SiC薄膜的制备以及光电发射性质
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摘要
本论文研究了SiC薄膜制备以及光电发射性质,并且讨论了在脉冲栅控行波管中SiC薄膜涂层对抑制栅极电子发射影响,以及薄膜涂层在高温栅网表面的物理化学性质以及结构的变化,探索薄膜系统的工作机理。在样品制备过程中,利用射频(RF)磁控溅射复合靶技术和N2气氛保护高温退火的后处理方法,在Mo衬底上制备出了碳化硅(SiC)薄膜,为了仿真现实行波管的工作背景环境,采取化学方法在薄膜表面沉积BaO,并且使用拉曼发光谱( Raman)、扫描电子显微镜(SEM)、X射线衍射(XRD)等测量手段,研究了薄膜在973K到1273K的不同温度退火时候薄膜的结构、形貌以及光电发射等性质。同时对于SiC涂层抑制行波管栅极电子发射能力的影响,结果表明BaO/SiC/Mo系统高温退火后能够有效的去除栅网中的BaO的沉积玷污,结合XRD的实验结果以及吉布斯函变的计算研究分析样品表明温退火后样品表面的BaO与Si,C的不饱和键易于反应消除其低功函数的影响提高样品的功函数,并且最终的反应产物SiC和SiO_2均为高功函数的物质。从而论述SiC薄膜抑制行波管的栅电子发射的机理。
Pulsed-controlled grid traveling wave tubes become the key components in the national defenses, modern weapon, and navigation in the space and GPS system. It is also especial importance to prolong the working life of tubs for its short function period. In this paper, we discuss the preparation and photo-electron emission character of SiC thin film by the measurement of the Raman Spectrum (Raman), Scanning electron microscopy (SEM), X-ray diffraction (XRD) etc. Furthermore we research the structure and phase change of molybdenum grid coated with silicon and carbon composite thin films under high temperature. And the effect that si-c composite thin film has on the suppressing grid emission in pulsed-controlled grid traveling wave tubes has been studied.
Si-C composite thin films were deposited on molybdenum grids by radio-frequency magnetron sputtering technology from the silicon and carbon composite target. The as-deposited films were annealed in the temperature range from 973K to 1273K. In order to simulate the working conditions of the grids contaminated by BaO from the activation of hot cathode in Pulse-controlled grid traveling-wave tubes (TWTs). BaO layers were deposited on the surface of the as-deposited thin films by the chemical method. The compositional and phase change of the samples were investigated after annealing from 973K to 1273K.The structure and phase change of BaO/Si-C/Mo systems under high temperature are discussed according to the experimental results and the calculation of the reaction free energy. The results indicate that graphite and silicon on the surface of Mo grids can prevent BaO from accumulating on the grid surfaces. SiC (about 4.4eV) and SiO2 (about 3.1eV) with high work function are the last products on the surface of Mo grids. Therefore, the silicon and carbon composite thin films deposited on the Mo grid surface can effectively suppress the grid electron emission.
Pulsed-controlled grid traveling wave tubes become the key components in the national defenses, modern weapon, and navigation in the space and GPS system. It is also especial importance to prolong the working life of tubs for its short function period. In this paper, we discuss the preparation and photo-electron emission character of SiC thin film by the measurement of the Raman Spectrum (Raman), Scanning electron microscopy (SEM), X-ray diffraction (XRD) etc. Furthermore we research the structure and phase change of molybdenum grid coated with silicon and carbon composite thin films under high temperature. And the effect that si-c composite thin film has on the suppressing grid emission in pulsed-controlled grid traveling wave tubes has been studied.
Si-C composite thin films were deposited on molybdenum grids by radio-frequency magnetron sputtering technology from the silicon and carbon composite target. The as-deposited films were annealed in the temperature range from 973K to 1273K. In order to simulate the working conditions of the grids contaminated by BaO from the activation of hot cathode in Pulse-controlled grid traveling-wave tubes (TWTs). BaO layers were deposited on the surface of the as-deposited thin films by the chemical method. The compositional and phase change of the samples were investigated after annealing from 973K to 1273K.The structure and phase change of BaO/Si-C/Mo systems under high temperature are discussed according to the experimental results and the calculation of the reaction free energy. The results indicate that graphite and silicon on the surface of Mo grids can prevent BaO from accumulating on the grid surfaces. SiC (about 4.4eV) and SiO2 (about 3.1eV) with high work function are the last products on the surface of Mo grids. Therefore, the silicon and carbon composite thin films deposited on the Mo grid surface can effectively suppress the grid electron emission.
