基于光激电流法研究聚酰亚胺薄膜陷阱能谱
摘要
作为综合性能非常优异的聚合物材料,聚酰亚胺在航空航天、微电子技术等高技术领域得到广泛的应用。长期工作在电应力的作用下,空间电荷行为对绝缘材料的老化和击穿特性带来巨大的影响,而陷阱的性质决定着电荷的存贮和输运。因此,研究聚合物材料的陷阱结构和分布对提高其性能有重要的意义。
光激电流(PSD)法是研究聚合物材料中陷阱结构及空间电荷存贮和输运的有效工具,能实现无损、等温测量,可以用来研究能级较深的电荷陷阱。本文较详细的介绍了实验系统,并对实验系统的可行性及可靠性进行了验证,结果表明此系统完全可以达到实验要求。
利用该装置测量了未注入、不同注入时间和不同注入电压条件下的普通聚酰亚胺薄膜和纳米杂化聚酰亚胺薄膜的光激电流谱,并对注入电荷后的样品进行多次扫描。通过对实验结果的分析发现,两种型号的PI薄膜的陷阱能级分布为带状,分别为3.1eV-4.2eV和3.1eV-4.3eV;增加注入时间,光激电流随之增大,注入时间由60min增加到90min,电流峰向短波方向移动,表明注入到陷阱内的电荷首先被较浅的陷阱俘获,在电场的作用下,注入电荷或部分已被浅陷阱俘获的电荷向相对深陷阱能级移动;增大注入电压,光激电流值随之增大。同时,对聚酰亚胺的老化和击穿机制进行分析,发现破坏发生在空间电荷脱陷过程中。
In varied polymers, the comprehensive performance of polyimide is better than others, and it has been widely used in high-tech fields, as aerospace, microelectronics technology, et al. Aging and breakdown can occur in polyimide under long-term electric stressing due to space charge behavior. Charge storage and transport is decided by trap characteristics, so it is significant for improving polymer material properties through researching structure and distribution of trap.
Photo-stimulated discharge (PSD) is an effective tool to study structure of trap, the storage and transport of charge in polymer. It is an isothermal measurement process. The PSD measurement is no damage. Deep trsps can be researched by this method. The paper described experimental system detailedly, verified stability and reliadility. The results showed that the measurement device meet experimental requirements well.
PSDs in PI-100HN and PI-100CR film were tested under no charged, different injection time and different injection voltage, and multiple scans. The measurement results were shown that the distribution of trap levels in two types film is banded, 3.1eV-4.2eV for PI-100HN, 3.1eV-4.3eV for PI-100CR; the current increased when the injection time increased, peaks moved to the shortwave when injection time was increased from 60min to 90min, it showed that the injection charge was captured by shallow trap, and then some of trapped charge moved to the relative deeper trap with new injection charge under electric field; the current increased when the injection voltage increased. In addition, the aging and breakdown mechanisms in PI were analysed, it was found out that the broken was occurred in detrapping process.
光激电流(PSD)法是研究聚合物材料中陷阱结构及空间电荷存贮和输运的有效工具,能实现无损、等温测量,可以用来研究能级较深的电荷陷阱。本文较详细的介绍了实验系统,并对实验系统的可行性及可靠性进行了验证,结果表明此系统完全可以达到实验要求。
利用该装置测量了未注入、不同注入时间和不同注入电压条件下的普通聚酰亚胺薄膜和纳米杂化聚酰亚胺薄膜的光激电流谱,并对注入电荷后的样品进行多次扫描。通过对实验结果的分析发现,两种型号的PI薄膜的陷阱能级分布为带状,分别为3.1eV-4.2eV和3.1eV-4.3eV;增加注入时间,光激电流随之增大,注入时间由60min增加到90min,电流峰向短波方向移动,表明注入到陷阱内的电荷首先被较浅的陷阱俘获,在电场的作用下,注入电荷或部分已被浅陷阱俘获的电荷向相对深陷阱能级移动;增大注入电压,光激电流值随之增大。同时,对聚酰亚胺的老化和击穿机制进行分析,发现破坏发生在空间电荷脱陷过程中。
In varied polymers, the comprehensive performance of polyimide is better than others, and it has been widely used in high-tech fields, as aerospace, microelectronics technology, et al. Aging and breakdown can occur in polyimide under long-term electric stressing due to space charge behavior. Charge storage and transport is decided by trap characteristics, so it is significant for improving polymer material properties through researching structure and distribution of trap.
