TWI829727B - Adhesive composition, film-like adhesive, adhesive sheet, and method for manufacturing semiconductor device - Google Patents

Adhesive composition, film-like adhesive, adhesive sheet, and method for manufacturing semiconductor device Download PDF

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TWI829727B
TWI829727B TW108126244A TW108126244A TWI829727B TW I829727 B TWI829727 B TW I829727B TW 108126244 A TW108126244 A TW 108126244A TW 108126244 A TW108126244 A TW 108126244A TW I829727 B TWI829727 B TW I829727B
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adhesive
film
component
mass
epoxy resin
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TW108126244A
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TW202012580A (en
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平本祐也
夏川昌典
谷口紘平
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日商力森諾科股份有限公司
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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
    • 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
    • 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
    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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 potential barriers, e.g. a 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
    • H01L21/52—Mounting semiconductor bodies in containers
    • 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 potential barriers, e.g. a 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
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
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    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32135—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
    • H01L2224/32145—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
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    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
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    • H01L2224/484—Connecting portions
    • H01L2224/4847—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a wedge bond
    • H01L2224/48472—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a wedge bond the other connecting portion not on the bonding area also being a wedge bond, i.e. wedge-to-wedge
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    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
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  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
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Abstract

本發明揭示一種接著劑組成物，含有：環氧樹脂、酚樹脂、彈性體及填料，以環氧樹脂、酚樹脂、彈性體及填料的總量為基準，填料的含量為40質量%～68質量%，且環氧樹脂包含具有萘骨架的環氧樹脂。The invention discloses an adhesive composition, which contains: epoxy resin, phenol resin, elastomer and filler. Based on the total amount of epoxy resin, phenol resin, elastomer and filler, the content of the filler is 40% by mass to 68% by mass. % by mass, and the epoxy resin contains an epoxy resin having a naphthalene skeleton.

Description

接著劑組成物、膜狀接著劑、接著片及半導體裝置的製造方法Adhesive composition, film-like adhesive, adhesive sheet, and method for manufacturing semiconductor device

本發明是有關於一種接著劑組成物、膜狀接著劑、接著片及半導體裝置的製造方法。The present invention relates to an adhesive composition, a film adhesive, an adhesive sheet, and a method for manufacturing a semiconductor device.

先前，於半導體元件與半導體元件搭載用支撐構件的接合中，主要使用銀糊。然而，隨著近年來半導體元件的大型化、半導體封裝的小型化及高性能化，對於所使用的半導體元件搭載用支撐構件亦開始要求小型化及細密化。對於此種要求，由於因浸潤擴散性、滲出、半導體元件的傾斜等所引起的打線接合（wire bonding）時的不良情況、厚度控制的困難性、孔隙產生等，銀糊無法充分應對。因此，近年來，代替銀糊而開始使用包括膜狀接著劑的接著片（例如參照專利文獻1、專利文獻2）。於單片貼附方式、晶圓背面貼附方式等半導體裝置的製造方法中使用此種接著片。Previously, silver paste was mainly used for bonding semiconductor elements and semiconductor element mounting support members. However, in recent years, as semiconductor elements have become larger in size and semiconductor packages have become smaller and higher in performance, there has been a demand for smaller and more compact support members used for mounting semiconductor elements. Silver paste cannot fully respond to such requirements due to defects in wire bonding caused by wetting diffusion, bleed-out, tilt of semiconductor elements, etc., difficulty in thickness control, and the generation of voids. Therefore, in recent years, adhesive sheets including film-like adhesives have begun to be used instead of silver paste (see, for example, Patent Document 1 and Patent Document 2). This adhesive sheet is used in manufacturing methods of semiconductor devices such as single chip attachment method and wafer backside attachment method.

於藉由單片貼附方式來製造半導體裝置的情況下，首先，藉由切削（cutting）或衝壓（punching）而將捲筒狀的接著片切成單片後，將膜狀接著劑貼合於半導體元件搭載用支撐構件。其後，將藉由切割（dicing）步驟而單片化的半導體元件接合於帶有膜狀接著劑的半導體元件搭載用支撐構件。之後，經過打線接合、密封等組裝步驟，製造半導體裝置（例如參照專利文獻3）。但是，於單片貼附方式的情況下，需要用於切出接著片並接著於半導體元件搭載用支撐構件的專用的組裝裝置，與使用銀糊的方法相比，存在製造成本變高的問題。When manufacturing a semiconductor device by the single-piece bonding method, first, the roll-shaped adhesive sheet is cut into individual pieces by cutting or punching, and then the film-like adhesive is bonded. Supporting member for mounting semiconductor elements. Thereafter, the semiconductor elements singulated by a dicing step are bonded to the semiconductor element mounting supporting member with a film-like adhesive. Thereafter, a semiconductor device is manufactured through assembly steps such as wire bonding and sealing (for example, see Patent Document 3). However, in the case of the single-chip bonding method, a dedicated assembly device is required for cutting out the bonding sheet and attaching it to the supporting member for mounting the semiconductor element. Compared with the method using silver paste, there is a problem that the manufacturing cost becomes higher. .

另一方面，於藉由晶圓背面貼附方式來製造半導體裝置的情況下，首先，於半導體晶圓的背面貼附膜狀接著劑，進而於膜狀接著劑的另一面貼合切割片。其後，藉由切割，於貼合有膜狀接著劑的狀態下將半導體晶圓單片化，製作半導體元件。繼而，拾取帶有膜狀接著劑的半導體元件，接合於半導體元件搭載用支撐構件。之後，經過打線接合、密封等組裝步驟，製造半導體裝置（例如參照專利文獻4）。該晶圓背面貼附方式與單片貼附方式不同，不需要專用的組裝裝置，可直接使用現有的銀糊用的組裝裝置，或附加熱盤等對裝置進行一部分改良後使用。因此，於使用接著片的半導體裝置的製造方法中，晶圓背面貼附方式有可相比較而言抑制製造成本的傾向。On the other hand, when manufacturing a semiconductor device by the wafer backside bonding method, first, a film-like adhesive is bonded to the backside of the semiconductor wafer, and then a dicing sheet is bonded to the other side of the film-like adhesive. Thereafter, by dicing, the semiconductor wafer is diced into individual pieces with the film-like adhesive bonded thereto, and a semiconductor element is produced. Next, the semiconductor element with the film-like adhesive is picked up and bonded to the semiconductor element mounting support member. Thereafter, a semiconductor device is manufactured through assembly steps such as wire bonding and sealing (for example, see Patent Document 4). This wafer backside attachment method is different from the single-chip attachment method. It does not require a dedicated assembly device. The existing assembly device for silver paste can be directly used, or the device can be partially modified by adding a hot plate. Therefore, in the manufacturing method of a semiconductor device using an adhesive sheet, the wafer backside attaching method tends to reduce the manufacturing cost comparatively.

於晶圓背面貼附方式中，就組裝步驟的簡略化的觀點而言，有時使用如下接著片，其為於膜狀接著劑的其中一面貼合（積層）切割片的接著片，即，兼具作為切割片的功能及作為黏晶（die bond）膜的功能的接著片（以下有時稱為「切割･黏晶一體型接著片」）。若使用此種切割･黏晶一體型接著片，則可簡化切割片的貼合，可降低晶圓破裂的風險。切割片的軟化溫度通常為100℃以下。因此，對於切割･黏晶一體型接著片而言，考慮到切割片的軟化溫度或半導體晶圓的翹曲，必須能夠在低於100℃的溫度下貼附於半導體晶圓，特別是就抑制半導體晶圓的翹曲的觀點而言，要求能夠在40℃～80℃下貼附於半導體晶圓。In the wafer backside attaching method, from the viewpoint of simplifying the assembly steps, an adhesive sheet in which a dicing sheet is bonded (laminated) to one side of a film-like adhesive may be used, that is, An adhesive sheet that has both functions as a dicing sheet and a die bond film (hereinafter sometimes referred to as "dicing and die bonding integrated adhesive sheet"). If this type of integrated dicing and die-bonding bonding piece is used, the bonding of the dicing piece can be simplified and the risk of wafer breakage can be reduced. The softening temperature of cutting blades is usually below 100°C. Therefore, the dicing and die-bonding integrated bonding sheet must be able to be attached to the semiconductor wafer at a temperature lower than 100°C, taking into account the softening temperature of the dicing sheet or the warpage of the semiconductor wafer. In particular, it is necessary to suppress From the viewpoint of warpage of the semiconductor wafer, it is required to be able to adhere to the semiconductor wafer at 40°C to 80°C.

但，於對半導體元件實施打線接合連接時，有時會於半導體元件與半導體元件搭載用支撐構件之間產生偏移或剝離。推測其是由於如下情況而產生：在通常的接合溫度即175℃附近，已將半導體元件與半導體元件搭載用支撐構件接著的膜狀接著劑變軟而發生變形。隨著半導體元件的小面積化，該現象會成為更大的問題。因此，對於切割･黏晶一體型接著片的硬化後的膜狀接著劑，要求作為打線接合特性，高溫儲存彈性係數充分高（例如，175℃下的儲存彈性係數為100 MPa以上）及玻璃轉移溫度充分高（例如，玻璃轉移溫度為190℃以上）。However, when a semiconductor element is connected by wire bonding, misalignment or peeling may occur between the semiconductor element and the semiconductor element mounting support member. It is estimated that this occurs because the film-like adhesive that has joined the semiconductor element and the semiconductor element mounting support member becomes soft and deforms at around 175°C, which is a normal bonding temperature. As semiconductor devices become smaller in area, this phenomenon will become a bigger problem. Therefore, hardened film adhesives for cutting and die-bonding integrated bonding sheets are required to have a sufficiently high high-temperature storage elastic coefficient (for example, a storage elastic coefficient of 100 MPa or more at 175°C) and glass transfer as wire bonding properties. The temperature is sufficiently high (for example, the glass transition temperature is above 190°C).

迄今為止，為了滿足低溫下對半導體晶圓的貼附特性（低溫貼附性）及打線接合特性，提出有將玻璃轉移溫度（Tg）較低的熱塑性樹脂及熱硬化性樹脂組合而成的接著劑組成物（例如參照專利文獻5）。 [現有技術文獻] [專利文獻]Until now, in order to satisfy the adhesion characteristics (low-temperature adhesion) and wire bonding characteristics of semiconductor wafers at low temperatures, adhesives that combine thermoplastic resins with low glass transition temperatures (Tg) and thermosetting resins have been proposed. agent composition (for example, refer to Patent Document 5). [Prior art documents] [Patent Document]

專利文獻1：日本專利特開平3-192178號公報 專利文獻2：日本專利特開平4-234472號公報 專利文獻3：日本專利特開平9-017810號公報 專利文獻4：日本專利特開平4-196246號公報 專利文獻5：日本專利特開2005-247953號公報Patent Document 1: Japanese Patent Application Publication No. 3-192178 Patent Document 2: Japanese Patent Application Publication No. 4-234472 Patent document 3: Japanese Patent Application Publication No. 9-017810 Patent Document 4: Japanese Patent Application Laid-Open No. 4-196246 Patent Document 5: Japanese Patent Application Publication No. 2005-247953

[發明所欲解決之課題][Problem to be solved by the invention]

但是，隨著半導體元件的小面積化，打線接合時所要求的膜狀接著劑的高溫儲存彈性率變得更高，對於膜狀接著劑要求進一步改善特性。However, as semiconductor devices become smaller in area, the high-temperature storage elastic modulus of film-like adhesives required for wire bonding becomes higher, and film-like adhesives are required to further improve their characteristics.

