The Field-Emission Characteristics of Aluminum-Doped and Silver Doped Zinc Oxide Nanorods
陳信樟、李世鴻
E-mail: [email protected]
ABSTRACT
In this study, aluminum-doped zinc oxide (ZnO) and silver-doped zinc oxide nanorods were grown by a hydrothermal method and the effect of varying the doping concentration on the field emission characteristics of the synthesized ZnO nanorods were studied.
The growth procedure of ZnO nanorods is first spin-coating a seeding layer on silicon substrates, followed by the growth in the mixed solution of zinc nitrate hexahydrate (Zn(NO3)2 6H2O), hexamethylenetetramine (C6H12N4), and aluminum nitrate (Al(NO3)3 9H2O) or silver nitrate (AgNO3) at 90oC for 2 hours. The ratio of volume concentration of zinc nitrate hexahydrate to hexamethylenetetramine is 1:1. The purpose of aluminum nitrate and silver nitrate was to supply dopant atoms and the volume concentration was varied from 0.2% to 4% (i.e. 0.0000M to 0.0008M). Field-emission scanning electron microscopy (FE-SEM), field-emission tunneling electron spectroscopy (FE-TEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD) were used to investigate the surface morphology, chemical compositions, and microstructure of aluminum-doped ZnO and silver-doped ZnO nanorods, the electrical properties were determined by Hall effect measurement, and the field emission characteristics of ZnO nanorods were measured in high vacuum. As found by EDS results, dopant atoms such as aluminum (Al) or silver (Ag) have been successfully incorporated into the crystalline structure of ZnO nanorods, and the conductivity, the concentration and mobility of majority carrier of ZnO nanorods have been modified accordingly. As can be seen in SEM results, the surface morphology of ZnO nanorods can be affected by impurity doping. It is found from XRD and FE-TEM results that