臺灣博碩士論文加值系統

本研究使用射頻磁控濺鍍法沉積氧化鋅摻氟(ZnO:F, FZO)薄膜於EagleXG玻璃基板、聚亞醯胺(Polyimide, PI)基板與聚對苯二甲二乙酯 (polyethylene terephthalate, PET)基板上，在沉積FZO薄膜前先以電漿增強式化學氣相沉積(Plasma Enhance Chemical Vapor Deposition, PECVD)系統進行氧電漿預處理，研究不同基板經預處理後基板表面水接觸角度、表面形貌與光學特性之變化，再沉積FZO薄膜以研究預處理後薄膜的表面形貌、結構、成分、電性及光學特性之變化，最後搭配稀鹽酸(HCl)蝕刻表面，並製作成矽薄膜結構太陽電池，以探討不同預處理時間對光電轉換效率的影響。
PET基板、glass基板及PI基板經氧電漿預處理30~120秒後其基板表面特性會由疏水性轉為親水性，而經預處理420秒後由於生成含氧極性官能基的減緩導致水接觸角開始上升，會使基板表面特性呈現疏水性狀態。隨預處理時間的增加，所有基板表面粗糙度會呈現越來越粗糙的表面形貌。
FZO薄膜經預處理30秒後沉積薄膜可得到最佳光電特性表現的FZO薄膜，其PET基板、PI基板及glass基板電阻率為 5.489×10-3 Ω-cm、3.153×10-3 Ω-cm及4.214*10-3 Ω-cm，而可見光平均光學穿透率皆約為90 %以上。
FZO薄膜在稀鹽酸蝕刻後薄膜的電阻率會稍微的上升且表面形貌明顯變粗糙，預處理30秒後沉積之FZO 薄膜經過 0.2 % 稀鹽酸蝕刻後，玻璃基板在可見光平均霧度(haze ratio)從 1.79 % 增加到21.96 % ，而PI基板在可見光平均霧度(haze ratio)從2.05 % 增加到21.22 % 。
最後將glass基板與PI基板所沉積之FZO薄膜製作成非晶矽薄膜太陽電池，從結果可看出經過稀鹽酸蝕刻後玻璃基板轉換效率從3.42 % 增加至3.99 % 於預處理30秒後 ，而PI基板轉換效率從3.35 % 增加至3.68 % 於預處理30秒後。

Fluorine-doped zinc oxide (FZO) thin films were deposited on EagleXG glass, PI (polyimide) and PET (polyethylene terephthalate) substrates by RF magnetron sputtering. Prior to the FZO films deposited using a single-chamber plasma enhanced chemical vapor deposition system for oxygen plasma pre-treatment. Influence of surface water contact angle, surface morphology and optical properties was investigated with oxygen plasma pre-treatment for different substrates and treatment times. Then, FZO thin films were deposited on the treated substrates to explore the surface, structural, composition, electrical, and optical properties. Finally, we used dilute hydrochloric acid (HCl) to etch the films to form textured surfaces as front electrodes of amorphous silicon thin film solar cells.. Effect of plasma treatment time on conversion efficiency of the solar cell was investigated.
The surfaces of PET, glass and PI substrates presented hydrophilic characteristic from hydrophobic characteristic after oxygen plasma pretreatment for 30 to 120 s. The water contact angle got rising due to slow oxygen containing polar functional group generated after pre-treated 420 s, then the surface properties of the all substrates presented a hydrophobic surface condition. The surface roughness of the all substrates increased as the pre-treatment time increased.
The FZO films with pre-treatment time of 30 s show the optimum opto-electronic properties. Resistivity of PET, PI and glass substrates were 5.489 *10-3 Ω-cm, 3.153*10-3 Ω-cm and 4.214*10-3 Ω-cm, respectively, while the average optical transmittance in wavelength range of 400-700 nm was over 90 %.
The resistivity and surface roughness were increased as FZO films were etched by 0.2 % HCl solution. After pre-treatment of 30 s and 0.2 % dilute HCl etching, the haze ratio of the FZO film on glass substrate increased from 1.79 % to 21.96 %, while that on the PI substrate increased from 2.05 % to 21.22 %.
The I-V measurement of the fabricated amorphous silicon thin film solar cells employed the etched FZO films as the front electrodes shows that the conversion efficiency increased from 3.42 % to 3.99 % for glass substrates, and from 3.35 % to 3.68 % for PI substrates after a 30-sec oxygen plasma pretreatment.

