片式多层陶瓷电容器银铜粉电极材料研究
|
摘要
片式多层陶瓷电容器(MLCC)是表面组装技术中应用最广泛的元件,电极浆料是MLCC关键和基础的材料,电极浆料的性能对MLCC的发展起着举足轻重的作用。目前,MLCC基本使用贵金属Ag和Ag-Pd浆料,而Ag浆料、Ag-Pd浆料在某些条件下还存在一些不足,如Ag浆料制得的电极耐焊性差和银在高湿强电场作用下的迁移率高等;另外,Ag-Pd浆料的电阻率较高、价格昂贵。为了适应快速发展的微电子技术,国内外都在寻求性能优良、价格低廉的贱金属材料作为电子浆料的导电相。用贱金属Ni、Cu代替贵金属,成为国内外研究的热点。目前,铜粉用于电子浆料领域研究的重点是提高其抗氧化性,使其能在大气气氛下烧结,以降低元件成本。对铜粉进行表面处理是防止铜粉氧化最主要的方法。
本实验通过用滴入化学反应法在铜粉表面包覆一层银,来提高铜粉的抗氧化性。通过正交实验,对样品进行微观形貌观察,XRD图谱分析,粒度测试以及TG分析,得出以下结论:制备银包覆铜粉的最佳工艺参数为:Ag、Cu摩尔比为0.8;银氨浓度0.12mol/L;明胶浓度20g/L;滴速10滴/分钟,反应温度50℃。其中Ag、Cu摩尔比对包覆粉的包覆效果起着决定性作用。采用滴入化学法制备银包覆铜粉,可控性高,包覆层致密、均匀。实验制备的银包覆铜粉,其大气下抗氧化温度在800℃以上,能够满足大气下高温烧结的要求。
用上述包覆粉制备了银铜电极浆料,讨论了金属粉形状、玻璃粉含量、烧结温度和保温时间对电极性能的影响,得出结论如下:电极浆料中金属粉采用球状银包覆铜粉,金属粉与玻璃粉的混合粉占浆料的80%,其中玻璃粉占混合粉的6%,有机载体占浆料的20%。电极烧结工艺为:烧结温度为800℃,保温时间为10min。经过测试,银铜粉电极有良好的导电性,附着力能够达到元件使用要求,耐焊性优于银电极,可焊性与银电极相当。
Multi-layer ceramic capacitor (MLCC) is the most important chip component in the surface mount technology, and electrode paste is the key and foundation materials for MLCC, electrode paste capability of MLCC played a dominant role in the development of it. Currently, MLCC used precious metals Ag and Ag-Pd as the function phase of the electrode paste. But Ag and Ag-Pd electrode paste have some defects, such as paste of silver system of electrode bear the soldering bad and the silver is under the high and wet strong electric field action of migration etc, the resistivity of the Ag- Pd paste is higher, the price is expensive. For adapting the development of micro-electronics technique, people begin searching for the cheap base metals material as conduct phase of the electronic paste. The copper powder because of its lower resistivity, has become the main substitute of the precious metal paste. Recently, the main research of the copper powder is raising the antioxidation temperature of it.
We use the method of chemistry substitution reaction coating silver in the copper powder surface in order to improve the temperature of oxidation resistance. The surface topography, microstructure and oxidation resistance of the coated powder were characterized by SEM, XRD, TG and other methods. We get the results as following:
The ratio of Ag and Cu is 0.8; the solution concentration of silver ammonia is 0.12mol/L; the gelatin concentration is 20g/L; the dropping velocity is 10 drop/min and the reaction temperature is 50℃. the coating effect is largely responsible for ratio of Ag and Cu, The process of coating powder adopted drop chemical method, have better controllability, and coating is compact. The silver coated copper powder we prepared had higher antioxidation temperature, and can sintering at the oxidized atmosphere.
With silver coated copper powder, we fabricated electrodes paste, and analysed the adhesion force, square resistance, get a conclusion as follows: Taking the globosity copper powder as the function phase, the content of the glass phase is 6%, sintering at the temperature of 800℃and maintaining 10mins, we can get the excellent electrode film.
