CN1946795B - Dual-stage wafer applied underfills - Google Patents

Dual-stage wafer applied underfills Download PDF

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CN1946795B
CN1946795B CN 200480034404 CN200480034404A CN1946795B CN 1946795 B CN1946795 B CN 1946795B CN 200480034404 CN200480034404 CN 200480034404 CN 200480034404 A CN200480034404 A CN 200480034404A CN 1946795 B CN1946795 B CN 1946795B
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underfill composition
underfill
composition according
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selected
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CN1946795A (en
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凯兰·高希
多里安·A·卡内拉斯
艾德沃德·E·科莱
阿曼达·W·许勒斯
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洛德公司
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Priority to PCT/US2004/017749 priority patent/WO2005056675A1/en
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Abstract

A 100% non-volatile, one-part liquid underfill encapsulant is disclosed for application to the active side of a large wafer or integrated circuit chip. Upon coating, the encapsulant is converted to a liquefiable, tack-free solid by exposure to radiation, particularly in the UV, visible and infrared spectrum. The underfill-coated wafer exhibits outstanding shelf aging of months without advancementof cure. The large wafer can be singulated into smaller wafer sections and stored for months after which during solder reflow assembly, the wafer connects are fixed and the underfill liquefies, flowsout to a fillet and transitions to a thermoset state on heat activated crosslinking.

Description

晶片用双阶段底部填充胶 With the bottom of the wafer stage bis underfill

发明领域 Field of the Invention

[0001] 本发明涉及微电子芯片组件,尤其涉及将底部填充胶应用于集成电路晶片的方法 [0001] The present invention relates to microelectronic chip assemblies and more particularly to a method applied underfill integrated circuit die

和材料。 And materials.

[0002] 发明背景 [0002] Background of the Invention

[0003] 电子部件的表面装配在自动封装组件系统中已经得到了良好的发展。 [0003] surface of the electronic component mounting assembly in an automatic packaging system has been well developed. 集成电路由如下组成:诸如晶体管和二极管的器件,诸如电阻和电容的元件,所述器件和元件通过导电连接相连以形成一个或多个功能性电路。 Integrated circuits are made as follows: the devices such as transistors and diodes, elements, devices and components such as the resistors and capacitors are connected by a conductive connection to form one or more functional circuits. 器件设置在具有表面的晶片或硅片上,所述表面用于进行一系列的制造步骤以形成通过晶片表面中的划线或锯线(saw streets)的重复矩形图案而隔开的相同集成电路图案,所述划线或矩形区用作小片、芯片或管芯(die)之间的边界。 Device provided with an upper surface of the wafer or wafers, the surface for a series of manufacturing steps to form the integrated circuit and separated by the same surface of the wafer scribe lines or saw wire (saw streets) repeating rectangular pattern pattern, said scribe line or rectangular region as a boundary between the chip or die (die) small pieces. 在制造过程的后期阶段中,来自晶片的单独小片与基片相连以形成IC封装。 At a later stage of the manufacturing process, the individual die from the wafer and the substrate are connected to form an IC package. [0004] 常规的倒装芯片技术通常是指集成电路管芯的正面与封装基片或印刷电路板(统称为PCB)相连的任意组件。 [0004] Conventional flip chip technology generally refers to any assembly connected to the front side of the integrated circuit die and the package substrate or printed circuit board (collectively referred to as PCB). 倒装芯片组件可以设计成具有或不具有底部填充胶的封装。 Flip-chip assembly can be designed with or without underfill encapsulation. 对于倒装芯片的用途,芯片上具有小的凸点或焊料球(下文称为"凸点"或"焊料凸点"),其位于与电路板表面的凹穴相对应的正面上。 For use flip chip, with small bumps or solder balls (hereinafter referred to as "bump" or "solder bumps") on the chip, which recess is located on the surface of the circuit board corresponding to the front. 通过将凸点与板套合而装配芯片,使得焊料凸点夹在板的焊点与芯片的对应焊点之间。 By engaging the plate bump chips are assembled, so that the solder bumps interposed between the corresponding solder pads of the chip plate. 在使用助焊剂之后,将组件加热达到焊料回流的点。 After the flux is used, the assembly is heated to achieve reflow of the solder points. 冷却后,焊料变硬,从而将倒装芯片安装在板的表面上。 After cooling, the solder hardens, thereby mounting the flip chip on the surface of the board.

[0005] 常规的底部填充胶用于多个不同的方法中,并施用至安装好的芯片中,用于为芯片提供对如下情况的保护:化学侵袭、湿气、空气传播污染等以及机械震动、振动和在运输与使用中遭遇的温度周期变化。 Conventional bottom of [0005] a plurality of filled gum different approach, and applied to a mounted chip to provide protection of a case of the chip: chemical attack, moisture, airborne pollution and mechanical shock , and vibration encountered in shipping and use temperature cycling. 常规的毛细倒装芯片底部填充胶法必须具有如下步骤:芯片和电路板的对准、助焊剂分配、焊料回流、助焊剂清洗、底部填充胶施用、底部填充胶流动和固化。 Conventional capillary flip chip underfill process must have the steps of: aligning the chip and the circuit board, flux dispensing, solder reflow, flux cleaning, underfill administration, underfill flow and curing.

[0006] 用于芯片封装中的底部填充胶提供了如下的功能:保护将芯片与封装或板互连的焊料接头免受诸如湿气和污染的环境因素的干扰,再分配机械应力,从而提高器件寿命。 [0006] for the bottom of the chip package underfill provides the following functions: protection of the chip and package or board interconnection solder joint interference from environmental factors such as moisture and contamination, mechanical stress redistribution, thereby improving life of the device. 其为芯片提供了对诸如湿气和所致金属互连腐蚀的污染的保护。 Which provides protection against contamination such as moisture and resulting corrosion of the metal interconnect chip. 然而,胶粘剂的错误选择会导致多种方式的倒装芯片封装失败,例如收縮、分层、水解不稳定性、腐蚀以及由于底部填充胶引起的污染。 However, the adhesive can lead to the wrong choice of flip chip package failures in various ways, such as shrinkage, delamination, hydrolytic instability, corrosion, and contamination by the underfill caused.

[0007] 芯片底部填充胶用于避免由于芯片、互连、底部填充胶和基片之间不同热膨胀系数而导致的粘附件之间的应力。 [0007] The bottom of the chip underfill for avoiding stress between the adherend due to the different coefficients of thermal expansion between the chip, interconnects, underfill and substrate caused. 如果基片是有机的,且当器件尺寸增长时,则由于应力引起的失败方式变得更普遍。 If the substrate is organic, and when the device size growth, due to the stress caused by the failure mode becomes more prevalent. 芯片底部填充胶必须提供粘附至诸如陶瓷或有机PCB(例如FR4环氧)的基片的功能,其中基片可被或未被如下材料涂覆:阻焊层;金属合金或有机互连;和集成电路管芯(芯片),所述管芯通常由硅或其它无机物构成,并可被或未被薄的钝化层涂覆。 Bottom of the chip underfill must provide adhesion to the organic functionality such as a ceramic or PCB (e.g. FR4 epoxy) of the substrate, wherein the substrate may or may not be coated with the following materials: solder resist layer; a metal alloy or organic interconnects; and an integrated circuit die (chip), the die is typically made of silicon or other inorganic material, and may or may not be coated with a thin passivation layer.

[0008] 在两种封装电子部件的原理方法的一种中,部件被焊接在与其在板上安装相同的一面。 [0008] In one method two principle encapsulating electronic components, the components are soldered to the board mounting thereto the same side. 这些器件被称为是"表面安装"的。 These devices are referred to as "mounting surface" of. 两种常规的底部填充胶在实践中用于表面安装的器件:毛细流型或"非流动"型。 Two conventional underfill for surface mounted devices in practice: capillary flow-type or "non-flow" type. 这些技术的详细描述可以在文献中找到。 Detailed description of these techniques can be found in the literature. 例如,参见JohnH丄au的著述Low Cost Flip Chip Technologies for DCA, WLCSP and PBGAAssemblies,McGraw-Hill, 2000。 For example, see JohnH Shang au writings Low Cost Flip Chip Technologies for DCA, WLCSP and PBGAAssemblies, McGraw-Hill, 2000. 对于这两种技术而言,通常施加热用于固化液态热固性配方或将固态膜层压为组件。 For both techniques, it is generally used for the application of heat curable liquid formulation or a solid thermoset film pressure assembly. 有时采用真空从系统中排出气泡。 Sometimes vacuum removal of air bubbles from the system. 底部填充胶通常应用在封装内芯片或板上芯片所用的表面安装(SMT)装配线中。 The underfill is typically applied on the surface mount chip or chip on board package used (SMT) assembly line. 常规的流动和非流动底部填充胶在SMT线上的使用需要多个步骤,且该方法通常是这些微电子装配线上的瓶颈。 Conventional flow and no-flow underfill using an SMT line requires a plurality of steps, and the process is usually the bottleneck on these microelectronics assembly lines.

[0009] 在美国专利No. 6, 180, 696中公开了代表性的常规非流动底部填充胶。 [0009] 6, 180, 696 discloses a typical conventional bottom-flow in U.S. Patent No. underfill. 首先将该底部填充胶材料分配在基片或半导体芯片上,然后焊料凸点回流,且底部填充胶密封剂同时发生固化。 The underfill material is first dispensed on the bottom of the substrate or the semiconductor chip, and solder bump reflow and the underfill encapsulant occurs simultaneously cured. 在美国专利No. 6, 180, 696中教导的底部填充胶包括环氧树脂和/或环氧树脂、有机羧酸酐硬化剂、固化促进剂、自熔剂、粘度控制剂、偶合剂、表面活性剂的混合物。 In U.S. Patent No. 6, 180, 696 taught underfill comprises epoxy resin and / or an epoxy resin, an organic carboxylic acid anhydride hardener, a hardening accelerator, since the flux, viscosity control agents, coupling agents, surfactants mixture. 底部填充胶配方的固化峰值温度为180-240°C。 Peak temperature curing underfill formulations bottom 180-240 ° C. 该底部填充胶必须储存在低于零度的温度(°C)下以避免促进固化。 The underfill must be stored at temperatures below zero (° C) to avoid promoting the curing.

[0010] 底部填充胶与作为图案化形成物涂覆于PC板上的可成像光致抗蚀剂物质不同,然而,在普遍存在的环氧树脂的使用上存在一定的相似性。 [0010] The underfill is formed and patterned as was coated on the PC board can be imaged photoresist material different, however, there are some similarities in the ubiquitous use of the epoxy resin. 用于光致抗蚀的涂层已知采用光引发剂,用于使通过掩膜暴露于活化辐射的区域固化,和在非辐射或阴影区域实现聚合的第二热活化自由基固化成分。 Coating a photoresist using known photoinitiators, through a mask for areas exposed to activating radiation curable, and the second heat radiation effect polymerization in the non-hatched region or activated radical curing component. 通常利用的一种第二固化机理依赖于向配方中加入热活化的过氧化物;然而,通常需要超过IO(TC的温度以引发过氧化物诱导的聚合,因此排除了涉及例如热敏性电子部件的使用。 Typically utilize a second cure mechanism relies on thermally activated peroxide was added to the formulation; however, generally requires temperatures of more than IO (TC peroxide to initiate polymerization induced, thus excluding relates to heat-sensitive electronic components e.g. use.

[0011] 美国专利No. 5, 077, 376公开了含有潜在性热固化成分的环氧胶粘剂。 [0011] U.S. Patent No. 5, 077, 376 discloses an epoxy adhesive containing a latent heat-curing component. '376公开的内容教导了液态环氧物已知的贮存稳定性的问题,其使得含有潜在性硬化剂例如双氰胺、二元酸二酰肼、三氟化硼_胺加合物、三聚氰二胺、蜜胺等的环氧树脂组合物被广泛使用。 '376 disclosure teaches the storage stability problems of known liquid epoxy thereof, so that for example, dicyandiamide, dibasic acid dihydrazide, boron trifluoride amine adduct _ contains a latent curing agent, tris guanamines, melamine, epoxy resin composition and the like are widely used. 然而,该专利教导双氰胺、二元酸二酰肼和三聚氰二胺具有的缺陷是它们需要15(TC或更高的高温以进行固化。 However, this patent teaches dicyandiamide, dibasic acid hydrazide and guanamine have the disadvantage that they require 15 (TC or higher temperature for curing.

[0012] 美国专利No. 5, 523, 443公开了二次固化的敷形涂层,其含有紫外线固化的可聚合体系和湿气固化机理。 [0012] U.S. Patent No. 5, 523, 443 discloses a secondary curing conformal coating system and which contains a polymerizable UV-curable moisture-curing mechanism. 该可聚合涂层体系是单组分体系,其含有至少一种烷氧基甲硅烷基-聚氨酯-丙烯酸酯或甲基丙烯酸酯、丙烯酸酯或甲基丙烯酸酯或乙烯基醚稀释剂、阳离子或自由基光引发剂类聚合弓I发剂和金属催化剂。 The polymeric coating system can be a one-component system containing at least one alkoxysilyl group - urethane - acrylate or methacrylate, an acrylate or methacrylate or vinyl ether diluents, cationic or radical photoinitiator bow I type polymerization initiator and a metal catalyst.

[0013] 美国专利No. 5, 249, 101 (IBM, 1993)教导,具有弹性模量大于约10000psi (69MPa) [0013] U.S. Patent No. 5, 249, 101 (IBM, 1993) teaches that has an elastic modulus greater than about 10000psi (69MPa)

的用于芯片载体的电路化表面上电路系统的保护性环氧涂层的脆度会导致破裂和分层。 Friability on the circuitized surface of a chip carrier of the circuitry of a protective epoxy coatings cause cracking and delamination.

US '101提出了含有丙烯酸酯化聚氨酯低聚物、丙烯酸酯化单体和光引发剂的涂层,用于 US '101 proposes coating contains an acrylated urethane oligomer, acrylated monomer and a photoinitiator for

提供弹性模量等于或小于10000psi且氯离子浓度低于10ppm的涂层。 Providing an elastic modulus of less than or equal to 10000psi and the concentration of chloride ions is less than 10ppm of the coating. 晶片用丙烯酸酯化 Wafer esterified with acrylic acid

聚氨酯底部填充胶不需要焊料回流,这是由于其缺乏足够的热绝缘性。 Polyurethane underfill bottom need not solder reflow, which is due to their lack of adequate thermal insulation.

[0014] 美国专利No. 5, 494, 981公开了环脂族环氧树脂、氰酸酯树脂、任选的多元醇、和 [0014] U.S. Patent No. 5, 494, 981 discloses a cycloaliphatic epoxy resin, cyanate ester resin, optionally a polyol, and

作为引发剂的布朗斯台德酸(Br加stedacid)的固化组合。 As an initiator a Bronsted acid (Br plus stedacid) of the curable composition. 在固化时,该组合物提供了互 Upon curing, the composition provides a cross

相渗透的聚合物网络(IPNs)。 Phase permeable polymer networks (IPNs). 该IPNs适用作高温稳定性减振材料、胶粘剂、研磨剂用粘合 The IPNs damping material suitable for use as high temperature stability, adhesives, abrasives, adhesive

剂和保护性涂层。 And protective coatings.

[0015] 美国专利No. 5, 672, 393公开了丙烯酸酯密封配方,当其暴露于波长为紫外线和可视范围内的辐射线时,其以高的速率反应,从而开始生成相对后的表皮,并最终固化成具有良好物理清晰度和表面性质的相对低应力的沉积物。 [0015] U.S. Patent No. 5, 672, 393 discloses a sealing acrylate formulations, when exposed to a wavelength of ultraviolet radiation and visible range, at a high reaction rate, so as to start generating the opposite skin , and eventually cure to a relatively low stress surface having good physical properties and clarity of the deposit. 该方法必须使对象物上的配方暴露于辐射下以引发光聚合和热聚合,且该装置包括紧紧并列的光化辐射和热能源。 This method must formulation on the object is exposed to radiation to initiate photopolymerization and thermal polymerization, and the device comprises a tightly juxtaposed actinic radiation and thermal energy. 催化剂体系包括光引发剂成分和对低于12(TC的温度有响应的热引发剂成分。[0016] 美国专利No. 5, 706, 579公开了组装集成电路封装的方法,所述封装由管芯、印刷 The catalyst system comprises a photoinitiator and a component 12 (lower than the temperature TC of the thermal responsive initiator component. [0016] U.S. Patent No. 5, 706, 579 discloses a method of assembling an integrated circuit package, the package from a tube core print

接线板和金属盖制得,该方法采用预先施用于盖子并含有热传导性填料物质的可13 -阶段 A metal wiring board and the cover prepared, using the method previously applied to the cover and containing the thermally conductive filler material may 13-- stage

树脂。 Resin. 通过在管芯和基片板上适当放置的盖子,将封装加热以引起树脂流动并形成与管芯 Through the die and the substrate is placed on a proper lid, the package is heated to cause the resin to flow and form the die

的连接。 Connection. 进一步的加热使得树脂固化并形成管芯与盖子之间的永久热桥连。 Further heating and curing the resin a permanent thermal bridge between the die and the lid attached.

