The effects of pyridine derivative additives on interface processes at nanocrystalline TiO2 thin film in dye‐sensitized solar cells

2‐Methyl‐4‐propoxypyridine, a new pyridine derivative, has been synthesized and used as an additive in the liquid electrolyte of dye‐sensitized solar cells (DSSCs). Compared with 2‐methylpyridne and 4‐tert‐pyridine, they were employed to study the influence of the pyridine derivative additives on the rate of recombination at the electrode/dye/electrolyte interfaces and band edge shift of TiO₂, which were measured by time‐resolved mid‐infrared absorption spectroscopy and Mott–Schottky analysis, respectively. It was found that the rate of interfacial charge recombination was enhanced when the pyridine derivative additives were present in the electrolyte. Meanwhile, the additives caused a negative shift of the band edge. However, the net effect of pyridine derivative addition was to improve the open‐circuit photovoltage according to the photoelectrochemical measurement, indicating that negative shift of conduction band of TiO₂ was a predominant factor in improving the open‐circuit photovoltage. Also, the result was strongly supported by the dark current measurement. Therefore, it provides a microscopic account for the function of the pyridine derivative additives on the open‐circuit photovoltage enhancement of the DSSCs. Furthermore, the decrease of the short‐circuit photocurrent of the cells was also attributed to the slower dye regeneration due to the addition of additives from the results of cyclic voltammetry measurement. Copyright © 2007 John Wiley & Sons, Ltd.     

长链双烷基次膦酸作为共吸附剂修饰TiO_2光阳极

对TiO2/染料/电解质界面进行修饰是提高染料敏化太阳电池(DSC)性能的有效手段,其中引入共吸附剂有机小分子和染料共同吸附在TiO2表面是一种简单有效提高DSC性能的方法.本文合成了长链的双正十二烷基次膦酸(DDdPA)作为染料的共吸附剂应用于染料敏化太阳电池.通过红外光谱(FT-IR)表征DDdPA在TiO2表面的吸附;借助电化学阻抗谱(EIS)及强度调制光电流谱(IMPS)/强度调制光电压谱(IMVS)等技术表征了电子的传输与复合动力学过程.研究发现,DDdPA可以很好地与染料共同吸附在TiO2表面;与二(3,3-二甲基丁基)次膦酸(DINHOP)相比,DDdPA的引入可以更好地抑制TiO2/染料/电解质界面处的电子复合;在优化浓度配比下,DDdPA的引入有效提高了器件的电子寿命,使TiO2导带边负移约30 mV,最终使器件的开路电压提高了47 mV,光电转换效率提升约10%.     

Electron energy levels in semiconductor electrochemistry

The significance of the flat-band potential and the energetic position of the band edges at the semiconductor/electrolyte interface in semiconductor electrochemistry and photoelectrochemistry is pointed out. Different methods for determining these parameters experimentally are discussed, such as methods based on the measurement of the photovoltage or photocurrent, as well as the method for determining the flat-band potential from interfacial capacitance measurements. The capacitance-voltage relationship of the ideal semiconductor/electrolyte Schottky barrier is described. Subsequently, possible complications of the capacitance behavior are discussed, and conditions indicated under which the determination of the flat-band potential from non-ideal capacitance results is still possible. A critical survey is then given of flat-band data for some selected semiconductor electrodes (ZnO, CdS, GaP, GaAs, TiO₂, SrTiO₃), comprising a discussion of problems encountere, factors on which the flat-band potential depends and discrepancies between different results. Attempts to predict the flat-band potential and the position of the band edges from atomic electronegativity data are reviewed. The relationship between flat-band potential or band-edge position and electrochemical behaviour is considered, i.e., as far as the magnitude of the photovoltage as well as the electrochemical and photoelectrochemical reactivity are concerned.     

