染料敏化太阳电池中TiO2膜内电子传输和背反应特性研究

采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)研究电池内部电子传输机理和电子背反应动力学特性.利用理论表达式对不同TiO2多孔膜厚度(d)的电池实验数据进行了拟合,得到了电池的吸收系数(a)、电子扩散系数(Dn)、电子寿命(τn)、电子传输时间(τd)和入射单色光光电转化效率(IPCE)等微观参数的数值.研究表明:膜薄有利于加快电子传输,膜厚有利于提高光生电子浓度,进而从微观层面上研究了薄膜厚度对于电池内部电子产生、传输和复合过程的影响.     

双添加剂处理电子传输层富勒烯衍生物[6,6]-苯基-C61丁酸甲酯对钙钛矿太阳能电池性能的影响

有机无机复合钙钛矿材料被证明是非常出色的光伏材料,目前主要通过优化钙钛矿材料的结晶和形貌来提高钙钛矿太阳能电池的效率.而对于电荷传输层,特别是p-i-n结构中电子传输层的研究相对较少.因此,本文制备了结构为ITO/PEDOT:PSS/CH3NH3Pb I3/PCBM/Al的钙钛矿太阳能电池通过在电子传输层富勒烯衍生物[6,6]-苯基-C61丁酸甲酯(PCBM)中添加聚苯乙烯(PS)和1,8-二碘辛烷(DIO)使得钙钛矿太阳能电池的光电转换效率从10.8%提升到了12.5%.分析了性能提高的原因主要是:1)添加剂PS的加入提升了PCBM的黏度,从而形成了质量更高、更平滑的膜层,这有利于抑制电子和空穴在钙钛矿层和电子传输层之间的复合;2)添加剂DIO的加入改善了电子传输层的形貌,有利于电荷的分离、传输和收集.研究结果表明用成本较低的添加剂处理可以改善电子传输层的形貌和膜层的质量达到了改善电荷传输特性的效果提升了钙钛矿太阳能电池的效率为提升钙钛矿太阳能电池性能提供了一条可行的路径.     

基于小分子NDT高效异质结的超快动力学研究（特邀）（英文）

利用飞秒瞬态吸收光谱对三个经不同处理且光电性能有明显差异的NDT基异质结薄膜(无己基取代混合膜,己基取代混合膜以及己基取代并做溶剂退火处理的混合膜)进行了研究。结果显示这三个异质结薄膜,其电荷分离态大部分都是由激子态直接演化来的,并没有经过电荷转移态。在这三个混合膜中,己基取代并做溶剂退火处理的混合膜表现出最大电荷分离产率,己基取代但不经过溶剂退火处理的混合膜拥有最长的电荷分离态寿命。结合它们的电子-空穴迁移率,从动力学的角度给出了己基取代及溶剂退火处理增强光电转换效率的原因在于提高了电荷分离态寿命、增强了电荷分离产率以及平衡了电子-空穴迁移率。此研究可为将来优化光电转换效率提供参考。     

低能电子束照射接地绝缘薄膜的负带电过程

为揭示低能电子束照射接地绝缘薄膜的负带电过程及其机理,建立了同时考虑电子散射与电子输运的计算模型,综合Monte Carlo方法和有限差分法进行了数值模拟,获得了内部空间电荷、泄漏电流和表面电位随电子束照射的演化规律.结果表明,入射电子因迁移、扩散效应会超越通常的散射区域产生负空间电荷分布,并经过一定的渡越时间后到达接地基板,形成泄漏电流,负带电暂态过程则随着泄漏电流的增加而趋于平衡.在平衡状态下,泄漏电流随电子束能量和电流而增大;薄膜净负电荷量和表面电位随膜厚而增加、随电子迁移率的增大而降低,随着电子束 关键词： 绝缘薄膜 电子束照射 带电效应 数值模拟     

纳米TiO2颗粒/亚微米球多层结构薄膜内电荷传输性能研究

本文主要利用TiO₂亚微米球较强的光散射特性设计了纳米TiO₂颗粒/亚微米球多层结构光阳极, 并借助强度调制光电流谱(intensity-modulated photocurrent spectroscopy)、电化学阻抗谱(electrochemical impedance spectroscopy)和入射单色光光电转化效率(incident photon-to-current conversion efficiency), 研究亚微米球的引入对多层结构薄膜内缺陷态、电子传输时间、电子收集效率和界面电荷转移性能的影响. 强度调制光电流谱反映出亚微米球表面缺陷态少, 但其颗粒间接触不紧密, 导致在接触部位形成了势垒, 阻碍了电子的传输, 导致电子传输时间增长. 电化学阻抗谱结果表明不同多层结构电池界面复合无明显差别, 同时底层采用纳米TiO₂ 透明薄膜结构的电池, 其光利用率要明显高于底层采用亚微米球薄膜结构的电池, TiO₂费米能级电子填充水平也相对增大, 使得电池的光电转换效率得到提升. 多层结构复合薄膜电荷传输和光伏特性的研究, 为高效染料敏化太阳电池光阳极设计提供了实验基础.     

