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.

[1] P. A Franken, A. E Hill, C. W. Peters, and G. Weinreich, “Generation of Optical Harmonics”, Phys. Rev. Lett. 7 (1961) 118

[2] P. D. Maker, R. W. Terhune, M. Nissenoff and C. M. Savage, “Effects of Dispersion and Focusing on the Production of Optical Harmonics”, Phys. Rev. Lett. 8 (1962) 21

[3] J. A. Giordmaine, “Mixing of Light Beams in Crystal”, Phys. Rev. Lett. 8 (1962) 19

[4] R. C. Miller, ”Optical Second Harmonic Generation in Piezoelectric Crystals”, Appl. Phys. Lett. 5 (1964) 17

[5] S. K. Kurtz, T. T. Perry, “A Powder Technique for the Evaluation of Nonlinear Optical Materials”, J. Appl. Phys. 39 (1968) 3798

[6] C. Chen, B. Wu, I. Jiang and G. You, Scientia Sinica Ser. B, 28 (1985) 235

[7] Y. H. Kao, Y. Hu, H. Zheng and J. D. Mackenzie, “Second Harmonic Generation in Transparent Barium Borate Glass-ceramics” J. Non-crys. Sol. 167 (1994) 247

[8] T. Komatsu, K. Shioya and K. Matushita, “Fabrication of Transparent Tellurite Glasses Containing Potassium Niobate Crystals by Incorporation Method” J. Am. Ceram. Soc. 76[11] (1993) 2923

[9] H. G. Kim, T. Komatsu, R. Sato and K. Matushita, “Fiber Drawing of LiNbO3-doped Mixed Alkali Tellurite Glasses” J. Ceram. Soc. Jpn. 103 (1995) 1061

[10] E. M. Levin and H. F. McMurdie, J. Res. Natl. Bur. Stand. 42 (1949) 131

[11] A. D. Mighell, A. Perloff and S. Block, Acta Crystallogr. 20 (1966) 819

[12] E. Brixner, G. D. Chen and T. C. Lee, Phys. Lett. 21 (1966) 259

[13] K. H. Hubner, Neues Jahrb. Mineral. Monatsh.,335 (1969)

[14] K. Miyazaki, H. Sakai and T. Sato, Opt. Lett.,11 (1986) 797

[15] C. Chen, B. Wu, G. You and Y. Huang, Digest of Technical Papers of the XIIIth International Quantum Electronics Conference, 1984, paper MCC5

[16] 盧紹芳,何美雲,黃金陵, “偏硼酸鋇低溫相的晶體結構” 物理學報, 第31卷,第7期,(1982) 948

[17] C. Chen, B. Wu, A. Jiang and G. You, “A New type Ultraviolet SHG Crystal β-BaB2O4”, Sci. Sinica(ser. B), 28 (1985) 235

[18] K. Kato, “Second Harmonic Generation to 2048 Å inβ-BaB2O4”, IEEE J. Quantum Electron, QE-22 (1986) 1013

[19] D. J. Amstrong, W. J. Alford, T. D. Raymond and A. V. Smith, “Absolute Measurement of the Effective Nonlinearities of KTP and BBO Crystals by Optical Parametric Amplification”, Appl. Opt. 35(12) (1996) 2032

[20] D. Eimerl, L. Davis and Velsko, “Optical, Mechanical and Thermal Properties of Barium Borate”, J. Appl. Phys. 62(5) (1987) 1968

[21] G. Zhang, Y. Yang and C. Zhang, “Low-temperature Absorption steps near Ultraviolet Intrinsic edge in Beta Barium Metaborate”, Appl. Phys. Lett. 53(11) (1988) 1019

[22] L. K. Cheng, W. Bosenberg and C. L. Tang, “Growth and Characterization of low Temperature phase Barium Metaborate Crystals”, J. Crystal Growth 89 (1988) 553

[23] R. S. Feigelson, R. J. Raymakers and R. K. Route, “Solution Growth of Barium Metaborate Crystals by Top Seeding”, J. Crystal Growth, 97 (1989) 352

[24] Y. Kozuki and M. Itoh, “Nonlinear Optical Material –BaB2O4 (BBO)” Nonlinear Opt. 1 (1991) 187

