JP2011151125A - Dicing-die attach film, semiconductor device, and dicing-die attach method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dicing-die attach film that has the excellent temporal stability of a heat laminate to a wafer and excellent die attach embedding performance without requiring special heat management in a wire bonding process and in a resin sealing process. <P>SOLUTION: The dicing-die attach film is configured as follows. An adhesive layer 15 is composed of a first adhesive sheet 13 and a second adhesive sheet 14. A first adhesive layer composition for forming the first adhesive sheet contains (A) carboxyl group-containing ethylene-acrylic rubber, (B) an epoxy resin whose weight average molecular weight is ≤5,000 and which is in a solid state at 5-40°C, and (C) aromatic polyamine having a diphenyl sulfone skeletal structure. A second adhesive layer composition for forming the second adhesive sheet contains (D) a (meta) acrylic resin having a weight average molecular weight of 50,000 to 1,500,000 and having an epoxy group and a structural unit represented by a chemical formula (1), (B), and (C). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a dicing die attach film that serves as both a dicing film and a die bonding material, a semiconductor device manufactured using the dicing die attach film, and a dicing die attach method using the dicing die attach film. It is about.

  For example, (i) a large-diameter silicon wafer on which an IC circuit is formed is fixed on an adhesive film and cut into semiconductor chips in a dicing (cutting) process. (Ii) the semiconductor chip is curable liquid. It is thermocompression bonded to the lead frame with an adhesive or the like (die bond material), the adhesive is cured and the chip is fixed (mounted), (iii) after wire bonding between the electrodes, (iv) improvement in handling property and Manufactured by sealing for protection from the external environment. As a form of sealing, a transfer molding method using a resin is most commonly used because it is excellent in mass productivity and inexpensive.

  In recent years, with the enhancement of functions of semiconductor devices, a support substrate (substrate) for mounting a semiconductor chip is also required to have high density and miniaturization. In such a situation, when a liquid adhesive is used as the die bond material, the adhesive tends to protrude from the end of the chip when the semiconductor chip is mounted, and contamination of the electrode is caused. Inclination tends to cause wire bonding defects. Therefore, in order to improve these drawbacks, it is desired to form an adhesive film.

  On the other hand, the substrate has uneven portions due to circuit elements such as wiring, and when the semiconductor chip is thermocompression bonded to such a substrate, the adhesive film as a die bond material, that is, the die attach film completely fills the recess. Otherwise, the unfilled portion remains as a void, which expands due to heating in the reflow furnace, and may damage the reliability of the semiconductor device by destroying the cured adhesive layer. In particular, in recent years, reflow resistance is required at a high temperature (265 ° C.) corresponding to lead-free solder, and the importance of preventing the formation of voids is increasing.

  As a first method for solving the above problem, since the molding with the sealing resin is performed at a high temperature and high pressure, the remaining void is heated and compressed in the resin sealing step to reduce the volume of the void. Further, there is a method of removing the void by absorbing it in the die attach film or by heating and curing the die attach film while reducing the volume of the void. This method does not require a special process and is advantageous in terms of manufacturing.

  By the way, conventionally, as the above-mentioned adhesive for die bonding, specifically, a low elastic modulus material including an acrylic resin, an epoxy resin, which is a resin having excellent adhesiveness, a phenol resin, which is a curing agent thereof, and a catalyst has been developed. (For example, Patent Documents 1 to 3).

  However, although these materials are excellent in adhesiveness, the adhesive film using the material cannot completely remove voids in the die attach process. In addition, although the material is a low elastic modulus material for removing voids in the resin sealing step, the adhesive film using the material has a fast curing reaction, so the resin sealing step Since the rate of increase in film melt viscosity is increased by heating in the previous wire bonding step, it is difficult to remove voids in the resin sealing step. That is, as a result of an increase in melt viscosity, the void volume cannot be sufficiently reduced, and the void cannot be absorbed into the resin. Furthermore, since these are low elastic modulus materials, there is a risk of adversely affecting the bonding reliability in the wire bonding process.

JP-A-10-163391 Japanese Patent Laid-Open No. 11-12545 JP 2000-154361 A

  Conventionally, an adhesive film for dicing and die attachment that serves as both a pressure-sensitive adhesive film (dicing film) and a die bonding material has been used. The present inventors have proposed Japanese Patent Application No. 2008- as an adhesive layer for this dicing and die attachment film. 166968 proposed a dicing die attach film using an adhesive composition containing an acrylic resin and an epoxy resin. In the manufacturing process of the semiconductor device using the dicing die attach film using this adhesive composition, the temporal stability of the thermal lamination to the wafer is very excellent, but the void formation as described above is formed. There was a problem.

  As a second method for solving the above-mentioned problem of void formation, there is a method of preventing void formation as much as possible when a semiconductor chip is thermocompression bonded to a substrate with a die attach film. According to this method, there is no void between the semiconductor chip and the substrate in the process after the die attach process, and it is not necessary to monitor the heating history in the wire bonding process. Is advantageous.

  Further, the present inventors have disclosed an adhesive composition containing an acrylic resin and an epoxy resin different from the above proposal in Japanese Patent Application No. 2009-258820 as an adhesive layer of a dicing die attach film suitable for the second method. We proposed a dicing die attach film using materials. However, a dicing die attach film using this adhesive composition has excellent package reliability after long-term storage, but has a drawback that it is inferior in the stability over time of the heat laminating property to the wafer in the above manufacturing process. It was.

  The present invention has been made in view of the above circumstances, and in a semiconductor device manufacturing process using a dicing die attach film, it is excellent in stability over time of thermal lamination to a wafer (thermal lamination to a wafer that is stable even in long-term storage). In other words, it is possible to heat laminate at low temperature even after storage over time, and because voids can be removed when heat-pressing the semiconductor chip to the substrate in the die attach process, A dicing die attach film that has excellent performance for filling recesses (hereinafter referred to as “die attach embedding performance”) and provides a highly reliable semiconductor device without requiring special heat management in the wire bonding process and the resin sealing process. , Semiconductor devices manufactured using the dicing die attach film, and And to provide a dicing die attach method using the dicing die attach film.

で示される構造単位を有する（メタ）アクリル系樹脂、
（Ｂ）重量平均分子量が５０００以下である５〜４０℃で固体状のエポキシ樹脂、及び
（Ｃ）ジフェニルスルホン骨格構造を有する芳香族ポリアミン
を含むことを特徴とするダイシング・ダイアタッチフィルムを提供する。 In order to solve the above problems, according to the present invention, there is provided a dicing die attach film including at least a base material, a pressure-sensitive adhesive layer on the base material, and an adhesive layer on the pressure-sensitive adhesive layer. The adhesive layer comprises a first adhesive sheet and a second adhesive sheet laminated on the first adhesive sheet, and a first adhesive layer composition for forming the first adhesive sheet The thing is at least
(A) a carboxyl group-containing ethylene-acrylic rubber,
(B) a solid epoxy resin having a weight average molecular weight of 5000 or less at 5 to 40 ° C., and (C) an aromatic polyamine having a diphenylsulfone skeleton structure, and the second adhesive sheet for forming the second adhesive sheet 2 The adhesive layer composition is at least
(D) The weight average molecular weight is 50,000 to 1,500,000, the epoxy group and the following formula (1)

(Meth) acrylic resin having a structural unit represented by
A dicing die attach film comprising (B) an epoxy resin solid at 5 to 40 ° C. having a weight average molecular weight of 5000 or less, and (C) an aromatic polyamine having a diphenylsulfone skeleton structure is provided. .

The adhesive layer in such a dicing die attach film is excellent in the initial process in the manufacturing process of a semiconductor device, the stability over time of thermal lamination to a wafer, and the die attach that thermocompresses the semiconductor chip in the next process to the substrate. Since the voids can be easily and sufficiently removed in the process, the adhesive layer in the dicing die attach film of the present invention has both excellent thermal laminating stability over time and excellent die attach embedding performance. Can do.
Moreover, the adhesive bond layer in such a dicing die attach film gives the adhesive hardened | cured material layer which is excellent in heat resistance while having high adhesive force with respect to various base materials by heat-hardening. Further, the adhesive layer is cured by heating to give a cured adhesive layer having a sufficient elastic modulus in the wire bonding process. For this reason, highly stable wire bonding can be performed by using a dicing die-attach film having such an adhesive layer. In addition, since the characteristics of the adhesive layer in the dicing die attach film are stabilized, the dicing die attach film of the present invention maintains stable characteristics over a long period in the semiconductor device manufacturing process. It can be suitably used as it is.
Therefore, such a dicing die attach film can manufacture a highly reliable semiconductor device.