the ZnO nanorods are of hexagonal wurtzite structure with [0001] as the most preferential direction of growth. It is also found that the Al-doped ZnO nanorods grown with 2% aluminum nitrate have the largest field emission current 127.78 (μA/cm2); while silver doped ZnO nanorods of field emission maximum is 77.5 (μA/cm2). In this study, it is demonstrated that the field emission characteristics of the ZnO nanorods can be effectively enhanced by doping impurities.
Keywords : zinc oxide (ZnO)、doping、field emission
Table of Contents
封面內頁 簽名頁 中文摘要．．．．．．．．．．．．．．．．．．．．．．．．iii 英文摘要．．．．．．．．．．．．
．．．．．．．．．．．．v 誌謝．．．．．．．．．．．．．．．．．．．．．．．．．．vii 目錄．．．．．．．．．
．．．．．．．．．．．．．．．．．viii 圖目錄．．．．．．．．．．．．．．．．．．．．．．．．．xi 表目錄．．
．．．．．．．．．．．．．．．．．．．．．．．xv 第一章 緒論 1.1氧化鋅的歷史與簡介．．．．．．．．．．．．
．．1 1.2研究動機．．．．．．．．．．．．．．．．．．．3 第二章 氧化鋅理論原理與文獻回顧 2.1氧化鋅簡介．．．
．．．．．．．．．．．．．．．5 2.2氧化鋅的應用之相關文獻．．．．．．．．．．．．6 2.3以水熱法製備氧化鋅奈米 柱相關文獻．．．．．．．8 2.4水熱法製備摻雜鋁氧化鋅奈米柱之導電特性．．．11 2.5水熱法製備p型氧化鋅奈米柱之光 電特性．．．．14 第三章 理論與研究方法 3.1電子場發射之原理．．．．．．．．．．．．．．19 3.2氧化鋅奈米柱的成 長機制．．．．．．．．．．．22 3.3氧化鋅的製備方法．．．．．．．．．．．．．．24 3.3.1水熱法．．．．．．．．
．．．．．．．．24 3.3.2鋅蒸氣氧化法．．．．．．．．．．．．．25 3.3.3化學氣相沉積法(CVD)．．．．．．．．．26 3.3.4溶膠─凝膠法．．．．．．．．．．．．．27 3.3.5模板法．．．．．．．．．．．．．．．．29 3.4實驗步驟與流程
．．．．．．．．．．．．．．．29 3.4.1實驗流程．．．．．．．．．．．．．．．29 3.4.2實驗基材與化學藥品．．．
．．．．．．．31 3.4.3基板清洗．．．．．．．．．．．．．．．31 3.4.4旋塗種子層．．．．．．．．．．．．．．31 3.4.5成長摻雜之氧化鋅奈米柱．．．．．．．．34 3.5實驗儀器與原理．．．．．．．．．．．．．．．35 3.5.1場發射掃 描式電子顯微鏡．．．．．．．．35 3.5.2能量散佈分析儀．．．．．．．．．．．．36 3.5.3 X光繞射儀．．．．．．．
．．．．．．．38 3.5.4場發射穿透式電子顯微鏡．．．．．．．．39 3.5.5場發射量測裝置與量測步驟．．．．．．．41 3.5.6霍爾效應量測裝置與原理．．．．．．．．42 第四章 實驗結果與討論 4.1摻雜鋁對氧化鋅奈米柱的研究與討論．．
．．．．47 4.1.1摻雜鋁氧化鋅奈米柱之FE-SEM分析．．47 4.1.2摻雜鋁氧化鋅奈米柱的成份分析(EDS分析)55 4.1.3摻雜鋁 氧化鋅奈米柱的霍爾效應量測分析．56 4.1.4摻雜鋁氧化鋅奈米柱電子場發射特性．．．59 4.2摻雜銀對氧化鋅奈米柱的研 究與討論．．．．．．64 4.2.1摻雜銀氧化鋅奈米柱之FE-SEM分析．．64 4.2.2摻雜銀氧化鋅奈米柱的成份分析(EDS分 析)71 4.2.3摻雜銀氧化鋅奈米柱的霍爾效應量測分析．71 4.2.4摻雜銀氧化鋅奈米柱電子場發射特性．．．74 4.3摻雜後氧化