因此，本發明的主要目的在於提供一種形成膜狀接著劑時的低溫貼附性優異，並且能夠形成具有充分的高溫儲存彈性係數、且具有充分的玻璃轉移溫度的硬化物的接著劑組成物。 [解決課題之手段]Therefore, a main object of the present invention is to provide an adhesive composition that is excellent in low-temperature adhesion when forming a film-like adhesive and can form a cured product having a sufficient high-temperature storage elastic coefficient and a sufficient glass transition temperature. [Means to solve the problem]

本發明的一方面提供一種接著劑組成物，含有：環氧樹脂、酚樹脂、彈性體及填料，以環氧樹脂、酚樹脂、彈性體及填料的總量為基準，填料的含量為40質量%～68質量%，且環氧樹脂包含具有萘骨架的環氧樹脂。根據此種接著劑組成物，形成膜狀接著劑時的低溫貼附性優異，並且能夠形成具有充分的高溫儲存彈性係數、且具有充分的玻璃轉移溫度的硬化物。One aspect of the present invention provides an adhesive composition, which contains: epoxy resin, phenol resin, elastomer and filler. Based on the total amount of epoxy resin, phenol resin, elastomer and filler, the content of the filler is 40% by mass. % to 68% by mass, and the epoxy resin contains an epoxy resin having a naphthalene skeleton. According to this adhesive composition, it is excellent in low-temperature adhesion when forming a film-like adhesive, and can form a cured product having a sufficient high-temperature storage elastic coefficient and a sufficient glass transition temperature.

具有萘骨架的環氧樹脂可為具有四官能以上的環氧基的環氧樹脂。以環氧樹脂及酚樹脂的總量為基準，具有萘骨架的環氧樹脂的含量可為14質量%～30質量%。具有萘骨架的環氧樹脂亦可包含由下述式（X）所表示的環氧樹脂。The epoxy resin having a naphthalene skeleton may be an epoxy resin having four or more functional epoxy groups. Based on the total amount of epoxy resin and phenol resin, the content of the epoxy resin having a naphthalene skeleton can be 14% by mass to 30% by mass. The epoxy resin having a naphthalene skeleton may include an epoxy resin represented by the following formula (X).

[化1] [Chemical 1]

本發明的一方面的接著劑組成物可於將第一半導體元件經由第一導線而以打線接合的方式連接於基板上，並且於第一半導體元件上壓接第二半導體元件而成的半導體裝置中，用來壓接第二半導體元件並且埋入第一導線的至少一部分。The adhesive composition according to one aspect of the present invention can be used in a semiconductor device in which a first semiconductor element is connected to a substrate by wire bonding via a first wire, and a second semiconductor element is press-bonded to the first semiconductor element. , used to press the second semiconductor component and bury at least a part of the first conductor.

進而，本發明可為有關於一種如下組成物的作為接著劑的應用（使用）或用來製造接著劑的應用（使用），所述組成物含有：環氧樹脂、酚樹脂、彈性體及填料，以環氧樹脂、酚樹脂、彈性體及填料的總量為基準，填料的含量為40質量%～68質量%，且環氧樹脂包含具有萘骨架的環氧樹脂，於所述應用（使用）中，所述組成物於將第一半導體元件經由第一導線而以打線接合的方式連接於基板上，並且於第一半導體元件上壓接第二半導體元件而成的半導體裝置中，用來壓接第二半導體元件並且埋入第一導線的至少一部分。Furthermore, the present invention may relate to the application (use) of a composition containing: epoxy resin, phenol resin, elastomer and filler as an adhesive or for manufacturing an adhesive. , based on the total amount of epoxy resin, phenol resin, elastomer and filler, the filler content is 40 mass% to 68 mass%, and the epoxy resin includes an epoxy resin with a naphthalene skeleton. In the application (use ), the composition is used in a semiconductor device in which a first semiconductor element is connected to a substrate by wire bonding via a first wire, and a second semiconductor element is crimped on the first semiconductor element. The second semiconductor element is crimped and at least a portion of the first conductor is buried.

本發明的另一方面提供一種膜狀接著劑，其是將所述接著劑組成物形成為膜狀而成。Another aspect of the present invention provides a film-like adhesive formed by forming the adhesive composition into a film shape.

本發明的又一方面提供一種接著片，包括：基材、及設置於基材上的所述膜狀接著劑。Another aspect of the present invention provides an adhesive sheet, including: a base material, and the film-like adhesive disposed on the base material.

基材可為切割帶。有時將基材為切割帶的接著片稱為「切割･黏晶一體型接著片」。The substrate can be cutting tape. The adhesive sheet whose base material is a dicing tape is sometimes called a "dicing and bonding integrated adhesive sheet".

本發明的又一方面提供一種半導體裝置的製造方法，包括：打線接合步驟，於基板上經由第一導線而電性連接第一半導體元件；層壓步驟，於第二半導體元件的單面貼附所述膜狀接著劑；以及黏晶步驟，經由膜狀接著劑而壓接貼附有膜狀接著劑的第二半導體元件，藉此將第一導線的至少一部分埋入膜狀接著劑中。Another aspect of the present invention provides a method for manufacturing a semiconductor device, including: a wire bonding step of electrically connecting a first semiconductor element on a substrate through a first wire; a lamination step of attaching a second semiconductor element to one side of the substrate. the film-like adhesive; and the die-bonding step, which is to press-bond the second semiconductor element to which the film-like adhesive is attached through the film-like adhesive, thereby burying at least part of the first conductor in the film-like adhesive.

再者，半導體裝置可為藉由將第一半導體元件經由第一導線而以打線接合的方式連接於半導體基板上，並且於第一半導體元件上，經由膜狀接著劑而壓接第二半導體元件，從而將第一導線的至少一部分埋入膜狀接著劑中而成的導線埋入型的半導體裝置；亦可為將第一導線及第一半導體元件埋入膜狀接著劑中而成的半導體元件（半導體晶片）埋入型的半導體裝置。 [發明的效果]Furthermore, the semiconductor device may be configured by connecting the first semiconductor element to the semiconductor substrate by wire bonding through the first wire, and pressing the second semiconductor element on the first semiconductor element through the film adhesive. , a wire-embedded semiconductor device in which at least part of the first wire is buried in the film-like adhesive; it may also be a semiconductor device in which the first wire and the first semiconductor element are buried in the film-like adhesive A semiconductor device with embedded elements (semiconductor wafer). [Effects of the invention]

根據本發明，可提供一種形成膜狀接著劑時的低溫貼附性優異，並且能夠形成具有充分的高溫儲存彈性係數、且具有充分的玻璃轉移溫度的硬化物的接著劑組成物。將該接著劑組成物形成為膜狀而成的膜狀接著劑可有效用作作為半導體元件（半導體晶片）埋入型膜狀接著劑的晶片上膜（Film Over Die，FOD）或作為導線埋入型膜狀接著劑的導線上膜（Film Over Wire，FOW）。另外，根據本發明，可提供使用此種膜狀接著劑的接著片及半導體裝置的製造方法。According to the present invention, it is possible to provide an adhesive composition that is excellent in low-temperature adhesion when forming a film-like adhesive and can form a cured product having a sufficient high-temperature storage elastic modulus and a sufficient glass transition temperature. The film adhesive formed by forming this adhesive composition into a film can be effectively used as a film over die (FOD) film adhesive for embedding semiconductor elements (semiconductor wafers) or as a lead embedding film. Film Over Wire (FOW) with molded film adhesive. Furthermore, according to the present invention, it is possible to provide an adhesive sheet using such a film-like adhesive and a method for manufacturing a semiconductor device.

以下，適當參照圖式來對本發明的實施形態進行說明。但，本發明並不限定於以下的實施形態。Hereinafter, embodiments of the present invention will be described with appropriate reference to the drawings. However, the present invention is not limited to the following embodiments.

本說明書中，(甲基)丙烯酸是指丙烯酸或與其對應的甲基丙烯酸。關於(甲基)丙烯醯基等其他的類似表述亦同樣。In this specification, (meth)acrylic acid refers to acrylic acid or its corresponding methacrylic acid. The same applies to other similar expressions such as (meth)acrylyl group.

[接著劑組成物] 一實施形態的接著劑組成物含有：（A）環氧樹脂、（B）酚樹脂、（C）彈性體、及（D）填料。接著劑組成物為熱硬化性，經過半硬化（B階段）狀態且於硬化處理後可成為完全硬化物（C階段）狀態。[Adhesive composition] The adhesive composition of one embodiment contains: (A) epoxy resin, (B) phenol resin, (C) elastomer, and (D) filler. The adhesive composition is thermosetting and can pass through a semi-hardened (B-stage) state and become a fully cured (C-stage) state after hardening treatment.

＜（A）成分：環氧樹脂＞ （A）成分包含（A-1）具有萘骨架的環氧樹脂。＜(A) Ingredient: Epoxy resin＞ The component (A) contains (A-1) an epoxy resin having a naphthalene skeleton.

（A-1）成分只要為具有萘骨架者則可無特別限制地使用。（A-1）成分可單獨使用一種或者將兩種以上組合使用。（A）成分藉由包含（A-1）成分，接著劑組成物的硬化物可成為具有充分的高溫儲存彈性係數、且具有充分的玻璃轉移溫度者。（A-1）成分可為具有四官能以上的環氧基的環氧樹脂。(A-1) Component can be used without particular restriction as long as it has a naphthalene skeleton. (A-1) The component can be used individually by 1 type or in combination of 2 or more types. (A) Component By including the component (A-1), the cured product of the adhesive composition can have a sufficient high-temperature storage elastic coefficient and a sufficient glass transition temperature. The component (A-1) may be an epoxy resin having four or more functional epoxy groups.

作為（A-1）成分的市售品，例如可列舉：「HP-4700」、「HP-4710」、「HP-4770」（商品名，均為迪愛生（DIC）股份有限公司製造）；「NC-7000-L」、「NC-7300-L」（商品名，均為日本化藥股份有限公司製造）等。Examples of commercially available products as component (A-1) include: "HP-4700", "HP-4710", and "HP-4770" (trade names, all manufactured by DIC Co., Ltd.); "NC-7000-L", "NC-7300-L" (trade names, both manufactured by Nippon Kayaku Co., Ltd.), etc.