  Moreover, it is preferable that the carboxyl group-containing ethylene-acrylic rubber as the component (A) is synthesized by high-pressure radical polymerization.

  Thus, it is preferable to synthesize the component (A) by high-pressure radical polymerization because there are few by-products and there is no need to add an emulsifier or the like.

  The component (C) is preferably 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, or a combination thereof.

  Thus, any of 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, and combinations thereof can be used industrially.

  Further, the total ratio of the component (B) and the component (C) in the first adhesive layer composition is the sum of the components (A) to (C) in the first adhesive layer composition. It is preferable that it is 20 mass% or more and less than 90 mass% with respect to.

  Thus, the total ratio of the component (B) and the component (C) in the first adhesive layer composition is the ratio of the components (A) to (C) in the first adhesive layer composition. 1st adhesive bond layer composition shows favorable applicability | paintability as it is 20 to 90 mass% with respect to the sum total, Furthermore, the 1st adhesive sheet obtained from the said 1st adhesive bond layer composition Is preferable because sufficient die attach embedding performance can be exhibited.

  The first adhesive layer composition and / or the second adhesive layer composition preferably further includes (E) a silica-based inorganic filler.

  Thus, the first adhesive layer composition and / or the second adhesive layer composition contains a silica-based inorganic filler as the component (E), thereby appropriately increasing the melt viscosity of the adhesive layer, Chip flow in the resin sealing step can be suppressed, and the moisture absorption rate and linear expansion rate of the resulting cured adhesive layer can be reduced.

  The first adhesive layer composition and / or the second adhesive layer composition preferably further includes (F) an adhesion assistant.

  As described above, the first adhesive layer composition and / or the second adhesive layer composition contains an adhesion assistant as the component (F), thereby improving the adhesiveness of the resulting cured adhesive layer. it can.

  The present invention also provides a semiconductor device manufactured using the dicing die attach film.

  When a semiconductor device is manufactured using the dicing die attach film of the present invention, the void is not sufficiently left after the die attach process is sufficiently embedded, and voids are generated between the semiconductor chip and the substrate after the die attach process. Therefore, the obtained semiconductor device has excellent reliability.

  The present invention also provides a dicing die attach method characterized by laminating a wafer on the dicing die attach film, dicing the laminated wafer, and then attaching the diced die to a substrate. To do.

  When the wafer is diced using the dicing die attach film of the present invention, the adhesive force between the adhesive layer of the dicing die attach film and the wafer is strong, that is, it exhibits excellent thermal laminating properties and its stability over time. It is preferable because it is excellent. Further, after the wafer is diced, it can be picked up stably with the adhesive layer attached to the back surface of the chip, so that the die can be mounted satisfactorily.

  The adhesive layer of the dicing die attach film of the present invention has excellent heat laminating properties at low temperatures, and also has excellent die attach embedding performance, and has high adhesive force to various substrates and heat resistance by heat curing. Gives a cured adhesive layer having excellent properties. Further, since the adhesive layer is cured by heating to give a cured product having a sufficient elastic modulus in the wire bonding step, highly stable wire bonding is performed by using the dicing die attach film of the present invention. be able to. Furthermore, the dicing die attach film of the present invention is excellent in property stability even after being stored for a long time.

It is a figure which shows an example of the dicing die attach film of this invention. It is explanatory drawing of the dicing process of the method of this invention. It is explanatory drawing which shows an example of the process of picking up the chip | tip obtained by the method of this invention, and die-attaching to a semiconductor device resin substrate. It is a figure which shows arrangement | positioning of the silicon chip in an embedding performance test.

  Hereinafter, the present invention will be described more specifically. In the present invention, the “weight average molecular weight” means a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). The “softening temperature” is a value measured by the ring and ball method defined in JIS K 7234.

  As described above, there has been a demand for a dicing die attach film that can have both the thermal laminating stability over time and the excellent die attach embedding performance.

で示される構造単位を有する（メタ）アクリル系樹脂、
（Ｂ）重量平均分子量が５０００以下である５〜４０℃で固体状のエポキシ樹脂、及び
（Ｃ）ジフェニルスルホン骨格構造を有する芳香族ポリアミン
を含むことを特徴とするダイシング・ダイアタッチフィルムであれば、ダイシング・ダイアタッチフィルムを用いた半導体装置製造工程において、ウエハーへの熱ラミネートの経時安定性に優れ、また、ダイアタッチ工程での半導体チップの基板への加熱圧着時にボイドを抜くことができるため、ダイアタッチ埋め込み性能に優れることを見出した。 The present inventors provide a dicing die attach film including at least a base material, a pressure-sensitive adhesive layer on the base material, and an adhesive layer on the pressure-sensitive adhesive layer, wherein the adhesive layer is a first adhesive. An adhesive sheet and a second adhesive sheet laminated on the first adhesive sheet, and the first adhesive layer composition for forming the first adhesive sheet comprises at least:
(A) a carboxyl group-containing ethylene-acrylic rubber,
(B) a solid epoxy resin having a weight average molecular weight of 5000 or less at 5 to 40 ° C., and (C) an aromatic polyamine having a diphenylsulfone skeleton structure, and the second adhesive sheet for forming the second adhesive sheet 2 The adhesive layer composition is at least
(D) The weight average molecular weight is 50,000 to 1,500,000, the epoxy group and the following formula (1)

(Meth) acrylic resin having a structural unit represented by
A dicing die attach film characterized by comprising (B) a solid epoxy resin having a weight average molecular weight of 5000 or less at 5 to 40 ° C. and (C) an aromatic polyamine having a diphenylsulfone skeleton structure. In the semiconductor device manufacturing process using a dicing die attach film, the thermal lamination to the wafer is excellent in stability over time, and voids can be removed during thermocompression bonding of the semiconductor chip to the substrate in the die attach process. It was found that the die attach performance is excellent.

< First adhesive sheet >
The first adhesive layer composition for forming the first adhesive sheet of the dicing die attach film of the present invention contains at least the above (A) to (C), and (E) silica-based inorganic as an optional component Including a filler, (F) adhesion aid, and other components, and maintaining the shape at room temperature, for example, a film-like thin film can be formed, while the dicing die attach film of the present invention is used in a semiconductor manufacturing process. When used, the first adhesive sheet faces the surface of the substrate to be die-attached in the die attach step, and is plasticized by heating, and further excellent for the substrate by performing die attach in this plastic state. Demonstrates die attach embedding performance. When a semiconductor device is manufactured using the dicing die attach film, generation of voids between the semiconductor chip and the substrate after the die attach step is suppressed. Moreover, the adhesive hardened | cured material layer obtained from this adhesive bond layer has high adhesiveness with respect to a base material, and has the outstanding heat resistance. Thus, the present invention solves the problem of void formation by the second method shown in the description of the background art.
Each component will be described below.

(A) A carboxyl group-containing ethylene-acrylic rubber (A) component is an ethylene-acrylic rubber containing a carboxyl group in the molecule. Examples of the ethylene-acrylic rubber include those synthesized by high-pressure radical polymerization and those synthesized by emulsion polymerization, but the generation of by-products is small, and there is no need to add an emulsifier or the like. Those synthesized by are preferred. The method of high-pressure radical polymerization is not particularly limited, and a known method can be used. (A) A component may be used individually by 1 type, or may use 2 or more types together.

