CN107771354A - 工程聚合物类电子材料 - Google Patents
工程聚合物类电子材料 Download PDFInfo
- Publication number
- CN107771354A CN107771354A CN201680018886.XA CN201680018886A CN107771354A CN 107771354 A CN107771354 A CN 107771354A CN 201680018886 A CN201680018886 A CN 201680018886A CN 107771354 A CN107771354 A CN 107771354A
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- graphene
- alkene
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
- B23K35/3613—Polymers, e.g. resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
- B23K1/0016—Brazing of electronic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
- B23K1/203—Fluxing, i.e. applying flux onto surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
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Abstract
一种用于电子组装方法的组合物,该组合物包含分散在有机介质中的填料,其中:该有机介质包含聚合物;该填料包含石墨烯、官能化石墨烯、氧化石墨烯、多面体低聚倍半硅氧烷、石墨、二维材料、氧化铝、氧化锌、氮化铝、氮化硼、银、纳米纤维、碳纤维、金刚石、碳纳米管、二氧化硅和金属涂布的颗粒中的一种或多种,并且,基于组合物的总重量,该组合物包含0.001~40重量%的填料。
Description
技术领域
本发明涉及一种用于制造电子元件和器件以及电子组装和封装的聚合物组合物。
背景技术
表面贴装技术(SMT)是一种用于生产电子电路的方法,其中元件被直接贴装或放置在印刷电路板(PCB)的表面上。如此制造的电子器件被称为表面贴装器件(SMD)。在电子工业中,SMT已经在很大程度上取代了将导线***电路板孔中来安装元件的通孔技术施工方法。两种技术都可以在同一块板上用于不适合表面贴装的元件,如大型变压器和散热功率半导体。SMT元件通常小于其通孔对应物,因为它具有较小的引线或根本没有引线。它可以具有各种类型的短销或引线、平面触点、焊球(BGA)矩阵或元件主体上的端子。
在要放置元件的地方,印刷电路板通常具有平坦的、通常镀有锡铅、银或金的铜焊盘,没有孔,称为焊盘。首先通过丝网印刷工艺将焊膏——一种助焊剂和微小焊料颗粒的粘性混合物——用不锈钢或镍模板施加到所有焊盘上。它也可以通过类似于喷墨打印机的喷墨打印机制来施加。在上膏之后,板随后进入拾取放置机,在该处它们被放置在传送带上。待放置在板上的元件通常以缠绕在卷轴或塑料管上的纸/塑料带形式递送到生产线。一些大型集成电路被递送到无静电托盘中。数控拾取放置机从带、管或托盘中取出零件,并将其放在PCB上。然后将板输送到回流焊炉中。它们首先进入预热区域,其中板和所有元件的温度逐渐均匀地升高。然后,板进入到温度高到足以熔化焊膏中的焊料颗粒的区域,将元件引线接合到电路板上的焊盘。熔融焊料的表面张力有助于将元件保持在适当位置,并且如果正确设计焊盘几何形状,表面张力将自动对准其焊盘上的元件。有一些回流焊料的技术。一种是使用红外灯;这被称为红外回流。另一种是使用热气对流。另一种正在变得流行的技术是具有高沸点的特殊碳氟化合物液体,其使用称为气相回流的方法。
电子器件中的焊料接头易受热机械疲劳的影响。这是因为通过焊料接头连接的工件通常具有不同的热膨胀系数(CTE)。此外,期望电子器件中的焊料接头表现出高的机械强度和高的抗掉落冲击能力。因此,这种接头通常被称为“底部填充物(underfills)”的材料封装。底部填充物通常是有机聚合物和无机填料(例如二氧化硅)的复合材料。这种底部填充物的预固化和后固化性能在材料光谱的最末端。预固化的底部填充物预期在最小间隙(通常小于25微米)下像水一样自由流动。固化的底部填充物预计将呈现岩石般坚硬的无机样性质,同时牢固地粘合到无机硅和有机基底上。增加填料的量可以改善底部填充物的机械性能。然而,这也会增加组合物的粘度。因此,需要在未固化状态下显示出较低粘度以及在固化状态下显示出改进的机械性能的底部填充材料(或底部填充材料的替代物)。此外,常规的底部填充材料不能使用标准的SMT回流工艺和谱线(profiles)来固化。因此,当使用底部填充物时,需要单独不同的处理步骤,从而增加了工艺的复杂性。
在LED芯片结构中,倒装芯片是增长最快的芯片结构,从横向结构和垂直结构LED都获得市场份额。倒装芯片的LED市场渗透率预计将从2014年的<5%增长到2020年的>20%。此外,倒装芯片CSP(即2级)组装也有显著增长,其中CSP封装具有与倒装芯片LED晶粒(die)基本相同的表面区域(footprint),从而降低了封装成本和表面区域,以实现相同或增强的功率和流明输出。
