TW202039760A - Adhesive agent for semiconductor, method for producing semiconductor device, and semiconductor device - Google Patents

Adhesive agent for semiconductor, method for producing semiconductor device, and semiconductor device Download PDF

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TW202039760A
TW202039760A TW109110054A TW109110054A TW202039760A TW 202039760 A TW202039760 A TW 202039760A TW 109110054 A TW109110054 A TW 109110054A TW 109110054 A TW109110054 A TW 109110054A TW 202039760 A TW202039760 A TW 202039760A
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adhesive
semiconductor
mass
semiconductors
semiconductor device
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TW109110054A
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TWI834852B (en
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茶花幸一
秋吉利泰
林出明子
佐藤慎
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日商日立化成股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
    • H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
    • H01L25/065—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L27/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
    • H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
    • H01L25/07—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L29/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/18—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different subgroups of the same main group of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

Abstract

This adhesive agent for a semiconductor contains a resin having a weight-average molecular weight of less than 10,000, a curing agent, an inorganic filler, and a silicone rubber filler.

Description

半導體用接著劑、半導體裝置的製造方法及半導體裝置Adhesive for semiconductor, method for manufacturing semiconductor device, and semiconductor device

本揭示是有關於一種半導體用接著劑、半導體裝置的製造方法及半導體裝置。The present disclosure relates to an adhesive for semiconductor, a method of manufacturing a semiconductor device, and a semiconductor device.

先前，於將半導體晶片（chip）與基板連接時，一直廣泛地應用使用金線等金屬細線的打線接合（wire bonding）方式。另一方面，為了對應針對半導體裝置的高功能化、高積體化、高速化等要求，於半導體晶片或基板上形成稱為凸塊（bump）的導電性突起而將半導體晶片與基板直接連接的覆晶連接方式（FC（flip chip）連接方式）正在推廣。Previously, when connecting a semiconductor chip to a substrate, a wire bonding method using thin metal wires such as gold wires has been widely used. On the other hand, in order to meet the requirements for high-function, high-integration, and high-speed semiconductor devices, conductive bumps called bumps are formed on semiconductor wafers or substrates to directly connect semiconductor wafers and substrates. The flip chip connection method (FC (flip chip) connection method) is being promoted.

作為FC連接方式，已知有使用焊料、錫、金、銀、銅等使連接部金屬接合的方法、施加超音波振動使連接部金屬接合的方法、利用樹脂的收縮力保持機械接觸的方法等。就連接部的可靠性的觀點而言，通常為使用焊料、錫、金、銀、銅等使連接部金屬接合的方法。As the FC connection method, there are known methods of joining the metal of the connection part using solder, tin, gold, silver, copper, etc., the method of applying ultrasonic vibration to join the metal of the connection part, the method of using the shrinkage force of the resin to maintain mechanical contact, etc. . From the viewpoint of the reliability of the connection portion, it is usually a method of joining the connection portion metal using solder, tin, gold, silver, copper, or the like.

例如，關於半導體晶片及基板間的連接，球形柵格陣列（Ball Grid Array，BGA）、晶片尺寸封裝（Chip Size Package，CSP）等中盛行使用的板上晶片（Chip On Board，COB）型連接方式亦相當於FC連接方式。另外，FC連接方式亦廣泛用於在半導體晶片上形成連接部（凸塊或配線）而將半導體晶片間連接的堆疊晶片（Chip On Chip，COC）型的連接方式（例如，參照專利文獻1）。For example, regarding the connection between semiconductor chips and substrates, ball grid arrays (Ball Grid Array, BGA), chip size packages (Chip Size Package, CSP), etc. are popularly used in Chip On Board (COB) type connections The method is also equivalent to the FC connection method. In addition, the FC connection method is also widely used in a chip on chip (COC) type connection method in which connecting portions (bumps or wiring) are formed on semiconductor wafers to connect semiconductor wafers (for example, refer to Patent Document 1) .

另外，於強烈要求進一步的小型化、薄型化、高功能化的封裝中，將所述連接方式進行積層-多段化的晶片堆疊（chip stack）型封裝、封裝堆疊封裝（Package On Package，POP）、矽通孔（Through-Silicon Via，TSV）等亦開始廣泛普及。此種積層-多段化技術對半導體晶片等進行三維配置，因此與二維地配置的方法相比可縮小封裝。另外，所述積層-多段化技術於半導體的性能提高、雜訊減少、安裝面積的削減、省電力化方面亦有效，因此作為下一代的半導體配線技術而受到矚目。In addition, in a package that strongly requires further miniaturization, thinning, and high-functionality, the connection method is stacked-multi-staged chip stack type packaging, package on package (POP) , Through-Silicon Via (TSV), etc. have also begun to spread widely. This type of build-up and multi-stage technology arranges semiconductor wafers and the like in three dimensions, so the package can be reduced compared to the two-dimensional arrangement method. In addition, the multilayer-multistage technology is also effective in improving semiconductor performance, reducing noise, reducing mounting area, and saving power, and therefore attracts attention as a next-generation semiconductor wiring technology.

另外，就提高生產性的觀點而言，於半導體晶圓上壓接（連接）半導體晶片之後單片化而製作半導體封裝的晶片堆疊晶圓（Chip On Wafer，COW）、於半導體晶圓彼此壓接（連接）之後單片化而製作半導體封裝的晶圓堆疊晶圓（Wafer On Wafer，WOW）亦受到矚目。進而，就同樣的觀點而言，於將多個半導體晶片對位並暫時壓接在半導體晶圓上或鑄模陣列封裝（Mold Array Package，MAP）基板上之後，一併正式壓接該些多個半導體晶片來確保連接的多端子接合（Gang bonding）方式亦受到矚目。 [現有技術文獻] [專利文獻]In addition, from the viewpoint of improving productivity, the semiconductor wafer is crimped (connected) on a semiconductor wafer and then singulated to produce a chip on wafer (COW) of a semiconductor package. Wafer On Wafer (Wafer On Wafer, WOW), which is singulated after being connected (connected), is also attracting attention. Furthermore, from the same point of view, after aligning a plurality of semiconductor chips and temporarily crimping them on a semiconductor wafer or a mold array package (Mold Array Package, MAP) substrate, they are formally crimped together. The multi-terminal bonding (Gang bonding) method of semiconductor chips to ensure connection has also attracted attention. [Prior Art Literature] [Patent Literature]

專利文獻1：日本專利特開2008-294382號公報Patent Document 1: Japanese Patent Laid-Open No. 2008-294382

[發明所欲解決之課題] 在覆晶封裝中，有時由於半導體用接著劑與半導體晶片之間以及半導體晶片與基板之間的熱膨脹係數的差而產生應力，並在封裝中產生翹曲。隨著半導體晶片及半導體晶圓的薄膜化，更容易發生所述封裝的翹曲。[The problem to be solved by the invention] In the flip chip package, the difference in thermal expansion coefficient between the adhesive for semiconductor and the semiconductor wafer and between the semiconductor wafer and the substrate may cause stress and warp in the package. As semiconductor wafers and semiconductor wafers become thinner, the package warpage is more likely to occur.

另外，在所述積層-多段化的晶片堆疊型封裝中，與一段的晶片堆疊型封裝相比，翹曲容易變大。In addition, in the stacked-multi-stage wafer-stacked package, the warpage tends to become larger compared to the one-stage wafer-stacked package.

由於所述封裝的翹曲，容易發生無法進行二次成型（overmold）以及發生封裝的連接不良的問題。因此，強烈要求封裝的低翹曲化。Due to the warpage of the package, problems such as inability to overmold and poor connection of the package easily occur. Therefore, there is a strong demand for low warpage of the package.

此處，作為實現封裝的低翹曲化的方法，考慮到使半導體用接著劑低彈性化。作為使半導體用接著劑低彈性化的方法，考慮到使高分子成分的玻璃轉移溫度低溫化的方法、減少無機填料的添加量的方法、增加有機填料的添加量的方法等。但是，於利用該些方法使半導體用接著劑低彈性化的情況下，半導體用接著劑的操作性的惡化或熔融黏度的適當化變得困難，難以兼顧該些特性與封裝的低翹曲化。Here, as a method of achieving low warpage of the package, it is considered that the elasticity of the adhesive for semiconductors is low. As a method of lowering the elasticity of the adhesive for semiconductors, a method of lowering the glass transition temperature of a polymer component, a method of reducing the amount of addition of inorganic fillers, a method of increasing the amount of addition of organic fillers, and the like are considered. However, when these methods are used to lower the elasticity of the adhesive for semiconductors, it becomes difficult to deteriorate the workability of the adhesive for semiconductors or to optimize the melt viscosity, and it is difficult to balance these characteristics with the reduction of package warpage. .

本揭示為了解決所述課題而完成，目的在於提供一種可在抑制接著力及可靠性的降低的同時，實現所得的封裝的低翹曲化的半導體用接著劑、以及使用該半導體用接著劑的半導體裝置的製造方法及半導體裝置。 [解決課題之手段]The present disclosure was made in order to solve the above-mentioned problems, and the object is to provide an adhesive for semiconductors that can reduce the warpage of the resulting package while suppressing deterioration in adhesive force and reliability, and a semiconductor adhesive using the same Semiconductor device manufacturing method and semiconductor device. [Means to solve the problem]

為了達成所述目的，本揭示提供一種半導體用接著劑，含有重量平均分子量小於10000的樹脂、硬化劑、無機填料及矽酮橡膠填料。根據所述半導體用接著劑，藉由組合使用無機填料與矽酮橡膠填料作為填料，可在抑制接著力及可靠性的降低的同時，實現所得的封裝的低翹曲化。特別是藉由使用矽酮橡膠填料作為與無機填料併用的有機填料，可大幅度減少所得的封裝的翹曲。In order to achieve the objective, the present disclosure provides an adhesive for semiconductors, which contains a resin with a weight average molecular weight of less than 10,000, a hardener, an inorganic filler, and a silicone rubber filler. According to the adhesive for semiconductors, by using an inorganic filler and a silicone rubber filler as a filler in combination, it is possible to reduce the warpage of the resulting package while suppressing the decrease in adhesive force and reliability. In particular, by using silicone rubber fillers as organic fillers used in combination with inorganic fillers, the resulting package warpage can be greatly reduced.

所述矽酮橡膠填料的平均粒徑可為30 μm以下。該情況下，可在更充分地抑制接著力及可靠性的降低的同時，進一步減少所得的封裝的翹曲。The average particle size of the silicone rubber filler may be 30 μm or less. In this case, it is possible to further reduce the warpage of the resulting package while suppressing the deterioration of the adhesive force and reliability more sufficiently.

所述無機填料亦可含有二氧化矽填料。該情況下，可進一步提高接著力及可靠性。另外，無機填料與矽酮橡膠填料更容易均勻地分散，可以更高水準兼顧良好的接著力及可靠性與所得的封裝的低翹曲化。The inorganic filler may also contain silica filler. In this case, the adhesive force and reliability can be further improved. In addition, the inorganic filler and the silicone rubber filler are more easily dispersed uniformly, which can achieve a higher level of good adhesion and reliability and low warpage of the resulting package.

所述半導體用接著劑亦可進而含有重量平均分子量為10000以上的高分子成分。該情況下，可提高半導體用接著劑的耐熱性及膜形成性。The adhesive for semiconductors may further contain a polymer component having a weight average molecular weight of 10,000 or more. In this case, the heat resistance and film formability of the adhesive for semiconductors can be improved.

所述高分子成分的重量平均分子量可為30000以上。另外，所述高分子成分的玻璃轉移溫度亦可為100℃以下。若重量平均分子量為30000以上，則膜形成性變得良好。若玻璃轉移溫度為100℃以下，則對基板及半導體晶片的貼附性變得良好。The weight average molecular weight of the polymer component may be 30,000 or more. In addition, the glass transition temperature of the polymer component may be 100°C or less. If the weight average molecular weight is 30,000 or more, the film formability becomes good. If the glass transition temperature is 100°C or less, the adhesion to the substrate and the semiconductor wafer becomes good.

所述半導體用接著劑亦可為膜狀。該情況下，可提高半導體用接著劑的操作性，且可提高封裝製造時的作業性及生產性。The adhesive for semiconductors may be in the form of a film. In this case, the workability of the adhesive for semiconductors can be improved, and the workability and productivity during package manufacturing can be improved.

以半導體用接著劑的固體成分總量為基準，所述半導體用接著劑中的所述矽酮橡膠填料的含量可為0.1質量%～20質量%。該情況下，可以更高水準兼顧良好的接著力及可靠性與所得的封裝的低翹曲化。The content of the silicone rubber filler in the adhesive for semiconductors may be 0.1% by mass to 20% by mass based on the total solid content of the adhesive for semiconductors. In this case, it is possible to achieve a higher level of both good adhesive force and reliability and low warpage of the resulting package.

於所述半導體用接著劑中，所述矽酮橡膠填料的含量相對於所述無機填料的含量的質量比（矽酮橡膠填料的質量/無機填料的質量）可為0.05～0.5。該情況下，可以更高水準兼顧良好的接著力及可靠性與所得的封裝的低翹曲化。In the adhesive for semiconductors, the mass ratio of the content of the silicone rubber filler to the content of the inorganic filler (mass of the silicone rubber filler/mass of the inorganic filler) may be 0.05 to 0.5. In this case, it is possible to achieve a higher level of compatibility between good adhesive force and reliability and low warpage of the resulting package.