（A-1）成分例如可包含由下述式（X）所表示的環氧樹脂。The component (A-1) may include, for example, an epoxy resin represented by the following formula (X).

[化2] [Chemicalization 2]

就有可獲得具有更充分的高溫儲存彈性係數、且具有更充分的玻璃轉移溫度的接著劑組成物的硬化物的傾向而言，（A-1）成分的軟化點可為30℃以上。（A-1）成分的軟化點亦可為40℃以上、80℃以上、或90℃以上，且可為120℃以下、110℃以下、或100℃以下。The softening point of the component (A-1) may be 30° C. or higher in order to obtain a cured product of the adhesive composition that has a more sufficient high-temperature storage elasticity coefficient and a more sufficient glass transition temperature. The softening point of the component (A-1) may be 40°C or higher, 80°C or higher, or 90°C or higher, and may be 120°C or lower, 110°C or lower, or 100°C or lower.

（A-1）成分的環氧當量並無特別限制，可為10 g/eq～600 g/eq、100 g/eq～500 g/eq、或120 g/eq～450 g/eq。若（A-1）成分的環氧當量為此種範圍，則有可獲得更良好的反應性及流動性的傾向。The epoxy equivalent of the component (A-1) is not particularly limited, and may be 10 g/eq to 600 g/eq, 100 g/eq to 500 g/eq, or 120 g/eq to 450 g/eq. If the epoxy equivalent of the component (A-1) is within this range, better reactivity and fluidity tend to be obtained.

以（A）成分的總量為基準，（A-1）成分的含量可為20質量%～80質量%、30質量%～70質量%、或30質量%～60質量%。Based on the total amount of component (A), the content of component (A-1) may be 20 mass% to 80 mass%, 30 mass% to 70 mass%, or 30 mass% to 60 mass%.

就形成膜狀接著劑時的低溫貼附性更優異，接著劑組成物的硬化物中有可獲得更充分的高溫儲存彈性係數的傾向而言，以（A）成分及（B）成分的總量為基準，（A-1）成分的含量可為14質量%～30質量%。以（A）成分及（B）成分的總量為基準，（A-1）成分的含量亦可為15質量%以上或18質量%以上，且可為25質量%以下或22質量%以下。Since the low-temperature adhesion when forming a film-like adhesive is more excellent and the cured product of the adhesive composition tends to obtain a more sufficient high-temperature storage elastic coefficient, the total of component (A) and component (B) Based on the amount, the content of component (A-1) may be 14% by mass to 30% by mass. Based on the total amount of component (A) and component (B), the content of component (A-1) may be 15 mass% or more or 18 mass% or more, and may be 25 mass% or less or 22 mass% or less.

除（A-1）成分以外，（A）成分亦可包含（A-2）不具有萘骨架的環氧樹脂。作為（A-2）成分，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S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、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂、二苯乙烯型環氧樹脂、含三嗪骨架的環氧樹脂、含芴骨架的環氧樹脂、三苯酚甲烷型環氧樹脂、聯苯型環氧樹脂、伸二甲苯基型環氧樹脂、苯基芳烷基型環氧樹脂、聯苯芳烷基型環氧樹脂、多官能苯酚類、蒽等多環芳香族類（其中將萘除外）的二縮水甘油醚化合物等。該些可單獨使用一種或者將兩種以上組合使用。（A-2）成分可為雙酚型環氧樹脂。In addition to the component (A-1), the component (A) may also contain (A-2) an epoxy resin that does not have a naphthalene skeleton. Examples of the component (A-2) include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, phenol novolac-type epoxy resin, and cresol novolak-type epoxy resin. Oxygen resin, bisphenol A novolak type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, trisphenol Methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, phenyl aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, multifunctional phenols, anthracene and other polycyclic rings Aromatic diglycidyl ether compounds (except naphthalene), etc. These can be used individually by 1 type or in combination of 2 or more types. (A-2) The component may be bisphenol type epoxy resin.

（A-2）成分的環氧當量並無特別限制，可為90 g/eq～600 g/eq、100 g/eq～500 g/eq、或120 g/eq～450 g/eq。若（A-2）成分的環氧當量為此種範圍，則有可獲得更良好的反應性及流動性的傾向。The epoxy equivalent of the component (A-2) is not particularly limited and can be 90 g/eq to 600 g/eq, 100 g/eq to 500 g/eq, or 120 g/eq to 450 g/eq. If the epoxy equivalent of the component (A-2) is within this range, better reactivity and fluidity tend to be obtained.

以（A）成分的總量為基準，（A-2）成分的含量可為80質量%～20質量%、70質量%～30質量%、或70質量%～40質量%。Based on the total amount of component (A), the content of component (A-2) may be 80% to 20% by mass, 70% to 30% by mass, or 70% to 40% by mass.

以（A）成分、（B）成分、（C）成分及（D）成分的總量為基準，（A）成分的含量可為10質量%～50質量%。以（A）成分、（B）成分、（C）成分及（D）成分的總量為基準，（A）成分的含量亦可為12質量%以上、15質量%以上、或18質量%以上，且可為40質量%以下、30質量%以下、或25質量%以下。Based on the total amount of component (A), component (B), component (C) and component (D), the content of component (A) may be 10% by mass to 50% by mass. Based on the total amount of component (A), (B), (C) and (D), the content of component (A) may be 12 mass% or more, 15 mass% or more, or 18 mass% or more , and may be 40 mass% or less, 30 mass% or less, or 25 mass% or less.

＜（B）成分：酚樹脂＞ （B）成分只要為分子內具有酚性羥基者則可並無特別限制地使用。作為（B）成分，例如可列舉：使苯酚、甲酚、間苯二酚（resorcin）、鄰苯二酚、雙酚A、雙酚F、苯基苯酚、胺基苯酚等酚類及/或α-萘酚、β-萘酚、二羥基萘等萘酚類與甲醛等具有醛基的化合物於酸性觸媒下縮合或共縮合而獲得的酚醛清漆型酚樹脂；由烯丙基化雙酚A、烯丙基化雙酚F、烯丙基化萘二醇、苯酚酚醛清漆、苯酚等酚類及/或萘酚類與二甲氧基對二甲苯或雙(甲氧基甲基)聯苯所合成的苯酚芳烷基樹脂、萘酚芳烷基樹脂、聯苯芳烷基型酚樹脂、苯基芳烷基型酚樹脂等。該些可單獨使用一種或者將兩種以上組合使用。（B）成分可為酚醛清漆型酚樹脂。＜(B) Component: Phenol resin＞ (B) Component can be used without particular restriction as long as it has a phenolic hydroxyl group in the molecule. Examples of the component (B) include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and/or Novolak-type phenolic resin obtained by condensation or co-condensation of naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde and other compounds with aldehyde groups under an acidic catalyst; composed of allylated bisphenols A. Allylated bisphenol F, allylated naphthalenediol, phenol novolac, phenols and/or naphthols such as phenol and dimethoxy-p-xylene or bis(methoxymethyl) Phenol aralkyl resin, naphthol aralkyl resin, biphenyl aralkyl phenol resin, phenyl aralkyl phenol resin, etc. synthesized from benzene. These can be used individually by 1 type or in combination of 2 or more types. (B) The component may be a novolak type phenol resin.

作為（B）成分的市售品，例如可列舉：樂吉拓（Resitop）系列（群榮化學工業股份有限公司製造）；芬萊特（Phenolite）KA系列、TD系列（DIC股份有限公司製造）；米萊斯（Mirex）XLC系列、XL系列（三井化學股份有限公司製造）；HE系列（空氣水（AIR WATER）股份有限公司製造）等。Examples of commercially available products as component (B) include: Resitop series (manufactured by Qunyong Chemical Industry Co., Ltd.); Phenolite KA series and TD series (manufactured by DIC Co., Ltd.); Mirex XLC series, XL series (manufactured by Mitsui Chemicals Co., Ltd.); HE series (manufactured by AIR WATER Co., Ltd.), etc.

（B）成分的羥基當量並無特別限制，可為80 g/eq～400 g/eq、90 g/eq～350 g/eq、或100 g/eq～300 g/eq。若（B）成分的羥基當量為此種範圍，則有可獲得更良好的反應性及流動性的傾向。The hydroxyl equivalent of component (B) is not particularly limited, but may be 80 g/eq to 400 g/eq, 90 g/eq to 350 g/eq, or 100 g/eq to 300 g/eq. If the hydroxyl equivalent of component (B) is within this range, better reactivity and fluidity tend to be obtained.

就硬化性的觀點而言，（A）成分的環氧當量與（B）成分的羥基當量的比（（A）成分的環氧當量/（B）成分的羥基當量）可為0.30/0.70～0.70/0.30、0.35/0.65～0.65/0.35、0.40/0.60～0.60/0.40、或0.45/0.55～0.55/0.45。若該當量比為0.30/0.70以上，則有可獲得更充分的硬化性的傾向。若該當量比為0.70/0.30以下，則可防止黏度變得過高，可獲得更充分的流動性。From the viewpoint of curability, the ratio of the epoxy equivalent of component (A) to the hydroxyl equivalent of component (B) (epoxy equivalent of component (A)/hydroxyl equivalent of component (B)) can be 0.30/0.70 to 0.70/0.30, 0.35/0.65～0.65/0.35, 0.40/0.60～0.60/0.40, or 0.45/0.55～0.55/0.45. If the equivalent ratio is 0.30/0.70 or more, more sufficient hardenability tends to be obtained. If the equivalent ratio is 0.70/0.30 or less, the viscosity can be prevented from becoming too high and sufficient fluidity can be obtained.

以（A）成分、（B）成分、（C）成分及（D）成分的總量為基準，（B）成分的含量可為5質量%～30質量%。以（A）成分、（B）成分、（C）成分及（D）成分的總量為基準，（B）成分的含量亦可為8質量%以上、10質量%以上、或12質量%以上，且可為25質量%以下、20質量%以下、或18質量%以下。Based on the total amount of component (A), component (B), component (C) and component (D), the content of component (B) may be 5% by mass to 30% by mass. Based on the total amount of component (A), (B), (C) and (D), the content of component (B) may be 8 mass% or more, 10 mass% or more, or 12 mass% or more , and may be 25 mass% or less, 20 mass% or less, or 18 mass% or less.

