本研究之目的在於黃銅礦結構吸收層之開發，包含了二硫化銅銦
(CuInS2)與硫化銅錫鋅(Cu2ZnSnS4) 之太陽能吸收層薄膜成長與特性分析，並使用非真空製程開發其吸收層製程，包含塗佈及電鍍製程。成長黃銅礦結構吸收層薄膜有多種製備方式，最常見的為兩階段製程(two-step
process)，第一步先製備含銅銦/銅錫鋅薄膜前驅物，接著於第二步再將試片移至反應爐管以硫粉或硫化氫氣體作為硫源進行硫化反應(ex-situ 硫化)。本研究在使用非真空方式製備銅銦/銅錫鋅薄膜前驅物後，將薄膜置入H2S/Ar 混合氣體通入真空腔體中進行硫化反應，在硫化過程中探討影響前驅物對於硫化過程之影響。
在 CuInS2 薄膜方面，使用不同銅銦鹽類製備的Cu-In 氧化物，探討
其形成單一相的Cu2In2O5 及CuInGaO4 之機制。並添加不同比例的Cu2S
粉末於單一相Cu2In2O5 製成漿料並使用刮刀法成膜，探討其對於CuInS2薄膜之結晶性與薄膜性質之影響。最後於500 torr 10 % 硫化氫 / 90% 氬氣混和氣氛下，銅銦氧化物前驅物於450~550℃之間可硫化而轉變至CuInS2 薄膜。另外在添加Cu2S 改變前驅物Cu/In 比例為1.8 的CuInS2 薄膜，其具有改善二次相如CuIn5S8、CH-CuInS2 之比例以及1.30~1.38 之能隙之薄膜特性。
在 CZTS 吸收層方面，使用電鍍法製作不同堆疊順序之銅、錫及鋅金
屬薄膜前驅物，經由10 % 硫化氫/ 90% 氬氣混和氣氛熱處理。探討不同
堆疊金屬薄膜前驅物對於單一相Cu2ZnSnS4 形成之影響。最後，選擇最
佳堆疊與具有高純度Cu2ZnSnS4 相之薄膜進行相變化之研究，探討由金
屬相轉變為Cu2ZnSnS4 相之過程。經由SEM 觀察，375 ℃有150nm 薄膜
於銅錫鋅金屬層表面生成；經由XRD與Raman 分析，判定其可能為ZnS、
Cu2SnS3與Cu2ZnSnS4之混合相。最後經由高解析穿透式電子顯微鏡分析，在400 ℃可以發現Cu2ZnSnS4 相於ZnS 以及Cu2S 上生成。

The objective of this research is the growth and characterization of the Chalcopyrite-like solar absorption layer and the development of sulfurization process. Our studies include CuInS2 and Cu2ZnSnS4 materials. There were
numbers of methods to grow (for/of growing) CuInS2 thin films. The most common seen method is two-step process in which the precursor is prepared first and then subsequently removed into a reactive furnace for further sulfurization process using sulfur powder or H2S gas as sulfur sources. In our research, the precursors of CIS and CZTS thin film were made via a non-vacuum process. The precursor film was put into a quartz tube under 10% H2S/Ar atmosphere. During the sulfurization process, the main parameters affecting the resulted CuInS2 and Cu2ZnSnS4 thin films were layered structure of precursors, sulfurization temperature and sulfurization pressure.
In studies of CuInS2, the precipitates were then calcined at different temperatures for different durations. Depending on the type of salt and calcination condition, single phases Cu2In2O5, and CuInGaO4, or the mixture
of both oxides were obtained. Reaction mechanisms are proposed to explain the formation of the oxides obtained. For the formation of CuInS2 (CIS) coatings, sulfurization of single crystalline Cu2In2O5 nanoparticles (NPs) Cu2In2O5 NPs were synthesized using a chemical route. Thus formed NPs were applied to a Mo-coated glass substrate by a doctor-blading technique. After the doctor-blading, coatings were sulfurized under 560 torr of H2S at various temperatures. Selected doctor-bladed samples were heat treated at 430 °C in air for 30 min for the removal of carbon residual prior to the sulfurization. During the sulfurization, Cu2S (melting point 435 °C) was used
as the sintering aid. The weight ratio of Cu2S to Cu2In2O5 was varied. The effect of Cu2S on the CIS crystalline structure was explored using Raman analysis. It was found that Cu2S not only improves the sintering but also promotes the formation of desired CIS-chalcopyrite structure and reduces the impurity phase (CuIn5S8 and CH-CuInS2) in the resulting CIS coatings. Finally, at 500 torr 450~550℃, CuInS2 (Cu/In ratio: 1.8) will be formed from oxide precursor, the energy gap is 1.30~1.38.
In Cu2ZnSnS4, (CZTS) precursor layer was prepared using sequential electrodeposition of individual Cu, Zn, and Sn in different orders. In each stacking order the Cu/(Sn+Zn) ratio was varied. Detailed growth path is therefore reported. We also demonstrate that by controlling the stacking order and the Cu/(Sn+Zn) ratio, CZTS with a phase purity as high as 93% can
be obtained. Finally, selected CZTS film with high purity Cu2ZnSnS4 will be studied the phase transformation, and the formation path form metal to Cu2ZnSnS4 phase will be discussed. In SEM analysis, there is 150 nm film growing on the top of Cu-Sn-Zn precursor at 375 ℃. After XRD and Raman analysis, the mixture phase of ZnS, Cu2SnS3 and Cu2ZnSnS4 formed at 375 ℃. Finally, we found Cu2ZnSnS4 formed on the top of ZnS and Cu2S phase at 400 ℃ via TEM analysis.

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