掺钕钨酸铋钠激光晶体生长及性能研究
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摘要
本文对激光晶体进行了探讨，介绍了激光晶体和掺稀土的无机激光晶体、钨酸盐体系激光晶体。研究了Nd：NBW(分子式：Nd：NaBi(WO_4)_2)以及二元钨酸盐的国内外发展现状和应用前景。本文还对激光及其机理、用途、种类、发展方向等进行了比较详细的讨论。Nd：NBW晶体生长实验采用Czochralski(简称：Cz法)工艺，研究了Nd：NBW晶体的最佳生长工艺，得出了其最佳生长条件为：固-液界面中心的轴向温度梯度7—10℃／cm，径向温度梯度越小越好、生长速率0.2—0.5mm／h、晶体转速1—4rpm、冷却速率15℃／h。分析了晶体产生开裂的原因，采用严格控制生长参数的方法予以解决。在国内首次生长出尺寸为Φ8×20mm的Nd：NBW晶体。并对其进行了加工，制成了器件，利用XRD、吸收-透过光谱、发光光谱、振动光谱等方法对其进行了测试，分析了测试结果，确定了Nd：NBW晶体的晶格结构，研究了其吸收边红移现象的原因，验证了Nd：NBW晶体元件可用于LD(激光二极管)泵浦的激光发射，分析了~4F_(3/2)→~4I_(11/2)、~4F_(3/2)→~4I_(13/2)两个发光峰值的特点，并对Nd：NBW晶体中的红外与Raman进行了归属。以上对Nd：NBW晶体进行的性质研究，在国内尚属首次。
The laser crystal is studied in this paper, especially for rare earth doped double tungstates crystal. The present development and applied future of Nd:NaBi(WO4)2 (for short: Nd:NBW) crystal is introduced. The laser mechanism , usage, variety and development of laser crystal is researched in the discourse. The best condition of Nd:NBW crystal for growth by Czochralski method is resulted in the following: 7-10 /cm for axial temperature gradient along the centre of solid-fluid interface, 0.2-0.5mm/h for growth rate, 1-4rpm for crystal rotation rate, 15 /h for crystal cooling rate. The reasons of cleavage in the crystal is analyzed and solved by strict control of growth parameters. The size of grown Nd:NBW crystal is 8 20mm . Its units have been investigated by kinds of spectra and the construction of its lattice has been determined. The phenomenon of larger end wavelength in ultraviolet zone of this crystal has been explained. It can be inferred that Nd:NBW crystal fits to the aim of emission pumped by LD(Laser Diode). The properties of two channels of luminous pattern (4F3/2-I11/2,4F3/2 -4I13/2) have been studied. And the vibration patterns of this crystal have been analysed. All of the above have been evidenced as the first time research in China.
The laser crystal is studied in this paper, especially for rare earth doped double tungstates crystal. The present development and applied future of Nd:NaBi(WO4)2 (for short: Nd:NBW) crystal is introduced. The laser mechanism , usage, variety and development of laser crystal is researched in the discourse. The best condition of Nd:NBW crystal for growth by Czochralski method is resulted in the following: 7-10 /cm for axial temperature gradient along the centre of solid-fluid interface, 0.2-0.5mm/h for growth rate, 1-4rpm for crystal rotation rate, 15 /h for crystal cooling rate. The reasons of cleavage in the crystal is analyzed and solved by strict control of growth parameters. The size of grown Nd:NBW crystal is 8 20mm . Its units have been investigated by kinds of spectra and the construction of its lattice has been determined. The phenomenon of larger end wavelength in ultraviolet zone of this crystal has been explained. It can be inferred that Nd:NBW crystal fits to the aim of emission pumped by LD(Laser Diode). The properties of two channels of luminous pattern (4F3/2-I11/2,4F3/2 -4I13/2) have been studied. And the vibration patterns of this crystal have been analysed. All of the above have been evidenced as the first time research in China.