Photo-stimulated discharge (PSD) is an effective tool to study structure of trap, the storage and transport of charge in polymer. It is an isothermal measurement process. The PSD measurement is no damage. Deep trsps can be researched by this method. The paper described experimental system detailedly, verified stability and reliadility. The results showed that the measurement device meet experimental requirements well.
PSDs in PI-100HN and PI-100CR film were tested under no charged, different injection time and different injection voltage, and multiple scans. The measurement results were shown that the distribution of trap levels in two types film is banded, 3.1eV-4.2eV for PI-100HN, 3.1eV-4.3eV for PI-100CR; the current increased when the injection time increased, peaks moved to the shortwave when injection time was increased from 60min to 90min, it showed that the injection charge was captured by shallow trap, and then some of trapped charge moved to the relative deeper trap with new injection charge under electric field; the current increased when the injection voltage increased. In addition, the aging and breakdown mechanisms in PI were analysed, it was found out that the broken was occurred in detrapping process.
引文
[1]丁孟贤,何白天.聚酰亚胺新型材料[M].科学出版社, 1998: 267.
[2]张立德,牟季美.纳米材料和纳米结构[M].科学出版社, 2001: 33-41.
[3]陆宝琦.交流变频电机的绝缘[J].绝缘材料, 2001, 3: 29-34.
[4] KHALIL M S. Degradation of Insulating Materials under Electrical Stress [C]. IEEE Trans on Diel Elec Insul, 2000, 7: 590-601.
[5]黄兴溢,江平开,金天雄,等.聚合物纳米复合电介质[J].化学进展, 2007, 19(11): 1776-1782.
[6]李鸿岩,刘斌,姜其斌,等.聚酰亚胺/氧化铝纳米复合材料的热激电流研究[J].绝缘材料, 2009, 42(5): 38-44.
[7]江东亮,漆宗能.溶胶-凝胶法制备有机/无机纳米复合材料[J].哈尔滨工业大学出版社, 2006: 12-13.
[8] ZHANG Y, LWINER, Hanpton N. Evidence of Strong Correlation between Space Charge Buildup and Breakdown in Cable Insulators under dc Stress [C]. IEEE Trans Elect Insul, 1996, 31(6): 778-783.
[9] KAO K C, HWANG W.固体中的电输运[M].雷清泉译.科学出版社, 1991: 7-11.
[10] LEWIS T J. Nano Metric Dielectrics [C]. IEEE Trans on Dielretrics and Electrical Insulation, 1994, 1(1): 812-825.
[11]郑飞虎,张冶文,肖春.聚合物电介质的击穿与空间电荷的关系[J].材料科学与工程学报, 2006, 24(2): 316-320.
[12] BRODRIBB J D, HUGHES D M. The Energy Spectrum of Traps in Insulators by Photon-induced Current Spectroscopy [M]. Electrets, 1972: 177-187.
[13] YOSHIAKI T, KOJI M, TERUYOSHI M, et al. Investigation of Traps inγ-Irradiated Polyethylene by Photostimulated Detrapping Current Analysis [J]. Appl. Phys., 1976, 15(12): 2341-2347.
[14] ODA T, UTSUMI T, KUMANO T. Observation of Photo-stimulated Detrapping Currents of FEP Teflon Electrets [C]. IEEE 5th Intern. Conf. Electrets, G M Sessler and R Gerhard-Multhaupt, Eds., Piscataway, NJ, IEEE Service Center, 1985: 288-293.
[15] ODA T, UTSUMI T, MATSUBARA G. Observation of UV Photo-stimulatedCurrents of Teflon Electrets [C]. IEEE 6th Intern. Sympos. Electrets, D. K. Das-Gupta and A. W. Pattullo, Eds., Piscataway, NJ, IEEE Service Center. 1988: 142-146.
