CZTS (Cu2ZnSnS4)為近十幾年來薄膜太陽能領域常見之應用材料，其結構為Kesterite四方晶系，前身為CIGS (CuInxGa1-xSe2)，為克服其In、Ga材料昂貴且難以獲得問題，而演變替代的新世代薄膜太陽能光伏層。在CZTS四元系統概念下，本研究首先以簡化之三元系統CTS (Cu2Sn3S7)使用粉體混膠旋轉塗佈法成膜，並於不同硫化條件下對材料本質作光伏特性探討。其後，對於CZTS四元粉體系統作金屬單元、二元之200°C硫化，探討個別以及混合金屬元素在相對低溫之下，硫化反應發生時之相結構變化。
從三元系統CTS實驗結果得知，在不同溫度的熱處理條件下，薄膜表面形貌以及相組成均呈現不同趨勢成果。其中500°C硫化熱處理條件，無論在形貌、相組成以及光伏特性皆為最佳。此硫化熱處理試片於CTS與Mo基板間約有38nm之IMC，由解析得知其為CTS與Mo基板共同之硫化界面層。500°C硫化雖為CTS/CZTS最佳成相溫度，但為更清楚瞭解CZTS系統中各金屬在硫化過程的化合表現，因此以較低硫化熱處理條件(200°C)對Cu, Zn, Sn元素進行粉體硫化，探討金屬元素在硫化環境中的各別反應機制。
由單、二元金屬硫化的各種光學及相結構分析可知，硫化反應的發生趨勢，與Cu高度相關，Sn次之，Zn最低。在200°C相對低溫硫化條件下，在二元金屬硫化相成份中亦發現少許之三元(Cu-Sn-S)硫化相，可知在相對低溫下，Cu與Cu-Sn主導硫化反應發生的優先次序。
最後，依據Cu與S高度依存的特性，可使Mo基板在硫化過程避免生成過厚MoSx硫化層，同時考量抑制Cu在硫化熱處理過程中熱擴散而對其上n層(ZnS)的擴散汙染效應，因此設計三明治堆疊法Cu/Sn/Zn堆疊薄膜，分別以熱處理、電致結晶兩種方式，探討在熱能以及電子流驅動之下，Cu原子擴散以及金屬層間的界面行為。從實驗結果得知，在210°C熱處理條件下，Cu全面性擴散可跨越Sn層達表面Zn層，因熱效應全面完整反應，使得三明治結構層產生界面金屬間化合相Cu6Sn5及Cu5Zn8；而電致結晶(EIC)的處理試驗，Cu擴散量明顯受抑制，Cu-Sn界面主要生成Cu3Sn而非Cu6Sn5，由於電阻優選路徑，只有局部因較大電流產生較高焦耳熱之路徑，Zn-Sn界面產生局部島狀Cu5Zn8而非全面性成長。因此得知，在相對低溫之下，電子流主導Cu原子擴散方向，至溫度夠高時，Cu的擴散可克服電子遷移方向而成為擴散主導機制，相關數據可提供光伏產業應用參考。

Under sulfurization mechanism, the compound reaction of the two elements Cu and S is closely related both the CTS and CZTS system. The existence and distribution of Cu atoms in the multi-element system determines the extent and area of sulfurization by S atoms. In the CTS ternary system, under the fixed element material ratio (atomic ratio Cu:Sn:S = 2:3:7), the sulfurization treatment at 500°C has the best crystallization and photoelectric properties. In the sulfurization process of CZTS quaternary at 200°C, a Cu-Zn compound phase will also be formed. Therefore, under the trend that CuS and Cu5Zn8 are relatively stable, the Cu-Zn-S ternary phase is not easy to form. The Cu-Sn compound has a higher free energy than the Cu-Zn compound, and Sn atoms are slightly easier to combine with sulfur atoms than Zn atoms. Based on these two factors, it is deduced that during the sulfurization process, the Cu-Sn-S sulfide phase is likely to be preferentially generated at Cu-Sn interface than Cu-Zn interface. For the diffusion behavior of copper atoms in the Zn-Sn-Cu sandwich structure, Cu is the most prominently driven by heating and electric effects, followed by Sn atoms, and Zn atoms are the least affected by heating and electric effects.

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