＜（C）成分：彈性體＞ 作為（C）成分，例如可列舉：聚醯亞胺樹脂、丙烯酸樹脂、胺基甲酸酯樹脂、聚苯醚樹脂、聚醚醯亞胺樹脂、苯氧基樹脂、改質聚苯醚樹脂等具有交聯性官能基者。該些中，（C）成分可為丙烯酸樹脂。此處，所謂丙烯酸樹脂，是指包含源自(甲基)丙烯酸酯的結構單元的聚合物。丙烯酸樹脂可為包含源自具有環氧基、醇性或酚性羥基、羧基等交聯性官能基的(甲基)丙烯酸酯的結構單元作為結構單元的聚合物。另外，丙烯酸樹脂亦可為(甲基)丙烯酸酯與丙烯腈的共聚物等丙烯酸橡膠。丙烯酸樹脂可單獨使用一種或者將兩種以上組合使用。＜(C) Component: Elastomer＞ Examples of the component (C) include polyimide resin, acrylic resin, urethane resin, polyphenylene ether resin, polyetherimide resin, phenoxy resin, modified polyphenylene ether resin, etc. Those with cross-linking functional groups. Among these, (C) component may be an acrylic resin. Here, the acrylic resin refers to a polymer containing a structural unit derived from (meth)acrylate. The acrylic resin may be a polymer containing as a structural unit a structural unit derived from a (meth)acrylate having a crosslinkable functional group such as an epoxy group, an alcoholic or phenolic hydroxyl group, or a carboxyl group. In addition, the acrylic resin may be an acrylic rubber such as a copolymer of (meth)acrylate and acrylonitrile. Acrylic resin can be used individually by 1 type or in combination of 2 or more types.

作為丙烯酸樹脂的市售品，例如可列舉：「SG-70L」、「SG-708-6」、「WS-023 EK30」、「SG-280 EK23」、「HTR-860P-3」、「HTR-860P-3CSP」、「HTR-860P-3CSP-3DB」（商品名，均為長瀨化成（Nagase ChemteX）股份有限公司製造）。Examples of commercially available acrylic resins include "SG-70L", "SG-708-6", "WS-023 EK30", "SG-280 EK23", "HTR-860P-3", and "HTR -860P-3CSP", "HTR-860P-3CSP-3DB" (trade names, both manufactured by Nagase ChemteX Co., Ltd.).

（C）成分的玻璃轉移溫度（Tg）可為-50℃～50℃或-30℃～20℃。若（C）成分的Tg為-50℃以上，則形成膜狀接著劑後的黏性降低，有操作性進一步提升的傾向。若（C）成分的Tg為50℃以下，則有可更充分地確保接著劑組成物的流動性的傾向。此處，（C）成分的玻璃轉移溫度（Tg）是指使用示差掃描熱量計（Differential Scanning Calorimeter，DSC）（例如理學（Rigaku）股份有限公司製造的「Thermo Plus 2」）所測定出的值。(C) The glass transition temperature (Tg) of the component may be -50°C to 50°C or -30°C to 20°C. If the Tg of component (C) is -50°C or higher, the viscosity of the film-like adhesive after formation is reduced, and the workability tends to be further improved. If the Tg of the component (C) is 50° C. or less, the fluidity of the adhesive composition tends to be more fully ensured. Here, the glass transition temperature (Tg) of component (C) refers to a value measured using a differential scanning calorimeter (DSC) (for example, "Thermo Plus 2" manufactured by Rigaku Co., Ltd.) .

（C）成分的重量平均分子量（Mw）可為5萬～120萬、10萬～120萬、或30萬～90萬。若（C）成分的Mw為5萬以上，則有成膜性更優異的傾向。若（C）成分的Mw為120萬以下，則有流動性更優異的傾向。再者，Mw是藉由凝膠滲透層析法（Gel Permeation Chromatography，GPC）進行測定，並使用基於標準聚苯乙烯的校準曲線進行換算而得的值。(C) The weight average molecular weight (Mw) of the component may be 50,000 to 1.2 million, 100,000 to 1.2 million, or 300,000 to 900,000. If the Mw of the component (C) is 50,000 or more, film-forming properties tend to be more excellent. If the Mw of component (C) is 1.2 million or less, the fluidity tends to be more excellent. In addition, Mw is a value measured by gel permeation chromatography (GPC) and converted using a calibration curve based on standard polystyrene.

（C）成分的Mw的測定裝置、測定條件等如下。 泵：L-6000（日立製作所股份有限公司製造） 管柱：將凝膠包（Gelpack）GL-R440（日立化成股份有限公司製造）、凝膠包（Gelpack）GL-R450（日立化成股份有限公司製造）、及凝膠包GL-R400M（日立化成股份有限公司製造）（各10.7 mm（直徑）×300 mm）按該順序連結而成的管柱 溶離液：四氫呋喃（tetrahydrofuran，THF） 樣品：使試樣120 mg溶解於5 mL的THF中而成的溶液 流速：1.75 mL/分鐘(C) The measuring device, measurement conditions, etc. of the Mw of the component are as follows. Pump: L-6000 (manufactured by Hitachi Manufacturing Co., Ltd.) Column: Combine gel pack GL-R440 (manufactured by Hitachi Chemical Co., Ltd.), gel pack GL-R450 (manufactured by Hitachi Chemical Co., Ltd.), and gel pack GL-R400M (manufactured by Hitachi Chemical Co., Ltd.). Co., Ltd.) (each 10.7 mm (diameter) × 300 mm) pipe strings connected in this order Eluent: tetrahydrofuran (THF) Sample: A solution in which 120 mg of the sample was dissolved in 5 mL of THF. Flow rate: 1.75 mL/min

以（A）成分、（B）成分、（C）成分及（D）成分的總量為基準，（C）成分的含量可為5質量%～20質量%。以（A）成分、（B）成分、（C）成分及（D）成分的總量為基準，（C）成分的含量亦可為8質量%以上、10質量%以上、或12質量%以上，且可為19質量%以下、18質量%以下、或17質量%以下。若（C）成分的含量為5質量%以上，則有形成膜狀接著劑時的低溫貼附性更優異的傾向。若（C）成分的含量為20質量%以下，則接著劑組成物的硬化物中有可獲得更充分的高溫儲存彈性係數的傾向。Based on the total amount of component (A), component (B), component (C) and component (D), the content of component (C) may be 5% by mass to 20% by mass. Based on the total amount of component (A), (B), (C) and (D), the content of component (C) may be 8 mass% or more, 10 mass% or more, or 12 mass% or more , and may be 19 mass% or less, 18 mass% or less, or 17 mass% or less. When the content of component (C) is 5 mass % or more, the low-temperature adhesion properties when forming a film-like adhesive tend to be more excellent. When the content of component (C) is 20 mass % or less, a more sufficient high-temperature storage elastic coefficient tends to be obtained in the cured material of the adhesive composition.

＜（D）成分：填料＞ （D）成分可為無機填料。作為（D）成分，例如可列舉：氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、硼酸鋁晶鬚、氮化硼、結晶性二氧化矽、非晶性二氧化矽等。該些可單獨使用一種或者將兩種以上組合使用。該些中，（D）成分可包含二氧化矽。＜(D) Ingredient: filler＞ (D) Component may be an inorganic filler. Examples of the component (D) include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, Boron nitride, crystalline silicon dioxide, amorphous silicon dioxide, etc. These can be used individually by 1 type or in combination of 2 or more types. Among these, component (D) may contain silica.

就接著性進一步提升的觀點而言，（D）成分的平均粒徑可為0.005 μm～2.0 μm、0.005 μm～1.5 μm、0.005 μm～1.0 μm。此處，平均粒徑是指藉由根據布厄特（Brunauer-Emmett-Teller，BET）比表面積進行換算而求出的值。From the viewpoint of further improving the adhesiveness, the average particle diameter of component (D) may be 0.005 μm to 2.0 μm, 0.005 μm to 1.5 μm, or 0.005 μm to 1.0 μm. Here, the average particle diameter refers to a value calculated by conversion based on Brunauer-Emmett-Teller (BET) specific surface area.

就其表面與溶劑、其他成分等的相容性、接著強度的觀點而言，（D）成分可藉由表面處理劑進行表面處理。作為表面處理劑，例如可列舉矽烷系偶合劑等。作為矽烷系偶合劑的官能基，例如可列舉：乙烯基、(甲基)丙烯醯基、環氧基、巰基、胺基、二胺基、烷氧基、乙氧基等。From the viewpoint of surface compatibility with solvents, other components, etc., and adhesion strength, component (D) can be surface treated with a surface treatment agent. Examples of surface treatment agents include silane coupling agents. Examples of the functional group of the silane coupling agent include a vinyl group, a (meth)acrylyl group, an epoxy group, a mercapto group, an amino group, a diamine group, an alkoxy group, an ethoxy group, and the like.

以（A）成分、（B）成分、（C）成分及（D）成分的總量為基準，（D）成分的含量為40質量%～68質量%。以（A）成分、（B）成分、（C）成分及（D）成分的總量為基準，（D）成分的含量亦可為45質量%以上、48質量%以上、或50質量%以上，且可為65質量%以下、60質量%以下、或55質量%以下。若（D）成分的含量為40質量%以上，則接著劑組成物的硬化物中有可獲得更充分的高溫儲存彈性係數的傾向。若（D）成分的含量為68質量%以下，則有形成膜狀接著劑時的低溫貼附性優異的傾向。Based on the total amount of component (A), component (B), component (C) and component (D), the content of component (D) is 40% by mass to 68% by mass. Based on the total amount of component (A), (B), (C) and (D), the content of component (D) may be 45 mass% or more, 48 mass% or more, or 50 mass% or more , and may be 65 mass% or less, 60 mass% or less, or 55 mass% or less. When the content of component (D) is 40 mass % or more, a more sufficient high-temperature storage elastic coefficient tends to be obtained in the cured material of the adhesive composition. When the content of component (D) is 68 mass % or less, the low-temperature adhesion property when forming a film-like adhesive tends to be excellent.

＜（E）成分：硬化促進劑＞ 接著劑組成物可更含有（E）成分。藉由接著劑組成物含有（E）成分，而有可進一步兼具接著性及連接可靠性的傾向。作為（E）成分，例如可列舉：咪唑類及其衍生物、有機磷系化合物、二級胺類、三級胺類、四級銨鹽等。該些可單獨使用一種或者將兩種以上組合使用。該些中，就反應性的觀點而言，（E）成分可為咪唑類及其衍生物。＜(E) Ingredient: Hardening accelerator＞ The adhesive composition may further contain component (E). When the adhesive composition contains the component (E), there is a tendency that both adhesiveness and connection reliability can be further achieved. Examples of the component (E) include imidazoles and derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of reactivity, the component (E) may be imidazoles and derivatives thereof.

作為咪唑類，例如可列舉：2-甲基咪唑、1-苄基-2-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑等。該些可單獨使用一種或者將兩種以上組合使用。Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole. wait. These can be used individually by 1 type or in combination of 2 or more types.

以（A）成分、（B）成分、（C）成分及（D）成分的總量為基準，（E）成分的含量可為0.01質量%～0.15質量%。若（E）成分的含量為此種範圍，則有可進一步兼具接著性及連接可靠性的傾向。Based on the total amount of component (A), component (B), component (C) and component (D), the content of component (E) may be 0.01% by mass to 0.15% by mass. If the content of component (E) is within such a range, both adhesion and connection reliability tend to be improved.

