以化學水浴法製備氧化鋅光電極薄膜之研究｜國立中央大學博碩士論文系統

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研究生：	徐彥翔 Yan-Shiang Shiu
論文名稱：	以化學水浴法製備氧化鋅光電極薄膜之研究 Production of ZnO Photoelectrode Thin Film by Chemical Bath Deposition Method
指導教授：	洪勵吾 Lih-Wu Hourng
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 能源工程研究所 Graduate Institute of Energy Engineering
畢業學年度：	98
語文別：	中文
論文頁數：	80
中文關鍵詞：	化學水浴沉積法、半導體薄膜、光電流密度、晶型結構
外文關鍵詞：	water-splitting, photoelectrochemical, photoelectrode, crystal structure, Zinc Oxide
相關次數：	點閱：9 下載：0
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本研究探討氧化鋅(ZnO)半導體薄膜改變氨水濃度、沉積溫度、
熱處理氣氛及熱處理溫度，對薄膜成形性質、吸收率及光電流的影
響。以化學水浴法沉積法(CBD)於ITO 導電玻璃基材上進行鍍膜，來
製備光電極薄膜。利用光電化學原理於水溶液中吸收太陽能，並將其
解離成氫氣應用於氫能發電系統上。
本實驗探討不同氨水溶液濃度下對生成氧化鋅晶型結構之影
響，並比較在不同的晶型結構下，其晶型結構對穿透光譜及光電流性
質之影響。實驗結果發現，氨水濃度在1M、1.8M時，氧化鋅形成六
角柱型粗短及細長之晶型結構，氨水濃度在1.7M時，氧化鋅形成花
瓣狀之晶形結構。當其氨水濃度提升至10M時，而其氧化鋅半導體光
電特性在無施加偏壓下光電流密度可達到約0.17mA/cm2。進一步改
變沉積溫度、熱處理氣氛及熱處理溫度對薄膜沉積的影響；實驗結果
顯示，沉積溫度90℃、真空氣氛熱處理500℃下，氧化鋅薄膜之成膜
性質及吸收率最佳。
實驗結果亦顯示氧化鋅摻雜鎳後，其能隙值、吸收率及光電特性
的影響；在無施加偏壓下光電流密度約0.2mA/cm2。因此，化學水浴
法製備氧化鋅光電極乃成本低廉且製程簡易之方式。
關鍵字：半導體薄膜、化學水浴沉積法、晶型結構、光電流密度

In this study, zinc oxide (ZnO) thin film are formed under different
working parameters, and their absorption and photocurrent effect are
analyzed. ZnO thin films are deposited on ITO conductive glass substrate
by chemical bath deposition (CBD), which is one of the most promising
technique owing to its large-scale, cost-effective, environmental-benign
and low-temperature advantages. By photoelectrochemical water-splitting,
ZnO thin film can be used to produce H2.
Firstly, different concentrations of ammonia solution are adapted to
form zinc oxide thin film, and the resulting crystal structures are
compared. It shows that ZnO particles have short and long hexagonal
cylinder shapes at [NH3]=1 and1.8. The short hexagonal cylinder shapes
was further transformed to a flower-like structure as ammonia increases
to [NH3]=1.7. Experiments show that the photocurrent density of ZnO
photoelectrode is nearly 0.17 mA/cm2 at 0 bias. The best forming
properties of ZnO film occurs at [NH3]=10.
By doping Ni into ZnO the effects on energy gap, absorption and
photocurrent density of ZnO thin film is investigated. Photocurrent
density of ZnO film is nearly 0.2 mA/cm2 at 0 bias. Therefore, producing
ZnO photoelectrode by chemical bath deposition is proved to be a
low-cost and simple method.
Keyword: Zinc Oxide; crystal structure; photoelectrode;
photoelectrochemical; water-splitting

