热敏电阻局部化学镀铜制备良好欧姆接触电极及性能研究
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摘要
随着电子信息技术的迅猛发展，电子元件的微型化、集成化及高可靠性已经成为信息产业的主要趋势。因此，正温度系数钛酸钡基陶瓷热敏电阻元件的趋势则是小型化、片式化、低阻化和高可靠性。陶瓷基PTC材料作为电子元件，需要在其表面敷设一层金属。制备半导体欧姆接触电极的方法有很多，如烧渗银、化学镀镍、烧渗Al-Ag浆等。迄今为止，上述所提到的方法制备的陶瓷热敏电阻成本高，经济效益低。然而，一种新的局部表面化学镀铜法应用于钛酸钡基片式材料表面进行铜镀层的沉积，可进一步降低成本，并提高电子元件性能。镀层的性能研究结果表明：镀层与陶瓷基体之间有着良好的结合力，电极的电阻、抗拉力、耐电压性能、耐湿性能和焊接性能均满足工业生产的要求。同时利用X-射线衍射技术（XRD）对未涂覆浆料的陶瓷基体表面和制成的陶瓷热敏电阻元件的结构进行了表征。利用原子力显微镜（AFM）对电极制备过程中的表面形貌进行了研究。我们所发明的工艺用来制备的欧姆接触电阻的生产成本仅为按传统工艺流程所制备的电极的成本的25%。在电子元件制备领域，用该方法生产电阻也已经得到了大力的商业化推广。本文中,还提出了切实可行的测定镀液中甲醛和铜的分析方法。
With the rapid development of electronic information technology, theminiaturization, integration and high reliability of electronic components havebecome the main trend of the electronic information industry. Consequently,miniaturization, chip type,low-resistance and high reliability are becoming the maintendency of the BaTiO3-based positive temperature coefficient resistance(PTCR). Aselectronic components, the surface of ceramic-based thermistors have to be coatedwith a layer of metal. There are many ways of forming a ceramic-based electrode,including silver-layer coating, electroless Ni-plating and Al/Ag pastes coating. So far,the methods we mentioned above in the specifications are high for ceramic thermistorproduction. However, a new method of fabrication - a Cu-layer on the surfaces ofBaTiO3-based chip resistor is put forward in this paper, which is called the regionalelectroless Cu-plating. Furthermore, the performance of the coatings wereinvestigated. The major findings are: adhesion force between electrode and thesubstance, resistance, tensile resistance, the voltage-withstanding, moisture-resistance,solderability, and so forth, all meet the demands of the industry. Both thecharacterstics of the substrate surface without coated with pastes and that of thesubstrate with Cu-plating are studied by means of X-ray Diffraction. Also the processof forming an electrode is tested by means of Atomic Force Microscope(AFM). Theproduction cost of the technology we invented and used for the preparation of ohmiccontact resistance is merely 25% of that produced in a traditional way. In the field ofpreparation of electronic components, this method of fabrication composite electrodeon the surface of the ceramics bulk has been widely applied in the production ofPTCR thermistors.
Also, practical methods were proposed in this paper to detect the concentrationof formaldehyde and copper ion of the bath.
With the rapid development of electronic information technology, theminiaturization, integration and high reliability of electronic components havebecome the main trend of the electronic information industry. Consequently,miniaturization, chip type,low-resistance and high reliability are becoming the maintendency of the BaTiO3-based positive temperature coefficient resistance(PTCR). Aselectronic components, the surface of ceramic-based thermistors have to be coatedwith a layer of metal. There are many ways of forming a ceramic-based electrode,including silver-layer coating, electroless Ni-plating and Al/Ag pastes coating. So far,the methods we mentioned above in the specifications are high for ceramic thermistorproduction. However, a new method of fabrication - a Cu-layer on the surfaces ofBaTiO3-based chip resistor is put forward in this paper, which is called the regionalelectroless Cu-plating. Furthermore, the performance of the coatings wereinvestigated. The major findings are: adhesion force between electrode and thesubstance, resistance, tensile resistance, the voltage-withstanding, moisture-resistance,solderability, and so forth, all meet the demands of the industry. Both thecharacterstics of the substrate surface without coated with pastes and that of thesubstrate with Cu-plating are studied by means of X-ray Diffraction. Also the processof forming an electrode is tested by means of Atomic Force Microscope(AFM). Theproduction cost of the technology we invented and used for the preparation of ohmiccontact resistance is merely 25% of that produced in a traditional way. In the field ofpreparation of electronic components, this method of fabrication composite electrodeon the surface of the ceramics bulk has been widely applied in the production ofPTCR thermistors.