Recent progress in interface modification for dye-sensitized solar cells

Interface modification on the TiO₂/dye/electrolyte interface of dye-sensitized solar cells (DSCs) is one of the most effective approaches to suppress the charge recombination, improve electron injection and transportation, and thus ameliorate the conversion efficiency and stability of DSCs. Conventional research focusing on the photoanodes interface modification before sensitization in dye-sensitized solar cells has been carried out and reviewed. However, recent studies showed that post-modification after sensitization of the TiO₂ electrode also plays a significant role on the TiO₂/dye/electrolyte interface. This post-modification using the immersing method could deprotonate dye molecules, prohibit the dye aggregation and retard the recombination reaction. As a result, it has great influence on the devices’ photovoltaic performance. This interface modification could also provide an approach to broaden the response of the solar spectrum by introducing an alternative assembling structure. An in-situ meaning of using a co-adsorbent is employed to modify the interface in the DSCs, which could retard the aggregation of the dye molecules and enhance the conversion efficiency. In addition, electrolyte additives can be used to modify the TiO₂/dye/electrolyte interface through some unique mechanisms. Based on the background of interface modification of photoanodes before sensitization, this review introduces various interface modifications after sensitization of dye-sensitized solar cells and their mechanisms.     

染料敏化太阳电池中TiO2/染料/电解质界面的修饰

染料敏化太阳电池(DSC)作为新型太阳电池自问世以来受到了广泛关注, 其系统内部的接触界面尤其是TiO₂/染料/电解质界面一直是该领域的研究热点. 光敏染料的吸附以及电子的注入、传输和复合都发生在该界面, 其界面性质对DSC性能具有很大影响. 对染料敏化太阳电池中TiO₂/染料/电解质界面进行修饰可以有效抑制染料聚集和电子复合, 提高电子的注入效率与传输速率; 同时, 对TiO₂导带边的位置及染料吸附等也产生一定的影响, 最终提高电池的光电转换效率和稳定性. 本文主要从不同的修饰途径详细评述了TiO₂/染料/电解质界面修饰方法及机理研究进展,包括TiO₂光阳极的修饰改性、染料溶液中共吸附剂的引入和多种染料共敏化处理以及电解质中不同功能添加剂的应用. 指出了这些修饰方法目前存在的主要问题, 并对未来的发展方向进行了展望.     

CdS/TiO2–SrTiO3 heterostructure nanotube arrays for improved solar energy conversion efficiency

TiO₂–SrTiO₃ heterostructure nanotube arrays have been utilized as a novel oxide substrate for CdS quantum dot sensitized solar cells (QDSCs). SrTiO₃ on TiO₂ surface passivates surface states of TiO₂ and builds cascade-structured band alignment, which significantly reduces charge recombination at electrode surface. CdS/TiO₂–SrTiO₃ electrode exhibits a superior photoelectrochemical performance than CdS/TiO₂ electrode with ～ 70% increase in external quantum efficiency. This study suggests that the suppression of charge recombination at electrode surface is critical to efficient solar energy conversion.     

低温吸附制备Au-TiO2复合薄膜及其光电化学性质

在低温条件下将预先合成的Au溶胶吸附到TiO₂薄膜上以制备纳米Au-TiO₂复合薄膜,以超高分辨率场发射扫描电镜(FESEM)、X射线衍射(XRD)及X射线光电子能谱(XPS)表征Au-TiO₂膜,并在UV辐照下测定了Au-TiO₂薄膜电极的光电化学性质。纳米Au呈金属态,平均粒径为(4.3±1.2) nm,负载量高,均匀地沉积于TiO₂薄膜表面。光电化学测试表明,沉积纳米Au后,TiO₂电极的光生电流提高近5倍,光生电压明显向负值增大,说明纳米Au可增强光生载流子的分离效率,促进电荷在电极与溶液界面间的转移。Au-TiO₂电极的电荷传递法拉第阻抗(R_ct)是TiO₂电极的一半,说明负载的纳米Au粒抑制了光生电子-空穴的复合,提高了电极中载流子浓度。     

Mg(OOCCH(3))(2) as an electrolyte additive for quasi-solid dye-sensitized solar cells: with the purpose of enhancing both the photovoltage and photocurrent by modifying the TiO(2)/dye/electrolyte interfaces

