臺灣博碩士論文加值系統

本論文的工作是以化學合成的方法製備出摻錳硫化鋅奈米晶體，並使用X光繞射(XRD)、穿透式電子顯微鏡(TEM)、光激螢光(PL)、光激螢光激發(PLE)等量測技術研究樣品的結構、型態與光學特性。XRD圖譜顯示樣品呈現硫化鋅的閃鋅礦結構，晶體的粒徑約為3~4 nm，此與TEM的觀測結果一致。PL光譜則顯示兩個螢光譜峰，一個為紅橘螢光，約在590 nm位置，另一個為寬波段的藍光，約在410~500 nm。前者是來自於錳離子4T1-6A1的特性躍遷，後者則是由硫化鋅主結構的硫空位缺陷所致。樣品的PL螢光強度會隨錳離子配比濃度的上升而增強，在錳離子配比濃度為4 % 時達到最大值，之後隨著錳離子濃度的增加而減弱。樣品添加界面活性劑之後，發光效率有顯著的提升。藉由PLE光譜可推估主結構之能隙，其值隨晶體的粒徑縮小而增大，這是由於量子侷限效應所致。樣品經由325 nm之氦鎘雷射光照射後，出現光致螢光增強的現象。樣品的變溫PL光譜顯示錳離子發光波長隨溫度上升而藍位移，這是因為主結構晶格場改變所致。變溫PL光譜顯示，含界面活性劑之樣品與無界面活性劑者有著截然不同的特性：前者的發光強度隨溫度上升而增強，後者卻呈現隨溫度上升而衰減的趨勢。

Mn2+ doped ZnS nanocrystals were synthesized by chemical method. The structure, morphology and optical properties of these nano-particles were studied by the means of X-ray diffraction (XRD), transmission electron microscope (TEM), photoluminescence (PL) and photoluminescence excitation (PLE) measurements. The XRD patterns showed the structure of the ZnS:Mn nanocrystals is zinc-blende. From the XRD and TEM results, the size of these narocrystals was estimated at about 3 ~4 nm. From the PL spectra, two emission peaks were observed. One is the orange emission (about 590 nm) which is due to the 4T1-6A1 characteristic transition in the Mn2+ ions, the other is the broad blue emission (from 410~500 nm) which can be attributed to the S vacancies in the ZnS nanocrystals. The PL spectra also showed that the emission intensity of samples increases as the Mn2+ concentration increases up to 4 % and then decreases. The surfactant effect on the luminescence intensity was also studied. It was found that the adding of surfactant in the synthesis process can increase the luminescence intensity efficaciously. The energy gap of the ZnS:Mn nanocrystals was determined by the PLE spectra. It was found to increase as the crystal size decreases. This blue shift of the PLE peaks is due to the quantum confinement effect of nanocrystals. Irradiation-induced luminescence enhancement effect was observed. The luminescence intensity of fresh samples was increased under irradiation by 325 nm He-Cd laser beam. From the temperature-dependent PL spectra, a blue shift of the Mn2+ ions emission peaks was observed as the temperature increased. This phenomenon could be attributed to the variation of crystal-field strength. The temperature dependence of the PL spectra of samples with surfactant was different to that without surfactant. The luminescence intensity of samples with surfactant increases as the temperatire increases. However, for the samples without surfactant, the luminescence intensity deccreaes as the temperature increases.

第一章 緒論..............................................1
1.1 前言.................................................1
1.2 硫化鋅螢光體.........................................2
1.2.1硫化鋅螢光體的發展沿革..............................2
1.2.2 硫化鋅晶體結構.....................................3
1.2.3 硫化鋅的摻雜及應用.................................5
1.2.3.1 發光中心為深層施體-受體對........................5
1.2.3.2 發光中心為稀土族元素.............................7
1.2.3.3 發光中心為過渡金屬...............................7

第二章 實驗基本原理......................................9
2.1 膠體共沉澱法.........................................9
2.2 X光繞射.............................................11
2.3 光激螢光光譜原理....................................14
2.4 光激螢光激發光譜原理................................15
2.5 奈米材料與量子效應..................................15
2.5.1 量子侷限效應......................................16
2.5.2 表面效應..........................................17
2.6 濃度淬滅效應........................................19
2.7 晶格場理論..........................................19
2.8 摻錳硫化鋅奈米螢光體................................23
2.8.1 摻錳硫化鋅奈米螢光體的組成........................23
2.8.2 摻錳硫化鋅奈米螢光體的發光機制....................24