[0017] 美国专利No. 6, 194, 788公开了用于倒装芯片的集成热塑性、自熔双组分底部填 [0017] U.S. Patent No. 6, 194, 788 discloses a flip-chip integration for a thermoplastic, double bottom component from molten filler

充胶。 Underfill. 该底部填充胶包括环氧树脂和带有自熔型酸性环氧固化剂的乙酸酯稀释剂。 The underfill comprises an epoxy diluent, and acetate with self-fluxing type acid epoxy curing agent.

[0018] 美国专利No. 6, 323, 062 (Alpha Metals, 1999年9月14日提交)公开了将溶剂基 [0018] US Patent No. 6, 323, 062 (Alpha Metals, September 14, 1999 filed) discloses the use of solvent-based

片部填充胶用于倒装芯片的方法。 Method for filling plastic sheet portion of the flip chip. 该方法包括将带凸点的晶片粘合至可延展载体基片上的 The method comprises an adhesive wafer with bumps to the extensible carrier substrate

步骤,首先,锯开晶片以形成单独的芯片,将载体基片以双向方式延伸以在各单个芯片之间 Step, first, the wafer sawing to form individual chips, the carrier substrate in a bidirectional manner to extend between individual chips

形成通路,接着将底部填充胶物质应用至芯片的凸点表面并环绕在芯片的边缘。 Passage is formed, and then the underfill material applied to the surface of the chip bumps and around the edges of the chip. 该底部填 Fill the bottom

充胶物质并未公开,但其教导了底部填充胶可以在涂覆后干燥,接着在芯片之间的通道中 Underfill materials are not disclosed, but it teaches underfill may be dried after coating, followed by passage between chips

切割底部填充胶物质,并将涂覆底部填充胶的各单个芯片从载体移除。 Cutting the underfill material, underfill coated bottom and remove individual chips from the carrier.

[0019] 美国专利No. 6, 383, 659公开了低Tg环氧基底部填充胶的b_阶段膜,其含有分子 [0019] U.S. Patent No. 6, 383, 659 discloses a low Tg b_ bottom stage epoxy film filled gum, comprising the molecule

量为5, 000-200, 000的热塑性聚合物。 In an amount of 5, 000-200, 000 of the thermoplastic polymer. 该'659专利还教导了通常含有咪唑的自聚合型环 The '659 patent also teaches polymeric rings generally contain from imidazole

氧树脂组合物或酚固化型环氧树脂组合物,其显示出有限的储存稳定性、耐湿气性和固化 Oxygen or phenolic resin composition curable epoxy resin composition which exhibits a limited storage stability, moisture resistance and curing

组合物的高温性能,且难以控制B-阶段反应的进度。 High temperature properties of the composition, and difficult to control the progress of the reaction stage B-.

[0020] 上述现有技术例示了形成涂层的二次固化方法,但并未涉及在诸如硅晶片的脆性基片上含有二次固化化学物的b-阶段涂层的储存。 [0020] The prior art illustrates a method for forming the secondary coating curing, but does not relate to a brittle substrate such as a silicon wafer, comprising a secondary coating curing stage b- storing chemicals. 除在控制性环境下,运输或储存中可能会发生晶片变形、破裂以及在容易达到约5(TC的温度下长期环境储存。[0021] 当底部填充胶被施用以及固化后,接着放置数月直至用于双阶段固化底部填充胶的焊料回流步骤,在晶片用底部填充胶中遇到的问题是:液态涂层的初始润湿以及粘附;在环境温度下涂层固化而没有从晶片分层;涂覆晶片的长期环境温度储存,而没有因固化或凝胶含量增长导致回流能力降低;在分区或划线中避免从晶片分层;在晶片锯线内能够镂花涂装;在由焊料回流的初始加热中,开始缓慢地变稠;在未使用环绕环时,底部填充胶流出并环绕芯片以形成填角(fillet)的能力;在焊料回流步骤后在底部填充胶中没有空隙;以及在其有效使用寿命中,其在装置中的长期可靠性(无缺陷)。 In addition to the controlled environment, transport or storage chip deformation may occur, and rupture easily at up to about 5 (long-term storage at ambient temperature TC is. [0021] When the underfill is applied and cured, followed by standing for several months until the solder reflow step for the double bottom stage cured underfill, the wafer with the underfill problem encountered is: liquid coating incipient wetness and adhesion; coatings cured at ambient temperatures without points from the wafer layer; long-term ambient temperature storage of the coated wafer, with no cure or gel content increase due to lead to reduced capacity reflux; avoid delamination from the wafer in the scribe line or in the partition; saw wire within the wafer can be stenciling; by heating the initial solder reflow, slowly began to thicken; around the ring when not in use, the underfill flows out to surround the chip forming ability fillet (fillet); there is no gap at the bottom of the gel filled in the solder reflow step; and its useful life, the long term reliability (no defect) in the device.

[0022] 对于组装前长期储存的晶片用底部填充胶而言,由其所鉴别的所有这些技术问题 [0022] For long-term storage prior to assembly of the wafer with the underfill, all these technical problems identified by the

并未被现有技术的底部填充胶材料解决。 It has not been resolved prior art underfill material. 因此,目的在于提供用于将底层材料应用与倒装 Accordingly, an object to provide a substrate material for application to the flip

芯片组件分开的材料和方法,由此使液态底部填充胶通过常规的涂覆方法直接涂覆在大晶 Chip assembly and method for separating materials, whereby the liquid underfill by conventional coating methods directly coated large crystal

片的正面上,所述大晶片例如表面积为100-500m^及更大的晶片,接着进行固化,并将涂覆 On the front sheet, for example, the large surface area of ​​100-500m ^ wafer and larger wafer, followed by curing, and the coated

晶片或切割的芯片长时间储存,例如数月。 Dicing the wafer or chip prolonged storage, for example, several months. 在该情况中,其后的晶片连接方法必须避免与老 In this case, the subsequent wafer connection method must be avoided with the old

化底部填充胶的性质有关的问题。 The bottom of the problem related to the nature of the underfill.

[0023] 发明概述 [0023] Summary of the Invention

[0024] 本发明涉及晶片-底部填充胶组件以及将单组分、无溶剂、非自熔底部填充胶以通常约0. 003英寸-0. 070英寸(0. 076-1. 77mm)的涂层厚度直接施用至晶片正面的方法。 [0024] The present invention relates to a wafer - underfill component and one-component, solvent-free, non-self-fluxing underfill is typically about 0.003 inches to -0070 inch (0. 076-1 77mm.) Coating. a layer thickness applied directly to the front of the wafer method. 底部填充胶初始为部分或完全覆盖住晶片焊料凸点的液态涂层。 The underfill initial liquid coating partially or completely covers the solder bumps of the wafer. 底部填充胶包括填充的、100%固体(基本上非挥发)的液态涂层。 Filling the underfill comprises a 100% solids (essentially non-volatile) liquid coating. 底部填充胶通过在约50-2400mJ/cm2的光辐射下露置从而在晶片上凝固成热可液化的固态。 Underfill by light irradiation of about 50-2400mJ / cm2 exposed on the wafer is set so that solidifies into a solid heat-liquefiable. 底部填充胶可以以网格图案施用于晶片锯线之外,或者可形成能经受晶片被切割成单独区域或管芯的连续涂层。 The underfill may be applied to the outside of the wafer grid pattern saw wire, or may be formed to withstand being cut into individual wafer areas or dies continuous coating. 涂覆晶片或涂覆的单独区域能够于组装或焊料互连之前在周围环境下储存数月之久的不确定延迟时间。 Separate area of ​​the wafer coating or coating capable of storing several months uncertain long time delay before assembly or solder interconnects at ambient. 在采用了于晶片用底部填充胶周围施用的环绕密封剂的组装芯片中,热可液化的固态底部填充胶的热固化开始点可为15(TC或更高。在其中底部填充胶受热液化并流出至晶片边缘,且在某种程度上向上流动形成填角的实施方式中,底部填充胶的热固化活化温度必须高于170°C。用于回流焊料所施加的热足以在活化热固化体系前启动底部填充胶的熔体流动,其使得底部填充胶胶凝化成热固性的固态。在热固性固化状态下,底部填充胶显示出低于10Gpa的弯曲模量。 In administration using a wafer with the underfill surrounding sealant assembly around the chip, the starting point of the solid thermosetting bottom heat liquefiable underfill may be 15 (TC or higher. In which the underfill is heated and liquefied flows out to the edge of the wafer, and to some extent in the upward flow of the embodiment is formed in the fillet, the thermosetting underfill activation temperature must be above 170 ° C. for the heat applied is sufficient to reflow the solder in the thermally activated cure system start melt flow underfill before, which makes the thermosetting underfill gelled into a solid in the cured state the thermoset underfill exhibits a flexural modulus of less than 10Gpa.

[0025] 单组分液态底部填充胶包括如下的混合物:作为光固化成分的一种或多种烯键式不饱和单体、一种或多种可固化环氧材料、一种或多种光引发齐U、潜在性热固化齐IJ、导热且电绝缘的填料,其特征在于光固化成分占底部填充胶总重的5% _30%,且环氧树脂成分占底部填充胶总重的10% _45%。 [0025] The bottom liquid underfill single component mixture comprising: as a component in photocurable or more ethylenically unsaturated monomers, one or more curable epoxy material, one or more light Qi initiator U, latent thermal curing IJ together, thermally conductive and electrically insulative filler, characterized in that the photocurable composition 5% _30% of the total weight of the underfill, and an epoxy resin component accounted for 10% of the total weight of the underfill _45%. 优选的光固化成分包括100%的单官能烯键式不饱和丙烯酸酯或甲基丙烯酸酯单体。 Preferred photocurable composition comprises 100% of the monofunctional ethylenically unsaturated acrylate or methacrylate monomer. 优选的可光聚合成分为丙烯酸的单官能环醚和/或环状縮醛。 Preferred photopolymerizable component is acrylate monofunctional cyclic ether and / or cyclic acetal. [0026] 附图简述 [0026] BRIEF DESCRIPTION

[0027] 图1表示实施例6的DSC曲线,其显示出熔点、热固化起点和反应的峰值温度。 [0027] FIG. 1 shows a DSC curve for Example 6, which shows a peak melting point temperature, and thermal curing reaction of the starting point. [0028] 图2表示实施例7的DSC曲线,其显示出熔点、热固化起点和反应的峰值温度。 [0028] FIG. 2 shows a DSC curve of Example 7, a peak showing the melting point, thermal cure onset and response. [0029] 优选实施方式的详述 [0029] Detailed Description of preferred embodiment

[0030] 在方法方面,根据本发明的底部填充胶适于例如通过旋模成型、镂花涂装、印刷等应用至晶片正面的常规涂覆方法。 [0030] In a method aspect, the present invention is a bottom adapted to underfill application by conventional coating methods such as spincasting, stenciling, printing or the like to the front side of the wafer. 液态底部填充胶材料的流变学容易地适于所选择的涂覆方法。 The coating process selected rheology underfill material readily adapted to the bottom of the liquid. 液态底部填充胶被施用至承载在基片上的大型晶片的凸点或正面上,且进行光诱导的游离基聚合,并快速形成对晶片保持粘附性的固态自支撑层。 Liquid underfill is applied to the wafer on the large bumps or carried on a front substrate, and light-induced radical polymerization, and rapid formation of a solid wafer holding self-adhesive supporting layer. 光固化凝固得到了不发粘的固体底部填充胶表面,而没有晶片的变形。 Photocuring solidification was not tacky solid underfill the bottom surface without deformation of the wafer. 周围环境下显示固态的底部填充胶涂层在长时间周围环境储存下仍保持热可液化状态,其能于5(TC下暴露数月而对晶片不产生应力。[0031] 在形成焊料互连之前对以光固化、热可液化的固态底部填充胶涂覆的晶片或单独区域储存的延迟时间并没有限定,例如为数周、数月直至一年等。在延迟中的储存条件可包括将底部填充胶暴露于环境温度下而无需冷藏。晶片用底部填充胶与常规热塑性或热固性材料不同,其中所述热塑性或热固性材料从溶剂浇铸(cast)或使用热和/或真空进行熔融加工。然而,根据本发明,底部填充胶是100 %的固体材料,其通过加成聚合而光诱导性地凝固在晶片正面上,并保持为热塑性状态而一直显著延迟至第二热引发的固化开始均没有在室温下进一步的固化,并且热塑性填料具有如下特定的关键性质:无分层、无空隙形成、在焊料回 Solid underfill remain heat liquefiable coating state at ambient storage for a long time, which can be exposed for several months at 5 (TC no stress while the wafer display at ambient [0031] In the solder interconnect formation before the light curing, a solid bottom heat liquefiable underfill-coated wafer or a separate delay time storage area is not defined, for example, several weeks, several months up to one year, etc. the storage conditions may comprise a delay bottom filled with plastic and exposed to ambient temperatures without refrigeration. underfill wafer with a conventional thermoplastic or thermoset materials of different, wherein said thermoplastic or thermosetting material from a solvent cast (cast) or using heat and / or vacuum melt processed. However, according to the present invention, the underfill material is a 100% solids, by addition polymerization of photoinduced solidified on the front side of the wafer, and a thermoplastic state has been maintained a significant delay to the start of the second curable thermally induced homolytic not further curing at room temperature, and the critical nature of the thermoplastic filler has the following specific: no delamination, no voids are formed in the solder back 流条件下充分回流,以及在热固性状态中于重复的热循环条件下具有长期的粘附性而不会使器件失效或破损。热固性的固化底部填充胶在25t:具有1000-5000MPa的弯曲模量,且在低于玻璃化转变温度的温度下具有15-约60卯m广C的热膨胀系数(CTE),更通常为约25(+/-10)ppm/°C . Under conditions sufficient reflux stream, and a long-term adhesion under repeated thermal cycling conditions in the thermoset state without causing device failure or breakage of the bottom of the thermoset underfill cure in 25t:. 1000-5000MPa having a flexural modulus of and having a thermal expansion coefficient of 15 to about 60 C, d m wide (CTE) at temperatures below the glass transition temperature, more typically from about 25 (+/- 10) ppm / ° C.

[0032] 晶片级的底部填充胶包括100%的固体混合物。 [0032] wafer level underfill comprises a 100% solids mixture. 在长时间的环境储存中会造成重量损失的挥发性成分例如溶剂是不存在的。 In prolonged ambient storage will cause weight loss of volatile components such as solvents are not present. 不含挥发性成分免除了溶剂去除步骤,并提高了对收縮的控制以及光诱导性凝固涂层从晶片正面表面的分层。 Contain volatile components eliminates the step of removing the solvent, and improves the stratification of the contraction induced coagulation control coating and a light from the front surface of the wafer. 挥发性有机成分的免除防止了不可接受的收縮和应力,以及在焊料回流步骤中产生的废气,避免了在晶片或其区域与PCB之间形成的空隙。 Exclusion of volatile organic compounds prevents unacceptable shrinkage and stress, and the exhaust gas generated in the solder reflow step, avoiding the formation of voids between the PCB and the wafer in regions thereof. 底部填充胶是非自熔的。 Underfill non-self-fluxing. 换句话说,所采用的成分并不提供熔化作用,且是非酸性的。 In other words, the component used does not provide the effect of melting, and non-acidic. [0033] 在通常的方法方面,本发明包括将液态底部填充胶粘合剂施用至集成电路晶片上,施用控制量的光能(紫外线、可视光、红外线等),使底部填充胶凝固成热可液化或可熔融流动状态,任选通过划线或锯切将晶片分割,并在延迟期间内保存涂覆的晶片或小片。 [0033] In the conventional method aspect, the present invention comprises a liquid underfill adhesive on an integrated circuit wafer to be administered, administration controlling amount of light energy (ultraviolet, visible light, infrared, etc.), so that the underfill solidified into heat liquefiable or melt flowable state, optionally by scribing or sawing the wafer into, or coated wafer and stored in small pieces over a period of delay. 在延迟期间之后形成电连接,并且所施用的光固化固态底部填充胶受热液化,并在焊料回流过程中流动至器件的边缘,从而从受热液体经固化转化成热固性的固态。 After the delay period is formed electrically connected to the bottom of the solid photocurable and heat the applied underfill liquefied and flows to the edge of the device during the solder reflow process, thereby transforming the liquid from the heat cured to a thermoset solid. 在储存中的延迟时间内,本发明的涂层保持可液化的固态,且凝胶含量不增加。 Stored in the delay time, the coating of the invention remains solid liquefiable, and the gel content was not changed. 因此本发明的一方面提供了环境温度下稳定的集成电路晶片,其正面粘附于底部填充胶组合物,所述组合物包括光固化的单组分组合物,该单组分组合物以重量基准包括如下成分: [0034] 光固化丙烯酸酯成分, [0035] 多官能环氧树脂, [0036] 至少一种光引发剂, [0037] 非导电性填料,禾口 In one aspect the present invention thus provides an integrated circuit wafer is stable at ambient temperature, adhered to its front underfill composition, said composition comprising a photo-curable one-component composition, one component of the composition by weight reference comprises the following components: [0034] The photocurable acrylate component, [0035] The polyfunctional epoxy resin, [0036] at least one photoinitiator, [0037] non-conductive filler, Wo port

[0038] 非熔化性热活化环氧固化剂,其中所述底部填充胶在热固性状态下于25t:具有1000-5000MPa的弯曲模量,且在低于所述底部填充胶组合物玻璃化转变温度的温度下具有15-50卯m广C的热膨胀系数。 [0038] The melting of the non-heat activated epoxy curative, wherein the said underfill in the thermoset state to 25t: 1000-5000MPa having a flexural modulus, and the underfill below the glass transition temperature of the composition 15-50 d having a thermal expansion coefficient C m wide at the temperature.

