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研究生： 秦玉玲
Chin, Yu-Ling
論文名稱： 以反應性磁控濺鍍沈積氧化亞銅薄膜之結構與光電性質研究
The structural and opto-electrical properties of cuprous oxide films deposited by reactive magnetron sputtering
指導教授： 林天財
Lin, Tien-Chai
李世欽
Li, Shin-Chin
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2006
畢業學年度： 94
語文別： 中文
論文頁數： 75
中文關鍵詞： 反應性濺鍍法 、氧化亞銅 、太陽能電池 、微結構
外文關鍵詞： Cuprous Oxide, Reactive Sputter, Solar Cell, Microstructure
相關次數： 點閱：90  下載：4 
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    • 氧化亞銅具有在可見光區吸收係數大的特性，若應用在太陽能電池上，預期將增加太陽能電池對入射太陽光的吸收波長範圍變大。因此期望藉由改變製程參數，研究其對氧化亞銅薄膜之特性的影響。
    本研究以射頻磁控濺鍍系統，使用銅金屬靶搭配不同氧氣流量比例的氣氛進行反應性濺鍍，以及改變濺鍍時的基板溫度與射頻功率，藉以得到不同性質表現之氧化亞銅薄膜。之後以低銳角繞射(GIAXRD)進行薄膜結構分析，以掃描式電子顯微鏡(SEM)觀察表面形態，光電性質的表現則以紫外光-可見光光譜儀(UV-Vis)及四點探針做分析。
    實驗結果顯示，單相的氧化亞銅成長條件不易控制。氧化亞銅薄膜之表面形態、光性及電性與射頻功率、基板溫度以及氧氣流率有密切的關係。在GIAXRD中發現， Cu4O3(301)、Cu4O3(303)、CuO(021)對射頻功率、基板溫度以及氧氣流率三項變因很不敏感。另外，氧格隙可增加氧化亞銅的導電性，同時會使薄膜在可見光的吸收變強，有利於在太陽能電池上之應用。

    關鍵字：反應性濺鍍法、氧化亞銅、太陽能電池、微結構

    The cuprous oxide has high absorption coefficient in visible range. The film applied to solar cell application which is expected to enlarge the range of wavelength and to absorbe more sunlight energy. Therefore, we expect to change the procedure parameter and to deeply understand the cuprous oxide films characteristics.
    In this study, cuprous oxide films were prepared by RF magnetron reactive sputtering using a Cu target with various gas flow ratios. By changing the substrate heating temperatures and RF power during sputtering, the cuprous oxide films would exhibit different properties. The structure of cuprous oxide films were characterized by glancing incident angle X-ray diffraction (GIAXRD). The morphology of cuprous oxide films were observed by scanning electron microscope (SEM). The transmittance of cuprous oxide films was measured by UV-VIS spectrophotometer. Four-point probe were used to measure the resistivity of cuprous oxide films.
    The results showed that it is difficult to prepare single phase cuprous oxide films. The procedure parameters of RF power, oxygen flow ratio and substrate temperature have strong influences on the surface morphology, electrical and optical properties of Cu2O films. In GIAXRD analysed, we found that Cu4O3(301), Cu4O3(303) and CuO(021) phases are not sensitive to the procedure parameters of RF power, oxygen flow ratio and substrate temperature. Besides, the conductive mechanism is affected by the interstitial oxygen atoms, and there are obvious absorption in visible region can be applied in Solar Cell device.
