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研究生： 陳璟鋒
Chen, Ching-Feng
論文名稱： P型氧化鎳薄膜之製備與其光性、電性及材料特性之研究
Preparation of p-type NiO thin film and investigation on its optical, electrical and material characteristics
指導教授： 陳貞夙
Chen, Jen-Sue
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： 2004
畢業學年度： 92
語文別： 中文
論文頁數： 136
中文關鍵詞： 磁控濺鍍 、氧化鎳
外文關鍵詞： p-type TCO, nickel oxide
相關次數： 點閱：66  下載：12 
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    • 摘要
    　　氧化鎳是具有潛力成為p-type 透明導電氧化物(TCO)的材料之一，但由於氧化鎳的光電性質仍不足以實際應用，因此期望能藉由摻雜異質原子(N原子)以及改變其他相關製程參數，而得到更高的光學穿透率與較佳的導電率之氧化鎳薄膜。
    　　本研究以射頻磁控濺鍍系統，使用鎳金屬靶搭配不同氣體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鍍後的退火處理溫度，藉以得到不同性質表現的氧化鎳薄膜。之後以拉塞福背向散射分析(RBS)作成份定量與密度計算，以X光繞射(θ-2θXRD)、低掠角X光繞射(GIAXRD)以及穿透式電子顯微鏡的繞射圖進行薄膜結構與結晶性的分析，使用掃瞄式電子顯微鏡、穿透式電子顯微鏡與原子力顯微鏡觀察表面型態，以X光光電子能譜與傅立葉轉換紅外線光譜分析化學鍵結。而光學性質的表現則以紫外光-可見光光譜儀(UV-Vis)與穿透式的傅立葉轉換紅外線光譜儀量測不同範圍的光學穿透率，另外導電性質的表現則利用四點探針與霍爾量測，藉以得到電阻率以及載子濃度、載子遷移率等資訊。
    　　實驗結果顯示Ni-O薄膜中O/Ni比值隨著濺鍍時通入不同氣體流量比例而變化，所有O/Ni比值皆大於1。所得的Ni-O薄膜均呈現結晶狀態，並由XRD的分析結果，推論氧原子佔據格隙位置是薄膜中的O/Ni比值大於1的主要機制。經過室溫時效或退火處理後，薄膜中的氧原子可能以氧氣形態脫離，使得Ni-O薄膜的光電性質因此改變，隨著室溫時效時間增長或退火溫度增高均會使薄膜的電阻率上升以及光學穿透率增加。O/Ni比值高的Ni-O薄膜，由於載子濃度較高，故導電性質較佳；然而光學穿透率表現卻不佳，經由穿透率量測所計算的能隙也較小。而O/Ni比值低的薄膜性質表現與比值高者正好相反。當濺鍍時通入氮氣氣氛，並無法使氮原子有效地存留於Ni-O薄膜中，亦無法造成摻雜異質原子、增加自由載子之目的，甚至使Ni-O薄膜中的O/Ni比值下降，導致薄膜導電性質變差，然而薄膜結晶性比濺鍍時無通入氮氣氣氛者較佳。

    Abstract
    　　Nickel oxide films may be one of the potential candidates for p-type transparent conducting oxide (TCO). Because the optical and electrical properties of the nickel oxide films have not reached the optimal values, it is expected that doping impurities such as N atoms and changing prccess parameters may improve the transparency and conductivity of nickel oxide films.
    　　In this study, nickel oxide films were prepared with various gas flow ratios by RF magnetron reactive sputtering from a Ni target. By changing the substrate heating temperatures during sputtering and the annealing　temperatures after depositions, the nickel oxide films would exhibit different properties. Rutherford　backscattering spectrometry (RBS) analysis was used to determine the composition and density of nickel oxide　films. The structure and crystallinity of nickel oxide films were characterized by X-ray diffraction (θ-2θXRD), glancing incident angle X-ray diffraction (GIAXRD), and transmission electron microscope (TEM) diffraction patterns. The morphology of nickel oxide films were observed with scanning electron microscope (SEM), transmission electron microscope (TEM), and atomic force microscopy (AFM). The chemical bondings of nickel oxide films were investigated by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The transmittance of nickel oxide films was measured by UV-Vis spectrophotometer. Four-point probe and Hall measurement were used to measure resistivity of nickel oxide films. Besides, carrier concentrations and mobility were obtained from Hall measurement.
    　　The exprimental results reveal that O/Ni ratios in the nickel oxide films change with gas flow ratios during sputtering, and all O/Ni ratios are greater than 1. It is found that all nickel oxide films exhibit polycrystalline structures. From XRD results, it is suggested that oxygen interstitials are the dominant factor that results in the non-stoichiometry. After aging at room temperature and annealing treatments, oxygen atoms may evaporate from the nickel oxide films in forms of O2 gas and cause variations in the optical and electrical properties. Resistivity and transparency of the nickel oxide films increase with increasing aging time or annealing temperature. The nickel oxide film with high O/Ni ratio possesses better conductivity due to higher carrier concentrations, but transmittance is poor and the energy gap calculated from the transparency is smaller. The nickel oxide film with low O/Ni ratio exhibits opposite properties. It is found that nitrogen atoms would not be retained in the nickel oxide films during sputtering, and the purposes of doping N atoms and adding carrier concentrations are not achieved. Furthermore, it results in lower O/Ni raitos and inferior conductivity of the nickel oxide films. However, those nickel oxide films have better crystallinity.

