纳米晶TiO_2多孔薄膜光阳极的掺杂改性及其光电性能的研究
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摘要
能源与人类的生存和发展休戚相关,利用太阳能一直是人们梦寐以求的愿望。太阳能是一种取之不尽,用之不竭的无污染能源。从二十世纪五十年代开始特别是过去的十年中,世界光伏电池产业保持者50%的速度高速发展。相比于硅太阳能电池,染料敏化纳米晶太阳能电池是最近20年基于纳米技术发展起来的一种新型低成本太阳能电池,该电池被誉为最有应用前景的太阳能电池,特别是对于我们光伏产业的发展比较晚的国家来说,对这种新型电池进行研究和开发显得尤为重要。
TiO2作为一种无毒、稳定、廉价的宽禁带半导体是到目前为止制备染料敏化太阳电池(DSSC)光阳极性能最为优良的材料之一。DSSC的主要部分是一个TiO2│染料│电解质的三明治结构。本文采用磁控溅射的方法制备了TiO2薄膜,并将其敏化制备成DSSC。用原子力显微镜(AFM)、拉曼(Raman)光谱仪、紫外可见分光光度计和太阳能检测仪分别对TiO2薄膜的表面形貌、晶体结构、光学性质和DSSC的光伏性能进行了检测。研究了溅射功率、氧分压、掺杂等工艺对TiO2薄膜和染料敏化TiO2电极结构及光电性质的影响。
根据对拉曼光谱、透射光谱和AFM图的分析可知,在一个很小的溅射功率范围内沉积TiO2,Ti靶的溅射处于转变模式下,此时薄膜的沉积速率最大,并且开始形成锐钛矿结构；随着氧分压的增大,薄膜的表面形貌无明显变化,说明在溅射总气压不变时,溅射粒子到达基底的能量变化不大；掺W后,引入了较低导带电位的杂质能级,减小了TiO2的禁带宽度；少量Al的掺入则有助于TiO2薄膜表面形貌的改善并引起吸收边的蓝移。
通过对TiO2电极吸收光谱的分析可知,TiO2薄膜厚度的增加和Ti3+的减少均有利于染料吸附率的提高。通过对DSSC光伏性能的研究可以得到：TiO2晶体中金红石结构的形成有利于填充因子的增大；随着溅射功率的增大,TiO2薄膜厚度增大和锐钛矿形成均有助于短路电流的提高；而晶格缺陷的改善和铝的掺入也提高了短路光电流；开路电压则与TiO2的导带电位以及暗电流的大小有关,导带电位的降低、暗电流的增大降低了开路电压；光电转换效率由短路电流、开路电压和填充因子共同决定,掺杂Al的功率为5W时制备的样品的光电转换效率最高,为2.47%,而掺钨15W时,由于引入了低导带电位的离子,光电流显著下降,光电转换效率急剧降低。
Energy are related to the human existence and development, so making use of solar energy has been one dream. Solar energy is an inexhaustible and non-polluting energy. From the space applications of solar cells in 1950's to today's solar optoelectronic integreated buildings, especially the past decade, the PV industry in the world keep high growth rate of 50%. Compared to silicon solar cells,dye-sensitized solar cell is a new type of low-cost solar cell based on nano-technology development in the recent 20 years. This kind of solar cell are known as the most promising solar cells.Especially for the country whose development of PV industry are relatively late, this new type of battery research and development is very important。
As a wide band gap semiconductor with innocuity, stabilizaTiOn and cheapness, TiO2 is one of the best materials for preparing the anodes of DSSC. DSSC is a major part of the TiO2|dye| electrolyte sandwich structure.In this work, DSSCs were fabricted by dye-sensitized TiO2 thin films which had been deposited by dirrect current magnetron sputtering. The surface morphologies, crystal structure, optical characteristics and photoelectric conversion efficiency were characterized by atomic force microscopy (AFM), Raman spectrometer, UV-VIS spectrophotometer and solar detected instrment respectively. The effect of sputtering power, oxygen partial pressure and metal ion doping on photoelectric performance were studied.
From the analysis of Raman spectra, transimission spectra and AFM images, It is shown that deposiTiOn rate reached the largest maximum while anatase phase started to be formed, at the same time, the target plane was sputtered in transformaTiOn pattern to a small extent of powers. With the increase of oxygen partial power, the surface morphology varied very little, which proved that the energy of sputtered particle had little
change. With the increasing of the sputtering power and the doping of Al ions, The band gap reduced by doping with W in which exist lower conduTiOn band potential. However, doped with few Al contributed to the improvement of the surface morphologies and the blue shift of absopTiOn edge.
It is observed in the adsorpTiOn spectra that the adsorpTiOn onto TiO2 increase owing to the thickening of TiO2 thin films as well as the reducing of Ti3+. From the analysis of the photovoltaic performance, we can conclute to that the formaTiOn of rutile phase is beneficial to the raising of filling factor(FF). With the increasing of sputtering powers, the short-circuit current(ISC) increased attributed to the thickening of the TiO2 thin films and the formaTiOn of anatase phase. The improvement of lattice defects and the doping of Al ions also enhanced the ISC. The Open-circuit voltage(VOC) is related to the potential of the conducTiOn band of TiO2, which influences the dark current. Therefore, the Voc decreased owing to the raising of dark current and the reducing of conducTiOn band potential in TiO2. The photoelectric conversion efficiency(η) determined by ISC, VOC and FF together reached the maximum 2.47% when prepared with sputtering power of Al-doped at 5 W, but decreased sharply when the TiO2 electrode had prepared with W-doped power at 15 W for introducing lower potential of conducTiOn band.
