强度调制光电流谱研究纳晶薄膜电极过程

用强度调制光电流谱研究半导体纳晶薄膜电极光生电荷的界面转移和输运动力学过程.从测量不同外加电压和不同硫化钠溶液浓度下CdSe纳晶薄膜电极的光电流响应得到了参数:归一化稳态光电流和表面态寿命,分析界面空穴的直接转移和通过表面态的间接转移过程.通过测量不同背景光强下TiO2纳晶薄膜电极的电子扩散系数研究电子输运过程.应用HCl化学处理方法明显增大了电子扩散系数,改善了电子在TiO2纳晶薄膜电极中的输运性能.     

Electron transport in coumarin-dye-sensitized nanocrystalline TiO2 electrodes

We investigated electron transport kinetics in terms of electron diffusion coefficient (D) and electron lifetime (tau) in coumarin-dye-sensitized nanocrystalline TiO2 electrodes by intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS). We found that the values of tau for coumarin-dye-sensitized TiO2 electrodes were much shorter than that for an electrode coated with a Ru complex (N719 dye), suggesting that the back-electron-transfer process corresponding to recombination between conduction-band electrons in the TiO2 and I3- ions in the electrolyte occurs more easily in coumarin-dye-sensitized solar cells. In addition, the values of tau depended on the kind of coumarin dye, each of which has a different number of thiophene moieties, suggesting that the molecular structure of the adsorbed dyes also affects the kinetics of electron transport in the TiO2 electrodes.     

不对称菁染料敏化纳米TiO2的光生电流过程

用光电化学方法研究了不对称菁类染料敏化TiO2纳米结构电极的光电转换过程.结果表明,该染料的电子激发态能级位置与TiO2纳米粒子导带边位置匹配较好,光激发染料后,其激发态电子可以注入到TiO2纳米多孔膜的导带,从而使TiO2纳米结构电极的吸收光谱和光电流谱红移至可见光区,其 IPCE(Incident photon-to-electron conversion efficiency)值最高可达84.3%.并进一步结合现场紫外-可见吸收光谱研究了外加电势对激发态染料往TiO2纳米多孔膜注入电子过程的影响.     

Modified phthalocyanines for efficient near-IR sensitization of nanostructured TiO(2) electrode

A zinc phthalocyanine with tyrosine substituents (ZnPcTyr), modified for efficient far-red/near-IR performance in dye-sensitized nanostructured TiO(2) solar cells, and its reference, glycine-substituted zinc phthalocyanine (ZnPcGly), were synthesized and characterized. The compounds were studied spectroscopically, electrochemically, and photoelectrochemically. Incorporating tyrosine groups into phthalocyanine makes the dye ethanol-soluble and reduces surface aggregation as a result of steric effects. The performance of a solar cell based on ZnPcTyr is much better than that based on ZnPcGly. Addition of 3alpha,7alpha-dihydroxy-5beta-cholic acid (cheno) and 4-tert-butylpyridine (TBP) to the dye solution when preparing a dye-sensitized TiO(2) electrode diminishes significantly the surface aggregation and, therefore, improves the performance of solar cells based on these phthalocyanines. The highest monochromatic incident photo-to-current conversion efficiency (IPCE) of approximately 24% at 690 nm and an overall conversion efficiency (eta) of 0.54% were achieved for a cell based on a ZnPcTyr-sensitized TiO(2) electrode. Addition of TBP in the electrolyte decreases the IPCE and eta considerably, although it increases the open-circuit photovoltage. Time-resolved transient absorption measurements of interfacial electron-transfer kinetics in a ZnPcTyr-sensitized nanostructured TiO(2) thin film show that electron injection from the excited state of the dye into the conduction band of TiO(2) is completed in approximately 500 fs and that more than half of the injected electrons recombines with the oxidized dye molecules in approximately 300 ps. In addition to surface aggregation, the very fast electron recombination is most likely responsible for the low performance of the solar cell based on ZnPcTyr.     