＜（F）成分：偶合劑＞ 接著劑組成物可更含有（F）成分。藉由接著劑組成物含有（F）成分，則有可進一步提高異種成分間的界面結合的傾向。作為（F）成分，例如可列舉矽烷系偶合劑、鈦酸酯系偶合劑、鋁系偶合劑等。該些可單獨使用一種或者將兩種以上組合使用。該些中，（F）成分可為矽烷系偶合劑。＜(F) Component: Coupling agent＞ The adhesive composition may further contain (F) component. When the adhesive composition contains component (F), the interfacial bonding between dissimilar components tends to be further improved. Examples of the component (F) include silane coupling agents, titanate coupling agents, aluminum coupling agents, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, the component (F) may be a silane coupling agent.

作為矽烷系偶合劑，例如可列舉：乙烯基三氯矽烷、乙烯基三乙氧基矽烷、乙烯基三(β-甲氧基乙氧基)矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、乙烯基三乙醯氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、γ-苯胺基丙基三甲氧基矽烷、γ-苯胺基丙基三乙氧基矽烷、γ-(N,N-二甲基)胺基丙基三甲氧基矽烷、γ-(N,N-二乙基)胺基丙基三甲氧基矽烷、γ-(N,N-二丁基)胺基丙基三甲氧基矽烷、γ-(N-甲基)苯胺基丙基三甲氧基矽烷、γ-(N-乙基)苯胺基丙基三甲氧基矽烷、γ-(N,N-二甲基)胺基丙基三乙氧基矽烷、γ-(N,N-二乙基)胺基丙基三乙氧基矽烷、γ-(N,N-二丁基)胺基丙基三乙氧基矽烷、γ-(N-甲基)苯胺基丙基三乙氧基矽烷、γ-(N-乙基)苯胺基丙基三乙氧基矽烷、γ-(N,N-二甲基)胺基丙基甲基二甲氧基矽烷、γ-(N,N-二乙基)胺基丙基甲基二甲氧基矽烷、γ-(N,N-二丁基)胺基丙基甲基二甲氧基矽烷、γ-(N-甲基)苯胺基丙基甲基二甲氧基矽烷、γ-(N-乙基)苯胺基丙基甲基二甲氧基矽烷、N-(三甲氧基矽烷基丙基)乙二胺、N-(二甲氧基甲基矽烷基異丙基)乙二胺、甲基三甲氧基矽烷、二甲基二甲氧基矽烷、甲基三乙氧基矽烷、γ-氯丙基三甲氧基矽烷、六甲基二矽烷、乙烯基三甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、γ-脲基丙基三乙氧基矽烷等。Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, and γ-methacryloxypropyltrimethyl. Oxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane Silane, vinyltriacetyloxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-amino Propyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-(N, N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyl Trimethoxysilane, γ-(N-methyl)anilinopropyltrimethoxysilane, γ-(N-ethyl)anilinopropyltrimethoxysilane, γ-(N,N-dimethyl) Aminopropyltriethoxysilane, γ-(N,N-diethyl)aminopropyltriethoxysilane, γ-(N,N-dibutyl)aminopropyltriethoxysilane Silane, γ-(N-methyl)anilinopropyltriethoxysilane, γ-(N-ethyl)anilinopropyltriethoxysilane, γ-(N,N-dimethyl)amine Propylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N,N-dibutyl)aminopropylmethyl dimethoxysilane, γ-(N-methyl)anilinopropylmethyldimethoxysilane, γ-(N-ethyl)anilinopropylmethyldimethoxysilane, N-( Trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane Ethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-ureidopropyltriethoxy Silane etc.

以（A）成分、（B）成分、（C）成分及（D）成分的總量為基準，（F）成分的含量可為0.1質量%～5.0質量%。若（F）成分的含量為此種範圍，則有可進一步提高異種成分間的界面結合的傾向。Based on the total amount of component (A), component (B), component (C) and component (D), the content of component (F) may be 0.1% by mass to 5.0% by mass. If the content of component (F) is within this range, the interfacial bonding between dissimilar components tends to be further enhanced.

＜其他成分＞ 接著劑組成物可更含有抗氧化劑、流變控制劑、調平劑等作為其他成分。以（A）成分、（B）成分、（C）成分及（D）成分的總量為基準，該些成分的含量可為0.01質量%～3質量%。＜Other ingredients＞ The adhesive composition may further contain antioxidants, rheology control agents, leveling agents, etc. as other ingredients. Based on the total amount of component (A), component (B), component (C) and component (D), the content of these components may be 0.01% by mass to 3% by mass.

接著劑組成物可作為經溶劑稀釋的接著劑組成物的清漆來使用。溶劑只要為可溶解（D）成分以外的成分者則並無特別限制。作為溶劑，例如可列舉：甲苯、二甲苯、均三甲苯、枯烯、對異丙基甲苯等芳香族烴；己烷、庚烷等脂肪族烴；甲基環己烷等環狀烷烴；四氫呋喃、1,4-二噁烷等環狀醚；丙酮、甲基乙基酮、甲基異丁基酮、環己酮、4-羥基-4-甲基-2-戊酮等酮；乙酸甲酯、乙酸乙酯、乙酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯等酯；碳酸伸乙酯、碳酸伸丙酯等碳酸酯；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等醯胺等。該些可單獨使用一種或者將兩種以上組合使用。該些中，就溶解性及沸點的觀點而言，溶劑可為甲苯、二甲苯、甲基乙基酮、甲基異丁基酮、或環己酮。The adhesive composition can be used as a varnish of a solvent-diluted adhesive composition. The solvent is not particularly limited as long as it can dissolve components other than component (D). Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-isopropyltoluene; aliphatic hydrocarbons such as hexane and heptane; cyclic alkanes such as methylcyclohexane; and tetrahydrofuran. , 1,4-dioxane and other cyclic ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and other ketones; methyl acetate Esters, such as ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, etc.; carbonates such as ethyl carbonate, propyl carbonate, etc.; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide, etc. These can be used individually by 1 type or in combination of 2 or more types. Among these, the solvent may be toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone from the viewpoint of solubility and boiling point.

以接著劑組成物的清漆的總量為基準，接著劑組成物的清漆中的固體成分濃度可為10質量%～80質量%。The solid content concentration in the varnish of the adhesive composition may be 10% by mass to 80% by mass based on the total amount of the varnish of the adhesive composition.

接著劑組成物的清漆可藉由將（A）成分～（F）成分、溶劑、及其他成分加以混合、混煉而進行製備。再者，各成分的混合、混練的順序並無特別限制，可適當設定。混合及混煉可將通常的攪拌機、擂潰機、三輥磨機（three-rod roll mill）、球磨機（ball mill）、珠磨機（bead mill）等分散機適當組合而進行。 於製備接著劑組成物的清漆後，可藉由真空脫氣等將清漆中的氣泡去除。The varnish of the adhesive composition can be prepared by mixing and kneading components (A) to (F), a solvent, and other components. Furthermore, the order of mixing and kneading each component is not particularly limited and can be set appropriately. Mixing and kneading can be performed by appropriately combining a common mixer, crusher, three-rod roll mill, ball mill, bead mill and other dispersing machines. After preparing the varnish of the adhesive composition, the bubbles in the varnish can be removed by vacuum degassing or the like.

[膜狀接著劑] 圖1為表示一實施形態的膜狀接著劑的示意剖面圖。膜狀接著劑10為將以上所述的接著劑組成物形成為膜狀而成者。膜狀接著劑10可為半硬化（B階段）狀態。此種膜狀接著劑10可藉由將接著劑組成物塗佈於支撐膜而形成。於使用接著劑組成物的清漆的情況下，可將接著劑組成物的清漆塗佈於支撐膜，並進行加熱乾燥而將溶劑去除，藉此形成膜狀接著劑10。[Film-like adhesive] FIG. 1 is a schematic cross-sectional view showing a film adhesive agent according to one embodiment. The film-like adhesive 10 is formed by forming the above-described adhesive composition into a film shape. The film adhesive 10 may be in a semi-hardened (B-stage) state. Such film-like adhesive 10 can be formed by applying an adhesive composition to a support film. When using a varnish of an adhesive composition, the film-like adhesive 10 can be formed by applying the varnish of the adhesive composition to a support film and heating and drying to remove the solvent.

作為支撐膜，例如可列舉：聚四氟乙烯、聚乙烯、聚丙烯、聚甲基戊烯、聚對苯二甲酸乙二酯、聚醯亞胺等的膜。支撐膜的厚度例如可為10 μm～200 μm或20 μm～170 μm。Examples of the supporting film include films of polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polyimide, and the like. The thickness of the supporting film may be, for example, 10 μm to 200 μm or 20 μm to 170 μm.

作為將接著劑組成物的清漆塗佈於支撐膜的方法，可使用公知的方法，例如可列舉：刮塗法、輥塗法、噴塗法、凹版塗佈法、棒塗法、簾塗法等。加熱乾燥的條件只要為所使用的溶劑充分揮發的條件則並無特別限制，例如可為50℃～200℃下0.1分鐘～90分鐘。As a method of applying the varnish of the adhesive composition to the support film, a known method can be used, for example, a blade coating method, a roller coating method, a spray coating method, a gravure coating method, a rod coating method, a curtain coating method, etc. . The conditions for heating and drying are not particularly limited as long as the solvent used is sufficiently volatilized. For example, the conditions may be 0.1 to 90 minutes at 50°C to 200°C.

膜狀接著劑的厚度可根據用途而適當調整。就將半導體元件（半導體晶片）、導線、基板的配線電路等的凹凸等充分埋入的觀點而言，膜狀接著劑的厚度可為5 μm～200 μm、10 μm～110 μm、或15 μm～80 μm。The thickness of the film adhesive can be appropriately adjusted according to the intended use. From the viewpoint of fully burying the unevenness of semiconductor elements (semiconductor wafers), wires, wiring circuits of the substrate, etc., the thickness of the film adhesive may be 5 μm to 200 μm, 10 μm to 110 μm, or 15 μm. ~80 μm.

藉由將膜狀接著劑於110℃下加熱1小時，繼而於170℃下加熱1小時而獲得的膜狀接著劑的硬化物在175℃下的儲存彈性係數可為100 MPa以上，亦可為200 MPa以上、500 MPa以上、或1000 MPa以上。若膜狀接著劑的硬化物在175℃下的儲存彈性係數為100 MPa以上，則可抑制半導體元件與半導體元件搭載用支撐構件之間的偏移或剝離。膜狀接著劑的硬化物在175℃下的儲存彈性係數例如可為2000 MPa以下。膜狀接著劑的硬化物在175℃下的儲存彈性係數是指藉由實施例中記載的方法而測定的值。The storage elasticity coefficient of the cured product of the film-like adhesive obtained by heating the film-like adhesive at 110°C for 1 hour and then at 170°C for 1 hour at 175°C may be 100 MPa or more, or may be Above 200 MPa, above 500 MPa, or above 1000 MPa. If the storage elastic modulus of the cured product of the film-like adhesive at 175° C. is 100 MPa or more, the shift or peeling between the semiconductor element and the semiconductor element mounting support member can be suppressed. The storage elasticity coefficient of the cured product of the film-like adhesive at 175° C. may be, for example, 2000 MPa or less. The storage elastic coefficient at 175°C of the cured product of the film-like adhesive refers to a value measured by the method described in the Examples.

