崔勇,唐啸虎,张伟,李学田,邵忠财,邵鸿媚.溶液法制备铜钡锡硫硒和铜锶锡硫硒薄膜[J].表面技术,2022,51(12):295-302.
CUI Yong,TANG Xiao-hu,ZHANG Wei,LI Xue-tian,SHAO Zhong-cai,SHAO Hong-mei.Solution Process to Fabricate Cu2BaSn(S,Se)4 and Cu2SrSn(S,Se)4 Thin Film[J].Surface Technology,2022,51(12):295-302 |
| 溶液法制备铜钡锡硫硒和铜锶锡硫硒薄膜 |
| Solution Process to Fabricate Cu2BaSn(S,Se)4 and Cu2SrSn(S,Se)4 Thin Film |
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| DOI：10.16490/j.cnki.issn.1001-3660.2022.12.030 |
| 中文关键词: 铜钡锡硫硒薄膜 铜锶锡硫硒薄膜 硒化 薄膜表征 光电转换 |
| 英文关键词:Cu2BaSn(S,Se)4 Cu2SrSn(S,Se)4 selenization thin film characterization photoelectric conversion |
| 基金项目:辽宁省教育厅青年育苗项目(LG202021);国家自然科学基金资助项目(52004165) |
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| Author | Institution |
| CUI Yong | School of Environment and Chemical Engineering, Shenyang Ligong University, Shenyang 110159, China |
| TANG Xiao-hu | School of Environment and Chemical Engineering, Shenyang Ligong University, Shenyang 110159, China |
| ZHANG Wei | School of Environment and Chemical Engineering, Shenyang Ligong University, Shenyang 110159, China |
| LI Xue-tian | School of Environment and Chemical Engineering, Shenyang Ligong University, Shenyang 110159, China |
| SHAO Zhong-cai | School of Environment and Chemical Engineering, Shenyang Ligong University, Shenyang 110159, China |
| SHAO Hong-mei | School of Environment and Chemical Engineering, Shenyang Ligong University, Shenyang 110159, China |
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| 中文摘要: |
| 目的 在玻璃基底上制备2种铜钡锡硫和铜锶锡硫薄膜，研究薄膜硒化过程中硒化时间对薄膜形貌以及晶体生长的影响。方法 采用配位能力强的二甲基亚砜作为溶剂溶解金属氯化物-氯化亚铜、氯化钡、氯化亚锡、氯化锶前体盐以及硫脲，二甲基亚砜溶剂中硫原子具有的孤对电子可以与铜离子、钡离子、锡离子、锶离子进行配位，避免了金属硫化物沉淀的产生，制备的分子前体溶液可以在空气中稳定存在。采用液相旋涂的方法在镀有钼薄膜的玻璃基底上旋涂分子前体溶液，随后在充满氮气手套箱中320 ℃加热板上退火制备铜钡锡硫和铜锶锡硫预制膜，使用高温硒化这一可以显著改善铜基薄膜晶体质量的手段进行处理，引入硒原子部分替换硫原子，制备铜钡锡硫硒和铜锶锡硫硒薄膜。使用XRD、SEM、XPS分析表征手段对制备的铜钡锡硫硒和铜锶锡硫硒薄膜进行结构、形貌、元素价态表征。结果 硒化后的铜钡锡硫硒和铜锶锡硫硒薄膜表现出良好的晶体结构，XRD显示组成铜钡锡硫硒和铜锶锡硫硒薄膜由大晶粒组成。硒化后的铜钡锡硫硒薄膜表面由大晶粒组成，形成连续薄膜，不同硒化温度下的铜钡锡硫硒薄膜表面有孔洞出现。随着硒化温度的升高，铜钡锡硫硒薄膜中的小粒子层逐渐消失。硒化后的铜锶锡硫硒薄膜表面晶体层比较稀疏，无法形成连续薄膜，因此无法用于制备薄膜太阳能电池;铜离子、钡离子、锡离子、锶离子、硫离子、硒离子的价态分别为+1、+2、+4、+2、‒2、‒2。结论 旋涂制备的铜钡锡硫薄膜经过高温硒化之后，铜钡锡硫硒薄膜晶体组成比较致密，组装的玻璃基底/金属钼/铜钡锡硫硒薄膜/硫化镉/氧化锌/铟锡导电玻璃/铝薄膜太阳能电池，表现出光电转换信号。制备的铜钡锡硫硒薄膜太阳能电池的短路电流密度为63 μA/cm2，开路电压为0.169 V。 |
| 英文摘要: |
| Solution way to fabricate Cu-based thin film solar cell absorb layer is low-cost and easy operated method compared to vacuum vapor deposition way. In this paper, two kinds of Cu-based thin film- Cu2BaSn(S,Se)4 and Cu2SrSn(S,Se)4 are prepared on the Mo coated on the glass substrate via solution process. The effects of selenization time on the as-prepared Cu2BaSn(S,Se)4 and Cu2SrSn(S,Se)4 thin film for morphology and crystal growth are studied. DMSO, which is a kind of benign solvent, is used to dissolve copper chloride、barium chloride、tin chloride、strontium