[16] MELLINGER A, CAMACHO G F. Photo-Stimulated Discharge in Electret Polymers: an Alternative Approach for Investigating Deep Traps [C]. IEEE Trans. on DEI., 2004, 11(2): 218-226.
[17] CAMACHO G F, MELLINGER A. Photo-Stimulated Discharge of Highly Insulaing Polymers(PTFE and PETP) [C]. IEEE-CEIDP, 2002: 590-593.
[18] CAMACHO G F, MELLINGER A, GERHARD M R. Energy Levels of Charge Traps in Polyethylene Terephthalate Films [C]. IEEE-ISCD 2004, Toulouse, France, 2004.
[19] MELLINGER A, SINGH R, CAMACHO G F. In Situ Observation of Optically and Thermal Induced Charge Depletion in Chromophoredoped Cyclic Olefin Copolymers [C]. IEEE-CEIDP 2004, Boulder, Colorado, USA, 2004: 498-501.
[20] ZHU Z E, ZHANG Y W, AN Z L. Study on Charge Trap Distribution in LLDPE by Photo-Stimulated Discharge Current [C]. ICPADM2009, China, 2009: 930-933.
[21]巫松桢.电气绝缘材料科学与工程[M].西安交通大学出版, 1996: 147-151.
[22]张积之编著.固态电介质的击穿[M].杭州大学出版社, 1994: 56-60.
[23] BLAISE G, SARJEANT W J. Space Charge in Dielectrics Energy Storage and Transfer Relaxation Mechanism [C]. IEEE Trans on Elect Insul1993, 28(4): 437-443.
[24]尹毅,肖登明,屠德民.空间电荷在评估绝缘聚合物老化程度中的应用研究[J].中国电机工程学报, 2002, 22(1): 47.
[25]李世晋编著.高分子电介质[M].科技卫生出版社, 1959: 72-76.
[26] STEVEN B. A Rational Consideration of Space Charge [C]. IEEE Trans. DEI., 2004, 20(4): 22-27.
[27] LEGRESSUS C, VALIN F, HENRIOT M. Flashover in Wideband-gap High-purity Insulators:Methodology and Mechanisms [J]. Journal of Applied Physics, 1991, 69(9): 6325-6333.
[28]雷清泉.高聚物的结构与电性能[M].华中理工大学出版社, 1990: 214.
[29] STONEHAM A M. Electronic and Defect Processes in Oxides“The Polaron inAction”[C]. IEEE Transactions on DEI, 1997, 4(5): 604-613.
[30] TANAKA T. Space Charge Injected via Interfaces and Tree Initiation in Polymers[C]. IEEE Transaction on DEI, 2001, 8(5): 733-743.
[31] BLAISE G, GRESSUS C L. Charge Trapping-detrapping Processes and Related Breakdown Phenomena, in HV Vacuum Insulation, Basic Concepts and Technological Practice [M]. New York: Academic Press, 1995: 330-368.
[32] ZHENG F H, ZHANG Y W, XIAO C. An Z L 2008 IEEE Trans. On DEI. 15: 965.
[33] AHMED N H, SRINIVAS N N. Review of Space Charge Measurements in Dielectrics[C]. IEEE Trans. On DEI., 1997, (5): 644.
[34] FLEMING R J. Charge Trapping in Organic Polymers [J]. Radiat. Phys. Chem., 1990, 36(1): 59-68.
[35] FLEMING R J. Space Charge in Polymer, Particularly Polyethylene [J]. Brazilian Journal of Physics, 1999, 29(2): 280-294.
[36] CRINE J P. A Molecular Model to Evaluate the Impact of Aging on Space charges in Polymer Dielectrics [C]. IEEE Trans. DEI., 1997, 4: 487-495.
[37] DISSADO L A, MARRANTI G, MONTANARI G C. The Role of Trapped Space Charges in the Electrical Aging of Insulating Materials [C]. IEEE Trans. DEI., 1997, 4: 496-506.
[38] MASAYUKI I. Dielectric Breakdown Process of Polymer [C]. IEEE Trans. on EI., 1980, 15(3): 206-224.