引文
[1] 邮电五 O 六厂《行波管》编写组, 《行波管》, 人民邮电出版社, 1979
[2] 张永康, 朱清元, 张贻英, 电子科学学刊, 1987, 9(1), 42
[3] 刘学悫编著, 《阴极电子学》, 科学出版社, 1980
[4] 朱宏, 博士论文, 中国科学院上海冶金研究所,1995
[5] V. J. MINKIEWICZ, J. STASIAK AND R. L. WJOTE, SURFACE AND CAOTING TECHNOLOGY, 68/69(1994)229
[6] D. ENGEMANN, R. FISCHER, AND KOICH KITAMURA, APPL,PHYS. LETT.,32(9)(1978)567
[7] JOHN1. B.WILSON, ASIF QAYYNM, AND PHILIP JOHN, JNON-CRYSTALLINE SOLIDS, 115198984
[8]TOSHIRO FUTAGI, NOBORN, J. NON-CCRYSTALINE SOLIDS 137/138 (1991) 1271
[9] Y. HATTORI, D. KTUARGAM, K. KATOH AND Y. NITTA, PROC. 19TH IEEE PHOTOVOLTAIC SPECIAST CONF.,(1978)689
[10] S. W. TAM, J. P. KOPASZ, C. E. JOHNSON, J. NULEAR MATER ,219(1995)87~92
[11] CRC Handbook of Chemistry and Physics, 71st ed., CRC Press, Boston, 1990
[12] Pensl G1 Physica B 1993 , 185 : 2642283
[13] Barrett D L , Seidensticker R G, et al1 Journal of Crystal Growth 1991 , 109 : 17223
[14] 碳化硅宽带隙半导体技术 郝跃等编著 科学出版社 2000
[15] Tsvetkov V F , Allen S T, et al1 Inst1 Cont1 Ser1 1996 , 142 : 17221
[16] Lely J A1 Ber1 Dtsch1 Keram1 Ges1 , 1955 , 32 : 2292233
[17] Tairov YM, Tsvetkov V F1 J1 Cryst1 Growth , 1978 , 43 : 2092212
[18] Tairov Yu M, Tsetkov V F1 J1 Cryst1 Growth , 1981 , 52 : 1462150
[19] J.M.Powers,M.Pdelplanlke,ThinSolidFilms,1991,202,289
[20] 欧阳世翕,程吉平 功能材料,1992,23(4),217
[21] P.Durupt,J.P.Cauthier,ThinSolidFilms,1981,85,191
[22] Motoyama S, Kaneda S. Low temperature growth of 3C - SiC by the GSMBE methed[ J]. Applied Physics Letters, 1989,54(3): 242
[23] IL.B.Rowland,R .S.Kem,S. Tanakaa ndR .F.Davis,A ppl.Ph ys.Le t.,19 93,62:3333
[24] Masashi, Suenaga, Robert J. Prevau, Acta Astronautica 57 (2005) 215 – 223
[25] X. Liu, J. Vac. Sci. Technol. A 20 (2002) 1846.
[26] Jun Jiang, Bingyao Jiang, Congxin Ren, Fumin Zhang, Tao Feng, Xi Wang, Xianghuai Liu, Shichang Zou, Vacuum 80 (2006) 537–541
[27] J. Jiang, B.Y. Jiang, C.X. Ren, T. Feng, X. Wang, X.H. Liu, S.C. Zou Applied Surface Science 239 (2005) 437–444
[1] A. Sathyamoorthy and W. Weisweiler Thin Solid Films, Volume 87, Issue 1, 8 January 1982, Pages 33-42
[2] 刘金声著, 《离子束沉积薄膜技术及应用》, 国防工业出版社, 2003
[1] 刘世宏, 王当憨, 潘承璜编著, 《X 射线光电子能谱分析》, 科学出版社, 1988
[2] 王建祺, 吴文辉, 冯大明编著, 《电子能谱学(XPS/XAES/UPS)引论》, 国防工业出版社, 1992, 552
[3] 沙正东,硕士毕业论文,苏州大学物理系
[4] 陆家和, 陈长彦, 《现代分析技术》, 清华大学出版社, 1995
[1] SUN Guosheng , LUO Mu2chang , WAN G Lei , ZHAO Wan2shun CHINESE- JOURNAL OF LUMINESCENCE
[2] H.Y. Wang , Y.Y. Wang, Q. Song , T.M. Wang Materials Letters 35_1998.261–265
[3] Y. Sun, T.M. Yasato, Jpn. J. Appl. Phys. 037 (1998) 5485.
