关联染料敏化太阳能电池薄膜厚度与光伏性能的漂移-扩散数值模拟

建立漂移-扩散模型来模拟敏化电池的电荷分离过程.该模型能够计算在稳态和非稳态条件下光生电子的多步受限扩散及其与电子受体的复合反应.通过对电池的电流-电压曲线的数值模拟,优化了电池的薄膜厚度并获得了最大的光电转换效率.发现膜厚的增加降低了电荷收集效率,但有利于提高电子注入流率,光电流的输出正是受控于这两个因素.复合速率常数严重影响了膜厚优化的结果.较厚的薄膜适合于电子复合被充分抑制的电池,而较薄的薄膜有利于降低快复合电池的电子复合损失.在开路条件下,膜厚的提高会减小电子浓度,在造成光电压的降低的同时会提高电子寿命.     

The effect of TiCl4-treated TiO2 compact layer on the performance of dye-sensitized solar cell

In order to prevent the charge recombination at the interface between the transparent-conducting oxide (TCO) substrate and electrolyte, a TiO₂ compact layer was deposited on the substrate by hydrolysis of TiCl₄ aqueous solution. Optimum thickness of the compact layer was found to be ∼25 nm, which showed ∼24% increase in the power-conversion efficiency compared with the bare cell. Impedance spectra indicated that the interfacial charge-transfer resistance of TCO/electrolyte interface was increased by more than a factor of three with the TiO₂ compact layer at 0.4 V. Moreover, the electron-carrier lifetime of the 25 nm-deposited cell was improved by a factor of five compared with the bare cell.     

Cocktail effect of Fe2O3 and TiO2 semiconductors for a high performance dye-sensitized solar cell

The bi-semiconductors of TiO₂ and Fe₂O₃ were used as a photoelectrode material in a high performance dye-sensitized solar cell due to cocktail effects from the two conduction bands. The size of the semiconductors was reduced by using a paint shaker to enlarge the contact area of the semiconductor with the dye or electrolyte. The fill factor and the efficiency of the prepared dye-sensitized solar cell were improved by over 16% and 300%, respectively; these parameters were measured from a current-voltage curve that was based on the effects of the Fe₂O₃ co-semiconductor and the size reduction. A mechanism is suggested wherein the conduction band of Fe₂O₃ works to prohibit the trapping effects of electrons in the conduction band of TiO₂. This result is attributed to the prevention of electron recombination between electrons in the TiO₂ conduction band with dye or electrolytes. The mechanism is suggested based on impedance results, which indicate improved electron transport at the interface of the TiO₂/dye/electrolyte.     

负偏压作用下染料敏化太阳电池界面及光电性能研究

太阳电池组件由于局部电压不匹配,其中部分电池可能较长时间工作在负偏压状态下,从而影响电池光电性能.借助拉曼光谱、电化学阻抗谱和入射单色光量子效率(IPCE)等测试手段,研究长期负偏压作用下染料敏化太阳电池光电性能的变化及其影响机理.拉曼光谱研究结果表明:电池在1000 h负偏压作用下,电解质中阳离子(Li⁺)会向光阳极(TiO₂电极)移动并嵌入TiO₂薄膜中;长期负偏压作用还会致使TiO₂/电解质界面阻抗增大和IPCE下降,导致电池开路电压升高和短路电流减小.通过加入苯并咪唑(BI)添加剂,经1000 h负偏压后电池的拉曼光谱实验表明,BI能在一定程度阻碍Li⁺的嵌入,电池具有较好的长期稳定性.不同负偏压下的老化实验进一步表明,通过加入添加剂能够使电池在长期负偏压下保持较好的稳定性. 关键词： 染料敏化 太阳电池 组件 负偏压     

聚苯胺基固态染料敏化太阳电池中电子输运性能的研究

以导电聚苯胺为空穴传输材料，制备了固态染料敏化太阳电池(DSC).利用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)研究了TiO₂多孔膜内的电子输运及复合过程.通过TiO₂多孔膜内电子的平均传输时间(τ_d)和电子寿命(τ_n)及对IMPS实验数据的拟合，获得电子在TiO₂膜内的有效扩散系数(D_n)和扩散长度(L_n).这些聚苯胺基电池中的τ_n值为相应的液体型电池的1/10倍左右，表明在该固体电池中存在严重的光生电子的复合过程，这很可能主要是与氧化态染料分子和导电电子间的复合有关.随着TiO₂膜厚的增加，τ_n和τ_d均变小，但D_n和L_n随之增加，只有在合适的膜厚范围内才能获得较高的光伏性能. 关键词： 聚苯胺 染料敏化太阳电池 IMPS IMVS     