[0039] 在另一个方面,本发明涉及对晶片用底部填充胶组合物进行固化的双阶段方法。 [0039] In another aspect, the present invention relates to a dual-stage process for the wafer with an underfill composition for curing.

该方法包括将底部填充胶组合物以液态形式施用至半导体晶片的正面。 The method includes the underfill composition is applied to the front surface of the semiconductor wafer in liquid form. 施用的方法包括将 The method comprises administering

液态非挥发性(100%固体)涂料通过旋模成型、印刷或镂花涂装直接涂覆至芯片的正面。 Non-volatile liquid (100% solids) by spin coating molding, printing or stenciling applied directly to the front surface of the chip.

以选定用量的UV辐射对涂覆晶片进行凝固从而形成固态涂层。 The amount of UV radiation at a selected solidification of the coated wafer to form a solid coating. 任选地可将固态的涂覆晶 The solid may optionally be coated crystal

片划线分区。 Scribing partition. 晶片或诸区域能够于环境温度下储存,接着为第二阶段,在焊料回流步骤中建 Wafer area capable of storing all or at ambient temperature, followed by a second stage, built in a solder reflow step

立焊料凸点至PCB的电连接,然后将固态底部填充胶热固化成热固性状态。 Li solder bump is electrically connected to the PCB, and filling the bottom of the solid thermosetting adhesive to a thermoset state.

[0040] 100%固体底部填充胶组合物基本上包括含单官能烯键式不饱和单体和/或低 [0040] The underfill 100% solids composition essentially comprising a bottom monofunctional ethylenically unsaturated monomer and / or a low

聚物的光固化丙烯酸酯成分、多官能环氧树脂、光引发剂、潜在性环氧热引发剂、以及无机 Photocurable acrylate component oligomer, a polyfunctional epoxy resin, a photoinitiator, a thermal initiator, latent epoxy, and inorganic

CTE-稀释填料。 CTE- diluted filler. 底部填充胶在固态下是非碱溶性的,且在液态光固化不饱和单体、低聚物和 Underfill in the solid state non-alkali-soluble, and in the liquid photocurable unsaturated monomers, oligomers, and

/或聚合物中不含有酸基,例如游离的羧基、磷酸根或硫酸根。 / Or polymer does not contain an acid group, for example a free carboxyl group, phosphate or sulfate. 晶片组合物中所用成分的重 Weight of ingredients used in the compositions of the wafer

量百分比以重量计,总计为100%,并如下所示: Amounts percentages are by weight, total 100%, and as follows:

[0041] 魁重暈% [0041] Halo Quebec weight%

[0042] 光固化丙烯酸酯成分..................................5-30% [0042] The photocurable acrylate component .................................. 5-30%

[0043] 液态多官能环氧树脂..................................10-45% [0043] The polyfunctional liquid epoxy resin .................................. 10-45%

[0044] 光引发剂............................................0.3-3% [0044] The photoinitiator ............................................ 0.3-3%

[0045] 低CTE填料...........................................40-70 % [0045] The low CTE filler ........................................... 40 -70%

[0046] 潜在性固化促进剂....................................1-3% [0046] The latent curing accelerator .................................... 1-3%

[0047] 在转化为热固性状态前,热可液化的固态底部填充胶组合物为自支撑、储存稳定并能在环境温度下经漫长的延迟时间仍维持与晶片或诸区域正面的粘附性,从而能够将底部填充胶的施用与焊料回流芯片安装步骤分开。 [0047] In the state before conversion into a thermoset, solid bottom heat liquefiable underfill composition is self-supporting, storage stable and can remain various areas of a wafer or the front adhesion by long delay time at ambient temperature, thereby separating the bottom of the underfill and solder reflow administration chip mounting step. 本发明能够在环境条件下储存晶片,供其后于PCB上的安装之用。 Wafer of the present invention can be stored at ambient conditions, for subsequent use in the mounting on the PCB.

[0048] 底部填充胶组合物的光固化成分包括在其结构中具有至少6个碳原子的烯键式不饱和单体或单体的混合物。 [0048] The photocurable component underfill composition comprises a mixture of ethylenically unsaturated monomer or monomers having at least 6 carbon atoms in their structure. 引入具有少于6个碳原子的单体会导致在光固化成固态时产生不可接受的挥发性问题,以及在转化成热可液化的光固化固态时导致收縮问题,该收縮倾向于对粘附于组合物的芯片增加应力。 Volatile issues into a single experience less than 6 carbon atoms result in unacceptable light cured to a solid, and the shrinkage results in problems when converted into heat liquefiable solid photocurable, the adhesion tends to shrink increased stress on the chip composition. 基于光固化成分总重含有高于10重量%液态多官能烯键式不饱和共聚单体的底部填充胶,会导致芯片安装过程中在焊料回流步骤中热可液化底部填充胶的熔融流动不足。 Containing more than 10 by weight of the total weight of liquid polyfunctional ethylenically unsaturated comonomers underfill% based on the photocurable composition, will result in the solder during the chip mounting reflow step heat-liquefiable underfill insufficient melt flow. 因此,优选的方面是在底部填充胶中不含多不饱和单体,或限制在不超过底部填充胶光固化成分重量的10重量%。 Thus, in a preferred aspect the underfill not contain polyunsaturated monomers, or not exceeding 10 wt limit underfill% by weight of a photocurable component.

[0049] 术语光固化成分统一是指无论以何种方式采用的烯键式不饱和单体和/或低聚物。 [0049] The term refers to a uniform photocurable composition ethylenically unsaturated monomer used in any way and / or oligomers. 更优选的是,烯键式不饱和材料包括乙烯基酯、乙烯基醚和/或a, P-不饱和丙烯酸酯。 More preferably, the ethylenically unsaturated materials include vinyl esters, vinyl ethers, and / or a, P- unsaturated acrylic ester. 优选的光固化成分是作为单体、不饱和低聚物或侧链不饱和低聚物及其组合的烯键式不饱和丙烯酸酯。 Preferred photocurable component as a monomer, oligomer or unsaturated pendant unsaturated oligomers and combinations thereof, ethylenically unsaturated acrylate. 术语低聚物是指在25t:下为液态、或能够溶解于光固化液体载体的不饱和化合物。 The term oligomer refers to 25t: the liquid state, or the compound can be dissolved in unsaturated photocurable liquid carrier. 可以使用非官能或饱和的热塑性聚合物稀释剂,例如聚丙烯酸酯、聚乙烯醚、聚乙烯酯、聚酯、聚酰胺、聚烯烃和官能化衍生物等,其条件是稀释剂的软化温度不会显著阻碍热可液化底部填充胶在焊料回流温度下的熔融流动。 Or you can use non-functional unsaturated thermoplastic polymer diluent, such as polyacrylates, polyvinyl ethers, polyvinyl esters, polyesters, polyamides, polyolefins and functionalized derivatives thereof, with the proviso that the softening temperature of the diluent is not significantly impede heat liquefiable underfill melt flowable at a solder reflow temperature. 这样的稀释剂可用于不同的特征,例如精确控制或提高熔融流动性和/或内聚强度。 Such a diluent may be used for different characteristics, such as precise control or enhance the cohesive strength and flowability of the molten / or.

[0050] 当含有光固化丙烯酸酯成分的晶片用底部填充胶在UV辐射的影响下聚合时,底部填充胶即在环境温度下从液态转变为固态。 [0050] When the wafer containing photocurable acrylate component with underfill polymerization under the influence of UV radiation, i.e., the underfill transition from the liquid state at ambient temperature, a solid state. 固体保持为热塑性,即其保持热可液化态直至热固化。 The solid remains thermoplastic, i.e. heat-liquefiable state it remains until heat cured. 光固化成分的规定量为底部填充胶总重的5_30重量%。 A predetermined amount of the photocurable component is the total weight of the underfill 5_30 wt%. 相对于光固化成分的重量而言,多官能环氧材料的用量对于光固化时提供充分的凝固以及在焊料回流步骤中保持熔融流动性是关键性的。 Relative to the weight of the photocurable composition, the amount of the polyfunctional epoxy material to provide sufficient photocuring solidification and remains in the solder reflow step is critical melt flowability. 在多官能环氧材料为高于10-45重量%的范围时,则底部填充胶在光固化后损坏晶片趋势也会增加。 Polyfunctional epoxy material that is higher than the range of 10-45% by weight, the underfill will increase trend in damage to the wafer after photocuring. 低于该范围,则在热可液化固体中没有足够的内聚强度,且在焊料回流前于环境温度储存中蠕变增加。 Below this range, there is not enough cohesive strength heat-liquefiable solid, and the creep increase storage at ambient temperature prior to solder reflow. 施于正面上的底部填充胶涂层的断面厚度最优选为使一部分焊料凸点被暴露的尺寸。 Applied to the bottom of section thickness on the front side and most preferably underfill coating is exposed portion of the solder bump size. 暴露是指金属暴露于空气中,或在焊料凸点的最外突出区域上,可能存在低于约0. 01 ii m的薄底部填充胶残余物。 Exposure refers to a metal exposed to the air, or on the outermost protruding regions of the solder bumps, there may be less than the bottom sheet of about 0. 01 ii m underfill residue. 在优选的实施方式中,光固化后底部填充胶涂层的厚度为焊料凸点剖面(profile)的50-90%。 In a preferred embodiment, the underfill coating after photocuring cross-sectional thickness of the solder bumps (Profile) of 50-90%. 剖面是延伸出晶片正面的表平面的焊料凸点部分的深度。 It is a cross-sectional view showing the depth of the solder bumps extending portion of the front surface plane of the wafer.

[0051] 本申请中任选使用的光固化低聚物在环境温度下为液态,或是能溶解于液态烯键式不饱和丙烯酸酯单体中的固体。 [0051] The present application optionally used in the photocurable oligomer is a liquid at ambient temperature, or can be dissolved in a liquid ethylenically unsaturated acrylate monomer solids. 低聚物含有一个或多个侧基或末端烯键式不饱和基团。 Oligomer containing one or more pendant or terminal ethylenically unsaturated groups. 典型的低聚物含有2个末端不饱和基团。 A typical oligomer containing two terminal unsaturated groups. 分子量为500-3000的低聚光固化丙烯酸酯成分中不饱和基团平均数可以为l-2。 Condensing a low molecular weight curable acrylate component of 500-3000 average number of unsaturated groups may be l-2. 光固化丙烯酸酯成分仅排除二、三或四以及更高的烯键式不饱和单体、二聚体或三聚体。 Photocurable acrylate component only negative di-, tri- or tetra-and higher ethylenically unsaturated monomers, dimers or trimers.

[0052] 本发明底部填充胶的实施方式在焊料回流条件下显示出足够的熔融流动,从而向外流出至芯片的边缘,并完全填充芯片下侧与PCB之间的空隙。 [0052] The bottom of the embodiments of the present invention the underfill embodiment exhibits sufficient melt flow under solder reflow conditions, thereby flowing out to the edges of the chip, and completely fill the gap between the lower side of the chip and the PCB. 在某些情况下,流出可包括沿管芯的边缘向上流动以形成填角,光固化的固体底部填充胶良好地粘合至晶片上,并具有供长期储存和/或划线而不会扭曲或破坏晶片所必需的足够内聚强度。 In some cases, may include an edge effluent flows upwards along the die to form a fillet, the bottom of the photocurable solid underfill adheres well to the wafer, and has for long-term storage and / or twisted without scribing or damage of the wafer necessary sufficient cohesive strength. 在储存的延迟期 In the delayed period of storage

间之后,当光固化丙烯酸酯成分与环氧功能性成分的重量比为i : io-i : 2,且光固化成分 After room, when the weight of the photo-curable epoxy acrylate component and the functional component is the i: io-i: 2, and the photo-curable composition

含有指定比例的单官能和多官能单体和/或低聚物时,热可液化固体在焊料回流步骤中遇 Containing the indicated proportions of monofunctional and polyfunctional monomers and / or oligomers, in the case of a solid heat liquefiable solder reflow step

到的受热下充分流动。 Under sufficiently fluid to heat. 在光固化成分与环氧功能性成分的比例低于i : io的情况下,底部填充胶通常缺乏足够的内聚强度和/或显示出不可接受的表面粘性。 In the photocurable composition and the proportion of the epoxy functional component is less than i: io case, the underfill often lack sufficient cohesive strength and / or exhibit unacceptable surface tack. 在该比例高于i : 2的情况下,晶片显示出扭曲、破坏和/或底部填充胶趋向于分层或用于形成填角的流动不充分。 In case the ratio is higher than the i: case 2, the wafer exhibits distortions, destruction and / or delamination underfill tends to flow or to insufficient formation of the fillet.

[0053] 本申请中可使用的例示性的单烯键式不饱和单体是具有至少6个碳原子的单体, [0053] Example monoethylenically unsaturated monomers in the present exemplary application that can be used are monomers having at least 6 carbon atoms,

11包括丙烯酸或c「c;烷基取代的丙烯酸的烷基C3-(^烷基酯,其统称为(烷基)丙烯酸酯。 11 include acrylic or c 'c; alkyl-substituted acrylic acid alkyl C3 - (^ alkyl ester, collectively referred to as (alkyl) acrylate.

合适的单官能单体的具体例子包括丙烯酸丁酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸环己酯、甲基丙烯酸三甲基环己酯、环醚丙烯酸酯和单环状縮醛丙 Specific examples of suitable monofunctional monomers include butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, cyclic ether acrylates and monocyclic acetal prop

烯酸酯。 Enoate. 单环状状縮醛丙烯酸酯是已知的,并在美国专利No.4,076,727中公开。 Shaped monocyclic acetal acrylates are known, and are disclosed in U.S. Patent No.4,076,727. 縮醛丙烯酸酯经如下衍生得到:将多元醇例如三羟甲基丙烷、三羟甲基乙烷、甘油、l,2,4-丁三醇、1,2,5-戊三醇和1,2,6_己三醇与醛反应,并与a , 13 -不饱和羧化物例如丙烯酸或酯进行酯交换而得到。 Formal acrylate was derived as follows: polyhydric alcohols such as trimethylolpropane, trimethylolethane, glycerol, l, 2,4- butanetriol, 1,2,5-pentanetriol and 1,2 , 6_ hexanetriol reacted with an aldehyde, and with a, 13 - unsaturated carboxylic acid or esters thereof, for example, obtained by transesterification. 例示性的光固化成分是含有环醚的丙烯酸酯如丙烯酸四氢糠酯(THFA)与环状羟烷基甲縮醛丙烯酸酯的组合。 Example Exemplary photocurable component containing an acrylate of cyclic ethers such as acrylic acid composition tetrahydrofurfuryl acrylate (THFA) and methylal cyclic hydroxyalkyl acrylate. 优选的单官能丙烯酸酯是丙烯酸四氢糠酯、甲基丙烯酸四氢糠酯、单甲基丙烯酸季戊四醇酯、单丙烯酸季戊四醇酯、三羟甲基丙烷单甲基丙烯酸酯、三羟甲基丙烷单丙烯酸酯、环状羟烷基甲縮醛丙烯酸酯和縮酮丙烯酸酯。 The preferred monofunctional acrylates are acrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, pentaerythritol monomethacrylate, pentaerythritol monoacrylate, trimethylolpropane monomethacrylate, trimethylolpropane mono acrylate, cyclic acetals hydroxyalkyl acrylate and methyl acrylate ketal. 縮醛丙烯酸酯和縮酮丙烯酸酯可以包括异构体混合物。 Acetals and ketals acrylic acrylates may include a mixture of isomers. 环状羟烷基甲縮醛丙烯酸酯和环状羟烷基縮酮丙烯酸酯可容易地通过使用衍生自三元醇的一羟基縮醛将丙烯酸酯或甲基丙烯酸酯酯化而制得,所述三元醇例如三羟甲基丙烷和三羟乙基丙烷。 A cyclic acetal hydroxyalkyl acrylates and hydroxyalkyl cyclic ketal acrylates may be easily accomplished by using an acetal derived from a triol of the hydroxy acrylate or methacrylate prepared by esterification, by said triols such as trimethylol propane and tris-hydroxyethyl-propane. 可与醛或酮反应,且使用丙烯酸酯或甲基丙烯酸酯进行丙烯酸酯化的合适三元醇原料的结构包括下式:[0054] 优选的环状羟烷基甲縮醛丙烯酸酯具有下述结构(AC)[0055] Suitable starting materials triol structure with an aldehyde or ketone, and an acrylate or methacrylate acrylated comprises the formula: [0054] A preferred cyclic acetal hydroxyalkyl acrylate has the following structure (AC) [0055]

12<formula>formula see original document page 13</formula> 12 <formula> formula see original document page 13 </ formula>

[0056] 其中,&是C「Q亚烷基,例如_CH2-、-CH2CH2-等,R2、R3和R4是H或C「Q烷基,例如-CH3、-CH2CH3等。 [0056] wherein, C is & "Q alkylene, e.g. _CH2 -, - CH2CH2-, etc., R2, R3 and R4 are H or C" Q alkyl, e.g. -CH3, -CH2CH3 and the like.