  As the component (A), for example, an ethylene monomer unit, one or both of an acrylate monomer unit and a methacrylate monomer unit, and a carboxyl group-containing monomer unit are included. Ethylene-acrylic rubber synthesized by high-pressure radical polymerization can be used. Examples of the acrylate monomer unit include a methyl acrylate monomer unit, an ethyl acrylate monomer unit, and a butyl acrylate monomer unit. Examples of the methacrylate ester monomer unit include a methyl methacrylate monomer unit, an ethyl methacrylate monomer unit, and a butyl methacrylate monomer unit. Examples of the carboxyl group-containing monomer unit include an acrylic acid monomer unit, a methacrylic acid monomer unit, and a maleic acid monomer unit.

  Since the component (A) has a carboxyl group, the obtained first adhesive layer composition is excellent in die attach embedding performance. The component (A) may contain two or more carboxyl groups in one molecule in consideration of the reaction with the epoxy resin as the component (B) and the aromatic polyamine compound as the component (C) described later. More desirable.

  Further, the proportion of carboxyl groups in component (A) (that is, the number of moles of carboxyl groups per 100 g of component (A)) is not particularly limited, but is preferably 0.001 to 0.5 per 100 g of component (A). Mol, more preferably 0.005 to 0.1 mol. When this ratio is 0.001 to 0.5 mol, firstly, the fluidity of the first adhesive layer composition is easily controlled, and therefore the first adhesive obtained from the first adhesive layer composition The sheet exhibits better die attach embedding ability, and secondly, the (A) component effectively suppresses gradually reacting with either or both of the (B) component and (C) component at room temperature. Therefore, it is easy to maintain good storage stability of the obtained first adhesive sheet.

  The weight average molecular weight of the component (A) is not particularly limited, but is preferably 50,000 to 1,000,000, more preferably 80,000 to 500,000, particularly preferably 100,000 to 400,000. .

  Specific examples of the component (A) include Baymac G, Baymac GXF, Baymac GLS, and Baymac HVG (all manufactured by DuPont Elastomer Co., Ltd., carboxyl group-containing ethylene-acrylic rubber synthesized by high-pressure radical polymerization). Etc.

(B) The epoxy resin (B) component which is solid at 5 to 40 ° C. having a weight average molecular weight of 5000 or less is a room temperature having a weight average molecular weight of 5000 or less, preferably 150 to 3000, ie, usually 5 to 40 ° C. In particular, it is a solid epoxy resin at 15 to 30 ° C. The component (B) preferably has at least two epoxy groups in one molecule. When the weight average molecular weight of the component (B) exceeds 5000, either or both of the dissolution and dispersion of the component (B) in the component (A) are insufficient, and both components may be separated. Component (B) can be used alone or in combination of two or more.

  Examples of the component (B) include bis (4-hydroxyphenyl) methane, 2,2′-bis (4-hydroxyphenyl) propane or diglycidyl ethers of halides thereof, and polycondensates thereof (so-called bisphenol F). Type epoxy resin, bisphenol A type epoxy resin, etc.); butadiene diepoxide; vinylcyclohexene dioxide; 1,2-dihydroxybenzene diglycidyl ether, resorcinol diglycidyl ether, 1,4-bis (2,3-epoxypropoxy) ) Diglycidyl ethers such as benzene, 4,4′-bis (2,3-epoxypropoxy) diphenyl ether, 1,4-bis (2,3-epoxypropoxy) cyclohexene; bis (3,4-epoxy-6-methyl) (Cyclohexylmethyl) adipate Polyglycidyl ether obtained by condensing polyphenol or polyhydric alcohol and epichlorohydrin; epoxy novolac obtained by condensing novolac phenol resin such as phenol novolak or cresol novolac or halogenated novolac phenol resin and epichlorohydrin (I.e., novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin); epoxidized polyolefin or epoxidized polybutadiene epoxidized by peroxidation method; naphthalene ring-containing epoxy resin; biphenyl type epoxy resin; phenol aralkyl Type epoxy resin; biphenyl aralkyl type epoxy resin; dicyclopentadiene type epoxy resin (that is, having a dicyclopentadiene skeleton) Epoxy resins). These epoxy resins are compounds having at least two epoxy groups in one molecule.

  Among these, a novolac type epoxy resin, a dicyclopentadiene type epoxy resin or a combination thereof is preferable. A dicing die attach film to which an adhesive composition containing these preferable epoxy resins is applied as a first adhesive layer composition is obtained by dicing film (adhesive) from the first adhesive sheet comprising the first adhesive layer composition. The component transfer to the base material on which the layer is formed is particularly small, and the first adhesive sheet made of the first adhesive layer composition has a better die attach embedding property during thermocompression bonding in the die attach step. Cheap.

で表される骨格、および、上記式で表される骨格から一部または全部の水素原子を除いた残りの骨格をいう。後者の骨格において、除かれる水素原子の数および位置に制限はない。中でも、上記式で表される骨格が好ましい。 In the present invention, the “dicyclopentadiene skeleton” refers to the following formula:

And the remaining skeleton obtained by removing some or all of the hydrogen atoms from the skeleton represented by the above formula. In the latter skeleton, there is no limit to the number and position of hydrogen atoms removed. Among these, a skeleton represented by the above formula is preferable.

  Moreover, you may use epoxy resins other than (B) component in combination with (B) component in the range which does not impair the characteristic of this invention. Examples of the epoxy resin other than the component (B) include known epoxy resins that do not belong to the component (B), and commercially available epoxy resins that do not belong to the component (B) can be used. The amount of the epoxy resin other than the component (B) that can be used in combination with the component (B) is preferably 0 to 50 parts by mass, more preferably 0 to 100 parts by mass of the component (B). 20 parts by mass. The blending amount of 0 to 50 parts by mass is preferable because there is no possibility of impairing the die attach embedding property.

  In particular, when the silicon wafer to be bonded to the dicing die attach film of the present invention is thin, the adhesive layer can be pressure-bonded at a lower temperature and a lower pressure in order to prevent the occurrence of cracks and warpage. The component is solid at 5 to 40 ° C. (room temperature), and preferably has a softening temperature of 100 ° C. or less. When the epoxy resin in the first adhesive layer composition is liquid at 5 to 40 ° C. (room temperature) (that is, when it contains a large amount of low molecular weight substances), the first adhesive layer composition is formed from the first adhesive layer composition. The adhesive sheet of 1 is easy to express tack and uses a dicing die attach film including a dicing film (base material on which an adhesive layer is formed) and the adhesive layer laminated on the dicing film. Therefore, it is difficult to take out (pick up) the chip after dicing.

  (B) The compounding quantity of a component becomes like this. Preferably it is 5-500 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 10-200 mass parts. When the blending amount is within the range of 5 to 500 parts by mass, the die attach embedding property of the first adhesive sheet formed from the first adhesive layer composition is effectively improved, and the first adhesive The flexibility of the first adhesive sheet formed from the layer composition is likely to be sufficient, the adhesive strength of the cured adhesive layer obtained from the adhesive layer composition is particularly excellent, and the adhesive layer adheres to the back surface The chip can be easily picked up from the dicing film.

(C) Aromatic polyamine having a diphenylsulfone skeleton structure The aromatic polyamine having a diphenylsulfone skeleton structure as the component (C) has a diphenylsulfone skeleton structure and has at least two amino groups directly bonded to an aromatic ring. It has a function as a curing agent for epoxy resin and a catalyst. The aromatic polyamine of component (C) has a benzene ring in the diphenylsulfone skeleton structure, but may further have another aromatic ring. When the aromatic ring in component (C) is only the benzene ring in the diphenylsulfone skeleton structure, at least two amino groups are directly connected to the benzene ring, and the aromatic ring in component (C) is diphenylsulfone skeleton. When it is a benzene ring in the structure and an aromatic ring other than the benzene ring, it is directly connected to one or both of the benzene ring and the aromatic ring other than the benzene ring.

  The aromatic polyamine (C) has a melting point exceeding 170 ° C., and has low reactivity under heating in the wire bonding step. Therefore, the curing reaction proceeds slowly in the composition containing the component (C). For this reason, in this composition, the raise of the melt viscosity by heat curing can be suppressed effectively. In addition, a cured product obtained by heat-curing a composition containing the aromatic polyamine (C) has excellent heat resistance. Therefore, the composition containing the aromatic polyamine as the component (C) has improved embedding performance and excellent heat resistance after curing as compared with the conventional composition. Component (C) can be used alone or in combination of two or more.

