TWI411049B - An adhesive for an electronic component, a lamination method for a semiconductor wafer, and a semiconductor device - Google Patents

An adhesive for an electronic component, a lamination method for a semiconductor wafer, and a semiconductor device Download PDF

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TWI411049B
TWI411049B TW097128044A TW97128044A TWI411049B TW I411049 B TWI411049 B TW I411049B TW 097128044 A TW097128044 A TW 097128044A TW 97128044 A TW97128044 A TW 97128044A TW I411049 B TWI411049 B TW I411049B
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adhesive
electronic component
semiconductor wafer
electronic
component
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TW097128044A
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Chinese (zh)
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TW200908166A (en
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Hideaki Ishizawa
Akinobu Hayakawa
Kohei Takeda
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Sekisui Chemical Co Ltd
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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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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    • 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
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Abstract

This invention provides an adhesive for an electronic component which can realize the connection of one electronic component to another electronic component or a support member parallel to each other while providing an accurate gap distance, semiconductor chip stacking method using the adhesive for an electronic component and a semiconductor device. The adhesive for an electronic component is used for stacking one electronic component and another electronic component or a support member parallel to each other while providing a gap distance of not more than 30 µm. The adhesive for an electronic component contains a curable compound, a curing agent, and spacer particles, and has a viscosity of not more than 50 Pa s as measured with E-type viscometer at 10 rpm and at a temperature at which the one electronic component is bonded to the another electronic component or the support member. The spacer particles have a CV value of not more than 10%. The average particle diameter is 40 to 70% of the gap distance between the one electronic component and the another electronic component or the support member.

Description

電子零件用接著劑、半導體晶片之積層方法以及半導體裝置Adhesive for electronic parts, laminated method of semiconductor wafer, and semiconductor device

本發明係關於一種能以平行且正確之間隙間距離將一電子零件與其他電子零件、或一電子零件與支持構件加以接合的電子零件用接著劑。又，亦關於一種使用該電子零件用接著劑之半導體晶片之積層方法、及半導體裝置。BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to an adhesive for electronic parts capable of joining an electronic component to another electronic component or an electronic component and a supporting member at parallel and correct inter-gap distances. Further, the present invention relates to a method of laminating a semiconductor wafer using the adhesive for electronic parts, and a semiconductor device.

近年來，伴隨對半導體封裝之小型化、高度積體化之要求，已逐漸往將複數個半導體晶片加以積層以製成多層半導體晶片積層體之3次元構裝的方向發展。又，亦正進行使該半導體晶片積層體進一步小型化之研究。In recent years, with the demand for miniaturization and high integration of semiconductor packages, a plurality of semiconductor wafers have been gradually laminated to form a three-dimensional structure of a multilayer semiconductor wafer laminate. Further, research is being conducted to further reduce the size of the semiconductor wafer laminate.

隨此，半導體晶片已變成極薄之薄膜，並且於半導體晶片上形成微細之配線。在此種3次元構裝之半導體晶片積層體，係要求在不損傷各半導體晶片下，且能保持平行來進行積層。Accordingly, the semiconductor wafer has become an extremely thin film, and fine wiring is formed on the semiconductor wafer. In such a three-dimensional structure, a semiconductor wafer laminate is required to be laminated without damaging each semiconductor wafer and in parallel.

保持半導體晶片彼此平行並予以積層接合之方法，已知有一種例如使用含有微粒之接著劑，並將接著劑塗布於一半導體晶片上，以形成具有微粒之粒徑以上之厚度的接著劑層，透過所形成之接著劑層疊合其他半導體晶片，然後對接著劑層加壓，以將接著劑壓入直至接著劑層之厚度等於微粒之粒徑為止的方法。A method of maintaining a semiconductor wafer parallel to each other and laminating them, for example, using an adhesive containing fine particles, and applying an adhesive to a semiconductor wafer to form an adhesive layer having a thickness larger than a particle diameter of the fine particles, The other semiconductor wafer is laminated through the formed adhesive, and then the adhesive layer is pressed to press the adhesive until the thickness of the adhesive layer is equal to the particle diameter of the fine particles.

含有該種微粒之接著劑，例如於專利文獻1記載有一種以硬質塑膠微粒為必要成分的接著劑，其中該硬質塑膠微粒具有實質上界定接著劑硬化後之膜厚之粒徑。實施例 中記載有使用摻合有平均粒徑為20 μm之硬質塑膠微粒的接著劑，以與平均粒徑同等厚度之接著劑層，將矽元件接著於導線架上。For example, Patent Document 1 discloses an adhesive containing a fine plastic fine particle as an essential component, wherein the hard plastic fine particle has a particle diameter substantially defining a film thickness after hardening of the adhesive. Example An adhesive using a hard plastic fine particle having an average particle diameter of 20 μm is used to bond the tantalum element to the lead frame with an adhesive layer having the same thickness as the average particle diameter.

又，專利文獻2亦記載有若使用摻合有平均粒徑為10~500 μm且長寬比在1.1以下之樹脂微粒的接著劑時，則樹脂微粒具有間隙調整材之功能。Further, Patent Document 2 also discloses that when an adhesive containing fine resin particles having an average particle diameter of 10 to 500 μm and an aspect ratio of 1.1 or less is used, the resin fine particles have a function as a gap adjusting member.

然而，因近年來對半導體封裝之小型化、高度積體化之要求，半導體晶片之間隙間日益變得狹窄，於摻合如專利文獻1所記載之與硬化後之膜厚大致相等之粒徑的粒子時，直至粒子本身可發揮間隙材功能之厚度前無法壓入接著劑，導致有時不能達成所欲之間隙間距離。又，有時亦無法將所要接合半導體晶片彼此正確地保持平行。However, in recent years, there has been a demand for miniaturization and high integration of semiconductor packages, and the gap between semiconductor wafers has become increasingly narrow, and the particle diameters which are substantially equal to the film thickness after hardening as described in Patent Document 1 are blended. In the case of the particles, the adhesive cannot be pressed until the particles themselves can exhibit the thickness of the function of the gap material, and the desired gap between the gaps may not be achieved. Moreover, it is sometimes impossible to accurately keep the semiconductor wafers to be bonded in parallel with each other.

專利文獻1：日本特開平11－189765號公報專利文獻2：日本特開2005－244188號公報Patent Document 1: Japanese Laid-Open Patent Publication No. H11-189765 (Patent Document 2)

本發明之目的在於提供一種能以平行且正確之間隙間距離，將一電子零件與其他電子零件、或一電子零件與支持構件加以接合之電子零件用接著劑。又，本發明之目的亦在於提供一種使用該電子零件用接著劑之半導體晶片之積層方法、及半導體裝置。SUMMARY OF THE INVENTION It is an object of the present invention to provide an adhesive for an electronic component that can bond an electronic component to another electronic component or an electronic component and a support member with parallel and correct inter-gap distances. Moreover, an object of the present invention is to provide a method of laminating a semiconductor wafer using the adhesive for electronic parts and a semiconductor device.

本發明係一種電子零件用接著劑，用以將一電子零件與其他電子零件、或一電子零件與支持構件，以30 μm以下之間隙間距離加以平行積層，係含有硬化性化合物、硬化劑及間隔粒子；在接合該一電子零件與其他電子零件、 或一電子零件與支持構件時之溫度下，使用E型黏度計以10rpm所測得的黏度為50Pa．s以下；該間隔粒子，其CV值為10%以下，且為該一電子零件與其他電子零件、或該一電子零件與支持構件之間隙間距離的40~70%。The invention relates to an adhesive for electronic parts, which is used for laminating an electronic component and other electronic components, or an electronic component and a supporting member in parallel with a gap of 30 μm or less, and contains a hardening compound and a hardener. Spacer particles; in joining the electronic component with other electronic components, Or at an electronic component and supporting member temperature, the viscosity measured at 10 rpm using an E-type viscometer is 50 Pa. s or less; the spacer particle has a CV value of 10% or less and is 40 to 70% of the distance between the electronic component and the other electronic component or the gap between the electronic component and the supporting member.

本發明人等發現一種含有用以接合一電子零件與其他電子零件、或一電子零件與支持構件之間隔粒子的接著劑，其具有既定黏度特性，所含之間隔粒子具有均勻之大小，且相對於該一電子零件與其他電子零件、或該一電子零件與支持構件之間隙間距離，其平均粒徑係在既定範圍內，可充分對應近年來半導體封裝之小型化、高度積體化所伴隨之窄間隔化，並能將一電子零件與其他電子零件、或一電子零件與支持構件以平行且正確之間隙間距離加以接合，從而完成本發明。The present inventors have found an adhesive containing spacer particles for bonding an electronic component and other electronic components, or an electronic component and a supporting member, which has a predetermined viscosity characteristic, and the spacer particles contained therein have a uniform size and are relatively The distance between the electronic component and the other electronic component or the gap between the electronic component and the supporting member is within a predetermined range, and can be sufficiently matched with the miniaturization and high integration of the semiconductor package in recent years. The invention is completed by narrowly spacing and joining an electronic component with other electronic components, or an electronic component and a support member in parallel and with a correct gap between the gaps.

此外，間隙間距離係意指將一電子零件與其他電子零件、或一電子零件與支持構件加以接著時，一電子零件與其他電子零件、或一電子零件與支持構件之距離。In addition, the inter-gap distance means the distance between an electronic component and other electronic components, or an electronic component and a supporting member, when an electronic component and other electronic components, or an electronic component and a supporting member are attached.

本發明之電子零件用接著劑，係將一電子零件與其他電子零件、或一電子零件與支持構件，以30 μm以下之間隙間距離加以平行積層的電子零件用接著劑。The adhesive for an electronic component according to the present invention is an adhesive for an electronic component in which an electronic component and another electronic component, or an electronic component and a supporting member are laminated in parallel at a gap of 30 μm or less.

該電子零件並無特別限制，可列舉例如半導體晶片、感測器、及EI型或EE型變壓器零件之線圈鐵心等。其中，適合使用半導體晶片。The electronic component is not particularly limited, and examples thereof include a semiconductor wafer, a sensor, and a coil core of an EI type or EE type transformer component. Among them, a semiconductor wafer is suitably used.

又，該支持構件只要是可支持該半導體晶片等電子零件之構件，則無特別限制，可列舉例如導線架、樹脂基板、 及陶瓷基板等以往公知之構件。In addition, the support member is not particularly limited as long as it can support an electronic component such as a semiconductor wafer, and examples thereof include a lead frame and a resin substrate. A conventionally known member such as a ceramic substrate.

本發明之電子零件用接著劑所要接合之該一電子零件與其他電子零件、或該一電子零件與支持構件之間隙間距離的上限為30 μm。在間隙間距離之下限為5 μm，上限為15 μm時特別有用。若以此種間隙間距離來接合該一電子零件與其他電子零件、或該一電子零件與支持構件時，即可充分對應近年來半導體封裝之小型化、高度積體化。The upper limit of the distance between the electronic component to be bonded to the other electronic component or the electronic component and the supporting member to be bonded by the adhesive for electronic parts of the present invention is 30 μm. It is particularly useful when the lower limit of the gap is 5 μm and the upper limit is 15 μm. When the electronic component and other electronic components, or the electronic component and the supporting member are joined by such a gap distance, the semiconductor package can be sufficiently miniaturized and highly integrated in recent years.

此處，接著劑硬化後之膜厚為間隔粒子之粒徑左右的習知接著劑，在以上述窄間隔進行電子零件彼此等之接合時，係難以將電子零件彼此等保持成平行，且難以正確控制該等間隙間距離。相對於此，本發明之電子零件用接著劑，係將電子零件彼此等接合溫度之黏度設於既定範圍內，並配合所欲之電子零件彼此等之間隙間距離，適當選擇所含之間隔粒子之粒徑，以使其在既定範圍內。此種本發明之電子零件用接著劑，即使在以上述窄間隔來接合電子零件彼此等時，亦可將所要接合之電子零件彼此等保持成平行，並正確控制該等間隙間距離。In the case where the thickness of the film after the adhesive is hardened is a conventional adhesive agent having a particle diameter of the spacer particles, when the electronic components are joined to each other at the narrow intervals, it is difficult to keep the electronic components in parallel with each other. Correctly control the distance between these gaps. On the other hand, in the adhesive for electronic parts of the present invention, the viscosity of the electronic components and the like are set within a predetermined range, and the distance between the gaps of the desired electronic components and the like is appropriately selected, and the spacer particles are appropriately selected. The particle size is such that it is within a predetermined range. In the adhesive for electronic parts of the present invention, even when the electronic components are joined to each other at the narrow intervals described above, the electronic components to be joined can be held in parallel with each other, and the distance between the gaps can be accurately controlled.

本發明之電子零件用接著劑係含有間隔粒子。The adhesive for electronic parts of the present invention contains spacer particles.

