臺灣博碩士論文加值系統

本實驗選擇以具有優異光電特性之ZnS當做螢光體之母體材料，並加入不同濃度之錳元素作為激活劑。實驗製程以反應沉澱法製備含錳之奈米硫化鋅微粒，並改變硫化鋅含錳量，配合在不同溫度下的熱處理，研究不同條件對其螢光特性之改變情形，與探討奈米粒徑對其帶來的影響。
非奈米級粒徑之ZnS:Mn螢光體，經由光激發光產生能量轉移至錳離子電子能階中，導致Mn2＋發出波長585nm（2.12 eV）橘黃色光之特性光譜，而這是由於Mn2+離子在3d軌域內電子遷移4T1→6A1所產生的結果。而本實驗中摻錳量1%之樣品，發光波長約在592nm，且摻錳量提高至5%後，其發光波長最高可偏至600nm。此較一般bulk之摻錳硫化鋅發光位置偏向長波長區域。
當粒子尺寸小至奈米等級時，各個離子所受到的結晶場影響將會減弱，同時亦可能受到量子侷限（Quantum confinement）的影響，使其電子遷移軌道產生改變，造成發光之波長偏移；奈米級之粒徑除了會造成發光波長往較長波長區偏移外，且吸收激光波長λex之位置也會隨著粒徑大小而改變。由研究中發現，若粒子的尺寸愈小，其λex愈偏向高能量之區域。
由FTIR光譜與PL螢光光譜中可知，熱處理溫度200℃對樣品並沒有造成影響，而熱處理至300℃與400℃後之樣品會具有較高的螢光強度，這是由於熱處理前樣品粉末內含有較多C=O與COO－之有機物，影響了能量之吸收與轉移過程，故熱處理300℃與400℃後有機物減少造成螢光強度上升。而含錳量5%之樣品在熱處理至400℃後，其螢光強度反而比在300℃下熱處理後之樣品還低；此乃是因為熱處理造成錳進入硫化鋅晶格中，而當含量超出其最適量時產生濃度消光之結果，使得螢光強度不增反減。

We choose ZnS as host material in this study because of its excellent photoelectric property, and adding Manganese element of different concentration as activator. Co-precipitation method is used to prepare manganese doped zinc sulfide nanocrystal, and PL analysis is performed to realize the change of PL property made by different manganese concentration and heat treatment. Also, the effect of nanosize to sample is discussed.
The recombination energy of electron-hole pairs in ZnS crystal transfer to Mn2＋ ion, causing it to emit characteristic spectra. This yellow spectra of bulk ZnS:Mn observed in photoluminescence has peak at 585nm (2.12 eV), and this is associated with the 4T1→6A1 transition of Mn2＋ ion in 3d orbit. The sample that 1% Mn doped has a λem of 592nm, and theλem shifts to 600nm when the concentration of Mn doped increases to 5%. Comparing to common bulk ZnS:Mn, the λem of ZnS:Mn nanocrystal we made shifts to longer wavelength.
When the particle size decreases to nanosize, the effect of crystal field to each ion will decrease. Also, as a result of quantum confinement, the electron transition orbit changes so that the emitting wavelength shifts. Nanosize not only makes emission wavelength shift to longer wavelength area but also causing the excitation wavelength λex changes with particle size; if the size of particle become smaller, the λex shifts to higher energy area.
We can know from FTIR and PL spectra that heat treatment temperature of 200℃ doesn’t almost do no changes to our sample, but 300℃ and 400℃ make sample having higher luminous strength. This result is due to the organic substance like C=O and COO－ in sample powder before heat treatment, and the organic substance affects absorption and transfer process of energy so that 300℃ and 400℃ heat treatment make sample having higher luminous strength by decreasing organic substance. But sample with 5% Mn heat treated to 400℃ has lower luminous strength than 300℃; this is due to the result of concentration quenching.

目 錄
摘要Ⅰ
目錄Ⅴ
表目錄Ⅷ
圖目錄Ⅸ
第一章 序論1
第二章 文獻回顧4
2-1 螢光材料之發展過程4
2-2 螢光材料的種類與應用8
2-3 電激發光（Electroluminscence）簡介9
2-3-1 電激發光之發展歷史9
2-3-2 電激發光之原理10
2-4 母體材料（Host materials）11
2-4-1 母體材料簡介11
2-4-2 硫化鋅之性質12
2-5 發光中心（Luminescent Centers）13
2-5-1 原子遷移（Atomic Transition）13
2-5-2 晶體場（Crystal Field）14
2-5-3 錳離子發光中心（Mn2＋ Luminescent Center）15
第三章 實驗流程17
3-1 實驗原料與使用設備17
3-1-1 原料17
3-1-2 設備17
3-2 實驗方法與流程18
3-2-1 含錳硫化鋅微粒製備18
3-2-2 熱處理19
3-3 特性分析19
3-3-1 DTA熱分析儀19
3-3-2 X－ray繞射儀19
3-3-3 TEM穿透式電子顯微鏡20
3-3-4 PL螢光分析儀20
3-3-5 FTIR紅外線光譜分析21
第四章 結果與討論22
4-1 DTA熱分析22
4-2 X-ray繞射分析22
4-2-1 成份與結構22
4-2-2 硫化鋅之氧化溫度23
4-2-3 粉體粒徑大小24
4-3 TEM穿透式電子顯微鏡24
4-4 PL螢光分析25
4-4-1 激光光譜（Photoluminescence Excitation Spectra）25
4-4-2 螢光光譜（Photoluminescence Spectrum）28
4-4-2-1 螢光效率28
4-4-2-2 硫化鋅螢光光譜29
4-4-2-3 摻錳奈米硫化鋅之螢光光譜29
4-5 FTIR紅外線光譜分析30
4-5-1 硫化鋅之紅外線光譜30
4-5-2 摻錳奈米硫化鋅之紅外線光譜分析31
第五章 結論33
第六章 參考文獻35

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