电沉积并硫化合成FeS_2薄膜制备工艺及光电性能
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摘要
立方晶系的FeS_2(pyrite)是一种具有合适禁带宽度(Eg≈0.95eV)和较高光吸收系数(λ≤700mn时,α≥5×10~5cm~(-1))的半导体材料,其组元元素储量十分丰富、无毒,环境相容性好,而且在制备太阳电池时可以以薄膜形式使用,成本较低,与已有半导体材料相比,是一种较有研究价值的太阳能电池材料。
本文采用恒流电沉积及氧化处理制备Fe_3O_4先驱体,再经热硫化退火使先驱膜转变为多晶FeS_2薄膜的方法,研究了硫化时间、压力、温度等硫化参数对薄膜组织结构和光电性能的影响。主要研究结果如下:
采用Na_2S_2O_3和FeSO_4水溶液电沉积200℃热处理,可以制备多孔Fe_3O_4薄膜。
在400℃硫化2h即有形成FeS_2的反应发生。硫化时间较短时,FeS_2薄膜基体保持先驱膜的多孔形态。随硫化时间延长,FeS_2晶体生长进一步完善,晶粒持续长大而晶格常数减小,先驱膜多孔遗传形态渐趋不明显,薄膜的光吸收系数、电阻率和载流子浓度升高。当硫化时间超过10h后,电学性能变化不明显。
400℃硫化20h时,较低的硫化压力易导致硫化反应不充分,薄膜组织中Fe_3O_4和FeS_2共存,较高的硫化压力易导致基底膜层同时被硫化。当硫化压力高于20kPa时,Fe_3O_4先驱膜可充分转变成具有细小晶粒形态的FeS_2,薄膜形态也由多孔疏松演变为均匀平整。硫化压力的变化可以导致相变微观应力、点缺陷数量的变化,有可能造成薄膜几何连续性及缺陷能级分布的变化,结果导致了在40kPa硫压条件下FeS_2薄膜的光吸收系数出现极小值。
能明显发生FeS_2合成反应的温度为300℃,温度超过400℃可使反应更为充分。然而,过高的硫化温度也会产生一些不利影响,如500℃易造成基底的硫化,600℃易造成晶粒的粗化。随硫化温度升高,薄膜的结晶性能得到改善,薄膜的先驱体形态逐步消失,并表现出明显的颗粒状形貌。晶粒尺寸随硫化温度的升高而增大。FeS_2晶格常数在500℃硫化时趋近标准值并且薄膜表现出最大的光吸收系数。薄膜的电阻率随硫化温度的升高而增大,而载流子浓度的变化却与此相反。
The iron pyrite (FeS_2) with cubic crystal structure has attracted considerable attention as a potential candidate for the absorber materials for photovoltaic applications or thin-film solar cells due to its high absorption coefficient (α≥5×10~5cm~(-1) as λ≤700nm) and suitable energy band gap (Eg≈0.95eV). Moreover, the constituent components of FeS_2 are abundant, cheap and non-toxic.In the investigation, the precursive Fe_3O_4 films were prepared by constant current electrodepositing and oxidation treating. The polycrystalline FeS_2 films were obtained by annealing the Fe_3O_4 in sulfurizing atmosphere. The effects of the sulfidation parameters, such as temperature, time and sulfur vapor pressure, on the microstructure and photoelectrical characteristics of FeS_2 thin films were investigated. Some research results were obtained as follows:The polyporous Fe_3O_4 films can be obtained by electrodepositing in the aqueous solution of Na_2S_2O_3 and FeSO_4 and annealing at 200 ℃.The reaction transformed from Fe_3O_4 to FeS_2 occurs under the condition of sulfurizing at 400 ℃ only for 2h. The FeS_2 thin films prepared by sulfurizing the precursive Fe_3O_4 films for a shorter period show a polyporous morphology similar to the aspect of precursive films. With prolonging the sulfidation time, the conversion reaction from Fe_3O_4 to FeS_2 tends to be further complete to results in the FeS_2 grain size propagates, lattice parameter decrease and polyporous morphology disappears. As a result, the optical absorption coefficient, electrical resistivity and charge carrier concentration increase. The electrical properties show an insignificant change when the sulfidation time is longer than 10h.There is an insufficient sulfurizing reaction of the precursive Fe_3O_4 to result in a mixed film structure of FeS_2 and Fe_3O_4 at lower sulfur vapor pressures. However, there is an inexpectant sulfurizing reaction in the substrate films beneath the Fe_3O_4 films at higher sulfur vapor pressures. The precursive Fe_3O_4 films are completely transformed into the polycrystalline FeS_2 films by sulfurization annealing at the sulfur vapor pressures higher than 20kPa. The morphology of the FeS_2 films can change from porous and loose structure into
smooth and compact structure with increasing the sulfur vapor pressure. The change of the sulfur vapor pressure can alter the microstrain level of phase transformation and the concentration of crystal point defects consequently to result in the possible variations in film geometrical integrality and defect energy state distributed in forbidden band. Therefore, the optical absorption properties of FeS2 films can change with the sulfur vapor pressure and there is the minimum value of absorption coefficient as sulfurization annealing at 40kPa.Obvious reaction transformed from Fe3C>4 to FeS2 can occur during sulfidation annealing at 300 °C. A higher temperature than 400°C makes a nearly complete transformation. However, higher sulfidation temperature has a disadvantage effect on film quality. For example, some unexpected reaction products can easily be formed in the substrate film at 500°C and the FeS2 grains heavily coarsened at 600 °C. With increasing the sulfidation temperature, the grain size of the FeS2 thin films increases and the presursive morphology disappears to display the granular-crystalline aspect because the crystallizing characterization is improved in higher sulfidation temperatures. The approximately normal lattice parameter and the maximal absorption coefficient are obtained in the FeS2 film from the sulfidation annealing at 500 °C. Moreover, the electrical resistivity decreases while the carrier concentration increases with increasing the sulfidation temperature.