該間隔粒子之CV值之上限為10%。若CV值超過10%時，間隔粒徑之偏差會變大，在接合一電子零件與其他電子零件、或一電子零件與支持構件時，無法以平行且正確之間隙間距離將此等加以接合，而不能充分發揮作為間隔粒子之功能。CV值之較佳上限為6%，更佳上限為4%。The upper limit of the CV value of the spacer particles is 10%. When the CV value exceeds 10%, the variation in the spacer grain size becomes large, and when an electronic component and other electronic components, or an electronic component and a supporting member are joined, the parallel and correct gap distances cannot be joined. , but can not fully play the role of spacer particles. The upper limit of the CV value is 6%, and the upper limit is 4%.

此外，本說明書中，CV值係指以下述式(1)所求出之 數值。In addition, in the present specification, the CV value is obtained by the following formula (1). Value.

間隔粒徑之CV值(%)＝(σ 2/Dn2)×100 (1)CV value (%) of the spacer particle diameter = (σ 2/Dn2) × 100 (1)

式(1)中，σ 2係表示粒徑之標準差，Dn2則表示數量平均粒徑。In the formula (1), σ 2 represents the standard deviation of the particle diameter, and Dn2 represents the number average particle diameter.

該間隔粒子之平均粒徑之下限以1 μm，上限以20 μm較佳。The lower limit of the average particle diameter of the spacer particles is 1 μm, and the upper limit is preferably 20 μm.

若該間隔粒子之平均粒徑未達1 μm時，則所要接合之電子零件彼此等之間隙會過窄，而無法以平行且正確之間隙間距離將此等加以接合。若該間隔粒子之平均粒徑超過20 μm時，則電子零件彼此等之間隔會大於所須，而無法充分對應近年來半導體封裝之小型化、高度積體化。該間隔粒子之平均粒徑之更佳下限為3 μm，較佳上限為10 μm。When the average particle diameter of the spacer particles is less than 1 μm, the gap between the electronic components to be joined and the like may be too narrow, and the parallel and correct inter-gap distances may not be joined. When the average particle diameter of the spacer particles exceeds 20 μm, the interval between the electronic components and the like is larger than necessary, and it is not possible to sufficiently cope with the miniaturization and high integration of the semiconductor package in recent years. A lower limit of the average particle diameter of the spacer particles is 3 μm, and a preferred upper limit is 10 μm.

又，該間隔粒子之平均粒徑，相對於上述一電子零件與其他電子零件、或上述一電子零件與支持構件之間隙間距離，其下限為40%，上限為70%。若該間隔粒子之平均粒徑未達40%時，則間隔粒子相對於所欲之電子零件間等之間隙間距離會過小，而難以將所要接合之電子零件間等保持在平行且正確之間隙間距離。若該間隔粒子之平均粒徑超過70%時，則間隔粒子相對於所欲之電子零件間等之間隙間距離會過大，而無法充分排除所要接合之電子零件或支持構件與間隔粒子之間的接著劑，其結果則會變成大 於所欲之間隙間距離。該間隔粒子之平均粒徑的較佳下限為45%，較佳上限為60%。Further, the average particle diameter of the spacer particles is 40% and the upper limit is 70% with respect to the distance between the one electronic component and the other electronic component or the gap between the one electronic component and the supporting member. If the average particle diameter of the spacer particles is less than 40%, the distance between the gap particles and the gap between the desired electronic components and the like may be too small, and it is difficult to keep the electronic components to be joined between parallel and correct. Interstitial distance. When the average particle diameter of the spacer particles exceeds 70%, the distance between the spacer particles and the gap between the desired electronic components and the like may be excessively large, and the electronic component to be bonded or the support member and the spacer particles may not be sufficiently excluded. With the agent, the result will become large The distance between the desired gaps. A preferred lower limit of the average particle diameter of the spacer particles is 45%, and a preferred upper limit is 60%.

該間隔粒子之平均粒徑，較佳在所添加之固體成分(不包括該間隔粒子)之平均粒徑的1.1倍以上。若該間隔粒子之平均粒徑未達1.1倍時，則有時會難以將電子零件彼此等之間隔設為上述窄間隔。更佳為使該間隔粒子之平均粒徑在1.2倍以上。The average particle diameter of the spacer particles is preferably 1.1 times or more the average particle diameter of the solid component to be added (excluding the spacer particles). When the average particle diameter of the spacer particles is less than 1.1 times, it may be difficult to set the interval between the electronic components and the like to be the above-described narrow interval. More preferably, the average particle diameter of the spacer particles is 1.2 times or more.

該間隔粒子，其粒徑分布之標準差較佳為在間隔粒子之平均粒徑的10%以下。藉由使粒徑分布之標準差在10%以下，當進行電子零件彼此等之接合時，可更穩定地將其平行接合。The standard deviation of the particle size distribution of the spacer particles is preferably 10% or less of the average particle diameter of the spacer particles. By setting the standard deviation of the particle diameter distribution to 10% or less, when the electronic parts are joined to each other or the like, they can be joined in parallel more stably.

該間隔粒子之材質並無特別限制，可使用有機粒子、無機粒子、有機無機混合粒子之任一種。其中，有機粒子或有機無機混合粒子較合適。The material of the spacer particles is not particularly limited, and any of organic particles, inorganic particles, and organic-inorganic hybrid particles can be used. Among them, organic particles or organic-inorganic hybrid particles are suitable.

該有機粒子並無特別限制，例如可舉樹脂粒子。The organic particles are not particularly limited, and examples thereof include resin particles.

構成該樹脂粒子之樹脂並無特別限制，例如可列舉聚乙烯、聚丙烯、聚甲基戊烯、聚氯乙烯、聚四氟乙烯、聚苯乙烯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醯胺、聚醯亞胺、聚碸、聚苯醚、及聚縮醛等。其中，由於易於調整間隔粒子之硬度及恢復率，且亦可提升耐熱性，因此以使用交聯樹脂較佳。The resin constituting the resin particles is not particularly limited, and examples thereof include polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polymethyl methacrylate, and polyparaphenylene. Ethylene formate, polybutylene terephthalate, polydecylamine, polyimine, polyfluorene, polyphenylene ether, polyacetal, and the like. Among them, it is preferable to use a crosslinked resin because it is easy to adjust the hardness and recovery rate of the spacer particles and also to improve heat resistance.

該交聯樹脂並無特別限制，例如可列舉環氧樹脂、酚醛樹脂、三聚氰胺樹脂、不飽和聚酯樹酯、二乙烯苯聚合物、二乙烯苯－苯乙烯共聚物、二乙烯苯－丙烯酸酯共聚物、 鄰苯二甲酸二烯丙酯聚合物、三聚異氰酸三烯丙酯聚合物、及苯代三聚氰胺聚合物等具有網目構造之樹酯。其中，由於在接合晶片後，對硬化步驟、焊料回焊步驟等熱處理步驟之耐性優異，因此以二乙烯苯聚合物、二乙烯苯－苯乙烯共聚物、二乙烯苯－甲基丙烯酸酯共聚物、及鄰苯二甲酸二烯丙酯聚合物較佳。The crosslinked resin is not particularly limited, and examples thereof include an epoxy resin, a phenol resin, a melamine resin, an unsaturated polyester resin, a divinylbenzene polymer, a divinylbenzene-styrene copolymer, and a divinylbenzene-acrylate. Copolymer, A resin having a mesh structure such as diallyl phthalate polymer, triallyl isocyanate polymer, and benzoguanamine polymer. Among them, since the resistance to the heat treatment step such as the hardening step and the solder reflow step is excellent after bonding the wafer, the divinylbenzene polymer, the divinylbenzene-styrene copolymer, and the divinylbenzene-methacrylate copolymer are used. And a diallyl phthalate polymer is preferred.

構成該無機粒子之材料並無特別限制，可列舉例如氧化矽、氧化鋁、氮化硼、氮化鋁、氮化矽、鑽石、氧化鈦、及氧化鋯等。The material constituting the inorganic particles is not particularly limited, and examples thereof include cerium oxide, aluminum oxide, boron nitride, aluminum nitride, tantalum nitride, diamond, titanium oxide, and zirconium oxide.

該有機無機混合粒子並無特別限制，例如可舉以烷氧矽烷為主成分之有機無機混合粒子等。此種以烷氧矽烷為主成分之有機無機混合粒子，例如可依照日本特許第2698541號說明書所記載之方法，藉由將烷氧矽烷予以加水分解縮聚來製造。The organic-inorganic hybrid particles are not particularly limited, and examples thereof include organic-inorganic hybrid particles containing alkoxysilane as a main component. Such an organic-inorganic hybrid particle containing alkoxysilane as a main component can be produced, for example, by hydrolyzing polycondensation of an alkoxysilane in accordance with the method described in Japanese Patent No. 2896541.

該間隔粒子，視需要，較佳為施以表面處理。The spacer particles are preferably subjected to a surface treatment as needed.

藉由對該間隔粒子施以表面處理，可在本發明之電子零件用接著劑，實現後述黏度特性。By applying a surface treatment to the spacer particles, the viscosity characteristics described later can be achieved in the adhesive for electronic parts of the present invention.

該表面處理方法並無特別限制，例如在接著組成物整體顯示疏水性時，以於表面賦予親水基較佳。此種方法並無特別限制，例如在使用該樹脂粒子作為間隔粒子時，可舉以具有親水基之偶合劑來處理樹脂粒子表面之方法等。The surface treatment method is not particularly limited. For example, when the composition exhibits hydrophobicity as a whole, it is preferred to impart a hydrophilic group to the surface. The method is not particularly limited. For example, when the resin particles are used as the spacer particles, a method of treating the surface of the resin particles with a coupling agent having a hydrophilic group may be mentioned.

該間隔粒子之形狀以球狀較佳。又，該間隔粒子之長寬比的較佳上限為1.1。藉由將長寬比設在1.1以下，在接合電子零件彼此等時，可穩定將此等間隔保持一定。此外， 本說明書中，長寬比係指針對粒子之長徑與短徑，其長徑長度對短徑長度之比(長徑長度除以短徑長度之值)。該長寬比之值愈接近1，則間隔粒子之形狀愈接近正圓。The shape of the spacer particles is preferably spherical. Further, a preferred upper limit of the aspect ratio of the spacer particles is 1.1. By setting the aspect ratio to 1.1 or less, it is possible to stably maintain the intervals while holding the electronic components and the like. In addition, In the present specification, the aspect ratio refers to the ratio of the long diameter to the short diameter of the long and short diameters of the particles (the length of the long diameter divided by the length of the short diameter). The closer the value of the aspect ratio is to 1, the closer the shape of the spacer particles is to a perfect circle.

該間隔粒子，其以下述式(2)所示之K值的較佳下限為980N/mm2 ，較佳上限為4900N/mm2 。The spacer particles have a preferred lower limit of the K value represented by the following formula (2) of 980 N/mm 2 and a preferred upper limit of 4900 N/mm 2 .

K＝(3/√2)．F．S－3/2．R－1/2 (2)K=(3/√2). F. S-3/2. R-1/2 (2)

式(2)中，F、S分別表示間隔粒子之10%壓縮變形的荷重值(kgf)、壓縮位移(mm)，R表示該間隔粒子之半徑(mm)。In the formula (2), F and S respectively represent a load value (kgf) and a compression displacement (mm) of 10% compression deformation of the spacer particles, and R represents a radius (mm) of the spacer particles.

該K值可藉由以下測量方法來測量。This K value can be measured by the following measurement method.

首先，將間隔粒子散布於具有平滑表面之鋼板上後，自其中選擇1個間隔粒子，使用微小壓縮測試機以鑽石製直徑為50 μm之圓柱的平滑端面來壓縮間隔粒子。此時，以電磁力電檢測出壓縮荷重，以動作變壓器之位移電檢測出壓縮位移。接著，從所獲得之壓縮位移－荷重之關係，分別求出10%壓縮變形之荷重值、壓縮位移，並從所獲得之結果算出K值。First, after the spacer particles were spread on a steel plate having a smooth surface, one spacer particle was selected therefrom, and the spacer particles were compressed by a micro-compression tester using a smooth end face of a cylinder having a diameter of 50 μm. At this time, the compression load is electrically detected by the electromagnetic force, and the compression displacement is detected by the displacement of the operating transformer. Next, from the relationship between the obtained compression displacement and the load, the load value and the compression displacement of 10% compression deformation were respectively obtained, and the K value was calculated from the obtained result.

該間隔粒子，其從20℃、10%之壓縮變形狀態釋放時之壓縮恢復率的較佳下限為20%。在使用具有此種壓縮恢復率之間隔粒子時，即使間隙間距離左右之較大粒子存在於所要積層之電子零件間，亦可藉由壓縮變形使形狀恢復而發揮間隙調整材之作用。因此，能以更穩定之一定間隔 來平行積層電子零件彼此等。The preferred lower limit of the compression recovery ratio of the spacer particles when released from a compression deformation state of 20 ° C and 10% is 20%. When spacer particles having such a compression recovery ratio are used, even if large particles having a distance between the gaps exist between the electronic components to be laminated, the shape can be restored by compression deformation to function as a gap adjusting material. Therefore, it can be more stable at certain intervals. Parallel stacking of electronic parts to each other.