[39] TURNHOUT J V. Thermally Stimulatede Discharge of Polymer Electret [M]. Amsterdam: Elsevier Sci Pub Com., 1975: 21.
[40]王力衡.介质的热刺激理论及其应用[M].科学出版社, 1988: 41.
[41] KRYSZEWSKI M, ULANSKI J, JEZKA J K. Chain and Carrier Mobility in Polymer Systems as Investigated by Thermally Stimulated Current Techniques [J]. Polymer Bull, 1982, 8: 187-192.
[42] LEI Q Q, FAN Y. Effect of Inorgamic Filler on Thermally Stimulated Current in Low-density Polyethylene [J]. Materials Sci. & Technol., 1997, 13(3): 223-226.
[43] SHIMIZU H, KITANO T, NATAYAMA K. An Application of Thermally Stimulated Current Technique to Molecular Motion Analysis of Polymers [J]. Proc. SE9, 1996: 552-557.
[44] LEI Q Q, WANG X, FAN Y. A New Method of Auto-separating ThermallyStimulated Current [J]. J. Appl. Phys., 1992 (9): 4254-4257.
[45] FAN Y, WANG X. Simultaneous Thermoluminescence and Thermally Stimulated Current in Polyamid [J]. Mater, Sci. Technol., 1998, 14(2): 357-360.
[46] BLAKE A E, CHARLESBY A, RANDLE K J. Simultaneous Thermoluminescence and Thermally Stimulated Current in Polyethylene [J]. Phys. D: Appl. Phys., 1976, 7(2): 759-770.
[47] GLOWAEKI I, ULANSKI J. Simultaneous Measurement of Thermoluminescence and Thermally Stimulated Currents in Poly(IV-Vinglcarbazole)/Polycarbonate Blends [J]. Appl. Phys., 1995, 78(2): 1019-1025.
[48]王暄.聚合物热发光与热激电流联合谱仪的研究[D].西安交通大学, 1999.
[49]王暄.热激电流的测量与分峰技术研究[D].哈尔滨电工学院, 1991: 85-88.
[50] DAMAMME G, LE G C, REHHI A S. Space Charge Characterization for the 21th century[C]. IEEE Trans Elect Insul, 1997, 4(5): 558-583.
[51]吴广宁,吴建东,周凯,等.高压脉冲电压下聚酰亚胺的电老化机理[J].中国电机工程学报, 2009, 29(13):124-130.
[52] BLAISE G, SARJEAT W J. Space Charge in Dielectrics Energy Storage ang Transfer Dynamics from Atomistic to Macroscopic Scale [C]. IEEE Trans. Elect. Insul., 1998, 5(5): 779-783.
[53]李吉晓,张冶文,夏钟福,等.空间电荷在聚合物老化和击穿过程中的作用[J].科学通报, 2000, 45 (23): 2469-2475.
[2]张立德,牟季美.纳米材料和纳米结构[M].科学出版社, 2001: 33-41.
[3]陆宝琦.交流变频电机的绝缘[J].绝缘材料, 2001, 3: 29-34.
[4] KHALIL M S. Degradation of Insulating Materials under Electrical Stress [C]. IEEE Trans on Diel Elec Insul, 2000, 7: 590-601.
[5]黄兴溢,江平开,金天雄,等.聚合物纳米复合电介质[J].化学进展, 2007, 19(11): 1776-1782.
[6]李鸿岩,刘斌,姜其斌,等.聚酰亚胺/氧化铝纳米复合材料的热激电流研究[J].绝缘材料, 2009, 42(5): 38-44.
[7]江东亮,漆宗能.溶胶-凝胶法制备有机/无机纳米复合材料[J].哈尔滨工业大学出版社, 2006: 12-13.
[8] ZHANG Y, LWINER, Hanpton N. Evidence of Strong Correlation between Space Charge Buildup and Breakdown in Cable Insulators under dc Stress [C]. IEEE Trans Elect Insul, 1996, 31(6): 778-783.
[9] KAO K C, HWANG W.固体中的电输运[M].雷清泉译.科学出版社, 1991: 7-11.
[10] LEWIS T J. Nano Metric Dielectrics [C]. IEEE Trans on Dielretrics and Electrical Insulation, 1994, 1(1): 812-825.
