本文分為相關的兩部份: (一)、鋁金屬片於空氣及液體環境下之脈衝雷射剝熔蝕，著重於坑洞周圍之相與微觀組織變化; (二)、脈衝雷射於水中碎化剛玉粉末效應。
第一部份以脈衝雷射在空氣和純水環境下，利用奈秒脈衝雷射以不同能量密度單一脈衝剝熔蝕純鋁多晶(粒徑約為3微米)靶材，以便比較產生的孔洞、熱影響區、微結構及奈米級氧化凝聚物回鍍並龜裂的差異。藉由掃瞄和穿透式電子顯微鏡的觀察發現大氣與水兩種環境對於所得孔洞直徑及周圍噴濺程度的影響力為大氣＞水，且隨能量越高孔洞皺摺程度就越大；而環境對熱影響區範圍的影響趨勢為大氣＞水，同樣隨能量越剝蝕範圍就越大。此外在空氣環境下分成已蝕刻薄化和未蝕刻兩種片狀靶材進行剝熔蝕，發現蝕刻過後的試片因厚度縮減，及蝕刻坑洞周圍於雷射剝熔蝕的過程中有較多的氧化凝聚物回鍍成比金屬鋁片熱導性差熱膨脹係數低的氧化鋁薄膜，因此於冷卻過程中出現坑洞附近較大的龜裂片及遠處的小龜裂片。穿透式電子顯微鏡觀察進一步發現，於空氣中回鍍於基材表面的氧化凝聚物，無論所使用的脈衝雷射能量多少，主要都是奈米級(5-20nm)不規則形狀的
α-Al2O3與θ-Al2O3、γ-Al2O3、δ*-Al2O3顆粒共存，而多晶鋁片基材熱影響區有明顯差排及不明顯晶粒重生的再結晶現象並於離洞口中心約200微米裂片大小趨近於原始晶粒大小。
本實驗第二部份主要是研究脈衝雷射於水中碎化剛玉粉末效應，以由上往下(top-down)的方式，於水中環境利用不同的雷射模式剝蝕(PLAL)浮動次微米級鋼玉α-Al2O3粉末，並使之碎化（fragmentation），觀察是否有碎裂並分析其結構和相變化的行。結果發現利用雷射模式為Q-switching，能量為400 mJ/pulse時，在電子顯微鏡明場像下可以明顯觀察出會有少部分粉末受雷射剝蝕顆粒尺寸縮少至20nm以下，和原本的尺寸有明顯的有巨大的變化;而當雷射模式改變成free-run，能量為1000 mJ/pulse時，反而沒有明顯縮小尺寸的現象，對兩者雷射模式下做選區繞射，並跟原始氧化鋁圖做比對和X-ray 繞射儀分析可知受兩種雷射模式下剝蝕的粉末和原始粉末相比並無太大的改變，大部分(>95%)仍然是
α-Al2O3與結構。經由高分辨解析後，可知奈秒或毫秒脈衝雷射剝熔蝕水中浮動的鋼玉α-Al2O3與粉末，仍可因熱震效應將其碎裂成粒徑較小的奈米顆粒，並發生α→δ*相變化，
δ*-Al2O3大部分為~20nm，部份顆粒表面有明顯的階檻並對單一顆粒做高分辨電鏡的解析，大部分是δ*相，其形狀接近不規則的形狀，經觀察晶格影像重建圖後，內部結構並沒有發現缺陷的存在但熱震效應及水的冷卻效應仍可造成固定靶材熱震影響區(heat-shock affected zone, HSAZ)之破裂，或浮動次微米顆粒碎化成奈米顆粒。此外，另有幾近球狀之γ-Al2O3雙晶奈米顆粒(15~20nm)誕生，應該是電漿中原分子聚簇成獨立的奈米顆粒，彼此再依照{111}表面貼合成雙晶，屬於主導的熱蒸發機制。