    KEY WORDS：Reactive Sputter, Cuprous Oxide, Solar Cell, Microstructure

    中文摘要.................................................................................................. I 英文摘要................................................................................................. II 致謝........................................................................................................ III 目錄.........................................................................................................IV 表目錄.................................................................................................. VII 圖目錄.................................................................................................. VIII 第一章 序論............................................................................................ 1 1-1 前言.................................................................................................. 1 1-2 研究目的與動機......................................................................... 2 第二章 理論基礎.................................................................................... 4 2-1 濺鍍原理....................................................................................... 4 2-1.1 電漿原理............................................................................... 4 2-1.2 濺鍍原理............................................................................... 5 2-1.3 射頻磁控濺鍍................................................................................ 8 2-1.4 反應性濺鍍................................................................................ 10 2-2 薄膜成長原理.......................................................................... 12 2-2.1 薄膜成核與成長............................................................. 12 2-2.2 薄膜組織結構................................................................. 15 2-3 陶瓷的點缺陷(point defects)理論........................................... 17 2-4 氧化亞銅的鍍層特性.............................................................. 20 2-4.1 基本性質......................................................................... 20 2-4.2 電學性質......................................................................... 22 2-4.3 光學性質......................................................................... 26 第三章 實驗方法與步驟...................................................................... 27 3-1 實驗材料.................................................................................. 27 3-2 實驗設備.................................................................................. 28 3-3 實驗流程.................................................................................. 30 3-3.1 基材清洗......................................................................... 31 3-3.2 鍍膜程序及參數設定..................................................... 33 3-4 鍍層性質分析.......................................................................... 34 3-4.1 低銳角X光繞射分析...................................................... 34 3-4.2 薄膜厚度量測與成長速率............................................. 34 3-4.3 表面型態觀察................................................................. 35 3-4.4 電性量測......................................................................... 36 3-4.5 光性量測......................................................................... 37 第四章 結果與討論.............................................................................. 38 4-1 製程條件對濺鍍速率的影響.................................................. 38 4-1.1 射頻功率對濺鍍速率的影響......................................... 38 4-1.2 氧氣流率對濺鍍速率的影響......................................... 38 4-1.3 基板加熱溫度對濺鍍速率的影響................................. 42 4-2 薄膜微結構分析...................................................................... 46 4-2.1 GIAXRD.......................................................................... 46 4-2.1.a 基板加熱溫度對薄膜晶體結構的影響............... 46 4-2.1.b 射頻功率對薄膜晶體結構的影響....................... 51 4-2.2 薄膜表面分析................................................................. 54 4-2.2.a 射頻功率對薄膜表面型態的影響....................... 54 4-2.2.b 氧氣流率對薄膜表面型態的影響....................... 55 4-2.2.c 基板加熱溫度對薄膜表面型態的影響............... 55 4-3 薄膜導電性質量測.................................................................. 63 4-4 薄膜光學性質量測.................................................................. 66 第五章 結論.......................................................................................... 67 參考文獻................................................................................................ 68 自述……………………………………………………………….75 表目錄 Table 1-1 以不同方法製備薄膜之優劣比較表................................... 3 Table 3-1 實驗參數設定..................................................................... 33 圖目錄 Fig. 2-1 正離子與靶材表面之交互作用............................................... 5 Fig. 2-2 二次電子射出率....................................................................... 