A novel TiO2 nanoparticles/nanowires composite core with ZrO2 nanoparticles shell coating photoanode for high-performance dye-sensitized solar cell based on different electrolytes

The novel TiO₂ nanopartilces/nanowires (TNPWs) composite with ZrO₂ nanoparticles (ZNPs) shell-coated photoanodes were prepared to fabricate high-performance dye-sensitized solar cell (DSSC) based on different types of electrolytes. Hafnium oxide (HfO₂) is a new and efficient blocking layer material applied over the TNPWs-ZNPs core-shell photoanode film. TiO₂ nanoparticles (TNPs) and TiO₂ nanowires (TNWs) were characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). DSSCs were fabricated using the novel photoanodes with an organic sensitizer D149 dye and different types of electrolytes namely liquid electrolyte, ionic liquid electrolyte, solid-state electrolyte, and quasi-solid-state electrolyte. The DSSC-4 made through the novel core-shell photoanode using quasi-solid-state electrolyte showed better photocurrent efficiency (PCE) as compared to the other DSSCs. It has such photocurrent-voltage characteristics: short circuit photocurrent (Jsc)?=?19 mA/cm², the open circuit voltage (Voc)?=?650 mV, fill factor (FF)?=?65 %, and PCE (η)?=?8.03 %. The improved performance of DSSC-4 is ascribed to the core-shell with blocking layer photoanode could increased electron transport and suppressed recombination of charge carriers at the TNPWs-ZNPs/dye/electrolyte interface.     

TiO2表面质子化对染料敏化太阳能电池性能及吸附染料稳定性的影响

采用致密平整TiO₂薄膜作为染料敏化太阳能电池光电极,并研究了HCl处理表面质子化对电池性能的影响. 结果表明,HCl处理后电池的短路电流显著提升,电池的开路电压则有轻微的下降,电池电流提升了31%,而能量转化效率则提升了25%. 这是因为TiO₂的表面质子化增强了吸附染料与TiO₂间的电学耦合,提高了染料中激发电子向TiO₂导带的注入速率. 而电压的下降,一方面是由于质子化会引起TiO₂导带能级     

Comparison of the performances of dye-sensitized solar cells based on different TiO2 electrode nanostructures

This article reports on the performances of dye-sensitized solar cells based on three different working electrode structures, i.e., (i) sintered TiO₂ nanoparticles (20–40 nm diameters), (ii) ordered arrays of TiO₂ nanotubules (150 nm external diameters and 80 nm internal diameters), and (iii) ordered arrays of TiO₂ nanorods (150 nm diameters). Even though the highest short-circuit current density was achieved with systems based on TiO₂ nanotubules, the most efficient cells were those based on ordered arrays of TiO₂ nanorods. This is probably due to higher open-circuit photovoltage values attained with TiO₂ nanorods than with TiO₂ nanotubules. The nanorods are thicker than the nanotubules and therefore the injected electrons, stored in the trap states of the inner TiO₂ molecules, are shielded from recombination with holes in the redox electrolyte at open circuit. The high short-circuit photocurrent densities seen in the ordered TiO₂ systems can be explained by the fact that, as opposed to the sintered nanoparticles, the parallel and vertical orientation of the ordered nanostructures provide well-defined electrons percolation paths thus significantly reduce the diffusion distance and time constant.     

The effect of TiO<Subscript>2</Subscript> coating on the electrochemical performance of ZnO nanorod as the anode material for lithium-ion battery

ZnO nanorods were coated with TiO₂ thin film using the atomic layer deposition (ALD) process. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy were used to characterize the crystal structure and surface morphology of the coated composites. Results of galvanostatic charge and discharge tests and cyclic voltammograms suggest that lithium ions can reversibly intercalate into and deintercalate from TiO₂-coated ZnO nanorods, and that stable cycling behavior in an ethylene carbonate-based electrolyte can be achieved. The TiO₂ coating is believed to reduce the degree of reaction electrodes have with the electrolyte during the charge–discharge process since the inactive coating layer prevents the electrode from having direct contact with the electrolyte. Furthermore, the one-dimensional nanorods provide a relatively higher surface area than those of their bulk form or thin film, which allows a much greater portion of atoms on the surface to undergo the electrochemical reaction. The electrochemical study indicates that the TiO₂-coated ZnO nanorod arrays might be a candidate for the anode material in Li-ion batteries.     