本实验通过用滴入化学反应法在铜粉表面包覆一层银,来提高铜粉的抗氧化性。通过正交实验,对样品进行微观形貌观察,XRD图谱分析,粒度测试以及TG分析,得出以下结论:制备银包覆铜粉的最佳工艺参数为:Ag、Cu摩尔比为0.8;银氨浓度0.12mol/L;明胶浓度20g/L;滴速10滴/分钟,反应温度50℃。其中Ag、Cu摩尔比对包覆粉的包覆效果起着决定性作用。采用滴入化学法制备银包覆铜粉,可控性高,包覆层致密、均匀。实验制备的银包覆铜粉,其大气下抗氧化温度在800℃以上,能够满足大气下高温烧结的要求。
用上述包覆粉制备了银铜电极浆料,讨论了金属粉形状、玻璃粉含量、烧结温度和保温时间对电极性能的影响,得出结论如下:电极浆料中金属粉采用球状银包覆铜粉,金属粉与玻璃粉的混合粉占浆料的80%,其中玻璃粉占混合粉的6%,有机载体占浆料的20%。电极烧结工艺为:烧结温度为800℃,保温时间为10min。经过测试,银铜粉电极有良好的导电性,附着力能够达到元件使用要求,耐焊性优于银电极,可焊性与银电极相当。
Multi-layer ceramic capacitor (MLCC) is the most important chip component in the surface mount technology, and electrode paste is the key and foundation materials for MLCC, electrode paste capability of MLCC played a dominant role in the development of it. Currently, MLCC used precious metals Ag and Ag-Pd as the function phase of the electrode paste. But Ag and Ag-Pd electrode paste have some defects, such as paste of silver system of electrode bear the soldering bad and the silver is under the high and wet strong electric field action of migration etc, the resistivity of the Ag- Pd paste is higher, the price is expensive. For adapting the development of micro-electronics technique, people begin searching for the cheap base metals material as conduct phase of the electronic paste. The copper powder because of its lower resistivity, has become the main substitute of the precious metal paste. Recently, the main research of the copper powder is raising the antioxidation temperature of it.
We use the method of chemistry substitution reaction coating silver in the copper powder surface in order to improve the temperature of oxidation resistance. The surface topography, microstructure and oxidation resistance of the coated powder were characterized by SEM, XRD, TG and other methods. We get the results as following:
The ratio of Ag and Cu is 0.8; the solution concentration of silver ammonia is 0.12mol/L; the gelatin concentration is 20g/L; the dropping velocity is 10 drop/min and the reaction temperature is 50℃. the coating effect is largely responsible for ratio of Ag and Cu, The process of coating powder adopted drop chemical method, have better controllability, and coating is compact. The silver coated copper powder we prepared had higher antioxidation temperature, and can sintering at the oxidized atmosphere.
With silver coated copper powder, we fabricated electrodes paste, and analysed the adhesion force, square resistance, get a conclusion as follows: Taking the globosity copper powder as the function phase, the content of the glass phase is 6%, sintering at the temperature of 800℃and maintaining 10mins, we can get the excellent electrode film.
引文
【1】范家成.我国电容器市场现状及 1996 年预测[J].电子元件与材料,1996,2:1-7
【2】陆国权.世界电子元件现状与发展趋势[J]. Spotlight Report,2003(12):34-41
