本研究論文主利用化學氣相傳導法以三氯化碘當傳導劑來成長Cu(In1-xAlx)S2、CuAl(S1-xSex)2、Ag(In1-xAlx)S2系列以及AgIn5S8半導體晶體，針對此系列晶體藉由光學特性量測方式進行研究與探討。銅及銀為基底的Cu(In1-xAlx)S2、CuAl(S1-xSex)2與Ag(AlxIn1-x)S2系列硫化合物是多種寬能隙範圍的直接能隙半導體，其屬於黃銅礦結構，但欲成長AgInS2晶體(四方體結構)則易形成AgIn5S8(立方尖晶石結構)單晶晶體。
從外觀上銅基及銀基黃銅礦化合物Cu(In1-xAlx)S2、CuAl(S1-xSex)2與Ag(In1-xAlx)S2呈現明顯(112)面並且擁有針狀的形貌，以銅為基底的黃銅礦化合物Cu(In1-xAlx)S2覆蓋光譜範圍相當廣從1.5 eV到3.5 eV，具有峰值的吸收響應從近紅外光（NIR）到紫外光（UV）區，可應用於類似之疊層串接式的太陽能電池之吸收層，也可藉由變化硒與硫元素CuAl(S1-xSex)2由紫外光延伸至紅光範圍，可以有效發揮在可見光範圍內的光電轉換應用。此外在真空環境下以銀為基底的黃銅礦化合物Ag(In1-xAlx)S2中，AgAlS2呈現白色透明的顏色，隨添加少許銦元素，Ag(In0.2Al0.8)S2呈現淡黃色透明，其它成份則略偏紅色，高鋁成份的Ag(In1-xAlx)S2化合物在溼氣(大氣)的環境下易與水氣反應，AgAlS2與水氣反應表面迅速呈現棕黑色，而且Ag(In0.2Al0.8)S2與水氣亦有反應但稍趨緩。由實驗的分析與討論下，利用高鋁Ag(In1-xAlx)S2對濕氣特性，擬製作成濕氣感測元件。
實驗部份由能量散射分析光譜儀(EDS)判斷晶體成份、X光繞射光譜儀(XRD)及拉曼光譜儀(Raman)量測確定單晶化合物結構。由光穿透(吸收)與熱調制光譜研究顯示此Cu(In1-xAlx)S2、CuAl(S1-xSex)2、Ag(In1-xAlx)S2及AgIn5S8 (1.73eV) 單晶晶體皆為直接能隙半導體，且能隙隨成份變化之關係皆可求得。此外光極化相關量測對於銅基及銀基I-III-VI2族黃銅礦晶體研究，可得知材料晶體之能隙具有光學非對稱性，不同基底黃銅礦半導體材料，能隙大小皆為極化相關，其原因來自於價帶頂端p軌道之晶場分裂 (crystal field splitting)，並由熱調制光譜顯示能隙附近存在著多個激子躍遷信號，而激子也有極化相關性，配合光穿透(吸收)量測、X光電子能譜儀(XPS)與光學熱調制量測下提出此類晶體可能的能帶結構。

Cu- and Ag-based chalcopyrites semiconductor crystals of Cu(In1-xAlx)S2, CuAl(S1-xSex)2, Ag(In1-xAlx)S2, and AgIn5S8 have been grown by chemical vapor transport method using ICl3 as a transport agent. In this dissertation, we analyze crystal structure and discuss optical properties of these series compounds. The Cu- and Ag-based chalcopyrites of Cu(In1-xAlx)S2, CuAl(S1-xSex)2, and Ag(In1-xAlx)S2 are wide band-gap semiconductors and crystallized in tetragonal structure.
The as-grown Cu- and Ag-based chalcopyrites Cu(In1-xAlx)S2,CuAl(S1-xSex)2, and Ag(In1-xAlx)S2 show significant (112) plane and needle-like morphology. The chalcopyrite Cu(In1-xAlx)S2series covers the widest spectral range of energy gap ranging from 1.5 eV (CuInS2) to 3.5 eV (CuAlS2) which possesses the peak-absorption responses from near infrared (NIR) to ultraviolet (UV) region. By adding selenium elements, CuAl(S1-xSex)2 series can cover the values of direct band gap ranging from 2.5 eV (CuAlSe2) to 3.5 eV (CuAlS2). The band gap of CuAlSe2 dominates at green to blue color region while the absorption range of CuAlS2 works in the UV portion. The as-grown AgAlS2 crystal essentially shows a transparent and white color in vacuum while the as-grown Ag(In0.2Al0.8)S2 shows a faint yellowish color. The other compositions ingredients show reddish. When putting the AgAlS2 and Ag(In0.2Al0.8)S2 crystals into atmosphere, the crystals surface spontaneously transformed into oxygen deficient sample with darkened and brownish colors because of surface reaction with water vapor. The final products are Ag(InxAl1-x)O2, Ag2O, and Al2O3 oxides. The chemical reaction of higher Al elements Ag-based chalcopyrite crystals with water vapor is easy to happen under atmospheric ambient.
Energy Dispersive Spectroscopy (EDS) verifies the stochiometry of the crystals. X-ray diffraction and Raman measurements confirm that the single crystals of Cu- and Ag-based I-III-VI2 series are crystallized in chalcopyrite structure with -42m symmetry and AgIn5S8 belongs to cubic structure (Fd-3m). The direct semiconducting behavior of all crystals has been verified by optical absorption and thermal modulation spectroscopy techniques. Furthermore, optical behaviors of E  < > and E || < > polarizations near band edge show slight variation for the Cu- and Ag-based chalcopyrites. Temperature-dependent TR spectra characterize the direct interband transitions of the Cu- and Ag-based chalcopyrites. Based on the optical and structural study, the fundamental properties of Cu- and Ag-based chalcopyrites crystals were thus realized. The good correspondence of the experimental results as well as the proposed band diagram verifies the crystalline quality of the chalcopyrites.

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