Photocurrents at polarized liquid|liquid interfaces enhanced by a gold nanoparticle film

Photocurrent responses associated with the interfacial quenching of the photo-excited water-soluble zinc meso-tetra(4-carboxyphenyl)porphyrin (ZnTPPC) by ferrocene have been studied at a water|1,2-dichloroethane interface in the absence and in the presence of adsorbed gold nanoparticles. Upon addition of methanol, a mirror-like gold film is formed and an important enhancement of the photocurrent response can be observed. Intensity modulated photocurrent spectroscopy experiments (IMPS) have been performed, in order to deconvolute in the frequency domain the contribution from the competition between the recombination and the product separation arising after the electron transfer, and the attenuation associated with the resistance and interfacial capacitance (RC(int)) time constant of the cell.     

Bifunctional single-crystalline rutile nanorod decorated heterostructural photoanodes for efficient dye-sensitized solar cells

A novel heterostructural TiO(2) nanocomposite, which consists of single-crystalline rutile TiO(2) nanorod decorated Degussa P25 nanoparticles, has been fabricated through a facile acidic hydrothermal method and successfully applied as the photoanodes for efficient dye-sensitized solar cells. The morphology, crystal structure, specific surface area and pore size distribution of the obtained nanocomposite were systematically investigated by X-ray diffraction (XRD), field-emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HRTEM), selected-area electron diffraction patterns (SAED) and nitrogen adsorption-desorption measurements. Under standard illumination conditions (AM 1.5, 100 mW cm(-2)), devices with these hybrid anodes exhibited considerably enhanced photocurrent density and overall conversion efficiency in comparison with that of the commercial Degussa P25 electrodes, which can be partially attributed to the light scattering effect in the long-wavelength region as evidenced from the incident photon-to-current conversion efficiency (IPCE) response and the diffuse reflectance spectroscopy. More importantly, devices employing these hybrid anodes have demonstrated extended electron lifetimes and larger electron diffusion coefficient as validated by the intensity-modulated photocurrent/photovoltage spectroscopy measurements, which can be mainly ascribed to the fast electron transport and collection superiority of the single-crystalline nanorods.     

Porosity dependence of electron percolation in nanoporous TiO2 layers

The electron diffusion coefficient at varying porosity has been determined in a series of nanostructured TiO(2) films of different initial thicknesses. The porosity was changed by applying different pressures prior to sintering, thereby modifying the internal morphology of the films though not their chemical and surface conditions. A systematic increase of the effective diffusion coefficient was observed as the porosity was decreased, indicating the improvement of the internal connectivity of the network of nanoparticles. The experimental results have been rationalized using percolation theory. First of all, applying a power law dependence, the diffusion coefficient as a function of porosity from different films collapsed in a single master curve. In addition, application of the models of effective medium approximation (EMA) allows us to compare the experimental results with previous data from Monte Carlo simulation. The different data show a similar dependence in agreement with the EMA predictions, indicating that the geometrical effect of electron transport due to variation of porous morphology in TiO(2) nanoparticulate networks is well described by the percolation concept.     

Mechanisms and applications of plasmon-induced charge separation at TiO2 films loaded with gold nanoparticles

Plasmon-induced photoelectrochemistry in the visible region was studied at gold nanoparticle-nanoporous TiO(2) composites (Au-TiO(2)) prepared by photocatalytic deposition of gold in a porous TiO(2) film. Photoaction spectra for both the open-circuit potential and short-circuit current were in good agreement with the absorption spectrum of the gold nanoparticles in the TiO(2) film. The gold nanoparticles are photoexcited due to plasmon resonance, and charge separation is accomplished by the transfer of photoexcited electrons from the gold particle to the TiO(2) conduction band and the simultaneous transfer of compensative electrons from a donor in the solution to the gold particle. Besides its low-cost and facile preparation, a photovoltaic cell with the optimized electron mediator (Fe(2+/3+)) exhibits an optimum incident photon to current conversion efficiency (IPCE) of 26%. The Au-TiO(2) can photocatalytically oxidize ethanol and methanol at the expense of oxygen reduction under visible light; it is potentially applicable to a new class of photocatalysts and photovoltaic fuel cells.     

