在第一部分中，利用BET分析於800~1100 ℃等溫燒結的奈米二氧化錫粉末，取得粉末表面對於氮氣的吸脫附行為，再利用掃瞄式電子顯微鏡的結果做為燒結變化的佐證，由實驗結果得知，乾壓的粉末比表面積較大，由於粒徑屬於雙峰分佈(50~80 nm；200~500 nm) ，顆粒間有不規則管狀孔洞且分佈散亂，而其比表面積會隨著熱處理時間增加而變小，燒結過程中由顆粒粗化與重排影響甚大。利用粉末比表面積折半所需時間(t0.5)與溫度的關係，以及阿瑞尼氏方程式求出早期燒結粗化與聚合所需之活化能為75±5 kJ/mol，而奈米二氧化錫粉末於空氣中進行初期燒結並且聚簇轉動貼合的溫度下限約為735 ℃。

第二部份，利用脈衝雷射(Q-switch 模式,532 nm, 400mJ)剝熔蝕在水中碎裂分解次微米級錫石粉末，實驗參數為液面高度(5, 10, 15和20 mm)及時間(5, 15, 20和30 min)。532 nm雷射對水有些許吸收現象並有效碎化成粒徑約5 nm的奈米凝聚物，另外也重新凝聚生成具有α-PbO2結構的SnO2奈米顆粒，推測水中剝熔蝕錫石粉末造成能隙值減小的因素是綜合粒徑明顯變小、內應力明顯增加及晶格內部大量增加了鍵橋Sn-OH基等的效應。

An onset coarsening-coalescence event based on the incubation time of cylindrical mesopore formation and a significant decrease of specific surface area by 50% relative to the dry pressed samples was determined by N2 adsorption-desorption hysteresis isotherm for cassiterite SnO2 nanoparticles (rutile-type structure with bimodal size distribution). In the temperature range of 800-1100oC, the nanoparticles underwent onset sintering coupled with coarsening-coalescence without appreciable polymorphic transformation or decomposition of SnO2. The apparent activation energy of such a rapid process for SnO2 nanoparticles was estimated as 75 ± 5 kJ/mol, respectively. The minimum temperature for sintering/coarsening/coalescence of the SnO2 nanoparticles is 735oC based on the extrapolation of steady specific surface area reduction rates to null.

PLA fragmentation of cassiterite SnO2 powder (rutile type, 20-50 nm in size) in water was conducted under Q-switch mode (532 nm, 400 mJ per pulse) having laser focal point fixed at 5, 10, 15 and 20 mm beneath the water level for an accumulation time of 5, 15, 20 and 30 min at 10 Hz. The 532 nm laser incidence suffered little water absorption and was effective to produce cassiterite nanocondensates as small as 5 nm in diameter and occasional nanocondensates of α-PbO2-type structure more or less in coalescence. The combined effects of nanosize, internal compressive stress and H+ and Sn2+ co-signature in the lattice may account for a lower minimum band gap.

目錄
論文審定書 i
摘要 ii
Abstract iii
目錄 iv
圖表目錄 viii
第一部份
壹、前言 1
貳、實驗流程 4
參、實驗步驟及方法 5
一、壓片 5
二、熱處理 5
三、BET/BJH量測 5
四、XRD量測 5
五、掃瞄式電子顯微鏡(SEM)觀察 5
六、穿透式電子顯微鏡(TEM)觀察 6
肆、實驗結果 7
一、BET比表面積 7
二、BJH氮氣吸脫附曲線 7
三、穿透式及掃瞄式電子顯微鏡觀察 7
四、XRD結果 8
伍、討論 9
一、吸脫附遲滯曲線及管狀孔洞 9
二、早期燒結粗化與聚合之活化能 9
三、奈米金屬二氧化物粉末燒結粗化與聚合之活化能比較 10
陸、結論 12
柒、參考文獻 13
第二部份
壹、前言 29
貳、實驗流程 31
參、實驗步驟及方法 32
一、配粉 32
二、雷射剝蝕 32
三、穿透式電子顯微鏡(TEM)觀察 32
四、XRD量測 32
五、UV–Vis吸收光譜分析 33
六、拉曼光譜分析（Raman） 33
七、霍式轉換紅外光譜分析(FTIR) 33
八、X光光電子能譜分析(XPS) 33
肆、實驗結果 34
一、X光繞射分析結果 34
二、UV–Vis吸收光譜分析結果 34
三、拉曼光譜分析（Raman）結果 34
四、霍式轉換紅外光譜分析(FTIR)結果 35
五、X光光電子能譜分析(XPS) 35
六、穿透式電子顯微鏡觀察 36
伍、討論 38
一、SnO2次微米粉末在水中雷射剝蝕碎化機制 38
二、在水中雷射剝蝕碎化產生之內應力 38
三、錫石於水中動態剝熔蝕環境的粒徑極限形狀與缺陷 39
四、能隙值之改變 39
五、缺陷化學 40
陸、結論 41
柒、參考文獻 42

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