引文
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2．刘景和，李建立，徐斌等。NaBi(WO_4)_2晶体生长与开裂研究。硅酸盐学报，2001，Vol．29，No．4：370
3. Alexander A. Kaminskii, et al. Jpn. J. Appl. Phys. Vol. 34(1995) 1461
4. A. Kaminskii, A. Kholov, P. Klevtsov and S. Khafizov:Phys. Status Solid a 114(1989) 713
5. A. Akimov, T. Stolpakova, E. Dudnik and E. Sinyakov;Fiz. Tverd. Tela 19 (1977) 1832
6. K. Alexandrov, S. Burkov, A. Zamkov, A. Kholov, S. Khafizov, L. Shabanova and P. Klevtsov:Fiz. Tverd. Tela 30(1988)609
7. A. Kaminskii, A. Kholov, P. klevtsov and S. Khafizov:Izv. Akad. Nauk SSSR, Ser. Neorgan Mater. 25 (1989) 1054
8. A. Grasyuk, I. Zubarev and S. Mikhailov:Kratkie Soobsheniya po Fiziki Lebedev Institute Reports N2(1976)03
9. J. Hanuza, A. Benzar et al. Structure and vibrational dynamics of tetragonal NaBi(WO_4)_2 scheelite crystal. Vibrational Spectroscopy 12(1996)25-36
10. L. G. Sillen, H. Sundvall, Arkiv Kemi. Min. Gelo. 17A(1943) 1
11. M. Mokhosoev, S. Aleikina, Izv. Akad. Nauk. Neorg. Mater. 2 (1966)2094
12. L. Sillen, H. Sundvall, Arkiv Kemi. Min. Geol. B17(1943) 10
13. J. Hanuza, A. Harnar, M. Maczka, A. Pietraszko, A. Lemiec, J. H. vander Maas, E. T. G. Lutz, J. Raman Spectr. 28(1997)953
14. D. Garcia. M. Faucher, J. Chem. Phys. 90 (1989)
15．涂朝阳，李坚富等。Nd~(3+)：KGd(WO_4)_2激光晶体的研究．人工晶体学报，Vol30．No．2(2001)，135
16．黄奕川，邱闽旺等。Nd~(3+)：NaY(WO_4)_2晶体的激光性能研究。量子电子学报，Vol．14，No．3(1997)，264
17．傅琨，王正平，程振祥，等。钛宝石泵浦Nd：NaY(WO_4)_2晶体激光性能研究。光电子·激光。Vol．12，No．8(2001)848
18. V.K. Tzunov, V.A. Efremov, Yu.A. Velihkodnyi, Crystallochemistry and Properties of Double Molybdates and Tungstates, Nauka, Leningrad, 1986(in Russian)
19. W.T. Carnall, G.L. Goodman, K. Rajnak, R. S. Rana, J. Chem. Phys. 90 (1989)
20. Eric J. Lerner, Laser Focus World, 11, 97(1998)
21. S.E. Bodner, Physics Today, 41,65(1998)
22. Rick DeMeis, Laser Focus World, 10, 18(1996)
23. David Appell, Laser Focus World, 3,90(1998)
24. Paul Mortensen, Ouddoor test success fully induced lighting stribe, Laser Focus World, 9,38(1997)
25. Shuji Nakamura, Bhe Lasers Meet Tough Commercial Requirements, Photonics Spectra, 5,130(1998)
26. Jorge Rocca, Researchers close the gap in the Hunt for Soft Lasers, Photonics Spectra, 7,102(1996)
27. Yvonne Carts-Powell, QC lasers produce high power, dual wavelengths, Laser Focus World, 1, 15(1999)
28. Simon Fafard, Quantum dots promise a new dimension for semiconductor lasers, Photonics Spectra, 5,160(1997)
29. J.C. Brice, Acta Electronics, 16, 291(1973)