本文采用恒流电沉积及氧化处理制备Fe_3O_4先驱体,再经热硫化退火使先驱膜转变为多晶FeS_2薄膜的方法,研究了硫化时间、压力、温度等硫化参数对薄膜组织结构和光电性能的影响。主要研究结果如下:
采用Na_2S_2O_3和FeSO_4水溶液电沉积200℃热处理,可以制备多孔Fe_3O_4薄膜。
在400℃硫化2h即有形成FeS_2的反应发生。硫化时间较短时,FeS_2薄膜基体保持先驱膜的多孔形态。随硫化时间延长,FeS_2晶体生长进一步完善,晶粒持续长大而晶格常数减小,先驱膜多孔遗传形态渐趋不明显,薄膜的光吸收系数、电阻率和载流子浓度升高。当硫化时间超过10h后,电学性能变化不明显。
400℃硫化20h时,较低的硫化压力易导致硫化反应不充分,薄膜组织中Fe_3O_4和FeS_2共存,较高的硫化压力易导致基底膜层同时被硫化。当硫化压力高于20kPa时,Fe_3O_4先驱膜可充分转变成具有细小晶粒形态的FeS_2,薄膜形态也由多孔疏松演变为均匀平整。硫化压力的变化可以导致相变微观应力、点缺陷数量的变化,有可能造成薄膜几何连续性及缺陷能级分布的变化,结果导致了在40kPa硫压条件下FeS_2薄膜的光吸收系数出现极小值。
能明显发生FeS_2合成反应的温度为300℃,温度超过400℃可使反应更为充分。然而,过高的硫化温度也会产生一些不利影响,如500℃易造成基底的硫化,600℃易造成晶粒的粗化。随硫化温度升高,薄膜的结晶性能得到改善,薄膜的先驱体形态逐步消失,并表现出明显的颗粒状形貌。晶粒尺寸随硫化温度的升高而增大。FeS_2晶格常数在500℃硫化时趋近标准值并且薄膜表现出最大的光吸收系数。薄膜的电阻率随硫化温度的升高而增大,而载流子浓度的变化却与此相反。
The iron pyrite (FeS_2) with cubic crystal structure has attracted considerable attention as a potential candidate for the absorber materials for photovoltaic applications or thin-film solar cells due to its high absorption coefficient (α≥5×10~5cm~(-1) as λ≤700nm) and suitable energy band gap (Eg≈0.95eV). Moreover, the constituent components of FeS_2 are abundant, cheap and non-toxic.In the investigation, the precursive Fe_3O_4 films were prepared by constant current electrodepositing and oxidation treating. The polycrystalline FeS_2 films were obtained by annealing the Fe_3O_4 in sulfurizing atmosphere. The effects of the sulfidation parameters, such as temperature, time and sulfur vapor pressure, on the microstructure and photoelectrical characteristics of FeS_2 thin films were investigated. Some research results were obtained as follows:The polyporous Fe_3O_4 films can be obtained by electrodepositing in the aqueous solution of Na_2S_2O_3 and FeSO_4 and annealing at 200 ℃.The reaction transformed from Fe_3O_4 to FeS_2 occurs under the condition of sulfurizing at 400 ℃ only for 2h. The FeS_2 thin films prepared by sulfurizing the precursive Fe_3O_4 films for a shorter period show a polyporous morphology similar to the aspect of precursive films. With prolonging the sulfidation time, the conversion reaction from Fe_3O_4 to FeS_2 tends to be further complete to results in the FeS_2 grain size propagates, lattice parameter decrease and polyporous morphology disappears. As a result, the optical absorption coefficient, electrical resistivity and charge carrier concentration increase. The electrical properties show an insignificant change when the sulfidation time is longer than 10h.There is an insufficient sulfurizing reaction of the precursive Fe_3O_4 to result in a mixed film structure of FeS_2 and Fe_3O_4 at lower sulfur vapor pressures. However, there is an inexpectant sulfurizing reaction in the substrate films beneath the Fe_3O_4 films at higher sulfur vapor pressures. The precursive Fe_3O_4 films are completely transformed into the polycrystalline FeS_2 films by sulfurization annealing at the sulfur vapor pressures higher than 20kPa. The morphology of the FeS_2 films can change from porous and loose structure into
smooth and compact structure with increasing the sulfur vapor pressure. The change of the sulfur vapor pressure can alter the microstrain level of phase transformation and the concentration of crystal point defects consequently to result in the possible variations in film geometrical integrality and defect energy state distributed in forbidden band. Therefore, the optical absorption properties of FeS2 films can change with the sulfur vapor pressure and there is the minimum value of absorption coefficient as sulfurization annealing at 40kPa.Obvious reaction transformed from Fe3C>4 to FeS2 can occur during sulfidation annealing at 300 °C. A higher temperature than 400°C makes a nearly complete transformation. However, higher sulfidation temperature has a disadvantage effect on film quality. For example, some unexpected reaction products can easily be formed in the substrate film at 500°C and the FeS2 grains heavily coarsened at 600 °C. With increasing the sulfidation temperature, the grain size of the FeS2 thin films increases and the presursive morphology disappears to display the granular-crystalline aspect because the crystallizing characterization is improved in higher sulfidation temperatures. The approximately normal lattice parameter and the maximal absorption coefficient are obtained in the FeS2 film from the sulfidation annealing at 500 °C. Moreover, the electrical resistivity decreases while the carrier concentration increases with increasing the sulfidation temperature.
引文
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