另外，本揭示提供一種半導體裝置的製造方法，為製造半導體晶片及配線電路基板各自的連接部相互電性連接的半導體裝置、或者多個半導體晶片各自的連接部相互電性連接的半導體裝置的方法，所述半導體裝置的製造方法包括：使用所述半導體用接著劑對所述連接部的至少一部分進行密封的步驟。根據所述製造方法，可獲得半導體晶片與配線電路基板或半導體晶片之間的接著力及可靠性優異且翹曲減少的半導體裝置。In addition, the present disclosure provides a method of manufacturing a semiconductor device, which is a method of manufacturing a semiconductor device in which the respective connection portions of a semiconductor wafer and a wiring circuit board are electrically connected to each other, or a semiconductor device in which respective connection portions of a plurality of semiconductor wafers are electrically connected to each other The method of manufacturing the semiconductor device includes a step of sealing at least a part of the connection portion with the adhesive for semiconductor. According to the manufacturing method, it is possible to obtain a semiconductor device with excellent adhesion and reliability between the semiconductor wafer and the wiring circuit board or the semiconductor wafer and with reduced warpage.

進而，本揭示提供一種半導體裝置，包括：由半導體晶片及配線電路基板各自的連接部相互電性連接而成的連接結構、或者由多個半導體晶片各自的連接部相互電性連接而成的連接結構；以及將所述連接部的至少一部分密封的接著材料，所述接著材料包含所述半導體用接著劑的硬化物。所述半導體裝置成為半導體晶片與配線電路基板或半導體晶片之間的接著力及可靠性優異且翹曲減少的半導體裝置。 [發明的效果]Furthermore, the present disclosure provides a semiconductor device including: a connection structure in which the respective connection portions of a semiconductor chip and a wiring circuit board are electrically connected to each other, or a connection in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other Structure; and an adhesive material that seals at least a part of the connecting portion, the adhesive material including a cured product of the semiconductor adhesive. The semiconductor device is a semiconductor device having excellent adhesion and reliability between the semiconductor wafer and the wiring circuit board or the semiconductor wafer, and having reduced warpage. [Effects of the invention]

根據本揭示，可提供一種可在抑制接著力及可靠性的降低的同時，實現所得的封裝的低翹曲化的半導體用接著劑、以及使用該半導體用接著劑的半導體裝置的製造方法及半導體裝置。According to the present disclosure, it is possible to provide an adhesive for semiconductors that can reduce the warpage of the resulting package while suppressing deterioration in adhesion and reliability, and a method for manufacturing a semiconductor device using the adhesive for semiconductors, and a semiconductor Device.

以下，視情況，參照圖式對本揭示的適宜實施形態進行詳細說明。 再者，圖式中，對相同或相當部分標註相同符號，省略重覆說明。另外，上下左右等位置關係只要無特別說明，則視為基於圖式所示的位置關係。 進而，圖式的尺寸比率不限於圖示的比率。Hereinafter, as appropriate, suitable embodiments of the present disclosure will be described in detail with reference to the drawings. In addition, in the drawings, the same or corresponding parts are denoted with the same symbols, and repeated descriptions are omitted. In addition, the positional relationship such as up, down, left, and right is regarded as based on the positional relationship shown in the drawings, unless otherwise specified. Furthermore, the size ratio of the drawing is not limited to the ratio shown in the figure.

本說明書中，使用「～」表示的數值範圍表示分別包含「～」的前後記載的數值作為最小值及最大值的範圍。於本說明書中階段性記載的數值範圍中，某一階段的數值範圍的上限值或下限值可與其他階段的數值範圍的上限值或下限值任意組合。於本說明書中記載的數值範圍中，所述數值範圍的上限值或下限值亦可替換成實施例所示的值。所謂「A或B」只要包含A及B中的任一者即可，亦可兩者都包含。本說明書中例示的材料只要無特別說明，則可單獨使用一種或者組合使用兩種以上。本說明書中，所謂「(甲基)丙烯酸」是指丙烯酸或與其對應的甲基丙烯酸。In this specification, the numerical range indicated by "～" means a range that includes the numerical values described before and after "～" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper limit or lower limit of the numerical range of a certain stage can be arbitrarily combined with the upper limit or lower limit of the numerical range of other stages. In the numerical range described in this specification, the upper limit or lower limit of the numerical range can also be replaced with the values shown in the examples. The so-called "A or B" may include any one of A and B, or both. Unless otherwise specified, the materials exemplified in this specification can be used alone or in combination of two or more. In this specification, "(meth)acrylic acid" refers to acrylic acid or methacrylic acid corresponding to it.

＜半導體用接著劑＞ 本實施形態的半導體用接著劑含有重量平均分子量小於10000的樹脂（以下視情況稱為「（a）成分」）、硬化劑（以下視情況稱為「（b）成分」）、無機填料（以下視情況稱為「（e）成分」）及有機填料（以下視情況稱為「（f）成分」）。另外，本實施形態的半導體用接著劑含有矽酮橡膠填料作為有機填料。進而，本實施形態的半導體用接著劑可視需要含有重量平均分子量為10000以上的高分子化合物（以下視情況稱為「（c）成分」）及/或助熔劑（以下視情況稱為「（d）成分」）。以下，對各成分進行說明。＜Adhesive for semiconductors＞ The adhesive for semiconductors of this embodiment contains a resin with a weight average molecular weight of less than 10,000 (hereinafter referred to as "component (a)" as appropriate), a curing agent (hereinafter referred to as "component (b)" as appropriate), and inorganic filler (hereinafter As the case may be referred to as "(e) component") and organic filler (hereinafter as the case may be referred to as "(f) component"). In addition, the adhesive for semiconductors of this embodiment contains a silicone rubber filler as an organic filler. Furthermore, the adhesive for semiconductors of the present embodiment may optionally contain a polymer compound having a weight average molecular weight of 10,000 or more (hereinafter referred to as "(c) component" as appropriate) and/or flux (hereinafter as appropriate as “(d) )ingredient"). Hereinafter, each component will be described.

（a）重量平均分子量小於10000的樹脂 作為（a）成分，並無特別限制，就耐熱性的觀點而言，較佳為與（b）成分的硬化劑反應的成分。作為（a）成分，較佳為分子內具有兩個以上的反應基者。作為（a）成分，例如可列舉：環氧樹脂、酚樹脂、醯亞胺樹脂、脲樹脂、三聚氰胺樹脂、矽酮樹脂、(甲基)丙烯酸化合物、乙烯基化合物。該些中，就耐熱性及保存穩定性優異的觀點而言，較佳為環氧樹脂、酚樹脂、醯亞胺樹脂，更佳為環氧樹脂、醯亞胺樹脂。該些（a）成分亦可單獨使用或者作為兩種以上的混合物或共聚物來使用。(A) Resins with a weight average molecular weight less than 10,000 The component (a) is not particularly limited, but from the viewpoint of heat resistance, a component that reacts with the curing agent of the component (b) is preferred. As the component (a), those having two or more reactive groups in the molecule are preferred. As the (a) component, an epoxy resin, a phenol resin, an imine resin, a urea resin, a melamine resin, a silicone resin, a (meth)acrylic compound, and a vinyl compound are mentioned, for example. Among these, from the viewpoint of excellent heat resistance and storage stability, epoxy resin, phenol resin, and amide resin are preferable, and epoxy resin and amide resin are more preferable. These (a) components can also be used individually or as a mixture or copolymer of two or more types.

作為環氧樹脂，若為分子內具有兩個以上的環氧基者，則並無特別限制，例如可列舉：雙酚A型、雙酚F型、萘型、苯酚酚醛清漆型、甲酚酚醛清漆型、苯酚芳烷基型、聯苯型、三苯基甲烷型及二環戊二烯型等環氧樹脂、以及各種多官能環氧樹脂。環氧樹脂可單獨使用一種或者組合使用兩種以上。該些中，就耐熱性及操作性的觀點而言，較佳為雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂及三苯基甲烷型環氧樹脂。The epoxy resin is not particularly limited as long as it has two or more epoxy groups in the molecule, and examples include bisphenol A type, bisphenol F type, naphthalene type, phenol novolak type, and cresol phenol Varnish type, phenol aralkyl type, biphenyl type, triphenylmethane type, dicyclopentadiene type and other epoxy resins, as well as various multifunctional epoxy resins. The epoxy resin can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of heat resistance and operability, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, and Triphenylmethane type epoxy resin.

作為醯亞胺樹脂，若為分子內具有兩個以上的醯亞胺基者，則並無特別限制，例如可列舉：耐地醯亞胺樹脂、烯丙基耐地醯亞胺樹脂、順丁烯二醯亞胺樹脂、醯胺醯亞胺樹脂、醯亞胺丙烯酸酯樹脂、各種多官能醯亞胺樹脂及各種聚醯亞胺樹脂。醯亞胺樹脂可單獨使用一種或者組合使用兩種以上。As the imine resin, if it has two or more imine groups in the molecule, it is not particularly limited. For example, examples include: dianimide resin, allyl dianimide resin, and butylene Endiimide resin, amide amide resin, amide acrylate resin, various polyfunctional amide resins and various polyimide resins. The imine resin can be used individually by 1 type or in combination of 2 or more types.

就抑制於高溫下的連接時分解而產生揮發成分的觀點而言，於連接時的溫度為250℃的情況下，（a）成分較佳為使用250℃下的熱重量減少量係數為5%以下的樹脂，於連接時的溫度為300℃的情況下，較佳為使用300℃下的熱重量減少量係數為5%以下的樹脂。From the viewpoint of suppressing decomposition during connection at high temperature and generating volatile components, when the temperature during connection is 250°C, it is preferable to use component (a) with a thermal weight reduction coefficient at 250°C of 5% For the following resins, when the temperature at the time of connection is 300°C, it is preferable to use a resin having a thermal weight loss coefficient at 300°C of 5% or less.

於使用環氧樹脂作為（a）成分的情況下，雙酚A型或雙酚F型的液狀環氧樹脂的1%熱重量減少溫度為250℃以下，因此有於高溫加熱時分解而產生揮發成分之虞。因此，較佳為使用於室溫（1氣壓、25℃）下為固體的環氧樹脂。於使用液狀環氧樹脂的情況下，較佳為與固體環氧樹脂組合使用。When epoxy resin is used as component (a), the 1% thermal weight loss temperature of bisphenol A type or bisphenol F type liquid epoxy resin is 250°C or less, so it decomposes when heated at high temperature. Concern about volatile ingredients. Therefore, it is preferable to use an epoxy resin that is solid at room temperature (1 atmosphere, 25°C). When a liquid epoxy resin is used, it is preferably used in combination with a solid epoxy resin.

（a）成分的重量平均分子量小於10000，就膜形成的觀點而言，較佳為小於10000，就熔融黏度的適當化的觀點而言，較佳為100以上。 因此，（a）成分的重量平均分子量較佳為100以上且小於10000，更佳為300以上且8000以下，進而較佳為300以上且5000以下。(A) The weight average molecular weight of the component is less than 10,000, and from the viewpoint of film formation, it is preferably less than 10,000, and from the viewpoint of optimizing the melt viscosity, it is preferably 100 or more. Therefore, the weight average molecular weight of the component (a) is preferably 100 or more and less than 10,000, more preferably 300 or more and 8,000 or less, and still more preferably 300 or more and 5,000 or less.

以半導體用接著劑的固體成分總量為基準，（a）成分的含量例如為5質量%～75質量%，較佳為15質量%～60質量%，更佳為30質量%～50質量%。藉由將（a）成分的含量設為5質量%以上，接著力及可靠性優異，若為75質量%以下，則防止硬化物變得過硬，容易減少封裝的翹曲。Based on the total solid content of the semiconductor adhesive, the content of component (a) is, for example, 5 mass% to 75 mass%, preferably 15 mass% to 60 mass%, more preferably 30 mass% to 50 mass% . By setting the content of the component (a) to 5 mass% or more, the adhesive strength and reliability are excellent, and if it is 75 mass% or less, the cured product is prevented from becoming too hard, and it is easy to reduce the warpage of the package.

（b）硬化劑 作為（b）硬化劑，例如可列舉：酚樹脂系硬化劑、酸酐系硬化劑、胺系硬化劑、咪唑系硬化劑及膦系硬化劑。若（b）成分包含酚性羥基、酸酐、胺類或咪唑類，則顯示出抑制於連接部中生成氧化膜的助熔活性，從而可使連接可靠性及絕緣可靠性提高。以下對各硬化劑加以說明。(B) Hardener (B) Hardeners include, for example, phenol resin hardeners, acid anhydride hardeners, amine hardeners, imidazole hardeners, and phosphine hardeners. If the component (b) contains a phenolic hydroxyl group, acid anhydride, amines, or imidazoles, it exhibits fluxing activity that suppresses the formation of an oxide film in the connection portion, and can improve connection reliability and insulation reliability. The hardening agents are described below.