[0057] 最优选的环状羟烷基甲縮醛丙烯酸酯是三羟甲基丙烷甲縮醛丙烯酸酯(结构B,)。 [0057] The most preferred cyclic formals hydroxyalkyl acrylate is trimethylolpropane formal acrylate A (structure B,).

[0058] 单独使用或与任意的上述单体组合使用的其它光固化单体包括甲基丙烯酸乙酰乙酰氧基乙酯、丙烯酸-2_乙酰乙酰氧基乙酯、甲基丙烯酸_2-乙酰乙酰氧基丙酯、丙烯酸_2-乙酰乙酰氧基丙酯、甲基丙烯酸_2-乙酰乙酰氨基乙酯、丙烯酸-2-乙酰乙酰氨基乙酯、甲基丙烯酸_2-氰基乙酰氧基乙酯、丙烯酸-2-氰基乙酰氧基乙酯、N-(2-氰基乙酰氧基乙基)丙烯酰胺、丙烯酸-2-丙酰基乙酰氧基乙酯、N-(2-丙酰基乙酰氧基乙基)甲基丙烯酰胺、N-4-(乙酰乙酰氧基苄基)苯基丙烯酰胺、乙酸乙基丙烯酰酯、乙酸丙烯酰基甲酯、N-乙基丙烯酰氧基甲基乙酰乙酰胺、乙酰乙酸乙基甲基丙烯酰酯、N-烯丙基氰基乙酰胺、乙酰乙酸甲基丙烯酰酯、N-(2-甲基丙烯酰氧基甲基)氰基乙酰胺、甲基丙烯酸_乙基-a _乙酰乙酰氧酯、N- 丁基-N-丙烯酰氧基乙基乙酰乙酰胺,单丙烯酸酯化的多元 [0058] alone or with any other photocurable monomers of the monomer combination include acetoacetoxyethyl methacrylate, ethyl acrylate, -2_ acetoacetoxyethyl methacrylate, acetoacetoxyethyl methacrylate, _2- group, propyl acrylate _2- acetoacetoxy propyl methacrylate, acetoacetoxyethyl _2- amino ethyl, amino ethyl acrylate, 2-acetoacetoxyethyl methacrylate, _2- cyano acetoxyacetyl acrylate, 2-acetoxyethyl cyano, N- (2- cyanoacetoxyethyl) acrylamide, 2-propionyl-acetoxyethyl, N- (2- acetyl propionyl oxyethyl) methacrylamide, N-4- (acetoacetoxy) phenyl acrylamide, acryl acid ethyl ester, acrylic acid ester group, N- ethyl-acryloyloxymethyl acetoacetamide, ethyl acetoacetate methacryloyloxy ester, N- allyl cyanoacetamide, acetic acid methacholine acryl ester, N- (2- methacryloyloxy methyl) cyanoacetamide methacrylate _ _ -a acetoacetoxy ethyl acrylate, N- butyl -N- acryloyloxyethyl acetoacetamide, single acrylated polyol ,以及含羟基的丙烯酸酯与酸酐的反应产物如邻苯二甲酸单甲基丙烯酰氧基乙酯。 , And a reaction product of acrylate containing a hydroxyl group with an acid anhydride such as phthalic acid monomethyl methacryloyloxyethyl. 可与(烷基)丙烯酸酯单体共聚的共聚单体,前提是与丙烯酸酯单体相比,该聚合速率并没有减慢到明显的程度。 May, in comparison with the proviso that the acrylate monomers with (alkyl) acrylate comonomers copolymerizable monomers, the polymerization rate is not slowed to significant extent.

[0059] 丙烯酸单体的快速光固化是期望的特征。 [0059] Quick photocurable acrylic monomer is a desirable feature. 除丙烯酸酯和烷基丙烯酸酯之外的可光固化烯键式不饱和单体限于约6个碳原子或更高级,其例子包括但并不限于丁基乙烯基醚、异丁基乙烯基醚、环己基乙烯基醚对-(2_乙酰乙酰基)乙基苯乙烯、和4-乙酰乙酰基-l-甲基丙烯酰氧基哌嗪。 In addition to alkyl acrylates and acrylate photocurable ethylenically unsaturated monomer is limited to about 6 carbon atoms, or higher, examples of which include, but are not limited to butyl vinyl ether, isobutyl vinyl ether , cyclohexyl vinyl ether of - (2_ acetoacetyl) ethylstyrene, 4-acetyl-acetyl group and methacryloxy group -l- piperazinyl. 含有环氧反应性基团的烯键式不饱和单体并不用于光固化成分中,所述环氧反应性基团例如含有活性氢的基团。 Ethylenically unsaturated monomers containing epoxy groups are not reactive to the photocurable composition, the epoxy group-containing reactive group e.g. active hydrogen.

[0060] 已知多官能烯键式不饱和化合物的代表是烯二不饱和单体,例如二丙烯酸乙二醇酯、聚二丙烯酸乙二醇酯、二甲基丙烯酸乙二醇酯、二丙烯酸己二醇酯和二丙烯酸三甘醇酯。 Representative [0060] Known polyfunctional ethylenically unsaturated compound is an ethylenically diunsaturated monomers such as ethylene glycol diacrylate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, di-hexyl acrylate glycol diacrylate and triethylene glycol dimethacrylate. 代表性的三不饱和单体包括三羟甲基丙烷三丙烯酸酯(TMPTA)、三羟甲基丙烷三甲基丙烯酸酯、三丙烯酸甘油酯、三丙烯酸季戊四醇酯和三甲基丙烯酸季戊四醇酯。 Representative three unsaturated monomers include trimethylolpropane triacrylate (of TMPTA), trimethylolpropane trimethacrylate, glycerol triacrylate, pentaerythritol triacrylate and pentaerythritol trimethacrylate. 代表性的丙烯酸不饱和光固化材料是来自Sartomer, Exton, PA的SR205、 SR306、 CD401、 SR508、 SR603、SR9036。 Representative unsaturated photocurable acrylic material from Sartomer, Exton, PA's SR205, SR306, CD401, SR508, SR603, SR9036.

[0061] 可包含在光固化成分中的其它合适光聚合性低聚物材料有,例如基于双酚的聚醚丙烯酸酯、乙烯基醚封端的低聚物、羟基官能性丙烯酸酯和甲基丙烯酸酯与环氧化物的反应产物、丙烯酸酯化的聚醚、烯键式不饱和聚烷基醚、上述的环醚丙烯酸酯和环醚縮醛丙烯酸酯。 Other suitable photopolymerizable oligomer material [0061] may be included in the photocurable component are, for example, bisphenol based polyether acrylates, ether terminated oligomer of vinyl, hydroxyl functional acrylates and methacrylates ester reaction product with an epoxide, acrylated polyethers, ethylenically unsaturated polyalkylethers, the above-described cyclic ethers and cyclic ether acrylates formal acrylate.

[0062] 光聚合成分可以是单不饱和丙烯酸酯单体和数均分子量为500-5000,优选为1000-4000的烯键式不饱和低聚物的混合物。 [0062] The photopolymerizable component may be mono-unsaturated acrylate monomers number average molecular weight of 500-5000, preferably 1000-4000 mixture of ethylenically unsaturated oligomer. 液态光固化低聚物可包括不具有异氰酸酯活性基团的聚氨酯丙烯酸酯低聚物。 Liquid photocurable oligomer may comprise urethane acrylate having no isocyanate-reactive groups of the oligomer. 聚氨酯丙烯酸酯低聚物还可与烯键式不饱和丙烯酸酯单体组合。 Urethane acrylate oligomer and further ethylenically unsaturated acrylate monomer composition. 丙烯酸酯化的聚氨酯可以是脂族或芳族的。 Acrylated polyurethane may be aliphatic or aromatic. 市售的丙烯酸酯化聚氨酯的例子包括如下商品名的公知产品:来自Henkel Corp. Hoboken, NJ的PH0T0MER(如PH0T0MER6010);来自UCB Radcure Inc. Smyrna, Ga.的EBECRYL 220 (分子量为1000的六官能芳族聚氨酯丙烯酸酯)、EBECRYL 284(以1,6_己二醇二丙烯酸酯稀释的分子量为1200的脂族聚氨酯二丙烯酸酯)、EBECRYL 4827 (分子量为1600的芳族聚氨酯二丙烯酸酯)、EBECRYL4830 (通过四乙二醇二丙烯酸酯稀释的分子量为1600的芳族聚氨酯二丙烯酸酯)、EBECRYL6602 (以三羟甲基丙烷乙氧基三丙烯酸酯稀释的分子量为1300的三官能芳族聚氨酯丙烯酸酯)、和EBECRYL 840 (分子量为1000的脂族聚氨酯二丙烯酸酯);来自于Sartomer Co.,Exton,Pa.的SARTOMER (例如SARTOMER 9635, 9645, 9655, 963-B80,966-A80等)和来自于Morton International, Chicago, III的UVIT應E(例如UVIT應E 782)。 Examples of commercially available acrylated urethane products include well-known trade names as follows:. PH0T0MER (eg PH0T0MER6010) from Henkel Corp. Hoboken, NJ's; EBECRYL 220 from UCB Radcure Inc. Smyrna, Ga (molecular weight of 1000 to hexafunctional aromatic urethane acrylate), EBECRYL 284 (in 1,6_ hexanediol diacrylate diluted with 1200 molecular weight aliphatic urethane diacrylate), EBECRYL 4827 (molecular weight aromatic urethane diacrylate of 1600), EBECRYL4830 (tetraethylene glycol diacrylate by diluting a molecular weight of aromatic urethane diacrylate of 1600), EBECRYL6602 (trimethylol propane ethoxylate triacrylate diluted with molecular weight trifunctional aromatic urethane acrylate of 1300 ester), and EBECRYL 840 (1000 molecular weight aliphatic urethane diacrylate);. from Sartomer Co., Exton, Pa's SARTOMER (e.g. SARTOMER 9635, 9645, 9655, 963-B80,966-A80, etc.) and from Morton International, Chicago, III of UVIT should E (e.g. UVIT should E 782). [0063] 任选可包含于光固化丙烯酸酯成分中的是具有一个或多于一个光固化不饱和丙烯酸酯基团的、以丙烯酸酯改性的环氧材料,例如双酚A环氧树脂的二丙烯酸酯,尽管这样的混合物是不优选的。 [0063] optionally be included in the photocurable acrylate component is one having one or more photo-curable unsaturated acrylate group, epoxy acrylate-modified material, such as bisphenol A epoxy resin diacrylate, although such mixtures are not preferred. 代表性的丙烯酸酯改性环氧通过丙烯酸酯上的羟基与环氧乙烷基团反应而得到。 Representative epoxy acrylate obtained by modifying hydroxy groups with ethylene oxide, the acrylate reaction. 没有未反应的可固化环氧官能团残留。 Curable epoxy functional groups no unreacted residues. 丙烯酸酯化的环氧化物的市售例子包括来自Radcure Specialties的商品名为CMD的产品。 Examples of commercially available acrylated epoxies include goods from Radcure Specialties under the product name of CMD. 其它合适的丙烯酸不饱和环氧低聚物或聚氨酯丙烯酸酯低聚物有市售,例如来自Sartomer的CN929、 CN136、 CN970、 CN104、CN120C60。 Other suitable unsaturated epoxy acrylate oligomer or a urethane acrylate oligomers are commercially available, for example from Sartomer CN929, CN136, CN970, CN104, CN120C60. 特有的丙烯酸酯改性环氧液体可通过另外的单或多官能丙烯酸酯而配制。 Specific modified epoxy acrylate prepared by an additional liquid may be mono- or multi-functional acrylates. 任意的另外单或多官能丙烯酸酯单体的含量处于光固化成分的总组成范围内。 The total content of the composition within the range of any further mono- or multifunctional acrylate monomer in the photocurable composition. [0064] 代表性的二丙烯酸酯官能的光固化材料包括SR205、 SR306、 CD401、 SR508、 SR603、SR9036。 [0064] Representative diacrylate functional photocurable materials include SR205, SR306, CD401, SR508, SR603, SR9036. 代表性的三官能材料包括SR350、 SR444、 CD501、 SR9021。 Representative trifunctional materials include SR350, SR444, CD501, SR9021. 四官能的丙烯酸酯包括SR295、 SR355、 SR399、 SR9041。 Tetrafunctional acrylates include SR295, SR355, SR399, SR9041.

[0065] 底部填充胶的热固性多官能环氧树脂成分包括至少一种液体树脂,所述液体树 [0065] The thermosetting underfill polyfunctional epoxy resin component comprises at least one liquid resin, the liquid tree

脂含有至少两个环氧基,在25t:下具有低于约io,ooo泊的粘度,每环氧化物的平均重量 Lipid containing at least two epoxy groups in the 25t: having less than about io lower, OOO poise, the average weight per epoxide

(WPE)范围为约100-约IOOO,且平均分子量范围为约500-约3500。 (WPE) in the range of about 100 to about IOOO, and an average molecular weight ranging from about 500 to about 3500. 可容易使用的环氧化物是已知的,包括双酚A的二縮水甘油醚、2,2-双-4-(2,3-环氧丙氧基)-苯基)丙烷。 Epoxides can be readily used are known, include bisphenol A diglycidyl ether, 2,2-bis-4- (2,3-epoxypropoxy) - phenyl) propane. 市售的合适环氧化合物以如下商品名出售:来自Shell Chemical Co.的EPON 828、EP0N1004和EP0N1001F,和来自Dow Chemical Co的DER_331、 DER-332和DER_334。 Suitable commercially available epoxy compounds sold under the trade names: EPON 828 from Shell Chemical Co. of, EP0N1004 and EP0N1001F, and DER_331 from the Dow Chemical Co, DER-332 and DER_334. 其它合适的环氧树脂包括环脂族环氧化物、苯酚甲醛酚醛清漆的縮水甘油醚(例如来自DowChemical Co的DEN-431和DEN-428)。 Other suitable epoxy resins include cycloaliphatic epoxies, glycidyl ethers of phenol formaldehyde novolac (e.g. DowChemical Co from the DEN-431 and DEN-428). 自由基固化树脂和环氧树脂的共混物在美国专利No. 4, 751, 138 (Tumey等)和美国专利No. 5, 256, 170 (Harmer等)中有进一步描述。 Free radical curable epoxy resin and a blend of U.S. Patent No. 4, 751, 138 (Tumey et) and U.S. Pat. No. 5, 256, 170 in (Harmer, etc.) described further. 在优选的实施方式中,采用三种环氧树脂的组合,其是WPE为约192g/eq.的联苯环氧树脂、WPE为约172g/eq.的双酚F的二縮水甘油醚、WPE为约101g/eq.的对氨基苯酚的三縮水甘油醚的混合物。 In a preferred embodiment, the use of a combination of three epoxy resins, biphenyl epoxy resin which is a WPE of about 192g / eq., The WPE of about 172g / eq. Diglycidyl ether of bisphenol F, WPE about 101g / eq. of a mixture of a triglycidyl ether of p-aminophenol. 这三种环氧树脂的市售商品名分别为RSS、 EPICL0N和ARALDITE。 These three epoxy resins are commercially available under the trade name RSS, EPICL0N and ARALDITE. [0066] 液态晶片涂层含有约1-3重量%的至少一种光引发剂,其能使液体底部填充胶在暴露于常规级别的光化辐射时有效凝固成不发粘的表面。 [0066] wafer coating liquid containing about 1-3% by weight of at least one photoinitiator, which enables effective bottom liquid underfill solidified into non-tacky surface when exposed to actinic radiation regular level. 所选择的光引发剂类型取决于期望的固化深度、所采用的造影剂类型和优选采用的辐射波长。 The depth of cure photoinitiator selected agent depends on the type of the desired wavelength of radiation used and the type of contrast agent is preferably employed. 适用于本申请用途的、产生游离基的市售光引发剂包括,但并不限于二苯甲酮、安息香醚和酰基膦氧化物类光引发剂,例如以如下商品名出售的产品:来自Ciba Specialty Chemicals, Basel, Switzerland的IRGACURE⑧和DAROCUR⑧。 Suitable for the present application purposes, a commercially available free-radical generating photoinitiators include, but are not limited to benzophenone, benzoin ether and acylphosphine oxide photoinitiators, for example, products sold under the trade names: from Ciba Specialty Chemicals, Basel, Switzerland and the IRGACURE⑧ DAROCUR⑧.

