强度调制光电流谱研究纳晶CdSe薄膜电极的界面电荷转移过程

用强度调制光电流谱（ＩＭＰＳ）研究纳晶ＣｄＳｅ薄膜电极在多硫化钠溶液中的界 面电荷转移性能．从不同外加电压和不同溶液浓度下的光电流谱响应所得到的参数归 一化稳态光电流和表面态寿命,分析了界面电荷的直接转移和间接转移过程以及电荷 复合过程,并与多晶ＣｄＳｅ薄膜电极的结果进行了比较．     

大粒径TiO2反射层对染料敏化太阳能电池性能改进

使用大粒径和小粒径两种纳晶TiO2制备双层纳晶薄膜电极,并应用于染料敏化太阳能电池中.用有机碱四甲基氢氧化铵做胶化剂制备的两种大粒径纳晶TiO2(粒径为250 nm和150 nm),用它们分别制备薄膜做为反射层;用小粒径纳晶TiO2(10-20 nm)来制备的纳晶多孔薄膜为底层膜,用于吸收大量的染料.研究表明,反射层的加入,大大提高了对光的反射率,改善了光电输出,提高了光电转换效率.     

光电流法研究TiO2薄膜表面吸附氧对光催化活性的影响

采用溶胶-凝胶法制备了锐钛矿型和金红石型TiO2薄膜, 利用光电流和XPS技术研究了薄膜表面吸附氧对不同晶型TiO2光催化活性的影响. 并通过降解纯的环己烷溶液的实验来评估不同晶型TiO2的光催化活性. 结果表明, 在相同条件下, 锐钛矿型TiO2比金红石型具有明显的光催化活性. 这是由于锐钛矿型TiO2比金红石型TiO2具有较强的吸附氧的能力, 同时其光生电子与空穴的复合率相对较小所致.     

染料敏化太阳电池中双层结构TiO2薄膜空间的电子分布与接触界面转移过程

采用电化学阻抗谱(EIS)研究了双层结构TiO2薄膜的电子积累和与电解液接触界面的电子转移过程. 通过制备纳米颗粒单层和纳米颗粒/亚微米颗粒双层2种不同微结构的TiO2薄膜电极, 对其电容分布、 局域态密度、 薄膜内部电子传输和固/液界面电子转移过程进行了研究. 分析了纳米颗粒/亚微米颗粒双层结构电极对染料敏化太阳电池(DSC)性能的影响. 结果表明, 一定数量的电子会积累在亚微米颗粒层中引起薄膜电极化学电容的增加. 在纳米颗粒层上端覆盖亚微米颗粒后降低了界面复合电阻, 但对薄膜电极的传输性能影响较小. 因此在筛选和制备DSC散射层材料时除应具有良好的光散射性能外, 还应考虑材料的化学电容和界面转移电阻等因素.     

柔性染料敏化太阳电池的制备和性能研究

柔性染料敏化太阳电池作为具有低生产成本的实用化技术受到高度重视.本文研究以金属钛为基底的纳晶TiO2薄膜电极和以导电涂层聚合物为基底的对电极组成的柔性染料敏化太阳电池.为提高光电转换效率,采用直流低场电泳沉积、直流和脉冲电压下的电化学阳极氧化及丝网印刷,结合高温烧结方法,制备金属钛为基底的纳晶TiO2薄膜电极和TiO2...     

染料敏化太阳能电池用TiO2薄膜电极的改性制备及光电化学性能

以钛酸四异丙酯为钛源, 用水热法合成制备了具有典型锐钛矿晶型的TiO2纳米材料. 采用金属镍掺杂和表面包覆一层氧化钕, 对TiO2薄膜电极进行改性研究. 实验结果表明, 所制备纳米TiO2颗粒较均匀, 粒径约为17~18 nm. 经镍掺杂后, 颗粒团聚粒径明显增大, 但是仍保持均匀状态和多孔结构. 与改性前的TiO2薄膜电极相比, 金属掺杂和表面包覆有助于光生电子和空穴有效地分离, 电池的短路光电流提高了16%, 光电转换效率提高了17%.     

酞菁与TiO2超微粒间的光诱导电子转移相互作用

带有负电荷取代基的四磺化酞菁化合物与 TiO2超微粒在溶液中通过静电相互吸引 ,能够形成基态复合物 .通过吸收光谱和荧光光谱 ,计算了磺化酞菁与 TiO2在溶液中的表观缔合平衡常数 K.与相应的烷氧基取代酞菁化合物作比较 ,并通过单光子计数技术测定染料荧光寿命 .结合荧光光谱 ,证明了磺化酞菁与 TiO2在溶液中的缔合作用 ,有利于激发态酞菁染料向半导体 TiO2的导带注入电子 ,从而发生分子间的电子转移反应 .将磺化酞菁吸附在 TiO2纳晶薄膜电极上 ,进行光电性能测试 .结果表明,染料敏化 TiO2纳晶薄膜电极光电响应的大小与染料在电极表面吸附的强弱有关 .     