Stage2沉积速率对低温生长CIGS薄膜特性及器件的影响

研究了三步法第二步沉积速率对低温生长Cu(In,Ga)Se₂薄膜结构、 电学特性和器件特性的影响. 通过改变第二步沉积速率发现, 提高沉积速率可以显著促进薄膜晶粒生长, 提高晶粒紧凑程度降低晶界复合, 同时有效改善两相分离现象, 提高电池的开路电压和短路电流, 有助于Cu(In,Ga)Se₂电池光电转换效率的提高. 但同时研究表明, 随着第二步沉积速率的增加, 会促进暂态Cu_2-xSe晶粒的生长, 引起Cu(In,Ga)Se₂薄膜表面粗糙度增大, 并阻碍Na向Cu(In,Ga)Se₂薄膜表面的扩散, 造成施主缺陷钝化效应降低, 薄膜载流子浓度下降和电阻率升高, 且过高的沉积速率会引起电池内部复合增加并产生分流路径, 造成开路电压下降进而引起电池效率恶化. 最终, 通过最佳化第二步沉积速率, 在衬底温度为420℃时, 得到最高转换效率为11.24%的Cu(In,Ga)Se₂薄膜太阳电池.     

磁控溅射Cl掺杂CdTe薄膜的孪晶结构与电学性质

CdTe用作薄膜太阳能电池吸收层需要经过氯处理才能得到高的光电转换效率,其中Cl原子的作用机理仍然没有完全被理解.实验发现Cl原子主要偏聚在CdTe晶界处,对晶界有钝化作用,而有第一性原理计算认为Cl原子掺入CdTe晶格能够引入浅能级提高光电转换效率.为了验证Cl原子掺杂是否对CdTe的光电转换效率有益,本文通过磁控溅射制备了100 ppm(ppm=1/1000000)Cl原子掺杂的CdTe(CdTe:Cl)薄膜并研究了薄膜的晶体结构与电学性质,同时对比了正常氯处理的无掺杂CdTe薄膜与CdTe:Cl薄膜之间的性质区别.实验发现Cl原子掺杂会在CdTe:Cl中形成大量仅由几个原子层构成的孪晶,电子和空穴在CdTe:Cl薄膜中没有分离的传导通道,而在氯处理后的CdTe薄膜中电子沿晶界传导,空穴沿晶粒内部传导.磁控溅射沉积的CdTe:Cl多晶薄膜属于高阻材料,退火前载流子迁移率很低,退火后载流子浓度降低到本征数量级,电阻率提高.CdTe:Cl薄膜电池效率远低于正常氯处理的无掺杂CdTe薄膜电池效率.磁控溅射制备的非平衡重掺杂CdTe:Cl多晶薄膜不适合用作薄膜太阳能电池的吸收层.     

有机光伏电池物理性能的模拟

在分析有机聚合物光伏器件物理工作过程的基础上,依据光学原理和扩散理论建立了非相干光吸收模型和激子传输模型. 模拟了限制光伏效率的光学吸收和激子扩散两个主要过程,获得了薄膜厚度与光学吸收、转换效率之间的函数关系,为增强有机薄膜的光学吸收、激子分离与传输并获得高转换效率的有机光伏电池奠定理论基础. 关键词： 有机光伏电池 光学吸收 激子扩散 模拟     

钙钛矿太阳能电池中S形伏安特性研究

本文从理论模拟和实验角度研究了钙钛矿太阳能电池的伏安特性, 并着重探讨了由于界面电荷输运受限而产生的S形特征. 理论模拟表明, 当电池界面电荷输运速度逐渐降低时, 出现界面电荷积累, 影响电池输出性能. 实验研究表明, 当电池的背接触, 光阳极等界面电荷输运速度受限时, 即出现S形伏安特性, 降低电池效率. 然而, 由于电子和空穴在界面输运性质方面的差异, 以及电池中可能存在的独特的界面能带结构, 不同界面电荷输运受限而产生的S形伏安曲线又各具特征, 与电池内部实际的电荷分布以及输运方向有关. 本文的研究结果有助于阐明钙钛矿太阳能电池中存在的影响电荷输运的界面因素, 进而为界面设计和界面优化提供理论依据.     

