利用石墨层间化合物合成含硼金刚石
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摘要
通过掺杂硼，可以提高金刚石的导电性和热稳定性。本论文提出了利用含硼石墨层间化合物(GICs)高温高压(HTHP)合成含硼金刚石的新工艺。
本文以H_3BO_3，NH_4BF_4和KBH_4作为插层剂，采用真空熔盐、真空渗析熔盐、加压熔盐以及电解法制备含硼的GICs。利用XRD分析GICs的阶结构，并研究了GICs的稳定性。以含硼GICs作为碳源，在高温高压下合成金刚石。对含硼金刚石在SEM下进行形貌观察，通过红外拉曼光谱、X射线荧光(XRF)分析硼掺杂的存在状态和含量。分析了含硼金刚石的差热曲线，并测量了其电阻值。
实验结果表明，真空熔盐、真空渗析熔盐、加压熔盐以及电解法可以制备H_3BO_3-GICs，KBH_4-GICs和NH_4BF_4-GICs。获得的GICs是混合阶产物。GICs的阶数随着时间延长而降低。H_3NO_3-GICs水洗后不稳定，发生了水解脱插。利用这些GICs，在1250～1350℃、5～6GPa下合成了含硼金刚石，金刚石颜色随着硼含量增加而加深直至黑色，含硼金刚石生长成多晶颗粒，晶面发育不完整。通过红外吸收光谱分析，发现硼以取代原子或间隙硼的形式存在于金刚石中，并通过对红外光谱吸收率计算和XRF分析检测到硼含量在5ppm到2158ppm之间。含硼金刚石热稳定性和导电性随着硼含量增加而提高。含硼500ppm的金刚石抗氧化温度提高到1070℃。当含硼量为2158ppm时金刚石的电阻率为1.93Ω·cm。
The conductivity and thermo-stability of diamond with boron doping could be improved. In this paper, a new method was presented that B-doped diamond was synthesized at high pressure and high temperature (HTHP) using B-doped graphite intercalation compounds (GICs).
Using H3BO3, NH4BF4 and KBH4 as intercalant, GICs had been prepared by melt-salt in vacuum, melt-salt in vacuum infiltration, enhancing pressure melt-salt, and electrolyte intercalation. Structure of GICs had been analyzed by XRD, and stability of GICs had been studied. Diamond was synthesized using B-doped GICs as carbon sources by HTHP method. Morphology of B-doped diamond had been observed by SEM. Boron contents and impurity situation of B-doped diamond had been analyzed by FTIR/Raman and XRF. DTA curves of B-doped diamond had been studied, and the resistances had been measured.
The experimental results showed that H3BO3-GICs, NH4BF4-GICs and KBH4-GICs had been prepared successfully by melt-salt in vacuum, melt-salt in vacuum infiltration, enhancing pressure melt-salt, and electrolyte intercalation. GICs had mixed stage. Stage number of GICs decreased with intercalation duration prolonging. It is unstable when GICs was washed, and H3BO3-GICs was hydrolyzed. B-doped diamonds were obtained under the condition of 1250℃~1350℃ and 5GPa~6GPa. Color of diamond became deep with boron contents increasing, till becoming black. B-doped diamond was polycrystalline, and crystal surface was developed incompletely. It was found by FTIR that boron existed as substitute atom or interstitial atom. Boron contents of diamond changed from 5 ppm to 2158 ppm. Conductivity and thermo-stability of B-doped diamond increased with boron contents increasing. Anti-oxidation temperature of diamond with 500 ppm boron reached 1070 ℃ Specific resistance of diamond with 2158 ppm boron was 1.93 Ω cm.