The interface modification effect within quasi-solid dye-sensitized solar cells and the photovoltaic performance were investigated after the introduction of Mg(OOCCH(3))(2) as an additive into a polymer gel electrolyte. Electrochemical impedance spectroscopy showed that the addition of Mg(OOCCH(3))(2) into the polymer gel electrolyte can efficiently retard charge recombination at the TiO(2)/electrolyte interface. Mg(OOCCH(3))(2) in the electrolyte can also contribute to the enhancement of the incident photon-to-electron conversion efficiency by modifying the dye molecules. This results in an improvement in the photovoltage and photocurrent due to a barrier layer at the TiO(2)/electrolyte interface and the promotion of charge injection at the dye/TiO(2) interface, respectively. Photovoltaic measurements reveal that a conversion efficiency enhancement from 4.05% to 4.96% under 100 mW cm(-2) is obtained after the amount of Mg(OOCCH(3))(2) added was optimized.     

Correlating Photovoltaic Performance of Dye-Sensitized Solar Cell to the Film Thickness of Titania via Numerical Drift-Diffusion Simulations

The thickness of TiO₂ film is vital to realize the optimization on photovoltaic performance of dye sensitized solar cells (DSSCs). Herein, the process of charge separation in DSSCs was simulated by using a drift-diffusion model. This model allows multiple-trapping diffusion of photo-generated electrons, as well as the back reaction with the electron acceptors in electrolyte, to be mimicked in both steady and non-steady states. Numerical results on current-voltage characteristics allow power conversion efficiency to be maximized by varying the thickness of TiO₂ film. Charge collection efficiency is shown to decrease with film thickness, whereas the flux of electron injection benefits from the film thickening. The output of photocurrent is actually impacted by the two factors. Furthermore, recombination rate constant is found to affect the optimized film thickness remarkably. Thicker TiO₂ film is suitable to the DSSCs in which back reaction is suppressed sufficiently. On the contrary, the DSSCs with the redox couple showing fast electron interception require thinner film to alleviate the charge loss via recombination. At open circuit, electron density is found to decrease with film thickness, which engenders not only the reduction of photovoltage but also the increase of electron lifetime.     

Influence of light scattering particles in the TiO2 photoelectrode for solid-state dye-sensitized solar cell

A TiO₂ film was modified by adding light scattering particles and applied to an anode electrode in solid-state dye-sensitized solar cells (DSSCs). The TiO₂ films with 10 wt% (vs. TiO₂ weight) light scattering particles showed enhanced performance (28%), compared with nanocrystalline TiO₂ films, which were used as the controls. In particular, the photocurrent density (J_sc) reached approximately 12.6 mA/cm² under a one-sun condition. This was attributed to the light scattering effect and decrease in internal resistance through the macroporous structure with a minor loss of electron transport. However, in the case of a larger concentration of light scattering particles (>10 wt%), there was a decrease in the efficiency of DSSCs, which resulted from the decreased surface area and degraded electron transport and charge recombination properties, as confirmed by the measurement of stepped light-induced photocurrent and photovoltage transients. Furthermore, the diffusion properties and kinetics of the composite polymer electrolyte with the nanoporous and macroporous TiO₂ films were compared and evaluated from the electrochemical impedance spectra.     

Nanostructured CuO/SrTiO3 bilayered thin films for photoelectrochemical water splitting

Bilayered thin films of CuO/SrTiO₃ with varying thickness of CuO were deposited by sol–gel spin-coating technique on indium tin oxide substrate and used as photoelectrode in the photoelectrochemical cell for water splitting reaction. Maximum photocurrent density of 1.85 mA/cm² at ?0.9 V/saturated calomel electrode was exhibited by 590-nm-thick CuO/SrTiO₃ bilayered photoelectrode, which is approximately eight times higher than that for CuO and 30 times higher than that for SrTiO₃. The bilayered system offered increased photocurrent density and enhanced photoconversion efficiency, attributed to improved conductivity, which ameliorate separation of the photo-generated carriers at the CuO/SrTiO₃ interface and higher value of flatband potential. Details about synthesis and various characterisations involving X-ray diffraction and scanning electron microscopy have been discussed. An energy band diagram has been proposed to dwell upon the mechanism of charge carrier transfer across the interface.     

