染料敏化二氧化钛薄膜电极的制备及性能研究
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摘要
本论文综述了湿化学太阳能电池的研究现状，在对其工作机理和存在问题等的总结基础上，针对染料吸附量不好的问题，提出向初始溶液中添加高聚物，以达到改善薄膜样品的微观结构，提高染料吸附量的目的。
用溶胶凝胶浸渍-提拉法制备样品，以聚乙二醇(PEG)和羟基纤维素(HPC)作为添加剂，来改变样品的微观结构。对样品进行红外测试以研究添加剂对二氧化钛溶胶的作用机理。用电镜(SEM和TEM)，椭偏仪和XRD研究TiO_2薄膜的微观结构。用光吸收谱的差谱来表征TiO_2薄膜的染料吸附性能，用I-V曲线测试TiO_2薄膜的光电化学性能。对以PEG为添加物的TiO_2薄膜样品的研究表明：PEG的加入得到了具有疏松多孔结构的TiO_2薄膜，但二氧化钛颗粒有些团聚。PEG的含量和热处理温度对TiO_2薄膜的微观结构均有影响。TiO_2薄膜的气孔率随PEG的加入量的增多而增大。在本研究范围内PEG含量为6.92×10~(-3)克PEG/克初始溶液样品的气孔率最高。450℃-550℃温度范围内热处理研究结果表明，500℃热处理样品具有最高气孔率。PEG的加入增加了染料的吸附量。具有最高气孔率的样品的染料吸附量最大。它的填充因子FF为0.359，比不加PEG的样品的填充因子高。所以，PEG改善了TiO_2薄膜样品的光电化学性能。
对以HPC为添加物的TiO_2薄膜样品的研究表明：
HPC的加入形成了粒径为20-120nm的TiO_2薄膜。少量HPC的加入使TiO_2薄膜的微观结构变的疏松，粒径降低。当HPC含量为3m时，粒径最小。HPC含量继续增加，TiO_2薄膜的结构又变的致密，粒径增大。本研究中小的二氧化钛晶粒导致了TiO_2的晶格畸变，进而增大了TiO_2的禁带宽度，表现在光吸收谱的蓝移。利用HPC凝胶的红外谱建立了HPC对TiO_2薄膜微观结构的影响机理的模型，并用此模型解释了HPC含量对TiO_2薄膜微观结构的影响规律。TiO_2薄膜表面的染料分子的吸附量也随HPC的加入量而改变。HPC含量为3m时，染料分子的吸附量最大。另外，TiO_2薄膜的填充因子也随HPC含量而变化，HPC含量为3m时，填充因子最大，为0.59，比未加添加剂和加PEG的TiO_2薄膜的都大。
选填充因子最大的TiO_2薄膜电极组装了太阳能电池。测得电池的填充因子FF为0.393，光电转换效率为0.3％。填充因子和光电转换效率较低是因为所用
浙江人学颀十学位论义
导电基板的导电性不够好和电池组装过程中的工艺损失。
另外，提出了复合薄膜电极的设想，制备了TIOZ／WO3多孔复合薄膜电极，
其填充因子高于 TO。薄膜电极。
In the thesis, the principle, problems and prospect of the wet-type solar cells were reviewed. Polymers were added in the initial solution to adjust the microstructure of films and to improve the adsorption of dye.
Titania films were prepared by the sol-gel dip-coating method, with polyethylene glycol(PEG) and hydroxypropylcellulose(HPC) used as the additives. The FTIR spectra were employed to investigate the anchoring mechanism of HPC on the titanium colloid. The microstructures of the films were analyzed by electrical microscope (SEM and TEM), ellipsometry and X-ray diffraction (XRD). The optical absorption spectra were used to investigate the dye adsorption property and the photoelectrochemical properties of titania films were measured via I-V analyzer. From the investigation of titania films with PEG as additive, several significant conclusions could be drawn: Titanium dioxide films with porous microstructure could be prepared using PEG as additive; almost no conglomeration were observed with the titanium particle ; the microstructure of titania films could be modulated by the amount of PEG and treating temperature; at the same time, the porosity of the film improved with the increase of PEG; For the specimen treated at different temperatures, the greatest porosity could be achieved when treated at 500癈; The adding of PEG could greatly increase the dye adsorption amount. In this work, the dye adsorption reached its highest value with the sample of the greatest porosity , with the fill factor (FF) of that sample was 0.359. Also, it was demonstrated that titanium films with PEG as additive showed better photoelectrochemical properties than titanium films without PEG.
For the titania films with HPC as additive, we had the following opinions: Titania films with the particle size ranging from 20nm to 120nm could be obtained with HPC as dispersant; A little amount of HPC promoted the formation of a loose structure of the films and the decrease of particle size; The particle size hit the lowest point when the amount of HPC was 3m; The structure of titania films became denser and the particle size increased with further adding of HPC in the solution. When the
-3 -
particle size was small, the aberration of crystal lattice appeared and the bandgap energy increased, which resulted in the blue shift of absorption in the spectrum. The mechanism of HPC's influence on the microstructure was studied via FTIR spectrum. The adsorption of the dye on the titania films is affected by the amount of HPC. The adsorption amount was greatest when the amount of HPC was 3m, with FF was 0.59. FF of the HPC added titania film was better than that of the PEG added film and the films without any additives.
At the basis of the above research, the sample with highest fill factor was chosen as electrode to fabricate solar cell. The FF was 0.393 and the n was 0.3%. the reason why FF and n. were lower than other solar cells was that the resistance of conducting substrate was high and the losses in the fabrication of the batteries .
