本論文探討以退火方式，藉由表面的鋅薄膜擴散與下層的銅錫硒層反應形成四元半導體銅鋅錫硒（Cu2ZnSnSe4）吸收層。此種材料的電性也首次探討。在此論文中，為了製造出接近標準比例的銅鋅錫硒薄膜，我們採取不同的鋅薄膜厚度和退火的時間做比較。最終單一相的銅鋅錫硒薄膜在300奈米鋅薄膜堆疊於2.65微米銅錫硒薄(Cu2SnSe3)膜上，並於攝氏500度下退火1.5個小時可被形成。在拉曼散射分析之下，可確定由三元相銅錫硒薄（Cu2SnSe3）轉換至四元相銅鋅錫硒（Cu2ZnSnSe4），並且呈現沒有硒化鋅的單一相的銅鋅錫硒。在霍爾量測的分析下，這些樣本皆呈現低阻值且載子濃度高達1021cm-3的p型半導體特性。

最終，硒含量不足的問題藉由改變銅-錫先驅物的硒化溫度，從攝氏450度改變至攝氏250度所解決，因為來自低溫之下所形成二硒化銅（CuSe２）與硒化錫（SnSe）的硒含量比三元化合物銅錫硒（Cu2SnSe3）多。接近標準比例的銅鋅錫硒（Cu2ZnSnSe4）並且晶粒大小高達1.5微米可被獲得。

This thesis investigated the possible reaction route of quaternary semiconductor Cu2ZnSnSe4 (CZTSe) absorber synthesized by surface Zn diffusion to underneath Copper-Tin-Selenide ternary layer at 500oC. The electrical property of CZTSe was also investigated for the first time. In this thesis, Zn thickness and duration of annealing were optimized to fabricate near stoichiometric CZTSe film. Single phase CZTSe was produced by annealing 300 nm Zn/2.65 um Cu2SnSe3 at 500oC for 1.5 hours. Raman scattering analysis was used to identified the phase transformation from Cu2SnSe3 to CZTSe. It also showed that the synthesized film was single phase CZTSe without ZnSe binary compound. Hall measurement results showed that these films are p-type with low resistivity and high carrier concentration of 1021cm-3.

Finally, the insufficient Se ratio problem was resolved by replacing the of Cu-Sn selenization temperature from 450oC to 250oC so as to increase the incorpoaration of Se with Cu and Sn to form CuSe2 and SnSe instead of ternary. CZTSe film with grain size up to 1.5 um and nearly stichiometric ratio was obtained.

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