目錄
誌謝 I
中文摘要 II
Abstract III
目錄 V
圖目錄 VIII
表目錄 XI
第一章 緒論 1
1.1 透明導電薄膜 1
1.2 研究動機與目的 2
第二章 基礎理論與文獻回顧 4
2.1 氧化鋅 4
2.1.1 氧化鋅的結構與特性 4
2.1.2 氧化鋅摻氟(ZnO:F, FZO)薄膜 6
2.1.2.1 電學特性 6
2.1.2.2 光學特性 7
2.1.2.3 摻雜現象 7
2.2 電漿原理與特性 8
2.3 電漿表面改質 9
2.4 濺鍍系統 10
2.4.1 濺鍍原理 10
2.4.2 射頻磁控濺鍍系統 11
第三章 實驗步驟與方法 12
3.1 實驗製備與分析流程 12
3.2 靶材 13
3.2.1 靶材製作流程 13
3.2.2 粉末配製與靶材製作 14
3.3 基板切割與清洗 15
3.4 基板預處理與薄膜沉積 16
3.4.1 預處理與薄膜沉積設備 16
3.4.2 氧電漿預處理流程與實驗參數 16
3.4.3 FZO薄膜成長流程與實驗參數 17
3.4.4 稀鹽酸蝕刻流程與實驗參數 18
3.4.5 矽薄膜太陽能電池製作與實驗參數 19
3.5 薄膜量測與分析儀器 20
3.5.1 水接觸角量測 20
3.5.2 薄膜厚度量測 20
3.5.3 薄膜光學量測 21
3.5.4 薄膜電性量測 22
3.5.4.1 四點探針 22
3.5.4.2 霍爾量測 22
3.5.5 薄膜結構分析 23
3.5.5.1 XRD 結構分析 23
3.5.5.2 表面形貌分析 23
3.5.5.3 表面粗糙度分析 24
3.5.6 薄膜成分分析 24
第四章 結果與討論 25
4.1 氧電漿預處理對不同基板的影響 25
4.1.1 預處理氣體的選擇 25
4.1.2 水接觸角分析 26
4.1.3 基板表面AFM分析 29
4.1.4 光學分析 31
4.2 氧電漿預處理對FZO薄膜的影響 32
4.2.1 沉積速率 33
4.2.2 薄膜AFM分析 33
4.2.3 薄膜XRD分析 35
4.2.4 SEM表面結構 39
4.2.5 電性分析 41
4.2.6 XPS分析 48
4.2.7 光學分析 53
4.3 稀鹽酸蝕刻對FZO薄膜的影響 62
4.3.1 蝕刻速率 62
4.3.2 SEM 45度表面結構 62
4.3.3 電性分析 64
4.3.4 光學分析 64
4.4 矽薄膜太陽電池 66
第五章 結論 69
5.1 總結 69
5.2 未來工作 71
參考文獻 72