对于封装中的倒装芯片LED组件,有着使用基于SAC的焊膏来形成倒装芯片LED晶粒与封装衬底之间的倒装芯片互连的增加趋势。银环氧树脂或烧结金属材料也可用于在倒装芯片LED晶粒与封装衬底之间产生倒装芯片互连。
封装衬底(1级连接)上的倒装芯片LED组件以及CSP LED(2级)组件面临重大问题。在回流之后,如果使用不干净的焊膏,焊剂残留物通常留在基板周围以及阳极与阴极焊盘之间。如果回流没有适当进行,这可能导致在操作中,特别是在存在湿气的情况下,阳极和阴极焊料互连之间的潜在短路,这是由于通过互连的高电流以及施加在阳极和阴极之间的偏压。如果使用银环氧树脂或烧结金属材料来制造倒装芯片LED晶粒与封装衬底之间的倒装芯片互连或CSP LED封装和板,则可能会发生同样的问题。如果LED封装者或组装者考虑使用通常可用的底部填充材料,则需要单独的固化步骤来固化底部填充物(独立于回流焊步骤),导致低生产量和增加的成本。此外,使用焊膏的倒装芯片LED或CSP LED组件可能导致晶粒或封装浮动和倾斜。
发明内容
本发明寻求解决与现有技术相关的至少一些问题,或至少提供商业上可接受的替代解决方案。
本发明提供一种用于电子组装方法的组合物,该组合物包含分散在有机介质中的填料,其中:
该有机介质包含聚合物;
该填料包含石墨烯、官能化石墨烯、氧化石墨烯、多面体低聚倍半硅氧烷、石墨、二维材料、氧化铝、氧化锌、氮化铝、氮化硼、银、纳米纤维、碳纤维、金刚石、碳纳米管、二氧化硅和金属涂布的颗粒中的一种或多种,并且
基于组合物的总重量,该组合物包含0.001~40重量%的填料。
除非明确指出相反,否则本文定义的每个方面或实施方案可以与任何其他(多个)方面或(多个)实施方案组合。特别地,指示为优选或有利的任何特征可以与指示为优选或有利的任何其它特征组合。
本文使用的术语“石墨烯”包括单一原子平面的石墨(称为单层石墨烯),或几层石墨烯,或多层石墨烯或石墨烯微片(platelet)。
本文使用的术语“二维材料”包括在两个维度上具有比第三维度成比例地更大尺寸的材料。这种材料的例子是氮化硼、二硫化钼、二硒化钨、过渡金属的二硫族化物、镍HITP(2,3,6,7,10,11-六亚氨基三亚苯基)、锗烷(germanane)、石墨烷(graphane)、磷烯(phosphorene)、锡烯(stanene)、硅烯(silicine)、硼烯(borophene)、石墨炔(graphyne)、氟化石墨烯和二维合成金属如钯和铑。
本文使用的术语“氧化石墨烯”包括当氧化石墨分散在碱性介质中时获得的分子片。氧化石墨烯包括在其表面上具有含氧官能团的石墨烯片。
本文所用的术语“官能化石墨烯”包括在其表面上具有一个或多个官能团的石墨烯。
本文所用的术语“多面体低聚倍半硅氧烷”(POSS)包括具有经验式RSiO1.5的纳米结构,其中R可以是氢原子或有机官能团,例如烷基、亚烷基、丙烯酸酯、羟基或环氧化物。POSS可以被称为由二氧化硅笼芯以及连接到笼的角部的其它有机官能团组成的二氧化硅纳米颗粒。POSS为由无机硅和氧的内核和有机成分的外层组成的有机和无机物质,其可以是极性或非极性的。倍半硅氧烷结构可以是随机的、梯子型、笼型或部分笼型。POSS纳米结构的直径范围为1~3nm,因此可以认为是最小的现有二氧化硅颗粒。多面体低聚倍半硅氧烷的分子结构如下:
本文所用的术语“表面贴装技术”(SMT)包括一种用于制造电子电路的方法,其中元件被直接贴装或放置在印刷电路板(PCB)的表面上。
本文使用的术语“表面贴装工艺”是指使用SMT的工艺。
本文所用的术语“可固化”是指其所指的物质(即组合物或聚合物)能够经历由例如电子束、激光、UV、热或化学添加剂引起的聚合物链的交联。
本文使用的术语“电子组装方法”是指制造电子器件或元件的方法,其还包括通常称为SMT的工艺。
本文使用的术语“聚合物”通常是指热塑性或热固性聚合物。
发明人已经发现,与不含填料的组合物相比,该组合物显示出改善的机械强度和/或耐热疲劳性和/或阻隔特性。特别地,所述组合物可以显示一种或多种改进的机械和热性能,例如抗掉落冲击性、抗弯曲性、耐热冲击性、CTE、屈服强度、断裂韧性、模量、耐热循环性等。
当组合物用于制造电子器件的方法中时,这些特征是特别有利的,因为这种些性可以转移到器件上。例如,可以使用组合物代替常规的底部填充材料来加强(通过包封)倒装芯片与有机电路板之间形成的焊料接头,这可能由于倒装芯片和有机印刷电路板的不同热膨胀而经历热机械应变。
该组合物可在焊膏中用作焊剂。在加热两个工件之间的焊膏时,会形成焊料接头,并且组合物会固化并包封焊料接头,从而加强焊料接头。或者,组合物可以用于例如导电粘合剂中,其中期望最终粘合剂的粘结显示出高的机械强度和/或耐热疲劳性。
有利的机械和/或热疲劳性能可通过组合物以100%环高(collar height)或填角高度(fillet height)或低于100%环高或填角高度来显示。
聚合物的流动动力学和/或固化动力学可以有利地防止未回流的焊膏的脱落和可能的运输,并且可以有利地实现更高的Tg和有利的热机械性质。
聚合物可以是可固化聚合物。组合物可以使用标准的SMT线进行加工,并且可以使用标准的SMT回流工艺和谱线来固化或凝固。这是特别有利的,因为与传统的底部填充材料不同,在电子组装方法中不需要单独不同的处理步骤。因此,与使用常规底部填充材料的电子组装方法相比,使用本发明组合物的电子组装方法被简化。该组合物可以通过例如热、激光或UV固化。组合物通常使用热固化,例如在回流炉中与焊膏一起固化。使用的温度通常为200~300℃,例如约245℃作为峰值温度。