  In the present invention, the “diphenylsulfone skeleton structure” means a remaining structure obtained by removing a part or all of hydrogen atoms from diphenylsulfone, and there is no limitation on the number and position of hydrogen atoms to be removed. Among them, the following structural formula:

で示されるジフェニルスルホン骨格構造が好ましい。

The diphenylsulfone skeleton structure shown by these is preferable.

  When the component (C) has a benzene ring in the diphenylsulfone skeleton structure and an aromatic ring other than the benzene ring, the aromatic ring other than the benzene ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Also good. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring. As an aromatic heterocyclic ring, a pyridine ring, a quinoline ring, an isoquinoline ring etc. are mentioned, for example.

  Specific examples of the component (C) include 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-amino And phenoxy) phenyl) sulfone. Among these, 4,4′-diaminodiphenyl sulfone and 3,3′-diaminodiphenyl sulfone can be preferably used industrially. These aromatic polyamines are known as epoxy resin curing agents, and commercially available products can be used.

  The amount of component (C) is preferably such that the molar ratio of amino groups in component (C) to all epoxy groups in the first adhesive layer composition is 0.6 to 1.4, The amount is more preferably 0.8 to 1.2. When the component (C) in an amount such that the molar ratio is 0.6 to 1.4 is added to the first adhesive layer composition, the composition is sufficiently cross-linked, and the resulting cured product is cured. Properties are likely to be good, and adhesion and solder reflow resistance are effectively improved. In addition, the component (C) is less likely to remain as an unreacted product in the cured product and is not easily wasted. Therefore, it is easy to save resources and is economical.

  In addition to the epoxy resin of component (B), an epoxy group-containing component (for example, an epoxy group-containing silane coupling agent that can be blended as an adhesion aid for component (F)) is blended in the first adhesive layer composition. Therefore, the total epoxy group in the first adhesive layer composition means the total of the epoxy group in the component (B) and the epoxy group in the epoxy group-containing component other than the component (B). . The molar ratio of the epoxy groups in the component (B) to all epoxy groups in the first adhesive layer composition is preferably 0.8 to 1.0, more preferably 0.9 to 1.0. Here, when an epoxy group-containing component other than the component (B) is not included in the first adhesive layer composition, the amount of the component (C) is (C) relative to the epoxy group in the component (B). The molar ratio of amino groups in the component is preferably 0.2 to 2.0, and more preferably 0.5 to 1.5.

  The ratio of the sum total of (B) component and (C) component in a 1st adhesive bond layer composition is 20 mass% or more with respect to the sum total of (A)-(C) component in a 1st adhesive bond layer composition. The range is preferably less than 90% by mass, and more preferably in the range of 50% by mass to less than 90% by mass. When the proportion is in the range of 20% by mass or more and less than 90% by mass, the obtained first adhesive layer composition easily exhibits good coating property and sufficient die attach embedding property, and the obtained cured product is sufficient. It is easy to express a strong adhesive force.

(E) Silica-based inorganic filler The silica-based inorganic filler (E) component is an optional component that can be added to the first adhesive layer composition. Among the inorganic fillers, the silica-based inorganic filler of the component (E) is general-purpose and industrially preferable. (E) component moderately increases the melt viscosity of the first adhesive sheet composed of the first adhesive layer composition, suppresses chip flow in the resin sealing step, and provides a cured adhesive layer obtained. Reduces moisture absorption and linear expansion. There is no restriction | limiting in particular in (E) component, A well-known thing can be used. The component (E) is preferably surface-treated with an organosilicon compound such as organoalkoxysilane, organochlorosilane, organosilazane, and low molecular weight siloxane from the viewpoint of the fluidity of the resulting composition. The component (E) can be used alone or in combination of two or more.

    (E) The average particle diameter of a component becomes like this. Preferably it is 10 micrometers or less, More preferably, it is 5 micrometers or less. When the average particle size is 10 μm or less, the first adhesive sheet made of the first adhesive layer composition can easily maintain the smoothness of the surface. Moreover, it is preferable that the maximum particle diameter of (E) component is 20 micrometers or less. In the present invention, the “average particle diameter” means a volume-based average particle diameter corresponding to 50% of the cumulative distribution obtained by a particle size distribution measuring apparatus using a laser light diffraction method. The “maximum particle size” is the maximum value of the particle size in the cumulative distribution measured when the average particle size is obtained as described above.

  Examples of the component (E) include fine silica powder, and specifically, reinforcing silica such as fumed silica and precipitated silica; and crystalline silica such as quartz. More specifically, Aerosil R972, R974, R976 manufactured by Nippon Aerosil Co., Ltd .; SE-2050, SC-2050, SE-1050, SO-E1, SO-C1, SO-E2, manufactured by Admatechs Co., Ltd., SO-C2, SO-E3, SO-C3, SO-E5, and SO-C5; Musil 120A and Musil 130A manufactured by Shin-Etsu Chemical Co., Ltd. are exemplified, and a mixture thereof may be used.

  (E) When using a component, the compounding quantity becomes like this. Preferably it is 5-80 mass% with respect to the 1st adhesive bond layer composition total mass, Most preferably, it is 10-60 mass%. When the blending amount is in the range of 5 to 80% by mass, the moisture absorption rate and the linear expansion coefficient of the obtained cured adhesive layer can be effectively reduced, and the elastic modulus of the cured adhesive layer is obtained. Can be easily suppressed.

(F) Adhesion aid An adhesive aid of component (F) may be added to the first adhesive layer composition in order to improve the adhesion of the resulting cured adhesive layer. There is no restriction | limiting in particular in (F) component, A well-known adhesion aid can be used. Component (F) can be used alone or in combination of two or more. As the component (F), for example, a coupling agent (silane coupling agent) containing silicon can be used.

Specific examples of the component (F) include vinyl group-containing silane coupling agents such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and vinyltriethoxysilane; acryloyloxypropyltrimethoxysilane, acryloyloxypropylmethyldimethoxysilane, and acryloyloxy. (Meth) acryloyl group-containing silane coupling agents such as propyltriethoxysilane, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropylmethyldimethoxysilane, methacryloyloxypropyltriethoxysilane; glycidoxypropyltrimethoxysilane, glycidoxypropyl Epoxy group-containing silane coupling agents such as triethoxysilane; mercaptopropyltrimethoxysilane, mercaptopropylmethyl Silane, a silane coupling agent such as a mercapto group-containing silane coupling agent such as mercaptopropyl triethoxy silane.
In terms of the product name, specific examples of the component (F) include KBM-403, KBM-402, KBM-803, KBM-802, KBM-903, KBM-902, KBM-503, and KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd. Or X-12-414 or these partial hydrolysates etc. are mentioned.

  (F) When using a component, the compounding quantity changes with kinds etc. of the hardening | curing agent to be used, Preferably it is 0.2-10 mass% with respect to the 1st adhesive bond layer composition total mass, More preferably It is about 0.5-5 mass%.

Other components In addition to the components (A) to (C), optional components (E) and (F), the first adhesive layer composition contains other components to the extent that the properties of the composition are not impaired. You may mix. Other components include, for example, curing agents and catalysts for epoxy resins other than component (C); inorganic fillers other than component (E); organic fillers; colorants such as pigments and dyes; wettability improvers; Agents; heat stabilizers; solvents and the like. Other components can be used alone or in combination of two or more.

  Examples of the curing agent for epoxy resin other than the component (C) and the catalyst include known phenol compounds as the curing agent or catalyst for epoxy resin. The amount of the epoxy resin curing agent and the catalyst other than the component (C) is such that the effect of the aromatic polyamine compound of the component (C) is not hindered.

  Examples of the inorganic filler other than the component (E) include alumina, titanium oxide, carbon black, and conductive particles.

  A solvent may be added to the first adhesive layer composition from the viewpoints of ease of mixing the components and ease of application of the resulting composition. The solvent can be used alone or in combination of two or more. Examples of the solvent include aprotic polar solvents such as methyl ethyl ketone, toluene, cyclohexanone, and N-methylpyrrolidone (NMP).

