JP6356582B2 - Adhesive sheet, adhesive sheet with dicing sheet, and method for manufacturing semiconductor device - Google Patents

Description

  The present invention relates to an adhesive sheet, an adhesive sheet with a dicing sheet, and a method for manufacturing a semiconductor device.

  Regarding a method of a semiconductor device, for example, a method of a semiconductor device including a step of fixing a semiconductor chip to an adherend such as a lead frame with an adhesive sheet, a step of curing the adhesive sheet, and a step of wire bonding is known. (For example, refer to Patent Document 1).

  In recent years, there has been a shift from wire bonding using gold wires to wire bonding using inexpensive copper wires. Further, due to the demand for miniaturization of semiconductor devices, miniaturization of semiconductor chips is progressing.

JP2013-53190A

  Since copper wire is easily oxidized, it is difficult to bond to the pad of the semiconductor chip, and the molten ball is hard. Therefore, in wire bonding using a copper wire, the semiconductor chip is likely to vibrate due to the ultrasonic waves emitted from the wire bonding apparatus, and the bonding failure between the copper wire and the pad and chip cracking are likely to occur. A small semiconductor chip having a small area in contact with the lead frame is likely to vibrate, so that it is particularly likely to cause poor bonding and chip cracking.

  The present invention solves the above-mentioned problems and provides an adhesive sheet that can be cured in a short time, can reduce bonding failure between a copper wire and a pad, and cracks in a semiconductor chip, and an adhesive sheet with a dicing sheet. Objective. Another object of the present invention is to provide a method for manufacturing a semiconductor device, which can cure an adhesive sheet in a short time, and can reduce bonding failure between a copper wire and a pad and cracking of a semiconductor chip.

  The present invention relates to an adhesive sheet used for manufacturing a semiconductor device. The adhesive sheet of the present invention has the following properties. That is, in the DSC curve drawn by DSC measurement under the condition that the temperature is raised from 25 ° C. to 175 ° C. in 3 minutes and then maintained at 175 ° C. for 3 hours, the time from reaching 175 ° C. until the reaction peak disappears Less than 30 minutes. Since the time from reaching 175 ° C. until the reaction peak disappears is less than 30 minutes, it can be cured in a short time. The adhesive sheet of the present invention further has the following properties. That is, the tensile storage elastic modulus at 200 ° C. obtained by measuring the viscoelasticity of a cured product obtained by curing at 175 ° C. for 30 minutes at 10 Hz is 100 MPa or more. Since the tensile storage elastic modulus at 200 ° C. is 100 MPa or more, the vibration of the semiconductor chip can be reduced, and the bonding failure between the copper wire and the pad and the crack of the semiconductor chip can be reduced.

  The adhesive sheet of the present invention preferably further has the following properties. That is, it is preferable that the reaction calorie | heat_amount obtained by DSC measurement on the conditions which heat up in the range of 25 to 300 degreeC at 10 degree-C / min is 80 mJ / mg or more.

  The adhesive sheet of the present invention preferably further has the following properties. That is, it is preferable that Tg of the hardened | cured material obtained by making it harden | cure by heating at 175 degreeC for 30 minutes is 150 degreeC or more.

The adhesive sheet of the present invention preferably contains a silica filler having a BET specific surface area of 4 m ² / g or more. The content of the silica filler is preferably 50% by weight or more.

  The adhesive sheet of the present invention contains a resin component. Preferably, the resin component includes an epoxy resin, a phenol resin, and an acrylic resin. More preferably, the content of the acrylic resin in 100% by weight of the resin component is 14% by weight or less. The hydroxyl equivalent of the phenol resin is preferably 120 g / eq. It is as follows.

  The present invention also relates to an adhesive sheet with a dicing sheet comprising a substrate and a dicing sheet comprising an adhesive layer disposed on the substrate and an adhesive sheet disposed on the adhesive layer.

  The present invention also provides a step of preparing an adhesive sheet with a dicing sheet, a step of pressure-bonding a semiconductor wafer to the adhesive sheet, a semiconductor chip having a pad by dicing the semiconductor wafer disposed on the adhesive sheet, and a semiconductor chip A step of forming a die-bonding chip having an adhesive film disposed thereon, a step of forming an adherend with a chip by pressure-bonding the die-bonding chip to an adherend having a terminal portion, and an adherend with a chip The step of curing the adhesive film by heating the adhesive film, the step of bonding the one end of the wire containing copper and the pad, and the step of bonding the other end of the wire and the terminal portion. The present invention relates to a method for manufacturing a semiconductor device including:

It is a schematic sectional drawing of an adhesive sheet. It is a schematic sectional drawing of an adhesive sheet with a dicing sheet. It is a schematic sectional drawing of the adhesive sheet with a dicing sheet which concerns on a modification. It is sectional drawing which shows the outline of a mode that the semiconductor wafer has been arrange | positioned on the adhesive sheet with a dicing sheet. It is sectional drawing which shows the outline of a mode that the semiconductor wafer was separated into pieces. It is a schematic sectional drawing of a to-be-adhered body with a semiconductor chip. It is a schematic sectional drawing of a semiconductor device. 2 is a DSC curve of Example 2.

  The present invention will be described in detail below with reference to embodiments, but the present invention is not limited only to these embodiments.

[Embodiment 1]
(Adhesive sheet 3)
As shown in FIG. 1, the form of the adhesive sheet 3 is a sheet form. The adhesive sheet 3 has thermosetting properties.