【3】 蒋渝,陈家钊,刘 颖等. 多层片式陶瓷电容器 MLC 研发进展. 功能材料与器件学报, 2003,9(1):100-104
【4】Laurel. Sheppard Progress continnes in capacitor technology[J],Am Ceram Soc Bull,1993,3:45-57
【5】Patterson F K, Mones A H, Bacher R J. An air friable base metal conductor for optoelectronics[A], Proceeding of conference on hybrid microelectronics[C],1995:33-34
【6】杨邦朝,冯哲圣,卢云. 多层陶瓷电容器技术现状及未来发展趋势[J]. 电子元件与材料, 2001(6):17-19
【7】Akira Mauri, Doril P.chip monolithic caramic capacitors offer low voltage heigh capcitance[J]. JEE, 1995,32(342):30-33
【8】王祖佑,田连城等.纳米高性能介质陶瓷材料及大容量陶瓷材料及大容量 MLC[A],四川省纳米材料应用及产业化研讨会[C],2001.8
【9】薛泉林.高频电子陶瓷元器件在移动通信中应用及发展动向[J].电子元件与材料,1994(4):1-4
【10】陆锁链. 从数字看发展片式电容器面临的机遇与挑战[J].电子元件与材料,2003,22(6):48-53
【11】 陈祥冲,黄新友.贱金属内电极多层陶瓷电容器研发产业及现状[J]. 新材料产业.2005(3):57-60
【12】李文闺. 国内片式元件产业及市场研究[J].电子元件与材料,1997,12:12-18
【13】 张 宇,张承琚,王永春.多层陶瓷电容器及其发展趋势[J].江西科学,2005,23(4):374-376
【14】 魏建中,张良莹等.多层陶瓷电容器银/钯内电极浆料的烧结[J].压电与声光,1997,19(5):356-359
【15】 吕玉芳,包兴等.多层陶瓷电容器端电极附着力研究[J].天津大学学报,1999,32(1):102-105
【16】 李东豪,张靖东等.MLC 端头三层电极技术的应用[J].电子元件与材料,1991,10(6):36-38
【17】曹智强,李龙土等.高性能低烧 MLC 三层镀工艺研究[J].功能材料,1997,28(2),143-145
【18】将端六,李东豪.三层端电极渗边现象的研究[J].Electron Compon Mater,1996,15(4) :46-49
【19】杨雯,俞守耕.片式 MLC 三层端电极中 Sn-Pb 合金电镀[J].电子元件与材料,1994 ,12: 35-36
【20】傅俊川.MLC 银端电极浆料的研究[J].电子元件与材料,1994(8):17-21
【21】 庞溥生,姚卿敏.解决电容器内外电极间空隙工艺[J]. 电子工艺技术,2004,25(4):165-170
【22】王昆福,俞守耕等.片式多层瓷介电容器用 Pd-Ag 端电极浆料[J].贵金属,1998,19(1):18-20
【23】肖凤英,林庆红.MLC 端电极浆料中有机粘合剂的研究[J].实验技术与管理,2001,18(4),:112-114
【24】杜红云.超细金粉在电子浆料中的应用[J] . 电子元件与材料,2001,20(4):16-17
【25】俞守耕,仁金玉,陈峤等.多层陶瓷电容器可镀银端头材料[J].贵金属,1996,17(4):6-10
【26】李耀霖.厚膜电子元件[M].广州:华南理工大学出版社,1991
【27】李言荣,恽正中.电子材料导论[M].北京:清华大学出版社,2001
【28】张俊兵,樊自拴.厚膜镍导电浆料研究[J].电子元件与材料,2004(7):28-30
【29】周东祥,陈勇.空气中烧成镍电极浆料的研究[J].电子元件与材料,2003,22(8):11-12
【30】常柏灵,王朝晖.镍电极浆料研究[J].传感器技术,1997,16(1):42-44
【31】谭富彬,赵玲等.以镍代银的空气烧结镍导体浆料[J].贵金属,2000,21(1):22-25
【32】王文生.多层陶瓷电容器 Ni 内电极研究进展[J].电子元件与材料,1994,2:7-11
【33】何益艳,赵强,杜仕国,等. 铜粉表面防氧化处理技术研究进展[J].表面技术,2004,33(6):4-6
【34】郑福元,周立飞等.厚薄膜混合集成电路—设计、制造和应用[M]. 北京:科学出版社,1984
【35】林 硕,吴年强,李志章.黄铜系复合导电涂料的研究[J]. 涂料工业,1997(2) :8.
【36】T.Hori, A.Otani, Y.Oguri, M.Nakamura,H.Matsuda and J.Sato,IEMT/IMC Proceedings 1997,337-341
【37】Yun-Sen, Lin,Sheng Shiang Chiu and Chi-Shung Shi,Shen-LiFu. Int,l symposium on Electronic Materials and Packaging,2002,55-62
【38】路庆华.新型导电胶的研究(Ⅲ)[J].功能材料,1998,29(4):439-441
【39】JP 05614568 Mar.25.1997
【40】ChengKB, Ramakrishans, LeeKC. Electrostatic Discharge Properties of Knitted Copper Wire Glass Fiber Fabric Reinforced Polypropylene Composites [J]. Polymer Composites, 2001,22(2): 185-196
【41】许佩新,陈治中,谢文明. 铜导电胶电性能的研究[J].材料科学与工程, 1998, 16(1): 75-77.
【42】 XinruiXu, XiaoiunLuo,etal. Electroless silver coating on fine copper powder and its effects on oxidation resistance[J]. Materials Letters, 2003, 57:3987.
