heterojunction (LBHJ) have been compared. It is found that contrary to the much better performance obtained from CBHJ cells, the post-annealing deteriorates the performance of LBHJ devices. Aqueous contact angle and X-ray photoelectron spectroscopy measurements show that P3HT is dominant at the top surface of CBHJ film, while PCBM is dominant at the top surface of LBHJ film. The micron-scale morphology evolution of the active layer/Al interface upon post-annealing reveals that the PCBM-rich surface is beneficial for the nucleation and growth of PCBM crystal, which does harm to the contact between the active layer and the electrode and results in the decrease of the fill factor. However, the original P3HT-rich surface prevents the formation of large surface-segregated PCBM clusters upon post-annealing, which is highly desirable for the efficient polymer/fullerene solar cells.     

Effect of an Al-doped ZnO electron transport layer on the efficiency of inverted bulk heterojunction solar cells

Doping is a widely-implemented strategy for enhancing the inherent electrical properties of metal oxide charge transport layers in photovoltaic devices because higher conductivity of electron transport layer (ETL) can increment the photocurrent by reducing the series resistance. To improve the conductivity of ETL, in this study we doped the ZnO layer with aluminum (Al), then investigated the influence of AZO on the performance of inverted bulk heterojunction (BHJ) polymer solar cells based on poly [[4,8-bis [(2-ethylhexyl)oxy]benzo [1,2-b:4,5-b’]dithiophene-2,6-diyl]-[3-fluoro-2[(2-ethylhexyl)-carbonyl]-thieno-[3,4-b]thiophenediyl ]] (PTB7):[6,6]-phenyl C71 butyric acid methyl ester (PC₇₁BM). The measured conductivity of AZO was ~10⁻³ S/cm, which was two orders of magnitude higher than that of intrinsic ZnO (~10⁻⁵ S/cm). By decreasing the series resistance (R_s) in a device with an AZO layer, the short circuit current (J_sc) increased significantly from 15.663 mA/cm² to 17.040 mA/cm². As a result, the device with AZO exhibited an enhanced power conversion efficiency (PCE) of 8.984%.     

Thin Film Solar Cell Based on ZnSnN2/SnO Heterojunction

In this article, we report the growth of zinc‐tin nitride (ZnSnN₂) thin films as a potential absorber for photovoltaic applications by fabricating a heterojunction of n‐ZnSnN₂/p‐SnO. The performance of the heterojunction has been monitored through selective deposition of top electrode with different materials (Ni/Au or Al). The electron‐transfer process from the ZnSnN₂ layer to the cathode is facilitated by selecting metal electrode with relatively low work function, which also boosts up the electron injection or/and extraction. The diode exhibits a good J–V response in the dark with a rectification ratio of 3 × 10³ at 1.0 V and an ideality factor of 4.2 in particular with Al as the top electrode. Under illumination, the heterostructure solar cell demonstrates a power conversion efficiency of ≈0.37% with an open circuit voltage of 0.25 V and a short circuit current density of 4.16 mA cm^?2. The prime strategies, on how to improve solar cell efficiency concerning band offsets and band alignment engineering are also discussed.     

Polymer heterostructures with embedded carbon nanotubes for efficient photovoltaic cells

Polymer photovoltaic cells (PVC) are intensely investigated because of their potential advantages over Si-based PVCs. Their present drawbacks are low conversion efficiency, limited exciton diffusion length, poor hole carriers transport and short lifetime. The highest conversion efficiency achieved so far in spin-coated polymer blends is close to 5%. Recently, efficiency growing has been demonstrated in multilayer architectures involving a donor/acceptor bulk heterojunction. Alternatively, a nanomaterial has been added to the polymer active layer to facilitate excitons dissociation and carriers transport through the polymer matrix. In this work we investigate both these approaches, first embedding single wall Carbon Nanotubes (SWCNT) in the polymeric matrix to improve the electrical transport and second studying the optical absorption of different polymer thin films to optimize the spectral response of the donor/acceptor heterojunction.     

A physics-based analytical model for bulk heterojunction organic solar cells incorporating monomolecular recombination mechanism

We present an analytical model for bulk heterojunction organic solar cells incorporating the physics of recombination in the transport equations. Monomolecular recombination process is considered to be the dominant mechanism and treated explicitly. The proposed analytical model shows good agreement with the experimental data as well as with the numerical simulations. The improvements over the previous models are also presented to show the importance of considering the recombination process. The model can be used to find device characteristics such as current–voltage characteristic, efficiency etc. of bulk heterojunction organic solar cells avoiding the mathematical complexities of numerical models.     