Recombination zone and efficiency in bipolar single layer light-emitting devices: a numerical study

The efficiency of organic light-emitting devices (OLEDs) is closely related to the position and width of recombination zone (RCZ) in the emission layer. Based on the drift–diffusion theory of carrier motion in semiconductors, we developed a numerical model for the position and width of the RCZ in bipolar single layer OLEDs. The calculation results show that for a given operation voltage, the position and width of the RCZ are determined by the mobility difference of electrons and holes, and the energy barrier at the two contacts. When the anode and cathode contact are both ohmic, then RCZ will be near the electrode, from which the low-mobility carriers are injected, and the smaller the mobility difference, the wider the RCZ, and the width of RCZ will be maximal when the mobility of holes and electrons are equal. When the anode contact is Schottky, while the cathode contact is ohmic, then the position and width of RCZ will be determined by both the mobility difference and hole–injection energy barrier. When μ _p<μ _n, the RCZ will be at the anode side. When μ _p>μ _n, then RCZ will move away from the anode and become wider, with the increase of the hole injection barrier. For a given hole–injection barrier and mobility of holes and electrons, the position and width of RCZ change with the applied voltage.     

Electronic processes at the interfaces between photoactive layers and TiO<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript> buffer layers in organic solar cells

The effect a layer of TiO_x located between a photoactive layer and a metallic Al electrode has on the photovoltaic properties of an organic solar cell based on P3HT:PC₇₀BM polymer is studied. The optimum thickness of the TiO_x layer at which the efficiency of the solar cells is highest and the TiO_x layer ensures the transfer of electrons from the photoactive polymer layer to the electrode while blocking vacancies is found to be 10 nm. The effect oxygen has on electronic processes during the operation of the photovoltaic cell is discussed.     

Bifunctional photocatalysis of TiO2/Cu2O composite under visible light: Ti in organic pollutant degradation and water splitting

Photocatalytic experiment results under visible light demonstrate that both TiO₂ and Cu₂O have low activity for brilliant red X-3B degradation and neither can produce H₂ from water splitting. In comparison, TiO₂/Cu₂O composite can do the both efficiently. Further investigation shows that the formation of Ti³⁺ under visible light has great contribution. The mechanism of photocatalytic reaction is proposed based on energy band theory and experimental results. The photogenerated electrons from Cu₂O were captured by Ti⁴⁺ ions in TiO₂ and Ti⁴⁺ ions were further reduced to Ti³⁺ ions. Thus, the photogenerated electrons were stored in Ti³⁺ ions as the form of energy. These electrons trapped in Ti³⁺ can be released if a suitable electron acceptor is present. So, the electrons can be transferred to the interface between the composite and solution to participate in photocatalytic reaction. XPS spectra of TiO₂/Cu₂O composite before and after visible light irradiation were carried out and provided evidence for the presence of Ti³⁺. The image of high-resolution transmission electron microscopy demonstrates that TiO₂ combines with Cu₂O tightly. So, the photogenerated electrons can be transferred from Cu₂O to TiO₂.     

ZnS overlayer on in situ chemical bath deposited CdS quantum dot-assembled TiO2 films for quantum dot-sensitized solar cells

ZnS overlayers were deposited on the CdS quantum dot (QD)-assembled TiO₂ films, where the CdS QDs were grown on the TiO₂ by repeated cycles of the in situ chemical bath deposition (CBD). With increasing the CdS CBD cycles, the CdS QD-assembled TiO₂ films were transformed from the TiO₂ film partially covered by small CdS QDs (Type I) to that fully covered by large CdS QDs (Type II). The ZnS overlayers significantly improved the overall energy conversion efficiency of both Types I and II. The ZnS overlayers can act as the intermediate layer and energy barrier at the interfaces. However, the dominant effects of the ZnS overlayers were different for the Types I and II. For Type I, ZnS overlayer dominantly acted as the intermediate layer between the exposed TiO₂ surface and the electrolyte, leading to the suppressed recombination rate for the TiO₂/electrolyte and the significantly enhanced charge-collection efficiency. On the contrary, for Type II, it dominantly acted as the efficient energy barrier at the interface between the CdS QDs and the electrolyte, leading to the hindered recombination rate from the large CdS QDs to the electrolyte and thus enhanced electron injection efficiency.     