（b-i）酚樹脂系硬化劑 作為酚樹脂系硬化劑，若為分子內具有兩個以上的酚性羥基者，則並無特別限制，可使用：苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、苯酚芳烷基樹脂、甲酚萘酚甲醛縮聚物、三苯基甲烷型多官能酚樹脂及各種多官能酚樹脂等。該些可單獨使用或者作為兩種以上的混合物來使用。另外，液狀酚樹脂有於高溫加熱時分解而產生揮發成分之虞，因此理想的是使用於室溫（1氣壓、25℃）下為固體的酚樹脂。(B-i) Phenolic resin hardener As the phenol resin curing agent, if it has two or more phenolic hydroxyl groups in the molecule, it is not particularly limited. It can be used: phenol novolak resin, cresol novolak resin, phenol aralkyl resin, cresol naphthalene Phenol-formaldehyde condensation polymer, triphenylmethane type polyfunctional phenol resin and various polyfunctional phenol resins, etc. These can be used alone or as a mixture of two or more kinds. In addition, the liquid phenol resin may decompose during high-temperature heating and generate volatile components. Therefore, it is desirable to use a phenol resin that is solid at room temperature (1 atmosphere, 25°C).

就使硬化性、接著性及保存穩定性等良好的觀點而言，（b-i）酚樹脂系硬化劑相對於所述（a）成分的當量比（酚性羥基/（a）成分的反應基的莫耳比）較佳為0.3～1.5，更佳為0.4～1.0，進而較佳為0.5～1.0。若當量比為0.3以上，則有硬化性提高，接著力提高的傾向，若為1.5以下，則不會過剩地殘存未反應的酚性羥基，吸水率被抑制為低值，有絕緣可靠性提高的傾向。酚性羥基顯示出去除氧化膜的助熔活性，因此藉由半導體用接著劑含有酚樹脂系硬化劑，可提高連接性、可靠性。From the viewpoint of improving curability, adhesiveness, storage stability, etc., (bi) the equivalent ratio of the phenol resin curing agent to the component (a) (phenolic hydroxyl group/reactive group of component (a) The molar ratio) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and still more preferably 0.5 to 1.0. If the equivalent ratio is 0.3 or more, the curability is improved, and the adhesion tends to be improved. If it is 1.5 or less, unreacted phenolic hydroxyl groups will not remain excessively, the water absorption rate is suppressed to a low value, and the insulation reliability is improved. Propensity. The phenolic hydroxyl group exhibits fluxing activity to remove the oxide film. Therefore, the adhesive for semiconductors contains a phenol resin-based curing agent to improve connectivity and reliability.

（b-ii）酸酐系硬化劑 作為酸酐系硬化劑，例如可使用：甲基環己烷四羧酸二酐、偏苯三甲酸酐、均苯四甲酸酐、二苯甲酮四羧酸二酐及乙二醇雙偏苯三甲酸酐酯等。該些可單獨使用或者作為兩種以上的混合物來使用。另外，液狀酸酐有於高溫加熱時分解而產生揮發成分之虞，因此理想的是使用於室溫（1氣壓、25℃）下為固體的酸酐。(B-ii) Acid anhydride hardener As an acid anhydride hardener, for example, methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, and ethylene glycol bistrimellitic anhydride can be used Ester etc. These can be used alone or as a mixture of two or more kinds. In addition, the liquid acid anhydride may decompose during high-temperature heating and generate volatile components. Therefore, it is desirable to use an acid anhydride that is solid at room temperature (1 atmosphere, 25°C).

就使硬化性、接著性及保存穩定性等良好的觀點而言，（b-ii）酸酐系硬化劑相對於所述（a）成分的當量比（酸酐基/（a）成分的反應基的莫耳比）較佳為0.3～1.5，更佳為0.4～1.0，進而較佳為0.5～1.0。若當量比為0.3以上，則有硬化性提高，接著力提高的傾向，若為1.5以下，則不會過剩地殘存未反應的酸酐，吸水率被抑制為低值，有絕緣可靠性提高的傾向。酸酐顯示出去除氧化膜的助熔活性，因此藉由半導體用接著劑含有酸酐系硬化劑，可提高連接性、可靠性。From the viewpoint of improving curability, adhesiveness, storage stability, etc., (b-ii) the equivalent ratio of acid anhydride hardener to the component (a) (acid anhydride group/reactive group of component (a) The molar ratio) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and still more preferably 0.5 to 1.0. If the equivalent ratio is 0.3 or more, the curability is improved and the adhesion tends to be improved. If it is 1.5 or less, unreacted acid anhydride does not remain excessively, the water absorption rate is suppressed to a low value, and the insulation reliability tends to be improved. . The acid anhydride exhibits fluxing activity for removing oxide films. Therefore, the adhesive for semiconductors contains an acid anhydride hardener to improve connectivity and reliability.

（b-iii）胺系硬化劑 作為胺系硬化劑，可使用二氰二胺等。另外，液狀胺有於高溫加熱時分解而產生揮發成分之虞，因此理想的是使用於室溫（1氣壓、25℃）下為固體的胺。(B-iii) Amine hardener As the amine hardener, dicyandiamine or the like can be used. In addition, liquid amines may decompose during high-temperature heating and generate volatile components. Therefore, it is desirable to use amines that are solid at room temperature (1 atmosphere, 25°C).

就使硬化性、接著性及保存穩定性等良好的觀點而言，（b-iii）胺系硬化劑相對於所述（a）成分的當量比（胺/（a）成分的反應基的莫耳比）較佳為0.3～1.5，更佳為0.4～1.0，進而較佳為0.5～1.0。若當量比為0.3以上，則有硬化性提高，接著力提高的傾向，若為1.5以下，則不會過剩地殘存未反應的胺，吸水率被抑制為低值，有絕緣可靠性提高的傾向。胺類顯示出去除氧化膜的助熔活性，因此藉由半導體用接著劑含有胺系硬化劑，可提高連接性、可靠性。From the viewpoint of improving curability, adhesiveness, storage stability, etc., (b-iii) the equivalent ratio of the amine-based curing agent to the component (a) (amount of amine/reactive group of component (a)) The ear ratio) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and still more preferably 0.5 to 1.0. If the equivalence ratio is 0.3 or more, the curability is improved and the adhesion tends to be improved. If it is 1.5 or less, unreacted amines will not remain excessively, the water absorption rate will be suppressed to a low value, and the insulation reliability will tend to be improved. . Amines show fluxing activity to remove oxide films. Therefore, the adhesive for semiconductors contains an amine curing agent to improve connectivity and reliability.

（b-iv）咪唑系硬化劑（所含有的氮原子為三級氮原子） 作為咪唑系硬化劑，可列舉：1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑偏苯三甲酸酯、1-氰基乙基-2-苯基咪唑鎓偏苯三甲酸酯、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-十一烷基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-乙基-4'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、環氧樹脂與咪唑類的加成物等。該些中，就使硬化性、接著性及保存穩定性等良好的觀點而言，較佳為1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑偏苯三甲酸酯、1-氰基乙基-2-苯基咪唑鎓偏苯三甲酸酯、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-乙基-4'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物。該些可單獨使用或者組合使用兩種以上。另外，亦可使用將該些進行微膠囊化而提高潛在性的潛在性硬化劑。(B-iv) Imidazole-based hardener (the nitrogen atoms contained are tertiary nitrogen atoms) Examples of imidazole-based hardeners include: 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano Ethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine Oxazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole heterotrimerization Cyanate adduct, epoxy resin and imidazole adduct, etc. Among these, from the viewpoint of improving curability, adhesiveness, storage stability, etc., 1-cyanoethyl-2-undecylimidazole and 1-cyanoethyl-2-benzene are preferred. Imidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino- 6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-( 1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid addition Compound, 2-phenylimidazole isocyanuric acid adduct. These can be used alone or in combination of two or more. In addition, latent sclerosing agents that are microencapsulated to increase the potential can also be used.

相對於（a）成分100質量份，（b-iv）咪唑系硬化劑的含量較佳為0.1質量份～20質量份，更佳為0.1質量份～10質量份。若該含量為0.1質量份以上，則有硬化性提高的傾向，若為20質量份以下，則於金屬接合形成之前半導體用接著劑不會硬化，有不易產生連接不良的傾向。咪唑系硬化劑可單獨作為（b）硬化劑使用，亦可與所述（b-i）～（b-iii）的硬化劑一起作為硬化促進劑使用。The content of the (b-iv) imidazole hardener is preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the component (a). If the content is 0.1 parts by mass or more, the curability tends to be improved, and if it is 20 parts by mass or less, the adhesive for semiconductors does not harden before the formation of the metal junction, and there is a tendency that poor connection is less likely to occur. The imidazole-based curing agent may be used alone as the (b) curing agent, or may be used as the curing accelerator together with the curing agents (b-i) to (b-iii).

（b-v）膦系硬化劑 作為膦系硬化劑，可列舉：三苯基膦、四苯基鏻四苯基硼酸鹽、四苯基鏻四(4-甲基苯基)硼酸鹽、四苯基鏻(4-氟苯基)硼酸鹽等。(B-v) Phosphine hardener Examples of phosphine-based hardeners include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra(4-methylphenyl) borate, tetraphenylphosphonium (4-fluorophenyl) ) Borate, etc.

相對於（a）成分100質量份，（b-v）膦系硬化劑的含量較佳為0.1質量份～10質量份，更佳為0.1質量份～5質量份。若膦系硬化劑的含量為0.1質量份以上，則有硬化性提高的傾向，若為10質量份以下，則於金屬接合形成之前膜狀接著劑不會硬化，有不易產生連接不良的傾向。The content of the (b-v) phosphine-based hardener is preferably 0.1 parts by mass to 10 parts by mass, and more preferably 0.1 parts by mass to 5 parts by mass relative to 100 parts by mass of the component (a). If the content of the phosphine-based curing agent is 0.1 parts by mass or more, the curability tends to be improved, and if it is 10 parts by mass or less, the film-like adhesive does not harden before the metal bonding is formed, and there is a tendency that poor connection is less likely to occur.

酚樹脂系硬化劑、酸酐系硬化劑及胺系硬化劑分別可單獨使用一種或者作為兩種以上的混合物來使用。咪唑系硬化劑及膦系硬化劑分別可單獨使用，亦可與酚樹脂系硬化劑、酸酐系硬化劑或胺系硬化劑一併使用。The phenol resin curing agent, the acid anhydride curing agent, and the amine curing agent may be used alone or as a mixture of two or more. The imidazole-based curing agent and the phosphine-based curing agent may be used alone, respectively, or together with a phenol resin-based curing agent, an acid anhydride-based curing agent or an amine-based curing agent.

（c）重量平均分子量10000以上的高分子成分 作為（c）重量平均分子量10000以上的高分子成分，可列舉：苯氧基樹脂、聚醯亞胺樹脂、聚醯胺樹脂、聚碳二醯亞胺樹脂、氰酸酯樹脂、丙烯酸樹脂、聚酯樹脂、聚乙烯樹脂、聚醚碸樹脂、聚醚醯亞胺樹脂、聚乙烯縮醛樹脂、胺基甲酸酯樹脂、丙烯酸橡膠等。該些中，就耐熱性及膜形成性優異的方面而言，理想的是苯氧基樹脂、聚醯亞胺樹脂、丙烯酸橡膠、氰酸酯樹脂、聚碳二醯亞胺樹脂等，更佳為苯氧基樹脂、聚醯亞胺樹脂、丙烯酸橡膠，進而較佳為苯氧基樹脂。該些高分子成分可單獨使用或者作為兩種以上的混合物或共聚物使用。(C) Polymer components with a weight average molecular weight of 10,000 or more (C) Polymer components with a weight average molecular weight of 10,000 or more include: phenoxy resins, polyimide resins, polyimide resins, polycarbodiimide resins, cyanate ester resins, acrylic resins, and polyimide resins. Ester resin, polyethylene resin, polyether resin, polyether imine resin, polyvinyl acetal resin, urethane resin, acrylic rubber, etc. Among these, in terms of excellent heat resistance and film formability, phenoxy resin, polyimide resin, acrylic rubber, cyanate resin, polycarbodiimide resin, etc. are preferable, and more preferable Phenoxy resin, polyimide resin, acrylic rubber, more preferably phenoxy resin. These polymer components can be used alone or as a mixture or copolymer of two or more.

（c）成分、（a）成分與（b）成分的質量比並無特別限制，就使膜形成性及利用旋塗等的成膜性良好的觀點而言，相對於（c）成分1質量份，（a）成分及（b）成分的合計質量較佳為0.01質量份～5質量份，更佳為0.1質量份～4質量份，進而較佳為0.1質量份～3質量份。若該質量比為0.01質量份以上，則有可抑制半導體用接著劑的硬化性的降低、可抑制接著力的降低的傾向，若為5質量份以下，則有可使膜形成性及成膜性良好的傾向。The mass ratio of (c) component, (a) component and (b) component is not particularly limited. From the viewpoint of improving film formability and film formation by spin coating, it is relative to (c) component 1 mass Parts, the total mass of (a) component and (b) component is preferably 0.01 parts by mass to 5 parts by mass, more preferably 0.1 parts by mass to 4 parts by mass, and still more preferably 0.1 parts by mass to 3 parts by mass. If the mass ratio is 0.01 parts by mass or more, there is a tendency that the curability of the adhesive for semiconductors can be suppressed and the decrease in adhesive strength can be suppressed, and if the mass ratio is less than 5 parts by mass, film formation and film formation can be achieved. The tendency to have good sex.