  The adhesive sheet 3 further has the following properties. That is, in the DSC curve drawn by DSC measurement under the condition that the temperature is raised from 25 ° C. to 175 ° C. in 3 minutes and then maintained at 175 ° C. for 3 hours, the time from reaching 175 ° C. until the reaction peak disappears Less than 30 minutes. Since the time from reaching 175 ° C. until the reaction peak disappears is less than 30 minutes, it can be cured in a short time. Further, it can be cured completely or almost completely under standard wire bonding conditions, and the vibration of the semiconductor chip can be reduced. The time from when the temperature reaches 175 ° C. until the reaction peak disappears is preferably less than 25 minutes. On the other hand, the lower limit of the time from reaching 175 ° C. until the reaction peak disappears is, for example, 5 minutes, 10 minutes, 15 minutes, or the like.

  “The reaction peak disappears” means that the difference in input of thermal energy per unit time applied to both the measurement sample and the reference sample becomes constant so that the temperatures of the measurement sample and reference sample become equal.

  The time from when the temperature reaches 175 ° C. until the reaction peak disappears can be controlled by the type of curing accelerator, the content of curing accelerator, the type of resin, and the like.

  Preferably, the adhesive sheet 3 further includes the following properties. That is, the amount of reaction heat obtained by DSC measurement under the condition of raising the temperature in the range of 25 ° C. to 300 ° C. at 10 ° C. per minute is 80 mJ / mg or more, more preferably 85 mJ / mg or more. On the other hand, the amount of reaction heat is preferably 300 mJ / mg or less, more preferably 200 mJ / mg or less.

  The “reaction heat amount” is a value calculated by dividing the heat amount measured by DSC measurement under the condition of raising the temperature in the range of 25 ° C. to 300 ° C. at 10 ° C. per minute by the weight of the test piece.

The tensile storage elastic modulus at 200 ° C. obtained by measuring the viscoelasticity of the cured product obtained by curing the adhesive sheet 3 at 10 Hz is 100 MPa or more, preferably 200 MPa or more. Since it is 100 MPa or more, it is possible to reduce the vibration of the semiconductor chip, and to reduce the bonding failure between the copper wire and the pad and the crack of the semiconductor chip. The tensile storage elastic modulus at 200 ° C. is preferably 1000 MPa or less, more preferably 700 MPa or less. Examples of the upper limit of the tensile storage modulus at 200 ° C. include 500 MPa and 400 MPa.
The cured product is obtained by curing the adhesive sheet 3 by heating it at 175 ° C. for 30 minutes.

  The tensile storage elastic modulus at 200 ° C. of the cured product can be controlled by the hydroxyl group equivalent of the phenol resin, the content of the silica filler, the particle size of the silica filler, and the like. For example, the tensile storage elastic modulus at 200 ° C. can be increased by using a phenol resin having a small hydroxyl equivalent, increasing the content of the silica filler, and using a silica filler having a small particle size.

  The Tg of the cured product is preferably 150 ° C. or higher, more preferably 180 ° C. or higher. It is easy to set the tensile storage elastic modulus of 200 degreeC of hardened | cured material to 100 Mpa or more as it is 150 degreeC or more. On the other hand, Tg of hardened | cured material becomes like this. Preferably it is 250 degrees C or less, More preferably, it is 220 degrees C or less.

  The Tg (“glass transition temperature”) of the cured product can be controlled by the hydroxyl equivalent of the phenol resin.

  The adhesive sheet 3 includes a resin component. Examples of the resin component include acrylic resin, epoxy resin, and phenol resin.

  The acrylic resin is not particularly limited, and includes one or more esters of acrylic acid or methacrylic acid ester having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms. And a polymer (acrylic copolymer). Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, cyclohexyl group, 2- Examples include ethylhexyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, stearyl group, octadecyl group, and dodecyl group.

  In addition, the other monomer forming the polymer (acrylic copolymer) is not particularly limited, and for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid Or a carboxyl group-containing monomer such as crotonic acid, an acid anhydride monomer such as maleic anhydride or itaconic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth ) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4 -Hydroxymethylcyclo Hydroxyl group-containing monomers such as (xyl) -methyl acrylate, styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate Alternatively, a sulfonic acid group-containing monomer such as (meth) acryloyloxynaphthalene sulfonic acid or the like, or a phosphoric acid group-containing monomer such as 2-hydroxyethylacryloyl phosphate may be used.

  Among the acrylic resins, those having a weight average molecular weight of 100,000 or more are preferable, those having 300,000 to 3,000,000 are more preferable, and those having 500,000 to 2,000,000 are more preferable. It is because it is excellent in adhesiveness and heat resistance in this numerical range. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.

  The acrylic resin preferably contains a functional group capable of reacting with an epoxy group. Thereby, an acrylic resin can be bridge | crosslinked with an epoxy resin.

  Examples of the functional group capable of reacting with the epoxy group include a carboxyl group and a hydroxyl group. Of these, a carboxyl group is preferred because of its high reactivity with an epoxy group.

The acid value of the acrylic resin is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more. On the other hand, the acid value of the acrylic resin is preferably 40 mgKOH / g or less, more preferably 25 mgKOH / g or less.
In addition, an acid value can be measured by the neutralization titration method prescribed | regulated to JISK0070-1992.

  The content of the acrylic resin in 100% by weight of the resin component is preferably 14% by weight or less, more preferably 12% by weight or less, and still more preferably 11% by weight or less. The tensile storage elastic modulus of 200 degreeC can be improved as it is 14 weight% or less. The content of the acrylic resin in 100% by weight of the resin component is preferably 5% by weight or more, more preferably 7% by weight or more.

