臺灣博碩士論文加值系統

本論文主要探討以還原的氧化石墨烯(Reduced Graphene Oxide, RGO) ，摻雜於氧化鋅摻鋁(Aluminum doped Zinc Oxide,AZO)中並對薄膜作電性及光學特性上的分析。實驗方法以溶膠凝膠法(sol-gel)旋轉塗佈在玻璃基板上，分別以不同重量濃度0.0 wt%, 1.0 wt%, 1.5 wt%, 3.0 wt%作為摻雜比例，完成後以Ar:H2=9:1的混合氣體通入爐管中並以攝氏500℃作熱退火處理一小時。在電性量測中，未摻雜RGO的AZO薄膜所量測電阻率約為1.11ⅹ10-1 Ω-cm，在摻入RGO 1.0 wt%後得到最低電阻率為8.11ⅹ10-3 Ω-cm。光學分析中，摻入RGO 1.0 wt%時，AZO薄膜的透光率由未摻雜的92%下降至摻雜後的81%，實驗結果顯示RGO會吸收部分可見光，影響了AZO薄膜的透光率。
在掃描式電子顯微鏡(Scanning Electron Microscope, SEM)分析表面量測結果中，清楚顯示RGO顆粒均勻分散塗佈在AZO薄膜表面上。以能量散射光譜儀(Energy Dispersive Spectrometer, EDS)做成份分析，顯示AZO薄膜中碳的比例增加，證明本實驗中RGO有效摻雜於溶膠凝膠中。X光繞射分析( X-ray diffraction , XRD)中，RGO摻雜濃度的增加使得表面晶體顆粒逐漸增加，在摻雜至3.0 wt%時，繞射峰值的2θ角度由未摻雜的34.42。往右偏移至34.4。，由此證明RGO不同濃度的摻雜比例會影響薄膜結晶結構的分佈。

The addition of reduced graphene oxide (RGO) to aluminum doped zinc oxide was studied and analysis conducted on film for its electrical and optical characteristics. Sol-gel was applied in a circular pattern on glass substrate with the weight concentration of 0.0 wt%, 1.0 wt%, 1.5 wt% and 3.0 wt% as the proportion of mixing. A gaseous mixture of Ar:H2=9:1 was passed through furnace pipe and the substrate was annealed in 500℃ for an hour. In electric measurement, the resistivity was 1.11ⅹ10-1 Ω-cm for RGO-free AZO film, and the lowest resistivity was 8.11ⅹ10-3 Ω-cm with RGO at 1.0 wt%. For optical analysis, when 1.0 wt% of RGO is added, the transmittance of AZO film dropped from 92% without addition to 81% with addition.The experiment showed that RGO absorbed part of visible light and thus reduced the transmittance of AZO film.
When analyzing surface measurement using a scanning electron microscope(SEM), it clearly showed that the RGO particles were distributed evenly across the surface of AZO film. The composition analysis using energy dispersive spectrometer (EDS) revealed carbon content in the AZO film, demonstrating that RGO was mixed effectively in the sol-gel. In the X-ray diffraction (XRD) analysis, the increase of RGO mixing concentration contributed to the increasing grain size of crystals on the surface. When mixing to 3.0 wt%, the 2θ angle of refraction peak shifted to the right from 34.42° with no mixing to 34.4°. It showed that the different mixing proportions of RGO at various concentrations had influence on the distribution of crystalline structure of the film.

致 謝 i
摘 要 ii
Abstract iii
目 次 iv
圖 目 次 vii
表 目 次 ix
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 2
1.3 論文概述 3
第二章 文獻回顧及基礎理論 4
2.1 透明導電膜簡介 4
2.1.1 透明導電膜種類 4
2.1.2 透明導電膜導電機制 5
2.1.3 透明導電膜光學特性 7
2.1.4 透明導電膜鍍膜方法 9
2.2 氧化鋅薄膜簡介 10
2.2.1 氧化鋅薄膜結構 10
2.3 石墨烯簡介 12
2.3.1 氧化石墨烯特性及化學結構 12
2.4 溶膠凝膠法 17
2.4.1 基礎概論 17
2.4.2 溶膠凝膠法溶解機制 18
2.4.3 溶膠凝膠法製備 19
2.4.4 旋轉塗佈法鍍膜原理 19
第三章 實驗步驟與流程 20
3.1 實驗流程圖 20
3.2 實驗藥品與儀器介紹 21
3.2.1 實驗藥品 21
3.2.2 實驗儀器及工作原理 21
3.3 實驗步驟 24
3.3.1 AZO溶液調配 24
3.3.2 氧化石墨烯製備 25
3.3.3 還原氧化石墨烯製備 26
3.3.4 玻璃清洗與烘乾 27
3.3.5 旋轉塗佈 28
3.3.6 退火處理 29
第四章 實驗結果與討論 30
4.1 實驗參數 30
4.2 成份分析 32
4.2.1 TEM 分析 32
4.2.2 XPS 分析 34
4.2.3 EDS 分析 39
4.3 電性分析 40
4.3.1 四點探針量測片電阻 40
4.3.2 霍爾量測薄膜電阻率 41
4.3.3 霍爾量測薄膜載子濃度及遷移率 42
4.3.4 霍爾量測電性穩定性 43
4.4 結構分析 44
4.4.1 SEM表面分析 44
4.4.2 SEM膜厚分析 45
4.4.3 AFM粗糙度分析 46
4.4.4 XRD分析 48
4.5 光學分析 50
4.5.1 薄膜透光率的量測分析 50
4.5.2 薄膜能隙值分析 51
4.5.3 薄膜折射率與消光係數量測分析 51
第五章 結論 53
5.1 總結 53
5.2 未來展望 54
參考文獻 55