作為（c）成分使用的聚醯亞胺樹脂例如可利用公知的方法使四羧酸二酐與二胺進行縮合反應而獲得。更具體而言，於有機溶媒中，將四羧酸二酐與二胺以等莫耳或大致等莫耳混合（各成分的添加順序任意），於反應溫度80℃以下、較佳為0℃～60℃下進行加成反應。隨著反應的進行，反應液的黏度逐漸上升，生成作為聚醯亞胺的前驅物的聚醯胺酸。再者，為了抑制半導體用接著劑的各種特性的降低，較佳為所述四羧酸二酐利用乙酸酐進行再結晶精製處理。The polyimide resin used as the component (c) can be obtained by condensation reaction of tetracarboxylic dianhydride and diamine by a known method, for example. More specifically, in an organic solvent, tetracarboxylic dianhydride and diamine are mixed in equal or approximately equal moles (the order of addition of the components is arbitrary), and the reaction temperature is 80°C or less, preferably 0°C The addition reaction proceeds at ~60°C. As the reaction progresses, the viscosity of the reaction solution gradually rises, and polyimide is produced as a precursor of polyimide. Furthermore, in order to suppress the degradation of various characteristics of the adhesive for semiconductors, it is preferable that the tetracarboxylic dianhydride be subjected to recrystallization purification treatment with acetic anhydride.

所述聚醯胺酸亦可藉由於50℃～80℃的溫度下加熱使其解聚來調整其分子量。The polyamide acid can also be depolymerized by heating at a temperature of 50°C to 80°C to adjust its molecular weight.

聚醯亞胺樹脂可使所述反應產物（聚醯胺酸）脫水閉環而獲得。脫水閉環可利用進行加熱處理的熱閉環法或使用脫水劑的化學閉環法進行。The polyimide resin can be obtained by dehydration and ring closure of the reaction product (polyamide acid). The dehydration ring-closure can be performed by a thermal ring-closure method using heat treatment or a chemical ring-closure method using a dehydrating agent.

就使對基板及半導體晶片的貼附性良好的觀點而言，（c）成分的玻璃轉移溫度（Tg）較佳為100℃以下，更佳為75℃以下。若Tg為100℃以下，則利用半導體用接著劑容易將形成於半導體晶片上的凸塊或者形成於基板上的電極或配線圖案等的凹凸填埋，有可防止氣泡的殘存、抑制孔隙（void）的產生的傾向。再者，所述Tg是使用示差掃描熱量計（珀金埃爾默（PerkinElmer）公司製造，DSC-7型），在樣品量10 mg、升溫速度5℃/min、測定環境：空氣的條件下測定時的Tg。From the viewpoint of making the adhesion to the substrate and the semiconductor wafer good, the glass transition temperature (Tg) of the component (c) is preferably 100° C. or less, and more preferably 75° C. or less. If the Tg is 100°C or less, the bumps formed on the semiconductor wafer or the irregularities of the electrodes or wiring patterns formed on the substrate can be easily filled with the adhesive for semiconductors, which can prevent the remaining of bubbles and suppress voids. )’S tendency to produce. In addition, the Tg was measured using a differential scanning calorimeter (perkinElmer (PerkinElmer), DSC-7 type), under the conditions of a sample amount of 10 mg, a heating rate of 5°C/min, and a measurement environment: air Tg at the time of measurement.

（c）成分的重量平均分子量以聚苯乙烯換算計為10000以上，為了單獨顯示出良好的膜形成性，較佳為20000以上，更佳為30000以上，進而較佳為40000以上。於重量平均分子量小於10000的情況下，有膜形成性降低之虞。另外，考慮到流動性，（c）成分的重量平均分子量例如為100萬以下，較佳為50萬以下。(C) The weight average molecular weight of the component is 10,000 or more in terms of polystyrene, and in order to exhibit good film formability alone, it is preferably 20,000 or more, more preferably 30,000 or more, and still more preferably 40,000 or more. In the case where the weight average molecular weight is less than 10,000, the film formability may decrease. In addition, in consideration of fluidity, the weight average molecular weight of the component (c) is, for example, 1 million or less, and preferably 500,000 or less.

本說明書中，所謂重量平均分子量是指使用高效液相層析法（島津製作所製造的C-R4A）以聚苯乙烯換算測定時的重量平均分子量。In this specification, the weight average molecular weight refers to the weight average molecular weight when measured in terms of polystyrene using high performance liquid chromatography (C-R4A manufactured by Shimadzu Corporation).

（c）成分與（a）成分的含量的比並無特別限制，就良好地保持膜狀的觀點而言，相對於（c）成分1質量份，較佳為（a）成分為0.01質量份～5質量份，更佳為0.1質量份～2質量份。若該含量的比為0.01質量份以上，則有可抑制半導體用接著劑的硬化性的降低、可抑制接著力的降低的傾向，若為5質量份以下，則有可使膜形成性及成膜性良好的傾向。The ratio of the content of the component (c) to the component (a) is not particularly limited. From the viewpoint of maintaining the film shape well, the component (a) is preferably 0.01 part by mass relative to 1 part by mass of the component (c) ~5 parts by mass, more preferably 0.1 parts by mass to 2 parts by mass. If the ratio of the content is 0.01 parts by mass or more, there is a tendency that the curability of the adhesive for semiconductors can be suppressed, and the decrease in adhesive force tends to be suppressed, and if it is 5 parts by mass or less, the film formability and cost can be improved. Tendency to have good film properties.

（d）助熔劑 半導體用接著劑可含有（d）助熔劑、即、作為顯示出助熔活性（去除氧化物及雜質的活性）的化合物的助熔活性劑。作為助熔劑，例如可列舉如咪唑類及胺類般具有非共價電子對的含氮化合物、羧酸類、苯酚類及醇類。再者，與醇類相比，如羧酸類般的有機酸類更強烈地顯現出助熔活性，容易提高連接性。(D) Flux The adhesive for semiconductors may contain (d) a flux, that is, a flux activator that is a compound that exhibits flux activity (activity to remove oxides and impurities). Examples of fluxes include nitrogen-containing compounds having non-covalent electron pairs such as imidazoles and amines, carboxylic acids, phenols, and alcohols. Furthermore, compared with alcohols, organic acids such as carboxylic acids exhibit a stronger fluxing activity and are easier to improve connectivity.

就顯現出助熔活性並提高連接性的觀點而言，以半導體用接著劑的固體成分總量為基準，（d）成分的含量較佳為0.1質量%～5質量%，更佳為1質量%～5質量%。From the viewpoint of exhibiting flux activity and improving connectivity, the content of (d) component is preferably 0.1% by mass to 5% by mass, more preferably 1 mass based on the total solid content of the semiconductor adhesive %～5 mass%.

（e）無機填料 本實施形態的半導體用接著劑含有無機填料作為（e）成分。藉由含有（e）成分，可控制半導體用接著劑的黏度及硬化物的物性，可抑制將半導體晶片與基板連接時的孔隙的產生及吸濕率。另外，藉由含有（e）成分，半導體用接著劑可獲得優異的接著力，且可提高耐回焊性及耐濕性等可靠性。(E) Inorganic filler The adhesive for semiconductors of this embodiment contains an inorganic filler as the (e) component. By containing the component (e), the viscosity of the adhesive for semiconductors and the physical properties of the cured product can be controlled, and the generation of voids and the moisture absorption rate when connecting the semiconductor wafer to the substrate can be suppressed. In addition, by containing the component (e), the adhesive for semiconductors can obtain excellent adhesion and can improve reliability such as reflow resistance and moisture resistance.

作為（e）成分，例如可列舉絕緣性無機填料及晶鬚。作為絕緣性無機填料的材質，可列舉玻璃、二氧化矽、氧化鋁、二氧化矽-氧化鋁、氧化鈦、雲母、氮化硼等，其中，較佳為二氧化矽、氧化鋁、二氧化矽-氧化鋁、氧化鈦、氮化硼等，更佳為二氧化矽、氧化鋁、氮化硼，進而較佳為二氧化矽。作為晶鬚的材質，可列舉硼酸鋁、鈦酸鋁、氧化鋅、矽酸鈣、硫酸鎂、氮化硼等。Examples of the (e) component include insulating inorganic fillers and whiskers. Examples of materials for insulating inorganic fillers include glass, silica, alumina, silica-alumina, titania, mica, boron nitride, etc. Among them, silica, alumina, and silica are preferred. Silicon-alumina, titanium oxide, boron nitride, etc., more preferably silicon dioxide, aluminum oxide, boron nitride, and still more preferably silicon dioxide. Examples of the material of the whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride.

就分散性及接著力提高的觀點而言，（e）成分較佳為表面處理填料。作為表面處理，可列舉縮水甘油基系（環氧系）、胺系、苯基系、苯基胺基系、丙烯酸系、乙烯基系等。From the viewpoint of improvement in dispersibility and adhesion, the component (e) is preferably a surface treatment filler. Examples of surface treatments include glycidyl-based (epoxy-based), amine-based, phenyl-based, phenylamino-based, acrylic, vinyl, and the like.

作為表面處理，就表面處理的容易性而言，較佳為利用環氧矽烷系、胺基矽烷系、丙烯酸矽烷系等矽烷化合物進行的矽烷處理。作為表面處理劑，就分散性及流動性優異且進一步提高接著力的觀點而言，較佳為縮水甘油基系、苯基胺基系、(甲基)丙烯酸系的化合物。作為表面處理劑，就保存穩定性的觀點而言，較佳為苯基系、(甲基)丙烯酸系的化合物。As the surface treatment, in terms of ease of surface treatment, a silane treatment with a silane compound such as an epoxy silane-based, amino silane-based, acrylic silane-based, or the like is preferred. As the surface treatment agent, from the viewpoint of excellent dispersibility and fluidity and further improvement of adhesive force, glycidyl-based, phenylamino-based, and (meth)acrylic-based compounds are preferred. As the surface treatment agent, from the viewpoint of storage stability, phenyl-based and (meth)acrylic-based compounds are preferred.

關於（e）成分的粒徑，就防止覆晶連接時的含入的觀點而言，平均粒徑較佳為1.5 μm以下，就視認性(透明性)的觀點而言，平均粒徑更佳為1.0 μm以下。（e）成分的平均粒徑例如可藉由濕式-乾式粒度分佈測定裝置（貝克曼-庫爾特（beckman-coulter）製造，LS13 320）測定。Regarding the particle size of component (e), the average particle size is preferably 1.5 μm or less from the viewpoint of preventing inclusion during flip-chip bonding, and from the viewpoint of visibility (transparency), the average particle size is more preferable It is 1.0 μm or less. (E) The average particle size of the component can be measured by, for example, a wet-dry type particle size distribution analyzer (manufactured by Beckman-Coulter, LS13 320).

該些（e）成分亦可單獨使用或者作為兩種以上的混合體使用。關於（e）成分的形狀，並無特別限制。These (e) components can also be used individually or as a mixture of two or more types. There are no particular restrictions on the shape of the component (e).

以半導體用接著劑的固體成分總量為基準，（e）成分的含量較佳為20質量%～60質量%，更佳為30質量%～50質量%。若該含量為20質量%以上、特別是30質量%以上，則有可進一步抑制孔隙產生及吸濕率、可進一步提高接著力以及耐回焊性及耐濕性等可靠性的傾向。另一方面，若含量為60質量%以下、特別是50質量%以下，則有容易減少所得的封裝的翹曲且容易防止覆晶連接時的含入的傾向。Based on the total solid content of the adhesive for semiconductors, the content of the component (e) is preferably 20% by mass to 60% by mass, more preferably 30% by mass to 50% by mass. If the content is 20% by mass or more, particularly 30% by mass or more, there is a tendency that the generation of voids and the moisture absorption rate can be further suppressed, and the reliability of adhesion, reflow resistance, and moisture resistance can be further improved. On the other hand, if the content is 60% by mass or less, particularly 50% by mass or less, it tends to easily reduce the warpage of the resulting package and easily prevent inclusion during flip chip connection.

（f）有機填料 本實施形態的半導體用接著劑含有有機填料作為（f）成分。藉由含有（f）成分，可控制半導體用接著劑的黏度及硬化物的物性，可抑制將半導體晶片與基板連接時的孔隙的產生及吸濕率。(F) Organic filler The adhesive for semiconductors of this embodiment contains an organic filler as the (f) component. By containing the component (f), the viscosity of the semiconductor adhesive and the physical properties of the cured product can be controlled, and the generation of voids and the moisture absorption rate when connecting the semiconductor wafer to the substrate can be suppressed.

作為有機填料的材質，例如可列舉聚胺基甲酸酯、聚醯亞胺、矽酮、甲基丙烯酸甲酯樹脂及甲基丙烯酸甲酯-丁二烯-苯乙烯共聚樹脂（Methylmethacrylate Butadiene Styrene，MBS）。（f）成分與（e）成分相比，可於260℃等高溫下對半導體用接著劑及其硬化物賦予柔軟性，因此適於提高耐回焊性及耐溫度循環性。另外，由於賦予柔軟性，因此對提高膜形成性亦有效。Examples of the material of the organic filler include polyurethane, polyimide, silicone, methyl methacrylate resin, and methyl methacrylate-butadiene-styrene copolymer resin (Methylmethacrylate Butadiene Styrene, MBS). Compared with the component (e), the component (f) can impart flexibility to the semiconductor adhesive and its cured product at a high temperature such as 260°C, so it is suitable for improving reflow resistance and temperature cycle resistance. In addition, since it imparts flexibility, it is also effective for improving film formability.

該些（f）成分亦可單獨使用或者作為兩種以上的混合體使用。關於（f）成分的形狀，並無特別限制。These (f) components can also be used individually or as a mixture of two or more types. There are no particular restrictions on the shape of the component (f).