该组合物在室温下稳定,易于加工并与焊膏残留物相容。组合物通常表现出膏状或凝胶状稠度。
该组合物可用于低压和高压成型、过成型(over-molding)、灌封和包封。该组合物可以与印刷的和/或沉积的焊膏一起使用。
该组合物具有诸如例如用于制造***的标准电子组件的应用,例如电话、计算机、相机、平板电脑和显示器;半导体封装;和类似***的组件,例如光伏模块和电池。
电子组装方法的例子包括例如晶粒连接、倒装芯片、板上封装、球栅阵列(BGA)、表面贴装技术(SMT)和LED制造工艺。电子组装方法优选是表面贴装技术(SMT)工艺。
填料分散在有机介质中。换句话说,有机介质形成连续相,而填料构成了不连续相。
填料可以是例如球、棒、微片(platelet)和/或片状物(flake)的形式。填料可以具有1nm~25μm,例如1~100nm,或1~10nm,或0.1~25μm,或1~5μm(例如通过SEM测定)的最大尺寸(或当填料为球形时的最大直径)。
组合物可以是薄膜的形式,例如B阶膜(即组合物部分固化的膜)。薄膜可以预先施加到工件上,并且可使用冲压,例如热冲压围绕工件而形成。
当用于倒装芯片LED连接方法或倒装芯片CSP(芯片级封装)LED连接方法时,该组合物特别有利。
当在衬底(1级)的倒装芯片组装期间应用时,组合物可以加强晶粒连接互连(焊料、烧结金属或甚至AuSn),从而提高封装的可靠性。这种加强导致组装之后记录的晶粒切断值的改善。组合物也可以在倒装芯片或CSP封装板上组装(2级)时应用。该组合物增强了板上封装的焊料互连,这导致元件切断值的增加。
在传统的倒装芯片连接方法中,使用底部填充材料来抵抗来自衬底与晶粒之间的热膨胀系数(CTE)失配的应力来加强倒装芯片组件。然而,这种方法存在许多缺点。首先,焊料接头中的应力(来自晶粒与衬底之间的CTE失配)在组件冷却后立即产生,而后焊料接头回流。在回流之后,底部填充材料的应用仅仅增强了接头避免因回流应力和组件在可靠性测试和寿命期间的温度偏移期间可能遇到的附加应力导致的失效。这种方法不会阻止在回流步骤期间CTE失配应力的发展。其次,在晶粒连接(或封装连接)之后施用底部填充物。其通常围绕晶粒-衬底组件的边缘分配。然后,底部填充物通过毛细管力在焊料接头周围移动以填充晶粒(或封装)与衬底之间的空间。不幸的是,当焊点高度(stand-off height)(晶粒与衬底之间的高度)为约50微米或更小时,来自毛细管作用的驱动力不足以填充晶粒与衬底之间的间隙。最后,一旦填充了底部填充物,将组件放入烘箱中以固化底部填充物,以获得所需的用于加强焊料接头的性能。这种额外的底部填充物固化步骤可能需要额外的1~2小时。
使用本发明的组合物可以克服传统底部填充方法的缺点。由于组合物通常在制造焊料互连之前施用,因此对晶粒(或封装)与衬底之间的焊点高度没有限制。具有25微米(或更低)的焊点高度的组件可以轻松加强。其次,由于组合物在焊料回流步骤(通常在回流炉中)固化,所以不需要额外的固化步骤。这增加了组装生产量并降低了该方法的成本。最后,由于组合物已被固化并锁定在凸点之间或周围的组件中,随后组件在回流之后冷却下来,其首先抵消了在焊料接头周围的CTE失配应力的产生。
在形成焊料接头之后,本发明的组合物可以在焊料接头之间或周围固化成低应力热凝物(thermoset)。在随后的回流期间,它将晶粒保持下来,并有效地将焊料锁定出形状。这使得具有焊料接头的组件能够耐受多次回流,而不会改变接合线厚度或封装倾斜或浮动。该组合物能够在需要许多回流而没有与焊料接头重熔相关的屈服损失的应用中使用传统的基于SAC的合金用于晶粒连接。
随着倒装芯片和CSP LED越来越小,P/N焊盘之间的间隙越来越小直至70~100微米。在常规方法中,在回流后如果焊膏残留物未适当地清洁,则在高温、湿度和反向偏压的可靠性测试期间导致电流泄漏。有时使用小于50微米的焊点高度进行清洁是不实际的。在回流之前将本发明的组合物施用于焊盘之间可以消除反向偏压测试期间的电流泄漏。因此,可能会给LED制造商带来显著的可靠性改进,而无需任何额外的清洁步骤。
随着倒装芯片和CSP LED越来越小,由于晶粒(或封装)倾斜,回流时浮动和旋转,因此使用常规焊膏的组装变得具有挑战性。当焊料在回流期间熔化时,其表面张力提升(并移动)晶粒(或封装),并且这些元件的小重量不足以将晶粒固定在其位置。本发明的组合物在回流之前施用在焊盘上时,可以提供抵消来自熔融焊料的侧表面张力的粘性。该组合物可以确保该反作用力正好确保将元件固定到板上,而不会损害焊料润湿晶粒并制成接头的能力。
该组合物包含基于组合物总重量为0.001~40重量%的填料。优选地,该组合物包含基于组合物总重量为0.01~10重量%的填料,更优选基于组合物总重量为0.02~5重量%的填料,甚至更优选基于组合物总重量为0.03~4重量%的填料,甚至更优选基于组合物总重量为0.04~1重量%的填料,甚至更优选基于组合物总重量为0.04~0.8重量%的填料,甚至更优选基于组合物总重量为0.05~0.4重量%的填料。在替代的优选实施方案中,该组合物包含基于组合物总重量为30~40重量%的填料,优选33~37重量%的填料。这种组合物表现出特别有利的流变性能。在另一个优选实施方案中,该组合物包含基于组合物总重量为0.1~4重量%的填料。该组合物可以包含基于组合物总重量为至少0.01重量%的填料,优选至少0.02重量%的填料,更优选至少0.03重量%的填料,甚至更优选至少0.04重量%,甚至更优选至少0.05重量%的填料。该组合物可以包含基于组合物总重量为20重量%或更少的填料,优选10重量%或更少的填料,更优选5重量%或更少的填料,甚至更优选4重量%或更少的填料,甚至更优选1重量%或更少的填料,甚至更优选0.8重量%或更少的填料,甚至更优选0.4重量%或更少的填料。填料的存在提供改进的机械和/或热疲劳性能。较高含量的填料会增加预固化的组合物的粘度。因此,具有低粘度的组合物可以更容易地施用到具有小尺寸特征的电子器件和元件上。这对于表面贴装技术制造方法尤为重要。具有高粘度的组合物可能更适合用于电子组装应用的应用,例如印刷、针转印和无流动粘合剂组合物。
