埋入式电容器的设计及电学性能研究
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摘要
与传统的分立式电容设计技术相比,埋入式电容技术能够提高封装的有效性,改善元件的电气性能,同时使电子组装成本大大降低，在微电子行业具有重要的作用。电介质材料是埋入式电容的关键部分，其性能的好坏决定着埋入式电容性能的优劣。将具有高介电性能的陶瓷纳米颗粒和聚合物复合，利用陶瓷纳米粒子的高介电性能和聚合物的柔性等优点，利用层压及微电子加工技术，可以制备出性能优异的埋入式电容。
本文以具有优良电学性能的聚酰亚胺（PI）和环氧树脂（Epoxy）为基体，以具有高介电常数的无机陶瓷纳米粒子钛酸钡（BaTiO3）为填料，通过层压法及减层法等微电子加工技术，制备了埋入式电容。研究了介电薄膜微观结构及其对介电性能的影响，以及埋入式电容器在常温下及在变温下不同频率的介电性能。结果表明针对不同的聚合物基体，利用层压法和减层法制备的埋入式电容具有优良的介电性能。在100Hz~1MHz的频率范围内，以BT/Epoxy为基体的埋入式电容其介电常数可达到18，介电损耗＜0.02，介电强度为24V/μm，且在-30℃~100℃的温度范围内具有良好的温度稳定性。以BT/PI为基体的埋入式电容其介电常数可达30，介电损耗低于0.05，介电强度为210V/μm，在-50℃~150℃的温度范围内，也具有良好的温度稳定性，实验结果表明，以上两种介电薄膜为基底的埋入式电容能够有效的应用于微电子行业。
Compare with the design technology of traditional Discrete capacitors, thetechnology of embedded capacitor can improve the effectiveness of thepackage, enhance electric performance of device and reduce the cost ofelectronics assembly. The technology of embedded capacitor has a importanteffect on microelectronics technology. Dielectric materials are the importantpart of embedded capacitor and the property of dielectric materials decide onthe performance of embedded capacitor. Compound ceramic nanoparticle withpolymer and utilize the advantage of ceramic nanoparticle and polymer, suchas high dielectric constant of ceramic particle and flexibility of polymer, highquality of embedded capacitor can be manufactured using laminated andmicroelectronic technology.
In this paper, polyimide and epoxy resin have been chosen as the polymermatrix and BaTiO3nanoparticle as the filler. The embedded capacitors have been prepared through lamination and minus layer method. Microstructure ofdielectric film and the influence of microstructure on dielectric property havebeen studied. The dielectric property of embedded capacitors has been alsostudied at different frequency and temperature. The results show thatembedded capacitors of different polymer matrix have better dielectricproperty prepared through lamination and minus layer method. In thefrequency range of100Hz~1MHz, dielectric constant of embedded capacitorof BT/EP achieve18. dielectric loss＜0.02, dielectric strength is24V/μm. Ithas better temperature stability in the range of-30℃~100℃. The dielectricconstant of embedded capacitor of BT/PI reach30, dielectric loss is below0.05and dielectric strength is210V/μm. It also has better temperature stabilityin the range of-50℃~150℃. Experimental results show that the embeddedcapacitors with BT/EP and BT/PI dielectric films can be effective used inmicroelectronic technology.
本文以具有优良电学性能的聚酰亚胺（PI）和环氧树脂（Epoxy）为基体，以具有高介电常数的无机陶瓷纳米粒子钛酸钡（BaTiO3）为填料，通过层压法及减层法等微电子加工技术，制备了埋入式电容。研究了介电薄膜微观结构及其对介电性能的影响，以及埋入式电容器在常温下及在变温下不同频率的介电性能。结果表明针对不同的聚合物基体，利用层压法和减层法制备的埋入式电容具有优良的介电性能。在100Hz~1MHz的频率范围内，以BT/Epoxy为基体的埋入式电容其介电常数可达到18，介电损耗＜0.02，介电强度为24V/μm，且在-30℃~100℃的温度范围内具有良好的温度稳定性。以BT/PI为基体的埋入式电容其介电常数可达30，介电损耗低于0.05，介电强度为210V/μm，在-50℃~150℃的温度范围内，也具有良好的温度稳定性，实验结果表明，以上两种介电薄膜为基底的埋入式电容能够有效的应用于微电子行业。
Compare with the design technology of traditional Discrete capacitors, thetechnology of embedded capacitor can improve the effectiveness of thepackage, enhance electric performance of device and reduce the cost ofelectronics assembly. The technology of embedded capacitor has a importanteffect on microelectronics technology. Dielectric materials are the importantpart of embedded capacitor and the property of dielectric materials decide onthe performance of embedded capacitor. Compound ceramic nanoparticle withpolymer and utilize the advantage of ceramic nanoparticle and polymer, suchas high dielectric constant of ceramic particle and flexibility of polymer, highquality of embedded capacitor can be manufactured using laminated andmicroelectronic technology.
