太阳能电池CuInS_2薄膜和ZnS薄膜的制备与性能研究
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摘要
CuInS2(CIS)作为一种Ⅰ-Ⅲ-Ⅵ2型无机三元半导体化合物,是直接带隙的半导体,吸收系数较大,大约为104-105cm-1,其光学禁带宽度为1.50 eV左右,非常接近太阳能电池材料的最佳禁带宽度1.45 eV。与CuInSe2、CuInGaSe2、CdTe等化合物薄膜太阳能电池材料相比,CuInS2不含任何有毒的成分,是一种非常具有发展前途的太阳能电池材料。
目前,CIGS基薄膜太阳能电池的制备多采用CdS薄膜作为缓冲层,但CdS的薄膜禁带宽度只有2.4 eV,对电池吸收层的短波响应有一定的影响,而且CdS中的Cd是有毒重金属,与之相应的安全措施也增大了工业化成本,CdS的使用也不利于环境保护。因此,研究和开发无镉CIS/CIGS太阳电池已成为全球研究此类电池的热点。ZnS是一种n型Ⅱ-Ⅵ族宽禁带直接带隙半导体化合物,ZnS薄膜因其对环境友好,宽光学带隙(3.5-3.8 eV),制备成本低廉,而成为替代CdS薄膜缓冲层的优选材料之一。
论文围绕CuInS2薄膜太阳能电池材料进行了相关研究。采用磁控溅射法在玻璃衬底上制备了Mo背电极；采用了磁控溅射沉积铜铟合金预置膜,再进行N2保护下固态硫化热处理的方法制备铜铟硫太阳能电池吸收层材料；采用化学浴方法制备了替换CdS缓冲层的ZnS薄膜材料。深入分析了薄膜的制备工艺对薄膜的光学性能、物相结构、电学性能、表面形貌等的影响和相关机理。采用X射线衍射(XRD)、场发射扫描电镜(FE-SEM)、紫外可见光谱(UV-vis)等测试手段对样品的相关性能进行了测试和表征。主要研究结果如下：
(1)采用磁控溅射法制备的Mo背电极与玻璃基片附着良好,电阻较低(3.2Ω/cm)。
(2)所制备的CuInS2薄膜表面平整、结构致密。实验结果表明,硫化热处理温度对CuInS2的晶相形成具有重要影响,500℃开始出现CuInS2相,550℃形成高质量结晶,并且CuInS2薄膜呈(103)面择优取向生长。Tauc法得到的CuInS2薄膜光学带隙随着热处理温度的上升而逐渐减小。在550℃硫化热处理6h后CuInS2薄膜的XRD图谱中出现了对应于黄铜矿结构的(103)、(220)、(312)CuInS2晶体的衍射峰,SEM图片显示晶体颗粒为片状,尺寸在1μm,光学带隙为1.5 eV,更适合作为CuInS2吸收层。
(3)化学浴法制备的ZnS薄膜为非晶薄膜,在沉积温度为80℃、沉积时间1 h的条件下所制备薄膜的厚度为60.7 nm,薄膜透过率超过85%,光学带隙在3.8-3.9 eV范围之间变化。化学浴法制备的ZnS薄膜适合CIS/CIGS太阳电池中替换CdS缓冲层材料。
CuInS2(CIS) as aⅠ-Ⅲ-Ⅵ2 ternary semi-conductive inorganic compound is a direct band gap semiconductor, its absorptive coefficient is larger about 104-105 cm-1, its optical band gap is about 1.50 eV, very close to the best band gap (1.45 eV) of solar cell material. Comparing to CuInSe2, CuInGaSe2, CdTe and other thin film solar cell materials, CuInS2 contains no toxic ingredients, is a very promising solar cell materials.