[0067] 优选的光引发剂体系是如下混合物:25% -50%的酮_官能性光引发利和50% _75%的单酰基膦、二酰基膦氧化物或含有膦酸酯的光引发剂。 [0067] The preferred photoinitiator system is a mixture of the following: 25% -50% of a ketone functional photoinitiators _ Lee _75% and 50% of the monoacylphosphine, bisacylphosphine oxide or phosphonate containing light initiators. 酮光引发剂的例子包括1_羟基环己基苯基酮、羟基甲基苯基丙酮、二甲氧基苯基苯乙酮、2-甲基-1-[4(甲硫基)-苯基]-2-吗啉丙酮-1 , 1- (4-异丙基苯基)-2-羟基-2-甲基丙-1-酮、1- (4-十二烷基-苯基)-2-羟基-2-甲基丙-1-酮、4- (2-羟基乙氧基)苯基-2- (2-羟基-2-丙基)-酮、二乙氧基苯基苯乙酮、2, 4, 6-三甲基苯甲酰基二苯膦、2-羟基-2-甲基-1-苯基丙-1-酮、l-[4-(2-羟基乙氧基)苯基]_2-羟基-2-甲基丙-l-酮、2-羟基噻吨-9-酮。 Examples of the photoinitiator include 1_ hydroxycyclohexyl phenyl ketone, acetone-hydroxymethylphenyl, dimethoxyphenyl acetophenone, 2-methyl-1- [4 (methylthio) - phenyl ] -2-morpholino propanone-1, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecyl-phenyl) - - hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (2-hydroxy-2-propyl) - one, diethoxyphenyl acetophenone ketone, 2, 4, 6-trimethyl benzoyl diphenyl phosphine, 2-methyl-1-phenyl-propan-1-one, l- [4- (2- hydroxyethoxy) phenyl] -l- _2- hydroxy-2-methylpropane, 2-hydroxy-thioxanthen-9-one. 代表性的酰基膦氧化物光引发剂包括乙基-2, 4, 6-三甲基苯甲酰基二苯膦氧化物、2, 4, 6-三乙基苯甲酰基二苯基膦氧化物、2,4,6-三苯基苯甲酰基二苯基膦氧化物。 Representative acyl phosphine oxide photoinitiators include ethyl-2, 4, 6-trimethyl benzoyl diphenyl phosphine oxide, 2, 4, 6-trimethyl benzoyl diphenyl ethyl phosphine oxide , 2,4,6-triphenyl benzoyl diphenyl phosphine oxide. 供晶片用液体底部填充胶深度固化使用的光引发剂成分的特定例子是基于底部填充胶总重为0. 2-0. 5重量%的1-羟基环己基苯基酮以及基于底部填充胶总重为0. 5-0. 7重量%的苯基双(2, 4, 6-三甲基苯甲酰基)膦氧化物。 Specific examples for the liquid underfill adhesive wafer with the depth of light curing initiator component used is based on the total weight of the underfill 0. 2-0. 5% by weight of 1-hydroxycyclohexyl phenyl ketone based on the total underfill weight of 0. 5-0. 7% by weight of phenyl-bis (2, 4, 6-trimethyl benzoyl) phosphine oxide.

[0068] 不会将涂层温度升至高于12(TC的任意光化光剂量源均可用于将底部填充胶光固化凝固为可液化的固体凝胶状态。最容易采用的是紫外光,也可以是其它的形式,例如TypeRS日光灯、碳弧灯、氙弧灯、水银放电灯、钨卤化物灯等。辐射能可从点源发出,或以平行射线形式发出。然而,发散的光束也可作为光化光源。在100-2400mJ/cm2范围内的UV量能为底部填充胶有效提供约1. 2-1. 8mm的固化深度,且能在底部填充胶温度低于IO(TC下完成辐射聚合。底部填充胶组合物光固化成不发粘的表面。固化时间可通过选择合适的紫外光源、底部填充胶光固化成分浓度和造影剂进行调整。[0069] 在封装组件中,产品的自动目视检查需要使用颜料,用以在板、底部填充胶和芯片之间提供对比。合适的有诸如炭黑的造影剂和诸如以Clariant AG的Sandorin⑧牌购得的颜料。在一个实施方 [0068] The coating temperature is raised not higher than 12 (TC any source of actinic light dose may be used in filling the bottom of the light curing adhesive sets to a solid liquefiable gel state. Easiest used is ultraviolet light, and other forms may be, e.g. TypeRS fluorescent lamps, carbon arc lamps, xenon arc lamps, mercury discharge lamps, tungsten halide lamps. radiant energy may be emitted from a point source, or issued in the form of parallel rays. However, the divergent beam may be as the actinic light source. UV in an amount 100-2400mJ / cm2 range is able to provide a cured underfill effective depth of about 1. 2-1. 8mm, and can complete the radiation is less than IO (TC temperature in the underfill polymerization. underfill composition is photocurable to a non-tacky surface curing time can be filled with plastic light bottom curable component concentration and the contrast is adjusted by selecting a suitable ultraviolet source. [0069] in the package assembly, the product is automatically pigment visual inspection required to provide a contrast between the boards and chip underfill. suitable carbon black has such a contrast agent such as in Sandorin⑧ card and the commercially available pigment Clariant AG. in one embodiment 式中,将分散了15重量%炭黑的环氧树脂用于在底部填充胶中掺入0. 1_0.2重量%的炭黑,用作为自动目视检查提供有效的对比。[0070] 棚德《 Wherein the carbon black is 15 wt% dispersion of carbon black for the underfill epoxy resin incorporated 1_0.2 0.5% by weight, with the effective contrast as to provide an automatic visual inspection. [0070] Shed Germany "

[0071] 本发明中使用的环氧固化体系是含有潜在性促热剂的非熔化类型,其中所述促热剂的固化开始温度大于15(TC,优选大于160°C 士5t:,更优选为175°C 士5。C及更高。采用用于环氧树脂的潜在性热固化剂,用于使凝固、老化的底部填充胶在焊料回流发生后所遭遇的温度下引发固化至热固性阶段。双氰胺不能单独用作热固化剂,但可以少量地与潜在性促热剂联用,但优选不含双氰胺。优选的潜在性热固化剂包括胺、胺加合物;其包括咪唑和脲衍生物,例如2,4,6-三甲基-l,3-双(3,3-二甲基脲基)苯和1,5_双(3,3_二甲基脲基)萘。热固化剂必须是非卤化的。固化剂的例子可以以如下如美国专利No. 5, 543,486所教导的已知方法获得:将环氧化合物或异氰酸酯化合物与胺化合物混合,或者将环氧化合物或异氰酸酯化合物、胺化合物与活性氢化合物混合。各种 [0071] The epoxy curing system of this invention is used comprising non-melting type thermal latent promoting agent, wherein the curing initiation temperature of the heat promoting agent is greater than 15 (TC, preferably greater than 160 ° C and more preferably 5t :, disabilities 5.C disabilities to 175 ° C and higher. using latent heat-curing agent for epoxy resins, for solidified, aged underfill to initiate curing of the thermosetting stage occurs at the solder reflow temperatures encountered dicyandiamide can be used alone as a thermal curing agent, but can be used with a small amount of thermal latent pro-linking agent, preferably dicyandiamide, but is preferably free of latent thermal curing agents include amines, amine adduct;. which comprises imidazoles and urea derivatives, such as 2,4,6-trimethyl -l, 3- bis (3,3-dimethyl-ureido) benzene and bis 1,5_ (3,3_-dimethylureido ) naphthalene thermal curing agent must be non-halogenated examples of curing agents such as the following may be 5, 543,486 a method is known as taught in U.S. Patent No. obtained: epoxy compound or an isocyanate compound is mixed with an amine compound, or an epoxy compound or an isocyanate compound, an amine compound is mixed with an active hydrogen compound. various 端的胺(blocked amine)均可适用。优选的热固化剂是带有叔胺和脲部分的保护性胺。适用于热固化成分的例示性的咪唑是2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2_ i^—碳烯基咪唑、1-乙烯基-2-甲基咪唑、2-正十七烷基咪唑、2- i^—烷基咪唑、2-十七烷基咪唑、2-乙基-4-甲基咪唑、、l-节基-2-甲基咪唑、1-丙基_2-甲基咪唑、l-氰基乙基-2-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2- i^—烷基咪唑、1-氰基乙基-2-苯基咪唑、1-胍氨基乙基-2-甲基咪唑、2-(对二甲基氨基苯基)-4,5- 二苯基咪唑、2-(2-羟基苯基)-4, 5- 二苯基咪唑、2-苯基-4-羟基甲基咪唑、2-苯基_4, 5- 二(羟基甲基)_咪唑、二(4, 5- 二苯基-2-咪唑)-苯-1, 4, 2-萘基-4, 5- 二苯基咪唑、咪唑与偏苯三酸的加成产物、咪唑与2-正十七烷基-4-甲基咪唑的加 Terminal amine (blocked amine) can be applied. Preferred is a thermal curing agent and having a tertiary amine-protected urea moiety suitable for thermosetting component illustrative embodiment imidazole is 2-methylimidazole, 2-ethylimidazole , 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2_ i ^ - C-vinylimidazole, 1-vinyl-2-methylimidazole, 2 - n-heptadecylimidazole, 2- i ^ - alkyl imidazole, 2-heptadecyl imidazole, 2-ethyl-4-methylimidazole section ,, l--2-methylimidazole, 1- propyl _2- methylimidazole, l- cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-I ^ - alkyl imidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanidino-amino-2-methylimidazole, 2- (p-dimethylaminophenyl) -4,5-diphenyl imidazole, 2- (2-hydroxyphenyl) -4, 5-phenylimidazole, 2-phenyl-4-hydroxymethyl imidazole, 2-phenyl-_4, 5-bis (hydroxymethyl) _ imidazole, bis (4,5-diphenyl-2-imidazole) - benzene-1, 4-addition product, 2-naphthyl-4,5-diphenyl imidazole, imidazole and trimellitic acid, imidazole 2-n-heptadecyl-4-methylimidazole added 成产物、苯基咪唑、苄基咪唑、1-(十二烷基苄基)_2-甲基咪唑、2- (2-羟基-4-叔丁基苯基)-4, 5- 二苯基咪唑、2- (2-甲氧基苯基)-4, 5- 二苯基咪唑、2-甲基-4, 5- 二苯基咪唑、2, 3, 5-三苯基咪唑、2-苯乙烯基咪唑、2- (3-羟基苯基)-4, 5- 二苯基咪唑、1-节基-2-甲基咪唑和2-对甲氧基苯乙烯基咪唑。优选的热固化剂是从Air Products and Chemicals购得的名为CurezoKD 2-fflZ-S的 To a product, phenylimidazole, benzylimidazole, 1- (dodecyl benzyl) _2- methylimidazole, 2- (2-hydroxy-4-tert-butylphenyl) -4, 5-diphenyl imidazole, 2- (2-methoxyphenyl) -4,5-diphenyl-imidazole, 2-methyl-4,5-diphenyl imidazole, 2, 3, 5-triphenyl imidazole, 2 styrene-imidazole, 2- (3-hydroxyphenyl) -4, 5-diphenyl imidazole, 1-methylimidazole-2 section and 2- preferred thermal curing of the methoxystyryl imidazole agents are commercially available from Air Products and Chemicals called CurezoKD 2-fflZ-S in

A 口广PR o A mouth wide PR o

[0072] 替换性的热固化剂可以包括封端的路易斯酸,例如可以使用潜在性乙酰乙酸合金属-官能性固化剂,如铝螯合物,包括乙酰乙酸乙酯合金属二异丙醇盐、三(乙酰乙酸乙酯)合金属、乙酰乙酸烷酯合金属二异丙醇盐、单十六烷基丙酮合铝双(乙酰乙酸乙酯)、三(乙酰丙酮)合铝;环状铝低聚物的实例包括环状氧化铝异丙醇盐。 [0072] The alternative may include a heat curing agent blocked Lewis acids, for example, using metal bonding potential acetoacetate - functional curing agents, such as aluminum chelate include ethyl acetoacetate diisopropylate metal, tris (ethylacetoacetate), a metal, a metal bonded alkyl esters of acetoacetate diisopropylate, aluminum mono hexadecyl acetone bis (ethylacetoacetate), tris (acetylacetonato) aluminum; aluminum cyclic low examples of homopolymers include cyclic aluminum oxide isopropoxide.

[0073] 为了对可液化的光固化固体提供足够的回流,储存延迟期间在晶片或小片上的光固化固体涂层中的热固化体系不发生进展。 [0073] In order to provide adequate reflux for the photocurable liquefiable solid, solid photocurable storage progress on the wafer or die coating delays during the heat curing system does not occur. 通过对所采用的热固化剂进行选择而预先确定热固化开始的最低温度,并在焊料回流开始后在温度高于或等于15(TC下发生热固化。优选地,底部填充胶热固化开始的最低温度范围为150°C _225°C。热固化开始温度和固化速率峰值可以容易地通过差示扫描量热法确定,其是本领域内已知的。热固化开始温度取决于促进剂的选择和量,应不高于280°C。热固化开始时不能过于接近峰值温度,通常该峰值温度对于低共熔焊料为或接近25(TC,对于无铅焊料为或接近30(rC。通常的焊料回流时间为 By heat-curing agent used is selected in advance to determine the lowest temperature of the thermosetting started, and at a temperature higher than or equal to 15 starts after the solder reflow (heat curing occurs at TC. Preferably, the thermosetting underfill start minimum temperature range of 150 ° C _225 ° C., and heat curing initiation temperature of the curing rate peaks can be easily determined by differential scanning calorimetry to determine which are known in the art. heat curing initiation temperature depends on the choice of promoter and amounts, should not exceed 280 ° C. can not be too close to the peak temperature of the start time of thermal curing, usually at the peak temperature for eutectic solder or close to 25 (TC, for lead-free solder at or near 30 (rC. normal solder reflow time

163-4分钟,且底部填充胶在峰值温度下的暴露通常少于30秒。 163-4 minutes, and underfill exposed at the peak temperature is typically less than 30 seconds. 在低于15(TC的温度下引发的热固化导致底部填充胶液化和流动不充分。 Induced in (TC at a temperature below 15 cause the thermosetting underfill glue and insufficient flow.

[0074] 非传导性填料被用于限制底部填充胶中的CTE。 [0074] The non-conductive filler is used to limit the underfill CTE. 这些填料是已知的并有多种适合类型。 These fillers are well known and a variety of suitable types. 基于期望的属性与成本,可选择使用微电子级的熔融石英、晶体石英、氮化硼、铝和硅、氧化镁、硅酸镁和硅石涂覆的铝。 Based on the desired properties and cost, the option of using microelectronic grade fused silica, crystalline quartz, boron nitride, aluminum, and silicon, magnesium oxide, magnesium silicate and silica-coated aluminum. 在液态底部填充胶中形成的粘度是选择的标准。 Viscosity formed in the liquid underfill is selected criteria. 由于不含溶剂或非反应性稀释剂,根据本发明的底部填充胶实施方式可容易地适于采用相对低粘度涂层的方法,例如已知的旋涂法。 Since no solvent or non-reactive diluent, a bottom underfill embodiments of the present invention may be readily adapted embodiment using a relatively low viscosity of the coating method such as spin coating method is known. 根据本发明可旋转涂曝的底部填充胶实施方式具有的常规粘度,比通过镂花涂装或印刷而施用的底部填充胶的通常粘度相对更低。 According to the present invention may be the bottom of the spinner exposed underfill embodiment having a viscosity of conventional embodiment, than the bottom administered by stenciling or printing underfill is typically relatively lower viscosity. [0075] 在优选的实施方式中,底部填充胶以覆盖锯线间各晶片区域的至少70%的模式通过镂空印刷进行施用。 [0075] In a preferred embodiment, the underfill of at least 70% coverage pattern saw wire between each wafer area administered by a perforated print. 热固性状态中的底部填充胶的CTE范围为15-50ppm广C,要求一定水平的非传导性填料,优选为用量范围40重量% -70重量%的球形熔融石英粒子,优选为45 重量% -60重量% 。 The bottom of the thermoset state CTE underfill wide range 15-50ppm C, requires a certain level of non-conductive filler, preferably an amount ranging from 40 wt% to 70 wt% of spherical fused silica particles, preferably 45 wt% -60 % by weight. 更优选采用45-55重量%的低CTE无机填料。 45-55% by weight and more preferably using an inorganic filler low CTE. 优选的低CET无机填料的平均粒度为至少10 ym,且平均粒度不大于约75 ii m。 The average particle size of the inorganic filler is preferably a low CET is at least 10 ym, and an average particle size of not greater than about 75 ii m. 所用填料直径的上限必须小于上述的底部填充胶涂层的厚度。 The upper limit of the diameter of the filler used must be less than the thickness of the underfill coating.