  The epoxy resin is not particularly limited. For example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, phenol novolac type. Bifunctional epoxy resins such as ortho-cresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type, etc., and epoxy resins such as hydantoin type, trisglycidyl isocyanurate type, or glycidylamine type are used. Of these epoxy resins, novolac type epoxy resins, biphenyl type epoxy resins, trishydroxyphenylmethane type resins or tetraphenylolethane type epoxy resins are particularly preferred. This is because these epoxy resins are rich in reactivity with a phenol resin as a curing agent and are excellent in heat resistance.

The epoxy equivalent of the epoxy resin is preferably 120 g / eq. Or more, more preferably 140 g / eq. Or more, more preferably 150 g / eq. That's it. On the other hand, the epoxy equivalent of the epoxy resin is preferably 250 g / eq. Or less, more preferably 200 g / eq. It is as follows.
In addition, the epoxy equivalent of an epoxy resin can be measured by the method prescribed | regulated to JISK7236-2009.

  The phenol resin acts as a curing agent for the epoxy resin. For example, a novolak type phenol resin such as a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a tert-butylphenol novolak resin, a nonylphenol novolak resin, or a resol type phenol resin. And polyoxystyrene such as polyparaoxystyrene. Of these phenol resins, phenol novolac resins and phenol aralkyl resins are particularly preferred. This is because the connection reliability of the semiconductor device can be improved.

  The hydroxyl equivalent of the phenol resin is preferably 120 g / eq. Or less, more preferably 110 g / eq. It is as follows. 120 g / eq. It is possible to raise a crosslinking density as it is the following, and a 200 degreeC tensile storage elastic modulus can be raised. On the other hand, the hydroxyl group equivalent of the phenol resin is preferably 80 g / eq. Or more, more preferably 90 g / eq. That's it.

  The blending ratio of the epoxy resin and the phenol resin is preferably blended so that the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per equivalent of epoxy group in the epoxy resin component. More preferred is 0.8 to 1.2 equivalents. That is, if the blending ratio of both is out of this range, the sufficient curing reaction does not proceed and the properties of the cured product are likely to deteriorate.

  The total content of the epoxy resin and the phenol resin in 100% by weight of the resin component is preferably 86% by weight or more, more preferably 88% by weight or more, and further preferably 89% by weight or more. The tensile storage elastic modulus of 200 degreeC can be raised as it is 86 weight% or more. On the other hand, the total content of the epoxy resin and the phenol resin is preferably 95% by weight or less, more preferably 93% by weight or less.

It is preferable that the adhesive sheet 3 contains a silica filler having a BET specific surface area of 4 m ² / g or more.

The BET specific surface area of the silica filler is preferably 15 m ² / g or more. On the other hand, the BET specific surface area of the silica filler is preferably 100 m ² / g or less, more preferably 50 m ² / g or less.
The BET specific surface area is measured by a BET adsorption method (multipoint method). Specifically, the adhesive sheet 3 is ashed by igniting at 700 ° C. for 2 hours in an air atmosphere. The obtained ash was vacuum degassed at 110 ° C. for 6 hours or more, and then, using a quadruple specific surface area / pore distribution measuring device “NOVA-4200e type” manufactured by Quantachrome, in nitrogen gas at a temperature of 77.35K. Measure with

  The new Mohs hardness of the silica filler is preferably 4 or more. The tensile storage elastic modulus of 200 degreeC can be effectively improved as it is 4 or more. Although the upper limit of the new Mohs hardness of a silica filler is not specifically limited, For example, it is ten.

  The content of the silica filler in the adhesive sheet 3 is preferably 50% by weight or more, more preferably 51% by weight or more. The tensile storage elastic modulus of 200 degreeC can be raised as it is 50 weight% or more. On the other hand, the content of the silica filler is preferably 70% by weight or less, more preferably 65% by weight or less.

  The adhesive sheet 3 preferably contains a curing accelerator. The content of the curing accelerator is preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the resin component. It can be hardened in a short time as it is 0.1 weight part or more.

  The curing accelerator is not particularly limited, and examples thereof include imidazole compounds, triphenylphosphine compounds, amine compounds, triphenylborane compounds, and trihalogenborane compounds.

  Examples of imidazole compounds include 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11Z), 2-heptadecylimidazole (trade name; C17Z), and 1,2-dimethylimidazole (trade name). 1.2DMZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-phenylimidazole (trade name; 2PZ), 2-phenyl-4-methylimidazole (trade name; 2P4MZ), 1-benzyl 2-methylimidazole (trade name; 1B2MZ), 1-benzyl-2-phenylimidazole (trade name; 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name; 2MZ-CN), 1-cyanoethyl-2- Undecylimidazole (trade name; C11Z-CN), 1-cyanoethyl-2 Phenylimidazolium trimellitate (trade name; 2PZCNS-PW), 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (trade name; 2MZ-A), 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine (trade name; C11Z-A), 2,4-diamino-6- [2′-ethyl- 4′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine (trade name; 2E4MZ-A), 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s -Triazine isocyanuric acid adduct (trade name; 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name; 2PHZ-PW), 2-phenyl-4-methyl-5-hydroxy Methylimidazole (trade name; 2P4MHZ-PW), and the like (all made by Shikoku Kasei Co., Ltd.).

  The triphenylphosphine compound is not particularly limited, and examples thereof include triorganophosphine such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, diphenyltolylphosphine, and the like. , Tetraphenylphosphonium bromide (trade name; TPP-PB), methyltriphenylphosphonium (trade name; TPP-MB), methyltriphenylphosphonium chloride (trade name; TPP-MC), methoxymethyltriphenylphosphonium (trade name; TPP-MOC), benzyltriphenylphosphonium chloride (trade name; TPP-ZC), and the like (all manufactured by Hokuko Chemical Co., Ltd.).