鋅奈米柱的結晶方向分析與晶格繞射分析．．．．．．．．．．．．．．．．．．．．．．．79 第五章 結論．．．．．
．．．．．．．．．．．．．．．．．83 參考文獻．．．．．．．．．．．．．．．．．．．．．．．．85 圖目錄 圖2-1 SEM上視圖顯示，ZnO奈米線被曝光定義的圖形．．10 圖2-2 SEM上視圖顯示，樣品均以90?C成長8小時，(a) 無種子層拋 光Si基板；(b) 2 nm奈米金種子層；(c) 5 nm金薄膜；(d) 10 nm的ZnO奈米粒子．．．．．．．．．．10 圖2-3 奈米線的電子 場發射。短奈米線(0.2 μm)為成長2小時，直徑為60 nm。長奈米線(1.3 μm)為成長8小時，直徑為10 nm到20 nm．．．．
．．．．．．．．．．．．．11 圖2-4 不同濃度硝酸鋁所成長之ZnO奈米柱之X光繞射圖。(a) 0；(b) 0.5%；(c) 1.0%；(d) 1.5%；(e) 2.0%；(f) 3.0%．13 圖2-5 不同濃度硝酸鋁所成長之ZnO奈米柱之SEM圖。(a) 0；(b) 0.5%；(c) 1.0%；(d) 1.5%；(e) 2.0%；(f) 3.0%．．13 圖2-6 不同濃度硝酸鋁所成長之ZnO奈米柱之導電率曲線圖．．．．．．．．．．．．．．．．．．
．．．．14 圖2-7 未摻雜和摻雜的ZnO奈米柱的XRD比較圖．．．．16 圖2-8 為奈米柱SEM圖，(a)和(b)未摻雜之氧化鋅
；(c)和(d)摻雜3%的鉀的氧化鋅；(e)和(f)摻雜3%的銀的氧化鋅．17 圖2-9 奈米柱退火前後的電流-電壓曲線圖。(a)未經退火 的曲線圖(b)經過Ar/H2（95/5）％，在500℃下退火一小時．18 圖3-1 金屬-真空界面之電子場發射示意圖．．．．．．．
．19 圖3-2 理想化的氧化鋅晶體在[0001]的界面結構圖像．．．．23 圖3-3 鋅蒸氣氣化法製備氧化鋅四針狀鬚結構圖．．
．．．25 圖3-4 化學氣相沉積示意圖．．．．．．．．．．．．．．26 圖3-5 實驗流程圖．．．．．．．．．．．．．．
．．．．30 圖3-6 場發射掃瞄式電子顯微鏡(附EDS)．．．．．．．．37 圖3-7 高解析X光繞射儀．．．．．．．．．．．
．．．．38 圖3-8 場發射穿透式電子顯微鏡(附EDS)．．．．．．．．．40 圖3-9 場發射量測裝置．．．．．．．．．．．
．．．．．41 圖3-10 霍爾效應量測載子濃度之示意圖．．．．．．．．．43 圖3-11 各形狀的van der Pauw霍爾效應量測試 片：(a)不規則形狀，(b)圓形，(c)四葉形，(d)方形，(e)矩形，(f)十字形．．．．．．．．．．．．．．．．．．．．．45 圖3-12 霍爾效應量測裝置．．．．．．．．．．．．．．．46 圖4-1 不同濃度硝酸鋁所成長之摻雜鋁ZnO奈米柱之3K倍上 視圖，硝酸鋁濃度分別為：(a) 無摻雜，(b) 0.2%，(c) 1%，(d) 1.5%，(e) 2%，(f) 4%．．．．．．．．．．．．．51 圖4-2 不 同濃度硝酸鋁所成長之摻雜鋁ZnO奈米柱之30K倍上視圖，硝酸鋁濃度分別為：(a) 無摻雜，(b) 0.2%，(c) 1%，(d) 1.5%，(e) 2%，(f) 4%．．．．．．．．．．．．．52 圖4-3 不同濃度硝酸鋁所成長之摻雜鋁ZnO奈米柱之100K倍上視圖，硝酸鋁濃 度分別為：(a) 無摻雜，(b) 0.2%，(c) 1%，(d) 1.5%，(e) 2%，(f) 4%．．．．．．．．．．．．．53 圖4-4 不同濃度硝酸鋁所 成長之摻雜鋁ZnO奈米柱之20K倍剖面圖，硝酸鋁濃度分別為：(a) 無摻雜，(b) 0.2%，(c) 1%，(d) 1.5%，(e) 2%，(f) 4%．．
．．．．．．．．．．．54 圖4-5 4-5 不同濃度硝酸鋁所成長之摻雜鋁ZnO奈米柱之導電率曲線圖．．．．．．．．．．
．．．．．．．．．57 圖4-6 不同濃度硝酸鋁所成長之摻雜鋁ZnO奈米柱之載子遷移率曲線圖．．．．．．．．．．．．
．．．．．．．58 圖4-7 不同濃度硝酸鋁所成長之摻雜鋁ZnO奈米柱之載子濃度曲線圖．．．．．．．．．．．．．．．
．．．．．58 圖4-8 不同濃度硝酸鋁所成長之摻雜鋁ZnO奈米柱之電流密度與施加電場曲線圖(J-E圖)．．．．．．．．．