    第1章 序論................................................................1 1-1 前言..................................................................1 1-2 研究目的與動機........................................................5 第2章 理論基礎............................................................6 2-1 透明導電薄膜..........................................................6 2-1.1 光學性質............................................................7 2-1.2 導電性質............................................................9 2-1.3 n-type TCO.........................................................10 2-1.4 p-type TCO.........................................................11 2-2 NiO基本特性介紹......................................................14 2-3 陶瓷的點缺陷(point defects)理論......................................17 2-4 由穿透率量測計算Eg...................................................21 2-5 NiO相關文獻回顧......................................................23 第3章 實驗方法與步驟.....................................................27 3-1 實驗材料.............................................................27 3-2 實驗設備.............................................................28 3-2.1 濺鍍系統...........................................................28 3-2.2 氣氛退火系統.......................................................28 3-3 實驗流程.............................................................29 3-3.1 試片編號命名法.....................................................29 3-3.2 基材清洗...........................................................30 3-3.3 濺鍍製備氧化鎳薄膜.................................................30 3-3.4 退火處理...........................................................30 3-3.5 霍爾量測試片準備...................................................31 3-4 鍍層性質分析.........................................................36 3-4.1 薄膜厚度量測.......................................................36 3-4.2 拉塞福背向散射(Rutherford backscattering spectrometer,RBS)分析.....36 3-4.3 θ-2θ XRD繞射分析.................................................37 3-4.4 低掠角X光繞射(Glancing incident angle XRD, GIAXRD)分析.............37 3-4.5 掃描式電子顯微鏡(scanning electron microscope, SEM)分析............38 3-4.6 原子力顯微鏡(atomic force microscopy, AFM)分析.....................38 3-4.7 穿透式電子顯微鏡(transmission electron microscope, TEM)微結構分析..39 3-4.8 傅立葉轉換紅外線光譜(Fourier transform infrared spectroscopy, FTIR) 原子鍵結分析.............................................................39 3-4.9 X光光電子能譜(X-ray photoelectron spectroscopy, XPS)...............40 化學鍵結分析.............................................................40 3-4.10 薄膜光學性質量測..................................................41 3-4.11 薄膜導電性質量測..................................................42 3-4.11.a 四點探針量測(4-point probe).....................................42 3-4.11.b 霍爾量測(Hall measurement)......................................42 第4章 結果與討論.........................................................43 4-1 製程條件對濺鍍速率的影響.............................................43 4-2 薄膜成份分析以及密度計算.............................................45 4-2.1 成份分析定量.......................................................45 4-2.2 原子密度與質量密度的計算分析.......................................47 4-3 薄膜微結構分析.......................................................53 4-3.1 薄膜晶體結構與結晶性分析...........................................53 4-3.1.a θ-2θ XRD.......................................................53 4-3.1.b GIAXRD...........................................................62 4-3.2 薄膜表面型態與表面粗糙度分析.......................................67 4-3.2.a SEM表面與剖面觀察................................................67 4-3.2.b AFM表面粗糙度分析................................................72 4-3.3 TEM顯微結構觀察與繞射圖譜..........................................79 4-3.3.a TEM微結構觀察....................................................79 4-3.3.b TEM繞射圖譜......................................................80 4-3.4 化學鍵結分析.......................................................84 4-3.4.a FTIR鍵結分析.....................................................84 4-3.4.b XPS化學鍵結分析及成份組成半定量..................................86 4-4 薄膜光學性質量測.....................................................97 4-4.1 UV-Vis量測.........................................................97 4-4.2 Energy gap (Eg)計算...............................................102 4-4.3 紅外線穿透率量測..................................................107 4-4.4 UV-Vis穿透率於室溫下之時效效應(aging).............................109 4-5 薄膜導電性質量測....................................................114 4-5.1 四點探針量測(4-point probe).......................................114 4-5.2 霍爾效應分析(Hall measurement)....................................120 4-5.3 電阻率於室溫下之時效效應(aging)...................................123 第5章 結論..............................................................127 第6章 參考文獻..........................................................129

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