传统的发光二极管(LED)封装材料主要分为环氧树脂与有机硅树脂,它们存在易黄变、易老化、耐候性差和折射率低等诸多缺点。一些具有高折射率、紫外吸收性能优良的纳米金属氧化物(如二氧化钛、二氧化硅、氧化锌和二氧化锆等)与环氧树脂或有机硅树脂进行复合,不仅能大幅度提高封装材料的折射率,还能提高材料的热稳定性和机械性能。综述近年来无机纳米粒掺杂硅树脂或环氧树脂的制备方法,分析评估其工艺与封装材料性能,并介绍了国内外LED封装用有机无机复合材料的研究进展。
The traditional LED packaging materials are mainly divided into epoxy resins and silicone resins.They have some disadvantages such as easy yellowing,easy aging,poor weather ability and low refractive index,etc.Some metal oxides nanoparticles (titanium dioxide,silica,zinc oxide,zirconium dioxide,etc.) with high refractive index and ultraviolet absorption properties are compounded with epoxy resins or silicone resins,which can not only substantially increase the refractive index of the materials,but also improve their thermal stability and mechanical properties as an inorganic filler.The relevant reports in recent years on the preparation methods of inorganic nanoparticles doped silicon or epoxy resins were reviewed.The process and properties of the materials were analyzed and evaluated.The research progress of organic and inorganic composites for LED packaging at home and abroad was also reviewed.
[1] Novak B M.Hybrid nanocomposite materials-between inorganic glasses and organic polymers[J].Advanced Materials,2010,5(6):422-433.
[2] 崔婷,唐绍裘.有机/无机纳米复合材料的制备[J].中国陶瓷,2006,42(1):56-57.
[3] López-Manchado M,Herrero B,Arroyo M.Organoclay-natural rubber nanocomposites synthesized by mechanical and solution mixing methods[J].Polymer International,2010,53(11):1766-1772.
[4] Pötschke P,Bhattacharyya A R,Janke A.Carbon nanotube-filled polycarbonate composites produced by melt mixing and their use in blends with polyethylene[J].Carbon,2004,42(5):965-969.
[5] 韩英.铈基纳米氧化物改性有机硅封装胶的研究[D].大连:大连理工大学化工学院,2013.
[6] 万冰华,费敬银,高文娟.纳米粒子表面改性研究[J].材料开发与应用,2010,25(4):98-104.
[7] Sun Y,Gu A,Liang G,et al.Preparation and properties of transparent zinc oxide/silicone nanocomposites for the packaging of high-power light-emitting diodes[J].Journal of Applied Polymer Science,2011,121(4):2018-2028.
[8] 刘伟区,韩敏健,王政芳,等.一种具高折射率与力学强度LED封装材料用改性纳米二氧化硅及制备方法:中国,103408798A[P].2013-11-27.
[9] 中科院广州化学有限公司.有机氟改性环氧/纳米SiO2LED复合封装材料及其制法:中国,104530645A[P].2015-04-22.
[11] Chau J L,Lin Y M,Li A K,et al.Transparent high refractive index nanocomposite thin films[J].Materials Letters,2007,61(14):2908-2910.
[12] Chen C W,Yang X S,Chiang A S.An aqueous process for the production of fully dispersible t-ZrO2nanocrystals[J].Journal of the Taiwan Institute of Chemical Engineers,2009,40(3):296-301.
[13] Chung P T,Yang C T,Wang S H,et al.ZrO2/epoxy nanocomposite for LED encapsulation[J].Materials Chemistry & Physics,2012,136(2/3):868-876.
[14] Chung P T,Chiou S H,Tseng C Y,et al.Preparation and evaluation of a zirconia/oligosiloxane nanocomposite for LED encapsulation[J].ACS Applied Materials & Interfaces,2016,8(15):9986-9993.
[15] Tao P,Li Y,Siegel R W,et al.Transparent dispensible high-refractive index ZrO2/epoxy nanocomposites for LED encapsulation[J].Journal of Applied Polymer Science,2014,130(5):3785-3793.
[16] Huang P,Shi H Q,Xiao H M,et al.High performance surface-modified TiO2/silicone nanocomposite[J].Scientific Reports,2017,7(1):5951.