Au掺杂对TiO_2薄膜表面态及电荷传输性能的影响

采用两步法合成了不同Au掺杂量的TiO_2薄膜材料,并通过循环伏安(CV)和电化学阻抗谱(EIS)探究了不同Au掺杂量TiO_2薄膜的表面态数量及其在禁带中的分布情况.借助强度调制光电流/电压谱(IMPS/IMVS)研究了薄膜内电子传输时间和寿命及界面电荷转移性能等.结果表明,适量Au(摩尔分数0.2%)的掺入可有效降低薄膜的表面态数量,优化表面态分布情况,提高电子在TiO_2/染料/电解质界面的电阻,从而改善电子的传输性能,提升太阳电池的光电转换效率.     

透明TiO2纳米管/FTO电极制备及表征

采用射频磁控溅射方法在透明导电玻璃(FTO)上沉积纯钛薄膜, 室温条件下在H3PO4+HF电解液中通过恒压阳极氧化方法得到TiO2纳米管阵列, 并通过场发射扫描电子显微镜(FESEM)、X射线衍射(XRD)、UV-Vis透射光谱以及光电化学的方法对纳米管阵列进行了表征. 研究表明, 在电压为20 V、氧化时间为50 min时, 钛薄膜转化为TiO2纳米管阵列, 管长约为380 nm, 内径约为90 nm, 管壁约为15 nm; 再经过500 ℃空气热处理6 h之后得到锐钛矿型的TiO2纳米管/FTO透明电极, 在可见光区的平均透过率约为80%, TiO2禁带宽度为3.28 eV, 发生了蓝移, 带尾扩展到2.6 eV; 此外, 对结晶前后的复合电极分别在暗态和紫外光下进行线性扫描和瞬态光电流测试, 结果表明, 结晶的电极表现出更好的光电转换性能; 施加阳极电压和紫外光照射都能够促进TiO2光生载流子有效分离,使电子迅速传至导电玻璃表面通过外电路形成光电流.     

苯封四聚苯胺/TiO2/ITO薄膜电极光致界面电荷转移

采用水解胶溶法和旋转涂膜法分别制备出TiO2纳米粒子溶胶和TiO2/ITO薄膜, 采用浸泡法制备出苯封四聚苯胺(聚苯胺)/TiO2/ITO薄膜电极. 利用表面光电压谱、光致循环伏安和光电流作用谱测定了TiO2的禁带宽度和表面态能级、聚苯胺的 HOMO-LUMO能级宽度和双极化子能级, 确定了聚苯胺/TiO2/ITO薄膜电极能带结构. 进一步分析了聚苯胺/TiO2/ITO薄膜电极的光电转换特性及光致界面电荷转移的机理.     

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.     

Studies on the interfacial charge transfer processes of nanocrystalline CdSe thin film electrodes by intensity modulated photocurrent spectroscopy

Interfacial charge transfer kinetics of the nanocrystalline CdSe thin film electrodes have been studied in sodium polysulfide solutions by intensity modulated photocurrent spectroscopy (IMPS). The interfacial direct and indirect charge transfer and recombination processes were analyzed in terms of the parameters: normalized steady state photocurrents and surface state lifetimes obtained by measuring the IMPS responses under different applied potentials and different solution concentrations. IMPS responses of polycrystalline CdSe thin film electrodes were also presented for comparison.     

Detection of inhomogeneous dye distribution in dye sensitised nanocrystalline solar cells by intensity modulated photocurrent spectroscopy (IMPS)

The transport of photoinjected electrons in dye sensitised nanocrystalline TiO₂ photovoltaic cells has been studied by intensity modulated photocurrent spectroscopy (IMPS). The existence of a dye-free TiO₂ region adjacent to the substrate contact in some cells has been inferred from the characteristic shape of the IMPS response associated with delayed transport of photoinjected electrons across the dye-free region. The delay is absent in the case of cells with uniform dye distribution. The IMPS response of a cell with inhomogeneous dye loading was fitted using a simple two-layer model to describe the dye distribution. The results indicate that IMPS is a useful diagnostic tool to detect inhomogeneous dye distributions in nanocrystalline solar cells.     