藉由將膜狀接著劑於110℃下加熱1小時，繼而於170℃下加熱1小時而獲得的膜狀接著劑的硬化物的玻璃轉移溫度（Tg）可為190℃以上，亦可為195℃以上、200℃以上、或205℃以上。若膜狀接著劑的硬化物的玻璃轉移溫度（Tg）為190℃以上，則可抑制半導體元件與半導體元件搭載用支撐構件之間的偏移或剝離。膜狀接著劑的硬化物的玻璃轉移溫度（Tg）例如可為250℃以下。膜狀接著劑的硬化物的玻璃轉移溫度（Tg）是指藉由實施例中記載的方法而測定的值。The glass transition temperature (Tg) of the cured product of the film-like adhesive obtained by heating the film-like adhesive at 110°C for 1 hour and then at 170°C for 1 hour may be 190°C or more, or may be 195 ℃ or above, 200℃ or above, or 205℃ or above. If the glass transition temperature (Tg) of the cured product of the film-like adhesive is 190° C. or higher, misalignment or peeling between the semiconductor element and the semiconductor element mounting support member can be suppressed. The glass transition temperature (Tg) of the cured product of the film-like adhesive may be, for example, 250° C. or lower. The glass transition temperature (Tg) of the cured product of the film adhesive refers to a value measured by the method described in the Examples.

[接著片] 圖2為表示一實施形態的接著片的示意剖面圖。接著片100包括基材20及設置於基材上的以上所述的膜狀接著劑10。[continuation film] FIG. 2 is a schematic cross-sectional view showing an adhesive sheet according to one embodiment. The adhesive sheet 100 includes a base material 20 and the above-mentioned film-like adhesive 10 provided on the base material.

基材20並無特別限制，可為基材膜。基材膜可列舉所述支撐膜中例示者。The base material 20 is not particularly limited and may be a base film. Examples of the base film include those exemplified by the support film.

基材20亦可為切割帶。此種接著片可用作切割･黏晶一體型接著片。該情況下，由於對半導體晶圓的層壓步驟為一次，因此可有效率地作業。The base material 20 can also be a cutting tape. This type of adhesive sheet can be used as an integrated cutting and bonding adhesive sheet. In this case, since the step of laminating the semiconductor wafer is performed once, the work can be performed efficiently.

作為切割帶，例如可列舉：聚四氟乙烯膜、聚對苯二甲酸乙二酯膜、聚乙烯膜、聚丙烯膜、聚甲基戊烯膜、聚醯亞胺膜等塑膠膜等。另外，切割帶視需要可進行底塗塗佈、UV處理、電暈放電處理、研磨處理、蝕刻處理等表面處理。切割帶亦可為具有黏著性者。此種切割帶可為對所述塑膠膜賦予黏著性者，亦可為於所述塑膠膜的單面設置有黏著劑層者。Examples of the dicing tape include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. In addition, the cutting tape can be subjected to surface treatment such as primer coating, UV treatment, corona discharge treatment, grinding treatment, etching treatment, etc. if necessary. The cutting tape may also be adhesive. Such a cutting tape may be one that imparts adhesiveness to the plastic film, or may have an adhesive layer provided on one side of the plastic film.

接著片100可與形成以上所述的膜狀接著劑的方法同樣地，藉由將接著劑組成物塗佈於基材膜而形成。將接著劑組成物塗佈於基材20的方法可與將以上所述的接著劑組成物塗佈於支撐膜的方法相同。The adhesive sheet 100 can be formed by applying the adhesive composition to the base film in the same manner as the method of forming the film-like adhesive described above. The method of applying the adhesive composition to the base material 20 may be the same as the method of applying the above-mentioned adhesive composition to the support film.

接著片100可使用預先製作的膜狀接著劑來形成。該情況下，接著片100可藉由使用輥層壓機、真空層壓機等於規定條件（例如室溫（20℃）或加熱狀態）下進行層壓而形成。接著片100可連續地製造，就效率佳而言，較佳為於加熱狀態下使用輥層壓機來形成。The adhesive sheet 100 can be formed using a pre-made film-like adhesive. In this case, the adhesive sheet 100 can be formed by laminating using a roll laminator or a vacuum laminator under predetermined conditions (for example, room temperature (20° C.) or a heated state). The sheet 100 can then be manufactured continuously. In terms of efficiency, it is preferably formed using a roller laminator in a heated state.

圖3為表示另一實施形態的接著片的示意剖面圖。接著片110更包括積層於膜狀接著劑10的與基材20為相反側的面上的保護膜30。保護膜30可列舉所述支撐膜中例示者。保護膜的厚度例如可為10 μm～200 μm或20 μm～170 μm。Fig. 3 is a schematic cross-sectional view showing an adhesive sheet according to another embodiment. The adhesive sheet 110 further includes a protective film 30 laminated on the surface of the film-like adhesive 10 opposite to the base material 20 . Examples of the protective film 30 include the support films described above. The thickness of the protective film may be, for example, 10 μm to 200 μm or 20 μm to 170 μm.

[半導體裝置] 圖4為表示一實施形態的半導體裝置的示意剖面圖。半導體裝置200是藉由將第一階段的第一半導體元件Wa經由第一導線88而以打線接合的方式連接於半導體元件搭載用支撐構件14，並且於第一半導體元件Wa上，經由膜狀接著劑10而壓接第二半導體元件Waa，從而將第一導線88的至少一部分埋入膜狀接著劑10中而成的半導體裝置。半導體裝置可為將第一導線88的至少一部分埋入而成的導線埋入型的半導體裝置，亦可為將第一導線88及第一半導體元件Wa埋入而成的半導體裝置。另外，半導體裝置200中，進而經由第二導線98而將半導體元件搭載用支撐構件14與第二半導體元件Waa電性連接，並且藉由密封材42而將第二半導體元件Waa密封。[Semiconductor device] 4 is a schematic cross-sectional view showing a semiconductor device according to an embodiment. The semiconductor device 200 is formed by connecting the first semiconductor element Wa in the first stage to the semiconductor element mounting support member 14 by wire bonding via the first wire 88, and on the first semiconductor element Wa via a film-like adhesive. The second semiconductor element Waa is press-bonded with the adhesive 10 so that at least part of the first wire 88 is buried in the film adhesive 10 . The semiconductor device may be a lead-embedded semiconductor device in which at least part of the first lead 88 is buried, or may be a semiconductor device in which the first lead 88 and the first semiconductor element Wa are buried. In addition, in the semiconductor device 200 , the semiconductor element mounting support member 14 and the second semiconductor element Waa are electrically connected via the second wire 98 , and the second semiconductor element Waa is sealed with the sealing material 42 .

第一半導體元件Wa的厚度可為10 μm～170 μm，第二半導體元件Waa的厚度可為20 μm～400 μm。埋入至膜狀接著劑10的內部的第一半導體元件Wa可為用以驅動半導體裝置200的控制器晶片。The thickness of the first semiconductor element Wa may be 10 μm˜170 μm, and the thickness of the second semiconductor element Waa may be 20 μm˜400 μm. The first semiconductor element Wa embedded in the film adhesive 10 may be a controller chip used to drive the semiconductor device 200 .

半導體元件搭載用支撐構件14包括電路圖案84、電路圖案94分別於表面各形成有兩處的有機基板90。第一半導體元件Wa經由接著劑41而壓接於電路圖案94上。第二半導體元件Waa以覆蓋未壓接有第一半導體元件Wa的電路圖案94、第一半導體元件Wa、及電路圖案84的一部分的方式經由膜狀接著劑10而壓接於半導體元件搭載用支撐構件14。於由半導體元件搭載用支撐構件14上的電路圖案84、電路圖案94所引起的凹凸的階差中埋入有膜狀接著劑10。並且，利用樹脂製的密封材42而將第二半導體元件Waa、電路圖案84及第二導線98密封。The semiconductor element mounting support member 14 includes an organic substrate 90 in which circuit patterns 84 and 94 are formed at two places on the surface. The first semiconductor element Wa is press-bonded to the circuit pattern 94 via the adhesive 41 . The second semiconductor element Waa is press-bonded to the semiconductor element mounting support via the film adhesive 10 so as to cover the circuit pattern 94 to which the first semiconductor element Wa is not press-bonded, the first semiconductor element Wa, and a part of the circuit pattern 84 . Component 14. The film-like adhesive 10 is embedded in the uneven steps caused by the circuit patterns 84 and 94 on the semiconductor element mounting support member 14 . Furthermore, the second semiconductor element Waa, the circuit pattern 84 and the second lead wire 98 are sealed with the resin sealing material 42 .

[半導體裝置的製造方法] 本實施形態的半導體裝置的製造方法包括：於基板上經由第一導線而電性連接第一半導體元件的第一打線接合步驟；於第二半導體元件的單面貼附以上所述的膜狀接著劑的層壓步驟；以及經由膜狀接著劑來壓接貼附有膜狀接著劑的第二半導體元件，藉此將第一導線的至少一部分埋入膜狀接著劑中的黏晶步驟。[Method for manufacturing semiconductor device] The manufacturing method of a semiconductor device according to this embodiment includes: a first wire bonding step of electrically connecting a first semiconductor element on a substrate via a first wire; and attaching the above-mentioned film-like adhesive on one side of the second semiconductor element. and a die bonding step of burying at least part of the first conductor in the film adhesive by pressure-bonding the second semiconductor element with the film adhesive through the film adhesive.

圖5、圖6、圖7、圖8及圖9為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。本實施形態的半導體裝置200為將第一導線88及第一半導體元件Wa埋入而成的半導體裝置，可藉由以下程序而製造。首先，如圖5所示，於半導體元件搭載用支撐構件14上的電路圖案94上壓接具有接著劑41的第一半導體元件Wa，且經由第一導線88而將半導體元件搭載用支撐構件14上的電路圖案84與第一半導體元件Wa電性接合連接（第一打線接合步驟）。5, 6, 7, 8, and 9 are schematic cross-sectional views showing a series of steps of a method of manufacturing a semiconductor device according to an embodiment. The semiconductor device 200 of this embodiment is a semiconductor device in which the first wire 88 and the first semiconductor element Wa are embedded, and can be manufactured by the following procedure. First, as shown in FIG. 5 , the first semiconductor element Wa having the adhesive 41 is press-bonded to the circuit pattern 94 on the semiconductor element mounting support member 14 , and the semiconductor element mounting support member 14 is connected via the first wire 88 . The circuit pattern 84 on the semiconductor device Wa is electrically bonded and connected (first wire bonding step).