Pulsed laser ablation (PLA) in single shot on polycrystalline Al thin foil ca. 50μm in thickness was conducted in air and water to study the heat and shock affected zone (HSAZ) under specific wave length (532 nm), pulse duration time (16 ns) and laser input energy (400, 600 and 800 mJ/pulse) with a specified spot size of 0.03 mm2. The combined optical and electron microscopic observations indicated water is more effective than air to reduce HSAZ which increases with the increase of pulse energy yet with negligible recrystallization of Al substrate. Oxidation of the Al foil and redeposition of aluminum oxide nanocondensates on the laser incident side caused thermal mismatch between the coating and the Al substrate (especially when only 30μm in thickness), and hence intra- and intergranular cracking along thermally etched subgrain boundary and grain boundary, respectively. The minimum interspacing of successive shots for effective fabrication of aluminum oxide nanocondesates from Al substrate are 470 and 250μm, for the present PLA in air and water, respectively.
PLA fragmentation of α-Al2O3 powder (mainly 100 nm in size) in water was also conducted under free-run mode (1064 nm, 240 μs pulse duration) vs Q-switch mode (532 nm, 16 ns pulse duration) having laser spot size 0.03 mm2 and focal point 5 mm beneath the water level for an accumulation time of 20 min at 10 Hz. Comparing with the case of 1064 nm, the 532 nm laser incidence suffered less water absorption and was more effective to produce nanocondensates mainly in the form of γ and δ* derived phases ranging from 5 to 20 nm in diameter which were occasionally (111)-specifically coalesced as twinned bicrystals.

誌謝……………………………………………………………………………………i
摘要…………………………………………………………………………………ii
Abstract…………………………………………………………………………iv
Part I…………………………………………………………………1
一、 前言………………………………………………………………………2
二、 實驗步驟與方法…………………………………………………………5
2.1 原始金屬鋁靶材......................................................................................................5
2.1.1 準備靶材...............................................................................................................5
2.1.2 X-ray 繞射分析(XRD)......................................................................................5
2.1.3 穿透式電子顯微鏡(TEM)觀察...........................................................................5
2.1.4 掃瞄式電子顯微鏡(SEM)觀察...........................................................................5
2.2 雷射剝蝕後之鋁靶材.............................................................................................5
2.2.1 雷射剝蝕..............................................................................................................6
2.2.2 偏光顯微鏡觀察.................................................................................................5
2.2.3 掃瞄式電子顯微鏡觀察.....................................................................................6
2.2.4 穿透式電子顯微鏡觀察.....................................................................................6
三、 實驗結果..............................................................................................................8
3.1 第一部份：原始金屬鋁靶材................................................................................8
3.1.1 X-ray 繞射分析...................................................................................................8
3.1.2 掃瞄式電子顯微鏡觀察.....................................................................................8
3.1.3 穿透式電子顯微鏡觀察.....................................................................................8
3.2 第二部份：雷射剝蝕後之鋁靶材........................................................................8
3.2.1 掃瞄式電子顯微鏡觀察偏光顯微鏡觀察..........................................................8
3.2.2 偏光顯微鏡觀察..................................................................................................9
3.2.3 穿透式電子顯微鏡觀察.....................................................................................9
四、討論………………………………………………………………………11
4.1 單一脈衝雷射與環境條件對鋁薄片剝熔蝕孔洞大小與形狀的影響...............11
4.2 單一脈衝雷射與環境條件對鋁薄片造成的熱震效應.......................................12
4.3 單一脈衝雷射剝熔蝕鋁薄片造成氧化鋁回鍍的機制.......................................13
4.4 單一脈衝雷射與環境條件對鋁薄片造成的開裂...............................................13
五、結論………………………………………………………………………15
六、 參考文獻.............................................................................................................20
附錄…………………………………………………………………………………16
Part II…………...................................................................................................45
一、前言......................................................................................................................46
二、實驗步驟與方法..................................................................................................48
2.1 配置氧化鋁粉末..................................................................................................48
2.2 X-ray 繞射分析(XRD).........................................................................................48
2.3 雷射剝蝕..............................................................................................................48
2.4 掃瞄式電子顯微鏡觀察......................................................................................48
2.5 穿透式電子顯微鏡觀察 .....................................................................................48
三、實驗結果...............................................................................................................50
3.1 X-ray 繞射分析(XRD).........................................................................................50
3.2 掃瞄式電子顯微鏡觀察......................................................................................50
3.3 穿透式電子顯微鏡觀察......................................................................................50
四、討論.......................................................................................................................52
4.1 鋼玉浮動粉末與靜止多晶塊材之水中奈秒脈衝碎化效應比較.......................52
4.2 鋼玉粉末水中粒徑小化極限與相變化...............................................................52
4.3 奈秒脈衝雷射使水中鋼玉粉末粒徑變小的機制...............................................53
五、結論.......................................................................................................................54
六、文獻回顧...............................................................................................................60
附錄…………………………………………………………………………………55

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