[11]郑飞虎,张冶文,肖春.聚合物电介质的击穿与空间电荷的关系[J].材料科学与工程学报, 2006, 24(2): 316-320.
[12] BRODRIBB J D, HUGHES D M. The Energy Spectrum of Traps in Insulators by Photon-induced Current Spectroscopy [M]. Electrets, 1972: 177-187.
[13] YOSHIAKI T, KOJI M, TERUYOSHI M, et al. Investigation of Traps inγ-Irradiated Polyethylene by Photostimulated Detrapping Current Analysis [J]. Appl. Phys., 1976, 15(12): 2341-2347.
[14] ODA T, UTSUMI T, KUMANO T. Observation of Photo-stimulated Detrapping Currents of FEP Teflon Electrets [C]. IEEE 5th Intern. Conf. Electrets, G M Sessler and R Gerhard-Multhaupt, Eds., Piscataway, NJ, IEEE Service Center, 1985: 288-293.
[15] ODA T, UTSUMI T, MATSUBARA G. Observation of UV Photo-stimulatedCurrents of Teflon Electrets [C]. IEEE 6th Intern. Sympos. Electrets, D. K. Das-Gupta and A. W. Pattullo, Eds., Piscataway, NJ, IEEE Service Center. 1988: 142-146.
[16] MELLINGER A, CAMACHO G F. Photo-Stimulated Discharge in Electret Polymers: an Alternative Approach for Investigating Deep Traps [C]. IEEE Trans. on DEI., 2004, 11(2): 218-226.
[17] CAMACHO G F, MELLINGER A. Photo-Stimulated Discharge of Highly Insulaing Polymers(PTFE and PETP) [C]. IEEE-CEIDP, 2002: 590-593.
[18] CAMACHO G F, MELLINGER A, GERHARD M R. Energy Levels of Charge Traps in Polyethylene Terephthalate Films [C]. IEEE-ISCD 2004, Toulouse, France, 2004.
[19] MELLINGER A, SINGH R, CAMACHO G F. In Situ Observation of Optically and Thermal Induced Charge Depletion in Chromophoredoped Cyclic Olefin Copolymers [C]. IEEE-CEIDP 2004, Boulder, Colorado, USA, 2004: 498-501.
[20] ZHU Z E, ZHANG Y W, AN Z L. Study on Charge Trap Distribution in LLDPE by Photo-Stimulated Discharge Current [C]. ICPADM2009, China, 2009: 930-933.
[21]巫松桢.电气绝缘材料科学与工程[M].西安交通大学出版, 1996: 147-151.
[22]张积之编著.固态电介质的击穿[M].杭州大学出版社, 1994: 56-60.
[23] BLAISE G, SARJEANT W J. Space Charge in Dielectrics Energy Storage and Transfer Relaxation Mechanism [C]. IEEE Trans on Elect Insul1993, 28(4): 437-443.
[24]尹毅,肖登明,屠德民.空间电荷在评估绝缘聚合物老化程度中的应用研究[J].中国电机工程学报, 2002, 22(1): 47.
[25]李世晋编著.高分子电介质[M].科技卫生出版社, 1959: 72-76.
[26] STEVEN B. A Rational Consideration of Space Charge [C]. IEEE Trans. DEI., 2004, 20(4): 22-27.
[27] LEGRESSUS C, VALIN F, HENRIOT M. Flashover in Wideband-gap High-purity Insulators:Methodology and Mechanisms [J]. Journal of Applied Physics, 1991, 69(9): 6325-6333.
[28]雷清泉.高聚物的结构与电性能[M].华中理工大学出版社, 1990: 214.
[29] STONEHAM A M. Electronic and Defect Processes in Oxides“The Polaron inAction”[C]. IEEE Transactions on DEI, 1997, 4(5): 604-613.
[30] TANAKA T. Space Charge Injected via Interfaces and Tree Initiation in Polymers[C]. IEEE Transaction on DEI, 2001, 8(5): 733-743.