本文以H_3BO_3，NH_4BF_4和KBH_4作为插层剂，采用真空熔盐、真空渗析熔盐、加压熔盐以及电解法制备含硼的GICs。利用XRD分析GICs的阶结构，并研究了GICs的稳定性。以含硼GICs作为碳源，在高温高压下合成金刚石。对含硼金刚石在SEM下进行形貌观察，通过红外拉曼光谱、X射线荧光(XRF)分析硼掺杂的存在状态和含量。分析了含硼金刚石的差热曲线，并测量了其电阻值。
实验结果表明，真空熔盐、真空渗析熔盐、加压熔盐以及电解法可以制备H_3BO_3-GICs，KBH_4-GICs和NH_4BF_4-GICs。获得的GICs是混合阶产物。GICs的阶数随着时间延长而降低。H_3NO_3-GICs水洗后不稳定，发生了水解脱插。利用这些GICs，在1250～1350℃、5～6GPa下合成了含硼金刚石，金刚石颜色随着硼含量增加而加深直至黑色，含硼金刚石生长成多晶颗粒，晶面发育不完整。通过红外吸收光谱分析，发现硼以取代原子或间隙硼的形式存在于金刚石中，并通过对红外光谱吸收率计算和XRF分析检测到硼含量在5ppm到2158ppm之间。含硼金刚石热稳定性和导电性随着硼含量增加而提高。含硼500ppm的金刚石抗氧化温度提高到1070℃。当含硼量为2158ppm时金刚石的电阻率为1.93Ω·cm。
The conductivity and thermo-stability of diamond with boron doping could be improved. In this paper, a new method was presented that B-doped diamond was synthesized at high pressure and high temperature (HTHP) using B-doped graphite intercalation compounds (GICs).
Using H3BO3, NH4BF4 and KBH4 as intercalant, GICs had been prepared by melt-salt in vacuum, melt-salt in vacuum infiltration, enhancing pressure melt-salt, and electrolyte intercalation. Structure of GICs had been analyzed by XRD, and stability of GICs had been studied. Diamond was synthesized using B-doped GICs as carbon sources by HTHP method. Morphology of B-doped diamond had been observed by SEM. Boron contents and impurity situation of B-doped diamond had been analyzed by FTIR/Raman and XRF. DTA curves of B-doped diamond had been studied, and the resistances had been measured.
The experimental results showed that H3BO3-GICs, NH4BF4-GICs and KBH4-GICs had been prepared successfully by melt-salt in vacuum, melt-salt in vacuum infiltration, enhancing pressure melt-salt, and electrolyte intercalation. GICs had mixed stage. Stage number of GICs decreased with intercalation duration prolonging. It is unstable when GICs was washed, and H3BO3-GICs was hydrolyzed. B-doped diamonds were obtained under the condition of 1250℃~1350℃ and 5GPa~6GPa. Color of diamond became deep with boron contents increasing, till becoming black. B-doped diamond was polycrystalline, and crystal surface was developed incompletely. It was found by FTIR that boron existed as substitute atom or interstitial atom. Boron contents of diamond changed from 5 ppm to 2158 ppm. Conductivity and thermo-stability of B-doped diamond increased with boron contents increasing. Anti-oxidation temperature of diamond with 500 ppm boron reached 1070 ℃ Specific resistance of diamond with 2158 ppm boron was 1.93 Ω cm.
引文
1 郝润蓉，方锡义，钮少冲．无机化学丛书·第三卷碳硅锗分族．北京：科学出版社，1988：3，7，12
2 王光祖，院兴国．超硬材料．郑州：河南科学技术出版社，1996：1，26
3 中国大百科全书·化学．北京：中国大百科全书出版社，1989：906-907
4 Michio Inagald. Carbon Materials Structure, Texture and Intercalation. Solid State Ionics. 1996,(86-88):833-839
5 刘广志．人造金刚石工业在我国迅猛崛起．中国工程科学．2000，2(5)：31-33
6 吉林大学固体物理教研室高压合成组．人造金刚石．北京：科学出版社，1975：52
7 李志宏，刘金昌．我国人造金刚石工业现状及发展．金刚石与磨料磨具工程．2002，127(1)：49-53
8 G.R.Brandes, C.P.Beetz, C.A. Feger, R.L.Wright. Diamond Junction Cold Cathode. Diamond and Related Materials. 1995,(4):586-590