Laser prepared organic heterostructures based on star-shaped arylenevinylene compounds

This paper presents some studies about the preparation by matrix-assisted pulsed laser evaporation (MAPLE) technique of organic bulk heterojunctions made from the mixture of a star-shaped arylenevinylene compound, 4,4′,4″-tris[(4′-diphenylamino)styryl] triphenylamine as donor and fullerene derivative, [6, 6]-phenyl C61 butyric acid butyl ester, as acceptor, in the weight ratio 1:2. The mixed layer has been characterized by spectroscopic (UV–Vis, Fourier transform infrared) and microscopic (AFM) methods, and the effects of the deposition conditions (number of pulses) and of a buffer layer of poly(aniline-co-aniline propane sulfonic acid) or poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) have been analyzed. The study of the electrical properties has revealed a typical solar cell behavior for the heterostructure glass/ITO/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/4,4′,4″-tris[(4′-diphenylamino)styryl] triphenylamine: [6, 6]-phenyl C61 butyric acid butyl ester/Al, confirming that MAPLE could be an adequate method for the preparation of active layer based on bulk heterojunction for solar cells.     

Fabrication and characterization of ZnTPP:PCBM bulk heterojunction (BHJ) solar cells

Bulk heterojunction (BHJ) solar cells were fabricated based on blended films of a porphyrin derivative 5,10,15,20-Tetraphenyl-21H,23H-porphine zinc (ZnTPP) and a fullerene derivative [6,6]-phenyl-C₆₁ butyric acid methyl ester (PCBM) as the active layer. The ZnTTP:PCBM BHJ solar cells were fabricated by spin-casting of the blended layer. The weight ratios of ZnTPP and PCBM were varied from 1:1 to 0:10. The electronic and optical properties of each cell were investigated. Optical density (OD) of the blended film for each cell was extracted from its reflection and transmission curves. OD and average absorption coefficients of the active materials were used to determine film thicknesses. Absorption spectra of each component material were compared with the spectra of the blended films. Current density–Voltage (J–V) characteristics were recorded under dark as well as under the illumination of AM 1.5G (1 sun) solar spectrum. The BHJ solar cell with ZnTPP:PCBM ratio of 1:9 showed the best performance . The values of RR, V_OC , J_SC , FF and η for these ratios were 106.3, 0.4 V, 1.316 mA/cm², 0.4 and 0.21%, respectively. The cross-section of this device using SEM was also examined.     

阳极缓冲层修饰对聚合物太阳能电池性能的影响

为提高聚合物太阳能电池的能量转换效率,将聚乙二醇(PEG)掺入PEDOT∶PSS阳极缓冲层,研究了阳极缓冲层修饰对聚合物太阳能电池性能的影响。首先研究了聚乙二醇对PEDOT∶PSS薄膜电导率的影响,发现PEG会与PEDOT和PSS相互作用,使得PEDOT链重新排布,有利于电荷载流子的传输,从而显著改善了PEDOT∶PSS薄膜的电导率,当PEDOT∶PSS中掺入体积分数为2%~4%的PEG时,可得到较大的电导率。然后,以PEG修饰的PEDOT∶PSS薄膜作为阳极缓冲层制备了聚合物太阳能电池,研究了PEG的掺入对聚合物太阳能电池性能的影响。实验发现,PEG改善的PEDOT∶PSS电导率有利于提高电池的短路电流密度和填充因子,从而改善了器件光伏性能。当PEDOT∶PSS中掺入体积分数为2%的PEG时,聚合物太阳能电池的能量转换效率最高,比未掺杂的器件提高了24.4%。     

Raman spectroscopic identification of fullerene inclusions in polymer/fullerene blends

Thin films of the conjugated polymer poly(3‐hexylthiophene) (P3HT) and blends of the soluble fullerene derivative[6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) with P3HT—a well studied but not completely understood donor–acceptor system for organic solar cells—have been studied by means of UV–visible absorption and resonant Raman spectroscopy. Additionally, we have employed atomic force microscopy phase imaging to characterize the nanomorphology of the P3HT : PCBM thin film, revealing a close intermixing of two phases with domain sizes ranging from a few to several tens of nanometers. A systematic analysis of pristine polymer and blend Raman spectra provides evidence that features attributable to PCBM, possibly even depending on the charge state of the fullerene molecule, can be observed. Hence our results suggest that fullerene inclusions in polymer/fullerene blends can be identified via Raman spectroscopy. Copyright © 2011 John Wiley & Sons, Ltd.