In this paper, polyimide and epoxy resin have been chosen as the polymermatrix and BaTiO3nanoparticle as the filler. The embedded capacitors have been prepared through lamination and minus layer method. Microstructure ofdielectric film and the influence of microstructure on dielectric property havebeen studied. The dielectric property of embedded capacitors has been alsostudied at different frequency and temperature. The results show thatembedded capacitors of different polymer matrix have better dielectricproperty prepared through lamination and minus layer method. In thefrequency range of100Hz~1MHz, dielectric constant of embedded capacitorof BT/EP achieve18. dielectric loss＜0.02, dielectric strength is24V/μm. Ithas better temperature stability in the range of-30℃~100℃. The dielectricconstant of embedded capacitor of BT/PI reach30, dielectric loss is below0.05and dielectric strength is210V/μm. It also has better temperature stabilityin the range of-50℃~150℃. Experimental results show that the embeddedcapacitors with BT/EP and BT/PI dielectric films can be effective used inmicroelectronic technology.
引文
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[8]施建章,汪宏,沈智元,王楠,姚熹.埋入式厚膜多层电容器的制备及其性能研究[J].稀有金属材料与工程,2007,36,954-956
[9] Ulrich RK, Schaper LW, Integrated passive component technology[J].IEEEPress,Wiley-Interscience, Hoboken, NJ, USA,2003
[10] Tohge N,Takahashi S,Minami T, Preparation of PbZrO3-PbTiO3ferroelectric thin films bythe sol-gel process[J]. J Am Ceramic Soc1991,74(1):67-71
[11] Q. M. Zhang, H. F. Li, M. Poh, F. Xia, Z. Y. Cheng and H. S. Xu. An all-organic compositeactuator material with a high dielectric constant[J], Nature,2002,419,284-287,.
[12] J.Wang,Q. Shen,C.Yang and Q.Zhang, High dielectric constant composite ofP(VDF-TrFE) with grafted copper phthalocyanine oligmer[J], Macromolecules,2004,37,2294-2298,.
[13] C.Huang, Q.M.Zhang and J.Su, High dielectric constant all polymer percolativecomposites[J],Appl Phys Lett.2003,82,3502-3504,.
[14] J.Lu, K.S.Moon, B.K. Kim and C.P.Wong, High dielectric constant polyaniline/epoxycomposites via in-situ polymerization for embedded capacitor applications[J],Polymer,2007,48,1510-1516.