30. V. Volkov, C. Zaldo. Czochralski pulling of scheelite-type NaBi(WO_4)_2 single crystals. J. Crystal Growth, 1999, 206: 60-64
31. H. M. Dess, Crystallization from Solution and Melts ed J.A. Palermo, M.A. Larson, 100(1969)
32．张克从．《晶体生长》，科学出版社，1981
33. V. Nikolov, et al.,J. Crystal Growth, 88,324(1988)
34. J.A. Burton, et al., J. Chem. Phys.,21,1987(1953)
35. A. Kaminskii, S. Sarkisov, G. Denisenko, Phys. Stat. Sol. (a)85(1984)533
36．扬南如。《无机非金属材料测试方法》，武汉工业大学出版社，1996
37．钱逸泰。《结晶化学导论(第二版)》，中国科学技术大学出版社，1999
38．姚连增。《晶体生长基础》，科学技术出版社，1995
39．扬茹，邱法林。《分光光度学》，机械工业出版社，1998
40．朱贵云，扬景和。《激光光谱分析法》，科学出版社，1989
41．李艳红，李建立，洪元佳，等。Nd：KGW多波长激光晶体生长与光谱特性。中国激光，2002，Vol．A29，No．5，444
42．陈国珍，黄贤智等。《紫外-可见光分光光度计》，原子能出版社，1987
43. A. A, Kaminskii, phys. stat. sol. (a) 102,389(1987)
44. L. Fornasiero, T. Kellner, S. kuck, J. P. Meyn, P. E. A. Moberrt, G. Huber, Appl. Phys. B68 (1999)67
45. A. A. Kaminskii. Laser Crystals, Their Physics and Spectroscopy, Springger-Verlag, 1981
46. Wu Ke-chen, Chen Chuang-tian. Absorption-Edge Calculations of Inorganic Nonlinear Optical Crystals [J].Appl. Phts. A, 1992,54:209-220
47．温元凯，邵俊。离子极化导论[M]。安徽：安徽教育出版社，1985
48．陈英方。《红外和喇曼光谱技术》，纺织工业出版社，1988
49．陈允魁。《红外吸收光谱法及其应用》，上海交通大学出版社，1993
50. J. Banuza, M. Maczka, and J.H. van der Maas. Journal of Solid State Chemistry117,177 (1995)
2．刘景和，李建立，徐斌等。NaBi(WO_4)_2晶体生长与开裂研究。硅酸盐学报，2001，Vol．29，No．4：370
3. Alexander A. Kaminskii, et al. Jpn. J. Appl. Phys. Vol. 34(1995) 1461
4. A. Kaminskii, A. Kholov, P. Klevtsov and S. Khafizov:Phys. Status Solid a 114(1989) 713
5. A. Akimov, T. Stolpakova, E. Dudnik and E. Sinyakov;Fiz. Tverd. Tela 19 (1977) 1832
6. K. Alexandrov, S. Burkov, A. Zamkov, A. Kholov, S. Khafizov, L. Shabanova and P. Klevtsov:Fiz. Tverd. Tela 30(1988)609
7. A. Kaminskii, A. Kholov, P. klevtsov and S. Khafizov:Izv. Akad. Nauk SSSR, Ser. Neorgan Mater. 25 (1989) 1054
8. A. Grasyuk, I. Zubarev and S. Mikhailov:Kratkie Soobsheniya po Fiziki Lebedev Institute Reports N2(1976)03
9. J. Hanuza, A. Benzar et al. Structure and vibrational dynamics of tetragonal NaBi(WO_4)_2 scheelite crystal. Vibrational Spectroscopy 12(1996)25-36
10. L. G. Sillen, H. Sundvall, Arkiv Kemi. Min. Gelo. 17A(1943) 1
11. M. Mokhosoev, S. Aleikina, Izv. Akad. Nauk. Neorg. Mater. 2 (1966)2094
12. L. Sillen, H. Sundvall, Arkiv Kemi. Min. Geol. B17(1943) 10
13. J. Hanuza, A. Harnar, M. Maczka, A. Pietraszko, A. Lemiec, J. H. vander Maas, E. T. G. Lutz, J. Raman Spectr. 28(1997)953
14. D. Garcia. M. Faucher, J. Chem. Phys. 90 (1989)