[31] BLAISE G, GRESSUS C L. Charge Trapping-detrapping Processes and Related Breakdown Phenomena, in HV Vacuum Insulation, Basic Concepts and Technological Practice [M]. New York: Academic Press, 1995: 330-368.
[32] ZHENG F H, ZHANG Y W, XIAO C. An Z L 2008 IEEE Trans. On DEI. 15: 965.
[33] AHMED N H, SRINIVAS N N. Review of Space Charge Measurements in Dielectrics[C]. IEEE Trans. On DEI., 1997, (5): 644.
[34] FLEMING R J. Charge Trapping in Organic Polymers [J]. Radiat. Phys. Chem., 1990, 36(1): 59-68.
[35] FLEMING R J. Space Charge in Polymer, Particularly Polyethylene [J]. Brazilian Journal of Physics, 1999, 29(2): 280-294.
[36] CRINE J P. A Molecular Model to Evaluate the Impact of Aging on Space charges in Polymer Dielectrics [C]. IEEE Trans. DEI., 1997, 4: 487-495.
[37] DISSADO L A, MARRANTI G, MONTANARI G C. The Role of Trapped Space Charges in the Electrical Aging of Insulating Materials [C]. IEEE Trans. DEI., 1997, 4: 496-506.
[38] MASAYUKI I. Dielectric Breakdown Process of Polymer [C]. IEEE Trans. on EI., 1980, 15(3): 206-224.
[39] TURNHOUT J V. Thermally Stimulatede Discharge of Polymer Electret [M]. Amsterdam: Elsevier Sci Pub Com., 1975: 21.
[40]王力衡.介质的热刺激理论及其应用[M].科学出版社, 1988: 41.
[41] KRYSZEWSKI M, ULANSKI J, JEZKA J K. Chain and Carrier Mobility in Polymer Systems as Investigated by Thermally Stimulated Current Techniques [J]. Polymer Bull, 1982, 8: 187-192.
[42] LEI Q Q, FAN Y. Effect of Inorgamic Filler on Thermally Stimulated Current in Low-density Polyethylene [J]. Materials Sci. & Technol., 1997, 13(3): 223-226.
[43] SHIMIZU H, KITANO T, NATAYAMA K. An Application of Thermally Stimulated Current Technique to Molecular Motion Analysis of Polymers [J]. Proc. SE9, 1996: 552-557.
[44] LEI Q Q, WANG X, FAN Y. A New Method of Auto-separating ThermallyStimulated Current [J]. J. Appl. Phys., 1992 (9): 4254-4257.
[45] FAN Y, WANG X. Simultaneous Thermoluminescence and Thermally Stimulated Current in Polyamid [J]. Mater, Sci. Technol., 1998, 14(2): 357-360.
[46] BLAKE A E, CHARLESBY A, RANDLE K J. Simultaneous Thermoluminescence and Thermally Stimulated Current in Polyethylene [J]. Phys. D: Appl. Phys., 1976, 7(2): 759-770.
[47] GLOWAEKI I, ULANSKI J. Simultaneous Measurement of Thermoluminescence and Thermally Stimulated Currents in Poly(IV-Vinglcarbazole)/Polycarbonate Blends [J]. Appl. Phys., 1995, 78(2): 1019-1025.
[48]王暄.聚合物热发光与热激电流联合谱仪的研究[D].西安交通大学, 1999.
[49]王暄.热激电流的测量与分峰技术研究[D].哈尔滨电工学院, 1991: 85-88.
[50] DAMAMME G, LE G C, REHHI A S. Space Charge Characterization for the 21th century[C]. IEEE Trans Elect Insul, 1997, 4(5): 558-583.
[51]吴广宁,吴建东,周凯,等.高压脉冲电压下聚酰亚胺的电老化机理[J].中国电机工程学报, 2009, 29(13):124-130.
[52] BLAISE G, SARJEAT W J. Space Charge in Dielectrics Energy Storage ang Transfer Dynamics from Atomistic to Macroscopic Scale [C]. IEEE Trans. Elect. Insul., 1998, 5(5): 779-783.
[53]李吉晓,张冶文,夏钟福,等.空间电荷在聚合物老化和击穿过程中的作用[J].科学通报, 2000, 45 (23): 2469-2475.