該壓縮恢復率可藉由以下測量方法來測量。The compression recovery rate can be measured by the following measurement method.

藉由與測量該K值時之相同方法，以動作變壓器之位移電檢測出壓縮位移，在壓縮中逐漸減少荷重直至反轉荷重值為止，測量該情形下荷重與壓縮位移之關係。從所得之測量結果算出壓縮恢復率。然而，去荷重之終點並非荷重值為零，而係0.1g以上之原點荷重值。By the same method as when measuring the K value, the compression displacement is electrically detected by the displacement of the action transformer, and the load is gradually reduced until the load value is reversed during compression, and the relationship between the load and the compression displacement in this case is measured. The compression recovery rate was calculated from the obtained measurement results. However, the end point of the de-loading is not that the load value is zero, but the origin load value of 0.1 g or more.

該間隔粒子之摻合量的較佳下限為0.01重量%，較佳上限為10重量%。若該間隔粒子之摻合量未達0.01重量%時，則在接合電子零件彼此等時，有時會無法穩定將電子零件彼此之間隔保持一定。若該間隔粒子之摻合量超過10重量%時，則有時會降低作為接著劑之功能。A preferred lower limit of the amount of the spacer particles to be blended is 0.01% by weight, and a preferred upper limit is 10% by weight. When the blending amount of the spacer particles is less than 0.01% by weight, when the electronic components are joined to each other, the interval between the electronic components may not be stably maintained. When the blending amount of the spacer particles exceeds 10% by weight, the function as an adhesive may be lowered.

又，除了該間隔粒子以外，在含有具備該間隔粒子之平均粒徑以上之直徑的固體成分時，此種固體成分之摻合量的較佳上限為1重量%。又，該固體成分之熔點以硬化溫度以下較佳。Further, in addition to the spacer particles, when a solid component having a diameter equal to or larger than the average particle diameter of the spacer particles is contained, a preferred upper limit of the blending amount of the solid component is 1% by weight. Further, the melting point of the solid component is preferably at least the curing temperature.

再者，該固體成分之最大粒徑，係以間隔粒子之平均粒徑的1.1~1.5倍較佳，以1.1~1.2倍更佳。Further, the maximum particle diameter of the solid component is preferably 1.1 to 1.5 times the average particle diameter of the spacer particles, more preferably 1.1 to 1.2 times.

本發明之電子零件用接著劑係含有硬化性化合物。The adhesive for electronic parts of the present invention contains a curable compound.

該硬化性化合物並無特別限制，例如可使用藉由加成聚合、縮聚、加成縮聚、複加成、加成縮合或開環聚合反應所硬化之化合物。具體而言，可列舉例如尿素樹脂、三聚氰胺樹脂、酚醛樹脂、間苯二酚樹脂、環氧樹脂、丙烯酸樹脂、聚酯樹酯、聚醯胺樹脂、聚苯並咪唑樹脂、鄰苯 二甲酸二烯丙酯樹脂、二甲苯樹脂、烷基－苯樹脂、環氧丙烯酸酯樹脂、矽樹脂、及聚胺酯樹脂等熱硬化性化合物。其中，由於接合後所製得之半導體裝置的可靠性及接合強度優異，因此以環氧樹脂、丙烯酸樹脂較佳，以具有醯亞胺骨架之環氧樹脂更佳。The curable compound is not particularly limited, and for example, a compound which is hardened by addition polymerization, polycondensation, addition polycondensation, re-addition, addition condensation or ring-opening polymerization can be used. Specific examples thereof include urea resin, melamine resin, phenol resin, resorcin resin, epoxy resin, acrylic resin, polyester resin, polyamide resin, polybenzimidazole resin, and phthalic acid. A thermosetting compound such as diallyl dicarboxylate resin, xylene resin, alkyl-benzene resin, epoxy acrylate resin, oxime resin, or polyurethane resin. Among them, since the semiconductor device obtained after bonding has excellent reliability and bonding strength, an epoxy resin or an acrylic resin is preferable, and an epoxy resin having a quinone imine skeleton is more preferable.

該環氧樹脂並無特別限制，可列舉例如雙酚A型、雙酚F型、雙酚AD型、雙酚S型等雙酚型環氧樹脂、酚醛清漆型、甲酚清漆型等酚醛型環氧樹脂、三酚甲烷三縮水甘油醚等芳香族環氧樹脂、萘型環氧樹脂、芴型環氧樹脂、倍環戊二烯型環氧樹脂、間苯二酚型環氧樹脂(間苯二酚縮水甘油醚)、及此等之氫化物等。其中，由於可製得耐熱性高之電子零件用接著劑，因此以萘型環氧樹脂、芴型環氧樹脂、及間苯二酚型環氧樹脂較佳。The epoxy resin is not particularly limited, and examples thereof include a bisphenol type epoxy resin such as a bisphenol A type, a bisphenol F type, a bisphenol AD type, and a bisphenol S type, and a phenol type such as a novolak type or a cresol type. Aromatic epoxy resin such as epoxy resin, trisphenol methane triglycidyl ether, naphthalene epoxy resin, fluorene epoxy resin, cyclopentadiene epoxy resin, resorcinol epoxy resin Hydroquinone glycidyl ether), and such hydrides. Among them, a naphthalene type epoxy resin, a fluorene type epoxy resin, and a resorcinol type epoxy resin are preferable because an adhesive for electronic parts having high heat resistance can be obtained.

該萘型環氧樹脂之中，市售品可列舉例如HP－4032、HP－4032D、HP－4700、HP－4701(以上，Dainippon Ink and Chemicals公司製)等。又，該芴型環氧樹脂之中，市售品可列舉例如EX－1010、1011、1012、1020、1030、1040、1050、1051、1060(以上，NAGASE CHEMTEX公司製)等。又，該間苯二酚型環氧樹脂之中，市售品可舉例如EX－201(NAGASE CHEMTEX公司製)等。Among the commercially available products, for example, HP-4032, HP-4032D, HP-4700, HP-4701 (above, manufactured by Dainippon Ink and Chemicals Co., Ltd.), and the like are mentioned. In addition, as a commercial item, for example, EX-1010, 1011, 1012, 1020, 1030, 1040, 1050, 1051, 1060 (above, NAGASE CHEMTEX Co., Ltd.), etc. are mentioned. Further, among the resorcinol-type epoxy resins, for example, EX-201 (manufactured by NAGASE CHEMTEX Co., Ltd.) or the like can be mentioned.

該萘型環氧樹脂、芴型環氧樹脂、間苯二酚型環氧樹脂，以使用其軟化點在60℃以下之樹脂較佳。藉由使用軟化點在60℃以下之樹脂，可減少為了降低電子零件用接著劑之黏度而使用之稀釋劑等液狀成分的添加份數，而可製 得在硬化時及硬化後揮發成分較少之電子零件用接著劑。以使用軟化點在40℃以下之樹脂更佳，再更佳為使用軟化點在室溫以下之樹脂。該市售品之中，以HP－4032、HP－4032D、EX－1020、及EX－201較佳。The naphthalene type epoxy resin, the fluorene type epoxy resin, and the resorcinol type epoxy resin are preferably those having a softening point of 60 ° C or less. By using a resin having a softening point of 60 ° C or less, it is possible to reduce the number of parts of the liquid component such as a diluent used to reduce the viscosity of the adhesive for electronic parts. An adhesive for electronic parts which has less volatile components during hardening and hardening. It is more preferable to use a resin having a softening point of 40 ° C or less, and more preferably a resin having a softening point of not more than room temperature. Among the commercially available products, HP-4032, HP-4032D, EX-1020, and EX-201 are preferred.

在使用萘型環氧樹脂、芴型環氧樹脂或間苯二酚型環氧樹脂其中一種或複數種作為該硬化性化合物時，該硬化性化合物中該萘型環氧樹脂、芴型環氧樹脂或間苯二酚型環氧樹脂其中一種或複數種之摻合量的較佳下限為40重量%。若該萘型環氧樹脂、芴型環氧樹脂或間苯二酚型環氧樹脂其中一種或複數種之摻合量未達40重量%時，則有時無法製得具有充分耐熱性之電子零件用接著劑。該萘型環氧樹脂、芴型環氧樹脂或間苯二酚型環氧樹脂其中一種或複數種之摻合量的更佳下限為60重量%。又，該萘型環氧樹脂、芴型環氧樹脂或間苯二酚型環氧樹脂其中一種或複數種之摻合量的較佳上限為90重量%。When one or more of a naphthalene type epoxy resin, a fluorene type epoxy resin or a resorcinol type epoxy resin is used as the curable compound, the naphthalene type epoxy resin and the fluorene type epoxy resin are used in the curable compound. A preferred lower limit of the blending amount of one or a plurality of the resin or the resorcinol type epoxy resin is 40% by weight. If the blending amount of one or more of the naphthalene type epoxy resin, the fluorene type epoxy resin or the resorcinol type epoxy resin is less than 40% by weight, electrons having sufficient heat resistance may not be obtained. The parts use an adhesive. A more preferred lower limit of the blending amount of one or a plurality of the naphthalene type epoxy resin, the fluorene type epoxy resin or the resorcinol type epoxy resin is 60% by weight. Further, a preferred upper limit of the blending amount of one or a plurality of the naphthalene type epoxy resin, the fluorene type epoxy resin or the resorcinol type epoxy resin is 90% by weight.

該環氧樹脂進一步可使用具有NBR、CTBN、聚丁二烯、及丙烯酸橡膠等橡膠成分之橡膠改質環氧樹脂、可撓性環氧化合物等環氧化合物。使用此種環氧樹脂時，在硬化後可賦予柔軟性。又，亦可使用以往公知之環氧樹脂。Further, as the epoxy resin, an epoxy compound such as a rubber-modified epoxy resin or a flexible epoxy compound having a rubber component such as NBR, CTBN, polybutadiene or acrylic rubber can be used. When such an epoxy resin is used, flexibility can be imparted after curing. Further, a conventionally known epoxy resin can also be used.

該硬化性化合物，其吸濕率之較佳上限為1.5%，更佳上限為1.1%。具有此種吸濕率之硬化性化合物，可列舉例如萘型環氧樹脂、芴型環氧樹脂、倍環戊二烯型環氧樹脂、酚醛清漆型環氧樹脂、甲酚清漆型環氧樹脂、及間苯二酚型環氧樹脂等。The curable compound preferably has a moisture absorption rate of 1.5%, more preferably 1.1%. Examples of the curable compound having such a moisture absorption rate include a naphthalene type epoxy resin, a fluorene type epoxy resin, a cyclopentadiene type epoxy resin, a novolac type epoxy resin, and a cresol type epoxy resin. And resorcinol type epoxy resin.

本發明之電子零件用接著劑係含有硬化劑。The adhesive for electronic parts of the present invention contains a curing agent.

該硬化劑並無特別限制，可配合該硬化性化合物適當選擇以往公知之硬化劑。在使用環氧樹脂作為硬化性化合物時之硬化劑，可列舉例如三烷四氫鄰苯二甲酸酐等加熱硬化型酸酐系硬化劑、酚系硬化劑、胺系硬化劑、二氰二胺等潛在性硬化劑、及陽離子系觸媒型硬化劑等。該等硬化劑可單獨使用，亦可併用2種以上。The curing agent is not particularly limited, and a conventionally known curing agent can be appropriately selected in combination with the curable compound. The curing agent in the case of using an epoxy resin as the curable compound may, for example, be a heat curing type acid anhydride type curing agent such as trioxane tetrahydrophthalic anhydride, a phenol type curing agent, an amine type curing agent, dicyandiamide or the like. A latent curing agent, a cationic catalyst type curing agent, and the like. These hardeners may be used alone or in combination of two or more.

該硬化劑之摻合量並無特別限制，在使用與該硬化性化合物之官能基等量反應的硬化劑時，相對於該該硬化性化合物之官能基量，以80~110當量較佳。又，若使用作為觸媒功能之硬化劑時，相對於該硬化性化合物100重量份，該硬化劑之摻合量的較佳下限為1重量份，較佳上限為20重量份。The amount of the curing agent to be blended is not particularly limited, and when a curing agent which reacts in an equivalent amount with the functional group of the curable compound is used, it is preferably 80 to 110 equivalents based on the amount of the functional group of the curable compound. Further, when a curing agent as a catalyst function is used, a preferred lower limit of the amount of the curing agent to be added is 1 part by weight, and a preferred upper limit is 20 parts by weight based on 100 parts by weight of the curable compound.

本發明之電子零件用接著劑，為了調整硬化速度或硬化物之物性等，除了該硬化劑以外亦可進一步添加硬化促進劑。In the adhesive for electronic parts of the present invention, in addition to the curing agent, a curing accelerator may be further added in order to adjust the curing rate or the physical properties of the cured product.