Also, practical methods were proposed in this paper to detect the concentrationof formaldehyde and copper ion of the bath.
引文
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[32]詹益增，邓九京，吴世俊，铝电极对PTC陶瓷老化的影响，现代技术陶瓷,2003，97(3)：12-15
[33]周东祥，陈勇，邓传益等，空气中烧成镍电极浆料的研究，电子元件与材料，2003，22(8)：10-11
[34]陈勇，郭琳，周桃生等，欧姆接触镍电极的研究，压电与声光，2005，27(1)：85-88
[35]罗小巧,邓传益，欧姆接触锌电极的研制，功能材料，1999，30(1)：74-75
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[37]张甦，沈十林，周欣山等，化学镀镍工艺条件对陶瓷热敏电阻性能的影响，电镀与涂饰，2004，23(1)：28-30
[38] Zhang D. L., Zhou D. X. ,Jiang S.L., et al, The ac electrical failurebehaviors and mechanisms of current limiting BaTiO3-basedpositive-temperature-coefficient(PTC) ceramic thermistors coatedwith electroless nickel-phosphorous electrode, Sens. Actuators , A,2002,101(1-2):123
[39]钱朝勇，沈十林，周欣山，片式陶瓷基片式电子元件的制造方法，中国，中国专利，1624816，2005
[40]潘延陵，陈楚，表面工程-热喷技术，电焊机，1994，(5)：1-3
[41]熊天英，吴杰，金花子等，一种热敏陶瓷欧姆接触电极的制备方法，中国专利，1447349，2003
[42]吴杰，刘志文，金花子等，用冷喷涂法制备PTC陶瓷Al表面技术，2002，31(5)：4-7
[43]周东祥，赵加强，龚树萍等，直流磁控溅射BaTiO3系PTCR元件电极及其性能对比的研究.功能材料，2003，34 (6)：665-667
[44] Hao Y.D., Zhao J.Q., Zheng Y.K., et al, Magnetron sputtering electrode on theBaTiO3-based PTCR ceramics and the effect of heat treatment on their properties,Mater. Sci. Eng. B, 2003, 99:516-519
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[2]宋秀峰，傅仁利，何洪等，氧化铝陶瓷基板化学镀铜金属化及层结构，电子元件与材料，2007，26(2)：40-42
[3]薛泉林，PTC热敏电阻应用与展望，国外科技，1990，10：22-23
[4]朱盈权，PTC热敏电阻的现状与发展趋势，电子元件与材料，2002，21(6)：26-28
[5]朱盈权，PTC热敏电阻的现状与发展趋势（续一），电子元件与材料，2002，21(7)：24-26
[6]朱盈权，PTC热敏电阻的现状与发展趋势（续二），电子元件与材料，2002，21(8)：22-25
[7]陈璐，Ni/石墨/BaTiO3基PTC陶瓷复合材料的研究：[硕士学位论文]，天津：天津大学，2006
[8]王盛，杭志宏，陆申龙，新型PTC热敏电阻的特性测量及其应用[J]，大学物理，2000，19(6)：31-33
[9]宋忠慎，陶瓷PTC与有机PTC的性能比较及应用[J]，电信技术,1999，（1）：33-34
[10] Hayman P. W., Dam R. W., Klasens H. A., Method of preparation ofsemiconducting materials,German Patent,929350,1955-6-23
[11] Cheng H. F., Lin T. F., Hu C. T., Effect of sintering aids on microstructures andPTCR characteristic of (Sr0.2Ba0.8) TiO3 ceramics. J. Am. Ceram. Soc., 1993, 76:827–832
[12] Jaffe B., Cook W. R., Jaffe H., Piezoelectric Ceramics , AcademicPress, London and New York ,1971
[13]周东祥等，半导体陶瓷及应用，武汉：华中理工大学出版社[M]，1991
[14] Kuwabara M., Kumamoto K., A new phenomenon in barium-lead titanateceramics with positive temperature coefficients of resistivity,J.Am.Ceram.Soc., 1986,69(8):176-177