chloride metal salts and thiourea in order to form homogeneous solution. The homogeneous solution can be formed because the two pairs of lone electrons in sulfur atom can be coordinated with metal cations (copper ion, tin ion, barium ion and strontium ion). Therefore no metal sulfide precipitation is generated during the dissolved process and homogeneous solution can be stable existed in the air. Homogeneous metal precursor solutions are spin-coated on the Mo coated on the glass substrate, and Cu2BaSnS4 and Cu2SrSnS4 thin films are obtained after as-prepared thin film annealed on the hotplate with 320 ℃ in the glovebox filled with nitrogen. Selenization process is an important and effective way to improve the crystal quality of as-prepared Cu2BaSnS4 and Cu2SrSnS4 thin film, because Se atoms can substitute S atom and the grains that are composed of Cu2BaSnS4 and Cu2SrSnS4 thin film can be growth larger during the selenization process, and Cu2BaSn(S,Se)4 and Cu2SrSn(S,Se)4 thin film are obtained. The analytic methods of XRD、XPS and SEM are used to characterize the structure、valence state、surface and cross-section morphology of the obtained Cu2BaSn(S,Se)4 and Cu2SrSn(S,Se)4 thin film. After selenization, Cu2BaSn(S,Se)4 and Cu2SrSn(S,Se)4 thin film display good crystal structure. The crystals composed of Cu2BaSn(S,Se)4 and Cu2SrSn(S,Se)4 thin film are large grains which can be inferred from the XRD patterns. The surface of Cu2BaSn(S,Se)4 thin film is composed of large grains to form continuous film. There are pinholes on the surface of Cu2BaSn(S,Se)4 thin film at different selenization temperatures. The structure of Cu2BaSn(S,Se)4 thin film cross-section displays that small grain layer will eliminate gradually with the increased temperature for the selenization process. For the Cu2SrSn(S,Se)4 thin film, the crystal density on the surface of Cu2SrSn(S,Se)4 thin film is relatively sparse and cannot form continuous film after selenization; it illustrates that Cu2SrSn(S,Se)4 thin film is sensitive to the selenization process. Therefore, it could not be used to prepare thin film solar cells; the valence states of copper ion, barium ion, tin ion, strontium ion, sulfide ion and selenide ion are +1, +2, +4, +2, ‒2 and ‒2 respectively. After high temperature selenization, large grain composed the Cu2BaSn(S,Se)4 thin film are prepared. The crystal composition of Cu2BaSn(S,Se)4 thin film is relatively dense. The as-fabricated glass/Mo/Cu2BaSn(S,Se)4/CdS/i-ZnO/ITO/Al heterojunction Cu-based thin film solar cell display the photoresponse behavior under 1.5 AM illumination. The parameters of as-fabricated Cu2BaSn(S,Se)4 thin film solar cell are listed as follows:the short current is 63 μA/cm2, and the open voltage is 0.169 V. |
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