Theory of positive corona in SF6 due to a voltageimpulse

A theoretical examination is made of the mechanism of corona formation for a positive point-plane gap in SF₆ at 100 kPa. The impulse voltage applied has a rise time of 15 ns and peak value of 200 kV. Seed electrons are released 1 ns after the start of the voltage rise. For a 0.5-cm diameter positive sphere located 6.5 cm from a negative plane, the calculated circuit current initially consists of subnanosecond corona onset pulses, and then the current steadily rises to a maximum, as the voltage reaches a maximum, followed by a rapid fall in current. During the current rise a streamer moves out into the gap along a 100-μm channel, with the electric field in the streamer trail E>E*, where E* is the critical field where ionization equals attachment. The light output during the discharge is predicted to be a maximum at the anode with only a minor pulse of light at the streamer head, making it hard to detect. After the current maximum, recombination rapidly reduces the numbers of positive ions, negative ions, and electrons, but the net charge density remains constant and thus so does the electric field. The electric field is E~E* in the streamer trail, but has a sharp maximum, E≫E* at the head of the streamer trail. The origin of mid-gap precursors, observed when the streamer channel reilluminates after some 100 ns, is attributed to this field maximum in the remnant electric field. The evolution of positive ions, negative ions, and electrons is described by one-dimensional continuity equations, with the space-charge electric fields determined by the disk method. The effects of ionization, attachment, recombination, electron diffusion, and photoionization are all included. New numerical methods allow resolution of the streamer head and the anode fall region to be obtained with a 1-μm mesh, while following the streamer propagation for ~2 cm     

Function and analytical formula for nanocrystalline dye-sensitization solar cells

Based on the experimental observations that the three-phase nano-TiO₂/F:SnO₂/I^-/I^- ₃ electrolyte front contact has to have pronounced rectifying properties (reverse reaction with electrolyte suppressed) for efficient operation of the dye-sensitization solar cell and plays an active part in the generation of photoelectrochemical energy, an analytical formula is derived which allows the understanding of the relevance and involvement of a variety of kinetic and cell parameters. Essentially, the TiO₂ layer is treated as a photocathode, donating electrons to a kinetically controlled front contact, with the counter-charges being transported by the electrolyte within the pores. The formula was expanded to include photochemical kinetics of the sensitizer, for which photodegradation properties were also calculated. The branching ratio, the ratio of regeneration-rate constant of the sensitizer and of product-formation rate, turned out to be critical for long-term stability. It may have to be improved by one order of magnitude for efficient cells to reach a lifetime of 20 years. The degree of rectifying character of the nano-TiO₂/F:SnO₂/I^-/I^- ₃ electrolyte interface (electric-field-dependent charge transfer to the front contact versus recombination-rate constant with I₃ ^- distinguishes between a low-efficiency (‘dynamic’) Galvani-type solar cell (efficiency determined by photoinduced chemical potential gradients, no rectifying contact) and a more highly efficient ‘junction-type’ solar cell (separation and collection of charges additionally assisted by junction potential). Several controversial subjects are addressed. The key challenges for the improvement of such cells are discussed, especially with respect to photodegradation and to solid-state devices. Received: 18 September 2000 / Accepted: 17 January 2001 / Published online: 20 June 2001     

Natural dye-based photoelectrode for improvement of solar cell performance

In the present paper, photovoltaic studies of dye-sensitized solar cells (DSSCs) based on betacyanin/TiO₂ and betacyanin/WO₃–TiO₂ have been done. The cell performances were compared through I–V curves and wavelength dependant photocurrent measurements for the two new types of DSSCs. The TiO₂-coated DSSC showed the photovoltage and photocurrent of 300 mV and 4.96 mA/cm², whereas the cell employing WO₃–TiO₂ photoelectrode showed the values 435 mV and 9.86 mA/cm², respectively. The conversion efficiency of TiO₂ based dye-sensitized solar cell was found to be 0.69 %, while WO₃–TiO₂-based cell exhibited a higher conversion efficiency of 2.2 %. The better performance of the WO₃–TiO₂ dye-sensitized solar cell photoelectrode is thought to be due to an inherent energy barrier at the electrode/electrolyte interface leading to the reduced recombination of photoinduced electrons.     