[15] Gregorio R, Cestari M, Bernardino FE, Dielectric behavior of thin films ofbeta-PVDF/PZT and beta-PVDF/BaTiO3composites[J]. J Mater Sci,1996,31:2925–2930
[16] Bai Y, Cheng ZY, Bharti V, Xu HS, Zhang QM. High-dielectric-constant ceramic-powderpolymer composites[J]. Appl Phys Lett,2000,76:3804–3806
[17] Mazur K, Polymer-ferroelectric ceramic composites in ferroelectric polymers: chemistry,physics, and applications[J]. In: Nalwa HS (ed) Marcel Dekker Inc., New York,1995
[18] Dasgupta DK, Doughty K,Polymer-ceramic composite materials with high dielectricconstants[J]. Thin Solid Films,1988,158:93–105
[19] Liang S, Chong S, Giannelis E. Barium titanate/epoxy composite dielectric materials forintegrated thin film capacitors[J].Proceedings of48th Electronic Components andTechnology Conference,1998,171–175
[20] Windlass H, Raj PM, Balaraman D, Bhattacharya SK, Tummala RR, Processing ofpolymer-ceramic nanocomposites for system-on-package applications[J]. Proceedings ofthe51st Electronic Components and Technology Conference,2001,1201-1206
[21] Rao Y, Ogitani S, Kohl P, Wong CP, Novel polymer-ceramic nanocomposite based on highdielectric constant epoxy formula for embedded capacitor application[J]. J Appl PolymerSci2002,83:1084-1090
[22] Dang ZM, Lin YH, Nan CW, Novel ferroelectric polymer composites with high dielectricconstants[J]. Adv Mater2003,15:1625–1629
[23] Cho SD, Lee JY, Hyun JG, Paik KW, Study on epoxy/BaTiO3composite embeddedcapacitor films (ECFs) for organic substrate applications[J].Mater Sci Eng B2004,110(3):233–239
[24] Zhang QM, Bharti V, Zhao X, Giant electrostriction and relaxor ferroelectric behavior inelectron-irradiated poly(vinylidene fluoride-trifluofoethylene) copolymer[J].Science1998,280:2101–2104
[25] Rao Y, Wong CP, Material characterization of a high-dielectric-constant polymer-ceramiccomposite for embedded capacitor for RF applications[J]. J Appl Polymer Sci2004,92:2228–2231
[26] Arbatti M, Shan XB, Cheng ZY, Ceramic-polymer composites with high dielectricconstant[J]. Adv Mater2007,19:1369–1372
[27] Kim P, Jones SC, Hotchkiss PJ, Haddock JN, Kippelen B, Marder SR, Perry JW,Phosphonic acid-modified barium titanate polymer nanocomposites with high permittivityand dielectric strength[J]. Adv Mater2007,19:1001–1005
[28] Rao Y, Wong CP, Xu J, Ultra high k polymer metal composite for embedded capacitorapplication[P]. US Patent6864306,2005
[29] Pecharroman C, Moya JS, Experimental evidence of a giant capacitance ininsulator-conductor composites at the percolation threshold[J].Adv Mater2000,12:294–297
[30] Xu J, Wong CP, Low loss percolative dielectric composite[J].Appl Phys Lett2005,87:082907
[31] Dang ZM, Shen Y, Nan CW, Dielectric behavior of three-phasepercolativeNi–BaTiO3/Polyvinylidene fluoride composites[J].Appl Phys Lett2002,81:4814–4816
[32] Choi HW, Heo YW, Lee JH, Kim JJ, Lee HY, Park ET, Chung YK, Effects of BaTiO3ondielectric behavior of BaTiO3-Ni-polymethylmethacrylate composites[J].Appl Phys Lett2006,89:132910
[33] Xu J, Wong CP, Super high dielectric constant carbon black-filled polymer composites asintegral capacitor dielectrics[J]. Proceedings of the54th IEEE Electronic Components andTechnology Conference, Las Vegas, NV, USA,2004,536–541
[34] Lu J, Moon KS, Xu J, Wong CP, Synthesis and dielectric properties of novel high-Kpolymer composites containing in-situ formed silver nanoparticles for embedded capacitorapplications[J]. J Mater Chem2006,16(16):1543–1548