本實施形態的半導體用接著劑含有矽酮橡膠填料作為（f）成分。藉由半導體用接著劑含有矽酮橡膠填料，可實現所得的封裝的低翹曲化。The adhesive for semiconductors of this embodiment contains a silicone rubber filler as the (f) component. Since the adhesive for semiconductors contains silicone rubber filler, the resulting package can be reduced in warpage.

矽酮橡膠填料只要是含有矽酮橡膠作為填料的構成成分的填料即可，可為僅包含矽酮橡膠的填料，亦可為與其他成分複合化的填料。矽酮橡膠填料可為具有核-殼型結構的粒子。作為核-殼型的結構，可列舉具有核層（核材料）以及以被覆核層的方式設置的殼層（表面層）的結構。核層與殼層的組成可相同亦可不同。再者，核層與殼層未必具有清楚的邊界線。作為矽酮橡膠填料，例如可使用核層由矽酮橡膠粒子構成、殼層由矽酮橡膠粒子以外的其他成分構成的複合粒子。作為此種複合粒子，較佳為可列舉核層由矽酮橡膠粒子構成、殼層由具有比核層的矽酮橡膠粒子高的玻璃轉移溫度及彈性係數的矽酮樹脂構成的矽酮複合粉末。此種矽酮複合粉末可藉由殼層來抑制核層的矽酮橡膠粒子因溶劑或半導體用接著劑的構成材料發生膨潤而在矽酮橡膠粒子彼此之間形成凝聚體。The silicone rubber filler may be a filler containing silicone rubber as a constituent component of the filler, and may be a filler containing only silicone rubber or a filler compounded with other components. The silicone rubber filler may be particles with a core-shell structure. Examples of the core-shell structure include a structure having a core layer (core material) and a shell layer (surface layer) provided to cover the core layer. The composition of the core layer and the shell layer may be the same or different. Furthermore, the core layer and the shell layer may not have a clear boundary line. As the silicone rubber filler, for example, composite particles in which the core layer is composed of silicone rubber particles and the shell layer is composed of components other than silicone rubber particles can be used. As such composite particles, preferably, a core layer is composed of silicone rubber particles, and the shell layer is composed of silicone resin having a higher glass transition temperature and a coefficient of elasticity than the core layer of silicone rubber particles. . Such a silicone composite powder can suppress the swelling of the silicone rubber particles of the core layer due to the solvent or the constituent material of the semiconductor adhesive and the formation of aggregates between the silicone rubber particles by the shell layer.

矽酮橡膠填料的平均粒徑較佳為0.1 μm～50 μm，更佳為0.1 μm～30 μm，進而較佳為0.1 μm～10 μm。若平均粒徑為50 μm以下，則有安裝時的連接性變得良好的傾向。矽酮橡膠填料的平均粒徑例如可藉由濕式-乾式粒度分佈測定裝置（貝克曼-庫爾特（beckman-coulter）製造，LS13 320）測定。The average particle size of the silicone rubber filler is preferably 0.1 μm-50 μm, more preferably 0.1 μm-30 μm, and still more preferably 0.1 μm-10 μm. If the average particle size is 50 μm or less, the connectivity during mounting tends to become good. The average particle size of the silicone rubber filler can be measured by, for example, a wet-dry particle size distribution analyzer (manufactured by Beckman-Coulter, LS13 320).

以半導體用接著劑的固體成分總量為基準，矽酮橡膠填料的含量較佳為0.1質量%～20質量%，更佳為1質量%～18質量%，進而較佳為3質量%～15質量%。若該含量為0.1質量%以上，則有容易低彈性化的傾向，若為20質量%以下，則有容易使熔融黏度適當化的傾向。Based on the total solid content of the semiconductor adhesive, the content of the silicone rubber filler is preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 18% by mass, and still more preferably 3% by mass to 15% by mass. quality%. If the content is 0.1% by mass or more, the elasticity tends to be easily lowered, and if it is 20% by mass or less, the melt viscosity tends to be easily adjusted.

就更充分地獲得本揭示的效果的觀點而言，以（f）成分總量為基準，矽酮橡膠填料的含量在（f）成分中所佔的比例較佳為50質量%以上，更佳為80質量%以上。再者，矽酮橡膠填料的含量的比例亦可為100質量%。From the viewpoint of obtaining the effect of the present disclosure more fully, based on the total amount of the component (f), the content of the silicone rubber filler in the component (f) is preferably 50% by mass or more, more preferably It is 80% by mass or more. Furthermore, the ratio of the content of the silicone rubber filler may be 100% by mass.

矽酮橡膠填料的含量相對於（e）成分的含量的質量比（矽酮橡膠填料的質量/無機填料的質量）較佳為0.05～0.5，更佳為0.08～0.4，進而較佳為0.1～0.3。藉由使該質量比為所述範圍內，可以更高水準兼顧良好的接著力及可靠性與所得的封裝的低翹曲化。The mass ratio of the content of the silicone rubber filler to the content of component (e) (mass of silicone rubber filler/mass of inorganic filler) is preferably 0.05 to 0.5, more preferably 0.08 to 0.4, and still more preferably 0.1 to 0.3. By making the mass ratio within the above-mentioned range, it is possible to achieve a higher level of both good adhesion and reliability and low warpage of the resulting package.

以半導體用接著劑的固體成分整體為基準，（e）成分及（f）成分的合計含量較佳為30質量%～90質量%，更佳為40質量%～80質量%。若含量為30質量%以上，則有可更充分地提高接著力的傾向。若含量為90質量%以下，則有可抑制黏度變高而產生半導體用接著劑的流動性的降低及填料向連接部的含入（陷入（trapping）），可獲得良好的連接可靠性的傾向。Based on the entire solid content of the adhesive for semiconductors, the total content of the (e) component and the (f) component is preferably 30% by mass to 90% by mass, and more preferably 40% by mass to 80% by mass. If the content is 30% by mass or more, the adhesive force tends to be more sufficiently improved. If the content is 90% by mass or less, it is possible to suppress the increase in viscosity and the decrease in fluidity of the semiconductor adhesive and the incorporation (trapping) of filler into the connection part, which tends to achieve good connection reliability. .

就絕緣可靠性的觀點而言，填料較佳為絕緣性。半導體用接著劑較佳為不含銀填料、焊料填料等導電性金屬填料。不含導電性填料（導電性粒子）的半導體用接著劑（電路連接材料）亦有時被稱為非導電膜（Non-Conductive-FILM，NCF）或非導電膠（Non-Conductive-Paste，NCP）。本實施形態的半導體用接著劑可適宜地用作NCF或NCP。From the viewpoint of insulation reliability, the filler is preferably insulating. The adhesive for semiconductors preferably does not contain conductive metal fillers such as silver fillers and solder fillers. Adhesives for semiconductors (circuit connection materials) that do not contain conductive fillers (conductive particles) are sometimes called non-conductive films (Non-Conductive-FILM, NCF) or non-conductive pastes (Non-Conductive-Paste, NCP). ). The adhesive for semiconductors of this embodiment can be suitably used as NCF or NCP.

亦可於半導體用接著劑中進一步調配離子阱、抗氧化劑、矽烷偶合劑、鈦偶合劑、調平劑等。該些可單獨使用一種，亦可組合使用兩種以上。關於該些調配量，只要適宜調整以顯現出各添加劑的效果即可。Ion traps, antioxidants, silane coupling agents, titanium coupling agents, leveling agents, etc. can also be further formulated in the adhesive for semiconductors. These may be used alone or in combination of two or more. Regarding these blending amounts, it is only necessary to adjust them appropriately so as to express the effects of each additive.

本實施形態的半導體用接著劑可成形為膜狀。以下示出使用了本實施形態的半導體用接著劑的膜狀接著劑的製作方法的一例。The adhesive for semiconductors of this embodiment can be formed into a film shape. An example of a method for producing a film adhesive using the adhesive for semiconductors of this embodiment is shown below.

首先，將（a）成分～（f）成分及添加劑中的必要成分添加至有機溶媒中，藉由攪拌混合、混煉等進行溶解或分散而製備樹脂清漆。其後，於實施了脫模處理的基材膜上，使用刮刀塗佈機、輥塗佈機、敷料器等來塗佈樹脂清漆後，藉由加熱而將有機溶媒去除，藉此可於基材膜上形成膜狀接著劑。First, the necessary components among components (a) to (f) and additives are added to an organic solvent, and dissolved or dispersed by stirring, mixing, kneading, etc., to prepare a resin varnish. After that, after applying a resin varnish on the base film subjected to the mold release treatment using a knife coater, a roll coater, an applicator, etc., the organic solvent is removed by heating, whereby the base film can be A film-like adhesive is formed on the material film.

膜狀接著劑的厚度並無特別限制，例如較佳為連接前的凸塊的高度的0.5倍～1.5倍，更佳為0.6倍～1.3倍，進而較佳為0.7倍～1.2倍。The thickness of the film adhesive is not particularly limited. For example, it is preferably 0.5 to 1.5 times the height of the bump before connection, more preferably 0.6 to 1.3 times, and even more preferably 0.7 to 1.2 times.

若膜狀接著劑的厚度為凸塊的高度的0.5倍以上，則可充分抑制因未填充接著劑而引起的孔隙的產生，從而可進一步提高連接可靠性。另外，若厚度為1.5倍以下，則可充分抑制在連接時自晶片連接區域被擠出的接著劑的量，因此可充分防止接著劑向不必要的部分的附著。若膜狀接著劑的厚度大於1.5倍，則凸塊必須排除大量的接著劑，容易產生導通不良。另外，對於由窄間距化-多針腳化引起的凸塊的弱化（凸塊直徑的微小化）而言，排除大量的樹脂的情況會增大對凸塊的損傷，因此欠佳。When the thickness of the film-like adhesive is 0.5 times or more the height of the bump, the generation of voids due to the unfilled adhesive can be sufficiently suppressed, and the connection reliability can be further improved. In addition, if the thickness is 1.5 times or less, the amount of the adhesive that is squeezed out from the wafer connection area during connection can be sufficiently suppressed, and therefore the adhesion of the adhesive to unnecessary parts can be sufficiently prevented. If the thickness of the film-like adhesive is greater than 1.5 times, the bumps must remove a large amount of the adhesive, which is likely to cause poor conduction. In addition, with regard to the weakening of the bumps (minification of the bump diameter) caused by the narrowing of the pitch and the multi-stitching, the removal of a large amount of resin increases the damage to the bumps, which is not preferable.

通常凸塊的高度為5 μm～100 μm，據此，膜狀接著劑的厚度較佳為2.5 μm～150 μm，更佳為3.5 μm～120 μm。Generally, the height of the bump is 5 μm-100 μm, and accordingly, the thickness of the film-like adhesive is preferably 2.5 μm-150 μm, more preferably 3.5 μm-120 μm.

作為樹脂清漆的製備中使用的有機溶媒，較佳為具有可使各成分均勻地溶解或分散的特性者，例如可列舉：二甲基甲醯胺、二甲基乙醯胺、N-甲基-2-吡咯啶酮、二甲基亞碸、二乙二醇二甲醚、甲苯、苯、二甲苯、甲基乙基酮、四氫呋喃、乙基溶纖劑、乙基溶纖劑乙酸酯、丁基溶纖劑、二噁烷、環己酮、及乙酸乙酯。該些有機溶媒可單獨使用或者組合使用兩種以上。製備樹脂清漆時的攪拌混合及混煉例如可使用攪拌機、磨碎機、三輥、球磨機、珠磨機或均質機來進行。The organic solvent used in the preparation of the resin varnish is preferably one having the property of uniformly dissolving or dispersing each component, for example, dimethylformamide, dimethylacetamide, N-methyl -2-pyrrolidone, dimethyl sulfide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate , Butyl cellosolve, dioxane, cyclohexanone, and ethyl acetate. These organic solvents can be used alone or in combination of two or more. The stirring, mixing and kneading at the time of preparing the resin varnish can be performed using, for example, a stirrer, an attritor, a three-roller, a ball mill, a bead mill, or a homogenizer.

作為基材膜，若為具有可耐受使有機溶媒揮發時的加熱條件的耐熱性者則並無特別限制，可例示：聚丙烯膜、聚甲基戊烯膜等聚烯烴膜；聚對苯二甲酸乙二酯膜、聚萘二甲酸乙二酯膜等聚酯膜；聚醯亞胺膜及聚醚醯亞胺膜。基材膜並不限定於包含該些膜的單層者，亦可為包含兩種以上的材料的多層膜。The base film is not particularly limited as long as it has heat resistance that can withstand the heating conditions when the organic solvent is volatilized, and examples include polyolefin films such as polypropylene films and polymethylpentene films; polyparaphenylene Polyester films such as ethylene dicarboxylate film and polyethylene naphthalate film; polyimide film and polyetherimide film. The base film is not limited to a single layer including these films, and may be a multilayer film including two or more materials.

使有機溶媒自塗佈於基材膜的樹脂清漆中揮發時的乾燥條件較佳設為有機溶媒充分揮發的條件，具體而言較佳為進行50℃～200℃、0.1分鐘～90分鐘的加熱。有機溶媒較佳為被去除至相對於膜狀接著劑總量而為1.5質量%以下。The drying conditions when volatilizing the organic solvent from the resin varnish coated on the substrate film is preferably set to a condition where the organic solvent is sufficiently volatilized, and specifically it is preferably heating at 50°C to 200°C for 0.1 to 90 minutes . The organic solvent is preferably removed to 1.5% by mass or less with respect to the total amount of the film-like adhesive.