[0076] 任选地,底部填充胶可含有粘附改良剂。 [0076] Optionally, the underfill may contain an adhesion improving agent. 通常的使用量为3_8重量%。 It is usually used in an amount of 3_8% by weight. 粘合改进剂是已知的,包括有机硅烷、有机聚硅氧烷、有机氢聚硅氧烷、预水解有机硅烷、硅氧烷和倍半硅氧烷。 Adhesion improving agents are known, including organic silane, an organopolysiloxane, an organohydrogenpolysiloxane, an organic pre-hydrolyzed silanes, siloxanes and silsesquioxanes. 例示性的有机硅烷含有环氧官能团,例如单(环氧烃基)三烷氧基硅烷,如Y-环氧丙氧基丙基三甲氧基硅烷、Y _环氧丙氧基丙基甲基二乙氧基硅烷和13 _(3,4-环氧环己基)乙基三甲氧基硅烷;或优选烯键式不饱和基。 Exemplary organosilanes comprising epoxy functional groups, for example, mono (ethylene hydrocarbyl) trialkoxysilanes, such as Y- glycidoxypropyl trimethoxysilane, glycidoxypropyl the Y _ methylenebis 13 _ silane and (3,4-epoxycyclohexyl) ethyltrimethoxysilane; or preferably an ethylenically unsaturated group. 烯键式不饱和有机硅化合物包括单或多烯基官能性有机硅烷,例如3-(甲基)丙烯酰氧基丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、烯丙基三甲氧基硅烷以及多烯基-官能性硅氧烷,例如1,1,3,3-四甲基二硅氧烷和1, 2 , 4-三乙烯基环己烷和/或1 , 3 , 5-三乙烯基环己烷的氢化硅烷化物。 Ethylenically unsaturated mono- or organosilicon compounds include alkenyl functional organic silanes, such as 3- (meth) acryloxy propyl trimethoxy silane, vinyl triethoxysilane, allyl-trimethoxyphenyl silane and polyene group - functional siloxanes such as 1,1,3,3-tetramethyl disiloxane, and 1, 2, 4-trivinylcyclohexane and / or 1, 3, 5 - trivinylcyclohexane hydrosilylation thereof. [0077] 将底部填充胶施用至晶片的一种方法须采用已知的丝网印刷技术。 [0077] The underfill is applied to the wafer to be a method of screen printing using known techniques. 根据本发明的晶片用底部填充胶可以以覆盖在锯线之外的晶片表面区域上的方式而有利地印刷至晶片上。 May be on the way out of the coverage area of ​​the surface of the wafer saw wire and is advantageously printed on the wafer to wafer according to the present invention underfill. 优选地,通过印刷方法施用的填料含有任选的流变控制剂。 Preferably, the filler is applied by a printing method comprising an optional rheology control agent. 适合的已知类型是无定形熏硅或硅烷化的无定形熏硅,例如可由Cabot Corporation购得。 Suitable known type amorphous or silanized fumed silica, amorphous fumed silica, Cabot Corporation, for example, may be available.

[0078] 任选地可使用公知的流动调节剂。 [0078] Optionally, may be used a known flow control agents. 热塑性流动调节剂提高了在焊料回流中热可液化的底部填充胶流出的趋势。 Thermoplastic flow control agents increase the trend in the solder reflow heat liquefiable underfill flows out. 代表性的流动调节剂包括IV通常为0.2-0.6的聚甲基丙烯酸酯共聚物,例如商品名为Elvacite⑧的市售产品。 Representative IV include flow control agents is generally 0.2 to 0.6 polymethacrylate copolymers, for example under the trade name Elvacite⑧ commercial product. 例子是ICI Acrylics的Elvacite⑧ 2013,其确定为IV是0.2的64%甲基丙烯酸丁酯/36%甲基丙烯酸甲酯的共聚物。 Examples of ICI Acrylics is Elvacite⑧ 2013, it is determined as 64% of IV 0.2 butyl methacrylate / 36% methyl methacrylate copolymer. 本领域内已知的其他流动调节剂包括如Lubrizol, Wickliffe, Ohio, USA的Lanco⑧Flow P10和购自Solutia, St. Louis, Mo的MODAFLOW⑧Powder。 Other flow control agents known in the art include, for example Lubrizol, Wickliffe, Ohio, USA and the Lanco⑧Flow P10 available from Solutia, St. Louis, Mo of MODAFLOW⑧Powder. 流动调节剂可以基于SAN 或a _烯烃聚合物等。 Flow control agents can be based on olefin polymers _ A SAN or the like. 优选的流动调节剂是分子量为60, 000的热塑性PMMA共聚物,例如来自INE0S Acrylics, Inc.的Elvacite⑧4026。 Preferred flow control agents having a molecular weight of 60, 000 thermoplastic PMMA copolymer, such as from INE0S Acrylics, Inc. of Elvacite⑧4026. 任选的热塑性流动调节剂的建议量相对于光固化成分为1. 0-10. 0重量%。 The recommended amount of the thermoplastic optional flow control agent to the photocurable component 1. 0-10. 0 wt%. 为了调节底部填充胶在热可液化的光固化状态下的流动性,可以以低于10重量%的较少量使用例如羧基酯的增塑剂,或例如亚乙基双硬脂酰胺的润滑剂。 In order to adjust the flowability underfill heat liquefiable light cured state, the amount may be less than 10% by weight, for example, carboxyl ester plasticizer or a lubricant, for example, ethylene bis stearamide .

[0079] 测试方法 [0079] Test Method

[0080] 1.玻璃化转变温度(Tg) [0080] 1. The glass transition temperature (Tg)

17[0081] 使用b阶段或热固性固化材料,以5°C /min的加热速率使用热力学分析仪、以5°C /min的加热速率使用动态力学分析仪、以5°C /min的加热速率使用差示扫描量热仪,测量玻璃化转变温度。 17 [0081] a b phase or thermosetting curable material at a heating rate of 5 ° C / min using a thermomechanical analyzer at a heating rate of 5 ° C / min using a dynamic mechanical analyzer, to 5 ° C / min heating rate using a differential scanning calorimeter, the glass transition temperature. [0082] 2.热膨胀系数 [0082] 2. The coefficient of thermal expansion

[0083] 在高于或低于Tg下的热膨胀系数的测定中,通过使用常规的热力学分析仪进行确定。 [0083] In the measurement higher or lower than the coefficient of thermal expansion of Tg, determined using conventional thermomechanical analyzer.

[0084] 3.粘度 [0084] 3. Viscosity

[0085] 适用的有Brookfield VDIII+锥形和平板流变仪,但使用Haake⑧RheoStress I。 [0085] Suitable have Brookfield VDIII + cone and plate rheometer, but using Haake⑧RheoStress I. [0086] 4.根据ASTM D1002测试剪切(die shear)粘附性 [0086] The ASTM D1002 test Shear (die shear) Adhesion

[0087] 5.通过热重分析测定热和氧化稳定性。 [0087] The thermal and oxidative stability measured by thermogravimetric analysis. 底部填充胶在空气中于30(TC下显示出低 Underfill in air at 30 (TC exhibits low

于5%的重量损失。 To 5% weight loss.

[0088] 光聚合条件 [0088] Photopolymerization conditions

[0089] 使用AETEK UV处理单元的下述条件足以使液态底部填充胶在整个涂层深度均实 [0089] Using AETEK UV treatment unit following conditions sufficient to allow liquid underfill throughout the coating depth are real

现凝固 Now solidification

[0090]灯l(W) 灯2(W) 皮带速度(fpm) 固化能量(mj/cm2) [0090] Light l (W) lamp 2 (W) belt speed (fpm) curing energy (mj / cm2)

[0091] 400 400 34 1170 [0091] 400400341170

[0092] 200 200 30 761 [0092] 20020030761

[0093] 200 200 45 515 [0093] 20020045515

[0094] 200 200 60 384 [0094] 20020060384

[0095] 200 200 65 349 [0095] 20020065349

[0096] 200 200 70 327 [0096] 20020070327

[0097] 125 125 30 712 [0097] 12512530712

[0098] 125 125 70 297 [0098] 12512570297

[0099] 200 0 45 274 [0099] 200045274

[0100] 200 0 60 205 [0100] 200060205

[0101] 200 0 70 176 [0101] 200070176

[0102] 125 0 70 149 [0102] 125070149

[0103] 125 0 90 116 [0103] 125090116

[01(H] 生产方式 [01 (H] production

[0105] 通过向Hauschild⑧杯中添加各成分并在3000rpm下混合30秒而制备底部填充胶实施例1-4。 [0105] The underfill was prepared and Examples 1-4 mixed for 30 seconds at 3000rpm by adding the ingredients to Hauschild⑧ cup. 将制剂旋涂至4英寸(10. 1cm)直径乂400+/1111厚度的1;11^0化©半导体晶片上。 The formulation was spin-coated to 4 inches (10. 1cm) 400 + qe diameter / thickness of 1 1111; ^ © 0 of the semiconductor wafer 11. 以Aetec UV烘箱在200W/200W的设置下于30fpm及N2atm下对涂覆的晶片进行一次性光固化。 In Aetec UV coated wafer oven for one-time and light-cured at 30fpm N2atm provided at 200W / 200W of. 可液化凝胶状态的膜不发粘。 Liquefiable gel state film is not tacky. 通过DSC证实,光固化状态下的底部填充胶储存8个月不会导致进一步的固化活性。 Confirmed by DSC, the bottom of the photocurable state underfill stored for 8 months do not cause further curing activity. 热固化开始温度为150°C 士2t:,在166t:出现放热曲线的峰值。 Heat-curing initiation temperature of 150 ° C in persons 2t :, 166t: peak exotherm occurs. [0106] 实施例1<table>table see original document page 19</column></row> <table>[0110] [0106] Embodiment 1 <table> table see original document page 19 </ column> </ row> <table> [0110] Example

[0112] [0112]

4. 三官能丙烯酸酯(SR351,如购自Sartomer) 4. trifunctional acrylate (SR351, such as available from Sartomer)

5. 光引发剂Irgacure 184 Irgacure819 5. photoinitiators Irgacure 184 Irgacure819

6.熔融石英(F5BLDX,如购自Denka) 6. fused silica (F5BLDX, such as available from Denka)

总计 total

[0111] 实施例3 [0111] Example 3

成厶、 As Si,

6.00 6.00

1.50 1.50 1.50 1.50

50.00 50.00

100.00 100.00

重量份 Parts by weight

[0113] [0114] [0113] [0114]

1. 双酚A-表氯醇-环氧树脂(表氯醇残量〈lppm) (RSL-1462,如购自Shell Resins, lnc.(CAS #25068-38-6)) 1. bisphenol A- epichlorohydrin - epoxy resin (residual epichlorohydrin <lppm) (RSL-1462, as available from Shell Resins, lnc (CAS # 25068-38-6).)

2. 潜在性胺促进剂 2. latent amine accelerator

(Ancamine 2441,如购自Air Products & Chem) (Ancamine 2441, as available from Air Products & Chem)

3. 双氰胺 3. dicyandiamide

(Dyhard® 100s,如购自SKWCHem.) (Dyhard® 100s, such as available from SKWCHem.)

4. 三官能丙烯酸酯(SR351,如购自Sartomer) 4. trifunctional acrylate (SR351, such as available from Sartomer)

5. 光引发剂Irgacure 184 Irgacure819 5. photoinitiators Irgacure 184 Irgacure819

6. 熔融石英 6. fused silica

(F5BLDX,如购自Denka) (F5BLDX, such as available from Denka)

总计 total

实施例4 Example 4

36.29 2.18 2.54 6.00 36.29 2.18 2.54 6.00

2.00 1.00 2.00 1.00

50.00 50.00

100.01 100.01

20成分 20 Ingredient

重量份 Parts by weight

1. 双酚A-表氯醇-环氧树脂(表氯醇残量〈l卯m) (RSL-1462,如购自Shell Resins, lnc.(CAS #25068-38-6)) 1. bisphenol A- epichlorohydrin - epoxy resin (residual epichlorohydrin <l d m) (RSL-1462, as available from Shell Resins, lnc (CAS # 25068-38-6).)

2. 丙烯酸酯改性的环氧低聚物(CN136,如购自Sartomer) 2. acrylate modified epoxy oligomer (CN136, such as those available from Sartomer)

3. 潜在性胺促进剂 3. latent amine accelerator

(Ancamine 2441,如购自Air Products & Chem) (Ancamine 2441, as available from Air Products & Chem)

4. 双氰胺— 4. dicyandiamide -

(Dyhard® 100s,如购自SKWCHem.) (Dyhard® 100s, such as available from SKWCHem.)

5. 三官能丙烯酸酯 The trifunctional acrylate

(SR351,如购自Sartomer) (SR351, such as those available from Sartomer)

6. 光引发剂 6. photoinitiator

Irgacure 184 Irgacure819 Irgacure 184 Irgacure819

7. 熔融石英 7. fused silica

(F5BLDX,如购自Denka) (F5BLDX, such as available from Denka)

总计 total

18.15 18.15

19.50 19.50

2.18 2.18

2.54 2.54

6.00 6.00

1.50 1.50 1.50 1.50

50.00 50.00

101.37 101.37

[0115] 制备实施例5-7并旋涂至4英寸(10. 1cm)直径X 400+/-ym厚度的Umicore⑧半导体晶片上。 [0115] Preparation Example 5-7 and spin-coated on to 4 inches (10. 1cm) Umicore⑧ thickness of the semiconductor wafer 400 +/- ym diameter X. 以Aetec UV烘箱,在200W/200W的设置下于30fpm和N2atm下对涂覆的晶片进行一次性光固化。 In Aetec UV oven set at 200W / 200W coated wafer on a one-time and light-cured at 30fpm N2atm. 实施例5-7中处于热可液化状态的光固化膜不发粘。 Examples 5-7 in the photocurable film heat-liquefiable state is not tacky. [0116] 实施例5 [0116] Example 5

[0117] 在实施例5的制备中,将成分1-4在40g的Hauschild⑧杯中混合在一起,并加热至6(TC直至光引发剂完全溶解。然后在Hauschild⑧混合器上,于3000rpm下混合试样30 秒钟。分别加入剩余的成分,各次添加之间均进行混合。在混合下加入增量部分的二氧化 [0117] In Preparation Example 5, 1-4 mixing the ingredients together in Hauschild⑧ 40g cup, and heated to 6 (TC until the photoinitiator was completely dissolved. Then on Hauschild⑧ mixer, mixed at 3000rpm sample for 30 seconds. the remaining ingredients were added, mixing was carried out between each addition. dioxide is added in incremental portions under mixing

娃o成分 O baby component

描述 description

s量份 Parts amount s

[0118] [01]

[0119] [0120]1.2.3.4.5.6.8. [0119] [0120] 1.2.3.4.5.6.8.

CN136 SR203 Irgacure® 184 Irgacui'e® 819 RSL-1462 RSS-1407 Curezol® 2PHZ-S 填料总计 CN136 SR203 Irgacure® 184 Irgacui'e® 819 RSL-1462 RSS-1407 Curezol® 2PHZ-S total filler

氨基改性的、丙烯酸酯化的环氧THFMA 光引发剂光引发剂双酚A环氧的二缩水甘油醚联苯环氧树脂_ 咪唑潜在性固化剂熔融石英 Amino-modified, epoxy acrylated photoinitiators THFMA biphenyl diglycidyl ether photoinitiator bisphenol A epoxy resin epoxy curing agent _ latent imidazole fused silica

实施例5的热固化开始温度为167°C Heat-curing initiation temperature of Example 5 was 167 ° C

实施例5 Example 5

Tg-UV-B-阶段 23. 56 °C Tg-UV-B- stage 23. 56 ° C

Tg-热固化 106. 25°C Tg- thermosetting 106. 25 ° C

CTE-低于Tg 40. 37卯m/。 CTE- below Tg 40. 37 d m /. C C

CTE-高于Tg 107. 7卯m/。 D CTE- higher Tg 107. 7 m /. C C

储存模量(@25°C ) 2, 761Mpa Storage modulus (@ 25 ° C) 2, 761Mpa

储存模量(@175°C ) 0.025Gpa Storage modulus (@ 175 ° C) 0.025Gpa

6.70 12.40 6.70 12.40

0.30 0.30

0.50 14.35 14.35 0.50 14.35 14.35

1.43 49.99 100.02 1.43 49.99 100.02

[0121] 实施例6 [0121] Example 6

[0122] 除50%的熔融石英以外,在40g的Hauschild⑧杯中加入各成分并在3000rpm下混合30秒钟而制备实施例6。 [0122] other than 50% of fused silica, prepared in Example 6 were mixed at 3000rpm for 30 seconds was added to each cup component Hauschild⑧ and 40g. 然后加入熔融石英的剩余部分并在3000rpm下混合30秒钟。 The remaining portion of fused silica was then added and mixed for 30 seconds at 3000rpm. 在烘箱中于45t:下加热混合物30分钟以溶解光引发剂。 To 45t in an oven: the mixture was heated for 30 minutes to dissolve the photoinitiator. 在3000rpm下将溶液混合物再次混合30秒钟。 At 3000rpm The solution mixture was mixed again for 30 seconds.