第三章 實驗方法與儀器原理...............................30
3.1 實驗藥品............................................30
3.2 實驗儀器............................................32
3.2.1 合成樣品之設備....................................32
3.2.2 分析樣品之設備及基本原理..........................33
3.2.2.1 單光儀..........................................35
3.2.2.2 鎖相放大器......................................37
3.3 樣品合成............................................37
3.3.1 變化摻雜濃度組....................................38
3.3.2 變化界面活性劑濃度組..............................40
3.3.3 變化合成溫度組....................................42
3.3.4 界面活性劑中段加入組..............................44
3.3.5 熱退火組..........................................46
3.4 特性分析............................................47
3.4.1 結構分析..........................................47
3.4.2 尺寸分析..........................................48
3.4.3 光性分析..........................................49
3.4.3.1 光激螢光光譜量測................................49
3.4.3.2 光激螢光激發光譜量測............................50

第四章 結果與討論.......................................52
4.1變化摻雜濃度之樣品組.................................52
4.1.1 結構分析..........................................52
4.1.2 光激螢光光譜分析..................................55
4.2 變化界面活性劑濃度之樣品組..........................60
4.2.1 結構分析..........................................61
4.2.2 光激螢光光譜分析..................................63
4.2.3 光激螢光激發光譜分析..............................65
4.3 變化合成溫度組......................................66
4.3.1 結構分析..........................................66
4.3.2 光激螢光光譜分析..................................68
4.3.3 光激螢光激發光譜分析..............................69
4.4 界面活性劑中段加入組................................71
4.4.1 結構分析..........................................71
4.4.2 光激螢光光譜分析..................................73
4.4.3 光激螢光激發光譜分析..............................75
4.5 熱退火組............................................76
4.5.1 結構分析..........................................76
4.5.2 光激螢光光譜分析..................................78
4.5.3 光激螢光激發光譜分析..............................79
4.6 摻錳硫化鋅奈米晶體之其他光學性質....................80
4.6.1 紫外光照射增強螢光效率............................80
4.6.2 發光效率與溫度的關係..............................86
4.6.2.1 無添加界面活性劑之樣............................86
4.6.2.2 添加界面活性劑之樣品............................89
4.6.3 其他錳離子分離能階之吸收..........................92

第五章 結論.............................................93

第六章 未來工作計畫.....................................95
6.1 實際摻雜濃度之測量..................................95
6.2 更微小粒子之製作....................................95
6.3 時間解析光譜之分析..................................96

參考文獻................................................97
表目錄
表4-1 計算ZnS:Mn奈米晶體中激子能量時所用之參數..........70
表4-2 變化合成溫度組之實驗結果..........................70

圖目錄
圖1-1 硫化鋅閃鋅礦結構...................................4
圖1-2 硫化鋅纖鋅礦結構...................................4
圖1-3 螢光活化劑與螢光共活化劑的摻雜濃度比影響螢光波長示意圖.......................................................6
圖2-1 晶格繞射示意圖....................................11
圖2-2 X光繞射儀簡圖.....................................12
圖2-3 X光繞射圖譜.......................................13
圖2-4 八面體配位示意圖..................................20
圖2-5 3d軌域能階分裂示意圖..............................21
圖2-6 四面體配位示意圖..................................22
圖2-7 3d5電子軌域之田邊-管野能階圖......................26
圖2-8 摻錳硫化鋅之能量傳輸示意圖........................28
圖3-1 閃耀光柵截面圖....................................35
圖3-2 單光儀內部簡圖....................................36
圖3-3 變化摻雜濃度組製作流程圖..........................39
圖3-4 變化界面活性劑濃度組製作流程圖....................41
圖3-5 變化合成溫度組製作流程圖..........................43
圖3-6 界面活性劑中段加入組製作流程圖....................45
圖3-7 熱退火條件示意圖..................................46
圖3-8 X光繞射試片......................................47
圖3-9 穿透式顯微鏡試片..................................48
圖3-10 光激螢光光譜裝置圖...............................50
圖3-11 光激螢光光譜量測裝圖.............................51
圖4-1不同錳摻雜濃度的ZnS:Mn奈米晶體樣品的X光繞射圖譜....53
圖4-2 JCPDS卡之硫化鋅閃鋅礦結構的相關資料...............54
圖4-3 摻錳硫化鋅奈米晶體之TEM照片.......................54
圖4-4 不同錳摻雜濃度的ZnS:Mn奈米晶體樣品的光激螢光光譜..55
圖4-5 ZnS:Mn奈米晶體樣品的積分發光強度隨錳摻雜濃度變化的關係圖......................................................56
圖4-6 經過4個月後，不同錳摻雜濃度之ZnS:Mn奈米晶體樣品的光激螢光光譜................................................57
圖4-7 經過4個月後，ZnS:Mn奈米晶體樣品積分發光強度的變化情形......................................................58
圖4-8 不同錳摻雜濃度的ZnS:Mn奈米晶體樣品在藍光區域的光激螢光光譜....................................................59
圖4-9 經過4個月後，不同錳摻雜濃度的ZnS:Mn奈米晶體樣品在藍光區域的光激螢光光譜......................................59
圖4-10 錳摻雜濃度為0, 1, 3 %的ZnS:Mn奈米晶體樣品光激螢光光譜......................................................60
圖4-11 添加不同界面活性劑濃度的ZnS:Mn奈米晶體樣品的X光繞射圖譜......................................................62
圖4-12 添加不同界面活性劑濃度的ZnS:Mn奈米晶體樣品的光激螢光光譜....................................................64
圖4-13 ZnS:Mn奈米晶體樣品的積分發光強度隨界面活性劑之添加劑量變化的情形............................................64