另外，本實施形態的半導體用接著劑可直接形成於晶圓上。具體而言，例如可藉由將所述樹脂清漆直接旋塗於晶圓上而形成膜後將有機溶媒去除，而於晶圓上直接形成半導體用接著劑。In addition, the adhesive for semiconductors of this embodiment can be formed directly on a wafer. Specifically, for example, the resin varnish can be directly spin-coated on a wafer to form a film and then the organic solvent can be removed to form an adhesive for semiconductors directly on the wafer.

＜半導體裝置＞ 對於本實施形態的半導體裝置，以下使用圖1及圖2來進行說明。圖1是表示本揭示的半導體裝置的一實施形態的示意剖面圖。如圖1的（a）所示，半導體裝置100具有：相互相向的半導體晶片10及基板（配線電路基板）20、分別配置於半導體晶片10及基板20的相互相向的面上的配線15、將半導體晶片10及基板20的配線15相互連接的連接凸塊30、以及無間隙地填充於半導體晶片10及基板20間的空隙中的接著材料40。半導體晶片10及基板20藉由配線15及連接凸塊30而經覆晶連接。配線15及連接凸塊30由接著材料40密封而與外部環境阻隔。＜Semiconductor device＞ The semiconductor device of this embodiment will be described below using FIGS. 1 and 2. FIG. 1 is a schematic cross-sectional view showing an embodiment of the semiconductor device of the present disclosure. As shown in FIG. 1(a), the semiconductor device 100 has: a semiconductor wafer 10 and a substrate (wiring circuit board) 20 facing each other, wirings 15 respectively arranged on opposing surfaces of the semiconductor wafer 10 and the substrate 20, and The connection bumps 30 connecting the wiring 15 of the semiconductor wafer 10 and the substrate 20 to each other, and the adhesive material 40 filling the gap between the semiconductor wafer 10 and the substrate 20 without gaps. The semiconductor chip 10 and the substrate 20 are connected via a flip chip by wiring 15 and connection bumps 30. The wiring 15 and the connection bump 30 are sealed by the adhesive material 40 to be blocked from the external environment.

如圖1的（b）所示，半導體裝置200具有：相互相向的半導體晶片10及基板20、分別配置於半導體晶片10及基板20的相互相向的面上的凸塊32、以及無間隙地填充於半導體晶片10及基板20間的空隙中的接著材料40。半導體晶片10及基板20藉由相向的凸塊32相互連接而經覆晶連接。凸塊32由接著材料40密封而與外部環境阻隔。接著材料40為本實施形態的半導體用接著劑的硬化物。As shown in FIG. 1(b), the semiconductor device 200 has: a semiconductor wafer 10 and a substrate 20 facing each other, bumps 32 respectively arranged on the mutually facing surfaces of the semiconductor wafer 10 and the substrate 20, and filling without gaps Adhesive material 40 in the gap between the semiconductor wafer 10 and the substrate 20. The semiconductor chip 10 and the substrate 20 are connected to each other by the bumps 32 facing each other to be connected by flip chip. The bump 32 is sealed by the adhesive material 40 to block the external environment. The next material 40 is a cured product of the semiconductor adhesive of this embodiment.

圖2是表示本揭示的半導體裝置的另一實施形態的示意剖面圖。如圖2的（a）所示，半導體裝置300除了藉由配線15及連接凸塊30將兩個半導體晶片10覆晶連接的方面以外，與半導體裝置100相同。如圖2的（b）所示，半導體裝置400除了藉由凸塊32將兩個半導體晶片10覆晶連接的方面以外，與半導體裝置200相同。2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present disclosure. As shown in (a) of FIG. 2, the semiconductor device 300 is the same as the semiconductor device 100 except that the two semiconductor chips 10 are flip-chip connected by the wiring 15 and the connection bump 30. As shown in (b) of FIG. 2, the semiconductor device 400 is the same as the semiconductor device 200 except that the two semiconductor chips 10 are flip-chip connected by bumps 32.

半導體晶片10並無特別限定，可使用由矽、鍺等同一種類的元素所構成的元素半導體；砷化鎵、磷化銦等化合物半導體。The semiconductor wafer 10 is not particularly limited, and elemental semiconductors composed of elements of the same type such as silicon and germanium; compound semiconductors such as gallium arsenide and indium phosphide can be used.

作為基板20，若為電路基板則並無特別限制，可使用：於以玻璃環氧、聚醯亞胺、聚酯、陶瓷、環氧、雙順丁烯二醯亞胺三嗪等作為主要成分的絕緣基板的表面上，將金屬膜的不需要的部位蝕刻去除而形成的具有配線（配線圖案）15的電路基板；於所述絕緣基板的表面藉由金屬鍍敷等而形成有配線15的電路基板；藉由於所述絕緣基板的表面上印刷導電性物質而形成有配線15的電路基板。The substrate 20 is not particularly limited if it is a circuit substrate, and it can be used with glass epoxy, polyimide, polyester, ceramic, epoxy, bismaleimide triazine, etc. as the main component On the surface of the insulating substrate, the unnecessary part of the metal film is etched away to form a circuit substrate with wiring (wiring pattern) 15; on the surface of the insulating substrate, the wiring 15 is formed by metal plating or the like Circuit board; A circuit board with wiring 15 formed by printing a conductive material on the surface of the insulating substrate.

配線15及凸塊32等連接部含有金、銀、銅、焊料（主成分例如為錫-銀、錫-鉛、錫-鉍、錫-銅、錫-銀-銅）、鎳、錫、鉛等作為主成分，亦可含有多種金屬。The connection parts such as the wiring 15 and the bump 32 contain gold, silver, copper, solder (main components such as tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper), nickel, tin, and lead As a main component, multiple metals may be contained.

所述金屬中，就形成連接部的電傳導性-熱傳導性優異的封裝的觀點而言，較佳為金、銀及銅，更佳為銀及銅。就形成降低了成本的封裝的觀點而言，基於廉價而較佳為銀、銅及焊料，更佳為銅及焊料，進而較佳為焊料。若於室溫下於金屬的表面形成氧化膜，則存在生產性降低的情況及成本增加的情況，因此，就抑制氧化膜的形成的觀點而言，較佳為金、銀、銅及焊料，更佳為金、銀、焊料，進而較佳為金、銀。Among the metals, from the viewpoint of forming a package excellent in electrical conductivity and thermal conductivity of the connection portion, gold, silver, and copper are preferred, and silver and copper are more preferred. From the viewpoint of forming a cost-reduced package, silver, copper, and solder are preferred, copper and solder are more preferred, and solder is more preferred based on low cost. If an oxide film is formed on the surface of a metal at room temperature, productivity may decrease and cost may increase. Therefore, from the viewpoint of suppressing the formation of oxide film, gold, silver, copper, and solder are preferable. Gold, silver, and solder are more preferred, and gold and silver are still more preferred.

於所述配線15及凸塊32的表面上，亦可藉由例如鍍敷而形成有以金、銀、銅、焊料（主成分為例如錫-銀、錫-鉛、錫-鉍、錫-銅）、錫、鎳等作為主要成分的金屬層。該金屬層可僅包含單一的成分，亦可包含多種成分。另外，所述金屬層亦可呈單層或多個金屬層積層而成的結構。On the surface of the wiring 15 and the bump 32, gold, silver, copper, solder (the main components are, for example, tin-silver, tin-lead, tin-bismuth, tin- Copper), tin, nickel and other metal layers as main components. The metal layer may contain only a single component or multiple components. In addition, the metal layer may also have a structure formed by a single layer or multiple metal layers.

圖1的（b）中，設置於半導體晶片10的表面的凸塊32亦可具有包括銅柱部與焊料部的多層結構。該情況下，較佳為銅柱部配置於半導體晶片10側，焊料部設置於銅柱部的端部。In (b) of FIG. 1, the bumps 32 provided on the surface of the semiconductor wafer 10 may also have a multilayer structure including a copper pillar portion and a solder portion. In this case, it is preferable that the copper pillar part is arranged on the side of the semiconductor wafer 10, and the solder part is arranged at the end of the copper pillar part.

另外，本實施形態的半導體裝置中，半導體裝置100～半導體裝置400中所示的結構（封裝）亦可積層有多個。該情況下，半導體裝置100～半導體裝置400亦可藉由包含金、銀、銅、焊料（主成分為例如錫-銀、錫-鉛、錫-鉍、錫-銅、錫-銀-銅）、錫、鎳等的凸塊或配線而相互電性連接。In addition, in the semiconductor device of this embodiment, the structure (package) shown in the semiconductor device 100 to the semiconductor device 400 may be stacked in plural. In this case, the semiconductor device 100 to the semiconductor device 400 may also include gold, silver, copper, and solder (the main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper) , Tin, nickel and other bumps or wiring to be electrically connected to each other.

作為將半導體裝置積層多個的方法，如圖3所示，例如可列舉TSV（Through-Silicon Via）技術。圖3是表示本揭示的半導體裝置的另一實施形態的示意剖面圖，且為使用TSV技術的半導體裝置。於圖3所示的半導體裝置500中，形成於中介層（interposer）50上的配線15經由連接凸塊30而與半導體晶片10的配線15連接，藉此將半導體晶片10與中介層50覆晶連接。於半導體晶片10與中介層50之間的空隙中無間隙地填充有接著材料40。於所述半導體晶片10中的與中介層50為相反側的表面上，經由配線15、連接凸塊30及接著材料40而反覆積層有半導體晶片10。半導體晶片10的表背的圖案面的配線15是藉由在貫穿半導體晶片10內部的孔內所填充的貫通電極34而相互連接。再者，作為貫通電極34的材質，可使用銅、鋁等。As a method of stacking a plurality of semiconductor devices, as shown in FIG. 3, for example, TSV (Through-Silicon Via) technology can be cited. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present disclosure, and is a semiconductor device using TSV technology. In the semiconductor device 500 shown in FIG. 3, the wiring 15 formed on the interposer 50 is connected to the wiring 15 of the semiconductor chip 10 through the connection bumps 30, thereby flipping the semiconductor chip 10 and the interposer 50 connection. The gap between the semiconductor chip 10 and the interposer 50 is filled with an adhesive material 40 without any gap. On the surface of the semiconductor wafer 10 on the opposite side to the interposer 50, the semiconductor wafer 10 is repeatedly laminated via the wiring 15, the connection bump 30 and the adhesive material 40. The wirings 15 on the pattern surface of the front and back of the semiconductor wafer 10 are connected to each other by through electrodes 34 filled in holes penetrating the inside of the semiconductor wafer 10. In addition, as the material of the through electrode 34, copper, aluminum, or the like can be used.

藉由此種TSV技術，自通常不會使用的半導體晶片的背面亦可獲取訊號。進而，因於半導體晶片10內垂直地插通貫通電極34，故可縮短相向的半導體晶片10間、或者半導體晶片10及中介層50間的距離而進行柔軟的連接。於此種TSV技術中，本實施形態的半導體用接著劑可適用作相向的半導體晶片10間、或者半導體晶片10及中介層50間的半導體用接著劑。With this TSV technology, signals can also be obtained from the backside of a semiconductor chip that is not normally used. Furthermore, since the through electrode 34 is vertically inserted into the semiconductor wafer 10, the distance between the opposing semiconductor wafers 10 or between the semiconductor wafer 10 and the interposer 50 can be shortened and flexible connection can be made. In this TSV technology, the adhesive for semiconductors of this embodiment can be applied as an adhesive for semiconductors between opposing semiconductor wafers 10 or between the semiconductor wafers 10 and the interposer 50.

另外，於區域凸塊（area bump）晶片技術等自由度高的凸塊形成方法中，可不經由中介層而將半導體晶片直接封裝於母板（mother board）上。本實施形態的半導體用接著劑亦可適用於此種將半導體晶片直接封裝於母板上的情況。再者，於將兩個配線電路基板積層的情況下，將基板間的空隙密封時亦可適用本實施形態的半導體用接著劑。In addition, in a bump formation method with a high degree of freedom such as area bump wafer technology, the semiconductor wafer can be directly packaged on a mother board without an interposer. The adhesive for semiconductors of this embodiment can also be applied to such a case where a semiconductor chip is directly packaged on a mother board. Furthermore, in the case of laminating two wiring circuit boards, the adhesive for semiconductors of this embodiment can also be applied when sealing the gap between the boards.

＜半導體裝置的製造方法＞ 其次，對本實施形態的半導體裝置的製造方法進行說明。＜Method of manufacturing semiconductor device＞ Next, the manufacturing method of the semiconductor device of this embodiment will be described.

首先，在基板或半導體晶片上貼附膜狀接著劑。膜狀接著劑的貼附可藉由加熱壓製、輥層壓、真空層壓等來進行。膜狀接著劑的供給面積及厚度根據半導體晶片或基板的尺寸以及連接凸塊的高度適當設定。膜狀接著劑可貼附於半導體晶片上，亦可在貼附於半導體晶圓上後，藉由切割而單片化為半導體晶片，製作貼附有膜狀接著劑的半導體晶片。First, a film-like adhesive is attached to the substrate or semiconductor wafer. The film adhesive can be applied by heating and pressing, roll lamination, vacuum lamination, or the like. The supply area and thickness of the film adhesive are appropriately set according to the size of the semiconductor wafer or substrate and the height of the connection bumps. The film adhesive can be attached to the semiconductor chip, or after being attached to the semiconductor wafer, it can be singulated into a semiconductor chip by dicing to produce a semiconductor chip attached with the film adhesive.