22<table>table see original document page 23</column></row> <table>[0124] 参照图1 ,其表示实施例6的DSC扫描曲线。 22 <table> table see original document page 23 </ column> </ row> <table> [0124] Referring to FIG. 1, representing a graph of the DSC scan of Example 6. [0125] 用于差示扫描量热仪的条件是: Condition [0125] for a differential scanning calorimeter is:

[0126] 使用诸如Perkin-Elmer, model DSC 7的差示扫描量热仪[0127] 加热升温条件是-20。 [0126] with the proviso that the use of a heating ramp -20 Perkin-Elmer, model DSC Differential Scanning Calorimetry [0127] 7 such. C至30(TC,速率5°C /min To C 30 (TC, rate of 5 ° C / min

[0128] 将所有的试样在光固化状态下进行测试。 [0128] All samples were tested in the light cured state. 扫描示出固态环氧树脂的熔化温度在95. 23",固化开始温度为191.65",热固化的峰值反应温度为193. 71°C。 Scan showed a melting temperature of the solid epoxy resin 95.23 "curing initiation temperature of 191.65", the thermosetting reaction peak temperature of 193. 71 ° C. [0129] 实施例7 [0129] Example 7

[0130] 除了50X的熔融石英以夕卜,在40g的Hauschild⑧杯中加入各成分并在3000rpm下混合30秒钟而制备实施例7。 [0130] In addition to fused silica 50X Bu Xi, Hauschild⑧ in the cup and the ingredients were added 40g of Example 7 was prepared and mixed for 30 seconds at 3000rpm. 然后加入熔融石英的剩余部分并在3000rpm下混合30秒钟。 The remaining portion of fused silica was then added and mixed for 30 seconds at 3000rpm. 在烘箱中于45t:下加热混合物30分钟以溶解光引发剂。 To 45t in an oven: the mixture was heated for 30 minutes to dissolve the photoinitiator. 在3000rpm下将溶液混合物再次混合30秒钟。 At 3000rpm The solution mixture was mixed again for 30 seconds. <table>table see original document page 23</column></row> <table> <Table> table see original document page 23 </ column> </ row> <table>

[0132] 图2表示实施例7的DCS扫描曲线。 [0132] FIG. 2 shows a DCS curve of Example 7 scans. [0133] 用于差示扫描量热仪的条件是:[0134] 使用诸如Perkin-Elmer, model DSC 7的差示扫描量热仪[0135] 加热升温的条件是-20。 Condition [0133] for a differential scanning calorimeter is: [0134] A Perkin-Elmer, model DSC Differential Scanning Calorimetry [0135] 7 such as a heating temperature condition is -20. C至30(TC,速率5°C /min To C 30 (TC, rate of 5 ° C / min

[0136] 对所有的试样在光固化状态下进行测试。 [0136] All samples were tested in the light cured state. 扫描示出固体环氧树脂的熔化温度在99. 5°C,固化开始温度为189. 62t:,热固化的峰值反应温度为192. 6°C。 Scan showed a melting temperature of solid epoxy resin at 99. 5 ° C, the curing initiation temperature of the thermosetting 189. 62t :, peak reaction temperature of 192. 6 ° C. [0137] 实施例8 [0137] Example 8

[0138] 除50%的熔融石英以外,在40g的Hauschild⑧杯中加入各成分并在3000rpm下混合30秒钟而制备实施例8。 [0138] other than 50% of fused silica, prepared in Example 8 were mixed at 3000rpm for 30 seconds was added to each cup component Hauschild⑧ and 40g. 然后加入熔融石英的剩余部分并在3000rpm下混合30秒钟。 The remaining portion of fused silica was then added and mixed for 30 seconds at 3000rpm. 在烘箱中于45t:加热混合物30分钟以溶解光引发剂。 In an oven at 45t: heating the mixture for 30 minutes to dissolve the photoinitiator. 在3000rpm下将溶液混合物再次混合30秒钟。 At 3000rpm The solution mixture was mixed again for 30 seconds.

原料描述 Material description

[0139] [0139]

[0140] [0140]

<table>table see original document page 24</column></row> <table>[0141] 对比例A(77-5) <Table> table see original document page 24 </ column> </ row> <table> [0141] Comparative Example A (77-5)

实施例8 Example 8

储存模量(175°C ) 0. 0268Gpa Storage modulus (175 ° C) 0. 0268Gpa

. 成分 重量份 Ingredient parts by weight

[0142] [0142]

1. 丙烯酸酯改性的环氧低聚物与三(丙烯酰基)官能性单体的混合物 1. The mixture acrylate modified epoxy oligomer with tris (acryloyl) functional monomer

(CN120C60,如购自Sartomer) (CN120C60, such as those available from Sartomer)

2. 三(丙烯酰基)官能性单体(SR351,如购自Sartomer) 2. tri (acryl) functional monomer (SR351, such as those available from Sartomer)

3. 双氰胺 3. dicyandiamide

(Dyhard® 100s,如购自SKWCHem.) (Dyhard® 100s, such as available from SKWCHem.)

4. 光引发剂 4. photoinitiator

Irgacure 184 Irgacure819 Irgacure 184 Irgacure819

5. 熔融石英 The fused silica

(F5BLDX,如购自Denka) (F5BLDX, such as available from Denka)

总计 total

[0143] 对比例A在光固化后,于环境储存24小时后从晶片上分层,可以确定这是由于通过光固化诱导的过度收縮造成。 [0143] In the Comparative Example A after photocuring, stored for 24 hours to delaminate from the wafer, it may be determined This is because the photo-curing-induced shrinkage caused by excessive. 对比例B Comparative Example B

43.00 43.00

4.00 1.33 4.00 1.33

2.00 1.00 2.00 1.00

50.00 50.00

100.00 100.00

[0144] [0144]

1. 双酚A-表氯醇-环氧树脂(表氯醇残量〈lppm) (RSL-1462,如购自Shell Resins, lnc.(CAS #25068-38-6)) 1. bisphenol A- epichlorohydrin - epoxy resin (residual epichlorohydrin <lppm) (RSL-1462, as available from Shell Resins, lnc (CAS # 25068-38-6).)

2. 丙烯酸酯改性的环氧低聚物与三(丙烯酰基)官能性单体的混合物 2. Mixtures of acrylate modified epoxy oligomer with tris (acryloyl) functional monomer

(CN120C60,如购自Sartomer) (CN120C60, such as those available from Sartomer)

3. 潜在性胺促进剂 3. latent amine accelerator

(Ancamine⑧2441,如购自Air Products & Chem) (Ancamine⑧2441, such as those available from Air Products & Chem)

4. 双氰胺 4. dicyandiamide

(Dyhard® 100s,如购自SKWCHem.) (Dyhard® 100s, such as available from SKWCHem.)

18.15 18.15

20.: 20 .:

1.09 1.09

1.275. 光引发剂 1.275. Photoinitiators

Irgacure 184 1 50 Irgacure 184 1 50

Irgacure8:T9 1冊 Irgacure8: T9 1 Ce

[0145] ' [0145] '

6. 熔融石英 6. fused silica

(F5BLDX,如购自Denka) 50'00 (F5BLDX, such as available from Denka) 50'00

总计100,00 [0146] 对比例B在环境储存24小时后也发生分层。 Total 100.00 [0146] Comparative Example B also delamination after ambient storage for 24 hours.

[0147] 本发明发现了晶片用底部填充胶的特定工业实用性及其制备方法,本发明的组合物还可用于除底部填充胶以外的微电子应用,例如用于覆顶(glob top)、直接芯片连接和其它用于热固性组合物的应用。 [0147] The present invention finds particular industrial applicability and preparation method wafer with the underfill composition of the present invention may also be used for microelectronic applications other than underfill, for example, a top cover (glob top), direct chip connections and other applications for thermosetting compositions. 尽管已经描述了一些优选的实施方式,但根据上述的教导可作许多修改和改变。 While there have been described certain preferred embodiments, but may be made of the above teachings that many modifications and variations. 因此可以意识到,在不脱离所附权利要求范围的前提下,本发明可按具体描述之外的方式实施。 Thus it is appreciated that, without departing from the scope of the appended claims, than as specifically described according to the embodiment of the present invention.

Claims (46)

