摘要
为了解决能源危机问题,太阳能的开发和利用已经成为世界范围内的研究热点。其中,提高半导体材料的光电转换效率是一个重要的研究课题。多金属氧酸盐(多酸),是一种良好的电子接受体,能够捕获半导体材料中的光生电子,从而减小半导体中载流子的复合,以提高其光电转换效率。本文以多酸为修饰组分,制备了各种半导体/多酸复合膜材料,并考察了它们的光电转换性能。具体如下:
1.利用交替沉积自组装技术将PW_(12)和TiO_2制备成纳米复合膜,并用紫外可见光谱、红外光谱和原子力显微镜表征。光电流测试表明,PW_(12)/TiO_2膜的光电流响应强度与膜的层数有关。另外,与单独TiO_2膜相比,PW_(12)/TiO_2复合膜展示了更高的光电流响应和对甲醇的光电催化能力,并且PW_(12)/TiO_2膜的能量转换效率比单独TiO_2膜的能量转换效率提高了50%。
2.采用交替沉积自组装技术将P_2W_(18)和聚烯丙基胺盐酸盐修饰的CdS(CdS-PAH)制备成纳米复合膜。与单独的CdS-PAH膜相比,CdS-PAH/P_2W_(18)复合膜的光电流响应强度和能量转换效率都提高了约1.5倍。这表明,多酸扮演了一个有效的电子接受体,减小了CdS中光生电子-空穴对的复合,从而提高了CdS的光电性能。我们通过荧光和表面光电压测试进一步证明了这个机理。
3.使用交替沉积自组装技术将SiMo_(12)和CuPc制备成纳米复合膜。在全光和可见光的照射下,CuPc/SiMo_(12)膜都展示了比单独CuPc膜更高的光电流响应。并且,与CuPc薄膜相比,SiMo_(12)/CuPc复合膜的能量转换效率提高了约8.7倍。表面光电压测试表明,CuPc和SiMo_(12)之间发生了有效的光生电荷转移。另外,CuPc/SiMo_(12)复合膜对水合肼展示了很好的光电催化性能。
4.制备了多酸(PW_(12)、P_2W_(18))/TiO_2复合膜并组装成光电池。通过光电流、I-V曲线、电化学阻抗谱和开路光电压测试分析了不同的种类和含量的多酸/TiO_2复合膜的光电性能、电子转移和复合性质。在TiO_2中加入少量的多酸时(0.75%),显示了比单独TiO_2膜更高的光电流响应,并且PW_(12)(0.75%)/TiO_2膜和P_2W_(18)(0.75%)/TiO_2膜的能量转换效率分别是TiO_2膜的2.6倍和1.6倍。电化学阻抗谱表明,多酸的引入降低了TiO_2中载流子的复合,增加了载流子的转移,以至提高了TiO_2的能量转换效率。而在TiO_2膜中引入过量的多酸(7.5%),多酸则变成了电子陷阱填充位点,从而降低了光电性能。
5.制备了以TiO_2和PW_(12)/TiO_2为光阳极的染料敏化太阳能电池。与TiO_2光阳极相比,0.75%-PW_(12)/TiO_2复合光阳极的能量转换效率提高了33%,而7.5%-PW_(12)/TiO_2光阳极的能量转换效率却降低了。这主要是因为:(1)0.75%-PW_(12)/TiO_2复合膜能够吸附更多的染料;(2)多酸的引入减小了光生载流子的复合,提高了载流子的转移。而7.5%-PW_(12)/TiO_2光阳极中,可能形成了电子陷阱填充位点,降低了光电性能。
The utilization of solar energy has become a hotspot in the world to solve the shortage offossil energy. Among them, an important research topic is to improve light-to-electricityconversion efficiency of the semiconductor materials. Polyoxometalates (POMs) are a kind ofgood electron acceptors. They can transport photogenerated electrons in the semiconductors,which reduces the electron-hole recombination and then improves the photovoltaic response.In this paper, we prepared a series of semiconductors/POMs composite films and investigatedtheir photovoltaic performances.
1. We fabricated the nanocomposite films of PW_(12)and TiO_2by the layer-by-layer (LbL)self-assembly method. These films were characterized by UV-vis spectroscopy, IR spectra,and atomic force microscopy. Photocurrent measurements suggested that the photocurrentresponse of the PW_(12)/TiO_2composite film was highly dependent on the deposited number oflayers. Furthermore, the PW_(12)/TiO_2composite film demonstrated the higher photocurrent andphotoelectrooxidation activity for methanol than the TiO_2film, and the power conversionefficiency of the PW_(12)/TiO_2film was improved by50%.
2. We prepared the composite thin films of P_2W_(18)andpoly(allylaminehydrochloride)-modified CdS (CdS-PAH) by the LbL self-assembly method.The CdS-PAH/P_2W_(18)composite film displayed a ca.1.5-fold increase in the photocurrentresponse and power conversion efficiency, as compared to the single CdS-PAH film. Thisindicated that P_2W_(18)could act as electron acceptors to efficiently suppress electron holerecombination in CdS and improve the photovoltaic performance. Such a mechanism wasfurther proven by experimental data of fluorescence emission spectra and surfacephotovoltage spectroscopy.
3. A composite film containing CuPc and SiMo_(12)was fabricated by the LbLself-assembly method. Under both solar light and visible light irradiation, the photocurrentresponse of the CuPc/SiMo_(12)film was markedly enhanced in comparison with those of theCuPc/PSS film, and the CuPc/SiMo_(12)film displayed a ca.8.7-fold increase in the powerconversion efficiency. Surface photovoltage measurements indicated that the photoinducedelectron transfer occurred between CuPc and POMs. Furthermore, the CuPc/POMs compositefilm exhibited good photoelectrocatalytic performance for the oxidation of hydrazine.
4. We prepared the POMs(PW_(12)、P_2W_(18))/TiO_2composite films and assembled the cells.We study on the photoelectrochemical performance, the electron transport and electron–holerecombination of the different content and type POMs in TiO_2film by measurements ofelectrochemical impedance spectroscopy (EIS), photocurrent responses and I–V curves. ThePOMs/TiO_2films at low POMs loadings (0.75%) displayed the enhanced photovoltaicperformance. The power conversion efficiency of PW_(12)(0.75%)/TiO_2film andP_2W_(18)(0.75%)/TiO_2film was2.6times and1.6times that of TiO_2film, respectively. EISmeasurements proved that introducing POMs into TiO_2film could reduce electron-holerecombination and facilitate photogenerated electron transfer, which enhanced the light-to-electricity conversion efficiency. However, the excessive content (7.5%) of POMscould almost cause a negative effect on photovoltaic performance due to electron trap fillingsites.
5. We fabricated the DSSCs based on both the only TiO_2photoanode and the PW_(12)/TiO_2photoanode. Compared to the TiO_2photoanode, the power conversion efficiency of0.75%-PW_(12)/TiO_2photoanode was improved by33%, while the7.5%-PW_(12)/TiO_2photoanodecould cause a negative effect on photovoltaic performance. The reasons were as follows:(1)the0.75%-PW_(12)/TiO_2film could adsord more dye;(2) The incorporating of PW_(12)into TiO_2photoanode could reduce electron-hole recombination and improve electron transfer. However,electron trap filling sites were present in the7.5%-PW_(12)/TiO_2photoanode.
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