15．涂朝阳，李坚富等。Nd~(3+)：KGd(WO_4)_2激光晶体的研究．人工晶体学报，Vol30．No．2(2001)，135
16．黄奕川，邱闽旺等。Nd~(3+)：NaY(WO_4)_2晶体的激光性能研究。量子电子学报，Vol．14，No．3(1997)，264
17．傅琨，王正平，程振祥，等。钛宝石泵浦Nd：NaY(WO_4)_2晶体激光性能研究。光电子·激光。Vol．12，No．8(2001)848
18. V.K. Tzunov, V.A. Efremov, Yu.A. Velihkodnyi, Crystallochemistry and Properties of Double Molybdates and Tungstates, Nauka, Leningrad, 1986(in Russian)
19. W.T. Carnall, G.L. Goodman, K. Rajnak, R. S. Rana, J. Chem. Phys. 90 (1989)
20. Eric J. Lerner, Laser Focus World, 11, 97(1998)
21. S.E. Bodner, Physics Today, 41,65(1998)
22. Rick DeMeis, Laser Focus World, 10, 18(1996)
23. David Appell, Laser Focus World, 3,90(1998)
24. Paul Mortensen, Ouddoor test success fully induced lighting stribe, Laser Focus World, 9,38(1997)
25. Shuji Nakamura, Bhe Lasers Meet Tough Commercial Requirements, Photonics Spectra, 5,130(1998)
26. Jorge Rocca, Researchers close the gap in the Hunt for Soft Lasers, Photonics Spectra, 7,102(1996)
27. Yvonne Carts-Powell, QC lasers produce high power, dual wavelengths, Laser Focus World, 1, 15(1999)
28. Simon Fafard, Quantum dots promise a new dimension for semiconductor lasers, Photonics Spectra, 5,160(1997)
29. J.C. Brice, Acta Electronics, 16, 291(1973)
30. V. Volkov, C. Zaldo. Czochralski pulling of scheelite-type NaBi(WO_4)_2 single crystals. J. Crystal Growth, 1999, 206: 60-64
31. H. M. Dess, Crystallization from Solution and Melts ed J.A. Palermo, M.A. Larson, 100(1969)
32．张克从．《晶体生长》，科学出版社，1981
33. V. Nikolov, et al.,J. Crystal Growth, 88,324(1988)
34. J.A. Burton, et al., J. Chem. Phys.,21,1987(1953)
35. A. Kaminskii, S. Sarkisov, G. Denisenko, Phys. Stat. Sol. (a)85(1984)533
36．扬南如。《无机非金属材料测试方法》，武汉工业大学出版社，1996
37．钱逸泰。《结晶化学导论(第二版)》，中国科学技术大学出版社，1999
38．姚连增。《晶体生长基础》，科学技术出版社，1995
39．扬茹，邱法林。《分光光度学》，机械工业出版社，1998
40．朱贵云，扬景和。《激光光谱分析法》，科学出版社，1989
41．李艳红，李建立，洪元佳，等。Nd：KGW多波长激光晶体生长与光谱特性。中国激光，2002，Vol．A29，No．5，444
42．陈国珍，黄贤智等。《紫外-可见光分光光度计》，原子能出版社，1987
43. A. A, Kaminskii, phys. stat. sol. (a) 102,389(1987)
44. L. Fornasiero, T. Kellner, S. kuck, J. P. Meyn, P. E. A. Moberrt, G. Huber, Appl. Phys. B68 (1999)67
45. A. A. Kaminskii. Laser Crystals, Their Physics and Spectroscopy, Springger-Verlag, 1981
46. Wu Ke-chen, Chen Chuang-tian. Absorption-Edge Calculations of Inorganic Nonlinear Optical Crystals [J].Appl. Phts. A, 1992,54:209-220
47．温元凯，邵俊。离子极化导论[M]。安徽：安徽教育出版社，1985
48．陈英方。《红外和喇曼光谱技术》，纺织工业出版社，1988
49．陈允魁。《红外吸收光谱法及其应用》，上海交通大学出版社，1993
50. J. Banuza, M. Maczka, and J.H. van der Maas. Journal of Solid State Chemistry117,177 (1995)