| 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],51(12):295-302 |
| 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 |
| KeyWord:Cu2BaSn(S,Se)4 Cu2SrSn(S,Se)4 selenization thin film characterization photoelectric conversion |
| Author | Institution |
| CUI Yong |
School of Environment and Chemical Engineering, Shenyang Ligong University, Shenyang , China |
| TANG Xiao-hu |
School of Environment and Chemical Engineering, Shenyang Ligong University, Shenyang , China |
| ZHANG Wei |
School of Environment and Chemical Engineering, Shenyang Ligong University, Shenyang , China |
| LI Xue-tian |
School of Environment and Chemical Engineering, Shenyang Ligong University, Shenyang , China |
| SHAO Zhong-cai |
School of Environment and Chemical Engineering, Shenyang Ligong University, Shenyang , China |
| SHAO Hong-mei |
School of Environment and Chemical Engineering, Shenyang Ligong University, Shenyang , China |
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| Abstract: |
| 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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