於將膜狀接著劑貼附於基板或半導體晶片上後，使用覆晶接合機等連接裝置對半導體晶片的連接凸塊（焊料凸塊等）與基板的配線（銅配線等）進行對位。繼而，對半導體晶片與基板一邊以連接凸塊的熔點以上的溫度進行加熱一邊進行壓接，從而將半導體晶片與基板連接，並且藉由膜狀接著劑對半導體晶片與基板間的空隙進行密封填充。藉由以上所述而獲得半導體裝置。After attaching the film-like adhesive to the substrate or semiconductor wafer, use a connecting device such as a flip chip bonder to align the connection bumps (solder bumps, etc.) of the semiconductor wafer and the wiring (copper wiring, etc.) of the substrate. Then, the semiconductor wafer and the substrate are crimped while heating at a temperature above the melting point of the connecting bumps to connect the semiconductor wafer and the substrate, and the gap between the semiconductor wafer and the substrate is sealed and filled with a film-like adhesive . The semiconductor device is obtained as described above.

連接荷重可考慮連接凸塊的數量及高度的偏差、因加壓而產生的連接凸塊或承接連接部的凸塊的配線的變形量來設定。關於連接溫度，連接部的溫度較佳為連接凸塊的熔點以上，但只要為可形成各個連接部（凸塊或配線）的金屬接合的溫度即可。於連接凸塊為焊料凸塊的情況下，連接溫度亦可為約220℃以上。The connection load can be set in consideration of variations in the number and height of the connection bumps, and the amount of deformation of the connection bumps due to pressure or the wiring that receives the bumps of the connection portion. Regarding the connection temperature, the temperature of the connection portion is preferably equal to or higher than the melting point of the connection bump, but it may be a temperature at which the metal bonding of each connection portion (bump or wiring) can be formed. In the case where the connecting bumps are solder bumps, the connecting temperature may also be about 220°C or higher.

連接時的連接時間根據連接部的構成金屬而不同，但就生產性提高的觀點而言，時間越短越佳。於連接凸塊為焊料凸塊的情況下，連接時間較佳為20秒以下，更佳為10秒以下，進而較佳為5秒以下。於使用焊料凸塊以短時間連接進行連接的情況下，連接時間較佳為4秒以下，更佳為3秒以下，進而較佳為2秒以下。藉由以所述方式在短時間內進行連接，可製造更多的高可靠性的封裝。此處，連接時間是指所述連接溫度花費在連接凸塊上的時間。於銅-銅或銅-金的金屬連接的情況下，連接時間較佳為60秒以下。於連接凸塊為焊料凸塊的情況下，較佳為在連接時使焊料熔融，去除氧化膜及表面的雜質，在連接部形成金屬接合。The connection time at the time of connection differs depending on the constituent metal of the connection part, but from the viewpoint of productivity improvement, the shorter the time, the better. In the case where the connection bump is a solder bump, the connection time is preferably 20 seconds or less, more preferably 10 seconds or less, and still more preferably 5 seconds or less. In the case of using solder bumps for connection in a short time, the connection time is preferably 4 seconds or less, more preferably 3 seconds or less, and still more preferably 2 seconds or less. By connecting in a short time in this manner, more highly reliable packages can be manufactured. Here, the connection time refers to the time the connection temperature spends on the connection bump. In the case of copper-copper or copper-gold metal connection, the connection time is preferably 60 seconds or less. When the connection bump is a solder bump, it is preferable to melt the solder during the connection to remove the oxide film and surface impurities, and to form a metal joint at the connection portion.

於本實施形態的半導體裝置的製造方法中，亦可於對位後進行暫時固定（介隔有半導體用接著劑的狀態），並利用回焊爐進行加熱處理，藉此使連接凸塊熔融而將半導體晶片與基板連接。因於暫時固定的階段中並非必須形成金屬接合，故與所述一邊進行加熱一邊進行壓接的方法相比，可進行低荷重、短時間、低溫度下的壓接，生產性提高，並且可抑制連接部的劣化。In the manufacturing method of the semiconductor device of this embodiment, it is also possible to temporarily fix the position (with the adhesive for semiconductor interposed) after the positioning, and heat it in a reflow furnace to melt the connection bumps. Connect the semiconductor wafer to the substrate. Since it is not necessary to form a metal joint during the temporary fixing stage, compared with the method of pressing while heating, it is possible to perform pressing with a low load, a short time, and a low temperature, and the productivity is improved. Suppress the deterioration of the connection part.

另外，亦可於將半導體晶片與基板連接後利用烘箱等進行加熱處理，從而進一步提高連接可靠性-絕緣可靠性。加熱溫度較佳為膜狀接著劑進行硬化的溫度，更佳為完全硬化的溫度。加熱溫度、加熱時間可適當設定。In addition, after the semiconductor wafer and the substrate are connected, heat treatment may be performed in an oven or the like, thereby further improving connection reliability-insulation reliability. The heating temperature is preferably a temperature at which the film-like adhesive is cured, and more preferably a temperature at which the film-like adhesive is completely cured. The heating temperature and heating time can be set appropriately.

本實施形態的半導體裝置的製造方法中，亦可於基板或半導體晶片上供給糊狀的半導體用接著劑來代替膜狀接著劑。半導體用接著劑的供給可藉由旋塗等塗佈方法進行。In the method of manufacturing a semiconductor device of this embodiment, a paste-like semiconductor adhesive may be supplied on the substrate or semiconductor wafer instead of the film-like adhesive. The supply of the adhesive for semiconductors can be performed by a coating method such as spin coating.

以上，對本揭示的適宜的實施形態進行了說明，但本揭示並不限定於所述實施形態。 [實施例]As mentioned above, although the suitable embodiment of this indication was described, this indication is not limited to the said embodiment. [Example]

以下，藉由實施例來更具體地說明本揭示，但本揭示並不限定於實施例。Hereinafter, the present disclosure will be explained in more detail through examples, but the present disclosure is not limited to the examples.

各實施例及比較例中使用的化合物如下所述。 （a）成分：重量平均分子量小於10000的樹脂 （a-1）：含三苯酚甲烷骨架的多官能環氧樹脂（三菱化學股份有限公司製造，商品名「EP1032H60」，重量平均分子量：800～2000） （a-2）：雙酚F型液狀環氧樹脂（三菱化學股份有限公司製造，商品名「YL983U」，重量平均分子量：約340） （a-3）：可撓性半固體狀環氧樹脂（三菱化學股份有限公司製造，商品名「YX7110B60」，重量平均分子量：約1000～5000）The compounds used in the respective examples and comparative examples are as follows. (A) Component: resin with weight average molecular weight less than 10,000 (A-1): Multifunctional epoxy resin containing triphenolmethane skeleton (manufactured by Mitsubishi Chemical Corporation, trade name "EP1032H60", weight average molecular weight: 800-2000) (A-2): Bisphenol F type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "YL983U", weight average molecular weight: about 340) (A-3): Flexible semi-solid epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "YX7110B60", weight average molecular weight: about 1,000 to 5,000)

（b）成分：硬化劑：2,4-二胺基-6-[2'-甲基咪唑-(1')]-乙基-均三嗪異三聚氰酸加成物（四國化成股份有限公司製造，商品名「2MAOK-PW」）(B) Ingredients: Hardener: 2,4-Diamino-6-[2'-methylimidazole-(1')]-ethyl-s-triazine isocyanuric acid adduct (Shikoku Chemical Manufactured by Co., Ltd., trade name "2MAOK-PW")

（c）成分：重量平均分子量為10000以上的高分子化合物：苯氧基樹脂（東都化成股份有限公司製造，商品名「ZX1356」，Tg：約71℃，重量平均分子量：約63000）(C) Component: a polymer compound with a weight average molecular weight of 10,000 or more: phenoxy resin (manufactured by Dongdu Chemical Co., Ltd., trade name "ZX1356", Tg: about 71°C, weight average molecular weight: about 63,000)

（d）成分：助熔劑（羧酸）：戊二酸（熔點：約95℃）(D) Ingredients: flux (carboxylic acid): glutaric acid (melting point: about 95°C)

（e）成分：無機填料 （e-1）二氧化矽填料（亞都瑪科技（Admatechs）股份有限公司製造，商品名「SE2050」，平均粒徑：0.5 μm） （e-2）甲基丙烯酸表面處理奈米二氧化矽填料（亞都瑪科技（Admatechs）股份有限公司製造，商品名「YA050C-SM」，平均粒徑：約50 nm）(E) Ingredient: inorganic filler (E-1) Silica filler (manufactured by Admatechs Co., Ltd., trade name "SE2050", average particle size: 0.5 μm) (E-2) Methacrylic acid surface treatment nano-silica filler (manufactured by Admatechs Co., Ltd., trade name "YA050C-SM", average particle size: about 50 nm)

（f）成分：有機填料 （f-1）：矽酮複合粉末（信越化學工業股份有限公司製造，商品名「KMP-602」，平均粒徑：30 μm，球狀矽酮橡膠粉末的表面經矽酮樹脂被覆的球狀粉末） （f-2）：矽酮複合粉末（信越化學工業股份有限公司製造，商品名「KMP-600」，平均粒徑：5 μm，球狀矽酮橡膠粉末的表面經矽酮樹脂被覆的球狀粉末） （f-3）：矽酮複合粉末（信越化學工業股份有限公司製造，商品名「KMP-605」，平均粒徑：2 μm，球狀矽酮橡膠粉末的表面經矽酮樹脂被覆的球狀粉末） （f-4）：矽酮複合粉末（信越化學工業股份有限公司製造，商品名「X-52-7030」，平均粒徑：0.8 μm，球狀矽酮橡膠粉末的表面經矽酮樹脂被覆的球狀粉末） （f-5）：核殼型有機微粒子（日本羅門哈斯（Rohm and Haas Japan）股份有限公司製造，商品名「EXL-2655」，核部分：丁二烯/苯乙烯共聚聚合物，殼部分：PMMA/苯乙烯共聚聚合物）(F) Ingredient: organic filler (F-1): Silicone composite powder (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KMP-602", average particle size: 30 μm, spherical silicone rubber powder surface coated with silicone resin powder) (F-2): Silicone composite powder (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KMP-600", average particle size: 5 μm, spherical silicone rubber powder surface coated with silicone resin powder) (F-3): Silicone composite powder (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KMP-605", average particle size: 2 μm, spherical silicone rubber powder surface coated with silicone resin powder) (F-4): Silicone composite powder (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-52-7030", average particle size: 0.8 μm, surface of spherical silicone rubber powder coated with silicone resin Spherical powder) (F-5): Core-shell organic particles (manufactured by Rohm and Haas Japan Co., Ltd., trade name "EXL-2655", core part: butadiene/styrene copolymer, shell part) : PMMA/styrene copolymer)

（實施例1～實施例4及比較例1～比較例2） ＜膜狀接著劑的製作＞ 將表1所示的調配量（單位：質量份）的（a）成分、（b）成分、（c）成分、（d）成分、（e）成分及（f）成分以NV值（[乾燥後的塗料成分質量]/[乾燥前的塗料成分質量]×100）成為60質量%的方式添加於有機溶媒（甲基乙基酮）中。其後，添加與所述（a）成分～（f）成分及有機溶媒的總調配量相同質量的ϕ1.0 mm的二氧化鋯珠粒，利用球磨機（日本弗里茨（Fritsch Japan）股份有限公司製造，行星式微粉碎機P-7）攪拌30分鐘。於攪拌後藉由過濾而去除二氧化鋯珠粒，從而製作塗敷清漆。(Example 1 to Example 4 and Comparative Example 1 to Comparative Example 2) ＜Production of film adhesive＞ The (a) component, (b) component, (c) component, (d) component, (e) component, and (f) component of the blending amount shown in Table 1 (unit: parts by mass) are set to NV value ([dry After coating component mass]/[coating component mass before drying]×100), it is added to an organic solvent (methyl ethyl ketone) so that it becomes 60% by mass. After that, ϕ1.0 mm zirconia beads of the same mass as the total blending amount of the components (a) to (f) and the organic solvent were added, using a ball mill (Fritsch Japan Co., Ltd.) Made by the company, planetary micro pulverizer P-7) stirring for 30 minutes. After stirring, the zirconium dioxide beads are removed by filtration to produce a varnish.

利用台式塗佈機（平野金屬（HIRANO KINZOKU）公司製造）塗敷所得的塗敷清漆，於80℃下乾燥5分鐘，藉此獲得膜厚20 μm的膜狀接著劑。The obtained varnish was applied using a bench coater (manufactured by Hirano Kinzoku) and dried at 80°C for 5 minutes to obtain a film-like adhesive with a film thickness of 20 μm.

利用以下所示的評價方法評價實施例及比較例中所得的膜狀接著劑的接著力及可靠性、以及使用其製作的半導體裝置的翹曲。評價結果如表1所示。The following evaluation methods were used to evaluate the adhesive strength and reliability of the film-like adhesives obtained in the examples and comparative examples, and the warpage of the semiconductor device produced using the same. The evaluation results are shown in Table 1.