固化前组合物的典型粘度为12~20Pa.s,更典型地在室温下约为16Pa.s。通过使用平行板几何形状,通过流变仪在10/s的恒定剪切速率下测量粘度。未固化的组合物的粘度可能足够低以使组合物能够喷雾或喷射或分配。这可以使得组合物可用于保形涂布以及加强整个板或组件。
组合物优选为可固化组合物,并且/或者聚合物优选为可固化聚合物。
填料优选包含以下的一种或多种:石墨烯、氧化石墨烯、官能化石墨烯、多面体低聚倍半硅氧烷和二维材料。一旦聚合物组合物固化,这样的物质可以为组合物提供特别增强的机械和/或耐热疲劳性质。特别地,与不含填料或常规填料的组合物相比,这样的物质可以提供具有增加的抗掉落冲击性和冲击弯曲强度的固化的组合物。含有这种物质的组合物可用作用于粘结具有CTE失配的工件的低热膨胀系数(CTE)粘合剂。固化的组合物还可以表现出高硬度以用于耐刮擦应用。
为了提供这种性质,仅需要非常低水平的填料,例如石墨烯和官能化石墨烯。因此,含有这种低水平物质的组合物会表现出有利的机械和/或热疲劳特性,而未固化的组合物会表现出特别低的粘度。使用诸如石墨烯和/或官能化石墨烯的填料可以改善所得组合物的热稳定性,并且还可以增加组合物的玻璃化转变温度(Tg),从而增加组合物的工作极限。
使用氧化石墨烯可以减少能够渗透组合物的水分含量,从而提高密封封装/组件的密封性。石墨烯和/或官能化石墨烯的使用可用于去除/结合组合物中的游离离子,从而改善最终产品的电性能。
石墨烯可以是单层、几层或多层石墨烯(MLG)。使用这种石墨烯可以增强组合物的电导率和/或导热率。
多面体低聚倍半硅氧烷(POSS)作为结构单元,因为POSS大分子单体的独特结构,这是一种明确定义的聚集体,无机二氧化硅样核心被八个有机角基团包围。其被认为是氧化后形成二氧化硅的最小硅酸盐前体。在本发明中,POSS有利地结合到组合物中以克服传统的不能以分子水平分散在材料中的复合材料的缺点。当填料包含POSS时,固化的组合物显示出提高的抗掉落冲击强度和冲击弯曲强度。使用POSS可以提高材料的导热率。
填料优选包含:多面体低聚倍半硅氧烷;和石墨烯和官能化石墨烯(例如氧化石墨烯)中的一种或多种。这可以提供具有特别低粘度的组合物,以及具有特别有利的机械性能的组合物。与其中仅使用等量的仅POSS或石墨烯/官能化石墨烯的组合物相比,粘度通常较低,并且机械性能通常更有利。换句话说,POSS与石墨烯和/或官能化石墨烯(例如氧化石墨烯)的组合令人惊奇地提供了协同效应。使用POSS可以减少实现所需性能所需的石墨烯/官能化石墨烯的量。
官能化石墨烯可有助于控制石墨烯的表面性质,以及在固体和溶液形式下使脱落的石墨烯层稳定延长的时间。使用官能化石墨烯与常规石墨烯相比的优点包括例如改进的与聚合物基质的混合和分散以及相互作用,防止聚合物基质中的石墨烯层的重新排列和改善的水分和气体不渗透性。
填料优选包含官能化石墨烯,其中官能化石墨烯包含氧化石墨烯。使用氧化石墨烯可以为组合物提供特别有利的机械性能。
当填料包含官能化石墨烯时,官能化石墨烯可以用有机和/或无机基团,优选胺基、硅烷和/或钛酸酯基、环氧基、酯基和多面体低聚倍半硅氧烷中的一种或多种来官能化。使用这种官能化的石墨烯可以为组合物提供特别有利的机械性能。官能化石墨烯可以有利地用橡胶分子和/或焊剂官能团来官能化。官能化石墨烯可以用金属纳米颗粒(即具有1~500nm的最长尺寸的颗粒),例如包含银、铜、金和合金例如AgCu或AgAu中的一种或多种的纳米颗粒进行官能化。使用这种金属纳米颗粒可以增强组合物的电导率和/或导热率。官能化石墨烯可以用金属氧化物或类金属氧化物的纳米颗粒进行官能化。金属氧化物可以是例如碱土金属、过渡金属或后过渡金属的氧化物。使用这种氧化物可以增强组合物的水分和气体不渗透性和/或增强组合物的导热率。
石墨烯可以有利地用氟、例如氟化石墨烯、氟化氧化石墨烯或具有附着到基础sp2平面上的氟化有机分子的氧化石墨烯进行官能化。这种填料可以使组合物对水分和气体都是基本不渗透的。
填料优选包括官能化石墨烯,该官能化石墨烯包含用多面体低聚倍半硅氧烷官能化的石墨烯(和/或或氧化石墨烯)。使用这种填料可以使组合物具有特别低的粘度,并且固化的组合物具有特别有利的机械性能。
填料可以包含氮化硼。与石墨烯和其他石墨材料不同,氮化硼的使用不会改变组合物的颜色。
聚合物优选包含环氧树脂,更优选环氧树脂包含不同官能度的环氧树脂和/或通常具有高分子量的固体双官能(例如三-或四-)环氧树脂。这种树脂可能表现出高水平的交联,从而导致固化的组合物表现出特别有利的机械性能。固体环氧树脂的使用增加了组合物的固体含量。用于本发明的合适的聚合物包括例如双酚A的二缩水甘油醚、双酚F的二缩水甘油醚、对氨基苯酚的三缩水甘油醚、二氨基二苯基砜的四缩水甘油醚、二氨基二苯基甲烷的四缩水甘油醚、二氨基二苯基醚的四缩水甘油醚和三(2,3-环氧丙基)异氰脲酸酯。聚合物可以是热塑性的,例如聚烯烃热塑性塑料或丙烯酸类热塑性塑料。当组合物为薄膜形式时,热塑性塑料的使用可能是有利的。
在优选实施方案中:
填料包含氧化石墨烯,并且
组合物包含0.1~4重量%的氧化石墨烯。
这样的组合物可以为组合物提供特别有利的机械性能。
在该优选实施方案中,有机介质优选包含:
30~40重量%的沸点为至少280℃的有机溶剂;
5~10重量%的不同官能度的环氧树脂;
15~30重量%的固体双官能环氧树脂,优选具有高分子量;
3~10重量%的包含二羧酸的活化剂;
2~8重量%的包含取代的芳族胺的催化剂;
1~5重量%的包含膦基盐的催化剂;
1~5重量%的液体酸酐型硬化剂;
0.1~4重量%的液体型应力调节剂;和
0.1~3重量%的粘合促进剂。
优选地,有机介质还包含有机溶剂,优选具有至少280℃的沸点。使用这种溶剂可有助于保持组合物的低粘度,并可有助于为最终产品提供稳定性。本发明中使用的沸点为至少280℃的合适的有机溶剂包括例如丁基卡必醇、二甘醇单己基醚和二醇醚。
优选地,有机介质还包含活化剂,更优选地,其中活化剂包含二羧酸。活化剂可以除去施加组合物的表面上的任何被氧化的层(例如电子电路板焊盘),并且可以增加焊膏与组合物的润湿性能。
优选地,有机介质还包含催化剂。使用催化剂可以帮助可固化组合物进行交联。催化剂优选包含取代的芳族胺和/或膦基盐。这种催化剂表现出低反应性。因此,它们可以有助于提高组合物的室温稳定性,因为它们通常仅在升高的温度下进行交联。
优选地,有机介质还包含硬化剂,更优选地,其中该硬化剂包含液体酸酐型硬化剂。这种硬化剂的存在可以通过仅在升高的温度下与环氧树脂进行交联反应来帮助提高组合物的室温稳定性。
优选地,有机介质还包含应力调节剂,优选液体型应力调节剂。使用应力调节剂可用于降低环氧树脂的脆性。
有机介质优选还包含粘合促进剂。这可以用于增加组合物与焊料接头之间的结合。
在优选实施方案中,有机介质包含:
30~40重量%的沸点为至少280℃的有机溶剂;和/或
5~10重量%的不同官能度环氧树脂;和/或
15~30重量%的固体双官能环氧树脂,优选具有高分子量;和/或
3~10重量%的包含二羧酸的活化剂;和/或
2~8重量%的包含取代的芳族胺的催化剂;和/或
1~5重量%的包含膦基盐的催化剂;和/或
1~5重量%的液体酸酐型固化剂;和/或
0.1~4重量%的液体型应力调节剂;和/或
0.1~3重量%的粘合促进剂。
在特别优选的实施方案中,有机介质包括:
约39重量%的沸点为至少280℃的有机溶剂;
约8重量%的不同官能度环氧树脂;
约29重量%的固体双官能环氧树脂,优选具有高分子量;
约9重量%的包含二羧酸的活化剂;
约3重量%的包含取代的芳族胺的催化剂;
约4重量%的包含膦基盐的催化剂;
约2重量%的液体酸酐型固化剂;
约4重量%的液体型应力调节剂;和
约2重量%的粘合促进剂。
组合物可以使用以下中的一种或多种方式施加到装置上:薄膜转印、针转印、组分浸渍、糊剂分配、印刷、喷涂、浇铸和刮涂。浸渍高度和浸渍时间可以改变,以达到高达100%的不同环高。
组合物在高温下(例如,170~280℃)能通过使用毛细管添加剂而流动。
通过改变浸渍高度和/或浸渍时间,组合物的环高可以变化高达100%。例如,环高可以从大约30%变化到高达100%。用于实现不同环高的合适浸渍高度和浸渍时间的例子列于下表1中:
表1:实现各种环高的浸渍条件。
在优选的实施方案中,填料包含石墨烯、氧化石墨烯、石墨片、石墨烯微片、还原的氧化石墨烯、二维材料或它们中两种以上的组合。这可以提供具有高机械强度和/或高耐热疲劳性的组合物。
组合物可以包含彩色颜料。这可以赋予固化的组合物所需的颜色。
另一方面,本发明提供了包含本文所述的可固化组合物的底部填充物。
底部填充物可以是例如边缘填充物、角落填充物或边缘粘合剂。在优选的方面,底部填充物可以在一个或多个步骤中施用,优选其中该一个或多个步骤包括浸渍和/或分配。
另一方面,本发明提供了包含本文所述的组合物的焊剂。
另一方面,本发明提供了包含本文所述的可固化组合物的单面或双面增强材料(DSR)材料。
另一方面,本发明提供了包含本文所述的组合物的包封物。
另一方面,本发明提供了包含本文所述的组合物的阻隔材料。
另一方面,本发明提供了一种电子材料,包含:
焊料合金;和
本文所述的组合物。
焊料合金可以以例如焊球、粉末、棒或线的形式提供。可固化组合物可以至少部分地涂布该焊球、棒、线或粉末颗粒。合金可以是例如无铅合金,例如SAC合金。
另一方面,本发明提供了一种导电粘合剂,包含:
导电颗粒;和
本文所述的组合物。
导电颗粒通常包含金属(例如银、铜和金中的一种或多种)、合金(例如,诸如SAC合金的无铅合金)和/或涂布有金属和/或合金的颗粒。导电颗粒可以是板、棒和/或球体的形式。导电颗粒通常具有1nm~40μm,例如1~500nm量级的最长尺寸(如果为球形则指直径)。导电颗粒分散在聚合物组合物中。
另一方面,本发明提供了一种非导电粘合剂,包含:
非导电颗粒;和
本文所述的组合物。
非导电颗粒通常包括金属或类金属氧化物、碳化物、氮化物(例如氧化铝、氮化硼、碳化硅、氮化铝)。金属可以是例如碱土金属、过渡金属或后过渡金属。
非导电颗粒可以是板、棒和/或球体的形式。非导电颗粒通常具有1nm~40μm,例如1~500nm量级的最长尺寸(如果为球形则指直径)。非导电颗粒分散在聚合物组合物中
另一方面,本发明提供一种焊膏,包含:
焊料颗粒;和
本文所述的组合物。
焊料颗粒通常包含金属(例如银、铜和金中的一种或多种)、合金(例如,诸如SAC型合金的无铅合金)和/或涂布有金属和/或合金的颗粒。焊料颗粒可以是板、棒和/或球体的形式。焊料颗粒通常具有1nm~40μm,例如1~500nm的最长尺寸(如果为球形则指直径)。焊料颗粒分散在聚合物组合物中。
本发明的组合物、焊剂、电子材料、导电粘合剂、焊膏、底部填充物、增强(DSR)材料、包封物和/或阻隔材料可以包含无铅、零卤素免清洗焊膏,例如LUMETTM P39
另一方面,本发明提供了至少部分地用组合物包封的焊料接头,该组合物是本文所述的可固化聚合物组合物。焊料接头通常基本上用固化的聚合物组合物包封,更典型地完全用固化的聚合物组合物包封。
另一方面,本发明提供了一种形成焊料接头的方法,该方法包括:
在待接合的两个或更多个工件之间提供本文所述的焊膏;并且
加热该焊膏以形成焊料接头。
通常将焊膏加热到170~280℃的温度。
另一方面,本发明提供了一种制造本文所述的组合物的方法,该方法包括:
提供包含聚合物的有机介质;并且
将填料分散在有机介质中,
其中:
该填料包含石墨烯、二维材料、官能化石墨烯、氧化石墨烯、多面体低聚倍半硅氧烷、石墨、氧化铝、氧化锌、氮化铝、氮化硼、银、纳米纤维、碳纤维、金刚石、碳纳米管、二氧化硅和金属涂布的颗粒中的一种或多种,并且
基于组合物的总重量,该组合物包含0.001~40重量%的填料。
在使填料分散在其中之前,有机介质的组分通常在最高达150℃,更通常为50~120℃,甚至更通常约90℃的温度下混合,以形成均匀的混合物。然后通常将有机介质研磨,例如使用三辊研磨机。在确认FOG<10微米后,通常停止研磨过程。将填料分散在有机介质中可以包括机械共混。
另一方面,本发明提供了本文所述的组合物在选自以下的方法中的用途:电子组装方法、表面贴装技术(SMT)方法、晶粒连接方法、回流焊接方法、电路板制造方法和太阳能电池制造方法。
另一方面,本发明提供了本文所述的组合物在电子封装、倒装芯片、LED组件和气密密封中的用途。
另一方面,本发明提供了石墨烯和/或官能化石墨烯的用途以增加组合物的流动能力。
另一方面,本发明提供了一种组合物,其包含分散在有机介质中的填料,该有机介质包含可固化聚合物,其中:
该填料包含石墨烯、二维材料、官能化石墨烯、氧化石墨烯、多面体低聚倍半硅氧烷、石墨、氧化铝、氧化锌、氮化铝、氮化硼、银、纳米纤维、碳纤维、金刚石、碳纳米管、二氧化硅和金属涂布的颗粒中的一种或多种,并且
基于组合物的总重量,该组合物包含0.001~40重量%的填料。
组合物可以例如用作焊剂,或用于导电粘合剂,或用作底部填充材料,或用于制造电子器件,或用于焊料接头的增强,或用作单面或双面增强材料(DSR),或用作包封物,或用作粘合剂,或用作阻隔材料(例如,防止进入例如焊料接头的材料)。
另一方面,本发明提供了一种用于表面贴装工艺的组合物,该组合物包含分散在有机介质中的填料,其中:
该有机介质包含聚合物;
该填料包含石墨烯、官能化石墨烯、氧化石墨烯、多面体低聚倍半硅氧烷、石墨、二维材料、氧化铝、氧化锌、氮化铝、氮化硼、银、纳米纤维、碳纤维、金刚石、碳纳米管、二氧化硅和金属涂布的颗粒中的一种或多种,并且
基于聚合物组合物的总重量,该组合物包含0.001~40重量%的填料。
另一方面,本发明提供填料的用途,用于提供一种组合物,该组合物的粘度为12~20Pa.s,并具有改善的机械强度、改善的耐热疲劳性和改善的阻隔特性中的一种或多种,该填料包含石墨烯、官能化石墨烯、氧化石墨烯、多面体低聚倍半硅氧烷、石墨、二维材料、氧化铝、氧化锌、氮化铝、氮化硼、银、纳米纤维、碳纤维、金刚石、碳纳米管、二氧化硅和金属涂布的颗粒中的一种或多种。
另一方面,本发明提供了本文所述的组合物在电子组装应用例如印刷、针转印和无流动粘合剂组合物中的用途,该组合物具有大于20Pa.s的粘度。如上所述,这样的应用受益于较高的粘度。较高的粘度可以通过例如增加填料的水平来提供。
另一方面,本发明提供了填料的用途,用于控制组合物的热膨胀系数(CTE),填料包含石墨烯、官能化石墨烯、氧化石墨烯、多面体低聚倍半硅氧烷、石墨、二维材料、氧化铝、氧化锌、氮化铝、氮化硼、银、纳米纤维、碳纤维、金刚石、碳纳米管、二氧化硅和金属涂布的颗粒中的一种或多种。控制CTE可增强组合物的热疲劳寿命。
附图说明
现在将参考以下非限制性附图描述本发明,其中:
图1是显示本发明多种组合物的冲击弯曲试验结果的图。
图2是显示本发明多种组合物的抗掉落冲击试验结果的图。
具体实施方式
现在将结合以下非限制性实施例描述本发明。
实施例1
使用改进的Hummers方法由天然片状石墨制备石墨氧化物。边搅拌边将市售的石墨粉末和10g硝酸钠添加到500mL的浓(98%)硫酸中,然后保持在冰浴中。然后在15分钟后缓慢加入10g石墨粉(300目),并搅拌10分钟以得到均匀的混合物。非常缓慢地小心地向其中加入67g高锰酸钾,同时在冰浴中搅拌整个反应混合物。30分钟后,将整个反应混合物转移到保持在约40℃的热板上,然后搅拌约2.5小时,直到反应混合物的颜色变红。然后将其在室温下冷却约30分钟。然后在搅拌下非常缓慢地将500mL去离子水加入到其中。搅拌10~15分钟后,向反应混合物中加入1L温热去离子水,然后加入100ml 30体积%的过氧化氢,搅拌约5分钟。通过离心分离最终产物,离心在4000rpm下进行,持续8分钟时间,并在相同的离心条件下用去离子水彻底严格地洗涤。该步骤重复几乎约20次,以便丢弃所有未反应的化学品、副产物并使pH接近约7。然后用丙酮洗涤3~4次,并保持在设定在65℃的烘箱中以完全干燥。然后获得固体形式的石墨氧化物粉末并准备进一步使用。
然后制备有机介质,其包含:
a)具有高沸点的有机溶剂39重量%
b)不同官能度的环氧树脂8重量%
c)具有高分子量和双官能的固体环氧树脂29%
d)二羧酸作为活化剂9重量%
e)取代的芳族胺作为催化剂3重量%
f)膦基盐作为催化剂4重量%
g)液体酸酐型硬化剂/催化剂2重量%
h)液体型应力调节剂4重量%
i)粘合促进剂2重量%
将所有上述物质(a)~(i)以所需的比例混合并加热至90℃直到获得均匀的混合物。然后对混合物进行三辊研磨。在确认FOG<10微米后,停止研磨过程。然后使用机械共混将石墨氧化物粉末分散在有机介质中,以提供包含0.1~4重量%氧化石墨烯的可固化组合物。
热循环测试:
将组合物与焊料颗粒混合以形成焊膏。还使用上述组合物,但不存在填料来制备焊膏(比较例)。焊膏用于使用SMT方法在印刷电路板上形成焊料接头。
使用以下步骤进行热循环测试:
设备:
·Espec热循环室(Air-Air)TSA-101S。
·Agilent 34980A数据记录仪。
测试条件:
·根据IPC 9701-A标准进行测试。
·-40℃(10min)至+125℃(10min),1000次循环。
失效定义:
·根据IPC 9701-A:标称电阻增加20%(最多5次连续读数扫描之内)。
失效分析:
·240、500、750和1000次循环之后的截面,以及显微镜分析。
结果列于下表2。
表2:热循环结果。
可以看出,与不含填料的组合物相比,本发明的组合物表现出改善的耐热循环特性。
冲击弯曲试验:
冲击弯曲试验采用以下程序进行:
测试条件:
·将测试车辆连接到数据记录仪。
·使用固定板偏转为1.2mm。
·测试直到第一次失效。
·元件上的冲击点:在元件的角落。
·冲击销形状:圆形
测试车辆:
·表面处理:EniG。
·50×50mm,厚度0.8mm。
·元件:BGA84。
失效定义:
·增加200Ω的电阻。
结果示于图1。与其中组合物不含任何填料的比较例(左侧和中部)相比,实施例1(右手侧)的组合物显示出更大的抗冲击弯曲性。
抗掉落冲击试验:
使用以下步骤进行抗掉落冲击试验:
设备
·Lansmont HC18冲击试验机。
·Lansmont TP4。
·AnaTech事件检测器。
测试条件
·遵循JEDEC标准JESD22-B111“手持电子产品元件的板级掉落测试方法”。
·使用服务条件B(1500Gs,0.5msec脉冲,半正弦曲线)。
发现实施例1的抗掉落冲击强度大于不含填料或常规填料的比较例。抗掉落冲击试验的结果示于图2(菱形:本发明,方形/圆形:参考例)。
前面的详细描述已经通过解释和说明的方式提供,并不意图限制所附权利要求的范围。本文所示的当前优选实施方案中的许多变化对于本领域普通技术人员将是显而易见的,并且保持在所附权利要求及其等同方案的范围内。
Claims (45)
1.一种用于电子组装方法的组合物,该组合物包含分散在有机介质中的填料,其中:
该有机介质包含聚合物;
该填料包含石墨烯、官能化石墨烯、氧化石墨烯、多面体低聚倍半硅氧烷、石墨、二维材料、氧化铝、氧化锌、氮化铝、氮化硼、银、纳米纤维、碳纤维、金刚石、碳纳米管、二氧化硅和金属涂布的颗粒中的一种或多种,并且
基于组合物的总重量,该组合物包含0.001~40重量%的填料。
2.权利要求1的组合物,其包含基于组合物总重量为0.01~10重量%的填料,优选基于组合物总重量为0.02~5重量%的填料,更优选基于组合物总重量为0.03~4重量%的填料,甚至更优选基于组合物总重量为0.04~1重量%的填料,甚至更优选基于组合物总重量为0.04~0.8重量%的填料。
3.权利要求1的组合物,其包含基于组合物总重量为0.05~0.4重量%的填料。
4.前述权利要求中任一项的组合物,其中该组合物是可固化组合物,和/或该聚合物是可固化聚合物。
5.前述权利要求中任一项的组合物,其中该填料包含:石墨烯、氧化石墨烯、官能化石墨烯和多面体低聚倍半硅氧烷中的一种或多种。
6.前述权利要求中任一项的组合物,其中该填料包含:
多面体低聚倍半硅氧烷;和
石墨烯和官能化石墨烯中的一种或多种。
7.前述权利要求中任一项的组合物,其中该填料包含官能化石墨烯,并且该官能化石墨烯包含氧化石墨烯。
8.前述权利要求中任一项的组合物,其中该填料包含官能化石墨烯,该官能化石墨烯用有机和/或无机基团,优选胺基、硅烷和/或钛酸酯基、环氧基团、酯基和多面体低聚倍半硅氧烷中的一种或多种来官能化。
9.前述权利要求中任一项的组合物,其中该填料包含官能化石墨烯,该官能化石墨烯包含用多面体低聚倍半硅氧烷官能化的石墨烯。
10.前述权利要求中任一项的组合物,其中该聚合物包含环氧树脂,优选其中该环氧树脂包含不同官能度的环氧树脂和/或高分子量的固体双官能环氧树脂。
11.权利要求1~5中任一项的组合物,其中:
该填料包含氧化石墨烯,并且
该组合物包含0.1~4重量%的氧化石墨烯。
12.权利要求11的组合物,其中该有机介质包含:
30~40重量%的沸点为至少280℃的有机溶剂;
5~10重量%的不同官能度的环氧树脂;
15~30重量%的固体双官能环氧树脂,优选具有高分子量;
3~10重量%的包含二羧酸的活化剂;
2~8重量%的包含取代的芳族胺的催化剂;
1~5重量%的包含膦基盐的催化剂;
1~5重量%的液体酸酐型硬化剂;
0.1~4重量%的液体型应力调节剂;和
0.1~3重量%的粘合促进剂。
13.前述权利要求中任一项的组合物,其中该有机介质还包含一种或多种有机溶剂。
14.权利要求13的聚合物组合物,其中该有机溶剂的沸点为至少280℃。
15.前述权利要求中任一项的组合物,其中该有机介质还包含活化剂,优选其中该活化剂包含二羧酸。
16.前述权利要求中任一项的组合物,其中该有机介质还包含催化剂,优选其中该催化剂包含取代的芳族胺和/或膦基盐。
17.前述权利要求中任一项的组合物,其中该有机介质还包含硬化剂,优选其中该硬化剂包含液体酸酐型硬化剂。
18.前述权利要求中任一项的组合物,其中该有机介质还包含应力调节剂,优选液体型应力调节剂。
19.前述权利要求中任一项的组合物,其中该有机介质还包含粘合促进剂。
20.前述权利要求中任一项的组合物,其中该有机介质包含:
30~40重量%的沸点为至少280℃的有机溶剂;和/或
5~10重量%的不同官能度的环氧树脂;和/或
15~30重量%的高分子量的固体双官能环氧树脂;和/或
3~10重量%的包含二羧酸的活化剂;和/或
2~8重量%的包含取代的芳族胺的催化剂;和/或
1~5重量%的包含膦基盐的催化剂;和/或
1~5重量%的液体酸酐型硬化剂;和/或
0.1~4重量%的液体型应力调节剂;和/或
0.1~3重量%的粘合促进剂。
21.前述权利要求中任一项的组合物,其中该有机介质包含:
约39重量%的沸点为至少280℃的有机溶剂;
约8重量%的不同官能度的环氧树脂;
约29重量%的具有高分子量的固体双官能环氧树脂;
约9重量%的包含二羧酸的活化剂;
约3重量%的包含取代的芳族胺的催化剂;
约4重量%的包含膦基盐的催化剂;
约2重量%的液体酸酐型固化剂;
约4重量%的液体型应力调节剂;和
约2重量%的粘合促进剂。
22.前述权利要求中任一项的组合物,其中该组合物可通过使用以下中的一种或多种施加到装置上:薄膜转移、针转印、组分浸渍、分配、喷射、印刷、喷涂、浇铸和刮涂。
23.前述权利要求中任一项的组合物,其中该组合物在高温下能通过使用毛细管添加剂而流动。
24.前述权利要求中任一项的组合物,其中固化的组合物的环高可通过改变浸渍高度和/或浸渍时间而变化至多100%。
25.前述权利要求中任一项的组合物,其中该填料包含石墨烯、氧化石墨烯、石墨片、石墨烯微片、还原的氧化石墨烯或它们中两种以上的组合。
26.前述权利要求中任一项的组合物,其中该组合物包含彩色颜料。
27.前述权利要求中任一项的组合物,其为薄膜的形式。
28.一种底部填充物,其包含前述权利要求中任一项的组合物。
29.权利要求28的底部填充物,其中该底部填充物可以在一个或多个步骤中施用,优选其中该一个或多个步骤包括浸渍和/或分配。
30.一种焊剂,其包含权利要求1~27中任一项的组合物。
31.一种单面或双面增强材料,其包含权利要求1~27中任一项的组合物。
32.一种电子材料,包含:
焊料合金;和
权利要求1~27中任一项的组合物。
33.一种导电粘合剂,包含:
导电颗粒;和
权利要求1~27中任一项的组合物。
34.一种非导电粘合剂,包含:
非导电颗粒;和
权利要求1~27中任一项的组合物。
35.一种焊膏,包含:
焊料颗粒;和
权利要求1~27中任一项的组合物。
36.一旦固化的权利要求1~27中任一项所述的组合物。
37.一种至少部分地用固化的聚合物组合物包封的焊料接头,该聚合物组合物是根据权利要求1~27中任一项的聚合物组合物。
38.一种形成焊料接头的方法,该方法包括:
在待接合的两个或更多个工件之间提供权利要求35的焊膏;并且
加热该焊膏以形成焊料接头。
39.权利要求38的方法,其中,在待接合的两个或更多个工件之间提供焊膏的步骤包括将该焊膏施加到至少一个该工件,其中该膏为薄膜的形式,并且其中加热该焊膏包括热冲压。
40.一种制造权利要求1~27中任一项的组合物的方法,该方法包括:
提供包含聚合物的有机介质;并且
将填料分散在该有机介质中,
其中:
该填料包含石墨烯、氧化石墨烯、二维材料、官能化石墨烯、氧化石墨烯、多面体低聚倍半硅氧烷、石墨、氧化铝、氧化锌、氮化铝、氮化硼、银、纳米纤维、碳纤维、金刚石、碳纳米管、二氧化硅和金属涂布的颗粒中的一种或多种,并且
基于组合物的总重量,该组合物包含0.001~40重量%的填料。
41.权利要求1~27中任一项的组合物在选自以下的方法中的用途:电子组装方法、晶粒连接方法,回流焊接方法,电路板制造方法和太阳能电池制造方法。
42.权利要求1~27中任一项的组合物在电子封装、倒装芯片、LED组件和气密密封中的用途。
43.填料的用途,用于提供一种组合物,该组合物的粘度为12~20Pa.s并具有改善的机械强度、改善的耐热疲劳性和改善的阻隔特性中的一种或多种,该填料包含石墨烯、氧化石墨烯、官能化石墨烯、多面体低聚倍半硅氧烷、石墨、二维材料、氧化铝、氧化锌、氮化铝、氮化硼、银、纳米纤维、碳纤维、金刚石、碳纳米管、二氧化硅和金属涂布的颗粒中的一种或多种。
44.权利要求1~27中任一项的组合物在电子组装应用例如印刷、针转印和无流动粘合剂组合物中的用途,该组合物的粘度大于20Pa.s。
45.填料的用途,用于控制可固化组合物的热膨胀系数(CTE),该填料包含石墨烯、氧化石墨烯、官能化石墨烯、多面体低聚倍半硅氧烷、石墨、二维材料、氧化铝、氧化锌、氮化铝、氮化硼、银、纳米纤维、碳纤维、金刚石、碳纳米管、二氧化硅和金属涂布的颗粒中的一种或多种。
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