[25] H. Nakatani, W. Bosenberg, L. K. Cheng and C. L. Tang, “Linear Electro-optic Effect in Barium Metaborate”, Appl. Phys. Lett. 52(16) (1988) 1288

[26] C. A. Ebbers, “Linear Electro-optic Effect inβ-BaB2O4”, Appl. Phys. Lett. 52(23) (1988) 1948

[27] H. Komine, “Optical Parametric Oscillation in a Beta-barium Borate Crystal pumped by XeCl Excimer Laser”, Opt. Lett. 13(8) (1988) 643

[28] D. Y. Tang, R.K. Route and R. S. Feigelson, “Growth of Barium Metaborate Single Crystal Fibers by the Laser-heated Pedestal Growth Method”, J. Crystal Growth, 91 (1988) 81

[29] W. R. Bosenberg, L. K. Cheng and C. L. Tang, “Ultraviolet Optical Parametric Oscillation inβ-BaB2O4”, Appl. Phys. Lett. 54(1) (1989) 13

[30] S. Imai, T. Yamada, Y. Fujimori and K. Ishikawa, “Third-harmonic Generation of an Alexandrite Laser inβ-BaB2O4”, Appl. Phys. Lett. 54(13) (1989) 1206

[31] R. Guo and A. S. Bhalla, “Pyroelectric, Piezoelectric and Dielectric Properties ofβ-BaB2O4 Single Crystal”, J. Appl. Phys. 66(12) (1989) 6186

[32] 魯士平,袁桻謙,楊立,吳存愷, “在BBO中獲得230.8－223.2nm高功率和頻輸出”, 物理學報, 第39卷, 第2期, (1990) 190

[33] 魯士平,袁桻謙,楊立, “β-BaB2O4晶體中367.3－379.4nm的和頻產生”, 物理學報, 第39卷, 第10期, (1990) 1570

[34] 范琦康,吳碧珍,洪治, “用BBO晶體產生196－228nm波長的紫外輻射”, 光學學報, 第12卷, 第5期, (1992) 402

[35] 楊鏡新,孟紹賢, “對採用BBO晶體鎖模Nd：YAG激光器的實驗研究”, 光學學報, 第12卷, 第12期, (1992) 1072

[36] Y. Ding, A. Osaka and Y. Miura, “Enhanced Surface Crystallization of β–barium Borate on Glass due to Ultrasonic Treatment”, J. Am. Ceram. Soc. 77[3] (1994) 749

[37] H. Kimura, T. Numazawa and M. Sato, “Solid State Phase Transformation of BaB2O4 during the Isothermal Annealing process”, J. Mat. Sci. 31 (1996) 2361

[38] S. C. Sabharwal and Sangeeta, “Effect of Sodium Doping on Thermoluminescence and Optical Properties of Barium Borate Single Crystals”, J. Crystal Growth 187 (1998) 253

[39] S. Singh, “Non-linear Optical Materials”, in : Handbook of Lasers, ed. Pressley, R. J., Chemical Rubber Company, Cleveland, Ohio, (1971) 489

[40] K. F. Hulme, “Nonlinear Optical Crystals and their Applications”, Rep. Prog. Phys. 36 (1973) 497

[41] R. G. Smith, “Optical Parametric Oscillators”, in：Lasers, ed. A. K. Levine and A. J. DeMaria, Marcel Dekker, New York, (1976) 189

[42] D. N. Nikogosyan, “Nonlinear Optics Crystal (review and summary of data)”, Sov. J. Quantum Electron, 7 (1977) 1

[43] F. C. Zumsteg, J. D. Bierlein and T. E. Gier, “KxRb1－xTiOPO4：A new Nonlinear Optical Material”, J. Appl. Phys. 47 (1976) 4980

[44] C. Chen, Y. Wu, A. Jiang, B. Wu, G. You, R. Li and S. Lin, “New Nonlinear-optical Crystal：LiB3O5”, J. Opt. Soc. Am., B6 (1989) 616

[45] D. A. Bryan, R. Gerson and H. E. Tomaschke, “Increased Optical Damage Resistance in Lithium Niobate”, Appl. Phys. Lett. 44 (1984) 847

[46] S. D. Zhong, “Recent Developments in the Growth and Nonlinear Optical Applications of KNbO3 Crystals”, Prog. Crystal Growth and Charact. 20 (1990) 161