＜接著力的測定＞ 將膜狀接著劑剪切成既定的尺寸(縱3.2 mm×橫3.2 mm×厚度0.02 mm)，於70℃下貼附至矽晶片(縱3 mm×橫3 mm×厚度0.725 mm)上，使用熱壓接試驗機(日立化成電子工廠股份有限公司製造)，壓接(壓接條件：於壓接頭溫度190℃下壓接5秒後，於壓接頭溫度240℃下壓接5秒，荷重0.5 MPa)至另一矽晶片(縱5 mm×橫5 mm×厚度0.725 mm)。其後，於潔淨烘箱(愛斯佩克(ESPEC)公司製造)中，進行硬化(175℃，2小時)，從而獲得試驗樣品。<Measurement of Adhesion> Cut the film-like adhesive into a predetermined size (length 3.2 mm × width 3.2 mm × thickness 0.02 mm) and attach it to a silicon wafer (length 3 mm × width 3 mm × thickness 0.725 mm) at 70°C, and use Thermal compression testing machine (manufactured by Hitachi Chemical Electronics Co., Ltd.), crimping (crimping conditions: crimping at a crimping joint temperature of 190°C for 5 seconds, then at a crimping joint temperature of 240°C for 5 seconds, and a load of 0.5 MPa) to another silicon wafer (length 5 mm × width 5 mm × thickness 0.725 mm). After that, it was cured (175°C, 2 hours) in a clean oven (manufactured by ESPEC) to obtain a test sample.

將所述試驗樣品於85℃、相對濕度85%的恆溫恆濕槽(愛斯佩克(ESPEC)公司製造)內放置24小時，並在取出後，於250℃的加熱板上使用接著力測定裝置(達歌(DAGE)公司製造)，於距下側的矽晶片的上表面的工具高度0.05 mm、工具速度0.05 mm/s的條件下測定接著力(吸濕後的250℃下的接著力)。The test sample was placed in a constant temperature and humidity bath (manufactured by ESPEC) at 85°C and 85% relative humidity for 24 hours, and after taking it out, the adhesive force was measured on a hot plate at 250°C The device (manufactured by DAGE) measures the adhesive force (adhesive force at 250°C after moisture absorption at a tool height of 0.05 mm from the upper surface of the silicon wafer on the lower side and a tool speed of 0.05 mm/s) ).

＜耐回焊性的評價＞ 將膜狀接著劑剪切成既定的尺寸（縱7.3 mm×橫7.3 mm×厚度0.04 mm），貼附至帶焊料凸塊的半導體晶片（晶片尺寸：縱7.3 mm×橫7.3 mm×厚度0.15 mm，連接部的金屬：銅柱+焊料、凸塊高度（銅柱+焊料的合計高度）：約45 μm）的凸塊側的面上，利用覆晶安裝裝置「FCB3」安裝（安裝條件：於以100℃/0.5 MPa/1 s暫時壓接後，升溫至180℃/0.5 MPa/2 s，其後於260℃/0.5 MPa/5 s的條件下進行正式壓接）在玻璃環氧基板（玻璃環氧基材的厚度：0.42 mm、銅配線的厚度：9 μm）上，獲得半導體裝置。膜狀接著劑藉由積層兩片膜厚20 μm者而使膜厚為40 μm。壓接時放置基板的載物台溫度為80℃。使用密封材料（日立化成股份有限公司製造，商品名「CEL9750ZHF10」），於180℃、6.75 MPa、90秒的條件下成型所述半導體裝置，於潔淨烘箱（愛斯佩克（ESPEC）公司製造）中，進行硬化（175℃，2小時），從而獲得試驗樣品。＜Evaluation of reflow resistance＞ Cut the film-like adhesive into a predetermined size (length 7.3 mm × width 7.3 mm × thickness 0.04 mm), and attach it to a semiconductor wafer with solder bumps (wafer size: length 7.3 mm × width 7.3 mm × thickness 0.15 mm , The metal of the connection part: copper pillar + solder, bump height (total height of copper pillar + solder: about 45 μm) on the bump side surface, use the flip chip mounting device "FCB3" to install (mounting conditions: in After temporarily crimping at 100°C/0.5 MPa/1 s, the temperature is increased to 180°C/0.5 MPa/2 s, and then the formal crimping is carried out at 260°C/0.5 MPa/5 s.) The thickness of the glass epoxy substrate: 0.42 mm and the thickness of the copper wiring: 9 μm) were used to obtain a semiconductor device. The film-like adhesive layered two sheets with a thickness of 20 μm to make the film thickness 40 μm. The temperature of the stage where the substrate is placed during crimping is 80°C. Using a sealing material (manufactured by Hitachi Chemical Co., Ltd., trade name "CEL9750ZHF10"), the semiconductor device was molded at 180°C, 6.75 MPa, and 90 seconds, in a clean oven (manufactured by ESPEC) In, curing (175°C, 2 hours) was performed to obtain a test sample.

其次，於電子裝置工程聯合委員會（Joint Electron Device Engineering Council，JEDEC）水準2的條件下處理所述試驗樣品後，使其通過3次（最高到達溫度260℃）回焊爐（田村製作所股份有限公司製造）。使用萬用錶（科斯特（CUSTOM）公司製造）測定回焊前後的封裝的連接電阻值。將回焊前後的連接電阻值的變化量為5 Ω以下的情況作為評價「A」，將變化量超過5 Ω或者連接不良的情況作為評價「B」。Secondly, after processing the test sample under the conditions of the Joint Electron Device Engineering Council (JEDEC) level 2 and then passing it through the reflow furnace (Tamura Manufacturing Co., Ltd. manufacture). A multimeter (manufactured by CUSTOM) was used to measure the connection resistance of the package before and after reflow. The case where the change in the connection resistance value before and after reflow is 5 Ω or less is regarded as evaluation "A", and the case where the change exceeds 5 Ω or the connection is poor is regarded as evaluation "B".

＜翹曲評價＞ 利用與耐回焊性的評價相同的方法製作半導體裝置，並將其作為試驗樣品。對於所述試驗樣品，使用非接觸式形狀測定裝置（索尼（SONY）公司製造），測量從上方觀察晶片時的對角方向的兩邊的形狀。將各邊的凹凸的最大值與最小值的差作為翹曲量（μm），利用兩邊的平均值評價翹曲量。將該翹曲量為70 μm以下的情況作為評價「A」，將超過70 μm的情況作為評價「B」。＜Warpage evaluation＞ A semiconductor device was fabricated by the same method as the evaluation of reflow resistance, and this was used as a test sample. For the test sample, a non-contact shape measuring device (manufactured by SONY) was used to measure the shapes of both sides in the diagonal direction when the wafer was viewed from above. The difference between the maximum value and the minimum value of the unevenness of each side was taken as the amount of warpage (μm), and the amount of warpage was evaluated using the average value of both sides. The case where the amount of warpage is 70 μm or less is regarded as evaluation "A", and the case where the warpage exceeds 70 μm is regarded as evaluation "B".

[表1]   實施例 比較例 1 2 3 4 1 2 （a）成分 （a-1） 45 45 45 45 45 45 （a-2） 15 15 15 15 15 15 （a-3） 5 5 5 5 5 5 （b）成分 2 2 2 2 2 2 （c）成分 30 30 30 30 30 30 （d）成分 4 4 4 4 4 4 （e）成分 （e-1） 30 30 30 30 30 - （e-2） 45 45 45 45 45 - （f）成分 （f-1） 10 - - - - - （f-2） - 10 - - - - （f-3） - - 10 - - - （f-4） - - - 10 - - （f-5） - - - - 10 85 接著力（MPa） 10 10 10 9 10 3 耐回焊性 A A A A A B 翹曲 A A A A B A [Table 1] Example Comparative example 1 2 3 4 1 2 (A) Ingredients (A-1) 45 45 45 45 45 45 (A-2) 15 15 15 15 15 15 (A-3) 5 5 5 5 5 5 (B) Ingredients 2 2 2 2 2 2 (C) Ingredients 30 30 30 30 30 30 (D) Ingredients 4 4 4 4 4 4 (E) Ingredients (E-1) 30 30 30 30 30 - (E-2) 45 45 45 45 45 - (F) Ingredients (F-1) 10 - - - - - (F-2) - 10 - - - - (F-3) - - 10 - - - (F-4) - - - 10 - - (F-5) - - - - 10 85 Adhesive force (MPa) 10 10 10 9 10 3 Reflow resistance A A A A A B Warpage A A A A B A

根據表1所示的結果明確般，確認到含有無機填料及矽酮橡膠填料的實施例1～實施例4的半導體用接著劑與比較例1～比較例2的半導體用接著劑相比，接著力及耐回焊性優異，且可實現低翹曲化。From the results shown in Table 1, it was confirmed that the adhesives for semiconductors of Examples 1 to 4 containing inorganic fillers and silicone rubber fillers were compared with the adhesives for semiconductors of Comparative Examples 1 to 2. Excellent strength and reflow resistance, and can achieve low warpage.

10:半導體晶片 15:配線（連接部） 20:基板（配線電路基板） 30:連接凸塊 32:凸塊（連接部） 34:貫通電極 40:接著材料 50:中介層 100、200、300、400、500:半導體裝置10: Semiconductor wafer 15: Wiring (connection part) 20: Board (wiring circuit board) 30: Connection bump 32: Bump (connection part) 34: Through electrode 40: Adhesive materials 50: Intermediary layer 100, 200, 300, 400, 500: semiconductor device

圖1是表示本揭示的半導體裝置的一實施形態的示意剖面圖。 圖2是表示本揭示的半導體裝置的另一實施形態的示意剖面圖。 圖3是表示本揭示的半導體裝置的另一實施形態的示意剖面圖。FIG. 1 is a schematic cross-sectional view showing an embodiment of the semiconductor device of the present disclosure. 2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present disclosure. Fig. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present disclosure.

10:半導體晶片 10: Semiconductor wafer

15:配線(連接部) 15: Wiring (connection part)

20:基板(配線電路基板) 20: Board (wiring circuit board)

30:連接凸塊 30: Connection bump

32:凸塊(連接部) 32: bump (connection part)

40:接著材料 40: Adhesive materials

100、200:半導體裝置 100, 200: semiconductor device

Claims (10)

一種半導體用接著劑，含有重量平均分子量小於10000的樹脂、硬化劑、無機填料及矽酮橡膠填料。An adhesive for semiconductors, containing a resin with a weight average molecular weight of less than 10,000, a hardener, an inorganic filler, and a silicone rubber filler. 如請求項1所述的半導體用接著劑，其中所述矽酮橡膠填料的平均粒徑為30 μm以下。The adhesive for semiconductors according to claim 1, wherein the average particle diameter of the silicone rubber filler is 30 μm or less. 如請求項1或2所述的半導體用接著劑，其中所述無機填料含有二氧化矽填料。The adhesive for semiconductors according to claim 1 or 2, wherein the inorganic filler contains silica filler. 如請求項1至3中任一項所述的半導體用接著劑，進一步含有重量平均分子量為10000以上的高分子成分。The adhesive for semiconductors according to any one of claims 1 to 3, further containing a polymer component having a weight average molecular weight of 10,000 or more. 如請求項4所述的半導體用接著劑，其中所述高分子成分的重量平均分子量為30000以上，所述高分子成分的玻璃轉移溫度為100℃以下。The adhesive for semiconductors according to claim 4, wherein the weight average molecular weight of the polymer component is 30,000 or more, and the glass transition temperature of the polymer component is 100°C or less. 如請求項1至5中任一項所述的半導體用接著劑，為膜狀。The adhesive for semiconductors according to any one of claims 1 to 5 is in the form of a film. 如請求項1至6中任一項所述的半導體用接著劑，其中以半導體用接著劑的固體成分總量為基準，所述矽酮橡膠填料的含量為0.1質量%～20質量%。The adhesive for semiconductors according to any one of claims 1 to 6, wherein the content of the silicone rubber filler is 0.1% by mass to 20% by mass based on the total solid content of the adhesive for semiconductors. 如請求項1至7中任一項所述的半導體用接著劑，其中所述矽酮橡膠填料的含量相對於所述無機填料的含量的質量比為0.05～0.5。The adhesive for semiconductors according to any one of claims 1 to 7, wherein the mass ratio of the content of the silicone rubber filler to the content of the inorganic filler is 0.05 to 0.5. 一種半導體裝置的製造方法，為製造半導體晶片及配線電路基板各自的連接部相互電性連接的半導體裝置、或者多個半導體晶片各自的連接部相互電性連接的半導體裝置的方法， 所述半導體裝置的製造方法包括：使用如請求項1至8中任一項所述的半導體用接著劑對所述連接部的至少一部分進行密封的步驟。A method of manufacturing a semiconductor device is a method of manufacturing a semiconductor device in which the respective connection portions of a semiconductor wafer and a wiring circuit board are electrically connected to each other, or a semiconductor device in which the respective connection portions of a plurality of semiconductor wafers are electrically connected to each other, The manufacturing method of the semiconductor device includes a step of sealing at least a part of the connection portion using the adhesive for semiconductor according to any one of claims 1 to 8. 一種半導體裝置，包括：由半導體晶片及配線電路基板各自的連接部相互電性連接而成的連接結構、或者由多個半導體晶片各自的連接部相互電性連接而成的連接結構；以及 將所述連接部的至少一部分密封的接著材料， 所述接著材料包含如請求項1至8中任一項所述的半導體用接著劑的硬化物。A semiconductor device, comprising: a connection structure formed by electrically connecting the respective connecting portions of a semiconductor wafer and a wiring circuit board to each other, or a connecting structure formed by electrically connecting the respective connecting portions of a plurality of semiconductor wafers with each other; and An adhesive material that seals at least a part of the connecting portion, The adhesive material includes a cured product of the adhesive for semiconductors according to any one of claims 1 to 8.
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