本研究以溶膠凝膠法成長鋰摻雜氧化鋅薄膜與鋰和鎂共摻雜氧化鋅薄膜並探討薄膜結構之光與電特性的影響。將進行X光繞射分析、掃瞄式電子顯微鏡、光致螢光能譜與電特性量測，我們在n型鋰摻雜氧化鋅薄膜中發現了解離反應機制所主導的現象，此機制是指鋰原子取代鋅原子缺陷轉變成鋰間隙缺陷的現象，並且鋅空位缺陷也將伴隨著產生。而其中由施體受體對的電子電洞結合發光與FA能量躍遷訊號則分別證實了鋅空位受體與 鋰取代鋅受體其能階位置位於價帶頂端之上335±15 meV與100±3 meV處。觀察到晶粒大小與導電型態將會隨著鋰摻雜量變化而改變。而當鋰摻雜量增加時發現XRD之2θ值異常偏移且鋰間隙與氧空位缺陷濃度增加。推測這些施體缺陷將使導電型態改變。而鋰與鎂共摻雜氧化鋅薄膜其導電型態轉變成n型是因為薄膜內由富氧(O-rich)轉變為富鋅(Zn-rich)情形，進而導致鋰間隙與氧空位缺陷施體型缺陷的增加。

Abstract
The effect of Li(Li and Mg) doping on the optical and electrical
properties of sol-gel ZnO films was investigated in this study. According
to the observed results from by X-ray diffraction, scanning electron
microscope, photoluminescence and conductivity measurements, we
found that the domination of the dissociative mechanism in Li-doped
n-type ZnO films led to transformation from Li substituting for Zn (LiZn)
to Li interstitials, involving the formation of Zn vacancies (VZn). The
VZn (LiZn) acceptor state, with an energy level located at 335 ±15 (100 ± 3)
meV above the valence band maximum is identified from donor-acceptor
pair (free-to-neutral-acceptor) transitions. A dependence of crystallite size
and conduction type upon Li content has been found. The abnormal shift
in the 2θ value and defect concentration increase with increasing Li
content, suggesting that these donors (that is, interstitial Li and oxygen
vacancy) and the crystal structure interact to change the conduction type.
The authors pointed out that n-type conversion of LiZnMgO films is a
result of the increase of the donor density based on transformation from O
to Zn rich.

中文摘要 -------------------------------------------------- I
英文摘要 ------------------------------------------------- II
目錄 ------------------------------------------------- III
圖目錄 -------------------------------------------------- IV
表目錄 --------------------------------------------------- V

第一章 緒論----------------------------------------------- 1
1.1 前言 ------------------------------------------------ 1
1.2 氧化鋅簡介 ------------------------------------------- 3
1.3 研究動機 ¬------------------------------------------- 6

第二章 實驗儀器與儀器原理 --------------------------------- 8
2.1 光激螢光光譜儀 --------------------------------------- 8
2.1.1 光激螢光光譜簡介 -------------------------------- 8
2.1.2 光激螢光原理 ---------------------------------- 11
2.1.3 光激螢光儀器架構 ------------------------------- 16
2.2 X光繞射--------------------------------------------- 18
2.2.1 X光繞射簡介------------------------------------ 18
2.2.2 X光對晶體之繞射-------------------------------- 18
2.3 感應耦合電漿發射光譜分析------------------------------- 23
2.3.1 感應耦合電漿發射光譜簡介------------------------- 23
2.3.2 感應耦合電漿發射光譜原理------------------------- 24
2.4 霍爾效應量測----------------------------------------- 26
2.4.1 霍爾效應簡介----------------------------------- 26
2.4.2 霍爾效應原理----------------------------------- 26
2.4.3 凡得瓦量測法----------------------------------- 27

第三章 實驗步驟 ------------------------------------------ 31
3.1 ZnO、LixZn1-xO與LixZn1-x-yMgyO薄膜製作--------------- 31
3.1.1 溶膠凝膠法之溶膠配置---------------------------- 31
3.1.2 旋轉塗佈法沉積薄膜------------------------------ 32
3.1.3 薄膜樣品資訊----------------------------------- 34
3.2 儀器量測 -------------------------------------------- 35
3.2.1 ICP-OES量測----------------------------------- 35
3.2.2 X光繞射量測 ----------------------------------- 35
3.2.3 變溫PL量測------------------------------------- 35
3.2.4 霍爾效應量測 ---------------------------------- 35
3.2.5 FE-SEM量測 ----------------------------------- 36