[47] R. C. Eckardt, H. Masuda, Y. X. Fan and R. L. Byer, “Absolute and Relative Nonlinear Optical Coefficients of KDP, KD*P, BaB2O4, LiIO3, MgO：LiNbO3 and KTP Measured by Phase-matched Second Harmonic Generation”, IEEE J. Quantum Electron, 26 (1990) 922

[48] S. Ducharme, J. Feinberg and R. Neurgaonkar, “Electrooptic and Piezoelectric Measurements in Photorefractive Barium Titanate and Strontium Barium Niobate”, IEEE J. Quantum Electron, 23 (1987) 2116

[49] A. Liu, L. Hesselink, M. Lee and R. S. Feigelson, “Electro-optic and Photorefractive Two-beam Coupling Properties of Lead Barium Niobate Crystals”, J. Appl. Phys. 83(5) (1998) 2826

[50] Y. Amnon and Y. Pochi, “Nonlinear Optics”, in ：Optical Waves in Crystals, ed. W. John, New York, (1984) 512

[51] C. Y. Fond and Y. R. Shen, “Theoretical Studies on the Dispersion of the Nonlinear Optical Susceptibilities in GaAs, InAs and InSb”, Phys. Rev. B12 (1975) 2325

[52] C. R. Pidgeon, B. S. Wherrett, A. M. Johnston, J. Dempsey and A. Miller, “Two-photon Absorption in Zinc-blends Semiconductors”, Phys. Rev. Lett. 52 (1979) 1785

[53] P. Boucaud, F. H. Julien, D. D. Yang, J. M. Lourtioz, E. Rosencher, P. Bois and J. Nagale, “Detailed Analysis of Second Harmonic Generation Near 10.6μm in GaAs/AlGaAs Asymmetric Quantum well”, Appl. Phys. Lett. 57 (1990) 215

[54] B. M. Sheik, D. J. Hagan A. A. Said, T. H. Wei and E. W. Van Stryland, “Sensitive Measurement of Optical Nonlinearities using a Single Beam”, IEEE J. Quant. Elect. 26 (1990) 760

[55] B. M. Sheik, D. J. Hagan, D. C. Hutchings and E. W. Van Stryland, “Dispersion of Bound Electronic Nonlinear Refraction in Solids”, IEEE J. Quant. Elect. 27 (1991) 1296

[56] K.C. Long, R.A. Myers, S.R.J. Brueck, R. Ramer, K. Zheng, ”GaN Linear Electro-optic Effect”, Appl. Phys. Lett. 67 (10) (1995) 1349

[57] R.A. Mayers, N.Mukherjee, S.R. Brueck, “Large Second-order Nonlinearity in Poled Fused Silica”, Opt. Lett. 16(22) (1991) 1732

[58] X. C. Long, R. A. Mayers and S. R. Brueck, “Measurement of the Linear Electro-optic Coefficient in Poled Amorphous Silica”, Opt. Lett. 19(22) (1994) 1819

[59] K. Tanaka, K. Kashima, K. Hirao and N. Soga, “Second Harmonic Generation in Poled Tellurite Glasses”, Jpn. J. Appl. Phys. 32 (1993) L843

[60] K. Tanaka, K. Kashima, K. Hirao, N. Soga, A. Mito and H. Nasu, “Second Harmonic Generation in Electrically poled Li2O-Nb2O5-TeO2”, J. Non-Crys. Sol. 185 (1995) 123

[61] K. Tanaka, A. Narazaki, K. Hirao and N. Soga, “Optical Second Harmonic Generation in Poled MgO-ZnO-TeO2 and B2O3-TeO2 Glasses”, J. Non-Crys. Sol. 203 (1996) 49

[62] K. Tanaka, A. Narazaki, K. Hirao and N. Soga, “Poling Temperature Dependence of Optical Second-harmonic Intensity of MgO-ZnO-TeO2 Glasses”, J. Appl. Phys. 79(7) (1996) 3798

[63] A. Narazaki, K. Tanaka, K. Hirao and N. Soga, “Effect of Poling Temperature on Optical Second Harmonic Intensity of Sodium Zinc Tellurite Glasses”, J. Appl. Phys. 83(8) (1998) 3987