非晶硅太阳电池宽光谱陷光结构的优化设计

陷光是改善薄膜太阳电池光吸收进而提高其效率的关键技术之一. 以非晶硅（α-Si）薄膜太阳电池为例,设计了一种新的复合陷光结构：在Ag背电极与硅薄膜之间制备一维Ag纳米光栅,并通过保形生长在电池前表面沉积织构的减反膜. 采用有限元数值模拟方法,研究了该复合陷光结构对电池光吸收的影响,并对Ag纳米光栅的结构参数进行了优化. 模拟结果表明：该复合陷光结构可在宽光谱范围内较大地提高太阳电池的光吸收;当Ag纳米光栅的周期P为600 nm,高度H为90 nm,宽度W为180 nm时,在AM1.5光谱垂直入射条件下α-Si薄膜电池在300–800 nm波长范围内总的光吸收较无陷光结构的参考电池提高达103%,其中在650–750 nm长波范围内的光子吸收率提高达300%以上. 结合电场强度分布,对电池在各个波段光吸收提高的物理机制进行了分析. 另外,该复合陷光结构的引入,还较大地改善了非晶硅电池对太阳光入射角度的敏感性. 关键词： 非晶硅太阳电池 陷光 银纳米光栅 数值模拟     

Effects of ZnO coating on the performance of TiO2 nanostructured thin films for dye-sensitized solar cells

ZnO-coated TiO₂ (ZTO) thin films were deposited on ITO substrates by a sol–gel method for application as the work electrode for dye-sensitized solar cells (DSSCs). The I–V curve and the incident photon-to-current conversion efficiency (IPCE) value of DSSCs for ZTO thin films were studied and compared with single TiO₂ films. The results show that the short-circuit photocurrent (J _sc) and open-circuit voltage (V _oc) values increased from 3.7 mA/cm² and 0.68 V for the DSSCs with a single TiO₂ film to 4.5 mA/cm² and 0.72 V, respectively, for the DSSCs with a ZTO thin film. It indicated that the DSSCs with a ZTO thin film contributed to provide an inherent energy barrier that suppressed charge recombination significantly. In addition, the higher IPCE value in the ZTO thin film is attributed to the better charge separation by a fast electron transfer process using two semiconductors with different conduction band edges and energy positions.     

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     

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.     

Electrochemical properties of TiO2 nanoparticle/nanorod composite photoanode for dye-sensitized solar cells

A unique composite of TiO₂ nanoparticles (NPs) and nanorods (NRs) has been used to fabricate a photoelectrode for developing dye-sensitized solar cells (DSSCs) with higher sensitivity. The TiO₂ nanorods were synthesized using a mechanical process, in which electrospun TiO₂ nanofibers was grinded in a controlled way to obtain uniform size distribution. The characteristics of electron transport, recombination lifetime and charge collection were investigated by intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS). Photoelectrodes prepared with the composites of NRs and NPs showed significant improvements in electron transportation compared to only NP photoelectrodes, which would enhance the photovoltaic performance of DSSCs. IMPS and IMVS measurements show that fast electron transport and slightly decreased recombination lifetime resulted in the improvement of efficiency. The highest energy conversion efficiency obtained from the photoelectrodes fabricated with the as-prepared rutile TiO₂ nanofibers at 5 wt% NR content was up to 6.1% under AM1.5G solar illumination. The results demonstrate that the composite nanostructure can take advantage of both the fast electron transport of the nanorods and the high surface area of the nanoparticles.     

Dye-sensitized solar cells based on trench structured TiO2 nanotubes in Ti substrate

We have proposed dye-sensitized solar cells (DSSCs) with trench-type TiO₂ nanotube structure to improve the low device efficiency of conventional TiO₂ nanotube DSSCs using Ti substrate. Compared to the conventional standing-type TiO₂ nanotube structure based DSSCs, the trench-type TiO₂ nanotube structure based DSSCs have shown an improvement of device efficiency of approximately 40% due to the large increase of Jsc. In the trench-type TiO₂ nanotube structure, the contact area between the TiO₂ nanotube sidewall and the Ti substrate is significantly increased. This increase of contact area provides more charge transport paths than exist in the conventional standing-type TiO₂ nanotube structure and reduces the electrical resistance between the Ti substrate and the TiO₂ nanotubes. Therefore, the remarkable increase of Jsc is the result of the charge collection efficiency, which is improved due to the increase of contact area between the TiO₂ nanotube sidewall and the Ti substrate in the trench-type TiO₂ nanotube structure. The fabrication of the trench-type TiO₂ nanotube structure is an effective manufacturing process for improving the device efficiency of TiO₂ nanotube based DSSCs using Ti substrate. DSSCs having an 11.9 μm thick trench-type TiO₂ nanotube structure have shown an efficiency of 5.74%.     