强度调制光电流谱/光电压谱及其应用

本文介绍了强度调制光电流谱/光电压谱(IMPS/IMVS)的基本原理和测试方法,综述了IMPS/IMVS在各个领域中的研究进展,特别是在染料敏化太阳电池和半导体电极中电子传输动力学的应用,评述了研究过程中的问题和存在的争议,并对IMPS/IMVS的未来应用进行了展望。     

Determination of the density and energetic distribution of electron traps in dye-sensitized nanocrystalline solar cells

Electron transport and recombination in dye-sensitized nanocrystalline solar cells (DSCs) are strongly influenced by the presence of trapping states in the titanium dioxide particles, and collection of photoinjected electrons at the contact can require times ranging from milliseconds to seconds, depending on the illumination intensity. A direct method of determining the density and energetic distribution of the trapping states responsible for slowing electron transport has been developed. It involves extraction of trapped electrons by switching the cell from an open circuit to a short circuit after a period of illumination. An advantage of this charge extraction method is that it is less sensitive than other methods to shunting of the DSC by electron transfer at the conducting glass substrate. Results derived from charge extraction measurements on DSCs (with and without compact TiO(2) blocking layers) are compared with those obtained by analysis of the open circuit photovoltage decay.     

Interpretation of apparent activation energies for electron transport in dye-sensitized nanocrystalline solar cells

Electron transport in dye-sensitized nanocrystalline solar cells appears to be a slow diffusion-controlled process. Values of the apparent electron diffusion coefficient are many orders of magnitude smaller than those reported for bulk anatase. The slow transport of electrons has been attributed to multiple trapping (MT) at energy levels distributed exponentially in the band gap of the nanocrystalline oxide. In the MT model, release of immobile electrons from occupied traps to the conduction band is a thermally activated process, and it might therefore be expected that the apparent electron diffusion coefficient should depend strongly on temperature. In fact, rather small activation energies (0.1-0.25 eV) have been derived from time and frequency resolved measurements of the short circuit photocurrent. It is shown that the MT model can give rise to such anomalously low apparent activation energies as a consequence of the boundary conditions imposed by the short circuit condition and the quasi-static relationship between changes in the densities of free and trapped electrons. This conclusion has been confirmed by exact numerical solutions of the time-dependent generation/collection problem for periodic excitation that provide a good fit to experimental data.     

Impedance analysis of the transport of counter ions at polypyrrole-Nafion composite electrodes

The ion transport accompanying the redox reactions of polypyrrole at a polypyrrole-Nafion composite electrode was investigated with systems containing specifically selected electrolytes. From the cyclic voltammetric and impedance data obtained, transport of cations was found to be responsible for the charge transfer process and parameters such as the charge transfer resistance, R_ct, the low frequency polymer resistance, R_e, the limiting capacitance, C_e and the diffusion coefficient, D_ct for the related cations were estimated. The electrochemical behaviour (i.e., electronic insulation and electronic conductance) of polypyrrole-Nafion composite electrodes was found to be the same as that of the polypyrrole electrodes, except that they appeared in regions of more negative potentials.     

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.     

Effect of high rates of mass transport on oxygen reduction at copper electrodes: Implications for aluminium corrosion

The reduction of oxygen at copper microelectrodes (25 μm diameter) in aqueous solution (pH 7) has been studied under conditions of high mass transport, similar to those experienced by μm sized copper-containing inclusions in aluminium alloys during corrosion. Contrary to previous studies at copper electrodes operating at lower mass transport rates, oxygen reduction limiting currents show an apparent number of electrons which decrease towards 2 as the mass transport rate increases (mass transfer coefficients up to ca. 0.55 cm s⁻¹), rather than a 4-electron process. These new data suggest that the treatment of oxygen reduction as a 4-electron transfer process at micron and smaller-sized copper intermetallics in aluminium alloys may require revision.     

利用强度调制光电流/光电压谱研究碳点/KOH电解液界面的动力学行为

通过强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术研究在光电分解水制氢体系中碳点光阳极与KOH电解液界面的动力学行为。结果表明,光强在30–90 m W·cm~(-2)范围内,界面的电子传输时间(τ_d)、电子寿命(τ_n)、电子扩散系数(D_n)、电子扩散长度(L_n)均没有变化;当光强增加到110和130 m W·cm~(-2)时,τ_d和τ_n延长,而D_n减小。实验表明,不同于Ti O_2/电解液等界面,碳点光电极/电解液界面中碳点电极存在的缺陷少,因此电子主要以无陷阱限制扩散方式传输为主。且在30–130 m W·cm~(-2)的光强范围内,与τ_d和τ_n相关的载流子收集效率(η_(cc))相近。