[64] T. Komatsu, H. Tawarayama, H. Mohri and K. Matusita, “Properties and Crystallization Behaviors of TeO2-LiNbO3 Glasses”, J. Non-Crys. Sol. 135 (1991) 105

[65] H. G. Kim, T. Komatsu, R. Sato and K. Matusita, “Crystallization of LiNbO3 in Tellurite Glasses”, J. Non-Crys. Sol. 162 (1993) 201

[66] T. Komatsu, H. Tawarayama and K. Matusita, “Preparation and Optical Properties of Transparent TeO2-based Glasses Containing BaTiO3 Crystals”, J. Ceram. Soc. Jpn. 101 (1992) 46

[67] Y. J. Kim, S. H. Lee, T. W. Noh and J. Kim, “Infrared Properties of Barium Borate Glasses：Application of the Generalized Lyddane – Sachs - Teller Relation”, J. Non-Crys. Sol. 170 (1994) 190

[68] B. F. Levine, C. G. Bethea, C. D. Thurmond, R. T. Lynch and J. L. Bernstein, “An Organic Crystal with an Exceptionally Large Optical Second order Coefficient：2-methyl-4-nitroaniline”, J. Appl. Phys. 50 (1979) 2523

[69] C. C. Teng and A. F. Garito, “Dispersion of the Non-linear Second order Susceptibility of an Organic System：p-Nitroaniline”, Phys. Rev. Lett. 50 (1983) 350

[70] T. Yoshimura, “Characterization of the Electro-optic Effect in Styrylpyridinium Cyanine dye Thin-film Crystals by an ac Modulation method”, J. Appl. Phys. 62(5) (1987) 2028

[71] H. Minemoto, Y. Ozaki, K. Wakita and N. Sonoda, “Intracavity Second-harmonic Generation and Influence of Optical loss of Organic Nonlinear Optical Materials”, Jpn. J. Appl. Phys. 34 (1995) 497

[72] J. Xu, L. Zhou and M. Thakur, “Electro-optic Modulation using an Organic Single Crystal Film in a Fabry-Perot Cavity”, Appl. Phys. Lett. 72(2) (1998) 153

[73] A. Leyderman and Y. Cui, “Electro-optical Characterization of a 2-cyclo-octylamino-5-nitropyridine Thin Organic Crystal Film”, Opt. Lett. 23(12) (1998) 909

[74] L. M. Hayden, G. F. Sauter, F. R. Ore and P. L. Pasillas, “Second order Nonlinear Optical Measurements in Guest-host and Side-chain Polymers”, J. Appl. Phys. 68(2) (1990) 456

[75] C. C. Teng and H. T. Man, “Simple Reflection Technique for Measuring the Electro-optic Coefficient of Poled Polymers”, Appl. Phys. Lett. 56(18) (1990) 1734

[76] P. Rohl, B. Andress and J. Nordmann, “Electro-optic Determination of Second and Third-order Susceptibilities in Poled Polymer Films”, Appl. Phys. Lett. 59(22) (1991) 2793

[77] F. Qiu, K. Misawa, X. Cheng and A. Ueki, “Determination of Complex Tensor Components of Electro-optic Constants of Dye-doped Polymer Films with a Mach-Zehnder Interferometer”, Appl. Phys. Lett. 65(13) (1994) 1605

[78] M. Herold, W. Schmid, T. Vogtmann, R. Fischer, D. Haarer and M. Schwoerer, “Electro-optic Pockels and Kerr Effects for the Determination of χ(3) and χ(3)：Thin Films of Side-chain Polymers Containing Dimethylaminonitrostilbene and of the Polydiacetylene poly-(butoxycarbonylmethyleneurethane)”, Appl. Opt. 34(6) (1995) 996

[79] P. M. Lundquist and M. Jurich, “Electro-optical Characterization of Poled-polymer Films in Transmission”, Appl. Phys. Lett. 69(7) (1996) 901

[80] A. Fuh, C. Y. Huang and C. W. Lau, “Second Harmonic Generation Studies of Polymer-stabilized Cholesteric Texture Films”, Jpn. J. Appl. Phys. 36 (1997) 2754

[81] E. M. Levin and H. F. McMurdie, “The System BaO-B2O3”, J. Am. Ceram. Soc. 32(3) (1949) 99

