CN103003936A - 使用脉冲的uv光源来涂覆晶片背面的方法 - Google Patents

使用脉冲的uv光源来涂覆晶片背面的方法 Download PDF

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Publication number
CN103003936A
CN103003936A CN2011800281230A CN201180028123A CN103003936A CN 103003936 A CN103003936 A CN 103003936A CN 2011800281230 A CN2011800281230 A CN 2011800281230A CN 201180028123 A CN201180028123 A CN 201180028123A CN 103003936 A CN103003936 A CN 103003936A
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China
Prior art keywords
coating composition
acrylate
resin
coating
semiconductor wafer
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CN2011800281230A
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English (en)
Inventor
J·加萨
D·N·潘
J·利昂
S·哈杰拉
孔勝前
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Henkel American Intellectual Property LLC
Henkel IP and Holding GmbH
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Henkel Corp
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Publication of CN103003936A publication Critical patent/CN103003936A/zh
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Abstract

一种用涂料组合物涂覆半导体晶片的方法，其包含用脉冲的UV光固化该涂料，由此防止在回流过程中发生分层。在一种具体的实施方案中，该涂料组合物包含环氧和丙烯酸酯树脂二者。该环氧树脂可以热固化；该丙烯酸酯树脂是通过UV辐射来固化的。

Description

使用脉冲的UV光源来涂覆晶片背面的方法
交叉引用的相关申请
本申请要求2010年6月8日申请的美国临时专利申请系列No.61/352584的权益，其内容在此通过引用并入。
发明领域
本发明涉及一种涂覆半导体晶片的非活动侧(inactive side)(背面)的方法，其中涂料是使用脉冲的UV光源来固化的。
发明背景
半导体封装近期的发展已经通过以堆叠的排列(两个或者更多个半导体芯片彼此叠置)使用更薄的芯片(die)而导致了该封装的小型化。芯片的这种堆叠能够以小的占地面积(footprint)来提高功能性，允许降低整个半导体封装的尺寸。典型的，将粘合剂糊或者膜用于两个半导体芯片之间，来确保在制作操作过程中例如在线连接、模制和焊接回流过程中、以及在最终使用过程中封装的完整性。但是，芯片的细薄使得它们在制作过程的焊接回流步骤过程中易于翘曲和分层。因此需要一种晶片背面涂料，其能够经历回流加工，并且保持它的完整性和功能性。
发明内容
本发明是一种涂覆薄的半导体晶片的方法，其中使用脉冲的UV光来固化该涂层，和因此能够经历随后的回流方法而不分层。该方法包含：(A)提供涂料组合物；(B)将该涂料组合物置于晶片背面上；和(C)通过将所述的组合物曝露于足以固化该涂料组合物的量的脉冲的UV光，来对该涂料组合物进行B-阶段固化。在一种实施方案中，足以固化该涂料组合物的量典型地是0.1-10J/cm2。
在另外一种实施方案中，本发明是一种涂覆有固化的涂料组合物的半导体晶片，其中该涂料组合物是通过脉冲的UV光来B-阶段固化的。
具体实施方式
作为此处使用的，术语“B-阶段”(和它的变体)用于表示通过辐射来加工涂料，以使得该材料部分固化成发粘的或者更硬化的状态。如果该材料是可流动的粘合剂，B-阶段将在没有完全固化的情况下提供极低的流动性，这样在所述的粘合剂用于将制品彼此连接之后，可以进行另外的固化。
作为此处使用的，术语“固化剂”用于表示任何这样的材料或者材料的组合，其引起、促进或者加速了组合物的固化，并且其包括但不限于促进剂、催化剂、引发剂和硬化剂。
该半导体晶片可以是具体的工业应用所需的任何类型、尺寸或者厚度。在具体的实施方案中，该半导体晶片是薄的。目前，在半导体工业中，薄晶片是厚度为大约100微米(μm)的这些，虽然引入了甚至更薄的晶片，因为可以解决翘曲问题。
该涂料组合物可以是适于或者目前用于所述目的任何晶片背面涂料。合适的涂料组合物典型的是由环氧树脂来制备的，和在一种实施方案中是固体环氧树脂，例如选自下面的这些：甲酚酚醛清漆环氧树脂、苯酚酚醛清漆环氧树脂、双酚-A环氧树脂和缩水甘油基化的树脂(其含有由酚和稠环体系(例如二环戊烯基团)组成的主链)。在一种实施方案中，该环氧树脂的存在量是涂料的15-40wt%。在另外一种实施方案中，该环氧树脂是熔点为80-130°C的固体。