【43】闫军,崔海萍,杜仕国,何益艳. 偶联剂对环氧-铜粉复合导电涂料导电性能的影响[J].弹性体, 2003,13(4):18～21
【44】何纯孝.贵金属合金相图[M].北京:冶金工业出版社.1983
【45】林栋梁. 晶体缺陷[M].上海:上海交通大学出版社,1996:120.
【46】 汪晓波,殷梅珍,王岩.用正交设计方法选择有机载体配方[J].安徽教育学院学报,1998(1):34-35
【47】王听岳,崔殿亨.薄厚膜导体的金属体系及耐钎焊性[J].电子元件与材料,1987,6(5): 5-11
【48】谭富彬,蔡云卓,赵玲等.铜粉末化学镀银及其性能[J]. 贵金属,2000,21(3)8-11
【49】高保娇,高建峰,蒋红梅等.微米级铜-银合金粉镀层结构及其抗氧化性[J]. 物理化学学报, 2000,16(4):366-369.
【50】高保娇,蒋红梅,张忠兴. 用银氨溶液对微米级铜粉镀银反应机理的研究[J]. 无机化学学报, 2000,16(4): 669-673.
【51】Paunovic.Kinetics and Mechanism of Electroless Metal Deposition In Proceedings of The Symposium on Electroless Deposition of Metals and Alloys[M],ECS Inc, New Jersey, 1988
【52】高瑞平等.先进陶瓷物理与化学原理及技术[M].北京:科学出版社,2001,100-112
【2】陆国权.世界电子元件现状与发展趋势[J]. Spotlight Report,2003(12):34-41
【3】 蒋渝,陈家钊,刘 颖等. 多层片式陶瓷电容器 MLC 研发进展. 功能材料与器件学报, 2003,9(1):100-104
【4】Laurel. Sheppard Progress continnes in capacitor technology[J],Am Ceram Soc Bull,1993,3:45-57
【5】Patterson F K, Mones A H, Bacher R J. An air friable base metal conductor for optoelectronics[A], Proceeding of conference on hybrid microelectronics[C],1995:33-34
【6】杨邦朝,冯哲圣,卢云. 多层陶瓷电容器技术现状及未来发展趋势[J]. 电子元件与材料, 2001(6):17-19
【7】Akira Mauri, Doril P.chip monolithic caramic capacitors offer low voltage heigh capcitance[J]. JEE, 1995,32(342):30-33
【8】王祖佑,田连城等.纳米高性能介质陶瓷材料及大容量陶瓷材料及大容量 MLC[A],四川省纳米材料应用及产业化研讨会[C],2001.8
【9】薛泉林.高频电子陶瓷元器件在移动通信中应用及发展动向[J].电子元件与材料,1994(4):1-4
【10】陆锁链. 从数字看发展片式电容器面临的机遇与挑战[J].电子元件与材料,2003,22(6):48-53
【11】 陈祥冲,黄新友.贱金属内电极多层陶瓷电容器研发产业及现状[J]. 新材料产业.2005(3):57-60
【12】李文闺. 国内片式元件产业及市场研究[J].电子元件与材料,1997,12:12-18
【13】 张 宇,张承琚,王永春.多层陶瓷电容器及其发展趋势[J].江西科学,2005,23(4):374-376
【14】 魏建中,张良莹等.多层陶瓷电容器银/钯内电极浆料的烧结[J].压电与声光,1997,19(5):356-359
【15】 吕玉芳,包兴等.多层陶瓷电容器端电极附着力研究[J].天津大学学报,1999,32(1):102-105
【16】 李东豪,张靖东等.MLC 端头三层电极技术的应用[J].电子元件与材料,1991,10(6):36-38
【17】曹智强,李龙土等.高性能低烧 MLC 三层镀工艺研究[J].功能材料,1997,28(2),143-145
【18】将端六,李东豪.三层端电极渗边现象的研究[J].Electron Compon Mater,1996,15(4) :46-49
【19】杨雯,俞守耕.片式 MLC 三层端电极中 Sn-Pb 合金电镀[J].电子元件与材料,1994 ,12: 35-36
【20】傅俊川.MLC 银端电极浆料的研究[J].电子元件与材料,1994(8):17-21
【21】 庞溥生,姚卿敏.解决电容器内外电极间空隙工艺[J]. 电子工艺技术,2004,25(4):165-170
【22】王昆福,俞守耕等.片式多层瓷介电容器用 Pd-Ag 端电极浆料[J].贵金属,1998,19(1):18-20
