臺灣博碩士論文加值系統

本研究利用噴塗法，改變不同[Cu]/[In]比例之前驅物濃度，在S 充
足的情況下，沉積在ITO 導電玻璃上，之後經由熱處理500 oC 製備
出n-type CuInS2 薄膜，並且摻雜不同濃度之Zn，希望能提升光電流
表現及調整能階位置來做為p-n junction 能階設計的材料。結構分析
顯示為正方晶系黃銅礦結構的CuInS2，且隨著Cu 的量增加，結晶性
越高，另外無雜相的生成。在紫外光可見光波段，吸收係數大約在104
~ 105 之間，是很理想的光吸收材料，而各比例之能隙值變化不大，大
約介於1.5 ~ 1.55 eV 之間。而光電化學性質中，在電壓= 1.23 V vs.
RHE 時，電解質為犧牲試劑的情況下，n 型光電流表現能達到2.24
mA/cm2。n-type CuInS2 摻雜Zn 後，由XRD 觀察結晶相並沒有改變，
也無雜相生成。在光電流表現上，沒有達到提升光電流的效果。由UVvis
分析，隨著Zn 摻雜量的上升，能隙值有稍微變大的趨勢，不過能
隙值都位在1.5~1.6 eV 之間。摻雜Zn 後光電流表現並沒有下降特別
多，可以利用此特性，我們會進一步量測能階位置來判斷摻雜n-type
CuInS2 及Zn 之n-type CuInS2 是否能做為p-n junction 能階設計的材
料之一。

n-type CuInS2 thin films were fabricated with different [Cu]/[In] ratio
in precursor by spray pyrolysis method on a transparent indium-doped tin
oxide (ITO) substrate followed by calcination in the Ar at 500 oC. Further
we investigated the structural and optical properties of Zn-doped n-type
CuInS2. As the XRD patterns, shows the chalcopyrite CuInS2 structure
with the increase of the amount of Cu, the higher the crystallinity of CuInS2.
The optical study show the absorption coefficient (α) in the UV-visible
region is found to be in the order of 104~105 cm-1 which is the optimum
value for an efficient absorber. The synthesized n-type CuInS2 thin film has
an optical bandgap of 1.5~1.55 eV. CuInS2 thin film yielded a photocurrent
density of 2.24 mA cm-2 at 1.23 V vs. RHE in 0.25 M Na2S and 0.35 M
Na2SO3 under 300 W xenon lamp. Zn-doped CuInS2 has the same optical
bandgap of 1.5~1.6 eV as the n-type CuInS2. Zn-doped CuInS2 didn’t
facilitate photocurrent density, but photocurrent density didn’t drop too
much as well. For this characteristic, we will determine energy band
position of n-type CuInS2 and Zn-doped CuInS2 to be band position design
of the p-n junction material.

目錄
摘要 I
致謝 III
目錄 IV
圖目錄 VII
表目錄 X

一、緒論 1
1-1 前言 1
1-2 光觸媒分解水發展 2
1-3 研究動機 4
二、文獻回顧 6
2-1 半導體光觸媒分解水 6
2-1-1 半導體能帶 6
2-1-2 光觸媒分解水產氫原理 9
2-2 光觸媒材料 11
2-3 CuInS2 光觸媒 13
2-3-1 CuInS2 化學結構組成與電性關係 13
2-3-2 n-type CuInS2 16
2-3-3 元素摻雜CuInS2 18
2-4 噴霧熱裂解法製備CuInS2 20

三、實驗方法 22
3-1 實驗藥品 22
3-2 實驗儀器與分析儀器 24
3-3 實驗步驟 26
3-3-1 基材清洗 27
3-3-2 製備CuInS2 薄膜 28
3-3-3 製備摻雜Zn 之CuInS2 薄膜 28
3-3-4 光電化學量測 30

四、結果與討論 33
4-1 n-type CuInS2 33
4-1-1 n-type CuInS2：X 光繞射分析 (X-ray diffraction) 33
4-1-2 n-type CuInS2：拉曼光譜學(Raman spectroscopy) 35
4-1-3 n-type CuInS2：電子掃描顯微鏡 (Scanning Electron
Microscope)分析 37
4-1-4 n-type CuInS2：紫外光可見光光譜儀(UV-Visible
Spectrophotometer) 40
4-1-5 n-type CuInS2：光電化學量測 44
4-2 Zn-doped n-type CuInS2 46
4-2-1 Zn-doped n-type CuInS2：X 光繞射分析 (X-ray diffraction)
46
4-2-2 Zn-doped n-type CuInS2：拉曼光譜學(Raman spectroscopy)
48
4-2-3 Zn-doped n-type CuInS2：紫外光可見光光譜儀(UV-Visible
Spectrophotometer) 49
4-2-4 Zn-doped n-type CuInS2：光電化學量測 52
4-3 Mott-Schottky 測量 54

五、結論與未來展望 56
參考文獻 57
附錄 66

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