摘要............................................................................................................. I
Abstract ......................................................................................................II
誌謝...........................................................................................................III
目錄.......................................................................................................... IV
表目錄.....................................................................................................VII
圖目錄....................................................................................................VIII
符號說明.................................................................................................. XI
第一章 緒論...............................................................................................1
1.1 研究背景與動機...........................................................................1
1.2 太陽能產氫原理...........................................................................2
1.3 化學水浴沉積法原理...................................................................3
1.3.1 化學水浴法沉積氧化物之化學反應機制........................4
1.3.2 化學水浴法之薄膜成長機制.............................................5
1.3.3 薄膜沉積成長與溶解度之關係.........................................6
1.4 文獻回顧.......................................................................................7
1.4.1 化學水浴法文獻回顧.........................................................7
1.4.2 光觸媒文獻回顧.................................................................8
1.4.3 氧化鋅(ZnO)文獻回顧.......................................................9
1.5 研究動機與目的.........................................................................13
IV
第二章 實驗部分與研究方法................................................................15
2.1 實驗流程與參數設定.................................................................15
2.2 實驗藥品材料與實驗裝置........................................................15
2.2.1 實驗藥品...........................................................................15
2.2.2 實驗基材...........................................................................17
2.2.3 實驗設備...........................................................................17
2.2.4 實驗步驟...........................................................................19
2.2.4.1 基材裁切、清洗與組裝.........................................19
2.2.4.2 反應鍍液配製與鍍浴方法.....................................20
2.2.4.3 試片完成之後處理(電極封裝)..............................21
2.3 薄膜物性量測分析.....................................................................21
2.3.1 XRD (X-ray 繞射儀) ........................................................22
2.3.2 FE-SEM (場發掃描式電子顯微鏡)..................................23
2.3.3 UV-Visible (紫外/可見光光譜儀).....................................24
2.4 薄膜電性量測分析.....................................................................25
第三章 實驗結果與討論........................................................................27
3.1 不同錯合劑濃度對其晶形結構及成膜性質的影響.................28
3.2 沉積溫度對薄膜的影響............................................................31
3.3 不同氣氛熱處理對薄膜的影響................................................33
V
3.4 熱處理溫度對薄膜的影響........................................................34
3.5 摻雜鎳對氧化鋅薄膜的影響....................................................35
第四章 結論與未來展望........................................................................37
4.1 結論.............................................................................................37
4.2 未來展望.....................................................................................38
參考文獻...................................................................................................39
VI
表目錄
表 2-1 實驗參數設定..............................................................................45
表2-2 實驗藥品......................................................................................46
表3-1 實驗參數設定表..........................................................................47
表3-2 膜厚表..........................................................................................48
表3-3 摻雜鎳之實驗參數設定表..........................................................48
VII
圖目錄
圖 1-1 太陽能產氫原理圖[2] .................................................................49
圖1-2 化學水浴裝置圖[3] .....................................................................49
圖1-3 化學水浴成膜機制[10] ...............................................................50
圖1-4 薄膜成長機制[9] .........................................................................50
圖2-1 實驗流程規劃..............................................................................51
圖2-2 實驗步驟流程圖..........................................................................52
圖2-3 基材清洗流程圖..........................................................................53
圖2-4 X光粉末繞射(XRD)示意圖[40] ...............................................54
圖2-5 掃描式電子顯微鏡(SEM)示意圖[40] ........................................54
圖2-6 積分球示意圖[43] .......................................................................55
圖3-1 不同濃度下之晶形結構(沉積溫度90℃) ..................................56
圖3-2 濃度1.7M在不同倍率下之情形................................................57
圖3-3 晶形結構對結晶強度的影響......................................................58
圖3-4 晶形結構對穿透率的影響..........................................................58
圖3-5 晶形結構對反射率的影響..........................................................59
圖3-6 晶形結構對吸收率的影響..........................................................59
圖3-7 濃度對結晶強度的影響..............................................................60
圖3-8 不同濃度下對成膜性質的影響(沉積溫度90℃) ......................61
VIII
圖3-9 濃度對穿透率的影響..................................................................62
圖3-10 濃度對反射率的影響................................................................62
圖3-11 濃度對吸收率的影響................................................................63
圖3-12 濃度對光暗電流性質的影響....................................................63
圖3-13 沉積溫度對結晶強度的影響....................................................64
圖3-14 氧化鋅薄膜在不同沉積溫度下之情形([NH3]=10M) .............65
圖3-15 薄膜形成孔洞之情形(沉積溫度80℃) ....................................66
圖3-16 沉積溫度對穿透率的影響........................................................67
圖3-17 沉積溫度對反射率的影響........................................................67
圖3-18 沉積溫度對吸收率的影響........................................................68
圖3-19 沉積溫度對光暗電流性質的影響............................................68
圖3-20 不同沉積溫度之平帶電位........................................................69
圖3-21 熱處理氣氛對結晶強度的影響................................................69
圖3-22 熱處理氣氛對穿透率的影響....................................................70
圖3-23 熱處理氣氛對反射率的影響....................................................70
圖3-24 熱處理氣氛對吸收率的影響....................................................71
圖3-25 熱處理氣氛對能隙值的影響....................................................71
圖3-26 熱處理氣氛對光暗電流性質的影響........................................72
圖3-27 熱處理溫度對結晶強度的影響................................................72
IX
圖3-28 熱處理溫度對穿透率的影響....................................................73
圖3-29 熱處理溫度對反射率的影響....................................................73
圖3-30 熱處理溫度對吸收率的影響....................................................74
圖3-31 熱處理溫度對能隙值的影響....................................................74
圖3-32 熱處理溫度對光暗電流性質的影響........................................75
圖3-33 不同熱處理溫度之平帶電位....................................................75
圖3-34 摻雜鎳對結晶強度的影響........................................................76
圖3-35 有無摻雜鎳之表面形態([NH3]=10M,沉積溫度90℃) ...........77
圖3-36 摻雜鎳對穿透率的影響............................................................78
圖3-37 摻雜鎳對反射率的影響............................................................78
圖3-38 摻雜鎳對吸收率的影響............................................................79
圖3-39 摻雜鎳對能隙的影響................................................................79
圖3-40 摻雜鎳對光暗電流性質的影響................................................80

                                

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