能够与环氧化物组合使用的其他合适的树脂是丙烯酸酯树脂。合适的丙烯酸酯树脂包括选自下面的这些：(甲基)丙烯酸丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸正月桂酯、(甲基)丙烯酸烷酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸正十八烷酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸异冰片酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、全氟辛基乙基(甲基)丙烯酸酯、1,10癸二醇二(甲基)丙烯酸酯、壬基酚聚丙氧基化(甲基)丙烯酸酯。
其他丙烯酸酯树脂包括获自Kyoeisha Chemical Co.，LTD的聚戊氧基化四氢糠基丙烯酸酯；获自Sartomer Company，Inc的聚丁二烯氨基甲酸酯二甲基丙烯酸酯(CN302，NTX6513)和聚丁二烯二甲基丙烯酸酯(CN301，NTX6039，PRO6270)；获自Negami Chemical Industries Co.，LTD的聚碳酸酯氨基甲酸酯二丙烯酸酯(ArtResin UN9200A)；获自RadcureSpecialities，Inc的丙烯酸酯化的脂肪族氨基甲酸酯低聚物(Ebecryl230，264，265，270，284，4830，4833，4834，4835，4866，4881，4883，8402，8800-20R，8803，8804)；获自Radcure Specialities，Inc.的聚酯丙烯酸酯低聚物(Ebecry 1657，770，810，830，1657，1810，1830)；和获自Sartomer Company，Inc.的环氧丙烯酸酯树脂(CN104，111，112，115，116，117，118，119，120，124，136)。
另外的丙烯酸酯树脂包括单环缩醛丙烯酸酯，含有环缩醛的(甲基)丙烯酸酯(例如获自Sartomer的SR531)；THF丙烯酸酯(例如获自Sartomer的SR285)；取代的环己基(甲基)丙烯酸酯(例如获自Sartomer的CD420)；乙酰乙酰氧基乙基甲基丙烯酸酯，2-乙酰乙酰氧基乙基丙烯酸酯，2-乙酰乙酰氧基丙基甲基丙烯酸酯，2-乙酰乙酰氧基丙基丙烯酸酯，2-乙酰乙酰氨基乙基甲基丙烯酸酯，和2-乙酰乙酰氨基乙基丙烯酸酯；2-氰基乙酰氧基乙基甲基丙烯酸酯，2-氰基乙酰氧基乙基丙烯酸酯，N(2-氰基乙酰氧基乙基)丙烯酰胺；2-丙酰乙酰氧基乙基丙烯酸酯，N(2-丙酰乙酰氧基乙基)甲基丙烯酰胺，N-4-(乙酰乙酰氧基苄基苯基丙烯酰胺，乙基丙烯酰乙酸酯，丙烯酰甲基乙酸酯，N-乙基丙烯酰氧基甲基乙酰乙酰胺，乙基甲基丙烯酰乙酰乙酸酯，N-烯丙基氰基乙酰胺，甲基丙烯酰乙酰乙酸酯，N(2-甲基丙烯酰氧甲基)氰基乙酰胺，乙基-a-乙酰乙酰氧基甲基丙烯酸酯，N-丁基-N-丙烯酰氧乙基乙酰乙酰胺，单丙烯酸酯化的多元醇，单甲基丙烯酰氧乙基邻苯二甲酸酯，及其混合物。
在一种实施方案中，将该丙烯酸酯选择为粘度小于50mPas和沸点大于150°C。在一种具体的实施方案中，该丙烯酸酯包含在环中含有至少一个氧的5-或者6-元环。
在一种实施方案中，该丙烯酸酯树脂占涂料组合物的15-50wt%。
用于该环氧树脂的合适的固化剂大于0到50wt%的量存在，并且包括但不限于酚类、芳族二胺类、双氰胺、过氧化物、胺类、咪唑类(imidiazoles)、叔胺类和聚酰胺。合适的酚类市售自SchenectadyInternational，Inc。合适的芳族二胺是伯二胺，并且包括二氨基二苯基砜和二氨基二苯基甲烷，市售自Sigma-Aldrich Co。合适的双氰胺获自SKWChemicals，Inc。合适的聚酰胺市售自Air Products and Chemicals，Inc。合适的咪唑市售自Air Products and Chemicals，Inc。合适的叔胺获自Sigma-Aldrich Co。
用于丙烯酸酯树脂的合适的固化剂的存在量是0.1-10%，并且包括但不限于任何已知的苯乙酮系、噻吨酮系、苯偶姻系和过氧化物系光引发剂。例子包括二乙氧基苯乙酮、4-苯氧基二氯苯乙酮、苯偶姻、苯偶姻乙醚、苯偶姻异丙醚、苄基二甲基缩酮、二苯甲酮、4-苯基二苯甲酮、丙烯酸酯化的二苯甲酮、噻吨酮、2-乙基蒽醌等。有用的光引发剂的例子是由BASF销售的Irgacur和Darocur系的光引发剂。
在一种实施方案中，该涂料组合物包含能够热固化的树脂，和能够通过UV光引发的自由基聚合来固化的树脂。在一种具体的实施方案中，这样的双固化涂料组合物将包含环氧树脂(其是热固化的)和丙烯酸酯树脂(其可UV辐射固化的)。一种实施方案包含缩水甘油基化的邻甲酚甲醛酚醛清漆作为环氧树脂和三甲基环己基丙烯酸酯作为丙烯酸酯树脂。
在另一种实施方案中，该涂料组合物将包含反应性的硫化合物，例如硫醇和二硫酯。在一种实施方案中，该反应性的硫化合物选自十二烷基硫醇、叔十二烷基硫醇、巯基乙醇、辛基硫醇、己基硫醇，异丙基黄原酸二硫化物，和硫醇-侧基硅氧烷聚合物。反应性的硫化合物在该涂料组合物中的存在量是0.1-7重量%。
硫醇侧基硅氧烷聚合物的一个例子具有下面的结构
Figure BDA00002542752200051
其中n表示5-500的整数，其表示了重复单元的聚合数目，和m是1-5的整数。该聚合物硫醇侧基硅氧烷的存在量是涂料组合物的0.1-7重量%。