  The triphenylborane compound is not particularly limited, and examples thereof include tri (p-methylphenyl) phosphine. The triphenylborane compound further includes those having a triphenylphosphine structure. The compound having a triphenylphosphine structure and a triphenylborane structure is not particularly limited. For example, tetraphenylphosphonium tetraphenylborate (trade name; TPP-K), tetraphenylphosphonium tetra-p-triborate (trade name; TPP) -MK), benzyltriphenylphosphonium tetraphenylborate (trade name; TPP-ZK), triphenylphosphine triphenylborane (trade name; TPP-S) and the like (all manufactured by Hokuko Chemical Co., Ltd.).

  The amino compound is not particularly limited, and examples thereof include monoethanolamine trifluoroborate (manufactured by Stella Chemifa Corporation), dicyandiamide (manufactured by Nacalai Tesque Corporation), and the like.

  It does not specifically limit as a trihalogen borane type compound, For example, a trichloroborane etc. are mentioned.

  In addition to the above components, the adhesive sheet 3 may appropriately contain a compounding agent generally used in film production, such as a crosslinking agent.

  The adhesive sheet 3 can be manufactured by a normal method. For example, an adhesive composition solution containing each of the components described above is prepared, and the adhesive composition solution is applied on a base separator to a predetermined thickness to form a coating film, and then the coating film is dried. Thus, the adhesive sheet 3 can be manufactured.

  Although it does not specifically limit as a solvent used for adhesive composition solution, The organic solvent which can melt | dissolve, knead | mix or disperse | distribute each said component uniformly is preferable. Examples thereof include ketone solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, and cyclohexanone, toluene, xylene, and the like. The application method is not particularly limited. Examples of the solvent coating method include a die coater, a gravure coater, a roll coater, a reverse coater, a comma coater, a pipe doctor coater, and screen printing. Of these, a die coater is preferable in terms of high uniformity of coating thickness.

  As the base material separator, polyethylene terephthalate (PET), polyethylene, polypropylene, a plastic film or paper whose surface is coated with a release agent such as a fluorine-type release agent or a long-chain alkyl acrylate release agent can be used. Examples of the method for applying the adhesive composition solution include roll coating, screen coating, and gravure coating. Moreover, the drying conditions of a coating film are not specifically limited, For example, it can carry out in drying temperature 70-160 degreeC and drying time 1-5 minutes.

  As a method for producing the adhesive sheet 3, for example, a method of producing the adhesive sheet 3 by mixing the respective components with a mixer and press-molding the obtained mixture is also suitable. A planetary mixer etc. are mentioned as a mixer.

  Although the thickness of the adhesive sheet 3 is not specifically limited, 5 micrometers or more are preferable and 15 micrometers or more are more preferable. When the thickness is less than 5 μm, a portion where the warped semiconductor wafer or the semiconductor chip does not adhere may occur, and the adhesion area may become unstable. Further, the thickness of the adhesive sheet 3 is preferably 100 μm or less, and more preferably 50 μm or less. If it exceeds 100 μm, the adhesive sheet 3 may protrude excessively due to the load of die attachment, and the pad may be contaminated.

  The adhesive sheet 3 is used for manufacturing a semiconductor device. Specifically, it is used as a film for bonding an adherend such as a lead frame and a semiconductor chip (hereinafter referred to as “die attach film”). Examples of the adherend include a lead frame, an interposer, and a semiconductor chip.

  The adhesive sheet 3 is preferably used in the form of an adhesive sheet with a dicing sheet.

(Adhesive sheet with dicing sheet 10)
The adhesive sheet 10 with a dicing sheet will be described.

  As shown in FIG. 2, the adhesive sheet with dicing sheet 10 includes a dicing sheet 1 and an adhesive sheet 3 disposed on the dicing sheet 1. The dicing sheet 1 includes a base material 11 and an adhesive layer 12 arranged on the base material 11. The adhesive sheet 3 is disposed on the pressure-sensitive adhesive layer 12.

  As shown in FIG. 3, the dicing sheet-attached adhesive sheet 10 may have a configuration in which the adhesive sheet 3 is formed only on a work (semiconductor wafer 4 or the like) attachment portion.

  The base material 11 serves as a strength matrix of the adhesive sheet with a dicing sheet 10 and preferably has ultraviolet transparency. Examples of the base material 11 include low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolyprolene, polybutene, and polymethylpentene. Polyolefin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester (random, alternating) copolymer, ethylene-butene copolymer, ethylene -Hexene copolymers, polyesters such as polyurethane, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyetheretherketone, polyimide, polyetherimide, polyamide, wholly aromatic polyamid , Polyphenyl sulphates id, aramid (paper), glass, glass cloth, fluorine resin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, metal (foil), and paper.

  The surface of the base material 11 is chemically treated by conventional surface treatments such as chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc. in order to improve adhesion and retention with adjacent layers. Alternatively, a physical treatment or a coating treatment with a primer (for example, an adhesive substance described later) can be performed.

  The thickness of the substrate 11 is not particularly limited and can be determined as appropriate, but is generally about 5 to 200 μm.

  It does not restrict | limit especially as an adhesive used for formation of the adhesive layer 12, For example, common pressure sensitive adhesives, such as an acrylic adhesive and a rubber adhesive, can be used. As pressure-sensitive adhesives, acrylic adhesives based on acrylic polymers are used as the base polymer from the standpoint of cleanability of electronic components that are difficult to contaminate such as semiconductor wafers and glass with organic solvents such as ultrapure water and alcohol. preferable.