圖4-14 添加不同界面活性劑濃度的ZnS:Mn奈米晶體樣品的光激螢光激發光譜................................................65
圖4-15 不同合成溫度的ZnS:Mn奈米晶體樣品的X光繞射圖譜....67
圖4-16 不同合成溫度的ZnS:Mn奈米晶體樣品的光激螢光光譜...68
圖4-17 不同合成溫度的ZnS:Mn奈米晶體樣品的光激螢光激發光譜
........................................................69
圖4-18 位移能量 隨晶體粒徑變化的關係....................70
圖4-19 先添加界面活性劑再合成的ZnS:Mn奈米晶體樣品的X光繞射圖譜......................................................72
圖4-20 先添加界面活性劑再合成的ZnS:Mn奈米晶體樣品的光激螢光光譜....................................................73
圖4-21 先添加界面活性劑再合成的ZnS:Mn奈米晶體樣品在藍光區域的光激螢光光譜..........................................74
圖4-22 不同界面活性劑添加時機的ZnS:Mn奈米晶體樣品的光激螢光光譜....................................................74
圖4-23 先添加界面活性劑再合成的ZnS:Mn奈米晶體樣品的光激螢光激發光譜................................................75
圖4-24 以不同溫度退火的ZnS:Mn奈米晶體樣品之X光繞射圖譜..77
圖4-25 以不同溫度退火的ZnS:Mn奈米晶體樣品之光激螢光光譜.78
圖4-26 以不同溫度退火的ZnS:Mn奈米晶體樣品之光激螢光激發光譜......................................................80
圖4-27 ZnS:Mn奈米晶體樣品受不同功率之氦鎘雷射光照射下，發光強度隨時間變化的關係....................................81
圖4-28 影響錳離子激發態居量的因素.......................83
圖4-29 ZnS:Mn奈米晶體樣品受不同功率之氦鎘雷射光照射下，發光強度隨時間變化的關係。紅線為(4.6)式的擬合結果...........85
圖4-30 錳摻雜濃度為3 %的ZnS:Mn奈米晶體樣品之變溫光激螢光光譜......................................................88
圖4-31 錳摻雜濃度為3 %的ZnS:Mn奈米晶體樣品的錳離子積分發光強度隨溫度變化的關係。紅線為雙活化能模型的擬合曲線........88
圖4-32 添加界面活性劑而錳摻雜濃度為3 %的ZnS:Mn奈米晶體樣品的變溫光激螢光光譜........................................91
圖4-33 添加界面活性劑而錳摻雜濃度為3 %的ZnS:Mn奈米晶體樣品的積分發光強度隨溫度變化的關係............................91
圖4-34 添加界面活性劑而錳摻雜濃度為3 %之ZnS:Mn奈米晶體樣品的光激螢光激發光譜........................................92

第一章 緒論
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第二章 實驗基本原理
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第三章 實驗方法與儀器原理
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第四章 結果與討論
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第六章 未來工作計畫
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