圖目錄
圖2-1氧化鋅wurtzite結構(大：鋅原子，小：氧原子 5
圖2-2薄膜摻雜之光學能隙圖(a)未摻雜半導體(b)經摻雜後，傳導帶底部電子所佔據(c)能帶窄化現象 8
圖2-3濺鍍時可能產生之反應示意圖 11
圖3-1實驗製備與分析流程圖 12
圖3-2 FZO 靶材製作流程圖 13
圖3-3 FZO燒結曲線圖 14
圖3-4射頻磁控濺鍍系統示意圖 17
圖4-1為不同基板預處理對不同工作氣體之水接觸角影像圖(a)PET基板(b)glass基板(c)PI基板 26
圖4-2楊氏方程式示意圖 27
圖4-3不同基板氧電漿預處理之水接觸角比較圖 28
圖4-4不同基板之水接觸角影像圖(a)PET基板(b)glass基板(c)PI基板 28
圖4-5 PET基板於室溫下經氧電漿預處理後之AFM分析圖，預處理(a)0秒(b)30秒(c)420秒 29
圖4-6 glass基板於室溫下經氧電漿預處理後之AFM分析圖，預處理(a)0秒(b)30秒(c)420秒 30
圖4-7 PI基板於室溫下經氧電漿預處理後之AFM分析圖，預處理(a)0秒(b)30秒(c)420秒 30
圖4-8不同基板於室溫下經氧電漿預處理後之基板光學穿透率圖(a)PET基板(b)glass基板(c)PI基板 32
圖4-9 PET基板於室溫下經氧電漿預處理後之薄膜AFM分析圖，預處理(a)0秒(b)30秒(c)420秒 33
圖4-10 glass基板於室溫下經氧電漿預處理後之薄膜AFM分析圖，預處理(a)0秒(b)30秒(c)420秒 34
圖4-11 PI基板於室溫下經氧電漿預處理後之薄膜AFM分析圖，預處理(a)0秒(b)30秒(c)420秒 34
圖4-12不同預處理時間後之薄膜XRD分析圖，預處理(a)0秒(b)30秒(c)60秒(d)420秒 36
圖4-13不同基板經預處理後之薄膜半高寬與晶粒大小關係圖(a)PET基板(b)glass基板(c)PI基板 38
圖4-14不同預處理時間對薄膜應變關係圖 39
圖4-15 PET基板經預處理後之薄膜表面結構圖，預處理(a)0秒(b)30秒(c)420秒 40
圖4-16 glass基板經預處理後之薄膜表面結構圖，預處理(a)0秒(b)30秒(c)420秒 40
圖4-17 PI基板經預處理後之薄膜表面結構圖，預處理(a)0秒(b)30秒(c)420秒 41
圖4-18不同基板經預處理後之薄膜電性量測圖(a)Resistivity(b)Hall mobility(c)Carrier concentration 43
圖4-19不同基板經預處理後之薄膜載子濃度與遷移率關係圖 44
圖4-20 PET基板置於室溫下薄膜之可靠度分析圖(a)電性量測(b)正規化作圖 45
圖4-21 glass基板置於室溫下薄膜之可靠度分析圖(a)電性量測(b)正規化作圖 46
圖4-22 PI基板置於室溫下薄膜之可靠度分析圖(a)電性量測(b)正規化作圖 47
圖4-23不同基板經預處理前後沉積薄膜之XPS全頻譜圖，PI基板(a)未經預處理(b)預處理30秒；PET基板(c)未經預處理(d)預處理30秒 49
圖4-24 不同基板預處理前後XPS之O 1s峰值，PI基板(a)未經預處理(b)預處理30秒；PET基板(c)未經預處理(d)預處理30秒 50
圖4-25為不同基板預處理前後XPS之Zn 2p3/2峰值，PI基板(a)未經預處理(b)預處理30秒；PET基板(c)未經預處理(d)預處理30秒 51
圖4-26為不同基板預處理前後XPS之Zn 2p1/2峰值，PI基板(a)未經預處理(b)預處理30秒；PET基板(c)未經預處理(d)預處理30秒 52
圖4-27不同基板於室溫下經氧電漿預處理後之薄膜光學穿透率圖(a)PET基板(b)glass基板(c)PI基板 54
圖4-28不同預處理時間沉積之薄膜光學能隙圖(a)0秒(b)30秒(c)60秒(d)120秒(e)420秒 56
圖4-29不同預處理時間之薄膜光學能隙比較圖 57
圖4-30不同基板預處理後之薄膜藍移與載子濃度關係圖(a)PET基板(b)glass基板(c)PI基板 58
圖4-31不同基板預處理後之薄膜效益指數比較圖 59
圖4-32不同基板預處理後之薄膜折射率分佈圖(a)PET基板(b)glass基板(c)PI基板 60
圖4-33不同基板預處理後之薄膜消光係數分佈圖(a)PET基板(b)glass基板(c)PI基板 61
圖4-34 glass基板沉積薄膜蝕刻前後之表面形貌，未經預處理(a)蝕刻前(b)蝕刻後；經預處理30秒(c)蝕刻前(d)蝕刻後 63
圖4-35 PI基板沉積薄膜蝕刻前後之表面形貌，未經預處理(a)蝕刻前(b)蝕刻後；經預處理30秒(c)蝕刻前(d)蝕刻後 63
圖4-36未經氧電漿預處理後沉積之薄膜光學穿透率與霧度圖 65
圖4-37氧電漿預處理30秒後沉積之薄膜光學穿透率與霧度圖 65
圖4-38薄膜太陽電池之暗電流量測圖 66
圖4-39薄膜太陽電池之光電流量測圖 67

表目錄
表2-1氧化鋅基本特性 5
表2-2原子價數與離子半徑表 7
表3-1氧電漿預處理實驗參數 17
表3-2 FZO薄膜沉積實驗參數 18
表3-3稀鹽酸蝕刻實驗參數 19
表3-4矽薄膜太陽電池製作參數 19
表4-1不同工作氣體之水接觸角比較表 26
表4-2不同預處理時間之水接觸角比較表 29
表4-3不同預處理時間之基板平均光學穿透率比較表 31
表4-4不同預處理時間之薄膜沉積速率表 33
表4-5不同預處理時間薄膜之XRD相關數據表 37
表4-6不同基板預處理前後O 1s分峰之面積比較表 51
表4-7 不同基板預處理前後Zn 2p3/2及Zn 2p1/2分峰之面積比較表 52
表4-8不同預處理時間之薄膜平均光學穿透率比較表 54
表4-9不同預處理時間之薄膜光學能隙比較表 56
表4-10不同預處理時間之薄膜蝕刻速率表 62
表4-11不同預處理時間沉積之薄膜蝕刻前後的片電阻比較表 64
表4-12不同預處理時間沉積之薄膜在可見光區的平均光學穿透率與霧度比較表 64
表4-13薄膜理想因子比較表 67
表4-14薄膜太陽電池之相關數據比較表 68

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