Explanation of Effect of Added Water on Dye-Sensitized Nanocrystalline TiO2 Solar Cell： Correlation between Performance and Carrier Relaxation Kinetics

Time-resolved mid-IR transient absorption spectroscopy is employed to explore the mechanism of improving the performance of dye-sensitized TiO2 solar cell （DSSC） when a certain amount of H2 0 is added into the electrolyte. The relaxation kinetics of dye-sensitized TiO2 nanocrystalline film and the corresponding DSSC performance are investigated under different conditions. It is found that the interracial charge recombination is retarded and electron injection efficiency is increased in the water vapour and in the electrolyte when D20 is added. The values of open-circuit photovoltage Voc and the short-circuit photocarrent Jsc of the cells are linearly correlated to the product of the two decay time constants. We also observed that Voc well correlates with electron injection efficiency. It provides a preliminary microscopic account for the function of the added water in improving the performance of DSSCs.     

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.     

Analysis of electron recombination in dye-sensitized solar cell

A steady-state numerical model of dye-sensitized solar cell is based on continuity and transport equations for electrons, iodide and triiodide ions. The cell model consists of an active layer, where photovoltaic effect including diffusion of electrons in mesoporous TiO₂ and ions in electrolyte takes place, and a bulk electrolyte layer, where only ions diffuse. Exponential distribution of trap states in TiO₂ and Gaussian distributions of energy levels in the electrolyte within active layer are included in modeling of the recombination dynamics, according to Shockley-Read-Hall statistics and Marcus-Gerischer electron transfer theory. Recombinations at the front contact and a voltage drop at the platinum covered back contact are included in the model. Simulation results are compared with the measured current-voltage characteristics at different light intensities. In particular, light intensity dependence of open circuit voltage is studied over 4 decades. Optimization of cell efficiency regarding active layer and electrolyte layer thickness is carried out. Simulation results show that best efficiency is achieved when electrolyte layer thickness is minimized as much as possible and that active layer thickness is traded off with respect to recombination rates and/or diffusion limited current determined with the selection of the electrolyte.     

Low resistance dye-sensitized solar cells based on all-titanium substrates using wires and sheets

Low resistance dye-sensitized solar cells (DSSCs) based on all-titanium substrates were proposed in this paper. To minimize the internal resistance of DSSCs, the titanium wires and titanium sheets were used as the substrates of the photoanode and the counter electrode, respectively. Compared with the FTO substrate, titanium wires could absorb much diffused light by back reflection since the reflectivity in the titanium sheet was highly increased up to 53.12%. Furthermore, the transmittance of the front cover was increased by 13.2% using the super white glass instead of FTO substrate. The thickness of TiO₂ thin film coated on titanium wire was optimized to achieve a high cell performance. The efficiency of 5.6% for the cell was obtained with a J_sc of 15.41 mA cm⁻², V_oc of 0.59 V, and FF of 0.62. The results showed that the titanium-based DSSCs had superiority for producing the large-scale DSSCs without metal grid line.     

Influence of TiO2 nanotube morphology and TiCl4 treatment on the charge transfer in dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) were fabricated using TiO₂ nanoparticles (NPs), TiO₂ nanotube arrays (NTAs), and surface-modified NTAs with a TiCl₄ treatment. The photovoltaic efficiencies of the DSSCs using TiO₂ NP, NTA, and TiCl₄-treated NTA electrodes are 4.25, 4.74, and 7.47 %, respectively. The highest performance was observed with a TiCl₄-treated TiO₂ NTA photoanode, although in the case of the latter two electrodes, the amounts of N719 dye adsorbed were similar and 68 % of that of the NP electrode. Electrochemical impedance measurements show that the overall resistance, including the charge–transfer resistance, was smaller with NTA morphologies than with NP morphologies. We suggest that a different electron transfer mechanism along the one-dimensional nanostructure of the TiO₂ NTAs contributes to the smaller charge–transfer resistance, resulting in a higher short circuit current (J _sc), even at lower dye adsorption. Furthermore, the TiCl₄-treated NTAs showed even smaller charge–transfer resistance, resulting in the highest J _sc value, because the downward shift in the conduction band edge improves the electron injection efficiency from the excited dye into the TiCl₄-treated TiO₂ electrodes.