In this work, the preparation of “Ag” alloying Cu2ZnSnSe4 films using a two‐step process, comprising vacuum evaporated ([Sn/ZnSe/Ag/Sn/ZnSe/Cu] × 2) precursor layer deposition on glass substrates followed by low‐temperature pre‐annealing treatment (PAT) in Se ambiance (200–400 °C) for 30 min and high‐temperature annealing at 500 °C for 1 min, is reported. The low‐temperature PAT provides adequate Se diffusion into precursor layers and plays a pivotal influence on the growth and properties of (Cu,Ag)2ZnSnSe4 films. The Zn/Sn and Se/metals ratios are found to be varied in the range 0.77–1.32 and 1.07–0.86 with PAT (200–400 °C) followed by annealing at 500 °C for 1 min. The precursor layers are pre‐annealed at 300 °C for 30 min, followed by annealing at 500 °C for 1 min, found to be nearly stoichiometric with uniform distribution of constituents. The valence states of the constituents are confirmed by X‐Ray photoelectron spectroscopy. Both X‐Ray diffraction and Raman studies confirm the formation of single‐phase (Cu,Ag)2ZnSnSe4 along (112) orientation with a strong Raman mode at 194 cm−1. Large and well‐defined grains with a mean size of 0.7 μm are seen in the field‐emission scanning electron microscope images. The (Cu,Ag)2ZnSnSe4 films exhibit a direct bandgap of 1.12 eV and p‐type conductivity with high mobility, 5.23 cm2 V−1 s−1.

中文翻译：

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预退火处理对(Cu0.5Ag0.5)2ZnSnSe4薄膜生长和性能的影响

本工作中，制备了“Ag”合金铜2硒化锌4采用两步工艺制备薄膜，包括在玻璃基板上真空蒸发（[Sn/ZnSe/Ag/Sn/ZnSe/Cu]×2）前驱体层沉积，然后在 Se 气氛中进行低温预退火处理（PAT）（据报道，在 200–400 °C 下退火 30 分钟，并在 500 °C 下高温退火 1 分钟。低温 PAT 使 Se 充分扩散到前驱体层中，并对 (Cu,Ag) 的生长和性能产生关键影响2硒化锌4电影。发现使用 PAT (200–400 °C)，然后在 500 °C 退火 1 分钟时，Zn/Sn 和 Se/金属比率在 0.77–1.32 和 1.07–0.86 范围内变化。前驱体层在 300°C 下预退火 30 分钟，然后在 500°C 下退火 1 分钟，结果发现其接近化学计量且成分分布均匀。成分的价态由X射线光电子能谱证实。 X 射线衍射和拉曼研究均证实了单相（Cu、Ag）的形成2硒化锌4沿 (112) 方向，在 194 cm 处具有强拉曼模式−1。在场发射扫描电子显微镜图像中可以看到平均尺寸为 0.7 μm 的大而清晰的晶粒。 (铜、银)2硒化锌4薄膜表现出 1.12 eV 的直接带隙和具有高迁移率的 p 型导电性，5.23 cm2V−1s−1。