Self-assembly and photoelectric properties of cerium complexes with 3,4,9,10-perylenetetracarboxylic acid on nanocrystalline TiO_2 films

Self-assembled (SA) films (PMP, M = Ce3+ or Ce4+) of 3,4,9,10-perylenetetracarboxylic acid (PTA) on nanocrystalline TiO2 films with Ce3+ or Ce4+ as a bridge were fabricated and characterized with UV-Vis, IR, and XPS synchrotron radiation photoelectron spectroscopy (SRPES) which gave the HOMO energy levels for the SA films. It was shown that thin-layer sandwich-type solar cells based on these SA films possess good properties for photoelectric conversion. While PTA-loaded TiO2 electrode (P) generated 26.9% of incident monochromatic photon-to-electron conversion efficiency (IPCE), PMP-sensitized Ti02 electrodes yielded 55.8% and 39.1% for Ce4+ and Ce3+ respectively. PMP films can be considered as a kind of complexes whose HOMO energy levels were proved to be higher than that of film P, which is one of the major reasons for the increase in IPCE from film P to film PMP.     

N,N′-对羧苄基吲哚三菁敏化纳米TiO2电极的研究

应用光电化学方法研究了N, N′-对羧苄基吲哚三菁（Cy5）染料敏化TiO2纳米晶电极的光电化学行为,优化了敏化的条件.结合Cy5的循环伏安曲线和光吸收阈值,初步确定Cy5电子基态和激发态能级位置.结果表明,Cy5电子激发态能级位置能与TiO2纳米粒子导带边位置相匹配,因而使用该染料敏化可以显著提高TiO2纳米晶的光电流,使TiO2纳米晶电极吸收波长由紫外光区红移至可见光区和近红外区,光电转换效率得到明显改善,在膜厚为6.5μm、敏化时间为6 h的条件下IPCE值（incident photo-to-electricity conversion efficiency）最高可达46.4％,总的光电转换效率η为1.70％.     

Near-IR light-sensitized voltaic conversion system using nanocrystalline TiO2 film by Zn chlorophyll derivative aggregate

A Zn chlorophyll-a derivative, Zn chlorin-e6 (ZnChl-e6), adsorbed onto a nanocrystalline TiO2 film (ZnChl-e6/TiO2) electrode was prepared, and the photovoltaic properties of the ZnChl-e6/TiO2 electrode were studied. The absorption peaks of ZnChl-e6/TiO2 observed at 420, 654, and 795 nm were attributed to the ZnChl-e6 molecules aggregating onto TiO2 film. The fluorescence attributed to the ZnChl-e6 monomer and aggregate was observed at 710 and 820 nm, respectively, and the fluorescence in both cases was quenched by TiO2 particles. The maximum of the incident photon-to-current conversion efficiency (IPCE) value in the photocurrent action spectrum was 800 nm, and the IPCE value was 7.0%. ZnChl-e6 molecules formed aggregates on a nanocrystalline TiO2 film electrode. From the photocurrent-photovoltage characteristics of the ZnChl-e6/TiO2 electrode irradiated with 100 mW cm(-2), the short-circuit photocurrent (I(SC)) was found to be 0.19 mA cm(-2) and the open-circuit photovoltage (V(OC)) was found to be 375 mV. The maximum power was estimated to be 28.7 microW cm(-2), and the fill factor (FF) was estimated to be 40.1%. A near-IR light induced photovoltaic conversion system using a ZnChl-e6 aggregate formed onto a nanocrystalline TiO2 film electrode was achieved.     

不锈钢基底上TiO2薄膜型光催化剂的制备和化学结构

采用钛酸正丁酯作为前驱体,通过溶胶-凝胶法在不锈钢基片上制备了TiO2纳米薄膜。利用俄歇电子能谱(AES)和紫外反射光谱等研究手段,对TIO2薄膜的化学结构及基底材料界面相互作用进行了系统研究。结果发现,在不锈钢基底上形成的TiO2薄膜与基底材料发生了明显的界面扩散反应。在TiO2薄膜的形成过程中,不锈钢中Fe元素向TiO2薄膜层扩散,并与从大气氛中扩散到界面的氧发生化学反应,形成铁氧化物界面过渡层。界面氧化过程,导致了Fe向样品表面的偏析和扩散。在高温热处理过程中,Fe可以扩散到TiO2薄膜的表面。薄膜催化剂的紫外反射光谱表明,界面扩散反应导致了Fe扩散进入TiO2薄膜的晶格,从而改变了薄膜催化剂的光吸收性能。     