Preparation of First Adhesive Layer Composition The first adhesive layer composition comprises the above components (A) to (C), optional components (E), (F), and other components as required by conventional mixing means. It can be prepared by mixing at room temperature.

< Second adhesive sheet >
The second adhesive layer composition for forming the second adhesive sheet of the dicing die attach film of the present invention contains at least (D), (B), and (C) components, and (E ), (F) and other components, and in the same manner as the first adhesive layer composition, the shape is maintained at room temperature, so that, for example, a film-like thin film can be formed, while the dicing die attach of the present invention When the film is used in a semiconductor manufacturing process, the second adhesive sheet becomes a surface to be heat-laminated on the wafer, becomes a plastic state by heating, exhibits excellent thermal laminating properties, and has excellent temporal stability. Moreover, the cured product of the adhesive sheet has high adhesiveness to the substrate and excellent heat resistance. Thus, the present invention improves the heat laminating property that has been a problem in the past. Each component will be described below.

で示される構造単位を有する（メタ）アクリル系樹脂
即ち、（Ｄ）成分は、重量平均分子量が５０，０００〜１，５００，０００であり、エポキシ基および上記式（１）で表されるアクリロニトリル由来の構造単位を有する（メタ）アクリル系樹脂である。本発明において（メタ）アクリル系樹脂とは、アクリル酸、アクリル酸誘導体、メタクリル酸およびメタクリル酸誘導体からなる（メタ）アクリル系単量体に由来する構造単位を含む重合体をいう。（Ｄ）成分は、一種単独で使用しても二種以上を組み合わせて使用してもよい。二種以上を組み合わせて使用する場合、（Ｄ）成分は、エポキシ基を有する（メタ）アクリル系樹脂とエポキシ基を有しない（メタ）アクリル系樹脂との混合物であってもよい。 (D) The weight average molecular weight is 50,000 to 1,500,000, the epoxy group and the following formula (1)

The (meth) acrylic resin having the structural unit represented by formula (D), ie, the component (D) has a weight average molecular weight of 50,000 to 1,500,000, an acrylonitrile represented by the epoxy group and the above formula (1) It is a (meth) acrylic resin having a derived structural unit. In the present invention, the (meth) acrylic resin refers to a polymer containing a structural unit derived from a (meth) acrylic monomer composed of acrylic acid, an acrylic acid derivative, methacrylic acid and a methacrylic acid derivative. (D) A component may be used individually by 1 type, or may be used in combination of 2 or more type. When using in combination of 2 or more types, (D) component may be a mixture of (meth) acrylic resin having an epoxy group and (meth) acrylic resin having no epoxy group.

  The component (D) is, for example, a homopolymer or copolymer of the above (meth) acrylic monomer or a copolymer of the (meth) acrylic monomer and other monomers. And a polymer having a weight average molecular weight of 50,000 to 1,500,000 and having an epoxy group and a structural unit represented by the above formula (1). In the copolymer of the (meth) acrylic monomer and the other monomer, the content of the structural unit derived from the other monomer is preferably 0 to 0 in all the structural units of the component (D). It is 50 mol%, More preferably, it is 0-30 mol%. In the copolymer of (meth) acrylic monomers and other monomers, these monomers may be used alone or in combination of two or more.

  Examples of the acrylic acid derivative include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate and butyl acrylate; acrylic acid amides such as dimethyl acrylic acid amide; epoxy group-containing acrylic acid esters such as glycidyl acrylate; acrylonitrile Is mentioned.

  Examples of the methacrylic acid derivatives include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; methacrylic acid amides such as dimethyl methacrylate amide; and epoxy group-containing methacrylates such as glycidyl methacrylate. It is done.

  Examples of the other monomers include styrene, butadiene, and allyl derivatives (allyl alcohol, allyl acetate, etc.).

  (D) component has an epoxy group from the adhesive point of the adhesive agent hardened | cured material layer obtained. This epoxy group reacts with the (B) and (C) components. The epoxy group is introduced into the component (D) by synthesizing the component (D) using a monomer containing an epoxy group as a part of the monomer used as the raw material of the component (D), for example. can do. Examples of the monomer containing an epoxy group include an acrylic acid derivative containing an epoxy group and a methacrylic acid derivative containing an epoxy group, and more specifically, an epoxy group-containing acrylic acid such as glycidyl acrylate. An epoxy group-containing methacrylate such as an ester or glycidyl methacrylate is exemplified.

  The content of the epoxy group in the component (D) is preferably 0.002 to 0.1 mol, more preferably 0.005 to 0.05 mol, per 100 g of the component (D). When the content is in the range of 0.002 to 0.1 mol, a composition having sufficient embedding performance and a cured adhesive layer having sufficient adhesive strength can be easily obtained.

  The structural unit represented by the above formula (1) is obtained by synthesizing the component (D) using acrylonitrile as a part of the monomer used as the raw material of the component (D), for example, in the component (D) Can be introduced. In the component (D), the content of the structural unit derived from acrylonitrile (ratio of acrylonitrile in all monomers to be copolymerized) is preferably 5 to 50% by mass, particularly 10 to 40% by mass. preferable.

  The weight average molecular weight of the component (D) is 50,000 to 1,500,000, preferably 100,000 to 1,000,000. If the molecular weight is less than 50,000, the adhesiveness and strength of the resulting cured adhesive layer may be reduced. If the molecular weight exceeds 1,500,000, the resulting composition may be too viscous to be handled.

  Further, the (meth) acrylic resin of component (D) preferably has a glass transition point (Tg) measured by thermomechanical analysis (TMA) of -40 ° C to 100 ° C, more preferably -10 to 70. ° C.

Examples of the (B) epoxy resin (B) component that is solid at 5 to 40 ° C. having a weight average molecular weight of 5000 or less are the same as those in the first adhesive layer composition.
The blending amount of the component (B) in the second adhesive layer composition is preferably 5 to 100 parts by mass, more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the component (D). It is preferable for the blending amount to be in the range of 5 to 100 parts by mass because an adhesive layer having good heat laminating properties with good temporal stability can be obtained.

(C) Aromatic polyamine having a diphenylsulfone skeleton structure The aromatic polyamine having a diphenylsulfone skeleton structure as the component (C) may be the same as the first adhesive layer composition.
The amount of component (C) is preferably such that the molar ratio of amino groups in component (C) to all epoxy groups in the second adhesive layer composition is 0.6 to 1.4, The amount is more preferably 0.8 to 1.2. When the component (C) in such an amount that the molar ratio is 0.6 to 1.4 is added to the second adhesive layer composition, the composition is sufficiently crosslinked, and thus the resulting cured adhesive layer is obtained. , The curing characteristics tend to be good, and the adhesion and solder reflow resistance are effectively improved. In addition, the component (C) is less likely to remain as an unreacted product in the cured product and is not easily wasted. Therefore, it is easy to save resources and is economical.

  In addition to the epoxy resin of component (B), component (D) and other components containing epoxy groups can be blended in the second adhesive layer composition as components containing epoxy groups. Therefore, the total epoxy groups in the second adhesive layer composition are the epoxy groups in the component (B), the epoxy groups in the component (D), and the epoxy groups in the other components containing the epoxy groups. Means the sum of The total molar ratio of the epoxy groups in the component (B) and the epoxy groups in the component (D) to the total epoxy groups of the second adhesive layer composition is preferably 0.5 to 1.0, more preferably 0. .7 to 1.0. Moreover, the molar ratio of the epoxy group in the component (B) to all epoxy groups in the second adhesive layer composition is preferably 0.5 to 1.0, more preferably 0.6 to 0.9. Here, when the second adhesive layer composition contains no component having an epoxy group in addition to the component (B) and the component (D), the compounding amount of the component (C) is the amount in the component (B). The molar ratio of the amino groups in the component (C) to the total of the epoxy groups and the epoxy groups in the component (D) is preferably 0.6 to 1.4, preferably 0.8 to 1.2. It is more preferable that the amount is as follows.

