硒化鋅是一種具有直接能隙(2.7eV)II-VI族化合物半導體材料，且深具潛力的光電半導體材料，適合應用於異質接面太陽能池，一般均利用真空、高溫、高壓設備製備，若能利用電沈積的方法製備，由於不使用揮發性物質、不需在高溫且真空下操作，能降低成本，且更能符合經濟效益、更簡便的製備出硒化鋅薄膜，本研究是利用電解質(SeO2=100 mM，ZnSO4．7H2O=1 M)之電化學作用，在酸性溶液中(pH=2)沉積ZnSe薄膜於ITO玻璃基板上。
實驗結果顯示在電解析硒化鋅鍍層時，固定濃度、pH值，改變鍍液之溫度則所施加的析鍍電位也應相對改變，且愈接近電解析電位時，硒化鋅薄膜結晶性愈佳，在室溫之下電解析電位愈接近負時，沉積薄膜速度愈快，薄膜厚度增加，使得阻值增加，電流下降愈快，在高溫電解析鍍硒化鋅鍍層時，i-t曲線圖變的不平滑，因為在高溫電解析鍍硒化鋅鍍層時，溶液易產生氣泡，使得溶液擾動，所以使得i-t曲線不平滑。

Zinc selenide (ZnSe) film is successfully deposited by the electrodeposition technology. Due to ZnSe with a direct band-gap of 2.7 eV, it is widely used for optoelectronic applications. Recently, it is used as the window layer to improve the open circuit voltage in solar cells. The ZnSe film was prepared with vacuum, high temperature, and high pressure was usually used. However, these disadvantages limited the cost down and time to market. Electrodeposition is an easy use and very simple technology proposed to grow large area of ZnSe films. In this study, the electrodeposition of ZnSe film has been accomplished in an aqueous bath (pH = 2) during electrochemical reduction of an electrolyte containing SeO2 (100 mM) and ZnSO4•7H2O (1 M) on a indium tin oxide glass substrate.

Results clearly show that the film quality was strongly depend on the electrodeposited potential. The electro-potential is Indeed as a function of the substrate temperature, the concentration of solutes, and pH value of solution. The structure of as-deposited ZnSe thin film is polycrystalline measured by x-ray diffraction (XRD). The surface morphology of deposited films are investigated by Scanning electron microscopy (SEM). The high quality of film growth is achieved when the electro-potential applied is close to the electrodeposited potential of ZnSe. As the more negative of electrodeposited potential applied at room temperature, the growth rate, thickness and resistance of thin film are increase and the current is decrease. In addition, the i-t curve shows very rough due to the bubbles generated to disturb the solution while electrodeposited at the high temperature.

誌謝 I
摘要 II
Abstract II
目錄 IV
第一章 緒論 1
1-1 半導體材料 1
1-1-1 前言 1
1-1-2 半導體的晶體結構 1
1-1-3 半導體的成份 6
1-2 研究動機 9
第2章 實驗原理 10
2-1 硒化鋅介紹 10
2-1-1 硒化鋅材料特性 10
2-2 硒化鋅製備方式 11
2-2-1 濺鍍法(sputtering) 11
2-2-2 化學氣相沉積(Chemical Vapor Deposition，CVD) 12
2-2-3 分子束磊晶法 14
2-2-4 化學浴沉積 14
2-3 電化學原理 15
2-4 電鍍反應 16
2-4-1 法拉第定律(Faraday's Law) 16
2-4-2 電流效率(Current Efficiency) 16
2-4-3 氧化還原電位(Redox Potenial，E) 16
2-4-4 電鍍合金的原理(Principle of Alloy Plating) 16
2-5 電化學製程設備 19
2-6 恆電流法(即控制電流法) 23
2-7 恆電位法(即控制電位法) 21
2-8 電化學的優勢與劣勢 22
2-9 影響硒化鋅薄膜之因素 23
2-9-1 底材特性 24
2-9-2試片前處理 24
2-9-3 電鍍溶液 25
2-10 硒化鋅發展現況與特點 25
第三章 實驗方法與儀器設備 27
3-1 實驗材料與儀器設備 27
3-1-1 實驗材料 27
3-1-2 實驗設備 27
3-2 ITO電極的前處理 28
3-3 白金棒及白金片的前處理 29
3-4 溶液配製 30
3-4-1 硒溶液之配製 30
3-4-2 鋅溶液之配製 30
3-4-3 硒-鋅溶液之配製 31
3-5循環伏安法 31
3-5-1 硒溶液的CV量測實驗 33
3-5-2 鋅溶液的CV量測實驗 33
3-5-3 硒-鋅溶液的CV量測實驗 33
3-6 硒化鋅之析鍍 34
3-7 薄膜分析儀器 36
3-7-1 掃描式電子顯微鏡(Scanning Electron Microscopy) 36
3-7-2 X光繞射儀(X-ray Diffractormeter Spectrometer) 37
3-7-3 α-step分析 37
第四章 實驗結果 38
4-1 C-V關係圖 38
4-1-1 硒溶液CV量測 38
4-1-2 鋅溶液CV量測 39
4-1-3硒-鋅溶液CV量測在不同溫度 39
4-2 硒-鋅共沉積曲線圖 40
4-3 α-step膜厚分析 44
4-4 XRD繞射分析 44
4-4-1 ITO背景XRD圖 44
4-4-2 JCPDS-02-0479 ZnSe data base 45
4-4-3 室溫之下不同沉積電壓XRD圖 46
4-4-4 55℃之下不同沉積電壓XRD圖 49
4-4-5 65℃之下不同沉積電壓XRD圖 52
4-4-6 XRD半高寬比之分析 55
4-5 SEM觀察與分析 57
4-5-1 室溫之下不同氧化電壓製備鍍層的表面形貌 57
4-5-2 45℃之下不同氧化電壓製備鍍層的表面形貌 58
4-5-3 55℃之下不同氧化電壓製備鍍層的表面形貌 60
4-5-4 65℃之下不同氧化電壓製備鍍層的表面形貌 61
第五章 結論 64