7 Fig. 2-3 在外加電場與磁場下，電子之移動路徑示意圖.................. 9 Fig. 2-4 磁控濺鍍系統中，靶材磁場分布與電子移動路徑............... 9 Fig. 2-5 沉積速率與O2/Ar流量之關係圖............................................ 11 Fig. 2-6 基板表面上薄膜之成核與成長示意圖................................. 13 Fig. 2-7 Volmer - Weber樣式示意圖.................................................... 13 Fig. 2-8 Frank - Van der Merwe樣式示意圖........................................ 14 Fig. 2-9 Sranski - Krastanov樣式示意圖.............................................. 14 Fig. 2-10 物理氣相沉積薄膜之結構區模型....................................... 16 Fig. 2-11 本質離子缺陷示意圖........................................................... 19 Fig. 2-12 MgO經估算後其缺陷在能帶中的能階位置圖.................... 19 Fig. 2-13 Cu2O的結構…………………............................................... 21 Fig. 2-14 Cu2O的晶體結構示意圖....................................................... 21 Fig. 2-15 CMVB法之示意圖................................................................ 25 Fig. 2-16 Cu2O的電子結構示意圖....................................................... 25 Fig. 2-17 SrCu2O2的晶體結構.............................................................. 26 Fig. 3-1 射頻磁控濺鍍系統................................................................. 29 Fig. 3-2 實驗流程圖............................................................................. 30 Fig. 3-3 基板清洗步驟......................................................................... 32 Fig. 3-4 α-step示意圖............................................................................ 35 Fig. 3-5 四點探針示意圖..................................................................... 36 Fig. 4-1 固定工作壓力3×10-5 Torr、基板未加熱時，不同射頻 功率及氧氣流率對濺鍍速率關係圖..................................... 39 Fig. 4-2 固定工作壓力3×10-5 Torr、基板加熱至100℃時，不同 射頻功率及氧氣流率對濺鍍速率關係圖............................. 40 Fig. 4-3 固定工作壓力3×10-5 Torr、基板加熱至150℃時，不同 射頻功率及氧氣流率對濺鍍速率關係圖............................. 40 Fig. 4-4 固定工作壓力3×10-5 Torr、基板加熱至200℃時，不同 射頻功率及氧氣流率對濺鍍速率關係圖............................. 41 Fig. 4-5 固定工作壓力3×10-5 Torr、基板加熱至100℃時，不同 射頻功率及氧氣流率對濺鍍速率關係圖............................. 41 Fig. 4-6 固定工作壓力3×10-5 Torr、射頻功率20W時，不同基板 溫度與氧氣流率對濺鍍速率的關係圖................................. 44 Fig. 4-7 固定工作壓力3×10-5 Torr、射頻功率40W時，不同基板 溫度與氧氣流率對濺鍍速率的關係圖................................. 45 Fig. 4-8 固定工作壓力3×10-5 Torr、射頻功率60W時，不同基板 溫度與氧氣流率對濺鍍速率的關係圖................................. 45 Fig. 4-9 射頻功率20W、氧氣流率10％時，不同基板溫度的 GIAXRD圖.............................................................................. 47 Fig. 4-10 射頻功率20W、氧氣流率20％時，不同基板溫度的 GIAXRD圖............................................................................ 48 Fig. 4-11 射頻功率20W、氧氣流率30％時，不同基板溫度的 GIAXRD圖............................................................................ 48 Fig. 4-12 射頻功率40W、氧氣流率10％時，不同基板溫度的 GIAXRD圖........................................................................... 49 Fig. 4-13 射頻功率40W、氧氣流率30％時，不同基板溫度的 GIAXRD圖........................................................................... 49 Fig. 4-14 射頻功率60W、氧氣流率10％時，不同基板溫度的 GIAXRD圖........................................................................... 50 Fig. 4-15 射頻功率60W、氧氣流率20％時，不同基板溫度的 GIAXRD圖........................................................................... 50 Fig. 4-16 基板未加熱、氧氣流率10％時，不同功率的 GIAXRD圖........................................................................... 52 Fig. 4-17 基板100℃、氧氣流率10％時，不同功率的 GIAXRD圖........................................................................... 52 Fig. 4-18 基板150℃、氧氣流率10％時，不同功率的 GIAXRD圖........................................................................... 53 Fig. 4-19 基板100℃、氧氣流率20％時，不同功率的 GIAXRD圖........................................................................... 53 Fig. 4-20 基板溫度250℃、氧氣流率10％時，不同功率的 SEM影像.............................................................................. 57 Fig. 4-21 基板溫度100℃、氧氣流率20％時，不同功率的 SEM影像.............................................................................. 58 Fig. 4-22 基板溫度100℃、功率60W時，不同氧氣流率的 SEM影像.............................................................................. 59 Fig. 4-23 氧流率20％、射頻功率20W時，不同基板溫度的 SEM影像.............................................................................. 60 Fig. 4-24 氧流率30％、射頻功率40W時，不同基板溫度的 SEM影像.............................................................................. 62 Fig. 4-25 射頻功率60W、氧氣流率20％時，基板溫度對氧化亞銅 鍍膜之電阻率影響.............................................................. 64 Fig.4-26 以氧化亞銅為主要相之鍍膜電阻率與射頻功率 的關係....................................................................................65 Fig.4-27 射頻功率20W、氧氣流率20％時，以氧化亞銅為主要相 之鍍膜電阻率與基板溫度的關係.........................................65 Fig. 4-28 射頻功率20W、氧流率20％時，基板溫度對穿透率之 影響...................................................................................... 66

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