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研究生:才有益
研究生(外文):Yeou-Eah Tsai
論文名稱:以嵌入法製作含BBO晶體透明光學玻璃之研究
論文名稱(外文):Fabrication of Transparent Optical Glasses Containing BBO Crystals by Incorporation Method
指導教授:張炎輝張炎輝引用關係
指導教授(外文):Yen-Hwei Chang
學位類別:博士
校院名稱:國立成功大學
系所名稱:材料科學及工程學系碩博士班
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2003
畢業學年度:91
語文別:中文
論文頁數:112
中文關鍵詞:偏硼酸鋇非線性光學玻璃倍頻效率嵌入法
外文關鍵詞:second harmonic generation(SHG)nonlinear optical(NLO)incorporation methodβ-BaB2O4(BBO)
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  本研究主要探討在不同的再熔解實驗條件下,於B2O3系列玻璃中以嵌入法製作含偏硼酸鋇(BBO)晶體之透明非線性光學玻璃。主要之玻璃相有兩種,GPI:45BaO-24B2O3-31SiO2及GPII:40BaO-30B2O3-25SiO2- 5K2O,BBO結晶相之製作是利用BaO-B2O3之玻璃粉末於850℃持溫退火8小時。

  根據實驗結果,BBO結晶相均可成功存留於兩種玻璃基地中,且由於結晶相顆粒與原始玻璃相之折射率值接近,因此大部分之玻璃試片均呈現透明狀態。

  由實驗發現隨著結晶相的融入玻璃,玻璃將由於原子間配位數的改變而使折射率遞增,同時降低材料之玻璃轉變溫度Tg與結晶溫度Tx;而當玻璃基地存在結晶相顆粒時,介面的存在將降低材料的密度與折射率,隨著再熔解溫度的提高與持溫時間的延長,玻璃基地的結晶相顆粒粒徑降低並發生β至α的相變化。而玻璃之SHG值取決於基地中尚未熔解的BBO量。實驗顯示:在GPI系列中,最大的SHG效應發生在添加15wt﹪BBO結晶相,於再熔解溫度1020℃中持溫3min,其值大約為純BBO晶體之4.5﹪;而在GPII系列中,則發生在添加15wt﹪BBO,於960℃持溫5min,其值大約為純BBO晶體之10﹪。
  The fabrication of transparent B2O3-based glasses containing non-linear optical crystal of β-BaB2O4(BBO) particles by incorporation method was studied. For glass phases, 45BaO-24B2O3-31SiO2(GPI) and 40BaO-30B2O3-25SiO2-5K2O(GPII) were used. Besides, the BBO crystal phase was prepared by annealing the BaO-B2O3 powder at 850℃ for 5 hours.

  From the results of experimental, the BBO particle has been successfully incorporated into glasses by adjusting the melting temperature, soaking time and the amount of BBO. A small difference in the refractive index between matrix glass and incorporated crystals, is a significant reason for the transparency.

  The refractive index and thermal stability was increased for the change of coordination number when the BBO was dissolved. The β–phase could be transformed to α–phase when the remelting time and/or temperature was increased. We concluded that the efficiency of SHG was dependent on the content of BBO particles within the glass matrix. The SHG efficiency reached to 4.5% of pure BBO crystal when the GPI-glass containing 15wt% of BBO was remelted at a temperature of 1020℃ for 3min, and it reached to 10% for the GPII- glass at 960℃ for 5min.
中文摘要…………………………………………………………I
英文摘要…………………………………………………………II
目錄………………………………………………………………i
圖目錄……………………………………………………………v
表目錄……………………………………………………………ix
符號說明…………………………………………………………x

第一章 緒論……………………………………………………1
 1-1 簡介………………………………………………………1
 1-2 偏硼酸鋇(β-BaB2O4,BBO)晶體……………………4
 1-3 研究動機…………………………………………………6
 1-4 研究目的…………………………………………………6

第二章 文獻回顧………………………………………………7
 2-1 有關BBO晶體及其應用 …………………………………7
  2-1-1 BBO晶體之生長 ……………………………………8
  2-1-2 BBO晶體之基本性質 ………………………………10
  2-1-3 BBO晶體之應用 ……………………………………10
 2-2 非線性光學材料之種類…………………………………12
  2-2-1 晶體(Novel nonlinear crystals)………… 12
  2-2-2 半導體(Semiconductors)多晶材料 …………14
  2-2-3 玻璃材料(Glass materials)…………………14
  2-2-4 有機材料(Organic materials)………………16
 2-3 BaO-B2O3-SiO2系列玻璃………………………………16
 2-4 嵌入法之應用……………………………………………17

第三章 相關理論………………………………………………18
 3-1 玻璃製程…………………………………………………18
  3-1-1 玻璃的本質…………………………………………18
  3-1-2 玻璃結構之模型……………………………………20
  3-1-3 SiO2與B2O3的之結構特性…………………………24
 3-2 玻璃之光學性質…………………………………………26
  3-2-1 折射率與顆粒之關係………………………………27
  3-2-2 折射率與成分之關係………………………………29
 3-3 玻璃之電性質……………………………………………30
 3-4 結晶相顆粒之熔解與相變化……………………………30
 3-5 材料之非線性光學現象…………………………………34
 3-6 非線性光學材料之應用…………………………………36
  3-6-1 光放大器(Optical amplifier)………………36
  3-6-2 光開關(Optical switch) ……………………37
 3-7 BBO晶體之非線性光學現象…………………………… 38

第四章 實驗方法………………………………………………43
 4-1 實驗流程…………………………………………………43
 4-2 玻璃相之製備……………………………………………46
 4-3 BBO結晶相之製作……………………………………… 46
 4-4 混合………………………………………………………46
 4-5 再熔解……………………………………………………47
 4-6 淬火………………………………………………………47
 4-7 退火處理…………………………………………………48
 4-8 基本性質測試……………………………………………48
  4-8-1 密度量測……………………………………………48
  4-8-2 熱差分析……………………………………………48
 4-9 結構分析…………………………………………………48
  4-9-1 XRD結構分析……………………………………… 48
  4-9-2 掃描式電子顯微鏡觀察……………………………49
  4-9-3 穿透式電子顯微鏡觀察……………………………49
 4-10 光學性質量測 …………………………………………50
  4-10-1 折射率之量測…………………………………… 50
  4-10-2 光學穿透率之量測……………………………… 50
  4-10-3 SHG之量測…………………………………………50
 4-11 電阻的量測…………………………………………… 52

第五章 結果與討論……………………………………………54
 5-1 玻璃相I:BaO-B2O3-SiO2 ……………………………54
  5-1-1 基本性質之測試-密度的量測結果………………55
  5-1-2 基本性質之測試-DTA 熱差分析之結果…………57
  5-1-3 結構分析……………………………………………58
  5-1-4 顯微結構之觀察……………………………………61
  5-1-5 折射率之量測………………………………………61
  5-1-6 穿透率之量測………………………………………64
  5-1-7 SHG的量測………………………………………… 65
 5-2 玻璃相II:BaO-B2O3-SiO2-K2O………………………66
  5-2-1 基本性質之量測結果………………………………67
  5-2-2 X光結構分析……………………………………… 67
  5-2-3 顯微結構之觀察……………………………………68
  5-2-4 折射率之量測………………………………………69
  5-2-5 穿透率之量測………………………………………69
  5-2-6 SHG的量測………………………………………… 70
  5-2-7 電阻值之量測………………………………………71

第六章 結論……………………………………………………99

第七章 參考資料………………………………………………101
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