[4] Strane JW, Stein HJ, Lee SR, Picraux ST, Watanabe JK, Mayer JW. J. Appl. Phys. 1994;76:3656.
[5] Tan C, Wu XL, Deng SS, Huang GS, Liu XN, Bao XM. Phys. Lett. A 2003;310:236–40.
[6] L.J. Zhuge, X.M. Wu, Q. Li, W.B. Wang, S.L. Xiang, Physica E 23 (2004) 86
[7] Z.D. Sha, X.M. Wu, L.J. Zhuge, Vacuum 79 (2005) 250.
[8] J.F. Yan, Y.M. Lu, Y.C. Liu, H.W. Liang, B.H. Li, D.Z. Shen, J.Y. Zhang, X.W. Fan, J. Cryst. Growth 266 (2004) 505.
[9] Y. Maeda, Phys. Rev. B 51 (1995) 1658.
[10] X.L. Wu, S.J. Xiong, G.G. Huang, Y.F. Mei, Z.Y. Zhang, S.S. Deng, C. Tan, Phys. Rev. Lett. 91 (2003) 157402.
[1] S. Hayashi, K. Yamamoto, Journal of Luminescence 70 (1996) 352-363
[2] V.C. George, A. Das, M. Roy, A.K. Dua, P. Raj, D.R.T. Zahn, Thin Solid Films, 419 (2002) 114.
[3] A.Phez-Rodriguez a, A.Romano-Rotiguez, C. Serre, L. Calvo-Barrio, R. Cabezas, J.R. Morante, J. Calderer, H. Reuther, W. Skorupa,Nuclear Instruments and Methods in Physics Research B 120 (1996) 151- 155
[4] Jun Xu, Liang Yang, Yunjun Rui, Jiaxin Mei, Xin Zhang, Wei Li, Zhongyuan Ma, Ling Yu, Xinfan Huang, Kunji Chen, Solid State Communication 133(2005) 565-568
[5] Paul Celestin Bakala, Emmanuel Briot, Laurent Salles, Jean-Marie Bre geault Applied Catalysis A: General 300 (2006) 91–99
[6] CRC Handbook of Chemistry and Physics, 71st ed., CRC Press, Boston, 1990.
[7] O. Kubaschewski, E. LL. Evans., Metallurgical Thermao Chemistry, Pergamon Press, 1958
[8] 马家举主编, 普通化学, 化学工业出版社, 2003
[9] P. Reinke, P. Oelhafen, Diamond Relat.Mater. 8 (1999) 155.