Titania surface modification and photovoltaic characteristics with tungsten oxide

WO₃-coated TiO₂ film was prepared by depositing TiO₂ suspension containing small amounts of ammonium tungstate solution. The morphology and structure of the samples were characterized with high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and photoluminescence (PL) emission spectrum. The results showed that WO₃ formed a coating layer on surface of TiO₂ and significantly reduced the surface traps of TiO₂ nanoparticles. Transient photovoltage and electrochemical impedance measurements (EIS) were employed to study the charge separation/recombination process. The results revealed that the charge recombination was greatly retarded and the electron lifetime was increased due to the coating layer of WO₃. These observations showed good correlation with current-voltage analyses of dye-sensitized solar cell fabricated from these films, with WO₃ overlayer resulting in an increase in open-circuit voltage of up to 37 mV and 11% improvement in overall device efficiency.     

氧化锌掺铝绒面薄膜在有机光伏电池中的应用

目前有机光伏电池的吸光活性层电学传输特性和光学吸收特性的不匹配是制约其能量转换效率提升的主要原因之一. 通过陷光结构对入射光进行调控, 提高电池对光的约束和俘获能力从而达到“电学薄”和“光学厚”的等效作用, 是解 决有机光伏电池电学和光学不匹配的有效手段. 本文采用湿法刻蚀技术获得了系列时间梯度的绒面氧化锌掺铝薄膜, 并将其作为有机光伏电池的入射陷光电极, 显著增强了电池的光学吸收. 研究发现, 当使用浓度0.5%的稀HCL腐蚀30 s后的氧化锌掺铝薄膜作为入射电极后, 电池的光电性能和效率显著增强. 基于此绒面电极电池的电流密度比平面结构的电池提高了8.17%, 效率改善了11.29%. 通过对绒面电极表面的修饰处理, 实现了电极与光活性层之间良好的界面接触, 从而减小了对电池的开路电压和填充因子的影响.     

MoO3/Ag/Al/ZnO intermediate layer for inverted tandem polymer solar cells

We report an MoO3/Ag/Al/ZnO intermediate layer connecting two identical bulk heterojunction subcells with a poly(3-hexylthiophene) and [6,6]-phenyl-C61-butyric acid methyl ester(P3HT and PCBM) active layer for inverted tandem polymer solar cells. The highly transparent intermediate layer with an optimized thickness realizes an Ohmic contact between the two subcells for effective charge extraction and recombination. A maximum power conversion efficiency of 3.76% is obtained for the tandem cell under 100 mW/cm2 illumination, which is larger than that of a single cell(3.15%).The open-circuit voltage of the tandem cell(1.18 V) approaches double that of the single cell(0.61 V).     

Low‐Temperature‐Processed CdS as the Electron Selective Layer in an Organometal Halide Perovskite Photovoltaic Device

Organic–inorganic halide perovskites have recently been crowned as the leading next‐generation photovoltaic material due to their high efficiency and simple fabrication process. Herein, a low‐temperature‐processed CdS thin film (commonly used as a buffer layer in commercial CdTe or CIGSe solar cells) is reported as an electron selective layer in perovskite devices based on the following reasons: First, the photoelectric property of CdS thin film is investigated, illustrating the possibility of CdS as the electron selective layer in the application of methylammonium lead (II) iodide perovskite devices. More specifically, CdS semiconductor film presents a higher mobility compared with traditional TiO₂ thin film, which benefits the electron extraction and transmission; second, it is found that the perovskite thin film spun‐coating on the CdS substrates grows with an obvious tendency along the direction toward the thickness of thin film, which reduces the chance of recombination of electrons and hole, beneficial to their separation. It is also revealed that the perovskite‐device‐based CdS electron selective layer has a higher stability compared with that of TiO₂ due to the difference of substrates wetting.