Other components In addition to the above components (D), (B), and (C), other components may be added to the second adhesive layer composition as long as the properties of the composition are not impaired. Other components include, for example, epoxy resins other than the component (B); curing agents and catalysts for epoxy resins other than the component (C); fillers; adhesion assistants; colorants such as pigments and dyes; Antioxidants; heat stabilizers; solvents and the like.

(B) Epoxy Resin Other than Component In the second adhesive layer composition, an epoxy resin having a skeleton structure other than the dicyclopentadiene skeleton structure may be used in combination with the (B) component epoxy resin. Such epoxy resins other than the component (B) are known and commercially available products can be used. In addition, as the epoxy resin of component (B), for example, bisphenol F type epoxy resin; bisphenol A type epoxy resin; Naphthalene ring-containing epoxy resin; biphenyl type epoxy resin; phenol aralkyl type epoxy resin; biphenyl aralkyl type epoxy resin, and the like, preferably novolak type epoxy resin. These components (B) can be used in combination, or may be used in combination with an epoxy resin other than the component (B). (B) The compounding quantity of epoxy resins other than a component is 0-50 mass parts with respect to 100 mass parts of (B) component, Preferably it is 0-20 mass parts. If the blending amount exceeds 50 parts by mass, the laminating property, adhesiveness, and package reliability may be impaired.

(C) Epoxy resin curing agent and catalyst other than component (C) Examples of the epoxy resin curing agent and catalyst other than component (C) include known phenol compounds as epoxy resin curing agents or catalysts. The amount of the epoxy resin curing agent and the catalyst other than the component (C) is such that the effect of the aromatic polyamine of the component (C) is not hindered.

Filler You may mix | blend a filler with a 2nd adhesive bond layer composition. There is no restriction | limiting in particular in a filler, The thing of the (E) silica type inorganic filler described by the said 1st adhesive bond layer composition can be mentioned. A filler may be used individually by 1 type, or may be used in combination of 2 or more type. The blending amount of the filler is preferably 0 to 900 parts by mass, more preferably 0 to 500 parts by mass with respect to 100 parts by mass in total of the components (D), (B), and (C).
The blending amount of the silica particles is preferably 5 to 80% by weight, particularly 10 to 60% by weight, based on the total weight of the second adhesive layer composition, while adjusting the blending amount of the entire filler within the above range. It is preferable that When the blending amount is in the range of 5 to 80% by mass, the obtained cured adhesive layer can effectively reduce the moisture absorption rate and the linear expansion coefficient, and easily suppress the increase in the elastic modulus. .

(F) Adhesion aid An adhesion aid (F) may be added to the second adhesive layer composition in order to improve adhesion. The adhesion assistant can be used alone or in combination of two or more. As an adhesion assistant, for example, a coupling agent (silane coupling agent) containing silicon can be used. Examples of adhesion aids include epoxy group-containing silane coupling agents, mercapto group-containing silane coupling agents, amino group-containing silane coupling agents, (meth) acrylic group-containing silane coupling agents, etc. KBM-403, KBM-402, KBM-803, KBM-802, KBM-903, KBM-902, KBM-503, KBM5103 or X-12-414, or a partial hydrolyzate thereof, manufactured by Shin-Etsu Chemical Co., Ltd. Can be mentioned.

Solvent You may add a solvent to a 2nd adhesive bond layer composition from viewpoints of the ease of mixing of each component, the ease of application | coating of the composition obtained, etc. The solvent can be used alone or in combination of two or more. Examples of the solvent include aprotic polar solvents such as methyl ethyl ketone, toluene, ethyl acetate, cyclohexanone, and N-methylpyrrolidone (NMP).

Preparation of second adhesive layer composition The second adhesive layer composition was prepared by mixing the above (D), (B), (C), and optionally other components at room temperature by conventional mixing means. can do.

<Manufacture of first and second adhesive sheets>
For the first and second adhesive sheets, the first adhesive layer composition and the second adhesive layer composition are dissolved in a solvent at an appropriate concentration, applied onto the adhesive sheet forming substrate, and dried. Can be obtained. As the solvent, the solvents exemplified above can be used. The drying conditions are not particularly limited, and the drying can be performed at room temperature to 200 ° C., particularly 80 to 150 ° C. for 1 minute to 1 hour, particularly 3 to 10 minutes.

The film thickness of the adhesive layer is not particularly limited and can be selected according to the purpose. The film thickness of the first adhesive sheet is preferably 5 to 100 μm, particularly 10 to 50 μm. Is preferred. The film thickness of the second adhesive sheet is preferably 1 to 10 μm, and particularly preferably 3 to 7 μm.
In particular, it is preferable that the second adhesive sheet has a thickness of 1 to 10 μm because heat laminating stability over time can be obtained more reliably and there is no fear of causing wire bond failure.

  The base material for forming the adhesive sheet is usually in the form of a film, for example, polyethylene film, polypropylene film, polyester film, polyamide film, polyimide film, polyamideimide film, polyetherimide film, polytetrafluoroethylene film, paper. , A base material such as a metal foil, or the base material for forming an adhesive sheet whose surface has been subjected to mold release treatment can be used. The thickness of the base material for forming an adhesive sheet is preferably 10 to 100 μm, more preferably 25 to 50 μm.

<Dicing die attach film>
Hereinafter, the dicing die attach film of the present invention using the first and second adhesive sheets will be described in detail with reference to FIG.
The dicing die attach film 10 of the present invention includes a first adhesive sheet 13 and a second adhesive sheet 14 on a dicing film 16 having a base material 11 and a pressure-sensitive adhesive layer 12 provided thereon. It is a dicing die attach film in which the adhesive layer 15 formed is sequentially provided.
The dicing die attach film 10 of the present invention is formed by laminating the first adhesive sheet 13 and the second adhesive sheet 14 produced by the above method at 0 to 100 ° C., for example, and laminating the first adhesive. The agent sheet and the second adhesive sheet can be produced by laminating on the dicing film at normal temperature or low temperature.

  The dicing film 16 used in the dicing die attach film 10 of the present invention is preferably composed of at least two layers of a film-like base material 11 and a pressure-sensitive adhesive layer 12 serving as a base.

  If the said base material 11 is generally used in the dicing film, it will not be specifically limited. Examples of the substrate 11 include: (I) a single α-olefin such as polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ionomer. Polymer or copolymer, (II) engineering plastics such as polyethylene terephthalate, polycarbonate, polymethyl methacrylate, (III) polyurethane, styrene-ethylene-butene copolymer, styrene-ethylene-pentene copolymer, etc. A synthetic resin such as a thermoplastic elastomer can be used.

  The thickness of the substrate 11 is preferably 60 to 200 μm. When the thickness of the substrate 11 is in the range of 60 to 200 μm, the amount of epoxy resin transferred from the adhesive layer 15 to the dicing film 16 tends to be suppressed, so that the characteristics of the adhesive layer can be easily maintained. In addition, it is easy to mount the wafer on the dicing film, and it is possible to effectively prevent the base material from being fused to the chuck table by cutting heat during dicing.

  The pressure-sensitive adhesive layer 12 may be provided on at least one surface of the substrate 11. The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 12 is a dicing film obtained by dicing a wafer into pieces by dicing the wafer using the dicing die attach film of the present invention, while the adhesive layer is attached to the back surface of the chip. If it can pick up favorably, it will not specifically limit, The pressure-sensitive adhesive and the ultraviolet-ray (UV) curable adhesive currently used as a normal dicing tape can be used. More specifically, examples of the adhesive include rubber-based, acrylic-based, urethane-based, and silicone-based pressure-sensitive adhesives. Preferably, an acrylic adhesive, a urethane adhesive, or a silicone adhesive is used. It is preferable that the thickness of an adhesive layer is 1-50 micrometers, More preferably, it is 5-10 micrometers. The pressure-sensitive adhesive layer preferably has strong adhesion to the substrate to such an extent that chip skipping does not occur in the dicing process, and the 180-degree peeling force between the pressure-sensitive adhesive layer is 0.01 to 0.7 N / 25 mm. Is more preferable, and 0.1 to 0.4 N / 25 mm is more preferable.