[10] M.H. Juang, T.Y. Lin, S.L. Jang, Solid-State Electronics 50 (2006) 114–118
[11] Wolfgang Miiller, Applied Surface Science 111 (1997) 30-34 (2003) 435–439
[12] L. Xie, Y. Zhao, M.H. White, Solid-State Electronics 48 (2004) 2071–2077
[1] Yuehui Lu, Lanjian Zhuge, Xuemei Wu and Xianghuai Liu, J. Korean Phys. Soc. 45(3) (2004) 725
[2] Yuehui Lu, Xuemei Wu, Lanjian Zhuge and Xianghuai Liu, Nucl. Instr. and Meth. in Phys. Res. B 225(4) (2004) 555
[3] L.J. Zhuge, X.M. Wu, F.J. Qu, W.B. Wang, B.Y. Jiang and X.H. Liu Journal of Physics and Chemistry of Solids, Volume 67, Issue 7, July 2006, Pages 1394-1398
[4] Wang Jian, Wuxuemei, Zhuge Lanjian, Preparation and Structure of BaO/Hf/Mo (Chinese), The Twelfth Countrywide Plasma Technology Conference
[5] Jian.Wang, X.M Wu, L.J. Zhuge, Vacuum 81 (2007) 890–893
[2] 张永康, 朱清元, 张贻英, 电子科学学刊, 1987, 9(1), 42
[3] 刘学悫编著, 《阴极电子学》, 科学出版社, 1980
[4] 朱宏, 博士论文, 中国科学院上海冶金研究所,1995
[5] V. J. MINKIEWICZ, J. STASIAK AND R. L. WJOTE, SURFACE AND CAOTING TECHNOLOGY, 68/69(1994)229
[6] D. ENGEMANN, R. FISCHER, AND KOICH KITAMURA, APPL,PHYS. LETT.,32(9)(1978)567
[7] JOHN1. B.WILSON, ASIF QAYYNM, AND PHILIP JOHN, JNON-CRYSTALLINE SOLIDS, 115198984
[8]TOSHIRO FUTAGI, NOBORN, J. NON-CCRYSTALINE SOLIDS 137/138 (1991) 1271
[9] Y. HATTORI, D. KTUARGAM, K. KATOH AND Y. NITTA, PROC. 19TH IEEE PHOTOVOLTAIC SPECIAST CONF.,(1978)689
[10] S. W. TAM, J. P. KOPASZ, C. E. JOHNSON, J. NULEAR MATER ,219(1995)87~92
[11] CRC Handbook of Chemistry and Physics, 71st ed., CRC Press, Boston, 1990
[12] Pensl G1 Physica B 1993 , 185 : 2642283
[13] Barrett D L , Seidensticker R G, et al1 Journal of Crystal Growth 1991 , 109 : 17223
[14] 碳化硅宽带隙半导体技术 郝跃等编著 科学出版社 2000
[15] Tsvetkov V F , Allen S T, et al1 Inst1 Cont1 Ser1 1996 , 142 : 17221
[16] Lely J A1 Ber1 Dtsch1 Keram1 Ges1 , 1955 , 32 : 2292233
[17] Tairov YM, Tsvetkov V F1 J1 Cryst1 Growth , 1978 , 43 : 2092212
[18] Tairov Yu M, Tsetkov V F1 J1 Cryst1 Growth , 1981 , 52 : 1462150
[19] J.M.Powers,M.Pdelplanlke,ThinSolidFilms,1991,202,289
[20] 欧阳世翕,程吉平 功能材料,1992,23(4),217
[21] P.Durupt,J.P.Cauthier,ThinSolidFilms,1981,85,191
[22] Motoyama S, Kaneda S. Low temperature growth of 3C - SiC by the GSMBE methed[ J]. Applied Physics Letters, 1989,54(3): 242
[23] IL.B.Rowland,R .S.Kem,S. Tanakaa ndR .F.Davis,A ppl.Ph ys.Le t.,19 93,62:3333
[24] Masashi, Suenaga, Robert J. Prevau, Acta Astronautica 57 (2005) 215 – 223
[25] X. Liu, J. Vac. Sci. Technol. A 20 (2002) 1846.
[26] Jun Jiang, Bingyao Jiang, Congxin Ren, Fumin Zhang, Tao Feng, Xi Wang, Xianghuai Liu, Shichang Zou, Vacuum 80 (2006) 537–541
[27] J. Jiang, B.Y. Jiang, C.X. Ren, T. Feng, X. Wang, X.H. Liu, S.C. Zou Applied Surface Science 239 (2005) 437–444
[1] A. Sathyamoorthy and W. Weisweiler Thin Solid Films, Volume 87, Issue 1, 8 January 1982, Pages 33-42
[2] 刘金声著, 《离子束沉积薄膜技术及应用》, 国防工业出版社, 2003
[1] 刘世宏, 王当憨, 潘承璜编著, 《X 射线光电子能谱分析》, 科学出版社, 1988
[2] 王建祺, 吴文辉, 冯大明编著, 《电子能谱学(XPS/XAES/UPS)引论》, 国防工业出版社, 1992, 552
[3] 沙正东,硕士毕业论文,苏州大学物理系
[4] 陆家和, 陈长彦, 《现代分析技术》, 清华大学出版社, 1995
[1] SUN Guosheng , LUO Mu2chang , WAN G Lei , ZHAO Wan2shun CHINESE- JOURNAL OF LUMINESCENCE
[2] H.Y. Wang , Y.Y. Wang, Q. Song , T.M. Wang Materials Letters 35_1998.261–265
[3] Y. Sun, T.M. Yasato, Jpn. J. Appl. Phys. 037 (1998) 5485.