9 J. Davidson, W. Kang, K. Holmes, etc. CVD Diamond for Components and Emitters. Diamond and Related Materials. 2001,(10): 1736-1742
10 P.W. May, M. T. Kuo, M. N. R. Ashfold. Field Emission Conduction Mechanisms in Chemical-Vapour-Deposited Diamond and Diamond-like Carbon Films. Diamond and Related Materials. 1999,(8):1490-1495
11 康飞宇．关于GIC研究的几点见解．碳素技术．2000，109(4)：17-20
12 S. L. Molodtsov. Electronic Structure of Graphite Intercalated with 4f and 5f Elements. Journal of Electron Spectroscopy and Related Phenomena. 1998,96: 157-170
13 传秀云．石墨层间化合物的合成技术及应用前景．非金属矿．1997，118(4)：18-21
14 关正辉．石墨层间化合物的特性及应用前景．甘肃科技．2002，18(10)：48-49
15 魏环，宋庆功．石墨插层化合物的结构与特性．河北理工学院学报．1999，21(4)：67-72
16 张瑞军，刘建华，沈万慈．石墨层间化合物阶结构的标定方法．碳素．1998，(2)：5-9
17 Eunkyung Kim, Ilwhan Oh, Junhyoun Kwak. Atomic Structure of Highly Ordered Pyrolytic Graphite Doped with Boron. Electrochemistry Communications. 2001,(3):
608-612
18 刘光辉．石墨嵌入化合物的合成及其性能．吉首大学学报(自然科学版)．1998，19(1)：77-81
19 时虎，胡源．石墨层间化合物的合成和应用．碳素技术．2002，119(2)：29-32
20 传秀云．超微粉石墨层间化合物CuCl_2-NiCl_2-GICs合成及电学性能．材料科学与工程．1998，62(2)：68-71
21 李冷，曾宪滨．石墨层间化合物(GIC)的研究及应用．非金属矿．1994，97(1)：58-63
22 J. Walter, H. Shioyama. Boron Trichloride Graphite Intercalation Compound Studied by Selected Area Electron Diffraction and Scanning Tunneling Microscopy. Journal of Physics and Chemistry of Solids. 1999,(60):737-741
23 Sebastien Pruvost, Claire Herold, Albert Herold, Philippe Lagrange. On the Great Difficulty of Intercalating Lithium with a Second Element into Graphite. Carbon. 2003, (41):1281-1289
24 朱继平，程继贵．C_X~+·HSO_4~-插层化合物的水热法合成．合肥工业大学学报(自然科学版)．2001，23(6)：1076-1078
25 任慧，焦清介，乔小晶，王长福．三元石墨插层化合物的合成与表征．北京理工大学学报．2003，23(2)：248-251
26 Jiayan Xua, Yuan Hua, Lei Song, etc. Thermal Analysis of Poly(vinyl alcohol)/Graphite Oxide Intercalated Composites. Polymer Degradation and Stability 2001,73:29-31
27 E. Gheeraert, N. Casanova, A. Tajani, etc. n-Type Doping of Diamond by Sulfur and Phosphorus. Diamond and Related Materials. 2002,(11): 289-295
28 A. W. Otherspoon, J. W. Steeds, P. Coleman, etc. Photoluminescence Studies of Type IIa and Nitrogen Doped CVD Diamond. Diamond and Related Materials. 2002(11): 692-696
29 邵乐喜，刘小平，屈菊兰，等．原位氮掺杂对CVD金刚石薄膜生长和结构的影响．真空科学与技术．2002，22(3)：221-225
30 S. L. Molodtsov. Electronic Structure of Graphite Intercalated with 4f and 5f Elements. Journal of Electron Spectroscopy and Related Phenomena. 1998,96: 157-170
31 J. Davidson, W. Kang, K. Holmes, etc. CVD Diamond for Components and Emitters.
Diamond and Related Materials. 2001,(10): 1736-1742
32 谢二庆，金运范，王志光，贺德衍．C-N化合物合成研究．原子核物理评论．2000，17(3)：171-174
33 封进．含氮金刚石的合成与探讨．金刚石与磨料磨具工程．1999，133(5)：14-16
34 R. Kalish. Doping of diamond. Carbon. 1999,(37):781-785
35 张伟丽，夏义本，居建华，等．不同掺氮量的类金刚石薄膜的电导性能．半导体光电．2003，24(1)：41-45
36 周斌，黄耀东，李忻，等．自截止腐蚀制备Si平面薄膜中的B杂质分析．2002，36(4／5)：364-366
37 张仿清，谢二庆，杨斌，等．硼掺杂半导体金刚石薄膜的合成与红外吸收特性．半导体学报．1995，16(6)：468-472
38 R. Lecher, J. Wagner, F. Fuchs, etc. Boron Doped Diamond Films: Electrical and Optical Characterization and the Effect Compensating Nitrogen. Materials Science and Engineering, 1995(B29): 211-215.