其次，於半導體晶圓（例如厚度為100 μm、尺寸為8吋）的單面上層壓接著片100，並剝去基材20，藉此於半導體晶圓的單面貼附膜狀接著劑10（例如厚度為110 μm）。並且，於將切割帶貼合於膜狀接著劑10後，切割為規定的大小（例如7.5 mm見方），藉此如圖6所示，獲得貼附有膜狀接著劑10的第二半導體元件Waa（層壓步驟）。Next, the adhesive sheet 100 is laminated on one side of the semiconductor wafer (for example, the thickness is 100 μm and the size is 8 inches), and the base material 20 is peeled off, whereby the film-like adhesive 10 is attached to one side of the semiconductor wafer. (e.g. thickness 110 μm). Furthermore, after the dicing tape is bonded to the film adhesive 10, it is cut into a predetermined size (for example, 7.5 mm square), thereby obtaining a second semiconductor element with the film adhesive 10 attached as shown in FIG. 6 Waa (lamination step).

層壓步驟的溫度條件可為50℃～100℃或60℃～80℃。若層壓步驟的溫度為50℃以上，則可獲得與半導體晶圓的良好的密接性。若層壓步驟的溫度為100℃以下，則可抑制膜狀接著劑10於層壓步驟中過度流動，因而可防止引起厚度的變化等。The temperature condition of the lamination step may be 50°C to 100°C or 60°C to 80°C. If the temperature in the lamination step is 50° C. or higher, good adhesion to the semiconductor wafer can be obtained. If the temperature in the lamination step is 100° C. or lower, excessive flow of the film adhesive 10 during the lamination step can be suppressed, thereby preventing changes in thickness and the like.

作為切割方法，例如可列舉：使用旋轉刀刃的刀片切割、藉由雷射而將膜狀接著劑或晶圓與膜狀接著劑的兩者切斷的方法等。Examples of the dicing method include blade dicing using a rotating blade, a method of cutting both the film adhesive or the wafer and the film adhesive by laser, and the like.

並且，將貼附有膜狀接著劑10的第二半導體元件Waa壓接於經由第一導線88而接合連接有第一半導體元件Wa的半導體元件搭載用支撐構件14。具體而言，如圖7所示，以藉由膜狀接著劑10來覆蓋第一導線88及第一半導體元件Wa的方式載置貼附有膜狀接著劑10的第二半導體元件Waa，繼而，如圖8所示，藉由使第二半導體元件Waa壓接於半導體元件搭載用支撐構件14而將第二半導體元件Waa固定於半導體元件搭載用支撐構件14（黏晶步驟）。黏晶步驟可為將膜狀接著劑10於80℃～180℃、0.01 MPa～0.50 MPa的條件下壓接0.5秒～3.0秒。於黏晶步驟之後，亦可將膜狀接著劑10於60℃～175℃、0.3 MPa～0.7 MPa的條件下壓接5分鐘以上。Then, the second semiconductor element Waa to which the film-like adhesive 10 is attached is press-bonded to the semiconductor element mounting support member 14 to which the first semiconductor element Wa is bonded and connected via the first wire 88 . Specifically, as shown in FIG. 7 , the second semiconductor element Waa to which the film-like adhesive 10 is attached is placed in such a manner that the first conductive wire 88 and the first semiconductor element Wa are covered with the film-like adhesive 10, and then the second semiconductor element Waa is mounted. As shown in FIG. 8 , the second semiconductor element Waa is fixed to the semiconductor element mounting support member 14 by pressing the second semiconductor element Waa to the semiconductor element mounting support member 14 (die bonding step). The bonding step may be to press the film adhesive 10 under conditions of 80°C to 180°C and 0.01 MPa to 0.50 MPa for 0.5 seconds to 3.0 seconds. After the bonding step, the film adhesive 10 can also be pressed under the conditions of 60°C to 175°C and 0.3 MPa to 0.7 MPa for more than 5 minutes.

繼而，如圖9所示，於將半導體元件搭載用支撐構件14與第二半導體元件Waa經由第二導線98而電性連接後（第二打線接合步驟），利用密封材42將電路圖案84、第二導線98及第二半導體元件Waa密封。藉由經過此種步驟而可製造半導體裝置200。Next, as shown in FIG. 9 , after the semiconductor element mounting support member 14 and the second semiconductor element Waa are electrically connected via the second wire 98 (second wire bonding step), the circuit patterns 84 and 84 are sealed using the sealing material 42 . The second wire 98 and the second semiconductor element Waa are sealed. By going through such steps, the semiconductor device 200 can be manufactured.

作為其他實施形態，半導體裝置亦可為將第一導線88的至少一部分埋入而成的導線埋入型的半導體裝置。 [實施例]As another embodiment, the semiconductor device may be a lead-embedded semiconductor device in which at least part of the first lead 88 is buried. [Example]

以下，列舉實施例來對本發明進行更具體的說明。但本發明並不限定於該些實施例。Hereinafter, an Example is given and this invention is demonstrated more concretely. However, the present invention is not limited to these examples.

（實施例1～實施例5及比較例1～比較例3） ＜接著片的製作＞ 以表1所示的各成分及其含量，藉由以下的程序而製備接著劑組成物的清漆。首先，調配（A）環氧樹脂、（B）酚樹脂及（D）填料，向其中加入環己酮並進行攪拌，繼而，加入（C）彈性體、（E）硬化促進劑及（F）偶合劑，攪拌至各成分變得均勻，藉此獲得固體成分為40質量%的接著劑組成物的清漆。(Example 1 to Example 5 and Comparative Example 1 to Comparative Example 3) ＜Production of follow-up film＞ Using each component and its content shown in Table 1, a varnish of an adhesive composition was prepared by the following procedure. First, prepare (A) epoxy resin, (B) phenol resin and (D) filler, add cyclohexanone and stir them, then add (C) elastomer, (E) hardening accelerator and (F) coupling agent and stirred until each component became uniform, thereby obtaining a varnish of an adhesive composition having a solid content of 40 mass %.

再者，表1中的各成分如下所述。In addition, each component in Table 1 is as follows.

（A）成分：環氧樹脂 （A-1）成分：具有萘骨架的環氧樹脂 HP-4710（所述式（X）所表示的環氧樹脂，DIC股份有限公司製造，商品名「HP-4710」，軟化點：95℃，環氧當量：170 g/eq） （A-2）成分：不具有萘骨架的環氧樹脂 YDF-8170C（雙酚A型環氧樹脂，新日鐵住金化學股份有限公司製造，商品名「YDF-8170C」，環氧當量：160 g/eq） EXA-1514（雙酚S型環氧樹脂，DIC股份有限公司製造，商品名「EXA-1514」，環氧當量：300 g/eq）(A) Ingredients: Epoxy resin (A-1) Ingredient: Epoxy resin with naphthalene skeleton HP-4710 (Epoxy resin represented by the above formula (X), manufactured by DIC Co., Ltd., trade name "HP-4710", softening point: 95°C, epoxy equivalent: 170 g/eq) (A-2) Component: Epoxy resin without naphthalene skeleton YDF-8170C (Bisphenol A type epoxy resin, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., trade name "YDF-8170C", epoxy equivalent: 160 g/eq) EXA-1514 (Bisphenol S-type epoxy resin, manufactured by DIC Co., Ltd., trade name "EXA-1514", epoxy equivalent: 300 g/eq)

（B）成分：酚樹脂 PSM-4326（苯酚酚醛清漆型酚樹脂，群榮化學工業股份有限公司製造，商品名「樂吉拓（Resitop）PSM-4326」，軟化點：126℃，羥基當量：105 g/eq）(B) Ingredients: Phenol resin PSM-4326 (phenol novolak type phenol resin, manufactured by Qunyong Chemical Industry Co., Ltd., trade name "Resitop PSM-4326", softening point: 126°C, hydroxyl equivalent: 105 g/eq)

（C）成分：彈性體 HTR-860P-3（丙烯酸橡膠，長瀨化成股份有限公司製造，商品名「HTR-860P-3」，重量平均分子量80萬，玻璃轉移溫度：-13℃）(C) Ingredient: Elastomer HTR-860P-3 (Acrylic rubber, manufactured by Nagase Chemical Co., Ltd., trade name "HTR-860P-3", weight average molecular weight 800,000, glass transition temperature: -13°C)

（D）成分：填料 SC2050-HLG（二氧化矽填料，雅都瑪（Admatechs）股份有限公司製造，商品名「SC2050-HLG」，平均粒徑0.500 μm）(D) Ingredients: fillers SC2050-HLG (silica filler, manufactured by Admatechs Co., Ltd., trade name "SC2050-HLG", average particle size 0.500 μm)

（E）成分：硬化促進劑 2PZ-CN（1-氰基乙基-2-苯基咪唑，四國化成工業股份有限公司製造，商品名「固唑（Curezol）2PZ-CN」）(E) Ingredient: hardening accelerator 2PZ-CN (1-cyanoethyl-2-phenylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd., trade name "Curezol 2PZ-CN")

（F）成分：偶合劑 A-189（γ-巰基丙基三甲氧基矽烷，日本尤尼卡（Unika）股份有限公司製造，商品名「NUC A-189」） A-1160（γ-脲基丙基三乙氧基矽烷，日本尤尼卡股份有限公司製造，商品名「NUC A-1160」）(F) Ingredients: Coupling agent A-189 (γ-mercaptopropyltrimethoxysilane, manufactured by Japan Unika Co., Ltd., trade name "NUC A-189") A-1160 (γ-ureidopropyltriethoxysilane, manufactured by Japan Unica Co., Ltd., trade name "NUC A-1160")

其次，將所得的接著劑組成物的清漆塗佈於作為基材膜的厚度為38 μm且已實施脫模處理的聚對苯二甲酸乙二酯（PET）膜上，於140℃下加熱乾燥5分鐘。以該方式獲得於基材膜上設置有處於半硬化（B階段）狀態的厚度20 μm的膜狀接著劑的實施例1～實施例5及比較例1～比較例3的接著片。Next, the obtained varnish of the adhesive composition was applied to a release-treated polyethylene terephthalate (PET) film with a thickness of 38 μm as a base film, and it was heated and dried at 140°C. 5 minutes. In this manner, the adhesive sheets of Examples 1 to 5 and Comparative Examples 1 to 3 in which a film-like adhesive with a thickness of 20 μm in a semi-hardened (B-stage) state was provided on the base film were obtained.