  Examples of the acrylic polymer include (meth) acrylic acid alkyl esters (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, isopropyl ester). Pentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester, C1-C30, especially C4-C18 linear or branched alkyl esters of alkyl groups such as octadecyl ester and eicosyl ester) and Meth) acrylic acid cycloalkyl esters (e.g., cyclopentyl ester, etc. One or acrylic polymer using two or more of the monomer component cyclohexyl ester etc.). In addition, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester, and (meth) of the present invention has the same meaning.

  The acrylic polymer contains units corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester or cycloalkyl ester, if necessary, for the purpose of modifying cohesive force, heat resistance and the like. May be. Examples of such monomer components include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride Acid anhydride monomers such as itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate Hydroxyl group-containing monomers such as 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate; Sti Contains sulfonic acid groups such as sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid Monomers; Phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate; acrylamide, acrylonitrile and the like. One or more of these copolymerizable monomer components can be used. The amount of these copolymerizable monomers used is preferably 40% by weight or less based on the total monomer components.

  Furthermore, since the acrylic polymer is cross-linked, a polyfunctional monomer or the like can be included as a monomer component for copolymerization as necessary. Examples of such polyfunctional monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) An acrylate etc. are mentioned. These polyfunctional monomers can also be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably 30% by weight or less of the total monomer components from the viewpoint of adhesive properties and the like.

  The acrylic polymer can be obtained by subjecting a single monomer or a mixture of two or more monomers to polymerization. The polymerization can be carried out by any method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like. From the viewpoint of preventing contamination of a clean adherend, it is preferable that the content of the low molecular weight substance is small. From this point, the number average molecular weight of the acrylic polymer is preferably 300,000 or more, more preferably about 400,000 to 3,000,000.

  In addition, an external cross-linking agent can be appropriately employed for the pressure-sensitive adhesive in order to increase the number average molecular weight of an acrylic polymer as a base polymer. Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, or a melamine crosslinking agent and reacting them. When using an external cross-linking agent, the amount used is appropriately determined depending on the balance with the base polymer to be cross-linked and further depending on the intended use as an adhesive. Generally, it is preferable to add about 5 parts by weight or less, and further 0.1 to 5 parts by weight with respect to 100 parts by weight of the base polymer. Furthermore, additives such as various conventionally known tackifiers and anti-aging agents may be used for the pressure-sensitive adhesive, if necessary, in addition to the above components.

  The pressure-sensitive adhesive layer 12 can be formed of a radiation curable pressure-sensitive adhesive. The radiation curable pressure-sensitive adhesive can easily reduce its adhesive strength by increasing the degree of crosslinking by irradiation with radiation such as ultraviolet rays.

  By irradiating only the part 12a corresponding to the work pasting part of the pressure-sensitive adhesive layer 12 shown in FIG. 2, a difference in adhesive strength with the other part 12b can be provided. In this case, the portion 12b formed of the uncured radiation curable pressure-sensitive adhesive sticks to the adhesive sheet 3 and can secure a holding force when dicing.

  Further, by curing the radiation-curable pressure-sensitive adhesive layer 12 in accordance with the adhesive sheet 3 shown in FIG. 3, the portion 12a with significantly reduced adhesive strength can be formed. In this case, the wafer ring can be fixed to the portion 12b formed of an uncured radiation curable adhesive.

  That is, when the pressure-sensitive adhesive layer 12 is formed of a radiation curable pressure-sensitive adhesive, the portion 12a is irradiated with radiation so that the pressure-sensitive adhesive force of the portion 12a in the pressure-sensitive adhesive layer 12 <the pressure-sensitive adhesive strength of the other portion 12b. It is preferable.

  As the radiation curable pressure-sensitive adhesive, those having a radiation curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness can be used without particular limitation. Examples of the radiation curable pressure-sensitive adhesive include an addition-type radiation curable pressure-sensitive adhesive in which a radiation-curable monomer component or oligomer component is blended with a general pressure-sensitive pressure-sensitive adhesive such as the acrylic pressure-sensitive adhesive or rubber-based pressure-sensitive adhesive. An agent can be illustrated.

  Examples of the radiation curable monomer component to be blended include urethane oligomer, urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol. Examples include stall tetra (meth) acrylate, dipentaerystol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, and the like. Examples of the radiation curable oligomer component include various oligomers such as urethane, polyether, polyester, polycarbonate, and polybutadiene, and those having a molecular weight in the range of about 100 to 30000 are suitable. The compounding amount of the radiation-curable monomer component or oligomer component can be appropriately determined in accordance with the type of the pressure-sensitive adhesive layer, and the amount capable of reducing the adhesive strength of the pressure-sensitive adhesive layer. Generally, the amount is, for example, about 5 to 500 parts by weight, preferably about 40 to 150 parts by weight with respect to 100 parts by weight of a base polymer such as an acrylic polymer constituting the pressure-sensitive adhesive.

  In addition to the additive-type radiation curable adhesive described above, the radiation curable pressure-sensitive adhesive has a carbon-carbon double bond in the polymer side chain or main chain or at the main chain terminal as a base polymer. Intrinsic radiation curable pressure sensitive adhesives using Intrinsic radiation curable adhesives do not need to contain oligomer components, which are low molecular components, or do not contain many, so the oligomer components do not move through the adhesive over time and are stable. It is preferable because an adhesive layer having a layered structure can be formed.

  As the base polymer having a carbon-carbon double bond, those having a carbon-carbon double bond and having adhesiveness can be used without particular limitation. As such a base polymer, those having an acrylic polymer as a basic skeleton are preferable. Examples of the basic skeleton of the acrylic polymer include the acrylic polymers exemplified above.

  The method for introducing the carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be adopted. However, the carbon-carbon double bond can be easily introduced into the polymer side chain for easy molecular design. . For example, after a monomer having a functional group is previously copolymerized with an acrylic polymer, a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is converted into a radiation curable carbon-carbon double bond. A method of performing condensation or addition reaction while maintaining the above.