[4] Strane JW, Stein HJ, Lee SR, Picraux ST, Watanabe JK, Mayer JW. J. Appl. Phys. 1994;76:3656.
[5] Tan C, Wu XL, Deng SS, Huang GS, Liu XN, Bao XM. Phys. Lett. A 2003;310:236–40.
[6] L.J. Zhuge, X.M. Wu, Q. Li, W.B. Wang, S.L. Xiang, Physica E 23 (2004) 86
[7] Z.D. Sha, X.M. Wu, L.J. Zhuge, Vacuum 79 (2005) 250.
[8] J.F. Yan, Y.M. Lu, Y.C. Liu, H.W. Liang, B.H. Li, D.Z. Shen, J.Y. Zhang, X.W. Fan, J. Cryst. Growth 266 (2004) 505.
[9] Y. Maeda, Phys. Rev. B 51 (1995) 1658.
[10] X.L. Wu, S.J. Xiong, G.G. Huang, Y.F. Mei, Z.Y. Zhang, S.S. Deng, C. Tan, Phys. Rev. Lett. 91 (2003) 157402.
[1] S. Hayashi, K. Yamamoto, Journal of Luminescence 70 (1996) 352-363
[2] V.C. George, A. Das, M. Roy, A.K. Dua, P. Raj, D.R.T. Zahn, Thin Solid Films, 419 (2002) 114.
[3] A.Phez-Rodriguez a, A.Romano-Rotiguez, C. Serre, L. Calvo-Barrio, R. Cabezas, J.R. Morante, J. Calderer, H. Reuther, W. Skorupa,Nuclear Instruments and Methods in Physics Research B 120 (1996) 151- 155
[4] Jun Xu, Liang Yang, Yunjun Rui, Jiaxin Mei, Xin Zhang, Wei Li, Zhongyuan Ma, Ling Yu, Xinfan Huang, Kunji Chen, Solid State Communication 133(2005) 565-568
[5] Paul Celestin Bakala, Emmanuel Briot, Laurent Salles, Jean-Marie Bre geault Applied Catalysis A: General 300 (2006) 91–99
[6] CRC Handbook of Chemistry and Physics, 71st ed., CRC Press, Boston, 1990.
[7] O. Kubaschewski, E. LL. Evans., Metallurgical Thermao Chemistry, Pergamon Press, 1958
[8] 马家举主编, 普通化学, 化学工业出版社, 2003
[9] P. Reinke, P. Oelhafen, Diamond Relat.Mater. 8 (1999) 155.
[10] M.H. Juang, T.Y. Lin, S.L. Jang, Solid-State Electronics 50 (2006) 114–118
[11] Wolfgang Miiller, Applied Surface Science 111 (1997) 30-34 (2003) 435–439
[12] L. Xie, Y. Zhao, M.H. White, Solid-State Electronics 48 (2004) 2071–2077
[1] Yuehui Lu, Lanjian Zhuge, Xuemei Wu and Xianghuai Liu, J. Korean Phys. Soc. 45(3) (2004) 725
[2] Yuehui Lu, Xuemei Wu, Lanjian Zhuge and Xianghuai Liu, Nucl. Instr. and Meth. in Phys. Res. B 225(4) (2004) 555
[3] L.J. Zhuge, X.M. Wu, F.J. Qu, W.B. Wang, B.Y. Jiang and X.H. Liu Journal of Physics and Chemistry of Solids, Volume 67, Issue 7, July 2006, Pages 1394-1398
[4] Wang Jian, Wuxuemei, Zhuge Lanjian, Preparation and Structure of BaO/Hf/Mo (Chinese), The Twelfth Countrywide Plasma Technology Conference
[5] Jian.Wang, X.M Wu, L.J. Zhuge, Vacuum 81 (2007) 890–893