  1. 环境温度下稳定的集成电路晶片,其正面粘附于底部填充胶组合物,所述底部填充胶组合物包括光固化的单组分组合物,该单组分组合物包括如下的单组分混合物:液态光固化丙烯酸酯成分,多官能环氧树脂,至少一种光引发剂,非导电性填料,和非熔化的热活化环氧固化剂,其中所述底部填充胶组合物在固态下于25℃显示1000-5000MPa的弯曲模量,并在所述底部填充胶组合物玻璃化转变温度以下的温度下显示15-50ppm/℃的热膨胀系数。 ICs stable at ambient temperature, adhered to its front underfill composition, the underfill composition comprises a photo-curable one-component composition, the one-component one-component composition comprising a mixture of the following : liquid photocurable acrylate component, a polyfunctional epoxy resin, at least one photoinitiator, a non-conductive filler, and non-melting heat activated epoxy curative, wherein the underfill composition is in solid state at 25 ℃ 1000-5000MPa flexural modulus of the display, and the transition glass composition underfill coefficient of thermal expansion 15-50ppm / ℃ at a temperature below the display.
  2. 2. 100%固体的非自熔单组分液态底部填充胶组合物,其包括: 5重量% -30重量%的单官能不饱和光固化成分,10重量% -45重量%的多官能环氧树脂, 0. 3重量% -3重量%的至少一种光引发剂, 40重量% -70重量%的非导电性填料,所述底部填充胶组合物在热固性状态下于25t:显示1000-5000MPa的弯曲模量,并在其玻璃化转变温度以下的温度下显示15-50卯m广C的热膨胀系数。 2.100% solids non-liquid one-component self-fluxing underfill composition comprising: 5% to 30% by weight of the monofunctional unsaturated photocurable composition, 10 wt% to 45 wt% of polyfunctional epoxy resin, 0.3 wt% to 3 wt% of at least one photoinitiator, 40 wt% to 70 wt% of a non-electrically conductive filler, the underfill composition at a thermoset state to 25t: display 1000-5000MPa flexural modulus, and shows a thermal expansion coefficient of 15-50 C d m wide at a temperature below the glass transition.
  3. 3. 根据权利要求2的底部填充胶组合物,其中所述光固化成分包括具有至少6个碳原子的烯键式不饱和单体或单体的混合物。 3. The underfill composition of claim 2, wherein the photocurable composition comprises a mixture of an ethylenically unsaturated monomer or monomers having at least 6 carbon atoms.
  4. 4. 根据权利要求3的底部填充胶组合物,其中所述烯键式不饱和单体或单体的混合物选自:乙烯基酯、乙烯基醚,a, e-不饱和丙烯酸酯,及其混合物。 The underfill composition of 3, wherein said mixture of ethylenically unsaturated monomer or monomers selected from the group claim: vinyl esters, vinyl ethers, a, e- unsaturated acrylate, and mixture.
  5. 5. 根据权利要求4的底部填充胶组合物,其中所述光固化成分是烯键式不饱和丙烯酸酯单体或不饱和低聚物及其组合。 5. The underfill composition according to claim 4, wherein the photocurable component is an ethylenically unsaturated acrylate monomer or unsaturated oligomer, and combinations thereof.
  6. 6. 根据权利要求5的底部填充胶组合物,其中所述烯键式不饱和丙烯酸酯单体包括选自如下的至少一种化合物:丙烯酸C3-C12烷基酯,QQ烷基取代的丙烯酸C3-C12酯。 6. The underfill composition according to claim 5, wherein the ethylenically unsaturated acrylate monomers include at least one compound selected from: C3-C12 alkyl ester of acrylic acid, QQ C3 alkyl substituted acrylic acid -C12 ester.
  7. 7. 根据权利要求6的底部填充胶组合物,其中所述烯键式不饱和丙烯酸酯单体包括选自如下的至少一种化合物:丙烯酸丁酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸环己酯、甲基丙烯酸三甲基环己酯、环醚丙烯酸酯、单环状縮醛丙烯酸酯、甲基丙烯酸乙酰乙酰氧基乙酯、丙烯酸_2-乙酰乙酰氧基乙酯、甲基丙烯酸-2-乙酰乙酰氧基丙酯、丙烯酸-2-乙酰乙酰氧基丙酯、甲基丙烯酸-2-乙酰乙酰氨基乙酯、丙烯酸-2-乙酰乙酰氨基乙酯、甲基丙烯酸-2-氰基乙酰氧基乙酯、丙烯酸-2-氰基乙酰氧基乙酯、N-(2-氰基乙酰氧基乙基)丙烯酰胺、丙烯酸-2-丙酰基乙酰氧基乙酯、N-(2-丙酰基乙酰氧基乙基)甲基丙烯酰胺、N-4-(乙酰乙酰氧基苄基)苯基丙烯酰胺、乙酸乙基丙烯酰酯、乙酸丙烯酰基甲酯、N-乙基丙烯酰氧基甲基乙酰乙酰胺、乙酰乙酸乙 7. The underfill composition according to claim 6, wherein the ethylenically unsaturated acrylate monomers include at least one compound selected from: butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, cyclic ether acrylates, monocyclic formal acrylate, methacrylate, acetoacetoxyethyl acrylate, _ 2- acetoacetoxyethyl methacrylate, acetoacetoxyethyl methacrylate, 2-propyl acrylate, 2-acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, 2-amino ethyl acrylate, 2-acetyl acetamido ethyl methacrylate, 2-cyano-acetoxyethyl, 2-cyano-acetoxyethyl acrylate, N- (2- cyanoacetoxyethyl) acrylamide, -2 - propionyl acetoxyethyl, N- (2- propionyl-acetoxyethyl) methacrylamide, N-4- (acetoacetoxy) phenyl acrylamide, acryl acid ethyl ester , acrylic acid ester group, N- methyl-acryloyloxy-ethyl acetoacetamide, ethyl acetoacetate 甲基丙烯酰酯、 N-烯丙基氰基乙酰胺、乙酰乙酸甲基丙烯酰酯、N-(2-甲基丙烯酰氧基甲基)氰基乙酰胺、 甲基丙烯酸-乙基-a-乙酰乙酰氧酯、N- 丁基-N-丙烯酰氧基乙基乙酰乙酰胺,单丙烯酸酯化的多元醇、邻苯二甲酸单甲基丙烯酰氧基乙酯,及其混合物。 Esters of methacrylic acid, N- allyl cyanoacetamide, acetic acid methacholine acryl ester, N- (2- methacryloyloxy methyl) cyanoacetamide, methacrylic acid - ethyl - a- acetoacetoxy ester, N- -N- acryloyloxyethyl butyl acetoacetamide, esterified polyol monoacrylate, phthalic acid mono methacryloyloxy ethyl, and mixtures thereof.
  8. 8. 根据权利要求7的底部填充胶组合物,其中所述环醚丙烯酸酯选自:丙烯酸四氢糠酯,甲基丙烯酸四氢糠酯,单甲基丙烯酸季戊四醇酯,单丙烯酸季戊四醇酯,三羟甲基丙烷单甲基丙烯酸酯,三羟甲基丙烷单丙烯酸酯,环状羟烷基甲縮醛丙烯酸酯,縮酮丙烯酸酯,及其混合物。 8. The underfill composition of claim 7, wherein the cyclic ether acrylates are selected from: acrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, pentaerythritol monomethacrylate, pentaerythritol monoacrylate, triethylene trimethylolpropane monomethacrylate, trimethylolpropane monoacrylate, cyclic formals hydroxyalkyl acrylates, ketal acrylate, and mixtures thereof.
  9. 9.根据权利要求8的底部填充胶组合物,其中所述环状甲縮醛丙烯酸酯选自以下化合物:<formula>formula see original document page 3</formula>其中&是CrC4亚烷基,R2、 R3和R4是H或CrC4烷基。 9. The underfill composition of claim 8, wherein the cyclic formal acrylate is selected from the following compounds: <formula> formula see original document page 3 </ formula> is where & CrC4 alkylene, R2 , R3 and R4 are H or CrC4 alkyl.
  10. 10. 根据权利要求9的底部填充胶组合物,其中所述环状甲縮醛丙烯酸酯是三羟甲基丙烷甲縮醛丙烯酸酯。 10. The underfill composition according to claim 9, wherein the cyclic formal acrylate, trimethylol propane formal acrylate methyl.
  11. 11. 根据权利要求5的底部填充胶组合物,其中所述不饱和低聚物包含至少一个侧基或末端烯键式不饱和基团。 11. The underfill composition of claim 5, wherein said unsaturated oligomers comprising at least one side group or terminal ethylenically unsaturated groups.
  12. 12. 根据权利要求ll的底部填充胶组合物,其中所述不饱和低聚物包含两个末端不饱和基团。 According to claim ll underfill composition, wherein said unsaturated oligomers containing two terminal unsaturated groups.
  13. 13. 根据权利要求ll的底部填充胶组合物,其中所述不饱和低聚物当所述不饱和低聚物的分子量为500-3000时具有的不饱和基团的平均数为1-2。 13. ll underfill composition according to claim, wherein said unsaturated oligomers when the molecular weight unsaturated oligomers having an average number of unsaturated groups when 500-3000 is 1-2.
  14. 14. 根据权利要求5的底部填充胶组合物,其中所述不饱和低聚物选自:双酚聚醚丙烯酸酯,乙烯基醚封端的低聚物,丙烯酸酯化的环氧树脂,烯键式不饱和的聚烷基醚,聚(环状)醚丙烯酸酯,聚环状(醚)縮醛丙烯酸酯,聚氨酯丙烯酸酯低聚物,及其混合物。 14. The underfill composition according to claim 5, wherein the unsaturated oligomer is selected from: bisphenol polyether acrylates, oligomer of a vinyl ether terminated, acrylated epoxy resins, ethylenically poly-unsaturated alkyl ethers, poly (cyclic) ether acrylate, cyclic poly (ether) formal acrylate, urethane acrylate oligomer, and mixtures thereof.
  15. 15. 根据权利要求14的底部填充胶组合物,其进一步包括单不饱和的丙烯酸酯单体, 其中所述不饱和低聚物具有500-5, 000的数均分子量。 15. The underfill composition according to claim 14, further comprising a mono-unsaturated acrylate monomer, wherein said unsaturated oligomers 500-5 having a number average molecular weight of 000.
  16. 16. 根据权利要求15的底部填充胶组合物,其中所述不饱和低聚物具有1, 000-4, 000 的数均分子量. 16. The underfill composition according to claim 15, wherein said unsaturated oligomers having 1, 000-4, 000 number-average molecular weight.
  17. 17. 根据权利要求14的底部填充胶组合物,其中所述聚氨酯丙烯酸酯低聚物是脂族或芳族的。 17. The underfill composition according to claim 14, wherein said urethane acrylate oligomer is aliphatic or aromatic.
  18. 18. 根据权利要求17的底部填充胶组合物,其中所述聚氨酯丙烯酸酯低聚物选自:来自Henkel Corp. Hoboken, NJ的mOTOMER ;来自UCB Radcure Inc. Smyrna, Ga.的EBECRYL 220、 EBECRYL 284、 EBECRYL 4827、 EBECRYL 4830、 EBECRYL 6602 、禾口EBECRYL 840 ;和其混合物。 18. The underfill composition according to claim 17, wherein said urethane acrylate oligomer is selected: from Henkel Corp. Hoboken, NJ the mOTOMER; EBECRYL from UCB Radcure Inc. Smyrna, Ga of 220, EBECRYL 284 , EBECRYL 4827, EBECRYL 4830, EBECRYL 6602, Wo port EBECRYL 840; and mixtures thereof.
  19. 19. 根据权利要求3的底部填充胶组合物,其中所述烯键式不饱和单体选自:丁基乙烯基醚、异丁基乙烯基醚、环己基乙烯基醚对-(2-乙酰乙酰基)乙基苯乙烯、4-乙酰乙酰基-1-甲基丙烯酰氧基哌嗪、烯二不饱和单体、烯三不饱和单体。 19. The underfill composition according to claim 3, wherein the ethylenically unsaturated monomer is selected from: butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether of - (2-acetylamino acetyl) ethylstyrene, 4-acetyl-acetyl-1-methacryloyloxy-piperazine, two ethylenically unsaturated monomers, ethylenically unsaturated monomers three.
  20. 20. 根据权利要求19的底部填充胶组合物,其中所述烯二不饱和单体选自:二丙烯酸乙二醇酯、聚二丙烯酸乙二醇酯、二甲基丙烯酸乙二醇酯、二丙烯酸己二醇酯、二丙烯酸三甘醇酯。 20. The underfill composition according to claim 19, wherein said two ethylenically unsaturated monomers selected from: ethylene glycol diacrylate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, di hexanediol diacrylate, triethylene glycol diacrylate.
  21. 21. 根据权利要求19的底部填充胶组合物,其中所述烯三不饱和单体选自:三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、三丙烯酸甘油酯、三丙烯酸季戊四醇酯、 三甲基丙烯酸季戊四醇酯。 21. The underfill composition according to claim 19, wherein the ethylenically unsaturated monomer is selected from three: trimethylol propane triacrylate, trimethylol propane trimethacrylate, glycerol triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate.
  22. 22. 根据权利要求2的底部填充胶组合物,其中所述光固化成分还包括非官能或饱和的热塑性聚合物稀释剂。 22. The underfill composition according to claim 2, wherein the photocurable component further comprises a non-functional thermoplastic polymers or unsaturated diluent.
  23. 23. 根据权利要求22的底部填充胶组合物,其中所述非官能或饱和的热塑性聚合物稀释剂选自:聚丙烯酸酯、聚乙烯醚、聚乙烯酯、聚酯、聚酰胺、聚烯烃,及其混合物。 23. The underfill composition according to claim 22, wherein the non-functionalized or unsaturated diluent thermoplastic polymer is selected from: polyacrylates, polyvinyl ethers, polyvinyl esters, polyesters, polyamides, polyolefins, and mixtures thereof.
  24. 24. 根据权利要求2的底部填充胶组合物,其中所述多官能环氧树脂含有至少两个环氧基,在25t:下具有低于10, 000泊的粘度,每环氧化物的平均重量范围为100-1000,且平均分子量范围为500-3500。 24. The underfill composition according to claim 2, wherein the multifunctional epoxy resin containing at least two epoxy groups in the 25t: having less than 10, a viscosity of 000 poise, the average weight per epoxide in the range of 100-1000, and an average molecular weight range of 500-3500.
  25. 25. 根据权利要求24的底部填充胶组合物,其中所述多官能环氧树脂选自:双酚A的二縮水甘油醚、2, 2-双-4-(2, 3-环氧丙氧基)_苯基)丙烷、环脂族环氧化物、苯酚甲醛酚醛清漆的縮水甘油醚、每环氧化物的平均重量为192g/eq.的联苯环氧树脂、每环氧化物的平均重量为172g/eq.的双酚F的二縮水甘油醚、每环氧化物的平均重量为101g/eq.的对氨基苯酚的三縮水甘油醚,及其混合物。 25. The underfill composition according to claim 24, wherein the multifunctional epoxy resin is selected from: bisphenol A diglycidyl ether, 2,2-bis-4- (2, 3-glycidoxypropyl yl) _ phenyl) propane, cycloaliphatic epoxides, glycidyl ethers of phenol formaldehyde novolac, average weight per epoxide was 192g / eq. of biphenyl epoxy resin, the average weight per epoxide bisphenol F was 172g / eq. diglycidyl ether, average weight per epoxide was 101g / eq. of p-aminophenol triglycidyl ether, and mixtures thereof.
  26. 26. 根据权利要求2的底部填充胶组合物,包括1%到3%重量的所述至少一种光引发剂。 26. The underfill composition according to claim 2, comprising from 1% to 3% by weight of at least one photoinitiator.
  27. 27. 根据权利要求26的底部填充胶组合物,其中所述至少一种光引发剂选自:二苯甲酮、安息香醚、酰基膦氧化物类光引发剂,及其混合物。 27. The underfill composition according to claim 26, wherein said at least one photo initiator is selected from: benzophenone, benzoin ethers, acylphosphine oxide photoinitiators, and mixtures thereof.
  28. 28. 根据权利要求26的底部填充胶组合物,其中所述至少一种光引发剂是如下混合物:25% -50%的所述至少一种光引发剂酮-官能性光引发剂,和50% _75%的所述至少一种光引发剂含单酰基膦氧化物的光引发剂、含二酰基膦氧化物的光引发剂或含有膦酸酯的光引发剂。 28. The underfill composition according to claim 26, wherein said at least one photoinitiator mixture is as follows: 25% -50% of said at least one photoinitiator keto - functional photoinitiator, and 50 the% _75% of at least one photoinitiator photoinitiator agent containing mono acyl phosphine oxide photoinitiator containing a bisacylphosphine oxide or phosphonate-containing light initiators.
  29. 29. 根据权利要求28的底部填充胶组合物,其中所述酮-官能性光引发剂选自:l-羟基环己基苯基酮、羟基甲基苯基丙酮、二甲氧基苯基苯乙酮、2-甲基-1-[4(甲硫基)-苯基]_2-吗啉丙酮-1 , 1- (4-异丙基苯基)-2-羟基-2-甲基丙-1-酮、1- (4-十二烷基-苯基)-2-羟基-2-甲基丙-1-酮、4-(2-羟基乙氧基)苯基-2-(2-羟基-2-丙基)-酮、二乙氧基苯基苯乙酮、2,4,6-三甲基苯甲酰基二苯膦、2-羟基-2-甲基-1-苯基丙-1-酮、 1- [4- (2-羟基乙氧基)苯基]-2-羟基-2-甲基丙-1-酮、2-羟基噻吨-9-酮,及其混合物。 29. The underfill composition according to claim 28, wherein the ketone - functional photoinitiator is selected from: l- hydroxycyclohexyl phenyl ketone, acetone-hydroxymethylphenyl, dimethoxyphenylacetophenone ketone, 2-methyl-1- [4 (methylthio) - phenyl] _2- morpholino propanone-1, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane - 1-one, 1- (4-dodecyl - phenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (2- hydroxy-2-propyl) - one, diethoxyphenyl acetophenone, 2,4,6-trimethyl benzoyl diphenyl phosphine, 2-methyl-1-phenyl-propan- 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-9-one, and mixtures thereof.
  30. 30. 根据权利要求28的底部填充胶组合物,其中所述含单酰基膦氧化物的光引发剂选自:乙基-2,4,6-三甲基苯甲酰基二苯膦氧化物、2,4,6-三乙基苯甲酰基二苯基膦氧化物、 2, 4, 6-三苯基苯甲酰基二苯基膦氧化物,及其混合物。 30. The underfill composition according to claim 28, wherein the photoinitiator comprising a monoacylphosphine oxide selected from the group: ethyl-2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,4,6-triethyl benzoyl diphenyl phosphine oxide, 2, 4, 6-trimethyl-phenyl benzoyl diphenyl phosphine oxide, and mixtures thereof.
  31. 31. 根据权利要求28的底部填充胶组合物,其中所述至少一种光引发剂是基于底部填充胶总重为0. 2-0. 5重量%的1-羟基环己基苯基酮以及基于底部填充胶总重为0. 5-0. 7 重量%的苯基双(2,4,6-三甲基苯甲酰基)膦氧化物的混合物。 31. The underfill composition according to claim 28, wherein said at least one photoinitiator are based on total weight of the underfill 0. 2-0. 5% by weight of 1-hydroxycyclohexyl phenyl ketone and based on underfill mixture total weight of 0. 5-0. 7% by weight of phenyl-bis (2,4,6-trimethylbenzoyl) phosphine oxide.
  32. 32. 根据权利要求2的底部填充胶组合物,其中所述非导电性填料选自:熔融石英、晶体石英、氮化硼、铝和硅、氧化镁、硅酸镁、硅石涂覆的铝。 32. The underfill composition according to claim 2, wherein said non-conductive filler is selected from: fused silica, crystalline quartz, boron nitride, aluminum, and silicon, magnesium oxide, magnesium silicate, silica-coated aluminum.
  33. 33. 根据权利要求32的底部填充胶组合物,其中所述非导电性填料是球形熔融石英。 33. The underfill composition according to claim 32, wherein said non-conductive filler is spherical fused silica.
  34. 34. 根据权利要求33的底部填充胶组合物,其中所述球形熔融石英的平均粒度为10_75践。 34. The underfill composition of claim 33, wherein the spherical fused silica of average particle size 10_75 practice.
  35. 35. 根据权利要求2的底部填充胶组合物,其中所述非导电性填料的量为45-60重、 35. The underfill composition of the base according to claim 2, wherein the amount of the non-conductive filler is 45-60 weight,
  36. 36.根据权利要求35的底部填充胶组合物,其中所述非导电性填料的量为45-55重 36. The underfill composition according to claim 35, wherein the amount of the non-conductive filler is 45-55 weight
  37. 37.根据权利要求2的底部填充胶组合物,还含有粘附改良剂。 37. The underfill composition according to claim 2, further comprising an adhesion improver.
  38. 38. 根据权利要求37的底部填充胶组合物,其中所述粘附改良剂的量为3-8重量%。 38. The underfill composition according to claim 37, wherein the amount of the adhesive improving agent is 3-8 wt%.
  39. 39. 根据权利要求37的底部填充胶组合物,其中所述粘附改良剂选自:有机硅烷、有机聚硅氧烷、有机氢聚硅氧烷、预水解有机硅烷、硅氧烷、倍半硅氧烷。 39. The underfill composition according to claim 37, wherein said adhesion improver is selected from: an organosilane, an organopolysiloxane, an organohydrogenpolysiloxane, prehydrolysis organosilanes, siloxanes, silsesquioxane siloxane.
  40. 40. 根据权利要求39的底部填充胶组合物,其中所述粘附改良剂选自:Y-环氧丙氧基丙基三甲氧基硅烷,Y-环氧丙氧基丙基甲基二乙氧基硅烷,P-(3,4-环氧环己基)乙基三甲氧基硅烷,3-(甲基)丙烯酰氧基丙基三甲氧基硅烷,乙烯基三乙氧基硅烷,烯丙基三甲氧基硅烷,1, 1, 3, 3-四甲基二硅氧烷、1 , 2, 4-三乙烯基环己烷和1, 3, 5-三乙烯基环己烷的氢化硅烷化物。 40. The underfill composition according to claim 39, wherein said adhesion improver is selected from: Y- glycidoxypropyl trimethoxysilane, Y- glycidoxypropyl methyl diethyl silane, P- (3,4- epoxycyclohexyl) ethyltrimethoxysilane, 3- (meth) acryloxy propyl trimethoxysilane, vinyl triethoxysilane, allyl trimethoxysilane, 1, 1, 3, 3-tetramethyldisiloxane, 1, 2, 4-trivinylcyclohexane and 1, 3, 5-trivinyl cyclohexane hydrosilylation compounds.
  41. 41. 根据权利要求2的底部填充胶组合物,还含有选自无定形熏硅和硅烷化的无定形熏硅的流变控制剂。 41. The underfill composition of claim 2, further comprising fumed silica selected from amorphous and silanated amorphous silicon smoked rheology control agent.
  42. 42. 根据权利要求2的底部填充胶组合物,还包括流动调节剂。 42. The underfill composition according to claim 2, further comprising a flow control agents.
  43. 43. 根据权利要求42的底部填充胶组合物,其中所述流动调节剂相对于光固化成分为1. 0-10. 0重量%。 43. The underfill composition according to claim 42, wherein said flow control agent to the photocurable component 1. 0-10. 0 wt%.
  44. 44. 根据权利要求42的底部填充胶组合物,其中所述流动调节剂选自:IV为0. 2-0. 6的聚甲基丙烯酸酯共聚物,a -烯烃聚合物,分子量为60, 000的热塑性PMMA共聚物,羧基酯,亚乙基双硬脂酰胺,及其混合物。 44. The underfill composition according to claim 42, wherein said flow regulators are selected from:. IV is a polymethacrylate copolymer of 0. 2-06, a - olefin polymer, a molecular weight of 60, 000 thermoplastic PMMA copolymer, carboxyl ester, ethylene bis stearamide, and mixtures thereof.
  45. 45. 根据权利要求2的底部填充胶组合物,其中在所述底部填充胶组合物玻璃化转变温度以下的温度下显示15-35ppm广C的热膨胀系数。 45. The underfill composition according to claim 2, wherein the underfill composition of the glass transition 15-35ppm wide thermal expansion coefficient C is displayed below the temperature.
  46. 46. 根据权利要求45的底部填充胶组合物,其中在所述底部填充胶组合物玻璃化转变温度以下的温度下显示25卯m广C的热膨胀系数。 46. ​​The underfill composition according to claim 45, wherein the underfill composition of the glass transition coefficient of thermal expansion of 25 C d m wide temperature below the display.
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