  Examples of combinations of these functional groups include carboxylic acid groups and epoxy groups, carboxylic acid groups and aziridyl groups, hydroxyl groups and isocyanate groups. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is preferable because of easy tracking of the reaction. Moreover, the functional group may be on either side of the acrylic polymer and the compound as long as the acrylic polymer having the carbon-carbon double bond is generated by a combination of these functional groups. In the preferable combination, it is preferable that the acrylic polymer has a hydroxyl group and the compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. Further, as the acrylic polymer, those obtained by copolymerizing the above-exemplified hydroxy group-containing monomers, ether compounds of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, or the like are used.

  As the intrinsic radiation curable pressure-sensitive adhesive, the base polymer (particularly acrylic polymer) having the carbon-carbon double bond can be used alone, but the radiation curable monomer does not deteriorate the characteristics. Components and oligomer components can also be blended. The radiation-curable oligomer component or the like is usually in the range of 30 parts by weight, preferably in the range of 0 to 10 parts by weight with respect to 100 parts by weight of the base polymer.

  The radiation curable pressure-sensitive adhesive contains a photopolymerization initiator when cured by ultraviolet rays or the like. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α′-dimethylacetophenone, 2-methyl-2-hydroxypropio Α-ketol compounds such as phenone and 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- ( Acetophenone compounds such as methylthio) -phenyl] -2-morpholinopropane-1; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether; ketal compounds such as benzyldimethyl ketal; 2-naphthalenesulfo Aromatic sulfonyl chloride compounds such as luchloride; Photoactive oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; benzophenone, benzoylbenzoic acid, 3,3′-dimethyl Benzophenone compounds such as -4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 Thioxanthone compounds such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; camphorquinone; halogenated ketone; acyl phosphinoxide; acyl phosphonate. The compounding quantity of a photoinitiator is about 0.05-20 weight part with respect to 100 weight part of base polymers, such as an acryl-type polymer which comprises an adhesive.

  Examples of the radiation curable pressure-sensitive adhesive include photopolymerizable compounds such as an addition polymerizable compound having two or more unsaturated bonds and an alkoxysilane having an epoxy group disclosed in JP-A-60-196956. And rubber-based pressure-sensitive adhesives and acrylic pressure-sensitive adhesives containing photopolymerization initiators such as carbonyl compounds, organic sulfur compounds, peroxides, amines, and onium salt-based compounds.

  The radiation curable pressure-sensitive adhesive layer 12 may contain a compound that is colored by radiation irradiation, if necessary. By including a compound to be colored in the pressure-sensitive adhesive layer 12 by irradiation with radiation, only the irradiated portion can be colored. The compound that is colored by irradiation with radiation is a colorless or light color compound before irradiation with radiation, but becomes a color by irradiation with radiation, and examples thereof include leuco dyes. The use ratio of the compound colored by radiation irradiation can be set as appropriate.

  The thickness of the pressure-sensitive adhesive layer 12 is not particularly limited, but is preferably about 1 to 50 μm from the viewpoint of preventing chipping of the chip cut surface and compatibility of fixing and holding the adhesive sheet 3. Preferably it is 2-30 micrometers, Furthermore, 5-25 micrometers is preferable.

  The adhesive sheet with dicing sheet 10 is preferably protected by a separator (not shown). That is, it is preferable that a separator is disposed on the adhesive sheet 3. The separator has a function as a protective material that protects the adhesive sheet 3 until it is put to practical use. The separator is peeled off when the workpiece is stuck on the adhesive sheet 3. As the separator, it is also possible to use polyethylene terephthalate (PET), polyethylene, polypropylene, a plastic film or paper whose surface is coated with a release agent such as a fluorine release agent or a long-chain alkyl acrylate release agent.

  The adhesive sheet 10 with a dicing sheet can be manufactured by a normal method. For example, the adhesive sheet 10 with a dicing sheet can be manufactured by bonding the adhesive layer 12 of the dicing sheet 1 and the adhesive sheet 3 together.

  The peeling force when the adhesive sheet 3 is peeled off from the dicing sheet 1 under conditions of a peeling temperature of 25 ° C. and a peeling speed of 300 mm / min is preferably 0.1 N / 10 mm or more. If it is less than 0.1 N / 10 mm, there is a risk of chip jumping. On the other hand, the peeling force is preferably 0.2 N / 10 mm or less. If it exceeds 0.2 N / 10 mm, the pickup tends to be difficult.

(Method for manufacturing semiconductor device)
As shown in FIG. 4, the semiconductor wafer 4 is pressure-bonded to the adhesive sheet 10 with a dicing sheet. Examples of the semiconductor wafer 4 include a silicon wafer, a silicon carbide wafer, and a compound semiconductor wafer. Examples of compound semiconductor wafers include gallium nitride wafers.

  Examples of the crimping method include a method of pressing with a pressing means such as a crimping roll.

The pressing temperature (sticking temperature) is preferably 35 ° C. or higher, and more preferably 37 ° C. or higher. The upper limit of the pressure bonding temperature is preferably lower, preferably 50 ° C. or lower, more preferably 45 ° C. or lower. By crimping at a low temperature, it is possible to prevent the thermal effect on the semiconductor wafer 4 and to suppress warping of the semiconductor wafer 4. Moreover, it is preferable that it is 1 * 10 < ⁵ > Pa-1 * 10 < ⁷ > Pa, and it is more preferable that a pressure is 2 * 10 < ⁵ > Pa-8 * 10 < ⁶ > Pa.