Linking optical and electrical small amplitude perturbation techniques for dynamic performance characterization of dye solar cells

This paper unifies the analytical models used widely but thus far mostly separately for electrical and optical small amplitude perturbation measurements of nanostructured electrochemical dye solar cells (DSC): electrochemical impedance spectroscopy (EIS), intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS). The models are linked by expressing the kinetic boundary condition used for solving the time-dependent continuity equation of electrons in IMPS and IMVS analysis in terms of the series and parallel impedance components found in the complete equivalent circuit impedance model of DSC. As a result, analytical expressions are derived for potentiostatic IMPS and galvanostatic IMVS transfer functions of complete DSCs that are applicable at any operating point along the solar cell current-voltage (IV) curve. In agreement with the theory, impedance spectrum calculated as a ratio of IMVS and IMPS transfer functions measured near the maximum power point matches exactly with the impedance spectrum measured directly with EIS. Consequently, both IMPS-IMVS and EIS yield equal estimates for the electron diffusion length. The role of the chemical capacitance of the nanostructured semiconductor photoelectrode in the interpretation of the so-called RC attenuation of the IMPS response is clarified, as well as the capacitive frequency dispersion in IMPS and IMVS.     

水热法合成纳米TiO2及其在Grtzel电池中的应用

By varying the hydrolysis and hydrothermal processing parameters in preparing TiO2 nanoparticles different sizes of TiO2 nanoparticles are obtained.(1) At higher autoclaving temperature,lower pH and longer autoclaving period,larger sizes of TiO2 nanoparticles are prepared.(2) The nanoporous electrodes made from sintering smaller TiO2 nanoparticles show relatively poor IPCE and low absorption in UV Vis spectrum,(3) Higher IPCE can be achieved with TiO2 nanoporous electrodes made from sintering larger TiO2 nanoparticles.These electrodes are suitable for studying behavior of the photoelectrochemistry of dye sensitized nanoporous electrodes.     

水热法合成纳米TiO_2及其在Grtzel电池中的应用

By varying the hydrolysis and hydrothermal processing parameters in preparing TiO2 nanoparticles different sizes of TiO2 nanoparticles are obtained.(1) At higher autoclaving temperature,lower pH and longer autoclaving period,larger sizes of TiO2 nanoparticles are prepared.(2) The nanoporous electrodes made from sintering smaller TiO2 nanoparticles show relatively poor IPCE and low absorption in UV-Vis spectrum,(3) Higher IPCE can be achieved with TiO2 nanoporous electrodes made from sintering larger TiO2 nanoparticles.These electrodes are suitable for studying behavior of the photoelectrochemistry of dye sensitized nanoporous electrodes.     

聚3-甲基噻吩修饰硫化物量子点连接纳米结构TiO2膜的光电化学研究

采用原位化学法在纳米结构TiO₂膜上制备了量子点CdS, PbS (Q-CdS, Q-PbS), 并用电化学方法在TiO₂/Q-CdS, TiO₂/Q-PbS表面聚合3-甲基噻吩[poly(3-Methylthiophene, PMeT)]. 用光电化学方法研究了PMeT修饰Q-CdS, Q-PbS连接TiO₂纳米结构膜, 实验结果表明, PMeT和Q-CdS, Q-PbS单独修饰纳米结构TiO₂电极和PMeT修饰Q-CdS, Q-PbS连接纳米结构TiO₂电极的光电流产生的起始波长都向长波方向移动; 一定条件下在可见光区光电转换效率均较纳米结构TiO₂的光电转换效率有明显的提高; 聚3-甲基噻吩(PMeT)与Q-CdS, Q-PbS连接的纳米结构TiO₂之间存在p-n异质结. 在一定条件下p-n异质结的存在有利于光生电子/空穴的分离, 在本文实验条件下PMeT修饰Q-CdS, Q-PbS连接纳米结构TiO₂电极最高的单色光的光电转换效率分别为11%和7%.     