An Efficient Strategy for Boosting Photogenerated Charge Separation by Using Porphyrins as Interfacial Charge Mediators

Surface recombination at the photoanode/electrolyte junction seriously impedes photoelectrochemical (PEC) performance. Through coating of photoanodes with oxygen evolution catalysts, the photocurrent can be enhanced; however, current systems for water splitting still suffer from high recombination. We describe herein a novel charge transfer system designed with BiVO₄ as a prototype. In this system, porphyrins act as an interfacial‐charge‐transfer mediator, like a volleyball setter, to efficiently suppress surface recombination through higher hole‐transfer kinetics rather than as a traditional photosensitizer. Furthermore, we found that the introduction of a “setter” can ensure a long lifetime of charge carriers at the photoanode/electrolyte interface. This simple interface charge‐modulation system exhibits increased photocurrent density from 0.68 to 4.75 mA cm^?2 and provides a promising design strategy for efficient photogenerated charge separation to improve PEC performance.     

Lithium-modulated conduction band edge shifts and charge-transfer dynamics in dye-sensitized solar cells based on a dicyanamide ionic liquid

Lithium ions are known for their potent function in modulating the energy alignment at the oxide semiconductor/dye/electrolyte interface in dye-sensitized solar cells (DSCs), offering the opportunity to control the associated multichannel charge-transfer dynamics. Herein, by optimizing the lithium iodide content in 1-ethyl-3-methylimidazolium dicyanamide-based ionic liquid electrolytes, we present a solvent-free DSC displaying an impressive 8.4% efficiency at 100 mW cm(-2) AM1.5G conditions. We further scrutinize the origins of evident impacts of lithium ions upon current density-voltage characteristics as well as photocurrent action spectra of DSCs based thereon. It is found that, along with a gradual increase of the lithium content in ionic liquid electrolytes, a consecutive diminishment of the open-circuit photovoltage arises, primarily owing to a noticeable downward movement of the titania conduction band edge. The conduction band edge displacement away from vacuum also assists the formation of a more favorable energy offset at the titania/dye interface, and thereby leads to a faster electron injection rate and a higher exciton dissociation yield as implied by transient emission measurements. We also notice that the adverse influence of the titania conduction band edge downward shift arising from lithium addition upon photovoltage is partly compensated by a concomitant suppression of the triiodide involving interfacial charge recombination.     

Enhancing the Performance of Dye‐Sensitized Solar Cells with a Gold‐Nanoflowers Box

To improve the electron collection, electron lifetime, and light‐harvesting efficiency of dye‐sensitized solar cells simultaneously, Au nanoflowers were prepared and used to cover the entire TiO₂ film. Deposition of Au nanoflowers around the TiO₂ film formed a light‐scattering “box” that covered the entire TiO₂ film. Compared with a light‐scattering layer that only covers the top surface of TiO₂, the Au‐nanoflowers box exhibited better light‐harvesting efficiency due to omnidirectional light scattering, faster electron transport (attributed to the formation of electron channels between the metallic Au nanoflowers and the electron‐collection electrode), and slower charge recombination. As a consequence, the short‐circuit photocurrent and open‐circuit photovoltage were both enhanced significantly, which improved the power conversion efficiency from 8.12 to 10.91 % (34 %) when an Au‐nanoflowers box was wrapped around the photoanode.     