[35] Lu J, Moon KS, Wong CP, Development of novel silver nanoparticles/polymer compositesas high k polymer matrix by in-situ photochemical method[J]. IEEE Proceedings of the56th Electronic Components and Technology Conference, San Diego, CA,2006,1841–1846
[36] Qi L, Lee BI, Chen S, Samuels WD, Exarhos GJ,High-dielectric-constant silver-epoxycomposites as embedded dielectrics[J]. Adv Mater2005,17:1777–1781
[37] Shen Y, Lin Y, Li M, Nan C-W,High Dielectric performance of polymer composite filmsinduced by a percolating interparticle barrier layer.2007
[38] Frechette MF, Trudeau ML, Alamdari HD, Boily S, Introductory remarksonnanodielectrics[J]. IEEE Transactions on Dielectrics and Electrical Insulation2004,11:808–818
[39] Nicolais L, Carotenuto G, Metal-polymer nanocomposites. John Wiley&Sons,Inc.,Hoboken, New Jersey, USA,2005
[40] Uchino K, Sadanaga E, Hirose T, Dependence of the crystal-structure on particle-size inBaTiO3[J]. J Am Ceramic Soc1989,72:1555–1558
[41] Leonard MR, Safari A, Crystallite and grain size effects in BaTiO3[J]. Proceedings of theIEEE10th International Symposium on Ferroelectric Applications1996,2:1003–1005
[42] Bhattacharya SK, Tummala RR, Next generation integral passives: materials, processes,and integration of resistors and capacitors on PWB substrates[J]. J Mater Sci: MaterElectron2000,11:253–268
[43] Zhang QM, Li HF, Poh M, Xia F, Cheng ZY, Xu HS, Huang C, An all-organic compositeactuator material with a high dielectric constant[J]. Nature2002,419:284–287
[44] Wang J, Shen Q, Yang C, Zhang Q, High dielectric constant composite of P(VDF-TrFE)with grafted copper phthalocyanine oligmer[J]. Macromolecules2004,37:2294–2298
[45] S.O.Kasap, Principles of Electronic Materials and Devices/Third Edition[M],2009,07
[46] J.D. Klau.电磁学[M],人民邮电出版社,1979,3.
[47]李杰，韦平，汪根林，江平开.高介电复合材料及其介电性能研究[J].绝缘材料，2003，36(5):3-6
[48]陈岩,曾曙.埋入式电容印制电路板制作工艺.印制电路信息[J],2003,2,50-54
[49]肖长江,王春华.钛酸钡结构和性能尺寸效应的研究进展[J].硅酸盐通报,2008,271,111-114
[50]王海燕,党智敏,武晋萍,施昌勇. KH550硅烷偶联剂对复合材料结构和介电性能影响[J].功能材料,2006,37,1091-1093
[51] Seung-Hoon Choi,Il-Doo Kim,Jae-Min Hong,Ki-Hong Park,Seong-Geun Oh. Effect ofthe dispersibility of BaTiO3nanoparticles in BaTiO3/polyimidecomposites on the dielectricproperties[J]. Materials Letters,2007,61,2478–2481
[52]蒲永平,吴建鹏,陈守田.钛酸钡粉体四方相的XRD定量分析[J].压电与声光,2004,26,341-344.
[2] M.F.Davis, A.Sutono, K.Lim,et al. RF-microwave multi-layer integrated passives usingfully organic System on Package(SOP)technology[J]. IEEE MTT-S Int. MicrowaveSymp.Dig.,2001,2:1731-1734.
[3] W.Jillek, W.K.C. Yung. Embedded components in printed circuit boards: a processingtechnology review[J], Int J Adv Manuf Technol,2005,25:350–360
[4] Richard Ulrich, Embedded Resistors and Capacitors for Organic-Based SOP[J]. IEEETRANSACTIONS ON ADVANCED PACKAGING.2004,27,326-331
[5]天津大学无线电材料与原件教研室.电容器[M],技术标准出版社,1981,12
[6]陈永真.电容器及其应用[M].科学出版社,2005,10
[7]《电气电子绝缘技术手册》编委会.电气电子绝缘技术手册[M].机械工业出版社,2008,1
[8]施建章,汪宏,沈智元,王楠,姚熹.埋入式厚膜多层电容器的制备及其性能研究[J].稀有金属材料与工程,2007,36,954-956
[9] Ulrich RK, Schaper LW, Integrated passive component technology[J].IEEEPress,Wiley-Interscience, Hoboken, NJ, USA,2003
[10] Tohge N,Takahashi S,Minami T, Preparation of PbZrO3-PbTiO3ferroelectric thin films bythe sol-gel process[J]. J Am Ceramic Soc1991,74(1):67-71
[11] Q. M. Zhang, H. F. Li, M. Poh, F. Xia, Z. Y. Cheng and H. S. Xu. An all-organic compositeactuator material with a high dielectric constant[J], Nature,2002,419,284-287,.