39 韩佳宁，赵庆勋，辛红丽，文钦若．金刚石n型掺杂的研究进展．河北大学学报(自然科学版)．2002，22(1)：87-91
40 郑昌琼，张铭诚，冉均国．金刚石薄膜品质及其表征．材料研究学报．1997，11(3)：231-239
41 张仿清，张文军，胡搏，等．硼掺杂及未掺杂金刚石薄膜的电学和光电导特性．半导体学报．1995，16(10)：783-788
42 Chia-Fu Chen, Sheng Hsiung Chen. Electrical Properties of Boron-doped Diamond Films after Annealing Treatment. Diamond and Related Materials. 1995,(4): 451-455
43 威建兵，黄浩，赵玉成．含掺杂的金刚石．金刚石与磨料磨具工程．2001，(1)：16-18
44 Othon R. Monteiro. Plasma Synthesis of Hard Materials with Energetic Ions. Nuclear Instruments and Methods in Physics Research B.1999,148:12-16
45 R.A.劳迪斯，刘光照译．晶体生长．北京：科学出版社，1979：92-106
46 Zang. J. B., Wang. Y. H., Zhang. X. M., Huang. H., Zhao. Y. C. Synthesis of B-doped diamond using graphite intercalation compounds (GICs). Journal of Materials Processing Technology. 2002. 3(129): 454-457
47 顾学民，龚毅生，臧希文，等．无机化学丛书·第二卷铍碱土金属硼铝镓分族．北京：科学出版社，1990：374-380
48 徐仲榆，苏玉长．用原位-X射线衍射法研究石墨在98％硫酸中进行插(脱)层．碳素．1996，(4)：1-7
49 何雪梅．天然金刚石的红外光谱特征及其分类．地质与勘探．2000，36(4)：45-47
50 王松顺，程林，王民用．含硼T641石墨炭源合成含硼金刚石晶体的结构、性质与应用效果．炭素．2001，(1)：28-33
51 华南工学院，南京化工学院，清华大学．陶瓷材料物理性能．北京：中国建筑工业出版社，1979：113
2 王光祖，院兴国．超硬材料．郑州：河南科学技术出版社，1996：1，26
3 中国大百科全书·化学．北京：中国大百科全书出版社，1989：906-907
4 Michio Inagald. Carbon Materials Structure, Texture and Intercalation. Solid State Ionics. 1996,(86-88):833-839
5 刘广志．人造金刚石工业在我国迅猛崛起．中国工程科学．2000，2(5)：31-33
6 吉林大学固体物理教研室高压合成组．人造金刚石．北京：科学出版社，1975：52
7 李志宏，刘金昌．我国人造金刚石工业现状及发展．金刚石与磨料磨具工程．2002，127(1)：49-53
8 G.R.Brandes, C.P.Beetz, C.A. Feger, R.L.Wright. Diamond Junction Cold Cathode. Diamond and Related Materials. 1995,(4):586-590
9 J. Davidson, W. Kang, K. Holmes, etc. CVD Diamond for Components and Emitters. Diamond and Related Materials. 2001,(10): 1736-1742
10 P.W. May, M. T. Kuo, M. N. R. Ashfold. Field Emission Conduction Mechanisms in Chemical-Vapour-Deposited Diamond and Diamond-like Carbon Films. Diamond and Related Materials. 1999,(8):1490-1495
11 康飞宇．关于GIC研究的几点见解．碳素技术．2000，109(4)：17-20
12 S. L. Molodtsov. Electronic Structure of Graphite Intercalated with 4f and 5f Elements. Journal of Electron Spectroscopy and Related Phenomena. 1998,96: 157-170
13 传秀云．石墨层间化合物的合成技术及应用前景．非金属矿．1997，118(4)：18-21
14 关正辉．石墨层间化合物的特性及应用前景．甘肃科技．2002，18(10)：48-49
15 魏环，宋庆功．石墨插层化合物的结构与特性．河北理工学院学报．1999，21(4)：67-72
16 张瑞军，刘建华，沈万慈．石墨层间化合物阶结构的标定方法．碳素．1998，(2)：5-9
17 Eunkyung Kim, Ilwhan Oh, Junhyoun Kwak. Atomic Structure of Highly Ordered Pyrolytic Graphite Doped with Boron. Electrochemistry Communications. 2001,(3):
608-612
18 刘光辉．石墨嵌入化合物的合成及其性能．吉首大学学报(自然科学版)．1998，19(1)：77-81
19 时虎，胡源．石墨层间化合物的合成和应用．碳素技术．2002，119(2)：29-32
20 传秀云．超微粉石墨层间化合物CuCl_2-NiCl_2-GICs合成及电学性能．材料科学与工程．1998，62(2)：68-71
21 李冷，曾宪滨．石墨层间化合物(GIC)的研究及应用．非金属矿．1994，97(1)：58-63