Hereinafter, a method for manufacturing a semiconductor device using the dicing die attach film of the present invention will be described in detail.
As shown in FIG. 2, the dicing die attach film 20 of the present invention is bonded (laminated) to a wafer 21 such as a silicon wafer (FIG. 2A), and the wafer 21 is diced to obtain a chip 22 (FIG. 2). 2 (b)).
At this time, the heat laminating temperature of the dicing die attach film 20 on the wafer 21 is preferably 40 to 80 ° C., particularly 50 to 70 ° C.

  The chip 22 obtained by the above dicing is taken out with the adhesive layer attached (pickup) (FIG. 3A), and die-attached to the semiconductor device resin substrate (substrate) 32 (die attachment step) (FIG. 3 ( b)) A semiconductor device is manufactured through a wire bonding process and a sealing process.

In this case, if a portion that has not been embedded in the die attach process remains as a void after that, the resulting semiconductor device has low reliability.
Therefore, in order for the obtained semiconductor device to have reliability, the die attach process is sufficiently embedded and voids do not remain, and the adhesive film and the inside of the adhesive film and the process are subjected to a subsequent heat history process. It is necessary that no voids are generated or enlarged in the region adjacent to the adhesive film.

  Here, the adhesive layer needs to be semi-cured or completely cured under conditions where no voids are generated or expanded after die attachment, and then heated under the conditions of the wire bonding process.

  The die attach conditions for exhibiting sufficient die attach embedding property are, for example, 0.01 to 5 MPa, particularly 0.01 to 1 MPa, and a pressure of 100 to 150 ° C., particularly 110 to 140 ° C. Second to 10 seconds, especially 0.1 to 1 second. The conditions for semi-curing or complete curing of the adhesive film are not particularly defined, but are generally 100 to 200 ° C., particularly 110 to 150 ° C., 30 minutes to 8 hours, particularly 1 to 3 hours. Although there are various heating conditions in the wire bonding process, it is generally 30 minutes or more at 170 ° C.

  A semiconductor device can be manufactured as described above using the dicing die attach film of the present invention. The semiconductor device thus obtained has excellent reliability.

  The dicing die attach film of the present invention is not only used in the manufacture of electronic parts such as semiconductor devices, but also in the manufacture of various products including an adhesion process and a dicing process, for example, manufacture of LED parts, sensors, liquid crystal parts, etc. Can also be used.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by these description.

(Preparation of first adhesive layer composition)
The following components (A), (B), (C), (E), and (F) are rotated in the amounts shown in Table 1 (the amount of solid content (nonvolatile content) of each component, and the unit is parts by mass). First, the mixture was charged into a revolving mixer (manufactured by Sinky Co., Ltd.), and methyl ethyl ketone, toluene or cyclohexanone was added and mixed so that the total solid concentration of these components was 20 to 45% by mass. An adhesive composition solution was prepared. The components (A), (B), (C), (E), and (F) used are shown below.

(A) Component ethylene-acrylic rubber VAMAC-GLS: carboxyl group-containing ethylene-acrylic rubber (manufactured by DuPont Elastomer Co., Ltd.) synthesized by high-pressure radical polymerization, containing 0.056 mol / 100 g carboxyl group (B) component Epoxy resin HP-7200: dicyclopentadiene type epoxy resin (Dainippon Ink Co., Ltd.), weight average molecular weight 5000 or less, solid at room temperature, softening temperature = 62 ° C.
EOCN-1020: Cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.), weight average molecular weight 5000 or less, solid at room temperature, softening temperature = 55 ° C.
(C) Component aromatic polyamine compound 3,3′-DDS: 3,3′-diaminodiphenylsulfone (manufactured by Konishi Chemical Co., Ltd.), aromatic polyamine compound having a diphenylsulfone skeleton 4,4′-DDS: 4,4 '-Diaminodiphenylsulfone (manufactured by Wakayama Seika Co., Ltd.), silica-based inorganic filler of aromatic polyamine compound (E) component having diphenylsulfone skeleton Silica particles: SC-2050 (manufactured by Admatechs), spherical silica, average particle Diameter 0.5μm
(F) Component Adhesion Aid Silane Coupling Agent: X-12-414 (Shin-Etsu Chemical Co., Ltd.), Mercapto Silane Coupling Agent

(Preparation of second adhesive layer composition)
The following (D) and the same (B), (C), (E), (F) components used in the preparation of the first adhesive layer composition are shown in Table 2 in amounts (solid content of each component ( The amount of non-volatile content is in units of parts by mass) and charged into a rotating / revolving mixer (manufactured by Sinky Corp.), and the total solid content concentration of these components is 20 to 45% by mass. Then, methyl ethyl ketone, toluene or cyclohexanone was added and mixed to prepare a second adhesive composition solution. The component (D) used is shown below.

(D) (Meth) acrylic resin SG-P3: Acrylonitrile resin having an epoxy group (manufactured by Nagase ChemteX Corporation), containing 0.021 mol / 100 g of epoxy group, Tg = 12 ° C., weight average molecular weight = 85 Many

(Production of first and second adhesive sheets)
Next, the adhesive composition solutions shown in Tables 1 and 2 were applied onto a release-treated PET film having a thickness of 38 μm, dried by heating at 110 ° C. for 10 minutes, and a first film having a thickness of about 20 μm and 25 μm. Adhesive sheets, second adhesive sheets having thicknesses of about 5 μm and 25 μm were prepared.

(Production of dicing die attach film)
The 20-μm thick first-layer adhesive sheet prepared above and the second-layer adhesive sheet of about 5 μm thickness were laminated at 60 ° C. to prepare a laminated adhesive sheet having a total thickness of 25 μm. Next, the following dicing film was bonded at room temperature so that the first adhesive sheet was in contact with the pressure-sensitive adhesive layer surface of the dicing film to prepare a dicing die attach film.
Further, the first adhesive sheet alone and the second adhesive sheet alone, each having a thickness of about 25 μm, were bonded in the same manner to prepare a dicing die attach film of each layer and single layer.

Dicing film Pressure-sensitive dicing film: SD85TA (manufactured by Denki Kagaku Kogyo), thickness 85μm

(Examples 1-4, Comparative Examples 1-3)
The following tests were performed on the obtained dicing die attach film. The results are shown in Table 3.

Thermal Laminating Test The thermal laminating property was evaluated from the following (i) peel strength test of the adhesive layer (adhesive sheet) and (ii) pick-up property test. When the peel strength of the adhesive layer below (i) exceeds 2.0 N / 20 mm, the peel strength test result of the adhesive layer is ◯, and the value below this value is ×. (Ii) In the pick-up property test, when all the silicon chips were stably taken out with an adhesive layer, it was marked as ◯, and when even one silicon chip that could not be picked up was marked as x.

(I) Peeling force test of adhesive layer The dicing die attach film obtained above was heat laminated at 60 ° C. to the mirror surface side of a 725 μm silicon wafer, and then the dicing film was peeled off from the adhesive layer surface. . A strong adhesive tape UPH-110B (manufactured by Denki Kagaku Kogyo Co., Ltd.) was applied onto the remaining adhesive layer surface, and cut into a tape shape with a width of 20 mm so as to reach the silicon wafer surface. The peel peel strength at 180 ° from the wafer interface was measured on a tape-like sample having a width of 20 mm in which the adhesive tape and the adhesive layer were integrated. The peeling speed is 300 mm / min. As an evaluation of the change over time in the heat laminating property, the peel peel strength was measured immediately after the dicing die attach film was produced and after storage at 40 ° C. for 1 month.