[12] J.Wang,Q. Shen,C.Yang and Q.Zhang, High dielectric constant composite ofP(VDF-TrFE) with grafted copper phthalocyanine oligmer[J], Macromolecules,2004,37,2294-2298,.
[13] C.Huang, Q.M.Zhang and J.Su, High dielectric constant all polymer percolativecomposites[J],Appl Phys Lett.2003,82,3502-3504,.
[14] J.Lu, K.S.Moon, B.K. Kim and C.P.Wong, High dielectric constant polyaniline/epoxycomposites via in-situ polymerization for embedded capacitor applications[J],Polymer,2007,48,1510-1516.
[15] Gregorio R, Cestari M, Bernardino FE, Dielectric behavior of thin films ofbeta-PVDF/PZT and beta-PVDF/BaTiO3composites[J]. J Mater Sci,1996,31:2925–2930
[16] Bai Y, Cheng ZY, Bharti V, Xu HS, Zhang QM. High-dielectric-constant ceramic-powderpolymer composites[J]. Appl Phys Lett,2000,76:3804–3806
[17] Mazur K, Polymer-ferroelectric ceramic composites in ferroelectric polymers: chemistry,physics, and applications[J]. In: Nalwa HS (ed) Marcel Dekker Inc., New York,1995
[18] Dasgupta DK, Doughty K,Polymer-ceramic composite materials with high dielectricconstants[J]. Thin Solid Films,1988,158:93–105
[19] Liang S, Chong S, Giannelis E. Barium titanate/epoxy composite dielectric materials forintegrated thin film capacitors[J].Proceedings of48th Electronic Components andTechnology Conference,1998,171–175
[20] Windlass H, Raj PM, Balaraman D, Bhattacharya SK, Tummala RR, Processing ofpolymer-ceramic nanocomposites for system-on-package applications[J]. Proceedings ofthe51st Electronic Components and Technology Conference,2001,1201-1206
[21] Rao Y, Ogitani S, Kohl P, Wong CP, Novel polymer-ceramic nanocomposite based on highdielectric constant epoxy formula for embedded capacitor application[J]. J Appl PolymerSci2002,83:1084-1090
[22] Dang ZM, Lin YH, Nan CW, Novel ferroelectric polymer composites with high dielectricconstants[J]. Adv Mater2003,15:1625–1629
[23] Cho SD, Lee JY, Hyun JG, Paik KW, Study on epoxy/BaTiO3composite embeddedcapacitor films (ECFs) for organic substrate applications[J].Mater Sci Eng B2004,110(3):233–239
[24] Zhang QM, Bharti V, Zhao X, Giant electrostriction and relaxor ferroelectric behavior inelectron-irradiated poly(vinylidene fluoride-trifluofoethylene) copolymer[J].Science1998,280:2101–2104
[25] Rao Y, Wong CP, Material characterization of a high-dielectric-constant polymer-ceramiccomposite for embedded capacitor for RF applications[J]. J Appl Polymer Sci2004,92:2228–2231
[26] Arbatti M, Shan XB, Cheng ZY, Ceramic-polymer composites with high dielectricconstant[J]. Adv Mater2007,19:1369–1372
[27] Kim P, Jones SC, Hotchkiss PJ, Haddock JN, Kippelen B, Marder SR, Perry JW,Phosphonic acid-modified barium titanate polymer nanocomposites with high permittivityand dielectric strength[J]. Adv Mater2007,19:1001–1005
[28] Rao Y, Wong CP, Xu J, Ultra high k polymer metal composite for embedded capacitorapplication[P]. US Patent6864306,2005
[29] Pecharroman C, Moya JS, Experimental evidence of a giant capacitance ininsulator-conductor composites at the percolation threshold[J].Adv Mater2000,12:294–297
[30] Xu J, Wong CP, Low loss percolative dielectric composite[J].Appl Phys Lett2005,87:082907
