溶胶-凝胶法工艺参数对铜锌锡硫薄膜质量及性能影响研究  

Effect of sol-gel process parameters on quality and properties of CuZnSnS thin films

作　　者：王近 袁妍妍[1] 王久和 李涛 张琳 WANG Jin;YUAN Yanyan;WANG Jiuhe;Li Tao;ZHANG Lin(School of Materials Science and Engineering, Jiangsu University of Science and Technology,Zhenjiang 212003, China)

机构地区：[1]江苏科技大学材料科学与工程学院,江苏镇江212003

出　　处：《功能材料》2022年第3期3092-3099,3123,共9页Journal of Functional Materials

基　　金：国家自然科学基金项目(51702133);江苏省研究生创业项目(KYCX20_3129)。

摘　　要：以乙酸铜(Cu(CH_(3)COO)_(2)·H_(2)O)、乙酸锌(Zn(CH_(3)COO)_(2)·H_(2)O)、氯化亚锡(SnCl_(2)·2H_(2)O)、硫脲(CH_(4)N_(2)S)为原料,按一定配比制得前驱体溶液,以三乙醇胺(C_(6)H_(15)NO_(3))、乙醇胺(C_(2)H_(7)NO)为稳定剂采用溶胶-凝胶法旋涂制备铜锌锡硫(Cu_(2)ZnSnS_(4))薄膜。通过扫描电镜(SEM)、X射线衍射仪(XRD)、X射线能谱分析(EDS)、紫外-可见-近红外分光光度计表征手段对薄膜的表面形貌、物相结构、成分组成和光学性能等进行分析。研究烧结温度、旋涂转速、稳定剂加入等工艺参数对铜锌锡硫(CZTS)薄膜的形貌、物相结构及光学性能的影响规律。结果表明,前驱体溶液浓度为0.2 mol/L,旋涂速度为1000 r/min,时间为10 s,烧结温度为280℃时,得到了符合Cu_(2)ZnSnS_(4)相结构的薄膜样品;而浓度为0.3 mol/L,旋涂速度为3500 r/min,时间为15 s,增添乙醇胺(MEA)的稳定剂,烧结温度为260℃制备出的CZTS薄膜在表面相貌上有较大改善,其中添加1.5 mL三乙醇胺(TEA)及乙醇胺(MEA)稳定剂制备的CZTS薄膜形貌呈颗粒状,薄膜的表面均匀性提高,但薄膜的结晶质量不如0.2 mol/L溶液制备的样品,薄膜中Sn、S元素的流失而导致其他相的生成使得薄膜的带宽偏大。此外,样品的结晶随烧结时间延长而逐渐变好,但是没有大尺寸晶粒生成。In this paper,CuZnSnS thin films are prepared by sol-gel method.Firstly,precursor solution is prepared using copper acetate(Cu(CH_(3)COO)_(2)·H_(2)O),zinc acetate(Zn(CH_(3)COO)_(2)·H_(2)O),sthenous chloride(SnCl_(2)·2H_(2)O)and thiourea(CH_(4)N_(2)S)in a certain ratio.Then triethanola mine(C_(6)H_(15)NO_(3))and ethanola mine(C_(2)H_(7)NO)are as stabilizers to preprare Cu_(2)ZnSnS_(4)thin films.The surface morphology,phase structure,composition and optical properties of the films are characterized by scanning electron microscopy(SEM),X-ray diffraction(XRD),X-ray energy dispersive spectroscopy(EDS)and UV-visible-near-infrared spectroscopy.The effects of sintering temperature,rotating speed and stabilizer addition on the morphology,phase structure and optical properties of copper,zinc,tin and sulfur(CZTS)films are investigated.The results show that the Cu_(2)ZnSnS_(4)phase structure films are obtained when the concentration of precursor solution is 0.2 mol/L in the condition of 1000 r/min spin speed and 10 s coating time,and the sintering temperature is set as 280℃.When concentration is set as 0.3 mol/L and the spin speed is set as 3500 r/min with 15 s coating time,the surface appearance of CZTS films prepared by adding ethanola mine(MEA)stabilizer at sintering temperature of 260℃is greatly improved.The granular morphology of CZTS films prepared by adding 1.5 mL triethanola mine(TEA)and ethanola mine(MEA)stabilizer is observed,and the surface uniformity of CZTS films is improved.However,the crystal quality of the thin film is not as good as that of the sample prepared by 0.2 mol/L solution.The loss of Sn and S elements is founded and leads to the formation of other phases,resulting in a large bandwidth of the thin film.In addition,the crystallization of the sample becomes better with the extension of sintering time,but no large size grains are formed.

关 键 词：溶胶-凝胶法 结晶质量 铜锌锡硫薄膜 表面形貌 光学性能 

分 类 号：TB34[一般工业技术—材料科学与工程]