22 J. Walter, H. Shioyama. Boron Trichloride Graphite Intercalation Compound Studied by Selected Area Electron Diffraction and Scanning Tunneling Microscopy. Journal of Physics and Chemistry of Solids. 1999,(60):737-741
23 Sebastien Pruvost, Claire Herold, Albert Herold, Philippe Lagrange. On the Great Difficulty of Intercalating Lithium with a Second Element into Graphite. Carbon. 2003, (41):1281-1289
24 朱继平，程继贵．C_X~+·HSO_4~-插层化合物的水热法合成．合肥工业大学学报(自然科学版)．2001，23(6)：1076-1078
25 任慧，焦清介，乔小晶，王长福．三元石墨插层化合物的合成与表征．北京理工大学学报．2003，23(2)：248-251
26 Jiayan Xua, Yuan Hua, Lei Song, etc. Thermal Analysis of Poly(vinyl alcohol)/Graphite Oxide Intercalated Composites. Polymer Degradation and Stability 2001,73:29-31
27 E. Gheeraert, N. Casanova, A. Tajani, etc. n-Type Doping of Diamond by Sulfur and Phosphorus. Diamond and Related Materials. 2002,(11): 289-295
28 A. W. Otherspoon, J. W. Steeds, P. Coleman, etc. Photoluminescence Studies of Type IIa and Nitrogen Doped CVD Diamond. Diamond and Related Materials. 2002(11): 692-696
29 邵乐喜，刘小平，屈菊兰，等．原位氮掺杂对CVD金刚石薄膜生长和结构的影响．真空科学与技术．2002，22(3)：221-225
30 S. L. Molodtsov. Electronic Structure of Graphite Intercalated with 4f and 5f Elements. Journal of Electron Spectroscopy and Related Phenomena. 1998,96: 157-170
31 J. Davidson, W. Kang, K. Holmes, etc. CVD Diamond for Components and Emitters.
Diamond and Related Materials. 2001,(10): 1736-1742
32 谢二庆，金运范，王志光，贺德衍．C-N化合物合成研究．原子核物理评论．2000，17(3)：171-174
33 封进．含氮金刚石的合成与探讨．金刚石与磨料磨具工程．1999，133(5)：14-16
34 R. Kalish. Doping of diamond. Carbon. 1999,(37):781-785
35 张伟丽，夏义本，居建华，等．不同掺氮量的类金刚石薄膜的电导性能．半导体光电．2003，24(1)：41-45
36 周斌，黄耀东，李忻，等．自截止腐蚀制备Si平面薄膜中的B杂质分析．2002，36(4／5)：364-366
37 张仿清，谢二庆，杨斌，等．硼掺杂半导体金刚石薄膜的合成与红外吸收特性．半导体学报．1995，16(6)：468-472
38 R. Lecher, J. Wagner, F. Fuchs, etc. Boron Doped Diamond Films: Electrical and Optical Characterization and the Effect Compensating Nitrogen. Materials Science and Engineering, 1995(B29): 211-215.
39 韩佳宁，赵庆勋，辛红丽，文钦若．金刚石n型掺杂的研究进展．河北大学学报(自然科学版)．2002，22(1)：87-91
40 郑昌琼，张铭诚，冉均国．金刚石薄膜品质及其表征．材料研究学报．1997，11(3)：231-239
41 张仿清，张文军，胡搏，等．硼掺杂及未掺杂金刚石薄膜的电学和光电导特性．半导体学报．1995，16(10)：783-788
42 Chia-Fu Chen, Sheng Hsiung Chen. Electrical Properties of Boron-doped Diamond Films after Annealing Treatment. Diamond and Related Materials. 1995,(4): 451-455
43 威建兵，黄浩，赵玉成．含掺杂的金刚石．金刚石与磨料磨具工程．2001，(1)：16-18
44 Othon R. Monteiro. Plasma Synthesis of Hard Materials with Energetic Ions. Nuclear Instruments and Methods in Physics Research B.1999,148:12-16
45 R.A.劳迪斯，刘光照译．晶体生长．北京：科学出版社，1979：92-106
46 Zang. J. B., Wang. Y. H., Zhang. X. M., Huang. H., Zhao. Y. C. Synthesis of B-doped diamond using graphite intercalation compounds (GICs). Journal of Materials Processing Technology. 2002. 3(129): 454-457
47 顾学民，龚毅生，臧希文，等．无机化学丛书·第二卷铍碱土金属硼铝镓分族．北京：科学出版社，1990：374-380
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