表面In掺杂TiO2的N719/TiO2-Inx%/FTO薄膜电极的光电转换效率

采用溶胶-凝胶法制备出In 表面修饰的TiO₂ (TiO₂-Inx%)纳米粒子, x%代表在In 掺杂的TiO₂样品中In³⁺与In³⁺和Ti⁴⁺离子摩尔百分含量. 利用二(四丁基铵)顺式-双(异硫氰基)双(2,2''-联吡啶-4,4''-二羧酸)钌(II)(N719)作为敏化剂, 制备出N719/TiO₂/FTO (氟掺杂锡氧化物)和N719/TiO₂-Inx%/FTO染料敏化薄膜电极. 光电转换效率实验表明, 在薄膜电极+0.5 mol·L^-1 LiI+0.05 mol·L^-1 I₂的三甲氧基丙腈(MPN)溶液+Pt 光电池体系中,N719/TiO₂-Inx%/FTO薄膜电极的光电转换效率均高于N719/TiO₂/FTO, 其中N719/TiO₂-In0.1%/FTO的光电转换效率比N719/TiO₂/FTO提高了20%. 利用X 射线衍射(XRD)、X 射线光电子能谱(XPS)、漫反射吸收光谱(DRS)、荧光(PL)光谱和表面光电流作用谱确定了TiO₂-Inx%样品中In3+离子的存在方式和能带结构; 利用表面光电流作用谱研究了N719/TiO₂-Inx%/FTO薄膜电极的光致界面电荷转移过程. 结果表明, In3+离子在TiO₂表面形成O-In-Cl_n (n=1, 2)物种, 该物种的表面态能级位于导带下0.3 eV处; 在光电流产生过程中, O-In-Cl_n (n=1, 2)表面态能级有效地抑制了光生载流子在TiO₂-Inx%层的复合, 促进了阳极光电流的增加, 从而导致N719/TiO₂-Inx%/FTO薄膜电极的光电转化效率高于N719/TiO₂/FTO, 并进一步讨论了光致界面电荷转移的机理.     

Performance of dye-sensitized solar cells based on various sensitizers applied on TiO2-Nb2O5 core/shell photoanode structure

The present investigation described the performance of dye-sensitized solar cells (DSSCs) based on various sensitizers applied on TiO₂-Nb₂O₅ core/shell photoanode film. The novel photoanodes were prepared using composite of TiO₂ nanoparticles (TNPs) and TiO₂ nanorods (TNRs) as core (TNPRs) layer with Nb₂O₅ shell coating. As well, tantalum pentoxide (Ta₂O₅), a blocking layer applied over the core/shell film. The DSSCs were fabricated based on various sensitizers namely zinc phthalocyanine, indoline, indigo carmine, zinc porphyrin, N719, coumarin NKX-2700, polymer dye, quantum dots (QDs), perylene and squaraine. The I–V characteristics of the DSSCs, photocurrent density (Jsc), open-circuit voltage (Voc), fill factor (FF), and photoconversion efficiency (PCE) were determined under illumination of AM 1.5 G. Electrochemical impedance spectroscopy (EIS) analysis is carried out to study the charge transport and life-time of charge carriers at photoanode/dye/electrolyte interface of the DSSCs. The I–V and EIS results explicated that the core/shell with blocking layers were able to alleviate the electron transport and suppressed charge recombination at photoanode/dye/electrolyte interface of the DSSCs. Concerning the sensitizers, PCE of the DSSCs exemplify the order N719 > zinc porphyrin > coumarin NKX-2700 > indoline > squaraine > QDs > zinc phthalocyanine > perylene > polymer dye > indigo carmine dye. The results of the present work demonstrated that among the sensitizers studied, N719 showed the highest PCE and fill factor. Besides, the metal-free organic sensitizers (coumarin NKX-2700 and indoline) exhibited comparable PCE as compared to N719.     

TiO2纳米薄膜电极中光生载流子传输特性研究

采用sol-gel法制备了均匀透明的锐钛矿相纳米TiO₂薄膜电极. 通过瞬态光电流谱研究了液相电解液中所制备电极内光生载流子的传输特性. 结果表明: 在TiO₂/电解液界面处, TiO₂颗粒表面存在两种能够捕获光生电子的表面态. 一种是O₂吸附所形成的浅能级表面态(S_o), 能级位于导带下0.5 eV以内, 其捕获光生电子的起始电位约为－0.4 V; 另一种是晶格氧离子形成的深能级表面态(S_c), 能级位于带隙中部, 起电子-空穴对复合中心的作用. 二者对光生电子的捕获效率与电解液pH值及电极电位(U)有关. 高于0.4 V的电位能够显著增大光生载流子的传输速率, 降低TiO₂薄膜费米能级(E_Fn), 有效抑制表面态对光生电子的捕获, 进而提高阳极光电流的大小和稳定性.     