在一种实施方案中，该涂料组合物包含：(i)熔点80-130°C的固体环氧树脂；(ii)粘度小于50mPas和沸点大于150°C的丙烯酸酯树脂；和(iii)具有下面结构的聚合物硫醇-侧基聚硅氧烷
Figure BDA00002542752200052
其中n表示5-500的整数，和m是1-5的整数。
在一些实施方案中，存在着非导电性填料。合适的非导电性填料的例子包括包括氧化铝、氢氧化铝、二氧化硅、蛭石、云母、钙硅石、碳酸钙、二氧化钛、沙子、玻璃、硫酸钡、锆、炭黑、有机填料和有机聚合物，其包括但不限于卤代乙烯聚合物，例如四氟乙烯、三氟乙烯、偏二氟乙烯、氟乙烯、偏二氯乙烯和氯乙烯。
在其他实施方案中，存在着导电填料。合适的导电填料的例子包括炭黑、石墨、金、银、铜、铂、钯、镍、铝、碳化硅、氮化硼、金刚石和氧化铝。填料的具体类型不是关键的，并且可以由本领域技术人员选择来满足特定的最终用途的需要，例如应力降低和粘合层的控制。
间隔物(spacer)也可以包括在配方中来控制结合件的粘合层厚度，由本领域技术人员选择类型和量来满足具体应用的需要。
填料和间隔物的存在量可以是由本领域技术人员所确定的适于所选择的树脂体系和最终用途的任何量，并且典型的量范围是10-30wt%。
在一种实施方案中，该填料是球形，并且平均粒径大于2μm和具有单峰粒度分布。较小的粒度和双峰分布产生了不可接受的高触变指数，其反过来导致了差的旋涂性能和不均匀的涂层厚度。
其他的添加剂，包括但不限于本领域技术人员已知的类型和量的粘合促进剂、消泡剂、防渗剂、流变控制剂和助熔剂，也可以包括在涂料配方中。在一种优选的实施方案中，溶剂并非该组合物的一部分。
该涂层可以是用于适当的保护、结合所需的任何厚度，或者可以是用于具体的制造用途的加工性能所需的任何厚度，并且典型的厚度是12μm-60μm。在一种实施方案中，该涂层厚度是40μm。
将涂料通过工业上所用的任何有效的手段置于晶片上，例如诸如孔板印刷(stencil printing)、丝网印刷、喷涂方法(超声、压电、气动)、喷射方法(例如通过热或者压电(声学)头)，或者旋涂。
该涂料是通过曝露于180nm-800nm的脉冲UV光源来进行B-阶段固化的，并且总辐射曝光量是0.01–10J/cm2。该脉冲的UV光源在位于从晶片到灯泡12-38cm的距离处使用，并且使用15-300s。
UV固化方法典型的包括吸收波长<400nm的光的那部分。一种合适的脉冲的UV光源是Xenon灯(Xenon Corp.，Wilmington MA)。
用于所述的曝光和灯的合适的参数典型的将处于下面的范围内：
脉冲持续时间：1-1000微秒，在1/3峰值处测量。
能量/脉冲：1-2000焦耳
辐射时间：0.1-10s
灯类型：石英、透明石英或者蓝宝石
光谱：100-1000nm
灯外的波长选择：无或者IR滤光片
灯室窗：石英、透明石英或者蓝宝石
实施例
如下来配制粘合剂组合物。在80°C将缩水甘油基化的邻甲酚甲醛酚醛清漆(30.32g)(软化点85°C，环氧当量203)溶解在丙烯酸四氢糠酯(15.16g)中。将该溶液冷却到室温，并且加入下面的组分：三甲基环己基丙烯酸酯(15.16g)；由2，4，6-三甲基苯甲酰-二苯基-氧化膦和2-羟基-2-甲基-1-苯基-丙-1-酮组成的光引发剂混合物(2.39g)；2-苯基-4-甲基咪唑(0.80g)；硫醇侧基聚硅氧烷(0.16g)(分子量4000-7000)；和熔融二氧化硅(16.00g)(在5微米干筛)。将该混合物手工混合，并且送过三辊陶瓷研磨机4次。
将该粘结剂组合物以40微米(μm)的厚度旋涂到三个100微米(μm)厚的正方形硅晶片上，每个边15.24cm。每个晶片是通过UV辐射使用不同的UV源并且具有用于整个固化的优化设定来进行B-阶段固化的。
灯A是Fusion带驱动汞灯，其使用大约104cm/min的带速，强度是0.381W/cm和总曝光量是1.4J/cm2。
灯B是UVEXS Model 15647-12带驱动汞灯，其使用大约104cm/min的带速，强度是0.44W/cm和总曝光量是1.4J/cm2。
灯C是Xenon Model RC847-LH830脉冲UV光源，其在使用时处于从晶片到灯泡12.7cm的距离，并且进行60s，总曝光量是0.36J/cm2。
将UV切割胶带(dicing tape)(来自Denka)置于B-阶段粘结剂上，并且以1.4KgF/cm2(20psi)层合到晶片上。在该晶片上的电接触是随后将回流的焊料球。然后将该晶片切割成尺寸为10mmx15mm的芯片。
将各个芯片从切割胶带上去除，并且使用Toray FC-100M热压结合机(Toray Engineering Co.Ltd)在140°C的结合温度、15N的力和1s的结合时间结合到刚刚经炉子干燥的光滑电子基底(具有焊接掩模的BT芯，没有任何的金属化)的带子上，达到250μm(微米)的总厚度。将该基底和芯片组件在150°C的炉子中固化1小时，并且升温30分钟。
使用Sonix UHR-2000仪器(Sonix Inc.)采集扫描声学显微图(SAM)。将该基底和芯片的组件转移到湿气炉中，并且在85°C和85%湿度加热24小时。然后将该基底和芯片的组件送过260°C的回流炉三次来回流所述焊料，并且再次采集SAM。
在固化后，全部的样品(不管是否被灯固化)表现出清楚的SAM，并且没有观察到孔隙或者分层。在湿气炉和回流处理后，用fusion汞灯A固化的样品在全部的结合芯片中表现出明显的分层。在这些使用UVEXS灯固化的样品中，13个芯片中的3个失效和表现出分层。在这些通过Xenon灯固化的样品中，全部都表现出相对于它们初始的后热固化状态而言很小的变化。所以，使用该脉冲的UV光促进和允许使用薄的半导体芯片，产生更小的损坏。