(Ii) Pickup property test The dicing die attach film (initial and after storage) obtained above was thermally laminated at 60 ° C. on the back side of a 75 μm silicon wafer.
This silicon wafer was diced into 9 mm square chips under the following dicing conditions. Subsequently, 100 silicon chips of 9 mm square obtained in this way were picked up from the dicing film using a die bonder device (BESTEM-D02-TypeB) manufactured by NEC Machinery.
Dicing conditions:
Dicing machine: DAD-341 (manufactured by Disco)
Cutting method: Single cut Spindle speed: 40000 rpm
Dicing blade: NBC-ZH 104F 27HEEE (manufactured by Disco)
Feeding speed: 50mm / sec

Adhesion Test A silicon wafer having a diameter of 8 inches and a thickness of 725 μm was heat-laminated at 60 ° C. to the dicing die attach film prepared above, and diced into 3 mm × 3 mm chips.
Subsequently, it peeled from the interface of an adhesive bond layer and a dicing film surface, and the silicon chip with the adhesive bond layer was taken out. Next, on the 10 mm × 10 mm BT substrate on which the solder resist AUS308 (manufactured by Taiyo Ink Co., Ltd.) has been applied and cured, the obtained silicon chip with an adhesive layer is brought into contact with the surface to which the adhesive layer is attached. And fixed by thermocompression bonding at 170 ° C. and 0.1 MPa for 2 seconds. Thus, the board | substrate with which the silicon chip was fixed was heated at 175 degreeC for 6 hours, the adhesive bond layer was hardened, and the test piece (adhesion test piece) was produced. Using this adhesion test piece, the shear adhesive force between the cured adhesive layer and the substrate was measured at 260 ° C. with a bond tester (manufactured by DAGE, 4000PXY) (initial adhesion).
The same adhesion test piece as above was held at 85 ° C./60% RH for 168 hours, then passed through a 260 ° C. reflow furnace three times, and then the shear adhesive strength was measured at 260 ° C. as described above (wet heat) Later adhesiveness).

Die attach embedding performance test A silicon wafer having a diameter of 8 inches and a thickness of 75 μm was heat-laminated at 60 ° C. on the dicing die attach film prepared above. This silicon wafer was diced into 9 mm square chips under the following dicing conditions. Next, the 9 mm square silicon chip thus obtained was peeled from the pressure-sensitive adhesive layer of the pressure-sensitive dicing film with the adhesive layer attached to the back surface. This silicon chip was applied to a 50 mm × 50 mm × 250 μm thick resin substrate (solder resist AUS308 was applied) by using a die bonder device (BESTEM-D02-TypeB) manufactured by NEC Machinery Co., Ltd. The adhesive layer was placed in contact with the cured BT substrate) and thermocompression bonded for 1 second at 130 ° C. and 0.1 MPa. This point will be described in detail with reference to FIG. 4 (the layout of silicon chips in the embedding performance test). A square silicon chip 41 having a side of 9 mm is placed on a square resin substrate 42 having a side of 50 mm. 16 pieces are arranged in 4 rows and 4 columns at intervals of 3 mm, and the distance between the outermost silicon chip 41 and the outer edge of the resin substrate 42 is 2.5 mm. The resin substrate on which the silicon chip was thermocompression bonded in this way was observed with an ultrasonic image measuring device, and the presence or absence of voids in the region between the silicon chip and the resin substrate was examined (initial die attach embedding performance). .
Dicing conditions:
Dicing machine: DAD-341 (manufactured by Disco)
Cutting method: Single cut Spindle speed: 40000 rpm
Dicing blade: NBC-ZH 104F 27HEEE (manufactured by Disco)
Feeding speed: 50mm / sec

  The following observations were made to confirm that no voids were generated by any of phase separation, gas evolution, and the like during the heat curing of the adhesive layer. That is, the resin substrate to which the silicon chip is thermocompression bonded as described above is heated at 130 ° C. for 120 minutes to cure the adhesive layer, and the substrate is further heated at 170 ° C. corresponding to the heating temperature in the wire bonding step. After heating for a minute, it was observed with an ultrasonic image measuring device to examine the presence or absence of voids in the region between the silicon chip and the resin substrate (die attachment embedding performance after heating).

  When no void was confirmed by the above observation with the ultrasonic image measuring apparatus, it was evaluated that the die attach embedding performance was sufficient. On the other hand, when a void was confirmed by the above observation with an ultrasonic image measuring device, it was evaluated that the die attach embedding performance was insufficient. In Table 1, “◯” represents that the embedding performance was sufficient, and “x” represents that the embedding performance was insufficient.

Package Reliability Test A resin substrate similar to that used for observation by an ultrasonic image measuring device for the die attach embedding test after the heating described above is molded material KMC2500LM1B (Shin-Etsu) with a thickness of 600 μm from the substrate surface. Resin sealing (made by Chemical Industry Co., Ltd.) (175 ° C., sealing pressure 6.9 MPa, 90 seconds), and the mold material was heat-cured at 175 ° C. for 4 hours. The resin-encapsulated silicon chip is cut into individual pieces, and a total of 16 obtained packages are held for 168 hours under the condition of 85 ° C./60% RH, and then the solder having a maximum temperature of 260 ° C. After passing through the reflow furnace three times, the presence or absence of peeling between the silicon chip and the substrate was observed with an ultrasonic image measuring device. In Table 1, “◯” represents that no peeling was observed in any of the 16 packages, and “X” represents that peeling was observed in any one of the 16 packages.

※剥離試験サンプル作製時、接着剤層とウェーハとの密着力が弱過ぎたため、ウェーハから接着剤層が剥離し、測定が不可能であった。

* When the peel test sample was prepared, the adhesive force between the adhesive layer and the wafer was too weak, and the adhesive layer peeled off from the wafer, making measurement impossible.

  As shown in Table 3, the dicing die attach film (Examples 1 to 4) using the laminated adhesive layers (first adhesive sheet and second adhesive sheet) of the present invention is a single layer. Compared to the dicing die attach film (Comparative Examples 1 and 2) consisting of an adhesive sheet, it has excellent thermal laminating properties over time, and compared to the dicing die attach film (Comparative Example 3) consisting of a single-layer adhesive sheet, Excellent die attach embedding performance after heating. Furthermore, since the package containing the cured adhesive layer obtained from the composition of the present invention does not contain voids, the package reliability under moisture absorption is high.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. It is contained in the technical range.

DESCRIPTION OF SYMBOLS 10 ... Dicing die attach film, 11 ... Base material, 12 ... Adhesive layer 13 ... 1st adhesive sheet, 14 ... 2nd adhesive sheet, 15 ... Adhesive layer, 16 ... Dicing film, 20 ... Dicing Die attach film 21 ... wafer 22 ... chip 32 ... semiconductor device resin substrate (substrate)

Claims (8)

A dicing die attach film including at least a base material, a pressure-sensitive adhesive layer on the base material, and an adhesive layer on the pressure-sensitive adhesive layer, wherein the adhesive layer includes a first adhesive sheet, and the first Comprising a second adhesive sheet laminated on one adhesive sheet,
The first adhesive layer composition for forming the first adhesive sheet is at least:
(A) a carboxyl group-containing ethylene-acrylic rubber,
(B) a solid epoxy resin having a weight average molecular weight of 5000 or less at 5 to 40 ° C., and (C) an aromatic polyamine having a diphenylsulfone skeleton structure,
The second adhesive layer composition for forming the second adhesive sheet is at least:
(D) The weight average molecular weight is 50,000 to 1,500,000, the epoxy group and the following formula (1)

(Meth) acrylic resin having a structural unit represented by
(B) A dicing die attach film comprising an epoxy resin solid at 5 to 40 ° C. having a weight average molecular weight of 5000 or less, and (C) an aromatic polyamine having a diphenylsulfone skeleton structure.   The dicing die attach film according to claim 1, wherein the carboxyl group-containing ethylene-acrylic rubber as the component (A) is synthesized by high-pressure radical polymerization.   The dicing according to claim 1, wherein the component (C) is any one of 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, and a combination thereof.・ Die attach film.   The total ratio of the (B) component and the (C) component in the first adhesive layer composition is based on the total of the (A) to (C) components in the first adhesive layer composition. The dicing die attach film according to any one of claims 1 to 3, wherein the content is 20% by mass or more and less than 90% by mass.   The first adhesive layer composition and / or the second adhesive layer composition further includes (E) a silica-based inorganic filler, 5. The dicing die attach film described in 1.   6. The first adhesive layer composition and / or the second adhesive layer composition further includes (F) an adhesion assistant. Dicing die attach film.   The semiconductor device manufactured using the dicing die attach film of any one of Claims 1 thru | or 6.   A wafer is laminated on the dicing die attach film according to any one of claims 1 to 6, the laminated wafer is diced, and then the diced die is attached to a substrate. Dicing die attach method.

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