Abstract The phase equilibrium of the Ag2SnS3–ZnS pseudobinary system for the growth of Ag2ZnSnS4 (AZTS) crystals was investigated using the equilibration-quenching technique. The growth mechanism of AZTS follows the peritectic reaction liquid phase + ZnS phase ↔ AZTS phase, which occurs at a composition of ∼20 mol% ZnS and a temperature of approximately 700 °C. The AZTS polycrystalline sample was obtained from the stoichiometric melt growth. The kesterite structure of the AZTS sample without secondary phases was identified by a combination of X-ray diffraction and Raman spectroscopy measurements. The electron carrier concentration and conductivity, determined by the Hall effect measurement, were (3.0–6.3) ×1015 cm-3 and (5.6–9.2) ×10-4 S/cm, respectively. The slightly Zn-rich and S-poor composition led to n-type conduction in the AZTS because of the dominant Zn antisites on Ag (ZnAg) and S vacancy (VS) defects. Therefore, this study can make a significant contribution to the research and application of AZTS materials.

中文翻译：

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用于 Ag2ZnSnS4 晶体生长的 Ag2SnS3-ZnS 伪二元体系的相图

摘要 使用平衡-淬火技术研究了 Ag2SnS3-ZnS 伪二元体系在 Ag2ZnSnS4 (AZTS) 晶体生长中的相平衡。AZTS 的生长机制遵循包晶反应液相 + ZnS 相↔ AZTS 相，其发生在~20 mol% ZnS 的组成和大约 700 °C 的温度下。AZTS 多晶样品是从化学计量熔体生长中获得的。通过 X 射线衍射和拉曼光谱测量的组合，确定了没有第二相的 AZTS 样品的黄铜矿结构。由霍尔效应测量确定的电子载流子浓度和电导率分别为 (3.0–6.3) ×1015 cm-3 和 (5.6–9.2) ×10-4 S/cm。由于在 Ag (ZnAg) 和 S 空位 (VS) 缺陷上占主导地位的 Zn 反位点，略微富锌和贫硫的成分导致 AZTS 中的 n 型导电。因此，本研究可为AZTS材料的研究和应用做出重大贡献。