＜低溫貼附性的評價＞ 將實施例1～實施例5及比較例1～比較例3的各接著片切成長100 mm、寬50 mm，將其作為試驗片。於載置於支撐台上的矽晶圓（直徑8吋、厚度400 μm）的與支撐台相反一側的面上，以膜狀接著劑與矽晶圓接觸的方式積層該試驗片。一邊利用輥（溫度70℃、線壓39.2 N/cm（4 kgf/cm）、進給速度0.5 m/分鐘）進行加壓一邊進行膜狀接著劑的積層。此時，將在膜狀接著劑與矽晶圓之間未觀測到空隙（孔隙）的產生的情況視為低溫貼附性優異並評價為「A」，將觀測到空隙（孔隙）的產生的情況評價為「B」。將結果示於表1中。＜Evaluation of low-temperature adhesion＞ Each adhesive sheet of Examples 1 to 5 and Comparative Examples 1 to 3 was cut into a length of 100 mm and a width of 50 mm, and these were used as test pieces. The test piece was laminated on the surface of the silicon wafer (diameter 8 inches, thickness 400 μm) placed on the support table on the opposite side to the support table so that the film adhesive comes into contact with the silicon wafer. The film-like adhesive was laminated while applying pressure with a roller (temperature: 70°C, linear pressure: 39.2 N/cm (4 kgf/cm), feed speed: 0.5 m/min). At this time, the case where no voids (voids) are observed between the film adhesive and the silicon wafer is considered to have excellent low-temperature adhesion and is evaluated as "A", and the case where the formation of voids (pores) is observed is considered to be excellent. The situation is rated "B". The results are shown in Table 1.

＜硬化後的膜狀接著劑的高溫儲存彈性係數及玻璃轉移溫度的測定＞ 將實施例1～實施例5及比較例1～比較例3的各接著片於110℃下加熱1小時，其後，於170℃下加熱1小時，藉此獲得膜狀接著劑的硬化物。對於膜狀接著劑的硬化物，使用動態黏彈性測定裝置（流變（Rheology）公司製造，商品名DVE-V4）對膜狀接著劑的硬化物施加拉伸負荷，於頻率10 Hz、升溫速度3℃/分鐘的條件下，以自25℃測定至300℃的溫度依存性測定模式對膜狀接著劑的硬化物的黏彈性進行測定，藉此求出175℃下的儲存彈性係數（高溫儲存彈性係數）。高溫儲存彈性係數的數值越大（例如為100 MPa以上），則意味著打線接合特性越優異。另外，求出由損失彈性係數相對於高溫儲存彈性係數的比例所表示的損失正切（tanδ）的峰頂的溫度作為玻璃轉移溫度。玻璃轉移溫度的數值越大（例如為190℃以上），則意味著打線接合特性越優異。將結果示於表1中。<Measurement of the high-temperature storage elastic coefficient and glass transition temperature of the hardened film adhesive> Each adhesive sheet of Examples 1 to 5 and Comparative Examples 1 to 3 was heated at 110° C. for 1 hour, and then heated at 170° C. for 1 hour, thereby obtaining a cured product of a film-like adhesive. For the cured product of the film-like adhesive, a tensile load was applied to the cured product of the film-like adhesive using a dynamic viscoelasticity measuring device (manufactured by Rheology, trade name: DVE-V4) at a frequency of 10 Hz and a heating rate of 10 Hz. Under the condition of 3°C/min, the viscoelasticity of the cured product of the film adhesive was measured in the temperature dependence measurement mode from 25°C to 300°C, and the storage elastic coefficient at 175°C (high temperature storage elastic coefficient). The larger the value of the high-temperature storage elastic coefficient (for example, 100 MPa or more), the better the wire bonding characteristics are. In addition, the temperature at the peak of the loss tangent (tan δ) represented by the ratio of the loss elastic coefficient to the high-temperature storage elastic coefficient was determined as the glass transition temperature. The larger the value of the glass transition temperature (for example, 190°C or more), the better the wire bonding characteristics are. The results are shown in Table 1.

[表1] [Table 1]

如表1所示，於接著劑組成物中，以環氧樹脂、酚樹脂、彈性體及填料的總量為基準，填料的含量為40質量%～68質量%，且環氧樹脂包含具有萘骨架的環氧樹脂的實施例1～實施例5中，低溫貼附性、高溫儲存彈性係數及玻璃轉移溫度方面均優異。另一方面，填料的含量不足40質量%的比較例1在高溫儲存彈性係數的方面不充分。另外，填料的含量超過68質量%的比較例2在低溫貼附性的方面不充分。進而，環氧樹脂不包含具有萘骨架的環氧樹脂的比較例3在高溫儲存彈性係數及玻璃轉移溫度的方面不充分。由該些結果，確認到本發明的接著劑組成物於形成膜狀接著劑時的低溫貼附性優異，並且能夠形成具有充分的高溫儲存彈性係數、且具有充分的玻璃轉移溫度的硬化物。As shown in Table 1, in the adhesive composition, based on the total amount of epoxy resin, phenol resin, elastomer and filler, the filler content is 40 mass% to 68 mass%, and the epoxy resin contains naphthalene. Examples 1 to 5 of the epoxy resins of the skeleton were excellent in low-temperature adhesion, high-temperature storage elasticity, and glass transition temperature. On the other hand, Comparative Example 1 in which the filler content is less than 40% by mass is insufficient in terms of high-temperature storage elasticity. In addition, Comparative Example 2 in which the filler content exceeds 68% by mass is insufficient in terms of low-temperature adhesion properties. Furthermore, Comparative Example 3 in which the epoxy resin did not contain an epoxy resin having a naphthalene skeleton was insufficient in terms of high-temperature storage elastic modulus and glass transition temperature. From these results, it was confirmed that the adhesive composition of the present invention has excellent low-temperature adhesion when forming a film-like adhesive, and can form a cured product having a sufficient high-temperature storage elastic coefficient and a sufficient glass transition temperature.

10:膜狀接著劑 14:半導體元件搭載用支撐構件 20:基材 30:保護膜 41:接著劑 42:密封材 84、94:電路圖案 88:第一導線 90:有機基板 98:第二導線 100、110:接著片 200:半導體裝置 Wa:第一半導體元件 Waa:第二半導體元件10: Film adhesive 14:Supporting member for mounting semiconductor components 20:Substrate 30:Protective film 41: Adhesive 42:Sealing material 84, 94: Circuit pattern 88:First wire 90:Organic substrate 98:Second wire 100, 110: Next film 200:Semiconductor devices Wa: First semiconductor element Waa: second semiconductor element

圖1為表示一實施形態的膜狀接著劑的示意剖面圖。 圖2為表示一實施形態的接著片的示意剖面圖。 圖3為表示另一實施形態的接著片的示意剖面圖。 圖4為表示一實施形態的半導體裝置的示意剖面圖。 圖5為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。 圖6為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。 圖7為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。 圖8為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。 圖9為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。FIG. 1 is a schematic cross-sectional view showing a film adhesive agent according to one embodiment. FIG. 2 is a schematic cross-sectional view showing an adhesive sheet according to one embodiment. Fig. 3 is a schematic cross-sectional view showing an adhesive sheet according to another embodiment. 4 is a schematic cross-sectional view showing a semiconductor device according to an embodiment. 5 is a schematic cross-sectional view showing a series of steps of a method of manufacturing a semiconductor device according to an embodiment. 6 is a schematic cross-sectional view showing a series of steps of a method of manufacturing a semiconductor device according to an embodiment. 7 is a schematic cross-sectional view showing a series of steps of a method of manufacturing a semiconductor device according to an embodiment. 8 is a schematic cross-sectional view showing a series of steps of a method of manufacturing a semiconductor device according to an embodiment. 9 is a schematic cross-sectional view showing a series of steps of a method of manufacturing a semiconductor device according to an embodiment.

10:膜狀接著劑 10: Film adhesive

Claims (7)

一種接著劑組成物，含有：環氧樹脂；酚樹脂；彈性體；以及填料；以所述環氧樹脂、所述酚樹脂、所述彈性體及所述填料的總量為基準，所述填料的含量為40質量%~68質量%，以所述環氧樹脂、所述酚樹脂、所述彈性體及所述填料的總量為基準，所述彈性體的含量為10質量%~20質量%，所述環氧樹脂包含具有萘骨架的環氧樹脂，所述具有萘骨架的環氧樹脂為具有四官能以上的環氧基的環氧樹脂，且所述彈性體為丙烯酸樹脂。 An adhesive composition containing: epoxy resin; phenol resin; elastomer; and filler; based on the total amount of the epoxy resin, the phenol resin, the elastomer and the filler, the filler The content is 40 mass% to 68 mass%. Based on the total amount of the epoxy resin, the phenolic resin, the elastomer and the filler, the content of the elastomer is 10 mass% to 20 mass%. %, the epoxy resin includes an epoxy resin with a naphthalene skeleton, the epoxy resin with a naphthalene skeleton is an epoxy resin with four or more functional epoxy groups, and the elastomer is an acrylic resin. 如申請專利範圍第1項所述的接著劑組成物，其中以所述環氧樹脂及所述酚樹脂的總量為基準，所述具有萘骨架的環氧樹脂的含量為14質量%~30質量%。 The adhesive composition described in item 1 of the patent application, wherein based on the total amount of the epoxy resin and the phenolic resin, the content of the epoxy resin with a naphthalene skeleton is 14% by mass to 30% by mass. Mass %. 如申請專利範圍第1項或第2項所述的接著劑組成物，其中所述具有萘骨架的環氧樹脂包含由下述式(X)所表示的環氧樹脂：
Figure 108126244-A0305-02-0033-1
 The adhesive composition described in Item 1 or Item 2 of the patent application, wherein the epoxy resin having a naphthalene skeleton includes an epoxy resin represented by the following formula (X):
Figure 108126244-A0305-02-0033-1
 一種膜狀接著劑，其是將如申請專利範圍第1項至第3項中任一項所述的接著劑組成物形成為膜狀而成。 A film-like adhesive formed by forming the adhesive composition according to any one of claims 1 to 3 into a film shape. 一種接著片，包括：基材；以及設置於所述基材上的如申請專利範圍第4項所述的膜狀接著劑。 An adhesive sheet includes: a base material; and a film-like adhesive as described in Item 4 of the patent application provided on the base material. 如申請專利範圍第5項所述的接著片，其中所述基材為切割帶。 The adhesive sheet described in item 5 of the patent application, wherein the base material is a cutting tape. 一種半導體裝置的製造方法，包括：打線接合步驟，於基板上經由第一導線而電性連接第一半導體元件；層壓步驟，於第二半導體元件的單面貼附如申請專利範圍第4項所述的膜狀接著劑；以及黏晶步驟，經由所述膜狀接著劑而壓接貼附有所述膜狀接著劑的第二半導體元件，藉此將所述第一導線的至少一部分埋入所述膜狀接著劑中。 A method of manufacturing a semiconductor device, including: a wire bonding step of electrically connecting a first semiconductor element on a substrate through a first wire; a lamination step of attaching a single side of a second semiconductor element as described in Item 4 of the patent application The film-like adhesive; and the die-bonding step, wherein the second semiconductor element attached with the film-like adhesive is pressure-bonded through the film-like adhesive, thereby burying at least a portion of the first conductor. into the film adhesive.
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