該硬化促進劑並無特別限制，可列舉例如咪唑系硬化促進劑、及三級胺系硬化促進劑等。其中，由於易於進行反應系統的控制(用以調整硬化速度或硬化物之物性)，因此適合使用咪唑系硬化促進劑。該等硬化促進劑可單獨使用，亦可併用2種以上。The hardening accelerator is not particularly limited, and examples thereof include an imidazole-based hardening accelerator and a tertiary amine-based curing accelerator. Among them, an imidazole-based hardening accelerator is suitably used because it is easy to control the reaction system (to adjust the curing rate or the physical properties of the cured product). These hardening accelerators may be used alone or in combination of two or more.

該咪唑系硬化促進劑並無特別限制，可列舉例如以氰乙基保護咪唑之1位的1－氰乙基－2－苯咪唑、或以異三聚氰酸保護鹼性的咪唑系硬化促進劑(產品名「2MA－OK」，四 國化成工業公司製)等。該等咪唑系硬化促進劑可單獨使用，亦可併用2種以上。The imidazole-based hardening accelerator is not particularly limited, and examples thereof include 1-cyanoethyl-2-benzimidazole in which the cyanoethyl group is protected at the 1-position of the imidazole, or imidazole-based hardening promotion in which the basic is protected by iso-cyanuric acid. Agent (product name "2MA-OK", four Guohuacheng Industrial Co., Ltd.). These imidazole-based hardening accelerators may be used singly or in combination of two or more.

該咪唑系硬化促進劑之摻合量並無特別限制，相對於該硬化性化合物100重量份，較佳下限為1重量份，較佳上限為10重量份。The blending amount of the imidazole-based hardening accelerator is not particularly limited, and a preferred lower limit is 1 part by weight, and a preferred upper limit is 10 parts by weight based on 100 parts by weight of the curable compound.

該硬化劑及/或硬化促進劑，其熔點之較佳下限為120℃。藉由使熔點在120℃以上，在將本發明之電子零件用接著劑加熱時，可抑制凝膠化而可適當地接合半導體零件及調整半導體零件間之距離。又，以硬化劑及硬化促進劑中之任一者為粉體較佳。The preferred lower limit of the melting point of the hardener and/or hardening accelerator is 120 °C. When the melting point of the electronic component of the present invention is heated by the adhesive at 120 ° C or higher, gelation can be suppressed, and the semiconductor component can be appropriately bonded and the distance between the semiconductor components can be adjusted. Further, it is preferred that any of the curing agent and the curing accelerator be a powder.

該熔點為120℃以上之硬化劑，可列舉例如5－(2,5－二氧四氫－3－苯基)－3－甲基－3－環己烯－1,2－二羧酸酐、TD－2090等酚醛清漆樹脂、KH－6021等雙酚醛A清漆樹脂、KA－1165等鄰甲酚清漆樹脂、EH－3636AS、EH－3842、EH－3780、EH－4339S、EH－4346S(以上，旭電化工業公司製)等二氰二胺。The curing agent having a melting point of 120 ° C or higher may, for example, be 5-(2,5-dioxotetrahydro-3-phenyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride. Novolac resin such as TD-2090, bisphenol aldehyde varnish resin such as KH-6021, o-cresol varnish resin such as KA-1165, EH-3636AS, EH-3842, EH-3780, EH-4339S, EH-4346S (above, Dixyldiamine, etc., manufactured by Asahi Chemical Industry Co., Ltd.).

又，亦可適當使用以熔點在120℃以上之材質所被覆之微膠囊型硬化劑。Further, a microcapsule-type curing agent coated with a material having a melting point of 120 ° C or higher can also be suitably used.

該熔點在120℃以上之硬化促進劑，可列舉例如2MZ、2MZ－P、2PZ、2PZ－PW、2P4MZ、C11Z－CNS、2PZ－CNS、2PZCNS－PW、2MZ－A、2MZA－PW、C11Z－A、2E4MZ－A、2MA－OK、2MAOK－PW、2PZ－OK、2MZ－OK、2PHZ、2PHZ－PW、2P4MHZ、2P4MHZ－PW、2E4MZ－BIS、VT、VT－OK、MAVT、MAVT－OK(以上，四國化成工業公司製) 等。特別是，以至130℃為止穩定，135~200℃會活性化之硬化促進劑較佳，該硬化促進劑之中，以2MA－OK、2MAOK－PW較佳。在使用此等硬化促進劑時，可兼顧儲藏穩定性、製程時對熱之穩定性及快速硬化性。The hardening accelerator having a melting point of 120 ° C or higher may, for example, be 2MZ, 2MZ-P, 2PZ, 2PZ-PW, 2P4MZ, C11Z-CNS, 2PZ-CNS, 2PZCNS-PW, 2MZ-A, 2MZA-PW, C11Z- A, 2E4MZ-A, 2MA-OK, 2MAOK-PW, 2PZ-OK, 2MZ-OK, 2PHZ, 2PHZ-PW, 2P4MHZ, 2P4MHZ-PW, 2E4MZ-BIS, VT, VT-OK, MAVT, MAVT-OK ( Above, Shikoku Chemical Industrial Co., Ltd.) Wait. In particular, a curing accelerator which is stable at 130 ° C and which is activated at 135 to 200 ° C is preferable, and among the curing accelerators, 2MA-OK and 2MAOK-PW are preferable. When such a hardening accelerator is used, both storage stability, heat stability and rapid hardenability in the process can be achieved.

在使用環氧樹脂作為該硬化性化合物，且併用該硬化劑與硬化促進劑時，硬化劑之摻合量以相對於環氧基理論上所欲之當量以下較佳。若該硬化劑之摻合量超過理論上所欲之當量時，有時會在硬化後因水分而易於使氯離子溶析。亦即，若硬化劑過剩時，則例如以熱水從本發明之半導體零件用接著劑之硬化物萃取出溶析成分時，由於萃取水之pH為4~5左右，因此有時氯離子會從環氧樹脂大量溶析出。因此，將本發明之半導體零件用接著劑之硬化物1g以100℃之純水10g浸漬2小時後之純水的pH為6~8較佳，pH為6.5~7.5更佳。When an epoxy resin is used as the curable compound, and the curing agent and the hardening accelerator are used in combination, the blending amount of the curing agent is preferably equal to or less than the theoretical equivalent of the epoxy group. When the blending amount of the hardener exceeds the theoretically desired equivalent amount, chlorine ions may be easily eluted by moisture after hardening. In other words, when the amount of the hardener is excessive, for example, when the eluted component is extracted from the cured product of the semiconductor component adhesive of the present invention by hot water, the pH of the extracted water is about 4 to 5, so that the chloride ion may be It is widely dissolved from epoxy resin. Therefore, the pH of the pure water after the immersion of 1 g of the cured product of the semiconductor component of the present invention in 10 g of pure water at 100 ° C for 2 hours is preferably 6 to 8, and the pH is preferably 6.5 to 7.5.

又，本發明之電子零件用接著劑，作為該硬化劑亦可併用常溫下為固體之3官能以上之酸酐硬化劑、與常溫下為液體之2官能酸酐硬化劑的電子零件用接著劑。可使本發明之電子零件用接著劑之25℃儲藏彈性模數未達3GPa，150~180℃之溫度區域之儲藏彈性模數在30MPa以上，250~260℃之溫度區域之儲藏彈性模數在10MPa以上。藉由具有此種溫度區域之儲藏彈性模數，使用本發明之電子零件用接著劑，例如在接合半導體晶片與支持構件時，可使半導體晶片之接著特性優異，可防止因半導體晶片與支持構件之延伸率對溫度依存性之差異，而在半導體晶片產生 大的彎曲，此外亦可提高對所製造之半導體晶片積層體之打線處理等的可靠性，並且亦可確保耐焊料回焊性。In addition, as the curing agent for an electronic component of the present invention, an acid anhydride curing agent which is a trifunctional or higher functional solid at normal temperature and an adhesive for an electronic component which is a liquid bifunctional acid anhydride curing agent at normal temperature may be used in combination. The storage modulus of the 25 ° C storage elastic modulus of the electronic component adhesive of the present invention is less than 3 GPa, and the storage elastic modulus of the temperature region of 150 to 180 ° C is above 30 MPa, and the storage elastic modulus of the temperature region of 250 to 260 ° C is 10MPa or more. By using the storage elastic modulus of such a temperature region, the adhesive for electronic parts of the present invention can be used, for example, when bonding a semiconductor wafer and a supporting member, the semiconductor wafer can be excellent in adhesion characteristics, and the semiconductor wafer and the supporting member can be prevented. The difference in elongation versus temperature dependence, but in semiconductor wafers The large bending can also improve the reliability of the wire bonding process and the like of the manufactured semiconductor wafer laminate, and can also ensure solder reflow resistance.

在併用該常溫下為固體之3官能以上之酸酐硬化劑、與常溫下為液體之2官能酸酐硬化劑時，本發明之電子零件用接著劑之硬化物，會成為具有低彈性模數之海成分與高彈性模數之島成分的海島構造。具體而言，在該島成分成為高彈性模數且較硬之部分，本發明之電子零件用接著劑之硬化物，可以該島成分將高溫(例如，175℃)之儲藏彈性模數保持於較高之值(例如，30MPa以上)。另一方面，該海成分為低彈性模數且柔軟之部分，本發明之電子零件用接著劑之硬化物，可以該海成分將常溫(25℃)之儲藏彈性模數保持於較低之值(例如，未達1 GPa)。硬化物可藉由具有該海島構造，使該硬化物在常溫及高溫區域具有適度之柔軟性，並使半導體晶片等電子零件與支持構件之接著性優異，可防止在接合於支持構件之半導體晶片等電子零件產生大的彎曲。When the trifunctional or higher acid anhydride curing agent which is solid at normal temperature and the bifunctional acid anhydride curing agent which is liquid at normal temperature are used in combination, the cured product of the adhesive for electronic parts of the present invention becomes a sea having a low modulus of elasticity. An island structure with an island component of composition and high modulus of elasticity. Specifically, in the hardened portion of the adhesive for an electronic component of the present invention, the island component has a high elastic modulus and a hard portion, and the storage component can maintain the high temperature (for example, 175 ° C) storage elastic modulus of the island component. Higher value (for example, above 30 MPa). On the other hand, the sea component is a low elastic modulus and a soft portion, and the cured product of the adhesive for electronic parts of the present invention can maintain the storage modulus of the sea component at a normal temperature (25 ° C) at a low value. (for example, less than 1 GPa). By having the island structure, the cured product has moderate flexibility in a normal temperature and a high temperature region, and is excellent in adhesion between an electronic component such as a semiconductor wafer and a supporting member, and can prevent a semiconductor wafer bonded to the supporting member. Other electronic parts produce large bends.

硬化物具有該儲藏彈性模數之本發明之電子零件用接著劑，在藉由例如後述方法(1)製作硬化物時，可藉由改變該常溫下為固體之3官能以上之酸酐硬化劑、與常溫下為液體之2官能酸酐硬化劑的摻合比來達成。具體而言，例如適當調整常溫下為固體之3官能以上之酸酐硬化劑、與常溫下為液體之2官能基酸酐硬化劑的摻合比，即可將常溫之儲藏彈性模數在100MPa~3GPa之範圍內控制於所欲之值，可充分緩合因半導體晶片等電子零件與基板之延伸 率對溫度依存性之差異所產生之應力，以防止在半導體晶片等產生彎曲。又，可將175℃以上之儲藏彈性模數在0.1~100MPa之範圍內控制於所欲之值，以提高在以本發明之電子零件用接著劑所接著之半導體晶片實施打線處理時、或焊料回焊過程等的製程可靠性。In the cured product, the cured material for an electronic component of the present invention having a storage elastic modulus is used, and when the cured product is produced by the method (1) described later, for example, the trifunctional or higher acid anhydride curing agent which is solid at normal temperature can be changed. It is achieved by blending ratio with a bifunctional acid anhydride hardener which is liquid at normal temperature. Specifically, for example, the blending ratio of the trifunctional or higher acid anhydride curing agent which is solid at normal temperature and the bifunctional acid anhydride curing agent which is liquid at normal temperature can be appropriately adjusted, and the storage elastic modulus at normal temperature can be 100 MPa to 3 GPa. Controlling the desired value within the range, can fully delay the extension of electronic components and substrates due to semiconductor wafers The stress generated by the difference in temperature dependence to prevent bending in a semiconductor wafer or the like. Further, the storage elastic modulus of 175 ° C or higher can be controlled to a desired value in the range of 0.1 to 100 MPa to improve the soldering process of the semiconductor wafer to which the adhesive for electronic parts of the present invention is applied, or solder. Process reliability such as reflow process.