Development of a Core–Shell Heterojunction TiO2/SrTiO3 Electrolyte with Improved Ionic Conductivity

Lately, semiconductor-membrane fuel cells (SMFCs) have attained significant interest and great attention due to the deliverance of high performance at low operational temperatures, <550 °C. This work has synthesized the nanocomposite core-shell heterostructure (TiO₂−SrTiO₃) electrolyte powder by employing the simple hydrothermal method for the SMFC. The SrTiO₃ was grown in situ on the surface of TiO₂ to form a core-shell structure. A heterojunction mechanism based on the energy band structure is proposed to explain the ion transport pathway and promoted protonic conductivity. The core-shell heterostructure (TiO₂−SrTiO₃) was utilized as an electrolyte to reach the peak power density of 951 mW cm⁻² with an open-circuit voltage of 1.075 V at 550 °C. The formation of core-shell heterostructure among TiO₂ and SrTiO₃ causes redistribution of charges and establishes a depletion region at the interface, which confined the protons′ transport on the surface layer with accelerated ion transport and lower activation energy. The current work reveals novel insights to understand enhanced proton transport and unique methodology to develop low-temperature ceramic fuel cells with high performance.     

Effect of single-wall carbon nanotubes on the properties of polymeric gel electrolyte dye-sensitized solar cells

A hybrid of polymer/dispersed single-wall carbon nanotubes was utilized in networking a novel composition of gel electrolyte in dye-sensitized solar cells. The gel is composed of polyethylene glycol, polyvinyl pyrrolidone, single-wall carbon nanotubes, and I^?/I₃ ^? as electrolyte. Formation of the less conductive polyiodide species in electrolyte was prohibited by the addition of single-wall carbon nanotubes leading to the excellent photovoltaic behavior of the cell under simulated standard illumination of the fabricated device owing to the increased open circuit voltage (0.47 V). Electrochemical impedance spectroscopy was employed to quantify the charge transport resistance and the electron lifetime at the TiO₂ conduction band. Charge transport resistances at the TiO₂/dye/electrolyte interface were determined for the cells consisting of the non-gel reference and our new gel electrolytes, and it was indicated that the charge recombination between injected electrons and electron acceptors (I₃ ^?) in the redox electrolyte was remarkably retarded. Electrochemical parameters obtained by the fitting showed all of the resistances increased as compared to liquid electrolyte dye-sensitized solar cells that can be related to the increase in viscosity of the gel, which hinders the ionic transportation through the electrolyte. These results were also confirmed by the electron lifetime analyses. The characteristic peak shifted to a lower frequency in the Bode phase plot for the cell containing gel electrolyte which is an indication of a longer electron lifetime in comparison with that of the cell containing very conventional liquid electrolyte.     

Correlation between Energy and Spatial Distribution of Intragap Trap States in the TiO2 Photoanode of Dye‐Sensitized Solar Cells

The energy and spatial distribution of intragap trap states of the TiO₂ photoanode of dye‐sensitized solar cells and their impact on charge recombination were investigated by means of time‐resolved charge extraction (TRCE) and transient photovoltage (TPV). The photoanodes were built from TiO₂ nanospheroids with different aspect ratios, and the TRCE results allowed differentiation of two different types of trap states, that is, deep and shallow ones at the surface and in the bulk of the TiO₂ particles, respectively. These trap states exhibit distinctly different characteristic energy with only a slight variation in the particle size, as derived from the results of the density of states. Analyses of the size‐dependent TPV kinetics revealed that in a moderate photovoltage regime of about 375–625 mV, the dynamics of electron recombination are dominated by shallow trap states in the bulk, which can be well accounted for by the mechanism of multiple‐trap‐limited charge transport.