圖目次
圖2.1 Burstein-Moss shift示意圖 7
圖2.2 氧化鋅結構圖 10
圖2.3 石墨烯原子結構圖 12
圖2.4 C60、奈米碳管和石墨為石墨烯的衍生物質 13
圖2.5 石墨烯氧化物之化學結構 14
圖2.6 石墨烯氧化物還原後的分子模型 15
圖2.7 石墨烯能帶結構圖 17
圖2.8 溶膠凝膠的變化圖 18
圖2.9 旋轉塗佈示意圖 19
圖3.1 實驗流程圖 20
圖3.2 四點探針量測原理圖示 21
圖3.3 AZO溶液未攪拌樣品圖 24
圖3.4 AZO攪拌老化24小時後樣品圖 24
圖3.5 氧化石墨烯之製備流程圖 25
圖3.6 還原氧化石墨烯之製程圖 26
圖3.7 RGO摻入AZO攪拌2小時後溶液樣品 28
圖4.1 還原氧化石墨烯分析TEM影像 32
圖4.2 1wt% RGO摻雜AZO薄膜之TEM分佈影像 33
圖4.3 AZO薄膜之XPS全頻譜圖 34
圖4.4 摻雜1 wt% RGO之AZO薄膜之XPS全頻譜圖 34
圖4.5 不同RGO摻雜濃度XPS 之O 1S 峰值圖(a)0 wt%(b)1 wt% 35
圖4.6 不同RGO摻雜濃度XPS 之C 1S 峰值圖(a)0 wt%(b)1 wt% 36
圖4.7 不同RGO摻雜濃度XPS 之Zn2p3/2峰值圖(a)0 wt%(b)1 wt% 37
圖4.8 不同RGO摻雜濃度XPS 之Zn2p1/2峰值圖(a)0 wt%(b)1 wt% 38
圖4.9 不同RGO摻雜濃度XPS 之A l2p 峰值圖(a)0 wt%(b)1 wt% 38
圖4.10 不同RGO濃度摻雜於AZO薄膜之EDS分析範圍(a)0.0 wt% (b)
1 wt% 39
圖4.11 不同RGO濃度摻雜於AZO薄膜之EDS元素峰值(a)0.0 wt% (b)
1 wt% 39
圖4.12 不同RGO摻雜濃度對AZO薄膜片電阻值變化圖 40
圖4.13 不同RGO摻雜濃度對AZO薄膜電阻率影響變化圖 41
圖4.14 不同RGO摻雜濃度對載子濃度及遷移率影響變化圖 42
圖4.15 不同RGO摻雜濃度常溫下對薄膜穩定性影響變化圖 43
圖4.16 不同RGO摻雜濃度對AZO薄膜表面變化 44
圖4.17 不同RGO摻雜濃度對AZO薄膜剖面圖 45
圖4.18 摻雜0.0wt% RGO的AZO薄膜表面形貌圖 46
圖4.19 摻雜1.0wt% RGO的AZO薄膜表面形貌圖 46
圖4.20 摻雜1.5wt% RGO的AZO薄膜表面形貌圖 47
圖4.21 摻雜3.0wt% RGO的AZO薄膜表面形貌圖 47
圖4.22 不同RGO摻雜濃度XRD量測結果 49
圖4.23 不同RGO摻雜濃度晶粒尺寸及半高寬值變化圖 49
圖4.24 不同RGO摻雜濃度對AZO薄膜透光率影響變化圖 50
圖4.25 不同RGO摻雜濃度對AZO薄膜能隙值分析 51
圖4.26 不同RGO摻雜濃度對AZO薄膜FOM值分析 52
圖4.27 不同RGO摻雜濃度對AZO薄膜折射率分析 52
圖4.28 不同RGO摻雜濃度對AZO薄膜消光係數分析 56

表目次
表2.1 透明導電膜種類 5
表2.2 液體成膜法種類及優缺點介紹 9
表2.3 透明導電材料之片電阻、吸收系數與FOM的比較 11
表2.4 奈米碳管與石墨烯的特性比較 14
表2.5 石墨烯製備方法 16
表4.1 溶膠凝膠法製成RGO摻雜AZO薄膜之相關數據 31
表4.2 AZO薄膜在不同濃度之XPS 分析O1s 峰值面積比例 35
表4.3 AZO薄膜在不同濃度之XPS 分析C1s 峰值面積比例 36
表4.4 AZO薄膜在不同濃度之XPS 分析 Zn 2p3/2峰值面積比例 37
表4.5 AZO薄膜在不同濃度之XPS 分析 Zn 2p1/2峰值面積比例 38
表4.6 AZO薄膜在不同濃度之XPS 分析 Al 2p峰值面積比例 38
表4.7 1wt% RGO摻雜於AZO薄膜之EDS成份分析數據 39
表4.8 不同RGO摻雜濃度對AZO薄膜片電阻值影響數據 40
表4.9 不同RGO摻雜濃度對AZO薄膜電阻率影響數據 41
表4.10 不同RGO摻雜濃度對AZO薄膜載子濃度及遷移率影響變化圖 42
表4.11 不同RGO摻雜濃度對於AZO薄膜表面粗糙度變化 47
表4.12 不同RGO摻雜濃度對AZO薄膜影響之XRD相關數據 50
表4.13 不同RGO摻雜濃度薄膜FOM值數據 53

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