在該硬化物具有海島構造時，高彈性模數之島成分之直徑的較佳下限為0.1 μm，較佳上限為10 μm。若高彈跳模數之島成分的直徑未達0.1 μm時，則該硬化物之島成分會過小，有時無法確保高溫之彈性模數。若高彈性模數之島成分的直徑超過10 μm時，則有時常溫區域之柔軟性會不足。高彈性模數之島成分之直徑的更佳下限為0.5 μm，更佳上限為5 μm。此外，該島成分之直徑，係意指將本發明之電子零件用接著劑之硬化物切成厚度為70nm，將此以釕染色之後，以透過型電子顯微鏡(「JEM2100」、JEOL公司製)觀察時，所能觀察之島部分的長邊。又，亦可使用AFM從海部分與島部分之彈性模數之差求得島部分之直徑。此外，亦可使用紅外線分光，測量3官能以上之酸酐的存在部分，藉此測量島部分之直徑。When the cured product has an island structure, a preferred lower limit of the diameter of the island component of the high elastic modulus is 0.1 μm, and a preferred upper limit is 10 μm. If the diameter of the island component of the high elastic modulus is less than 0.1 μm, the island component of the cured product may be too small, and the elastic modulus of the high temperature may not be ensured. When the diameter of the island component of the high elastic modulus exceeds 10 μm, the softness in the normal temperature region may be insufficient. A lower limit of the diameter of the island component of the high elastic modulus is 0.5 μm, and a higher limit is 5 μm. In addition, the diameter of the island component means that the cured product of the adhesive for electronic parts of the present invention is cut into a thickness of 70 nm, and after dyeing with enamel, a transmission electron microscope ("JEM2100", manufactured by JEOL Co., Ltd.) is used. When observing, the long side of the island portion that can be observed. Further, the diameter of the island portion can be obtained from the difference between the elastic modulus of the sea portion and the island portion using the AFM. Further, it is also possible to measure the diameter of the island portion by measuring the presence of the trifunctional or higher acid anhydride using infrared spectroscopy.

又，在該硬化物中，以該島成分均勻分布於該海成分中較佳。若該島成分之分布不均勻時，則在使用本發明之電子零件用接著劑來接著電子零件與支持構件時，有時電子零件與支持構件之接著會不均勻、或硬化物之儲藏彈性模數會不均勻。此外，該島成分均勻分布於該海成分，係意指於任意之10 μm×10 μm內皆存在島與海。Further, in the cured product, it is preferred that the island component is uniformly distributed in the sea component. When the distribution of the components of the island is not uniform, when the electronic component and the supporting member are used in the adhesive for electronic components of the present invention, the electronic component and the supporting member may be unevenly followed, or the elastic modulus of the cured product may be stored. The number will be uneven. In addition, the island component is uniformly distributed in the sea component, which means that the island and the sea exist in any 10 μm×10 μm.

在該硬化物具有該海島構造時，以該海成分之25℃之儲藏彈性模數未達1 GPa較佳。若該海成分之25℃之儲藏彈性模數超過1 GPa時，則該硬化物在常溫區域之柔軟性會不足，在使用本發明之電子零件用接著劑來接著電子零件與支持構件時，無法緩合因半導體晶片與支持構件之延伸率對溫度依存性之差異所產生之應力，有時會在半導體晶片產生彎曲。該海成分之25℃之儲藏彈性模數之更佳上限為0.8 GPa，進一步更佳上限為0.6 GPa。When the cured product has the sea-island structure, it is preferable that the storage elastic modulus of the sea component at 25 ° C is less than 1 GPa. When the storage elastic modulus at 25 ° C of the sea component exceeds 1 GPa, the cured product may have insufficient flexibility in a normal temperature region, and when the electronic component and the support member are used in the adhesive for electronic components of the present invention, The stress generated by the difference in temperature dependence between the elongation of the semiconductor wafer and the supporting member is sometimes caused to be bent in the semiconductor wafer. A higher upper limit of the storage elastic modulus of the sea component at 25 ° C is 0.8 GPa, and a still further upper limit is 0.6 GPa.

又，該島成分之25℃之儲藏彈性模數之較佳下限為1 GPa。若該島成分之25℃之儲藏彈性模數未達1 GPa時，則無法將該硬化物在高溫之彈性模數保持較高，例如在使用本發明之電子零件用接著劑進行半導體晶片與支持構件之接合時，有時會無法對該半導體晶片進行打線處理。該島成分之25℃之儲藏彈性模數之更佳下限為2GPa，進一步更佳下限為4GPa。Further, a preferred lower limit of the storage elastic modulus of the island component at 25 ° C is 1 GPa. If the storage elastic modulus of the island component at 25 ° C is less than 1 GPa, the elastic modulus of the cured product at a high temperature cannot be kept high, for example, semiconductor wafer and support using the adhesive for electronic parts of the present invention. When the members are joined, the semiconductor wafer may not be wired. A lower limit of the storage elastic modulus of the island component at 25 ° C is 2 GPa, and a further lower limit is 4 GPa.

此外，在該硬化物具有海島構造時，將該島成分之170℃之儲藏彈性模數之值除以該海成分之170℃之儲藏彈性模數之值後之值的較佳下限為2。若該島成分之170℃之儲藏彈性模數之值除以該海成分之170℃之儲藏彈性模數之值後之值未達2時，則有時無法同時確保該硬化物中島成分之高溫區域之彈性模數、與海成分之常溫區域之低彈性模數。該島成分之170℃之儲藏彈性模數之值除以該海成分之170℃之儲藏彈性模數之值後之值的更佳下限為3，進一步更佳下限為5。Further, when the cured product has an island structure, a preferred lower limit of the value obtained by dividing the value of the storage elastic modulus of 170 ° C of the island component by the value of the storage elastic modulus of 170 ° C of the sea component is 2. If the value of the storage elastic modulus of 170 ° C of the island component is less than 2 by the value of the storage elastic modulus of 170 ° C of the sea component, the high temperature of the island component in the hardened material may not be ensured at the same time. The elastic modulus of the region and the low elastic modulus of the ambient temperature region of the sea component. A lower limit of the value of the storage elastic modulus of 170 ° C of the island component divided by the value of the storage elastic modulus of 170 ° C of the sea component is 3, and a further lower limit is 5.

此外，該海成分與島成分之彈性模數比，可使用例如原子力顯微鏡(AFM)(「SPA－400」、SOUNDPROOF HOUSING公司製)來測量。此外，構成該海成分之低彈性模數樹脂硬化物，藉由使用IT measurement control公司製之黏彈性測試機等來測量各樹脂硬化物之彈性模數，即可求出低彈性模數之海成分與高彈性模數之島成分的彈性模數。Further, the elastic modulus ratio of the sea component to the island component can be measured by, for example, an atomic force microscope (AFM) ("SPA-400", manufactured by SOUNDPROOF HOUSING Co., Ltd.). Further, the low-modulus modulus resin cured product constituting the sea component can be obtained by measuring the elastic modulus of each resin cured product by using a viscoelasticity tester manufactured by IT Measurement Control Co., Ltd. The modulus of elasticity of the composition of the island component with a high modulus of elasticity.

該常溫下為固體之3官能以上之酸酐硬化劑並無特別限制，3官能之酸酐硬化劑，可列舉例如酸酐苯偏三酸酐等，4官能以上之酸酐硬化劑可列舉例如苯均四酸酐、二苯甲酮四羧酸酐、甲基環己烯四羧酸酐、及聚壬二酸酐等。The trifunctional or higher acid anhydride curing agent which is a solid at room temperature is not particularly limited, and the trifunctional acid anhydride curing agent may, for example, be an anhydride trimellitic anhydride, and the tetrafunctional or higher acid anhydride curing agent may, for example, be pyromellitic anhydride. Benzophenonetetracarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, polyaphthalic anhydride, and the like.

該常溫下為液體之2官能酸酐硬化劑並無特別限制，可列舉例如鄰苯二甲酸酐、六氫酞酐、甲基四氫酞酐、甲基六氫酞酐、內亞甲四氫酞酐、甲基內亞甲四氫酞酐、及無水順丁烯二酸等。The bifunctional acid anhydride curing agent which is liquid at normal temperature is not particularly limited, and examples thereof include phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and endotetrahydroanthracene. Anhydride, methyl endois tetrahydrophthalic anhydride, and anhydrous maleic acid.

製備此種具有海島構造之硬化物的方法，可列舉例如(1)使用含有由硬化性化合物與常溫下為固體之3官能以上之酸酐硬化劑所構成之粒子(以下，亦稱為3官能以上之酸酐硬化劑粒子)、及硬化促進劑之本發明之電子零件用接著劑，藉由硬化時之加熱，在該3官能以上之酸酐硬化劑粒子發生熔融擴散之範圍，形成高交聯之硬化物(島成分)，另一方面藉由該硬化促進劑，使熔融之3官能以上之酸酐硬化劑粒子擴散區域以外之區域硬化，以形成低交聯之硬化物(海成分)的方法、及(2)使用含有硬化性化合物、硬化促進劑、及與該硬化性化合物相溶性不佳之高反應性硬化 劑之本發明之電子零件用接著劑，藉由與該硬化性化合物相溶性不佳之高反應性硬化劑，僅使該硬化劑周圍高交聯以形成高交聯之硬化物(島成分)，另一方面以該硬化促進劑使該高交聯之硬化物周圍以外之區域硬化，以得到低交聯之硬化物(海成分)的方法。其中，可適當使用該方法(1)。In the method of producing a cured product having a sea-island structure, for example, (1) a particle composed of a trifunctional or higher acid anhydride curing agent containing a curable compound and a solid at normal temperature (hereinafter, also referred to as a trifunctional or higher functional group) The adhesive for an electronic component of the present invention, which is an acid anhydride hardener particle, and a curing accelerator, is heated in a hardening state to form a high-crosslinking hardening in a range in which the trifunctional or higher acid anhydride hardener particles are melt-diffused. On the other hand, the hardening accelerator and the hardening accelerator are used to cure a region other than the molten trifunctional or higher acid anhydride hardener particle diffusion region to form a low-crosslinking cured product (sea component), and (2) use of a highly reactive hardening compound containing a curable compound, a hardening accelerator, and poor compatibility with the curable compound In the adhesive for electronic parts of the present invention, the highly reactive hardener having poor compatibility with the curable compound is used to form only a highly crosslinked cured product (island component) by high crosslinking around the hardener. On the other hand, the hardening accelerator hardens the region other than the periphery of the highly crosslinked cured product to obtain a low-crosslinked cured product (sea component). Among them, the method (1) can be suitably used.

該3官能以上之酸酐硬化劑粒子，其熔點之較佳下限為80℃。若熔點未達80℃時，則若不選擇成與該環氧化合物相溶性不佳之方式混合，則會在較低溫成為液態而擴散於本發明之電子零件用接著劑中，導致有時難以藉由硬化時之加熱以該方法(1)形成所欲之海島構造。此外，在將3官能基以上之酸酐硬化劑粒子選擇成與該環氧化合物相溶性不佳時，亦可使用熔點未達80℃之3官能以上之酸酐硬化劑粒子。The preferred lower limit of the melting point of the trifunctional or higher acid anhydride hardener particles is 80 °C. When the melting point is less than 80 ° C, if it is not mixed so as to be incompatible with the epoxy compound, it will be liquid at a lower temperature and diffused into the adhesive for electronic parts of the present invention, which may make it difficult to borrow. The desired island structure is formed by the method (1) by heating at the time of hardening. Further, when the trifunctional or higher acid anhydride hardener particles are selected to have poor compatibility with the epoxy compound, trifunctional or higher acid anhydride hardener particles having a melting point of less than 80 ° C may be used.

該3官能以上之酸酐硬化劑粒子的平均粒徑，較佳下限為0.1 μm，較佳上限為10 μm。若該3官能以上之酸酐硬化劑粒子的平均粒徑未達0.1 μm時，硬化時即使可形成海島構造，島成分亦會過小，而無法達成在高溫區域之高彈性模數。若該3官能以上之酸酐硬化劑粒子的平均粒徑超過10 μm時，則硬化時島成分會過大，導致在常溫區域下之柔軟性會不足，而無法改善半導體晶片等電子零件之彎曲。The average particle diameter of the trifunctional or higher acid anhydride hardener particles preferably has a lower limit of 0.1 μm, and a preferred upper limit is 10 μm. When the average particle diameter of the trifunctional or higher acid anhydride hardener particles is less than 0.1 μm, even if an island structure is formed during curing, the island component is too small, and a high elastic modulus in a high temperature region cannot be achieved. When the average particle diameter of the trifunctional or higher acid anhydride hardener particles exceeds 10 μm, the island component is too large during curing, and the flexibility in the normal temperature region is insufficient, so that the bending of the electronic component such as the semiconductor wafer cannot be improved.

又，本發明之電子零件用接著劑，亦可在不阻礙本發明之效果的範圍內含有稀釋劑。Further, the adhesive for electronic parts of the present invention may contain a diluent in a range that does not inhibit the effects of the present invention.