[31] Dang ZM, Shen Y, Nan CW, Dielectric behavior of three-phasepercolativeNi–BaTiO3/Polyvinylidene fluoride composites[J].Appl Phys Lett2002,81:4814–4816
[32] Choi HW, Heo YW, Lee JH, Kim JJ, Lee HY, Park ET, Chung YK, Effects of BaTiO3ondielectric behavior of BaTiO3-Ni-polymethylmethacrylate composites[J].Appl Phys Lett2006,89:132910
[33] Xu J, Wong CP, Super high dielectric constant carbon black-filled polymer composites asintegral capacitor dielectrics[J]. Proceedings of the54th IEEE Electronic Components andTechnology Conference, Las Vegas, NV, USA,2004,536–541
[34] Lu J, Moon KS, Xu J, Wong CP, Synthesis and dielectric properties of novel high-Kpolymer composites containing in-situ formed silver nanoparticles for embedded capacitorapplications[J]. J Mater Chem2006,16(16):1543–1548
[35] Lu J, Moon KS, Wong CP, Development of novel silver nanoparticles/polymer compositesas high k polymer matrix by in-situ photochemical method[J]. IEEE Proceedings of the56th Electronic Components and Technology Conference, San Diego, CA,2006,1841–1846
[36] Qi L, Lee BI, Chen S, Samuels WD, Exarhos GJ,High-dielectric-constant silver-epoxycomposites as embedded dielectrics[J]. Adv Mater2005,17:1777–1781
[37] Shen Y, Lin Y, Li M, Nan C-W,High Dielectric performance of polymer composite filmsinduced by a percolating interparticle barrier layer.2007
[38] Frechette MF, Trudeau ML, Alamdari HD, Boily S, Introductory remarksonnanodielectrics[J]. IEEE Transactions on Dielectrics and Electrical Insulation2004,11:808–818
[39] Nicolais L, Carotenuto G, Metal-polymer nanocomposites. John Wiley&Sons,Inc.,Hoboken, New Jersey, USA,2005
[40] Uchino K, Sadanaga E, Hirose T, Dependence of the crystal-structure on particle-size inBaTiO3[J]. J Am Ceramic Soc1989,72:1555–1558
[41] Leonard MR, Safari A, Crystallite and grain size effects in BaTiO3[J]. Proceedings of theIEEE10th International Symposium on Ferroelectric Applications1996,2:1003–1005
[42] Bhattacharya SK, Tummala RR, Next generation integral passives: materials, processes,and integration of resistors and capacitors on PWB substrates[J]. J Mater Sci: MaterElectron2000,11:253–268
[43] Zhang QM, Li HF, Poh M, Xia F, Cheng ZY, Xu HS, Huang C, An all-organic compositeactuator material with a high dielectric constant[J]. Nature2002,419:284–287
[44] Wang J, Shen Q, Yang C, Zhang Q, High dielectric constant composite of P(VDF-TrFE)with grafted copper phthalocyanine oligmer[J]. Macromolecules2004,37:2294–2298
[45] S.O.Kasap, Principles of Electronic Materials and Devices/Third Edition[M],2009,07
[46] J.D. Klau.电磁学[M],人民邮电出版社,1979,3.
[47]李杰，韦平，汪根林，江平开.高介电复合材料及其介电性能研究[J].绝缘材料，2003，36(5):3-6
[48]陈岩,曾曙.埋入式电容印制电路板制作工艺.印制电路信息[J],2003,2,50-54
[49]肖长江,王春华.钛酸钡结构和性能尺寸效应的研究进展[J].硅酸盐通报,2008,271,111-114
[50]王海燕,党智敏,武晋萍,施昌勇. KH550硅烷偶联剂对复合材料结构和介电性能影响[J].功能材料,2006,37,1091-1093
[51] Seung-Hoon Choi,Il-Doo Kim,Jae-Min Hong,Ki-Hong Park,Seong-Geun Oh. Effect ofthe dispersibility of BaTiO3nanoparticles in BaTiO3/polyimidecomposites on the dielectricproperties[J]. Materials Letters,2007,61,2478–2481
[52]蒲永平,吴建鹏,陈守田.钛酸钡粉体四方相的XRD定量分析[J].压电与声光,2004,26,341-344.