  As shown in FIG. 5, die bonding chips 41 are formed by dicing the semiconductor wafer 4. The die bonding chip 41 includes a semiconductor chip 5 and an adhesive film 31 disposed on the semiconductor chip 5. The semiconductor chip 5 includes a chip body 502 and pads 501 disposed on the chip body 502. The pad 501 is an electrode pad. Examples of the material of the pad 501 include aluminum. In this step, it is possible to employ a cutting method called full cut that cuts up to the adhesive sheet with dicing sheet 10. The dicing apparatus is not particularly limited, and a conventionally known apparatus can be used. Moreover, since the semiconductor wafer 4 is bonded and fixed by the adhesive sheet 10 with a dicing sheet, chip chipping and chip jumping can be suppressed, and damage to the semiconductor wafer 4 can also be suppressed.

  The die bonding chip 41 is picked up. The pickup method is not particularly limited, and various conventionally known methods can be employed. For example, there is a method in which each semiconductor chip 5 is pushed up by a needle from the dicing sheet-attached adhesive sheet 10 side, and then the die bonding chip 41 is picked up by a pickup device.

  When the pressure-sensitive adhesive layer 12 is an ultraviolet curable type, the pressure-sensitive adhesive layer 12 is picked up after being irradiated with ultraviolet rays. Thereby, since the adhesive force with respect to the die-bonding chip | tip 41 of the adhesive layer 12 falls, the chip | tip 41 for die-bonding can be picked up easily. Conditions such as irradiation intensity and irradiation time at the time of ultraviolet irradiation are not particularly limited, and may be set as necessary.

  As shown in FIG. 6, an adherend 61 with a semiconductor chip is obtained by pressure-bonding a die bonding chip 41 to the adherend 6. The adherend 61 with a semiconductor chip includes an adherend 6, an adhesive film 31 disposed on the adherend 6, and a semiconductor chip 5 disposed on the adhesive film 31. The adherend 6 includes a main body portion 602 and a terminal portion 601 disposed on the main body portion 602.

  The temperature at which the die bonding chip 41 is pressure-bonded to the adherend 6 (hereinafter referred to as “die attach temperature”) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher. The die attach temperature is preferably 150 ° C. or lower, more preferably 130 ° C. or lower.

  The adhesive film 31 is cured by heating the adherend 61 with a semiconductor chip under pressure. Thereby, the semiconductor chip 5 is fixed to the adherend 6. By curing the adhesive film 31 under pressure, voids existing between the adhesive film 31 and the adherend 6 can be eliminated, and an area where the adhesive film 31 contacts the adherend 6 can be secured. .

Examples of a method of heating under pressure include a method of heating the adherend 61 with a semiconductor chip disposed in a chamber filled with an inert gas. The pressure of the pressurized atmosphere is preferably 0.5 kg / cm ² (4.9 × 10 ⁻² MPa) or more, more preferably 1 kg / cm ² (9.8 × 10 ⁻² MPa) or more, and further preferably 5 kg. / Cm ² (4.9 × 10 ⁻¹ MPa) or more. If it is 0.5 kg / cm ² or more, voids existing between the adhesive film 31 and the adherend 6 can be easily eliminated. The pressure of the pressurized atmosphere is preferably 20kg ^/ cm 2 (1.96MPa), more preferably 18kg ^/ cm 2 (1.77MPa) or less, more preferably not more than 15kg ^/ cm 2 (1.47MPa). The protrusion of the adhesive film 31 due to excessive pressurization can be suppressed when it is 20 kg / cm ² or less.

  The heating temperature is preferably 80 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher. When the temperature is 80 ° C. or higher, the adhesive film 31 can have an appropriate hardness, and voids can be effectively eliminated by pressure curing. The heating temperature is preferably 260 ° C. or lower, more preferably 200 ° C. or lower, more preferably 180 ° C. or lower. The decomposition | disassembly of the adhesive film 31 can be prevented as it is 260 degrees C or less.

  The heating time is preferably 0.1 hour or longer, more preferably 0.2 hour or longer. The heating time is preferably 24 hours or less, more preferably 3 hours or less, still more preferably 1 hour or less, and particularly preferably 30 minutes or less.

  As shown in FIG. 7, a wire bonding step of electrically connecting the pad 501 and the terminal portion 601 with the bonding wire 7 is performed. Examples of the material of the bonding wire 7 include copper.

  The wire bonding process includes a step of bonding one end of the bonding wire 7 and the pad 501, a step of bonding the other end of the bonding wire 7 and the terminal portion 601, and the like.

  Specifically, the step of bonding one end of the bonding wire 7 and the pad 501 is performed by applying ultrasonic waves to the bonding wire 7 while pressing one end of the bonding wire 7 on the pad 501. It is a step to join.

  The bonding is preferably performed at 175 ° C. or higher, more preferably 200 ° C. or higher. On the other hand, the bonding is preferably performed at 300 ° C. or lower, more preferably 260 ° C. or lower.

  Specifically, the step of bonding the other end of the bonding wire 7 and the terminal portion 601 is performed by applying ultrasonic waves to the bonding wire 7 while pressing the other end of the bonding wire 7 to the terminal portion 601. And the terminal portion 601 are joined.

  After performing the wire bonding process, a sealing process for sealing the semiconductor chip 5 with the sealing resin 8 is performed. This step is performed to protect the semiconductor chip 5 and the bonding wire 7 mounted on the adherend 6. This step is performed by molding a sealing resin with a mold. As the sealing resin 8, for example, an epoxy resin is used. The heating temperature at the time of resin sealing is preferably 165 ° C. or higher, more preferably 170 ° C. or higher, and the heating temperature is preferably 185 ° C. or lower, more preferably 180 ° C. or lower.