該稀釋劑係以能在本發明之電子零件用接著劑加熱硬 化時進入硬化物之反應性稀釋劑較佳。其中，為了不使該硬化物之接著可靠性惡化，以1分子中具有2個以上官能基之反應性稀釋劑較佳。The diluent is heated by an adhesive for the electronic component of the present invention. The reactive diluent which enters the hardened material at the time of the formation is preferred. Among them, a reactive diluent having two or more functional groups in one molecule is preferred in order not to deteriorate the reliability of the cured product.

此種反應性稀釋劑，可列舉例如脂肪族型環氧樹脂、環氧乙烷改質環氧樹脂、環氧丙烷改質環氧樹脂、環己烷型環氧樹脂、倍環戊二烯型環氧樹脂、酚醛型環氧樹脂等。Examples of such a reactive diluent include an aliphatic epoxy resin, an ethylene oxide modified epoxy resin, a propylene oxide modified epoxy resin, a cyclohexane epoxy resin, and a cyclopentadiene type. Epoxy resin, phenolic epoxy resin, etc.

在本發明之電子零件用接著劑含有該稀釋劑時，其含量並無特別限制，相對於本發明之電子零件用接著劑所含有之硬化性化合物之合計100重量份，較佳下限為1重量份，較佳上限為50重量份。若該稀釋劑之含量未達1重量份時，則有時幾乎無法獲得添加該稀釋劑之效果。若該稀釋劑之含量超過50重量份時，則有時會使本發明之電子零件用接著劑的接著可靠性變差、或無法獲得後述黏度特性。該稀釋劑之含量的更佳下限為5重量份，更佳上限為20重量份。In the case where the adhesive for an electronic component of the present invention contains the diluent, the content thereof is not particularly limited, and the preferred lower limit is 1 part by weight based on 100 parts by weight of the total of the curable compound contained in the adhesive for electronic parts of the present invention. The upper limit is preferably 50 parts by weight. If the content of the diluent is less than 1 part by weight, the effect of adding the diluent may be hardly obtained. When the content of the diluent exceeds 50 parts by weight, the subsequent reliability of the adhesive for electronic parts of the present invention may be deteriorated or the viscosity characteristics described later may not be obtained. A more preferred lower limit of the content of the diluent is 5 parts by weight, and a still more preferred upper limit is 20 parts by weight.

本發明之電子零件用接著劑，以進一步含有具能與該硬化性化合物反應之官能基的高分子化合物較佳。藉由含有此種高分子化合物，可提升因熱導致變形時的接合可靠性。The adhesive for electronic parts of the present invention preferably further contains a polymer compound having a functional group reactive with the curable compound. By including such a polymer compound, the bonding reliability at the time of deformation due to heat can be improved.

具有能與該硬化性化合物反應之官能基的高分子化合物，在使用環氧樹脂作為該硬化性化合物時，可列舉例如具有胺基、聚胺酯基、醯亞胺基、羥基、羧基、及環氧基等之高分子化合物等。其中，以具有環氧基之高分子化合物較佳。藉由添加具有該環氧基之高分子化合物，本發明 之電子零件用接著劑之硬化物可顯現優異之可撓性。亦即，本發明之電子零件用接著劑之硬化物，可兼具源自具有以屬硬化性化合物之多環式羥骨架為主鏈的優異機械強度、耐熱性及耐濕性、與源自具有該環氧基之高分子化合物的優異可撓性。因此，本發明之電子零件用接著劑之硬化物，具有優異之耐冷熱循環性、耐焊料回焊性、及尺寸穩定性等，並顯現高接著可靠性或高絕緣可靠性。When a polymer compound having a functional group reactive with the curable compound is used, when an epoxy resin is used as the curable compound, for example, an amine group, a polyurethane group, a quinone group, a hydroxyl group, a carboxyl group, and an epoxy group are mentioned. A polymer compound or the like. Among them, a polymer compound having an epoxy group is preferred. The present invention by adding a polymer compound having the epoxy group The cured product of the adhesive for electronic parts can exhibit excellent flexibility. In other words, the cured product of the adhesive for electronic parts of the present invention can have excellent mechanical strength, heat resistance, moisture resistance, and origin derived from a polycyclic hydroxy skeleton having a sclerosing compound. Excellent flexibility of the polymer compound having the epoxy group. Therefore, the cured product of the adhesive for electronic parts of the present invention has excellent cold-heat cycle resistance, solder reflow resistance, dimensional stability, and the like, and exhibits high adhesion reliability or high insulation reliability.

該具有環氧基之高分子化合物，只要是在末端或側鏈(懸架位)其中之一具有環氧基之高分子化合物即可，可列舉例如含環氧基之丙烯酸橡膠、含環氧基之丁二烯橡膠、雙酚型高分子量環氧樹脂、含環氧基之苯氧樹脂、含環氧基之丙烯酸樹脂、含環氧基之聚胺酯樹脂、含環氧基之聚酯樹脂等。其中，由於可製得含大量環氧基之高分子化合物，而構成機械強度或耐熱性更優異之硬化物，因此可適當使用含環氧基之丙烯酸樹脂。此等具有環氧基之高分子化合物，可單獨使用，亦可併用2種以上。The polymer compound having an epoxy group may be a polymer compound having an epoxy group at one of a terminal or a side chain (suspension site), and examples thereof include an epoxy group-containing acrylic rubber and an epoxy group-containing compound. Butadiene rubber, bisphenol type high molecular weight epoxy resin, epoxy group-containing phenoxy resin, epoxy group-containing acrylic resin, epoxy group-containing polyurethane resin, epoxy group-containing polyester resin, and the like. Among them, an epoxy group-containing acrylic resin can be suitably used because a polymer compound containing a large amount of epoxy groups can be obtained and a cured product having more excellent mechanical strength or heat resistance can be obtained. These polymer compounds having an epoxy group may be used singly or in combination of two or more.

在使用該具有環氧基之高分子化合物，特別是使用含環氧基之丙烯酸樹脂，作為具有能與該硬化性化合物反應之官能基的高分子化合物時，重量平均分子量之較佳下限為1萬。若重量平均分子量未達1萬時，則本發明之電子零件用接著劑之造膜性會不足，有時無法充分提升本發明之電子零件用接著劑之硬化物的可撓性。When the polymer compound having an epoxy group, particularly an epoxy group-containing acrylic resin, is used as the polymer compound having a functional group reactive with the curable compound, the preferred lower limit of the weight average molecular weight is 1 Million. When the weight average molecular weight is less than 10,000, the film forming property of the adhesive for electronic parts of the present invention may be insufficient, and the flexibility of the cured product of the adhesive for electronic parts of the present invention may not be sufficiently improved.

在使用該具有該環氧基之高分子化合物，特別是使用含環氧基之丙烯酸樹脂，作為具有能與該硬化性化合物反 應之官能基的高分子化合物時，環氧當量之較佳下限為200，較佳上限為1000。若環氧當量未達200時，則有時會無法充分提升本發明之電子零件用接著劑之硬化物的可撓性。若環氧當量超過1000時，則有時本發明之電子零件用接著劑之硬化物的機械強度或耐熱性會不足。In the use of the polymer compound having the epoxy group, particularly an epoxy group-containing acrylic resin, as having the ability to react with the curable compound In the case of a polymer compound having a functional group, the preferred lower limit of the epoxy equivalent is 200, and the upper limit is preferably 1,000. When the epoxy equivalent is less than 200, the flexibility of the cured product of the adhesive for electronic parts of the present invention may not be sufficiently improved. When the epoxy equivalent exceeds 1,000, the mechanical strength or heat resistance of the cured product of the adhesive for electronic parts of the present invention may be insufficient.

具有能與該硬化性化合物反應之官能基的高分子化合物摻合量並無特別限制，相對於該硬化性化合物100重量份，較佳下限為1重量份，較佳上限為20重量份。若具有能與該硬化性化合物反應之官能基的高分子化合物摻合量未達1重量份時，則會無法獲得對熱變形之充分可靠性。若具有能與該硬化性化合物反應之官能基的高分子化合物摻合量超過20重量份時，則有時耐熱性會降低。The blending amount of the polymer compound having a functional group reactive with the curable compound is not particularly limited, and a lower limit is preferably 1 part by weight, and a preferred upper limit is 20 parts by weight based on 100 parts by weight of the curable compound. When the blending amount of the polymer compound having a functional group reactive with the curable compound is less than 1 part by weight, sufficient reliability against thermal deformation cannot be obtained. When the blending amount of the polymer compound having a functional group reactive with the curable compound exceeds 20 parts by weight, the heat resistance may be lowered.

本發明之電子零件用接著劑，進一步以含有搖變劑(thixotropy－imparting agent)較佳。藉由含有搖變劑，可使本發明之電子零件用接著劑達成所欲之黏度特性。The adhesive for electronic parts of the present invention is further preferably a thixotropy-imparting agent. By containing a rocking agent, the adhesive for electronic parts of the present invention can be used to achieve desired viscosity characteristics.

該搖變劑並無特別限制，可使用例如金屬微粒、碳酸鈣、燻矽土(fumed silica)、氧化鋁、氮化硼、氮化鋁、及硼酸鋁等無機微粒。其中，以燻矽土較佳。The rocking agent is not particularly limited, and inorganic fine particles such as metal fine particles, calcium carbonate, fumed silica, alumina, boron nitride, aluminum nitride, and aluminum borate can be used. Among them, the smoked bauxite is preferred.

又，該搖變劑，視須要，亦可使用經進行表面處理者。特別是以使用表面具有疏水基之粒子較佳。具體而言，以使用例如表面經疏水化之燻矽土等較佳。Further, the shaker may be used as it is, if necessary. In particular, it is preferred to use particles having a hydrophobic group on the surface. Specifically, it is preferred to use, for example, a surface-hydrophobized smoked earth.

在使用粒狀搖變劑作為該搖變劑時，平均粒徑之較佳上限為1 μm。若該搖變劑之平均粒徑超過1 μm時，則有時無法顯現所欲之搖變性。When a particulate shaker is used as the shaker, the preferred upper limit of the average particle diameter is 1 μm. If the average particle diameter of the shaker exceeds 1 μm, the desired shakeability may not be exhibited.

該搖變劑之摻合量並無特別限制，較佳下限為0.5重量%，較佳上限為20重量%。若該搖變劑之摻合量未達0.5重量%時，則無法獲得充分之搖變性。若該搖變劑之摻合量超過20重量%時，則在接合半導體晶片等電子零件時，則有時會降低本發明之電子零件用接著劑的排除性。該搖變劑之摻合量的更佳下限為2重量%，較佳上限為10重量%。The blending amount of the rocking agent is not particularly limited, and a preferred lower limit is 0.5% by weight, and a preferred upper limit is 20% by weight. If the blending amount of the rocking agent is less than 0.5% by weight, sufficient shakenness cannot be obtained. When the blending amount of the rocking agent exceeds 20% by weight, when the electronic component such as a semiconductor wafer is bonded, the repellent property of the adhesive for electronic parts of the present invention may be lowered. A more preferred lower limit of the blending amount of the rocking agent is 2% by weight, and a preferred upper limit is 10% by weight.

本發明之電子零件用接著劑，視須要，亦可含有溶劑。The adhesive for electronic parts of the present invention may contain a solvent as needed.

該溶劑並無特別限制，可列舉例如芳香族烴類、氯化芳香族烴類、氯化脂肪族烴類、醇類、酯類、醚類、酮類、乙二醇醚類(2－乙氧乙醇)、脂環式烴類、脂肪族烴類等。The solvent is not particularly limited, and examples thereof include aromatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, alcohols, esters, ethers, ketones, and glycol ethers (2-B). Oxyethanol), alicyclic hydrocarbons, aliphatic hydrocarbons, and the like.

本發明之電子零件用接著劑，視須要，亦可含有無機離子交換體。The adhesive for electronic parts of the present invention may contain an inorganic ion exchanger as needed.

該無機離子交換體之中，市售品可舉例如IXE系列(東亞合成公司製)等。Among the inorganic ion exchangers, commercially available products include, for example, the IXE series (manufactured by Toagosei Co., Ltd.).

該無機離子交換體之摻合量並無特別限制，較佳下限為1重量%，較佳上限為10重量%。The blending amount of the inorganic ion exchanger is not particularly limited, and a preferred lower limit is 1% by weight, and a preferred upper limit is 10% by weight.

此外，本發明之電子零件用接著劑，視須要，亦可含有其他防析出劑、咪唑矽烷偶合劑等接著性賦予劑等添加劑。Further, the adhesive for electronic parts of the present invention may contain additives such as other anti-precipitation agents and an adhesion-imparting agent such as an imidazolium coupling agent, as needed.

該防析出劑以經表面親水化處理之燻矽土較佳。The anti-precipitation agent is preferably a hydrous soil treated by surface hydrophilization.

