染料敏化TiO_2薄膜的结构及光电性质研究
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摘要
TiO_2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。本文采用磁控溅射的方法制备了TiO_2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TiO_2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TiO_2薄膜和染料敏化TiO_2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TiO_2,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TiO_2的禁带宽度;少量Al的掺入则有助于TiO_2薄膜表面形貌的改善并引起吸收边的蓝移。
通过对TiO_2电极吸收光谱的分析可知,TiO_2薄膜厚度的增加和Ti~(3+)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:TiO_2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,TiO_2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TiO_2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。
As a wide band gap semiconductor with innocuity,stabilization and cheapness,TiO_2 is one of the best materials for preparing the anodes of DSSC.In this work,DSSCs were fabricted by dye-sensitized TiO_2 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 TiO_2 increase owing to the thickening of TiO_2 thin films as well as the reducing of Ti~(3+).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(I_(sc)) increased attributed to the thickening of the TiO_2 thin films and the formation of anatase phase.The improvement of lattice defects and the doping of Al ions also enhanced the I_(sc).The Open-circuit voltage(V_(oc)) is related to the potential of the conduction band of TiO_2, which influences the dark current.Therefore,the V_(oc) decreased owing to the raising of dark current and the reducing of conduction band potential in TiO_2.The photoelectric conversion efficiency(η) determined by I_(sc),V_(oc) and FF together reached the maximum 2.47%when prepared with sputtering power of Al-doped at 5 W,but decreased sharply when the TiO_2 electrode had prepared with W-doped power at 15 W for introducing lower potential of conduction band.
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TiO_2,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TiO_2的禁带宽度;少量Al的掺入则有助于TiO_2薄膜表面形貌的改善并引起吸收边的蓝移。
通过对TiO_2电极吸收光谱的分析可知,TiO_2薄膜厚度的增加和Ti~(3+)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:TiO_2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,TiO_2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TiO_2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。
As a wide band gap semiconductor with innocuity,stabilization and cheapness,TiO_2 is one of the best materials for preparing the anodes of DSSC.In this work,DSSCs were fabricted by dye-sensitized TiO_2 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 TiO_2 increase owing to the thickening of TiO_2 thin films as well as the reducing of Ti~(3+).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(I_(sc)) increased attributed to the thickening of the TiO_2 thin films and the formation of anatase phase.The improvement of lattice defects and the doping of Al ions also enhanced the I_(sc).The Open-circuit voltage(V_(oc)) is related to the potential of the conduction band of TiO_2, which influences the dark current.Therefore,the V_(oc) decreased owing to the raising of dark current and the reducing of conduction band potential in TiO_2.The photoelectric conversion efficiency(η) determined by I_(sc),V_(oc) and FF together reached the maximum 2.47%when prepared with sputtering power of Al-doped at 5 W,but decreased sharply when the TiO_2 electrode had prepared with W-doped power at 15 W for introducing lower potential of conduction band.
引文
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