【23】肖凤英,林庆红.MLC 端电极浆料中有机粘合剂的研究[J].实验技术与管理,2001,18(4),:112-114
【24】杜红云.超细金粉在电子浆料中的应用[J] . 电子元件与材料,2001,20(4):16-17
【25】俞守耕,仁金玉,陈峤等.多层陶瓷电容器可镀银端头材料[J].贵金属,1996,17(4):6-10
【26】李耀霖.厚膜电子元件[M].广州:华南理工大学出版社,1991
【27】李言荣,恽正中.电子材料导论[M].北京:清华大学出版社,2001
【28】张俊兵,樊自拴.厚膜镍导电浆料研究[J].电子元件与材料,2004(7):28-30
【29】周东祥,陈勇.空气中烧成镍电极浆料的研究[J].电子元件与材料,2003,22(8):11-12
【30】常柏灵,王朝晖.镍电极浆料研究[J].传感器技术,1997,16(1):42-44
【31】谭富彬,赵玲等.以镍代银的空气烧结镍导体浆料[J].贵金属,2000,21(1):22-25
【32】王文生.多层陶瓷电容器 Ni 内电极研究进展[J].电子元件与材料,1994,2:7-11
【33】何益艳,赵强,杜仕国,等. 铜粉表面防氧化处理技术研究进展[J].表面技术,2004,33(6):4-6
【34】郑福元,周立飞等.厚薄膜混合集成电路—设计、制造和应用[M]. 北京:科学出版社,1984
【35】林 硕,吴年强,李志章.黄铜系复合导电涂料的研究[J]. 涂料工业,1997(2) :8.
【36】T.Hori, A.Otani, Y.Oguri, M.Nakamura,H.Matsuda and J.Sato,IEMT/IMC Proceedings 1997,337-341
【37】Yun-Sen, Lin,Sheng Shiang Chiu and Chi-Shung Shi,Shen-LiFu. Int,l symposium on Electronic Materials and Packaging,2002,55-62
【38】路庆华.新型导电胶的研究(Ⅲ)[J].功能材料,1998,29(4):439-441
【39】JP 05614568 Mar.25.1997
【40】ChengKB, Ramakrishans, LeeKC. Electrostatic Discharge Properties of Knitted Copper Wire Glass Fiber Fabric Reinforced Polypropylene Composites [J]. Polymer Composites, 2001,22(2): 185-196
【41】许佩新,陈治中,谢文明. 铜导电胶电性能的研究[J].材料科学与工程, 1998, 16(1): 75-77.
【42】 XinruiXu, XiaoiunLuo,etal. Electroless silver coating on fine copper powder and its effects on oxidation resistance[J]. Materials Letters, 2003, 57:3987.
【43】闫军,崔海萍,杜仕国,何益艳. 偶联剂对环氧-铜粉复合导电涂料导电性能的影响[J].弹性体, 2003,13(4):18～21
【44】何纯孝.贵金属合金相图[M].北京:冶金工业出版社.1983
【45】林栋梁. 晶体缺陷[M].上海:上海交通大学出版社,1996:120.
【46】 汪晓波,殷梅珍,王岩.用正交设计方法选择有机载体配方[J].安徽教育学院学报,1998(1):34-35
【47】王听岳,崔殿亨.薄厚膜导体的金属体系及耐钎焊性[J].电子元件与材料,1987,6(5): 5-11
【48】谭富彬,蔡云卓,赵玲等.铜粉末化学镀银及其性能[J]. 贵金属,2000,21(3)8-11
【49】高保娇,高建峰,蒋红梅等.微米级铜-银合金粉镀层结构及其抗氧化性[J]. 物理化学学报, 2000,16(4):366-369.
【50】高保娇,蒋红梅,张忠兴. 用银氨溶液对微米级铜粉镀银反应机理的研究[J]. 无机化学学报, 2000,16(4): 669-673.
【51】Paunovic.Kinetics and Mechanism of Electroless Metal Deposition In Proceedings of The Symposium on Electroless Deposition of Metals and Alloys[M],ECS Inc, New Jersey, 1988
【52】高瑞平等.先进陶瓷物理与化学原理及技术[M].北京:科学出版社,2001,100-112
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |