CN1552078A - 界面材料及其生产方法和用途 - Google Patents
界面材料及其生产方法和用途 Download PDFInfo
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Abstract
描述了包含一种树脂混合物和至少一种焊接材料的界面材料。树脂材料可以包含任何合适的树脂材料,但是优选的是该树脂材料是硅氧烷基的,包含诸如乙烯基硅氧烷、乙烯基Q树脂、氢化物官能的硅氧烷和铂-乙烯基硅氧烷的一种或多种化合物。焊接材料可以包含任何合适的焊接材料,如铟、银、铜、铝及其合金、镀银的铜和镀银的铝,但是优选的是焊接材料包含铟或铟基化合物和/或合金。该界面材料或聚合物焊料具有在高功率半导体器件中提高热耗散的能力并且保持稳定的热性能。该界面材料可以通过把组分混合在一起产生一种浆料来配制,所述浆料可以通过分配方法施加到任何特定表面上并在室温或较高温度固化。它还可以配制成高顺应性、固化的粘性弹性体薄膜或板,用于它可以应用的其它界面用途,如散热器或任何其它界面场合中。
Description
该部分继续申请要求1999年3月9日提交的美国实用新型申请系列号09/398989和2001年1月30日提交的09/774466的优先权,它们整体并入本文作为参考。
背景技术
电子元件用于数量不断增长的消费品和工业电子产品中。这些消费品和工业产品中的一些实例是电视、个人计算机、互联网服务器、蜂窝电话、传呼机、掌上型管理器、便携式收音机、汽车用立体声收音机、遥控器。随着对这些消费品和工业电子产品的需求增大,对于消费者和商业上来说,对这些产品还存在更小、功能更强和更便携的要求。
由于这些产品尺寸减小,构成这些产品的元件也必须变小。需要尺寸减小或按比例减小的元件中的一些实例是印刷电路和线路板、电阻、线路、键盘、触摸垫(touch pad)和芯片封装。
所以,正在分解和研究元件以确定是否有更好的建造材料和方法,可以使它们按比例缩小,以适应更小电子元件的要求。在叠层元件中,一个目标似乎是减少层数,同时增大层布线密度。但是,这一工作可能是困难的,因为为了运行该器件,一般应当存在若干层和若干层的元件。
因此,对于以下存在不断增长的需要:a)设计和生产满足消费者技术要求的叠层材料并使器件尺寸和层数最小化;和b)开发生产希望的叠层材料和包含这些叠层材料的元件的可靠方法。
发明内容
根据本发明,提供包含树脂混合物和至少一种焊接材料的界面材料。该树脂材料可以包含任何合适的树脂材料,但是优选的是树脂材料是硅氧烷基的,包含一种或多种诸如乙烯基硅氧烷、乙烯基Q树脂、氢化物官能的硅氧烷和铂-乙烯基硅氧烷的一种或多种化合物。焊接材料可以包含任何合适的焊接材料,如铟、银、铜、铝、锡、铋、镓及其合金、镀银的铜、镀银的铝,但是优选焊接材料包含铟或铟基化合物。
界面材料,或聚合物焊料,具有提高高功率半导体器件中的热耗散能力并保持稳定的热性能。其在热-机械应力或其中使用它的电子器件的功率循环波动过程中不产生界面层离或分相。
通过把组分混合在一起产生一种浆料可以配制该界面材料,所述浆料可以通过分布方法施加到任何特定表面并在室温或升高的温度下固化。它也可以配制成高顺应性、固化的、粘性的弹性薄膜或板,用于其它界面用途,在这些用途中,例如它可以预先施加到散热器上或预先施加在任何其它界面场合中。
另外,引入抗氧化剂以减少聚合物基树脂的氧化、引入润湿性增强剂以促进表面润湿、引入固化促进剂如可以在室温固化的固化促进剂、引入减粘剂以提高分散性和引入交联助剂也可能是有用的。有时还希望包含基本为球形颗粒的填料以限制界面材料在界面用途中的可压缩性,即限制或控制材料的厚度或层的厚度。
还发现,焊料体系的热导率,如填料与以上讨论的组合树脂的组合的热导率,可以通过与其它填料一起向体系中引入碳微纤维来改善。
发明详述
可以生产包含树脂混合物和至少一种焊接材料的界面材料。树脂材料可以包含任何合适的树脂材料,但是优选的是树脂材料是硅氧烷基的,其包含一种或多种化合物,如乙烯基硅氧烷、乙烯基Q树脂、氢化物官能的硅氧烷和铂-乙烯基硅氧烷。焊接材料可以包含任何合适的焊接材料或金属,如铟、银、铜、铝、锡、铋、镓及其合金、镀银的铜、镀银的铝。但是优选的是焊接材料包含铟或铟基化合物。
本文所用的术语“金属”是指在元素周期表d-区和f-区的那些元素,以及具有类金属性质的那些元素如硅和锗。本文所用的短语“d-区”是指具有填充元素原子核周围的3d、4d、5d和6d轨道的电子的那些元素。本文所用的“f-区”是指具有填充元素原子核周围的4f和5f轨道的电子的那些元素。包括镧系和锕系元素。优选的金属包括铟、银、铜、铝、锡、铋、镓及其合金、镀银的铜、以及镀银的铝。术语“金属”还包括合金、金属/金属复合材料、金属陶瓷复合材料、金属聚合物复合材料以及其它金属复合材料。本文所用的术语“化合物”是指具有恒定组成的物质,其通过化学过程可以分解成元素。
本文所述的界面材料具有直接涉及应用和元件工程的若干优点,例如:a)该界面材料/聚合物焊接材料可以用来填充2毫米或更小数量级的非常小的间隙,b)该界面材料/聚合物焊接材料在那些非常小的间隙以及较大的间隙中可以高效率地散热,与大多数传统焊接材料不同,和c)该界面材料/聚合物焊接材料可以容易地引入到微小元件、用于卫星的元件以及小电子元件中。
含树脂的界面材料和焊接材料,特别是包含硅氧烷树脂的那些,还可以有适当的热填料,这些界面材料和焊接材料可以具有小于0.5cm2℃/w的热容。与热油脂不同,在IC器件中热循环或流动循环后,材料的热性能不会降低,因为液体硅氧烷树脂在热活化时能交联形成软凝胶。
包含树脂如硅氧烷树脂的界面材料和焊接材料不会像热油脂那样在使用中产生“挤出”,并且在热循环过程中不会显示出界面层离。该新材料可以作为通过分配方法施加的可分配液体浆,然后任选固化。也可以作为高顺应性、固化的、和可能可交联的弹性体薄膜或板,用于在界面表面上的预涂敷如散热器。有利的是,使用热导率大于约2,优选至少约4w/m℃的填料。最佳的是,希望有热导率不小于10w/m℃的填料。该界面材料提高高功率半导体器件的热耗散。所述浆料可以配制成功能性硅氧烷树脂与热填料的混合物。
乙烯基Q树脂是-种活化固化专用的硅橡胶,其具有以下基础聚合物结构:
乙烯基Q树脂还是用于加成固化弹性体的透明增强添加剂。含有至少20%Q-树脂的乙烯基Q树脂分散体的实例是VQM-135(DMS-V41基)、VQM-146(DMS-V46基)和VQX-221(在二甲苯基中,50%)。
本文所用的术语“顺应性”包括材料在室温屈服并且可变形的性质,与在室温下为固体和不能屈服相反。本文所用的术语“可交联的”是指还没有交联的那些材料或化合物。
作为实例,期望的硅氧烷树脂混合物可以形成如下:
组分 | 重量% | 备注/功能 |
乙烯基硅树脂乙烯基Q树脂氢化物官能的硅氧烷铂-乙烯基硅氧烷 | 75(70-90的范围)20(0-25的范围)5(3-10的范围)20-200ppm | 乙烯基封端的硅氧烷增强添加剂交联剂催化剂 |
该树脂混合物可以在室温或较高的温度下固化,形成顺应性弹性体。该反应在催化剂例如铂的配合物或镍的配合物存在下,利用氢化物官能的硅氧烷,通过乙烯基官能的硅氧烷的氢甲硅烷基化(加成固化)进行。优选的铂催化剂是SIP6830.0、SIP6832.0和铂-乙烯基硅氧烷。
乙烯基硅氧烷的期望实例包括乙烯基封端的聚二甲基硅氧烷,分子量为约10000-50000。氢化物官能的硅氧烷的期望实例包括甲基氢硅氧烷-二甲基硅氧烷共聚物,其分子量为约500-5000。物理性质可以从非常低交联密度的非常软凝胶材料到高交联密度的硬弹性体网络变化。
分散在树脂混合物中的焊接材料期望是用于希望用途的任何合适的焊接材料。优选的焊接材料是铟锡(InSn)复合物、铟银(InAg)复合物和合金、铟基化合物、锡银铜复合物(SnAgCu)、锡铋复合物和合金(SnBi)、和铝基化合物和合金。特别优选的焊接材料是包含铟的那些材料。
热填料颗粒也可以分散在树脂混合物中。如果热填料颗粒存在于树脂混合物中,则那些填料颗粒应当有利地具有高热导率。合适的填料材料包括银、铜、铝、及其合金;氮化硼、铝球、氮化铝、镀银的铜、镀银的铝、碳纤维、和涂敷金属的碳纤维、金属合金、导电聚合物和其它复合材料。氮化硼和银或氮化硼与银/铜的组合还提供热导率的提高。氮化硼含量至少20重量%,铝球含量至少70重量%,银含量至少约60重量%是特别有用的。
具有特别效果的是一种包含颗粒形式碳纤维的填料,其称为“蒸气生长碳纤维”(VGCF),如得自Applied Sciences,Inc.,Cedarville,Ohio。VGCF或“碳微纤维”是通过热处理高度石墨化型的(热导率=1900w/m℃。添加约0.5重量%碳微纤维提供明显增大的热导率。这样的纤维可以变化的长度和直径获得;即1mm到数十厘米长和0.1-100微米以上的直径。一种有用的形式是直径不大于约1微米,长度约50-100微米,并且具有比直径大于5微米的其它普通碳纤维大约2或3倍的热导率。
在以上讨论的树脂体系如硅氧烷树脂混合物中难以混入大量VGCF。当碳微纤维,例如约1微米或更小,加入到该树脂中时,它们不能良好混合,因为为了有利地改善热导率,相对于树脂量,需要混入大量纤维。但是,我们发现,可以向具有较大量其它填料的树脂***中混入较大量的碳微纤维。当与其它填料一起加入时,与单独加入到聚合物中相比,可以加入到树脂中的碳微纤维量更大,因此在改善热界面材料热导率方面,提供了更大的益处。希望的是,如果在树脂体系中存在碳微纤维,则碳微纤维与聚合物的比例按重量计在0.05-0.50范围内。
引入基本球形的颗粒以便使堆积密度最大化也可能是有利的。另外,基本球形的形状等在压制过程中还提供厚度的某种控制。填料颗粒的分散可以通过加入官能性有机金属偶联剂或润湿剂来促进,如有机硅烷、有机钛酸酯、有机锆等。有机金属偶联剂,特别是有机钛酸酯还可以用来促进焊接材料在施加过程中的熔化。树脂材料中填料所用的典型颗粒尺寸可以在约1-20微米范围内,最大约100微米。
为了举例说明本发明,通过混合以下实施例A-J中所述的组分,制备了一些实施例。所示实施例包括一种或多种任选的添加剂,例如润湿性增强剂。这些添加剂的量可以变化,但是它们通常以以下合适的量有用地存在(重量%):填料最多为总量的95%(填料加树脂);润湿性增强剂0.1-5%(按总量计);和增粘剂0.01-1%(按总量计)。应当注意,添加至少约0.5%碳纤维明显提高热导率。这些实施例还表示期望的混合物的各种物理化学测量
聚合物焊料/界面材料实施例
实施例 | A | B | C | D | E | F | G | H | I | J |
硅氧烷混合物 | 16 | 5 | 8 | 5 | 5 | 5 | 5 | 5 | 4 | 4 |
有机钛酸酯 | 4 | 3 | 0 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
InSn | 92 | 92 | 82 | |||||||
InAg | 63 | |||||||||
In | 63 | |||||||||
SnAgCu | 92 | 82 | ||||||||
SnBi | 83 | 68 | ||||||||
Al | 80 | 10 | 29 | 29 | 10 | 10 | 25 | |||
模量(MPa) | 25 | 15 | 25 | 15 | 20 | 23 | 25 | 30 | 20 | 25 |
粘度(泊) | 1400 | 500 | 1200 | 450 | 1500 | 1600 | 500 | 750 | 650 | 1700 |
热阻(cm2℃/w) | 0.3 | 0.15 | 0.4 | 0.14 | 0.14 | 0.12 | 0.16 | 0.17 | 0.18 | 0.10 |
热导率(w/m℃) | 2.5 | 5.1 | 2.0 | 5.5 | 5.8 | 6.2 | 5.2 | 5.0 | 5.0 | 6.0 |
组分有机钛酸酯、InSn、InAg、In、SnAgCu、SnBi和Al按重量百分比或wt%给出。
实施例A不含焊接材料并且用于参考的目的。有机钛酸酯作用不仅是润湿增强剂,而且作为助熔剂,以促进焊接材料在施加过程中的熔化。
这些实施例的焊料组成如下:InSn=52%In(按重量计)和48%Sn(按重量计),熔点为118℃;InAg=97%In(按重量计)和3%Ag(按重量计),熔点为143℃;In=100%铟(按重量计),熔点为157℃;SnAgCu=94.5%锡(按重量计)、3.5%银(按重量计)和2%铜(按重量计),熔点为217℃;SnBi=60%锡(按重量计)和40%铋(按重量计),熔点为170℃。应当理解,包含不同组分百分比的其它组成也可以从本文所含的主题中推出。
处理温度如下:实施例A-E=150℃、30分钟;实施例F、J和I=200℃、30秒;实施例G和H=240℃、30秒和150℃、30分钟。
因此,已经公开了界面材料和聚合物焊接材料的具体实施方案和应用。但是,应当理解,对于本领域技术人员来说,除了已经描述的以外,许多变化是可能的而不离开本文的创造性概念。所以,本发明的主题不受限制,除非在所述权利要求的实质范围以外。而且,在解释说明书和权利要求时,所有的术语应当以与上下文一致的最宽可能方式解释。特别地,术语“包含”和“包括”应当解释为以非排除性方式指元素、组分或步骤,表明所提及的元素、组分或步骤可以存在或利用或与未明确提及的其它元素、组分或步骤组合。
Claims (33)
1.一种用于电子器件的界面材料,其包含至少一种树脂材料和至少一种焊料材料,
2.权利要求1的界面材料,其中所述界面材料还包含至少一种润湿增强剂。
3.权利要求1的界面材料,其中所述至少一种树脂材料包含硅氧烷树脂。
4.权利要求3的界面材料,其中所述硅氧烷树脂包括乙烯基封端的硅氧烷、增强添加剂、交联剂和催化剂。
5.权利要求4的界面材料,其中所述乙烯基封端的硅氧烷是乙烯基硅氧烷。
6.权利要求4的界面材料,其中所述增强添加剂是乙烯基Q树脂。
7.权利要求4的界面材料,其中所述交联剂包含氢化物官能的硅氧烷。
8.权利要求4的界面材料,其中催化剂包含铂配合物。
9.权利要求8的界面材料,其中铂配合物是铂-乙烯基硅氧烷化合物。
10.权利要求2的界面材料,其中润湿增强剂包含有机钛酸酯化合物。
11.权利要求1的界面材料,其中所述至少一种焊接材料包含铟基合金或化合物。
12.权利要求11的界面材料,其中所述铟基合金或化合物包含InSn、InAg或In。
13.权利要求1的界面材料,其中所述至少一种焊接材料包含锡基合金或化合物。
14.权利要求13的界面材料,其中所述锡基合金或化合物包含SnAgCu或SnBi。
15.权利要求1的界面材料,其中所述界面材料包含铝或铝基合金或化合物之一。
16.权利要求1的界面材料,其还包含填料材料。
17.权利要求16的界面材料,其中填料材料包含碳微纤维。
18.权利要求1的界面材料,其中所述材料的粘度大于450泊。
19.权利要求1的界面材料,其中所述材料的热阻小于0.3cm2℃/w。
20.一种界面的可分配浆料,其包含至少一种树脂材料和至少一种焊接材料。
21.权利要求20的可分配浆料,其中该浆料还包含至少一种润湿增强剂。
22.权利要求20的可分配浆料,其中该浆料用作电子器件的界面材料。
23.一种界面板或薄膜,其包含至少一种硅氧烷树脂材料和至少一种焊接材料。
24.权利要求23的板或薄膜,其中所述板或薄膜还包含至少一种润湿增强剂。
25.权利要求23的板或薄膜,其中所述板或薄膜用作电子器件的界面材料。
26.一种制造界面材料的方法,包括组合至少一种硅氧烷树脂材料和至少一种焊接材料。
27.权利要求26的方法,其还包含向界面材料中加入至少一种润湿增强剂。
28.权利要求26的方法,其还包含配制该界面材料的可分配浆料。
29.权利要求27的方法,其还包含配制界面材料的可分配浆料。
30.权利要求26的方法,其还包含把所述界面材料模制成板或薄膜,所述板或薄膜可以切割成一定的尺寸并用作电子器件中元件之间的界面。
31.一种提高权利要求1界面材料热导率的方法,包括向其中引入碳微纤维和至少一种导热填料。
32.权利要求31的方法,其中所述碳微纤维的用量至少约0.5重量%,或碳微纤维与聚合物的比例至少为0.05。
33.权利要求31的方法,其还包括引入包含银、铜、铝、及其合金;氮化硼、氮化铝、镀银的铜、镀银的铝、和碳纤维;及其混合物的填料。
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- 2002-05-07 CN CNB028082214A patent/CN100338690C/zh not_active Expired - Fee Related
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CN101945757A (zh) * | 2007-12-21 | 2011-01-12 | 霍尼韦尔国际公司 | 用硅酮基局部处理的低重量和高耐用性柔体装甲复合物 |
CN101807531A (zh) * | 2010-03-30 | 2010-08-18 | 上海凯虹电子有限公司 | 一种超薄芯片的封装方法以及封装体 |
US9693481B2 (en) | 2013-06-25 | 2017-06-27 | Henkel IP & Holding GmbH | Thermally conductive dielectric interface |
CN104254229B (zh) * | 2013-06-25 | 2017-08-08 | 汉高知识产权控股有限责任公司 | 热传导介电界面 |
CN106574151A (zh) * | 2014-08-29 | 2017-04-19 | 古河电气工业株式会社 | 导电性粘接膜 |
CN106574151B (zh) * | 2014-08-29 | 2020-06-09 | 古河电气工业株式会社 | 导电性粘接膜 |
CN104577704A (zh) * | 2015-01-29 | 2015-04-29 | 山东浪潮华光光电子股份有限公司 | 纤维网增强高纯铟复合焊料及其应用方法 |
CN106964919A (zh) * | 2017-06-04 | 2017-07-21 | 曾双 | 一种无卤助焊剂制备方法 |
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DE60216749T2 (de) | 2007-10-04 |
DE60216749D1 (de) | 2007-01-25 |
EP1763040A1 (en) | 2007-03-14 |
US20010038093A1 (en) | 2001-11-08 |
US20080044670A1 (en) | 2008-02-21 |
CN100338690C (zh) | 2007-09-19 |
JP2004533705A (ja) | 2004-11-04 |
EP1386327A1 (en) | 2004-02-04 |
TWI276116B (en) | 2007-03-11 |
ATE348392T1 (de) | 2007-01-15 |
CN101088697A (zh) | 2007-12-19 |
US20040185273A1 (en) | 2004-09-23 |
CA2442034A1 (en) | 2002-11-14 |
EP1386327A4 (en) | 2005-02-02 |
WO2002091395A1 (en) | 2002-11-14 |
EP1386327B1 (en) | 2006-12-13 |
KR20040030561A (ko) | 2004-04-09 |
US7172711B2 (en) | 2007-02-06 |
US6706219B2 (en) | 2004-03-16 |
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