The bicomponent films electrode was brought forward. The TiCVWOs bicomponent film was fabricated and the photoelectrochemical property was measured. The result showed that fill factor of bicomponent films electrode was higher than fill factor of titania electrode.
用溶胶凝胶浸渍-提拉法制备样品，以聚乙二醇(PEG)和羟基纤维素(HPC)作为添加剂，来改变样品的微观结构。对样品进行红外测试以研究添加剂对二氧化钛溶胶的作用机理。用电镜(SEM和TEM)，椭偏仪和XRD研究TiO_2薄膜的微观结构。用光吸收谱的差谱来表征TiO_2薄膜的染料吸附性能，用I-V曲线测试TiO_2薄膜的光电化学性能。对以PEG为添加物的TiO_2薄膜样品的研究表明：PEG的加入得到了具有疏松多孔结构的TiO_2薄膜，但二氧化钛颗粒有些团聚。PEG的含量和热处理温度对TiO_2薄膜的微观结构均有影响。TiO_2薄膜的气孔率随PEG的加入量的增多而增大。在本研究范围内PEG含量为6.92×10~(-3)克PEG/克初始溶液样品的气孔率最高。450℃-550℃温度范围内热处理研究结果表明，500℃热处理样品具有最高气孔率。PEG的加入增加了染料的吸附量。具有最高气孔率的样品的染料吸附量最大。它的填充因子FF为0.359，比不加PEG的样品的填充因子高。所以，PEG改善了TiO_2薄膜样品的光电化学性能。
对以HPC为添加物的TiO_2薄膜样品的研究表明：
HPC的加入形成了粒径为20-120nm的TiO_2薄膜。少量HPC的加入使TiO_2薄膜的微观结构变的疏松，粒径降低。当HPC含量为3m时，粒径最小。HPC含量继续增加，TiO_2薄膜的结构又变的致密，粒径增大。本研究中小的二氧化钛晶粒导致了TiO_2的晶格畸变，进而增大了TiO_2的禁带宽度，表现在光吸收谱的蓝移。利用HPC凝胶的红外谱建立了HPC对TiO_2薄膜微观结构的影响机理的模型，并用此模型解释了HPC含量对TiO_2薄膜微观结构的影响规律。TiO_2薄膜表面的染料分子的吸附量也随HPC的加入量而改变。HPC含量为3m时，染料分子的吸附量最大。另外，TiO_2薄膜的填充因子也随HPC含量而变化，HPC含量为3m时，填充因子最大，为0.59，比未加添加剂和加PEG的TiO_2薄膜的都大。
选填充因子最大的TiO_2薄膜电极组装了太阳能电池。测得电池的填充因子FF为0.393，光电转换效率为0.3％。填充因子和光电转换效率较低是因为所用
浙江人学颀十学位论义
导电基板的导电性不够好和电池组装过程中的工艺损失。
另外，提出了复合薄膜电极的设想，制备了TIOZ／WO3多孔复合薄膜电极，
其填充因子高于 TO。薄膜电极。
In the thesis, the principle, problems and prospect of the wet-type solar cells were reviewed. Polymers were added in the initial solution to adjust the microstructure of films and to improve the adsorption of dye.
Titania films were prepared by the sol-gel dip-coating method, with polyethylene glycol(PEG) and hydroxypropylcellulose(HPC) used as the additives. The FTIR spectra were employed to investigate the anchoring mechanism of HPC on the titanium colloid. The microstructures of the films were analyzed by electrical microscope (SEM and TEM), ellipsometry and X-ray diffraction (XRD). The optical absorption spectra were used to investigate the dye adsorption property and the photoelectrochemical properties of titania films were measured via I-V analyzer. From the investigation of titania films with PEG as additive, several significant conclusions could be drawn: Titanium dioxide films with porous microstructure could be prepared using PEG as additive; almost no conglomeration were observed with the titanium particle ; the microstructure of titania films could be modulated by the amount of PEG and treating temperature; at the same time, the porosity of the film improved with the increase of PEG; For the specimen treated at different temperatures, the greatest porosity could be achieved when treated at 500癈; The adding of PEG could greatly increase the dye adsorption amount. In this work, the dye adsorption reached its highest value with the sample of the greatest porosity , with the fill factor (FF) of that sample was 0.359. Also, it was demonstrated that titanium films with PEG as additive showed better photoelectrochemical properties than titanium films without PEG.
For the titania films with HPC as additive, we had the following opinions: Titania films with the particle size ranging from 20nm to 120nm could be obtained with HPC as dispersant; A little amount of HPC promoted the formation of a loose structure of the films and the decrease of particle size; The particle size hit the lowest point when the amount of HPC was 3m; The structure of titania films became denser and the particle size increased with further adding of HPC in the solution. When the
-3 -
particle size was small, the aberration of crystal lattice appeared and the bandgap energy increased, which resulted in the blue shift of absorption in the spectrum. The mechanism of HPC's influence on the microstructure was studied via FTIR spectrum. The adsorption of the dye on the titania films is affected by the amount of HPC. The adsorption amount was greatest when the amount of HPC was 3m, with FF was 0.59. FF of the HPC added titania film was better than that of the PEG added film and the films without any additives.
At the basis of the above research, the sample with highest fill factor was chosen as electrode to fabricate solar cell. The FF was 0.393 and the n was 0.3%. the reason why FF and n. were lower than other solar cells was that the resistance of conducting substrate was high and the losses in the fabrication of the batteries .
The bicomponent films electrode was brought forward. The TiCVWOs bicomponent film was fabricated and the photoelectrochemical property was measured. The result showed that fill factor of bicomponent films electrode was higher than fill factor of titania electrode.
引文
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