Claims (9)

1.一种用涂料组合物涂覆半导体晶片的方法，其包括：
(A)提供涂料组合物
(B)将该涂料组合物置于半导体晶片上；和
(C)通过将该组合物曝露于足以固化该涂料组合物的量的脉冲的UV光，来对该涂料组合物进行B-阶段固化。
2.根据权利要求1的方法，其中将该涂料组合物曝露于总共0.1-10J/cm2。
3.根据权利要求1的方法，其中该脉冲的UV光源在位于从晶片到灯泡12-38cm的距离处使用，并且使用15-300秒。
4.根据权利要求1的方法，其中该半导体晶片的厚度是100μm或者更低。
5.权利要求1的方法，其中该涂料组合物包含能够热固化的树脂和能够通过自由基聚合来固化的树脂。
6.权利要求5的方法，其中该能够热固化的树脂是环氧树脂，并且该能够通过自由基聚合来固化的树脂是丙烯酸酯树脂。
7.权利要求1的方法，其中该涂料组合物包含(i)熔点为80-130℃的固体环氧树脂，和(ii)具有下面的结构的聚合物硫醇侧基的聚硅氧烷
其中n是5-500的整数，和m是1-5的整数。
8.使用权利要求1的方法涂覆的半导体晶片。
9.使用权利要求1的方法涂覆的半导体晶片，其中该涂料组合物包含(i)熔点为80-130℃的固体环氧树脂，和(ii)粘度小于50mPas和沸点大于150℃的丙烯酸酯树脂。
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