Currently, CIGS-based thin film solar cells generally use CdS films as buffer layer. However, the band gap of CdS films is only 2.4 eV, it restricts the response to short-wave of absorbing layer to a certain extent. Cd in CdS is toxic heavy metal, and the appropriate safety measures increase the cost of industrialization, and the use of CdS is not beneficial to environmental protection. Consequently, research and development of cadmium-free CIGS solar cells has become a global hot spot. ZnS is an n-type,Ⅱ-Ⅵ,wide and direct optical band gap semi-conductive compound. ZnS film becomes a thin film material alternative to CdS buffer layer because of its environmentally friendly, the wide optical band gap (3.5-3.8 eV), low production cost.
Some relative researches on the materials of CuInS2 thin film solar cell were investigated in the thesis. First, Mo back electrode was prepared on glass substrate by magnetron sputtering. Second, copper indium alloy precursor, which had been fabricated by magnetron sputtering, was sulfured by heat treatment with solid-state sulfur in N2 to prepare CuInS2 absorbing layer thin film. Third, ZnS film, which replaces CdS buffer layer thin film, was prepared by chemical bath deposition. The influences of thin film process on the optical properties, phase structure, electrical properties, surface morphology and the related mechanisms were deeply researched. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), UV-visible spectrum (UV-vis) and other test methods were used to test and characterize the performance of samples. The major experimental results were as follows:
(1)Mo back electrode prepared by magnetron sputtering attached well to glass substrate with low resistance (3.2Ω／cm).
(2) CuInS2 thin film prepared was smooth with dense structure. The results showed that the temperature of heat treatment had a great effect on formation of crystalline phase CuInS2, CuInS2 phase started to form at 500℃, high-quality crystalline CuInS2 phase formed at 550℃and CuInS2 film was preferred orientation growth on (103) plane. The CuInS2 film optical band gap by Tauc method increased with the decrease of annealing temperature. After sulfured at 550℃for 6 h, CuInS2 film diffraction peaks appeared in XRD pattern corresponded to the (103), (220), (312) plane of chalcopyrite structure, SEM picture indicated crystal particles was laminar and size is 1μm, the optical band gap of CuInS2 thin film was 1.5 eV. CuInS2 thin film is more suitable for absorbing layer of CuInS2 solar cell.
(3) ZnS thin film prepared by chemical bath deposition was amorphous. The thickness of the deposited film was 60.7 nm after deposited 1h at 80℃, film transmittance was over 85%, the optical band gap varied between 3.8-3.9 eV. ZnS film prepared by chemical bath deposition was suit for replacing the CdS buffer layer in CIS/CIGS solar cell.
目前,CIGS基薄膜太阳能电池的制备多采用CdS薄膜作为缓冲层,但CdS的薄膜禁带宽度只有2.4 eV,对电池吸收层的短波响应有一定的影响,而且CdS中的Cd是有毒重金属,与之相应的安全措施也增大了工业化成本,CdS的使用也不利于环境保护。因此,研究和开发无镉CIS/CIGS太阳电池已成为全球研究此类电池的热点。ZnS是一种n型Ⅱ-Ⅵ族宽禁带直接带隙半导体化合物,ZnS薄膜因其对环境友好,宽光学带隙(3.5-3.8 eV),制备成本低廉,而成为替代CdS薄膜缓冲层的优选材料之一。
论文围绕CuInS2薄膜太阳能电池材料进行了相关研究。采用磁控溅射法在玻璃衬底上制备了Mo背电极；采用了磁控溅射沉积铜铟合金预置膜,再进行N2保护下固态硫化热处理的方法制备铜铟硫太阳能电池吸收层材料；采用化学浴方法制备了替换CdS缓冲层的ZnS薄膜材料。深入分析了薄膜的制备工艺对薄膜的光学性能、物相结构、电学性能、表面形貌等的影响和相关机理。采用X射线衍射(XRD)、场发射扫描电镜(FE-SEM)、紫外可见光谱(UV-vis)等测试手段对样品的相关性能进行了测试和表征。主要研究结果如下：
(1)采用磁控溅射法制备的Mo背电极与玻璃基片附着良好,电阻较低(3.2Ω/cm)。
(2)所制备的CuInS2薄膜表面平整、结构致密。实验结果表明,硫化热处理温度对CuInS2的晶相形成具有重要影响,500℃开始出现CuInS2相,550℃形成高质量结晶,并且CuInS2薄膜呈(103)面择优取向生长。Tauc法得到的CuInS2薄膜光学带隙随着热处理温度的上升而逐渐减小。在550℃硫化热处理6h后CuInS2薄膜的XRD图谱中出现了对应于黄铜矿结构的(103)、(220)、(312)CuInS2晶体的衍射峰,SEM图片显示晶体颗粒为片状,尺寸在1μm,光学带隙为1.5 eV,更适合作为CuInS2吸收层。