1. A.P.SAMANTILLEKE，M.H.BOYLE，J.YOUNG，I. M.DHARMADASA，
JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS 1998，Vol 9，Iss 4，pp 289-290
2. R.P.Wijesundera and W.Siripala，SOLAR ENERGY MATERIALS AND
SOLAR CELLS 2004，Vol 81，Iss 2，pp 147-154
3. R. Chandramohan，T. Mahalingam，J. P. Chu and P. J. Sebastian，SOLAR ENERGY MATERIALS AND SOLAR CELLS 2004，Vol 81，Iss 3，pp 371-378
4. R.Henríquez，H.Gómez，G.Riveros，J.F.Guillemoles，M.Froment，and D.Lincot，JOURNAL OF PHYSICAL CHEMISTRY B 2004，Vol 108，Iss 35，pp 13191-13199
5. Sylvie Rouquette-Sanchez，Gérard S.Picard，JOURNAL OF ELECTROANALYTICAL CHEMISTRY 2004，Vol 572，Iss 1，pp 173-183
6. Takahiro Ishizaki，Takeshi Ohtomo and Akio Fuwa，JOURNAL OF PHYSICS D-APPLIED PHYSICS 2004，Vol 37，Iss 2，pp 255-260
7. RIVEROS，G.；GÓMEZ，H；HENRÍQUEZ，R.；SSHREBLER，R.；CÓRDOVA， R.; MAROTTI，R. E.；DALCHIELE，E.A.，BOLETIN DE LA SOCIEDAD CHILENA DE QUIMICA 2002，Vol 47，Iss 4，pp 411-429
8. G.Riveros,D.Lincot，J.F.Guillemoles，R.Henríquez，R.Schrebler，R.Cordova and H.Gomez，JOURNAL OF ELECTROANALYTICAL CHEMISTRY 2003，Vol 558，Iss OCT，pp 9-17
9. S.Soundeswaran，O.Senthil Kumar，R.Dhanasekaran，P.Ramasamy，R.Kumaresen and M.Ichimura，MATERIALS CHEMISTRY AND PHYSICS 2003，Vol 82，Iss 2，pp 268-272
10. G.Riveros，J.F.Guillemoles，D.Lincot，H.Gomez Meier，M.Froment，M.C.Bernard，R.Cortes，ADVANCED MATERIALS 2002，Vol 14，Iss 18，pp 1286+
11. A.M.Chaparro，M.T.Gutiérrez and J.Herrero，ELECTROCHIMICA ACTA 2001，Vol 47，Iss 6，pp 977-986
12. A.R.de Moraes，D.H.Mosca，N.Mattoso，W.H.Schreiner，A.J.A.de Oliveira and W.A.Ortiz，PHYSICA B-CONDENSED MATTER 2002，Vol 320，Iss 1-4，pp 199-202
13. A.P. Samantilleke，I.M.Dharmadasa，K.A. Prior，K.L.Choy，J.Mei，R.Bacewicz，A.Wolska，JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS 2001, Vol 12，Iss 11，pp 661-666
14. G.Riveros，H.Gómez，R. Henríquez，R. Schrebler，R.E.Marotti and E.A.Dalchiele，SOLAR ENERGY MATERIALS AND SOLAR CELLS 2001，Vol 70，Iss 3，pp 255-268
15. Dori Gal and Gary Hodes，JOURNAL OF THE ELECTROCHEMICAL SOCIETY 2000，Vol 147，Iss 5，pp 1825-1828
16. G.Pezzatini，S.Caporali，M.Innocenti and M.L.Foresti，JOURNAL OF ELECTROANALYTICAL CHEMISTRY 1999，Vol 475，Iss 2，pp 164-170
17. S.Sanchez，C.Lucas，G.S.Picard，M.R.Bermejo and Y.Castrillejo，THIN SOLID FILMS 2000，Vol 361，Iss FEB，pp 107-112
18. 陳佳伶，以電解沈積法製備碲化鋅之研究，國立成功大學，頁1，1997
19. 鍾耀賢，電化學製備硫化鋅結構及其光學性質，國立台灣大學，頁1，2005