．．．62 圖4-9 不同濃度硝酸鋁所成長之摻雜鋁ZnO奈米柱之最大電流密度比較圖．．．．．．．．．．．．．．．．．
．63 圖4-10 不同濃度硝酸鋁所成長之摻雜鋁ZnO奈米柱之相對Fowler-Nordheim (F-N)圖．．．．．．．．．．．．．63 圖4-11 不同濃度硝酸鋁所成長之摻雜鋁ZnO奈米柱之相對應高電場Fowler-Nordheim (F-N)曲線圖．．．．．．．．64 圖4-12 不同濃度硝酸銀所成長之摻雜銀ZnO奈米柱之3K倍上視圖，摻雜濃度分別為：(a) 無摻雜、(b) 0.2%、(c) 1%、(d) 1.5%、(e) 2%、(f) 4%．．．．．．．．．．．．．67 圖4-13 不同濃度硝酸銀所成長之摻雜銀ZnO奈米柱之30K倍上視圖，
摻雜濃度分別為：(a) 無摻雜、(b) 0.2%、(c) 1%、(d) 1.5%、(e) 2%、(f) 4%．．．．．．．．．．．．．68 圖4-14 不同濃度 硝酸銀所成長之摻雜銀ZnO奈米柱之100K倍的上視圖，摻雜濃度分別為：(a) 無摻雜、(b) 0.2%、(c) 1%、(d) 1.5%、(e) 2%
、(f) 4%．．．．．．．．．．．．．69 圖4-15 不同濃度硝酸銀所成長之摻雜銀ZnO奈米柱之20K倍的剖面圖，摻雜濃度 分別為：(a) 無摻雜、(b) 0.2%、(c) 1%、(d) 1.5%、(e) 2%、(f) 4%．．．．．．．．．．．．．70 圖4-16 不同濃度硝酸銀所 成長之摻雜銀ZnO奈米柱之導電率曲線圖．．．．．．．．．．．．．．．．．．．．．72 圖4-17 不同濃度硝酸銀所成 長之摻雜銀ZnO奈米柱之載子遷移率曲線圖．．．．．．．．．．．．．．．．．．．73 圖4-18 不同濃度硝酸銀所成長 之摻雜銀ZnO奈米柱之載子濃度曲線圖．．．．．．．．．．．．．．．．．．．．73 圖4-19 不同濃度硝酸銀所成長之 摻雜銀ZnO奈米柱之電流密度與施加電場曲線圖(J-E圖)．．．．．．．．．．．．77 圖4-20 不同濃度硝酸銀所成長之摻雜 銀ZnO奈米柱之最大電流密度比較圖．．．．．．．．．．．．．．．．．．77 圖4-21 不同濃度硝酸銀所成長之摻雜 銀ZnO奈米柱之相對的Fowler-Nordheim (F-N)圖．．．．．．．．．．．．．78 圖4-22 不同濃度硝酸銀所成長之摻雜 銀ZnO奈米柱之相對應的高電場Fowler-Nordheim (F-N)曲線圖．．．．．．．78 圖4-23 摻雜不同元素的ZnO奈米柱之XRD 頻譜圖．．．．81 圖4-24 XRD晶體頻譜資料庫(1997 JCPDS-ICDD:36-1451)．．81 圖4-25 摻雜雜質後ZnO奈米柱
之FE-TEM影像：(a) 摻雜鋁ZnO奈米柱之高倍解析影像、(b) 摻雜鋁ZnO奈米柱之電子繞射圖、(c) 摻雜銀之高倍解析影像
、(d) 摻雜銀ZnO奈米柱之電子繞射圖．．．．．．．．．．．．．．．82 表目錄 表3-1 本實驗製備之基材．．．．．．
．．．．．．．．．32 表3-2 本實驗製備之化學試劑．．．．．．．．．．．．．32 表4-1 不同濃度硝酸鋁所成長之摻雜 鋁ZnO的直徑、高度及密度比較表．．．．．．．．．．．．．．．．．．．55 表4-2 不同濃度硝酸鋁所成長之摻雜 鋁ZnO奈米柱之成份比較表．．．．．．．．．．．．．．．．．．．．．．55 表4-3 不同濃度硝酸鋁所成長之摻雜 鋁ZnO奈米柱之霍爾效應量測之體積濃度原始數據．．．．．．．．．．．．59 表4-4 不同濃度硝酸鋁所成長之摻雜 鋁ZnO奈米柱之高電場F-N圖斜率及場增強因子．．．．．．．．．．．．61 表4-5 不同濃度硝酸銀所成長之摻雜銀ZnO 奈米柱的直徑、高度及密度比較表．．．．．．．．．．．．．．．．66 表4-6 不同濃度硝酸銀所成長之摻雜銀ZnO奈米 柱之成份比較表．．．．．．．．．．．．．．．．．．．．．．71 表4-7 不同濃度硝酸銀所成長之摻雜銀ZnO奈米柱之
霍爾效應量測體積濃度原始數據．．．．．．．．．．．．．74 表4-8 不同濃度硝酸銀所成長之摻雜銀ZnO奈米柱之高電 場F-N圖斜率及場增強因子．．．．．．．．．．．．76
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