[82] E. H. Hamilton, G. W. Cleek and O. H. Grauer, “Some Properties of Glasses in the System Barium Oxide-boric Oxide-silica”, J. Am. Ceram. Soc. 41(6) (1958) 209

[83] S. Hirota and T. Izumitani, “Effect Cations on the Inherent Absorption Wavelength and the Oscillator Strength of Ultraviolet Absorptions”, J. Non-Crys. Sol. 29 (1978) 109

[84] D. Warner and H. Rawson, “The Effect of Glass Composition on the Mean Dispersion of Barium Borate Glasses”, J. Non-Crys. Sol. 29 (1978) 231

[85] E. I. Kamitsos, M. A. Karakassides and G. D. Chryssikos, “Cation Network Interactions in Binary Alkali Metal Borate Glasses：a Far-infrared Study”, J. Phys. Chem. 91 (1987) 5807

[86] V. Ramakrishnan and N. Jayaraman, “Fatigue Behavior of Borosilicate Glass-ceramic Matrix, Nicalon (silicon carbide) Fiber Composites”, J. Mat. Sci. 28 (1993) 5580

[87] T. Mito, S. Fujino, H. Takebe and K. Morinaga, “Effect of High Valency Cations on High Refractive-index and Low Dispersion Characteristics of Borate Glasses”, J. Ceram. Soc. Jpn. 102 (1994) 1164

[88] Y. E. Tsai and Y. H. Chang, “Fabrication of Transparent Borate Glasses Containing β-BaB2O4 by Incorporation Method”, Mat. Sci. Eng. A251 (1998) 129

[89] Y. E. Tsai, Y. H. Chang and K. L. Lo, ”The Influence of Different Remelting Conditions on the Transparency and Optical Properties of Borate Glass Incorporated withβ-BaB2O4“, Mat. Sci. Eng. A293 (2000) 229

[90] F. L. Galeener, “The Structure and Vibrational Excitations of Simple Glasses”, J. Non-Crystal. Solids.,123 (1990) 182

[91] W. H. Zachariasen, “Characteristics of Glass Formation”, J. Am. Ceram. Soc. 54 (1932) 3841

[92] A. Dietzel, Z. Elektrochem., 48 (1942) 9

[93] W. Vogel, “Chemistry of Glass”, The American Ceramic Soc., Inc. Columbus, Ohio, (1985) 154

[94] 邱關明、黃良釧, “玻璃形成學”，兵器工業出版社 (1988)

[95] 謝克誠、劉光耀、羅康俊, “晶體折射率測試方法”, 壓電與聲光, 第18卷, 第1期, (1996) 62

[96] 原著：H. Onodera, J. Awai and J. Ikenoue, 翻譯：蔣長茂、閻月會, “塊體材料的折射率量測：稜鏡偶合法”, 光學技術, 第6期, (1992) 12

[97] 劉崇進、沈家瑞、李鳳仙, “橢偏儀測量粗糙面薄膜的厚度和折射率的研究”, 光學技術, 第3期, (1995) 18

[98] R. W. Wood, “Dispersion theory”, Phys. Opt. 3, Macmillan (1936) 469

[99] H. B. Aaron and G. R. Kotler, “Second Phase Dissolution”, Met. Trans. 2 (1971) 393

[100] D. A. Porter and K. E. Eastering, “Phase Transformation in Metals and Alloys”, second edition, (1992)

[101] R. W. Munn and C. N. Ironside, “Nonlinear Optical Phenomena”, in：Principle and Application of Nonlinear Optical Materials, ed. Boca Raton, Florida, (1993) 5

[102] C. T. Chen, Acta Phys. Sin. 25 (1976) 146

[103] T. Ishihara, K. Kometani, Y. Nishi and Y. Takita, “Improved Sensitivity of CuO-BaTiO3 Capacitive-type CO2 Sensor by Additives”, Sensors and Actuators, B28 (1995) 49

[104] S. Toschev, A. Milchev and S. Stoyanov, “On Some Probabilistic Aspects of the Nucleation Process”, J. Crystal Growth, 13/14 (1972) 123

[105] H. Nakamura, K. Tsukamoto and I. Sunagawa, “In-situ Observation of High Temperature Silicare Solutions”, J. Crystal Growth, 99 (1990) 1227

[106] E. M. Levin, J. Res. Natl. Bur. Standards, George Ugrinic, 51(1) (1953), RP2430