本發明之電子零件用接著劑，在接合該電子零件與其他電子零件、或該電子零件與支持構件之溫度下，使用E型黏度計以10rpm所測得之黏度的上限為50Pa．s。若在接 合該電子零件與其他電子零件、或該電子零件與支持構件之溫度下，使用E型黏度計以10rpm所測得之黏度的上限超過50Pa．s時，則在使用本發明之電子零件用接著劑，進行電子零件彼此等之接合時，會無法充分排除間隔粒子與電子零件或支持構件間之接著劑，結果會使所要接合之電子零件間等間隙間距離大於所欲之值。在接合該電子零件與其他電子零件、或該電子零件與支持構件之溫度下，使用E型黏度計以10rpm所測得之黏度的較佳上限為20Pa．s，更佳上限為10Pa．s。The adhesive for electronic parts of the present invention has an upper limit of 50 Pa measured at 10 rpm using an E-type viscometer at a temperature at which the electronic component and other electronic components or the electronic component and the supporting member are joined. s. If it is connected At the temperature of the electronic component and other electronic components, or the electronic component and the supporting member, the upper limit of the viscosity measured by using an E-type viscometer at 10 rpm exceeds 50 Pa. In the case of using the adhesive for electronic parts of the present invention, when the electronic parts are joined to each other, the adhesive between the spacer particles and the electronic parts or the supporting member cannot be sufficiently excluded, and as a result, the electronic parts to be joined are formed. The distance between the equal gaps is greater than the desired value. The preferred upper limit of the viscosity measured at 10 rpm using an E-type viscometer is 20 Pa at the temperature at which the electronic component and other electronic components, or the electronic component and the supporting member are joined. s, the upper limit is 10Pa. s.

又，在該接合溫度使用E型黏度計所測得之10rpm之黏度的較佳下限為5Pa．s。若在該接合溫度使用E型黏度計之10rpm之黏度未達5Pa．s時，則在接合電子零件與其他電子零件、或電子零件與支持構件時，有時會產生溢出等而難以確保塗布形狀穩定性。Moreover, the preferred lower limit of the viscosity of 10 rpm measured by the E-type viscometer at the bonding temperature is 5 Pa. s. If the E-type viscometer is used at the joint temperature, the viscosity of 10 rpm is less than 5Pa. In the case of s, when electronic components and other electronic components, or electronic components and supporting members are joined, overflow or the like may occur, and it is difficult to ensure coating shape stability.

又，本發明之電子零件用接著劑，在使用E型黏度計於25℃測量黏度時，0.5rpm之黏度的較佳下限為30Pa．s，較佳上限為200 Pa．s。若使用E型黏度計以25℃、0.5rpm之條件測得的黏度未達30Pa．s時，則本發明之電子零件用接著劑有時會欠缺形狀保持性。若使用E型黏度計以25℃、0.5rpm之條件測得的黏度超過200Pa．s時，則本發明之電子零件用接著劑有時會欠缺吐出穩定性。Moreover, in the adhesive for electronic parts of the present invention, when the viscosity is measured at 25 ° C using an E-type viscometer, the preferred lower limit of the viscosity at 0.5 rpm is 30 Pa. s, the upper limit is 200 Pa. s. If the E-type viscometer is used, the viscosity measured at 25 ° C and 0.5 rpm is less than 30 Pa. In the case of s, the adhesive for electronic parts of the present invention sometimes lacks shape retention. If the E-type viscometer is used, the viscosity measured at 25 ° C and 0.5 rpm exceeds 200 Pa. In the case of s, the adhesive for electronic parts of the present invention sometimes lacks discharge stability.

此外，本發明之電子零件用接著劑，以使用E型黏度計在25℃、1rpm之條件所測得的黏度為T1，以使用E型黏度計在25℃、10rpm之條件所測得的黏度為T2時，較 佳為T1/T2之下限為2，上限為6。藉由使該T1/T2在該範圍內，可使本發明之電子零件用接著劑具有適合塗布之搖變性。Further, the adhesive for electronic parts of the present invention has a viscosity of T1 measured at 25 ° C and 1 rpm using an E-type viscometer, and a viscosity measured at 25 ° C and 10 rpm using an E-type viscometer. When it is T2, it is The lower limit of T1/T2 is 2 and the upper limit is 6. By setting the T1/T2 within this range, the adhesive for electronic parts of the present invention can have a shakeability suitable for coating.

本發明之電子零件用接著劑，可藉由例如將該硬化性化合物、硬化劑、及視須要所添加之硬化促進劑、稀釋劑、其他添加劑等以既定量摻合並加以混合後，進一步摻合間隔粒子之方法來製造。The adhesive for an electronic component of the present invention can be further blended by, for example, mixing the curable compound, the curing agent, and, if necessary, a hardening accelerator, a diluent, and other additives. Manufactured by spacer particles.

該混合之方法並無特別限制，可使用例如行星式攪拌器、行星式混合機、勻相分散機、萬用混合機、密閉式混煉機、及揉合機等方法。The method of mixing is not particularly limited, and methods such as a planetary agitator, a planetary mixer, a homogeneous phase disperser, a universal mixer, a closed kneader, and a kneading machine can be used.

使用本發明之電子零件用接著劑，將一半導體晶片積層於其他半導體晶片或支持構件之方法，可適當使用具有以下步驟之方法：(1)塗布步驟，係將本發明之電子零件用接著劑塗布於該半導體晶片或支持構件，以形成接著劑層、(2)半導體晶片積層步驟，係透過該接著劑層來積層該一半導體晶片、及(3)硬化步驟，係使該一半導體晶片與該其他半導體晶片或支持構件間之接著劑層硬化。此種半導體晶片之積層方法亦為本發明之一。A method of laminating a semiconductor wafer to another semiconductor wafer or a supporting member using the adhesive for an electronic component of the present invention, and a method having the following steps can be suitably used: (1) a coating step for using an adhesive for an electronic component of the present invention Coating the semiconductor wafer or supporting member to form an adhesive layer, (2) a semiconductor wafer lamination step, laminating the semiconductor wafer through the adhesive layer, and (3) a hardening step to cause the semiconductor wafer to The adhesive layer between the other semiconductor wafer or support member is hardened. The method of laminating such a semiconductor wafer is also one of the inventions.

本發明之半導體晶片之積層方法，視須要，亦可在(1)塗布步驟之後，進行溶劑乾燥或B階段化。The method for laminating the semiconductor wafer of the present invention may be subjected to solvent drying or B-stage after the (1) coating step, as needed.

本發明之半導體晶片之積層方法，係具有(1)塗布步驟，用以將本發明之電子零件用接著劑塗布於該半導體晶片或支持構件，以形成接著劑層。The method for laminating a semiconductor wafer of the present invention has (1) a coating step for applying an adhesive for an electronic component of the present invention to the semiconductor wafer or the supporting member to form an adhesive layer.

該(1)塗布步驟中，將本發明之電子零件用接著劑塗布 於該半導體晶片或支持構件之方法，並無特別限制，可列舉例如滴注、噴墨法、網版印刷、平版印刷及凹版印刷法等以往公知之塗布法或印刷法等。In the (1) coating step, the electronic component of the present invention is coated with an adhesive The method of the semiconductor wafer or the supporting member is not particularly limited, and examples thereof include a conventionally known coating method or printing method such as dropping, inkjet printing, screen printing, lithography, and gravure printing.

形成於該該半導體晶片或支持構件之接著劑層的厚度，只要是至少大於所要製造之半導體晶片積層體之半導體晶片的間隔者，則無特別限制，相對於所要製造之半導體晶片積層體之半導體晶片的間隙間距離，以在30倍以內較佳。若形成於該半導體晶片或支持構件之接著劑層的厚度超過30倍時，則有時會難以以所欲之間隔來製造半導體晶片積層體。形成於該該半導體晶片或支持構件之接著劑層的厚度，更佳為20倍以內。The thickness of the adhesive layer formed on the semiconductor wafer or the supporting member is not particularly limited as long as it is at least larger than the interval of the semiconductor wafer of the semiconductor wafer laminate to be fabricated, and the semiconductor is laminated with respect to the semiconductor wafer laminate to be fabricated. The distance between the gaps of the wafer is preferably within 30 times. When the thickness of the adhesive layer formed on the semiconductor wafer or the supporting member exceeds 30 times, it may be difficult to manufacture the semiconductor wafer laminate at a desired interval. The thickness of the adhesive layer formed on the semiconductor wafer or the supporting member is more preferably 20 times or less.

本發明之半導體晶片之積層方法，係具有半導體晶片積層步驟(2)，用以透過該接著劑層來積層該一半導體晶片。The method for laminating a semiconductor wafer of the present invention has a semiconductor wafer lamination step (2) for laminating the semiconductor wafer through the adhesive layer.

本半導體晶片積層步驟(2)中，藉由所要積層之該一半導體晶片，施加按壓於該接著劑層，使該接著劑層之厚度成為目標之半導體晶片積層體之半導體晶片的間隔。In the semiconductor wafer lamination step (2), the semiconductor wafer to be laminated is applied with a spacer which is pressed against the adhesive layer so that the thickness of the adhesive layer becomes the semiconductor wafer of the target semiconductor wafer laminate.

藉由經過本步驟，形成使本發明之電子零件用接著劑所含之間隔粒子之平均粒徑相對於接著劑層之厚度成為40~70%的接著劑層。By this step, an adhesive layer in which the average particle diameter of the spacer particles contained in the adhesive for electronic parts of the present invention is 40 to 70% with respect to the thickness of the adhesive layer is formed.

本發明之半導體晶片之積層方法，係具有(3)硬化步驟，用以使該一半導體晶片與該其他半導體晶片或支持構件間之接著劑層硬化。The method of laminating a semiconductor wafer of the present invention has a (3) hardening step for hardening an adhesive layer between the semiconductor wafer and the other semiconductor wafer or supporting member.

使該接著劑層硬化之方法，並無特別限制，可配合本 發明之電子零件用接著劑所含之硬化性化合物適當予以選擇，例如，該硬化性化合物，在含有該環氧樹脂時，可舉將該接著劑層加熱之方法。The method of hardening the adhesive layer is not particularly limited, and can be used in conjunction with the present invention. The curable compound contained in the adhesive for electronic parts of the invention is appropriately selected. For example, the curable compound may be a method of heating the adhesive layer when the epoxy resin is contained.

藉由此種本發明之半導體晶片之積層方法，可將2個以上之半導體晶片加以積層成多層，並藉由密封劑等加以密封以製作半導體裝置。According to the method for laminating a semiconductor wafer of the present invention, two or more semiconductor wafers can be laminated into a plurality of layers, and sealed by a sealing agent or the like to form a semiconductor device.

此種藉由本發明之半導體晶片之積層方法製作而成之半導體裝置，亦為本發明之一。Such a semiconductor device fabricated by the method of laminating a semiconductor wafer of the present invention is also one of the inventions.

根據本發明，可提供一種能將一電子零件與其他電子零件或支持構件以平行且正確之間隙間距離加以接合之電子零件用接著劑。又，亦可提供一種使用該電子零件用接著劑之半導體晶片之積層方法、以及半導體裝置。According to the present invention, an adhesive for an electronic component capable of joining an electronic component and other electronic components or supporting members in parallel and with a correct gap between the gaps can be provided. Further, a method of laminating a semiconductor wafer using the adhesive for electronic parts and a semiconductor device can be provided.

以下，雖揭示實施例以進一步詳細說明本發明，但本發明並非僅限於此等實施例。Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited thereto.

(實施例1~8、比較例1~10)(Examples 1 to 8 and Comparative Examples 1 to 10)

(1)電子零件用接著劑之調製(1) Modulation of adhesives for electronic parts

依照表1及表2之組成，將下述所示之間隔粒子以外之各材料，使用行星式攪拌機加以攪拌混合，以製作接著組成物。依照表1及表2之組成，將間隔粒子摻合於所製得之接著組成物，並進一步使用行星式攪拌機加以攪拌混合，藉此調製實施例1~8及比較例1~10之電子零件用接著劑。此外，表1及表2中各組成物之摻合量係表示重量份。According to the composition of Tables 1 and 2, each material other than the spacer particles shown below was stirred and mixed using a planetary mixer to prepare a subsequent composition. According to the composition of Tables 1 and 2, the spacer particles were blended into the obtained composition, and further stirred and mixed using a planetary mixer, thereby modulating the electronic parts of Examples 1 to 8 and Comparative Examples 1 to 10. Use an adhesive. Further, the blending amounts of the respective components in Tables 1 and 2 represent parts by weight.