第四章 實驗結果與討論 ------------------------------------ 37
4.1 Li摻雜ZnO薄膜---------------------------------------- 37
4.1.1 X光繞射分析------------------------------------ 37
4.1.2 變溫光激螢光光譜分析---------------------------- 42
4.1.3 霍爾電性量測----------------------------------- 47
4.1.4 掃描式電子顯微鏡量測---------------------------- 48
4.2 Li與Mg共摻雜ZnO薄膜---------------------------------- 50
4.2.1 X光繞射分析------------------------------------ 50
4.2.2 變溫光激螢光光譜分析---------------------------- 56
4.2.3 霍爾電性量測----------------------------------- 59
4.2.4 掃描式電子顯微鏡量測---------------------------- 61
第五章 結論 --------------------------------------------- 63
參考文獻 ------------------------------------------------- 65

圖目錄
圖1-1、各種常見的點缺陷在晶體結構上之示意圖-------------- 5
圖1-2、ZnO晶格結構圖---------------------------------- 5
圖1-3、ZnO相關缺陷能階位置圖--------------------------- 6
圖2-1、無機材料激發光激發過程-------------------------- 10
圖2-2、直接能隙與間接能隙能帶示意圖--------------------- 10
圖2-3、半導體內各種輻射躍遷的訊號----------------------- 15
圖2-4、DAP能量狀態示意圖------------------------------- 15
圖2-5、PL 系統架構示意圖------------------------------- 17
圖2-6、可見光對針孔的繞射圖形與其強度和空間的關係圖-------- 21
圖2-7、布拉格繞射示意圖-------------------------------- 21
圖2-8、掃描型態為ω-scan ------------------------------ 22
圖2-9、掃描型態為θ-2θscan ---------------------------- 22
圖2-10、ICP-OES 儀器的示意圖-------------------------- 26
圖2-11、霍爾效應示意圖-------------------------------- 29
圖2-12、凡得瓦霍爾量測與樣品示意圖---------------------- 29
圖2-13、幾何修正項F 與相對電阻比Rr 關係圖-------------- 30
圖3-1、實驗流程圖------------------------------------ 33
圖4-1、XRD 繞射光譜圖、(a)玻璃基板、(b)ZnO 薄膜、(c) Li0.008Zn0.992O薄膜、(d)Li0.013Zn0.987O 薄膜與(e)Li0.018Zn0.982O 薄膜------------ 41
圖4-2、PL 量測(10K)、(a)ZnO 薄膜、(b) Li0.008Zn0.992O 薄膜
、(c)Li0.013Zn0.987O 薄膜與(d)Li0.018Zn0.982O 薄膜------ 45
圖4-3、PL 量測Li0.008Zn0.992O 薄膜隨著溫度變化其峰值A 與峰值
B 的峰值位置關係圖-------------------------46
圖4-4、FE-SEM 圖(a)Li 0 . 0 0 8Zn0 . 9 9 2O、(b)Li 0 . 0 1 3Zn0 . 9 8 7O 與
(c)Li0.018Zn0.982O薄膜表面形貌 (倍率10萬)---------- 49
圖4-5、XRD 繞射光譜圖、玻璃基板、(a) Li0.008Zn0.933Mg0.059O
、(b) Li0.012Zn0.930Mg0.058O 與(c) Li0.022Zn0.918Mg0.060O 薄膜------- 53
圖4-6、經歸一化之PL 光譜圖(10 K)、(a) Li0.008Zn0.992O 與(b)
Li0.008Zn0.933Mg0.059O------------------------- 58
圖4-7、經歸一化之PL 光譜圖(10K)、(a) Li0.008Zn0.933Mg0.059O、
(b)Li0.012Zn0.930Mg0.058O(c)Li0.022Zn0.918Mg0.060O--------59
圖4 - 8 、F E- S EM 量測， ( a ) Li 0 . 0 0 8 Zn 0 . 9 3 3Mg 0 . 0 5 9O、( b )
Li0.012Zn0.930Mg0.058O與(c) Li0.022Zn0.918Mg0.060O表面形貌- 62

表目錄
表3-1、薄膜樣品資訊----------------------------------- 34
表4-1、(002)面繞射峰值位置、晶格常數c 與應力----------- 42
表4-2、PL 量測LixZn1-xO 薄膜之A 與B 峰值強度比值--------46
表4-3、ZnO 與LixZn1-xO 薄膜之霍爾量測數據---------- 48
表4-4、LixZn1-x-yMgyO 薄膜根據XRD 所估算之粒徑大小------54
表4-5、ZnO、Li0.008Zn0.992O 與Li0.008Mg0.059Zn0.85O 之XRD 數據----- 54
表4-6、ZnO、LixZn1-xO 與LixZn1-x-yMgyO 結構應力值---------- 55
表4-7、ZnO、LixZn1-xO 與LixZn1-x-yMgyO 薄膜霍爾量測--------61

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