Dye-sensitized TiO2 nanotube solar cells: fabrication and electronic characterization

TiO2 nanotubes (TNTs) with large aspect ratio and large specific surface area were prepared from P25 (Nippon Aerosil) and applied to dye-sensitized titanium dioxide solar cells (DSSCs). Optimization of fabrication conditions, i.e., pH of the starting paste, sintering temperature for the TiO2 electrodes, electrolyte compositions of DSSCs gave the high conversion efficiency with improved open circuit voltage (V(oc)) and fill factor (FF) when compared to DSSCs made of P25. The evaluation of dye adsorption and the photo-injected electron transport such as electron diffusion coefficient (D) and electron lifetime (tau) in TNTs electrodes revealed that the higher efficiency resulted from increase of electron density with keeping much longer tau in TNTs electrodes than in P25 electrodes.     

Trapping of charge carriers in colloidal particles of self-assembled films from TiO(2) and poly(vinyl sulfonic acid)

Self-assembled electrodes consisting of TiO(2) nanoparticles and poly(vinyl sulfonic acid) (PVS) were prepared by the layer-by-layer (LbL) technique. The electrostatic interaction between the TiO(2) nanoparticles and PVS allowed the growth of visually uniform multilayers of the composite, with high control of the thickness and nanoarchitecture. The electrochemical and chromogenic properties of these TiO(2)/PVS films were examined in an electrolytic solution of 0.5 M LiClO(4)/propylene carbonate. The presence of two intercalation sites was noted during the positive potential scan, and they were attributed to different mobilities of charge carriers. Several charge/discharge cycles demonstrated the trapping of charge carriers in the TiO(2) sites. The absorbance change associated with the oxidation of the trapping sites was attributed to electronic transitions involving energy states in the gap band formed due to the strong distortion of the TiO(2) host. Using the quadratic logistic equation (QLE), it was possible to analyze the electronic intervalence transfer from Ti(3+) to Ti(4+). Using the parameters obtained from this fitting, the amount of trapping sites in the LbL film was also determined. Electrochemical impedance spectroscopy (EIS) data gave the time constant associated with diffusion and the trapping sites. The diffusion coefficient of lithium ions changed from ca. 4.5 x 10(-13) cm(2) s(-1) to 3.0 x 10(-14) cm(2) s(-1) for all the potential range applied, indicating that PVS did not hinder the ionic transport within the LbL film. Finally, on the basis of the spectroelectrochemical data and scanning electron micrographs, the trapping effects were attributed to the colloidal particles of Li(0.55)TiO(2).     

三甲川菁染料敏化TiO2纳米结构电极的光电化学

研究了三甲川菁染料敏化ＴｉＯ２ 纳米结构电极的光电化学行为．结果表明,使用该染料敏化可显著提高ＴｉＯ２ 纳米结构电极的光电流,使电极的吸收波长红移至可见光区,光电转换效率得到明显改善,ＩＰＣＥ值最高可达１２－１ ％ ．     

Capacitance and field-driven electron transport in electrochemically self-assembled nanoporous ZnO/dye hybrid films

Electrodeposited nanoporous ZnO/eosin Y hybrid films have been investigated in view of their potential applications in dye-sensitized solar cells and supercapacitors. Intensity-modulated photocurrent spectra were measured at different electrode potentials at films of different thicknesses. It was found that the results represent either the RC constant of the cell and surface recombination of photogenerated holes with electrons or the diffusion of photogenerated electrons and are dependent on the electron concentration in the ZnO, which is influenced by the film thickness, the electrode potential, and the light intensity. The results suggest that the porosity of the electrodeposited ZnO increases with the film thickness and the films therefore consist of two parts, a less porous part deposited in the first few minutes that exhibits field-driven electron transport and a more porous outer part where electron transport is by diffusion. The results are supported by frequency-dependent capacitance measurements, which also show that the material is suitable for supercapacitors.