[15] Chang H. Y., Liu K. S., Chen H. W., V-shaped positive temperature coefficientof resistivity (PTCR) characteristics of microwave sintered(Sr0.4Pb0.6)Ti03Mater. Chem. Phys.,1995,42:258-263
[16] Wang D. Y., Umeya K., Elecrtical Porperties of PTCR Barium titanate, J.Am.Ceram.Soc., 1990,73(3):669-677
[17] Tseng T. Y., Wang S. H., ac electrical properties of high curie point barium-leadtitanate PTCR ceramics, Mater.lett., 1990(9): 164
[18]周海亮，杜懋陆，倪超等，PTC热敏电阻及其发展趋势[J]，内江师范学院学报，2004，19(6)：17-20
[19]席军，刘挺华，PTC热敏电阻的开发应用现状，塑料，2005，34(4)：79-84
[20]尤晓玲，PTC元件及其应用[J]，甘肃科技，2000，4
[21]徐政，倪宏伟，现代功能陶瓷[M]，北京：国防工业出版社，1998
[22] Al-Allak, Illingsworth J., Brinkman A. W., et al, current-voltage of donar dopedBaTiO3 semiconducting ceramics, J.Phys.D: Appl.Phys. 1989, 22(9): 1391-1397
[23] Nemoto H., Direct of examinations of PTC action of single grain boundaries insemiconducting BaTiO3 ceramics，J.Am.Ceram.Soc., 1980, 63(7-8): 398-401
[24]刘慕园，杨宾峰，PTC热敏电阻的特点及应用[J]，河南职业技术师范学院学报，2002，30(1)：50-52
[25]唱润忠，新型的发热材料－PTC热敏电阻[J ]，应用红外与光电子学，1994 ,(4)：14－16，30
[26]郝武斌，热磁寒通宝[ P]，中国专利，91101062. 9，1991
[27]薛泉林，PTC热敏电阻器发展与应用动态[J]，山东陶瓷，1997，20(4)：9-13
[28]周东祥，龚树萍，PTCR材料及应用,武汉：华中理工大学出版社，1990：181
[29] Seiter H., Heywang W., Semiconducting barium titanate[J]，J. Mater. Sci.，1971, 6: 1214-1226
[30]陈一，银铝锡欧姆接触易焊电极浆料的研制，电子元件与材料，1997，16(6)：37-40
[31]何晓明，刘胜利，张绍彬等，PTCR半导瓷用欧姆接触电极的研究，功能材料，1996，27(5)：407–409
[32]詹益增，邓九京，吴世俊，铝电极对PTC陶瓷老化的影响，现代技术陶瓷,2003，97(3)：12-15
[33]周东祥，陈勇，邓传益等，空气中烧成镍电极浆料的研究，电子元件与材料，2003，22(8)：10-11
[34]陈勇，郭琳，周桃生等，欧姆接触镍电极的研究，压电与声光，2005，27(1)：85-88
[35]罗小巧,邓传益，欧姆接触锌电极的研制，功能材料，1999，30(1)：74-75
[36]罗小巧，邓传益，空气中烧成锌电极浆料的研究，压电与声光，1998，20(5)：332-334
[37]张甦，沈十林，周欣山等，化学镀镍工艺条件对陶瓷热敏电阻性能的影响，电镀与涂饰，2004，23(1)：28-30
[38] Zhang D. L., Zhou D. X. ,Jiang S.L., et al, The ac electrical failurebehaviors and mechanisms of current limiting BaTiO3-basedpositive-temperature-coefficient(PTC) ceramic thermistors coatedwith electroless nickel-phosphorous electrode, Sens. Actuators , A,2002,101(1-2):123
[39]钱朝勇，沈十林，周欣山，片式陶瓷基片式电子元件的制造方法，中国，中国专利，1624816，2005
[40]潘延陵，陈楚，表面工程-热喷技术，电焊机，1994，(5)：1-3
[41]熊天英，吴杰，金花子等，一种热敏陶瓷欧姆接触电极的制备方法，中国专利，1447349，2003
[42]吴杰，刘志文，金花子等，用冷喷涂法制备PTC陶瓷Al表面技术，2002，31(5)：4-7
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