[17] Liu Y,Lin Z,Zhao X,et al.High refractive index and transparent nanocomposites as encapsulant for high brightness LED packaging[J].IEEE Transactions on Components Packaging & Manufacturing Technology,2014,4(7):1125-1130.
[18] Liao W H,Hsiao S T,Wu Y F,et al.Effect of silane-functionalized TiO2 on the optical properties and moisture barrier of silicone resin nanocomposites[J].RSC Advances,2014,4(73):38614-38622.
[19] 黄敏,黄佐华,林晓丹,等.溶胶-凝胶法制备高折射GPTMS/TiO2-ZrO2材料[J].电子与封装,2011,11(8):32-36.
[20] Chen W C,Lee S J,Lee L H,et al.Synthesis and characterization of trialkoxysilane-capped poly(methyl methacrylate)-titania hybrid optical thin films[J].Journal of Materials Chemistry,1999,9(12):2999-3003.
[21] Wang Y,Zhang D,Shi L,et al.Novel transparent ternary nanocomposite films of trialkoxysilane-capped poly(methyl methacrylate)/zirconia/titania with incorporating networks[J].Materials Chemistry & Physics,2008,110(2):463-470.
[22] Lei I A,Lai D F,Don T M,et al.Silicone hybrid materials useful for the encapsulation of light-emitting diodes[J].Materials Chemistry & Physics,2014,144(1/2):41-48.
[23] Ding K H,Wang G L,Zhang M.Preparation and optical properties of transparent epoxy composites containing ZnO nanoparticles[J].Journal of Applied Polymer Science,2012,126(2):734-739.
[24] Zhao X,Li L,Li Z,et al.Stretchable and transparent silicone/zinc oxide nanocomposite for advanced LED packaging[C].Orlando:Electronic Components and Technology Conference,IEEE,2014.
[25] 陈中华,张广发.原位聚合制备有机-无机复合材料的研究进展[J].材料导报,2008,22(s1):153-155.
[26] Hu Y,Zhou S,Wu L.Surface mechanical properties of transparent poly(methyl methacrylate)/zirconia nanocomposites prepared by in situ bulk polymerization[J].Polymer,2009,50(15):3609-3616.
[27] Ochi M,Nii D,Harada M.Preparation of epoxy/zirconia hybrid materials via in situ polymerization using zirconium alkoxide coordinated with acid anhydride[J].Materials Chemistry & Physics,2011,129(1/2):424-432.
[28] Wu K H,Cheng K F,Yang C C,et al.Thermal and optical properties of epoxy/siloxane hybrimer based on sol-gel-derived phenyl-siloxane[J].Open Journal of Composite Materials,2015,5(3):49-59.
[29] Liu Y,Luan X,Feng Y,et al.Self-adhesive epoxy modified silicone materials for light emitting diode encapsulation[J].Polymers for Advanced Technologies,2017,28(11):1473-1479.
[30] Tong L,Feng Y K,Sun X J,et al.High refractive index adamantine-based silicone resins for theencapsulation of light-emitting diodes[J].Polymers for Advanced Technologies,2018,29(8):2245-2252.
[31] Yong H K,Lim Y W,Lee D,et al.A highly adhesive siloxane LED encapsulant optimized for high thermal stability and optical efficiency[J].Journal of Materials Chemistry C,2016,4(46):10791-10796.
[32] Zhao M,Feng Y K,Li G,et al.Synthesis of an adhesion-enhancing polysiloxane containing epoxy groups for addition-cure silicone light emitting diodes encapsulant[J].Polymers for Advanced Technologies,2015,25(9):927-933.
[33] Zhao M,Feng Y,Li Y,et al.Fabrication of siloxane hybrid material with high adhesion and high refractive index for light emitting diodes (LEDs) encapsulation[J].Journal of Macromolecular Science(Part A-Chemistry),2014,51(8):653-658.
[34] Zhan X,Xing Q,Liu H,et al.A facile method for fabrication of titanium-doped hybrid materials with high refractive index[J].RSC Advances,2014,4(27):13909-13918.
[35] Yong H K,Bae J Y,Jin J,et al.Sol-Gel derived transparent zirconium-phenyl siloxane hybrid for robust high refractive index LED encapsulant[J].ACS Applied Materials & Interfaces,2014,6(5):3115-3221.
基金资助
国家自然科学基金(51673145,31370969);天津市科技计划项目(16ZXCLGX00010,16YFZCGX00280)