(3)化学浴法制备的ZnS薄膜为非晶薄膜,在沉积温度为80℃、沉积时间1 h的条件下所制备薄膜的厚度为60.7 nm,薄膜透过率超过85%,光学带隙在3.8-3.9 eV范围之间变化。化学浴法制备的ZnS薄膜适合CIS/CIGS太阳电池中替换CdS缓冲层材料。
CuInS2(CIS) as aⅠ-Ⅲ-Ⅵ2 ternary semi-conductive inorganic compound is a direct band gap semiconductor, its absorptive coefficient is larger about 104-105 cm-1, its optical band gap is about 1.50 eV, very close to the best band gap (1.45 eV) of solar cell material. Comparing to CuInSe2, CuInGaSe2, CdTe and other thin film solar cell materials, CuInS2 contains no toxic ingredients, is a very promising solar cell materials.
Currently, CIGS-based thin film solar cells generally use CdS films as buffer layer. However, the band gap of CdS films is only 2.4 eV, it restricts the response to short-wave of absorbing layer to a certain extent. Cd in CdS is toxic heavy metal, and the appropriate safety measures increase the cost of industrialization, and the use of CdS is not beneficial to environmental protection. Consequently, research and development of cadmium-free CIGS solar cells has become a global hot spot. ZnS is an n-type,Ⅱ-Ⅵ,wide and direct optical band gap semi-conductive compound. ZnS film becomes a thin film material alternative to CdS buffer layer because of its environmentally friendly, the wide optical band gap (3.5-3.8 eV), low production cost.
Some relative researches on the materials of CuInS2 thin film solar cell were investigated in the thesis. First, Mo back electrode was prepared on glass substrate by magnetron sputtering. Second, copper indium alloy precursor, which had been fabricated by magnetron sputtering, was sulfured by heat treatment with solid-state sulfur in N2 to prepare CuInS2 absorbing layer thin film. Third, ZnS film, which replaces CdS buffer layer thin film, was prepared by chemical bath deposition. The influences of thin film process on the optical properties, phase structure, electrical properties, surface morphology and the related mechanisms were deeply researched. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), UV-visible spectrum (UV-vis) and other test methods were used to test and characterize the performance of samples. The major experimental results were as follows:
(1)Mo back electrode prepared by magnetron sputtering attached well to glass substrate with low resistance (3.2Ω／cm).
(2) CuInS2 thin film prepared was smooth with dense structure. The results showed that the temperature of heat treatment had a great effect on formation of crystalline phase CuInS2, CuInS2 phase started to form at 500℃, high-quality crystalline CuInS2 phase formed at 550℃and CuInS2 film was preferred orientation growth on (103) plane. The CuInS2 film optical band gap by Tauc method increased with the decrease of annealing temperature. After sulfured at 550℃for 6 h, CuInS2 film diffraction peaks appeared in XRD pattern corresponded to the (103), (220), (312) plane of chalcopyrite structure, SEM picture indicated crystal particles was laminar and size is 1μm, the optical band gap of CuInS2 thin film was 1.5 eV. CuInS2 thin film is more suitable for absorbing layer of CuInS2 solar cell.
(3) ZnS thin film prepared by chemical bath deposition was amorphous. The thickness of the deposited film was 60.7 nm after deposited 1h at 80℃, film transmittance was over 85%, the optical band gap varied between 3.8-3.9 eV. ZnS film prepared by chemical bath deposition was suit for replacing the CdS buffer layer in CIS/CIGS solar cell.
引文
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