(硬化性化合物)(hardening compound)

倍環戊二烯型環氧樹脂(「HP－7200HH」、Dainippon Ink and Chemicals公司製)Pentacyclopentadiene type epoxy resin ("HP-7200HH", manufactured by Dainippon Ink and Chemicals)

萘型環氧樹脂(「HP－4032D」、Dainippon Ink and Chemicals公司製、在常溫下為液狀)Naphthalene type epoxy resin ("HP-4032D", manufactured by Dainippon Ink and Chemicals, liquid at room temperature)

間苯二酚型環氧樹脂(「EX201」、NAGASE CHEMTEX公司製、在常溫下為液狀)Resorcinol type epoxy resin ("EX201", manufactured by NAGASE CHEMTEX Co., Ltd., liquid at room temperature)

低黏度環氧樹脂(「EP－4088S」、旭電化公司製、黏度為250mPa．s/25℃)Low-viscosity epoxy resin ("EP-4088S", manufactured by Asahi Kasei Co., Ltd., viscosity 250mPa.s/25°C)

(硬化物)(hardened)

酸酐(「YH－307」、Japan Epoxy Resins公司製)Anhydride ("YH-307", manufactured by Japan Epoxy Resins Co., Ltd.)

(間隔粒子)(spaced particles)

樹脂粒子1(「Micropearl SP－210」、積水化學工業公司製、平均粒徑＝10 μm、CV值＝4%)Resin particle 1 ("Micropearl SP-210", manufactured by Sekisui Chemical Co., Ltd., average particle diameter = 10 μm, CV value = 4%)

樹脂粒子2(「Micropearl SP－207」、積水化學工業公司製、平均粒徑＝7 μm、CV值＝4%)Resin particle 2 ("Micropearl SP-207", manufactured by Sekisui Chemical Co., Ltd., average particle diameter = 7 μm, CV value = 4%)

樹脂粒子3(「Micropearl SP－205」、積水化學工業公司製、平均粒徑＝5 μm、CV值＝4%)Resin particle 3 ("Micropearl SP-205", manufactured by Sekisui Chemical Co., Ltd., average particle diameter = 5 μm, CV value = 4%)

樹脂粒子4(「Micropearl SP－203」、積水化學工業公司製、平均粒徑＝3 μm、CV值＝4%)Resin particle 4 ("Micropearl SP-203", manufactured by Sekisui Chemical Co., Ltd., average particle diameter = 3 μm, CV value = 4%)

樹脂粒子5(「Micropearl SP－204」、積水化學工業公司製、平均粒徑＝4.5 μm、CV值＝4%)Resin particle 5 ("Micropearl SP-204", manufactured by Sekisui Chemical Co., Ltd., average particle diameter = 4.5 μm, CV value = 4%)

樹脂粒子6(「Micropearl SP－206」、積水化學工業公司製、平均粒徑＝6 μm、CV值＝4%)Resin particle 6 ("Micropearl SP-206", manufactured by Sekisui Chemical Co., Ltd., average particle diameter = 6 μm, CV value = 4%)

樹脂粒子7(「Micropearl SP－204」、積水化學工業公司製、平均粒徑＝3.8 μm、CV值＝4%)Resin particle 7 ("Micropearl SP-204", manufactured by Sekisui Chemical Co., Ltd., average particle diameter = 3.8 μm, CV value = 4%)

樹脂粒子8(「Micropearl SP－208」、積水化學工業公司製、平均粒徑＝8 μm、CV值＝4%)Resin particle 8 ("Micropearl SP-208", manufactured by Sekisui Chemical Co., Ltd., average particle diameter = 8 μm, CV value = 4%)

球狀氧化矽1(「HS301」、Micron公司製、平均粒徑＝2.4 μm、CV值>10%)Spherical yttrium oxide 1 ("HS301", manufactured by Micron, average particle size = 2.4 μm, CV value > 10%)

球狀氧化矽2(「HS302」、Micron公司製、平均粒徑＝6.8 μm、CV值>10%)Spherical yttrium oxide 2 ("HS302", manufactured by Micron, average particle size = 6.8 μm, CV value > 10%)

(硬化促進劑)(hardening accelerator)

咪唑化合物(「2MA－OK」、四國化成工業公司製)Imidazole compound ("2MA-OK", manufactured by Shikoku Chemical Industry Co., Ltd.)

(搖變劑)(shake agent)

燻矽土(「AEROSIL R202S」、日本AEROSIL公司製)Smoked bauxite ("AEROSIL R202S", made by AEROSIL, Japan)

(含環氧基之高分子化合物)(Polyoxy compound containing epoxy group)

含環氧基之丙烯酸樹脂(「BLEMMER CP－30」、Japan Epoxy Resins公司製)Epoxy group-containing acrylic resin ("BLEMMER CP-30", manufactured by Japan Epoxy Resins Co., Ltd.)

(橡膠改質環氧樹脂)(Rubber modified epoxy resin)

CTBN改質環氧樹脂(「EPR－4023」、旭化成工業公司製)CTBN modified epoxy resin ("EPR-4023", manufactured by Asahi Kasei Industrial Co., Ltd.)

(2)半導體晶片積層體之製作(2) Fabrication of semiconductor wafer laminates

將所製得之電子零件用接著劑填充於10mL之注射器(岩下Engineering公司製)，將精密管嘴(岩下Engineering公司製、管嘴前端直徑0.3mm)安裝於注射器前端，使用分注裝置(「SHOT MASTER 300」、武藏Engineering公司製)，以吐出壓為0.4MPa、半導體晶片與針之間隙為200 μm、 塗布量為5mg塗布於基板上。The prepared electronic component was filled in a 10 mL syringe (manufactured by Iwate Engineering Co., Ltd.) with an adhesive, and a precision nozzle (manufactured by Iwate Engineering Co., Ltd., nozzle tip diameter: 0.3 mm) was attached to the tip of the syringe, and a dispensing device was used. SHOT MASTER 300", manufactured by Musashi Engineering Co., Ltd.), the discharge pressure is 0.4 MPa, and the gap between the semiconductor wafer and the needle is 200 μm. A coating amount of 5 mg was applied to the substrate.

進行塗布之後，藉由使用黏晶機(「BESTEM－D02」、CANON MACHINERY公司製)，以25℃、表1及表2所記載之時間進行按壓，積層矽晶片(厚度為80 μm、10mm×10mm見方)。此時，使目標之間隙間距離為10 μm。之後，以150℃進行60分鐘加熱，使電子零件用接著劑硬化，藉此製得半導體晶片積層體。After coating, the wafer was pressed at 25 ° C, Table 1 and Table 2 by using a die bonder ("BESTEM-D02", manufactured by CANON MACHINERY Co., Ltd.) to laminate a germanium wafer (thickness: 80 μm, 10 mm ×) 10mm square). At this time, the distance between the gaps of the target is made 10 μm. Thereafter, the film was heated at 150 ° C for 60 minutes to cure the electronic component with an adhesive, thereby producing a semiconductor wafer laminate.

(評價)(Evaluation)

針對實施例及比較例所調製之電子零件用接著劑、及所製作之半導體晶片積層體，藉由以下方法進行評價。將結果表示於表1及表2。The adhesive for electronic parts prepared in the examples and the comparative examples and the produced semiconductor wafer laminate were evaluated by the following methods. The results are shown in Tables 1 and 2.

(黏度測量)(viscosity measurement)

針對實施例及比較例所調製之電子零件用接著劑，使用E型黏度測量裝置(產品名「VISCOMETER TV－22」，TOKI SANGYO CO.LTD公司製、使用轉子為ψ 15mm、設定溫度為25℃)，測量轉速為0.5rpm、1 rpm、及10rpm之黏度。此外，針對實施例及比較例所調製之電子零件用接著劑，以使用E型黏度測量裝置在25℃、1 rpm之條件所測量之黏度為T1，以使用E型黏度測量裝置在25℃、10 rpm之條件所測量之黏度為T2，算出T1/T2之值。For the adhesive for electronic parts prepared in the examples and the comparative examples, an E-type viscosity measuring device (product name "VISCOMETER TV-22", manufactured by TOKI SANGYO CO. LTD, using a rotor of ψ 15 mm and a set temperature of 25 ° C was used. The measured rotational speeds were 0.5 rpm, 1 rpm, and 10 rpm viscosity. Further, the adhesive for electronic parts prepared by the examples and the comparative examples was measured to have a viscosity of T1 at 25 ° C and 1 rpm using an E-type viscosity measuring device, and an E-type viscosity measuring device was used at 25 ° C, The viscosity measured under the condition of 10 rpm is T2, and the value of T1/T2 is calculated.

(2)間隙間距離之測量(2) Measurement of the distance between the gaps

在製作半導體晶片積層體時，使用雷射位移計(「LT9010M」、「KS－1100」、KEYENCE公司製)，測量積層半導體晶片時之間隙間距離，以算出間隔粒子之平均 粒徑相對於間隙間距離的比例。In the production of a semiconductor wafer laminate, a laser displacement meter ("LT9010M", "KS-1100", manufactured by KEYENCE) was used to measure the gap between the layers of the semiconductor wafer to calculate the average of the spacer particles. The ratio of the particle size to the distance between the gaps.

所測量之樣品數為各25個，以晶片中心、及晶片周邊之2個部位的平均值為間隙間距離。又，以晶片中心、及晶片周邊之間隙間距離的差為傾斜。The number of samples measured was 25 each, and the average value of the two parts of the center of the wafer and the periphery of the wafer was the distance between the gaps. Further, the difference between the distance between the center of the wafer and the gap around the wafer is inclined.

(3)半導體晶片積層體之評價(3) Evaluation of semiconductor wafer laminates

針對所製作之半導體晶片積層體，在間隙間距離為10±3 μm、傾斜在±3 μm以下時評價為「○」，在間隙間距離為10±5 μm、傾斜在±5 μm以下時評價為「△」，在間隙間距離為10±5 μm、傾斜在±5 μm以上時評價為「×」，在間隙間距離為15 μm<時評價為「××」。The semiconductor wafer laminate produced was evaluated as "○" when the distance between the gaps was 10 ± 3 μm and the inclination was ± 3 μm or less, and was evaluated when the distance between the gaps was 10 ± 5 μm and the inclination was ± 5 μm or less. "△" was evaluated as "×" when the distance between the gaps was 10 ± 5 μm, and when the inclination was ± 5 μm or more, and "× ×" when the distance between the gaps was 15 μm.

根據本發明，可提供一種能將一電子零件與其他電子零件、或一電子零件與支持構件以平行且正確之間隙間距離加以接合之電子零件用接著劑。又，亦可提供一種使用該電子零件用接著劑之半導體晶片之積層方法、以及半導體裝置。According to the present invention, an adhesive for an electronic component capable of joining an electronic component and other electronic components, or an electronic component and a supporting member in parallel and with a correct gap therebetween can be provided. Further, a method of laminating a semiconductor wafer using the adhesive for electronic parts and a semiconductor device can be provided.

Claims (4)

一種電子零件用接著劑，用以將一電子零件與其他電子零件或電子零件與支持構件，以30 μm以下之間隙間距離加以平行積層，其特徵在於：係含有硬化性化合物、硬化劑及間隔粒子之電子零件用接著劑；在接合該一電子零件與其他電子零件或電子零件與支持構件時之溫度下，使用E型黏度計以10rpm所測得的黏度為50Pa．s以下；該間隔粒子，其CV值為10%以下，其平均粒徑為該一電子零件與其他電子零件或電子零件與支持構件之間隙間距離的40~70%。An adhesive for electronic components for laminating an electronic component and other electronic components or electronic components and supporting members in parallel with a gap of 30 μm or less, characterized in that it contains a hardening compound, a hardener, and a spacer. An adhesive for electronic parts of particles; at a temperature at which the electronic component and other electronic components or electronic components and supporting members are joined, the viscosity measured at 10 rpm using an E-type viscometer is 50 Pa. s or less; the spacer particle has a CV value of 10% or less, and the average particle diameter is 40 to 70% of the distance between the gap between the electronic component and the other electronic component or the electronic component and the supporting member. 如申請專利範圍第1項之電子零件用接著劑，其中，電子零件係半導體晶片。The adhesive for electronic parts according to claim 1, wherein the electronic component is a semiconductor wafer. 一種半導體晶片之積層方法，係使用申請專利範圍第1或2項之電子零件用接著劑，將一半導體晶片積層於其他半導體晶片或支持構件，其特徵在於，具有：塗布步驟(1)，係於該其他半導體晶片或支持構件塗布該電子零件用接著劑，以形成接著劑層；半導體晶片積層步驟(2)，係透過該接著劑層積層該一半導體晶片；及硬化步驟(3)，係使該一半導體晶片與該其他半導體晶片或支持構件間之接著劑層硬化。A method for laminating a semiconductor wafer, which comprises laminating a semiconductor wafer to another semiconductor wafer or a supporting member using an adhesive for an electronic component according to claim 1 or 2, comprising: a coating step (1); Applying the adhesive for the electronic component to the other semiconductor wafer or the supporting member to form an adhesive layer; the semiconductor wafer lamination step (2), laminating the semiconductor wafer through the adhesive; and the hardening step (3) An adhesive layer between the semiconductor wafer and the other semiconductor wafer or support member is cured. 一種半導體裝置，其特徵在於： 係藉由申請專利範圍第3項之半導體晶片之積層方法製造而成。A semiconductor device characterized by: It is manufactured by the lamination method of the semiconductor wafer of claim 3 of the patent application.
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