TiO2作为一种无毒、稳定、廉价的宽禁带半导体是到目前为止制备染料敏化太阳电池(DSSC)光阳极性能最为优良的材料之一。DSSC的主要部分是一个TiO2│染料│电解质的三明治结构。本文采用磁控溅射的方法制备了TiO2薄膜,并将其敏化制备成DSSC。用原子力显微镜(AFM)、拉曼(Raman)光谱仪、紫外可见分光光度计和太阳能检测仪分别对TiO2薄膜的表面形貌、晶体结构、光学性质和DSSC的光伏性能进行了检测。研究了溅射功率、氧分压、掺杂等工艺对TiO2薄膜和染料敏化TiO2电极结构及光电性质的影响。
根据对拉曼光谱、透射光谱和AFM图的分析可知,在一个很小的溅射功率范围内沉积TiO2,Ti靶的溅射处于转变模式下,此时薄膜的沉积速率最大,并且开始形成锐钛矿结构；随着氧分压的增大,薄膜的表面形貌无明显变化,说明在溅射总气压不变时,溅射粒子到达基底的能量变化不大；掺W后,引入了较低导带电位的杂质能级,减小了TiO2的禁带宽度；少量Al的掺入则有助于TiO2薄膜表面形貌的改善并引起吸收边的蓝移。
通过对TiO2电极吸收光谱的分析可知,TiO2薄膜厚度的增加和Ti3+的减少均有利于染料吸附率的提高。通过对DSSC光伏性能的研究可以得到：TiO2晶体中金红石结构的形成有利于填充因子的增大；随着溅射功率的增大,TiO2薄膜厚度增大和锐钛矿形成均有助于短路电流的提高；而晶格缺陷的改善和铝的掺入也提高了短路光电流；开路电压则与TiO2的导带电位以及暗电流的大小有关,导带电位的降低、暗电流的增大降低了开路电压；光电转换效率由短路电流、开路电压和填充因子共同决定,掺杂Al的功率为5W时制备的样品的光电转换效率最高,为2.47%,而掺钨15W时,由于引入了低导带电位的离子,光电流显著下降,光电转换效率急剧降低。
Energy are related to the human existence and development, so making use of solar energy has been one dream. Solar energy is an inexhaustible and non-polluting energy. From the space applications of solar cells in 1950's to today's solar optoelectronic integreated buildings, especially the past decade, the PV industry in the world keep high growth rate of 50%. Compared to silicon solar cells,dye-sensitized solar cell is a new type of low-cost solar cell based on nano-technology development in the recent 20 years. This kind of solar cell are known as the most promising solar cells.Especially for the country whose development of PV industry are relatively late, this new type of battery research and development is very important。
As a wide band gap semiconductor with innocuity, stabilizaTiOn and cheapness, TiO2 is one of the best materials for preparing the anodes of DSSC. DSSC is a major part of the TiO2|dye| electrolyte sandwich structure.In this work, DSSCs were fabricted by dye-sensitized TiO2 thin films which had been deposited by dirrect current magnetron sputtering. The surface morphologies, crystal structure, optical characteristics and photoelectric conversion efficiency were characterized by atomic force microscopy (AFM), Raman spectrometer, UV-VIS spectrophotometer and solar detected instrment respectively. The effect of sputtering power, oxygen partial pressure and metal ion doping on photoelectric performance were studied.
From the analysis of Raman spectra, transimission spectra and AFM images, It is shown that deposiTiOn rate reached the largest maximum while anatase phase started to be formed, at the same time, the target plane was sputtered in transformaTiOn pattern to a small extent of powers. With the increase of oxygen partial power, the surface morphology varied very little, which proved that the energy of sputtered particle had little
change. With the increasing of the sputtering power and the doping of Al ions, The band gap reduced by doping with W in which exist lower conduTiOn band potential. However, doped with few Al contributed to the improvement of the surface morphologies and the blue shift of absopTiOn edge.
It is observed in the adsorpTiOn spectra that the adsorpTiOn onto TiO2 increase owing to the thickening of TiO2 thin films as well as the reducing of Ti3+. From the analysis of the photovoltaic performance, we can conclute to that the formaTiOn of rutile phase is beneficial to the raising of filling factor(FF). With the increasing of sputtering powers, the short-circuit current(ISC) increased attributed to the thickening of the TiO2 thin films and the formaTiOn of anatase phase. The improvement of lattice defects and the doping of Al ions also enhanced the ISC. The Open-circuit voltage(VOC) is related to the potential of the conducTiOn band of TiO2, which influences the dark current. Therefore, the Voc decreased owing to the raising of dark current and the reducing of conducTiOn band potential in TiO2. The photoelectric conversion efficiency(η) determined by ISC, VOC and FF together reached the maximum 2.47% when prepared with sputtering power of Al-doped at 5 W, but decreased sharply when the TiO2 electrode had prepared with W-doped power at 15 W for introducing lower potential of conducTiOn band.
引文
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