本研究之目的在於二硫化銅銦(CuInS2) 之太陽能吸收層薄膜成長與特性分析，並開發其硫化製程包含in-situ及ex-situ硫化製程。成長CuInS2薄膜有多種製備方式，最常見的為兩階段製程(two-step process)，第一步先製備銅銦薄膜前驅物，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)，為了縮短製程時間與不破真空保持試片之潔淨度，本研究在熱蒸鍍製備銅銦薄膜前驅物後，後續直接將H2S/Ar混合氣體通入真空腔體中進行in-situ硫化反應之製程開發，在in-situ硫化過程中，主要影響CuInS2薄膜之實驗參數包含銅銦薄膜前驅物之交替層結構、硫化溫度與硫化壓力。最後於7.5 torr下，銅銦前驅物於450~550℃之間可完全硫化而轉變至CuInS2薄膜，其具有大於104 cm-1之吸收係數、大於90%吸收度以及10-1 Ω-cm尺度之電阻率之薄膜特性。在開發in-situ硫化製程後，接著研究CuInS2薄膜於硫化成長過程中之微結構與相轉變，本研究採用三種銅銦前驅物結構與兩種升溫曲線，於硫化過程中不同溫度與持溫時間下停止硫化，將試片移出並分析探討各種前驅物於硫化過程中之變化，結果發現無論銅銦前驅物結構為何，在不同升溫曲線下硫化時，CuInS2薄膜皆於310℃開始成長，此時GIXRD沒有偵測到介穩定相CuInS2-CA與CuIn5S8，但是Raman結果卻明顯指出CuInS2-CH、CuInS2-CA與CuIn5S8之共存，隨著硫化溫度上升至500℃時，後兩相明顯變少許多並隨著持溫時間而減少，同時由CuInS2-CH A1特徵峰藍移(blue shift)減少與半高寬值(FWHM)下降可得知薄膜品質變佳，然而，即使經過整個硫化升溫曲線後，Raman結果指出仍有少量的CuInS2-CA與CuIn5S8存在於CuInS2薄膜中。過去文獻中以XRD結果指出CuInS2薄膜是由Cu11In9或Cu16In9合金相成長所得，但本研究之TEM直接證據顯示，無論在310℃或500℃之硫化溫度下，CuInS2薄膜皆由Cu11In9合金相而非Cu16In9合金相成長所得。結合不同銅銦前驅物結構於不同升溫曲線硫化過程之GIXRD、Raman與TEM分析結果，本研究進一步提出了CuInS2薄膜之成長路徑與反應順序。
除了in-situ硫化，本研究亦同時發展ex-situ硫化製程，過程中，先比較穩定(密閉式)與流通(開放式)的H2S/Ar混和氣體環境中硫化所得CuInS2薄膜，由試片外觀與SEM結果，密閉式硫化效果較好。後續於密閉式硫化製程以硫化溫度與銅銦前驅物之Cu/In比做為實驗參數，其中特別探討Cu/In比對於硫化所得CuInS2薄膜特性(晶粒尺寸、表面形貌、表面粗糙度、微結構以及缺陷)之關聯，結果顯示高Cu/In比之前驅物硫化後所得CuInS2薄膜晶粒較大、表面較平坦、孔洞較少、介穩定相(CuInS2-CA與CuIn5S8)較少、CuS二次相較多與缺陷(1.45 eV)較少，因此薄膜品質也較佳，但CuS同時也形成於CIS/Mo介面使得附著性變差導致薄膜剝落。而硫化溫度的提升，也會降低介穩定相(CuInS2-CA與CuIn5S8)，同時CuInS2-CH A1特徵峰藍移與半高寬皆減小，表示薄膜品質提升，然而，隨溫度上升而增加之MoS2厚度在550℃下最厚並影響薄膜附著性，綜合上述結果，所得最佳效率之CuInS2薄膜太陽能電池是500℃硫化Cu/In為1.8之前驅物所得CuInS2薄膜，其效率為6.29%。

The objective in this research was the growth and characteristic of the CuInS2 solar absorption layer and the development of sulfurization process including in-situ and ex-situ sulfurization processes. There were numbers of metods to grow CuInS2 thin films. The most common seen method is two-step process in which the precursor is prepared first and then removed into a reactive furnace for further sulfurization process using sulfur powder or H2S gas as sulfur source. In order to reduce the process time and keep the sample clean without breaking the vacuum, the in-situ sulfurization process was developed by thermally evaporated precursor followed by directly introducing H2S/Ar mixture gas into the vacuum chamber in this research. During the sulfurization process, the main parameters which affected the resulting CuInS2 thin films were layered structure of precursors, sulfurization temperature and sulfurization pressure. The precursor could be completely convered into CuInS2 thin films at sulfurization temperature between 450~550℃ under 7.5 torr. The resulting CuInS2 thin films exhibited absorption coefficient higher than 104 cm-1, absorbance higher than 90% and resistivity of ~ 10-1 Ω-cm. After the development of in-situ sulfurization process, the microstructure and phase transformation of CuInS2 thin films during the sulfurization process were then investigated. Three kinds of precursor structures and two kinds of thermal processes were adopted in this research. The surization was broke off at different sulfurization temperatures and prolonged time. Then the sulfurized films were removed for further analyses and the variation of different sulfurized precursors would be discussed. The results showed that CuInS2 thin films started to grow at 310℃ in any kind of precursor and thermal process. In the meantime, Raman analysis revealed the coexistence of CuInS2-CH with the metastable phases of CuInS2-CA and CuIn5S8 which were not detected in GIXRD spectra. As sulfurization temperature increased to 500℃ and prolonged at 500℃, CuInS2-CA and CuIn5S8 significantly decreased, while the decrease of blue shift and FWHM of CuInS2-CH A1 mode indicated a better quality of CuInS2 thin films. Even after the sulfurization process, extremely small amount of CuInS2-CA and CuIn5S8 were still residual in the films. It has been reported that CuInS2 would grow from Cu11In9 or Cu16In9 phase using XRD analysis. However, the TEM results gave direct evidence that CuInS2 grew from Cu11In9 phase at temperature of 310 and 500℃. With the combination of GIXRD, Raman and TEM analyses of different precursor structures sulfurized by different thermal processes, the growth path and reaction sequence of CuInS2 thin films were proposed in this study.
In addition to in-situ sulfurization process, the ex-situ sulfurization process was also developed. CuInS2 films sulfurized under the steady (close system) and flowing (open system) H2S/Ar mixture gas environment were compared. The former resulted in better and uniform morphology of sulfurized films and was used in the following for sulfurization process. The sulfurization temperature and Cu/In atomic ratio were used as the parameters in the close system. The relationship between Cu/In ratio and the characteristics (grain size, surface morphology, roughness, microstructure and defects) of CuInS2 films were spectially discussed. The results showed that CuInS2 films with higher Cu/In ratio exhibited larger grain size, platter surface, less pin holes, less metastable phases of CuInS2-CA and CuIn5S8, more CuS secondary phase and lower defects (1.45 eV). As the results, film quality was also better. But formation of CuS in the CIS/Mo interface would result in bad adhesion and lead to peel-off. The increase of sulfurization temperature also reduced the metastable phases of CuInS2-CA and CuIn5S8, while the blue shift and FWHM of CuInS2-CH A1 mode also decreased. As the results, the films quality increased. However, the thickness of MoS2 increased with sulfurization temperature was the thickest at 550℃ would affect the film adhesion. As the results, the best efficiency of CuInS2 solar cells obtained from 500℃ sulfurized films having a Cu/In atomic ratio of 1.8 was 6.29%.

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