  If necessary, further heating may be performed after sealing (post-curing step). Thereby, the sealing resin 8 which is insufficiently cured in the sealing process can be completely cured. The heating temperature can be set as appropriate.

  As described above, the pad 501 is provided by preparing the adhesive sheet 10 with a dicing sheet, crimping the semiconductor wafer 4 to the adhesive sheet 3, and dicing the semiconductor wafer 4 disposed on the adhesive sheet 3. A step of forming a die bonding chip 41 including a semiconductor chip 5 and an adhesive film 31 disposed on the semiconductor chip 5, and an adhesion with a chip by pressing the die bonding chip 41 to an adherend 6 including a terminal portion 601 A step of forming the body 61, a step of curing the adhesive film 31 by heating the adherend 61 with a chip, a step of joining one end of the wire 7 containing copper and the pad 501, and the other end of the wire 7 and a terminal. Including a step of bonding the part 601 and a step performed after the step of curing the adhesive film 31. By law, it can manufacture a semiconductor device.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded.

The components used in the examples will be described.
Acrylic rubber: Teisan Resin SG-708-6 manufactured by Nagase ChemteX Corporation (acrylic ester copolymer containing carboxyl group and hydroxyl group, Mw: 700,000, acid value: 9 mgKOH / g, glass transition temperature: 4 ° C.)
Epoxy resin 1: EPPN-501HY (epoxy resin having an epoxy equivalent of 169 g / eq.) Manufactured by Nippon Kayaku Co., Ltd.
Epoxy resin 2: EOCN-1020 (epoxy resin having an epoxy equivalent of 198 g / eq.) Manufactured by Nippon Kayaku Co., Ltd.
Epoxy resin 3: jER828 manufactured by Mitsubishi Chemical Corporation (epoxy resin having an epoxy equivalent of 190 g / eq.)
Phenolic resin 1: MEH-7851S (phenolic resin having a hydroxyl group equivalent of 209 g / eq.) Manufactured by Meiwa Kasei Co., Ltd.
Phenol resin 2: P-180 manufactured by Arakawa Chemical Co. (phenol resin having a hydroxyl group equivalent of 105 g / eq.)
Silica filler: Ad-25X SO-25R (spherical silica having a BET specific surface area of 6.5 m ² / g and a new Mohs hardness of 7)
Catalyst: TPP-MK (tetraphenylphosphonium tetra-p-tolylborate) manufactured by Hokuko Chemical Co., Ltd.

[Preparation of adhesive sheet and adhesive sheet with dicing sheet]
According to the mixing ratio shown in Table 1, each component and solvent (methyl ethyl ketone) shown in Table 1 were placed in a stirring vessel of a hybrid mixer (HM-500 manufactured by Keyence), and stirred and mixed in a stirring mode for 3 minutes. The obtained varnish was applied to a release treatment film (MRA50 manufactured by Mitsubishi Resin Co., Ltd.) with a die coater and then dried to obtain an adhesive sheet having a thickness of 20 μm. A 230 mm diameter circular adhesive sheet is cut out from the adhesive sheet, and the circular adhesive sheet is attached to the adhesive layer of a dicing sheet (P2130G manufactured by Nitto Denko Corporation) at 25 ° C. to obtain an adhesive sheet with a dicing sheet. Produced.

[Evaluation]
The following evaluation was performed about the obtained adhesive sheet and the adhesive sheet with a dicing sheet. The results are shown in Table 1.

(Measurement of storage modulus and Tg)
The adhesive sheet was laminated at 60 ° C. to obtain a laminated sheet having a thickness of 400 μm. A processed product was obtained by processing the laminated sheet into a size of 10 mm × 30 mm × 400 μm. The workpiece was cured by heating at 175 ° C. for 30 minutes. After curing, the viscoelasticity of the processed product was measured using a dynamic viscoelasticity measuring device (RSA III manufactured by TA Instruments). The measurement conditions were a temperature range of −10 ° C. to 285 ° C., a heating rate of 10 ° C./min, and a chuck distance of 22.5 mm and 10 Hz. The storage elastic modulus at 200 ° C. was read from the obtained storage elastic modulus data. The temperature of the obtained tan δ peak was defined as Tg.

(Measurement of reaction heat)
A 10 mg test piece was cut out from the adhesive sheet. A measurement sample was prepared by sandwiching the test piece with an aluminum pan. A reference sample consisting only of an aluminum pan was also prepared. Measurement was performed at a temperature rising rate of 10 ° C./min and a temperature range of 25 ° C. to 300 ° C. using an suggested scanning calorimeter (DSC 6220 manufactured by Seiko Instruments Inc.). The heat of reaction was calculated by dividing the heat of the obtained exothermic reaction peak by the weight of the sample.

(Measurement of peak disappearance time)
A 10 mg test piece was cut out from the adhesive sheet. A measurement sample was prepared by sandwiching the test piece with an aluminum pan. A reference sample consisting only of an aluminum pan was also prepared. Using an suggested operation calorimeter (DSC 6220, manufactured by Seiko Instruments Inc.), the temperature was raised from 25 ° C. to 175 ° C. over 3 minutes, and then DSC was measured under the condition of maintaining 175 ° C. for 3 hours. The time from reaching 175 ° C. until the reaction peak disappeared was read from the DSC curve. Note that “the reaction peak disappears” means that the difference in input of thermal energy per unit time applied to both the measurement sample and the reference sample becomes constant so that the temperatures of the measurement sample and reference sample become equal. The DSC curve of Example 2 is shown in FIG.

(Wire bond property)
A wafer having a thickness of 100 μm was obtained by grinding a wafer having aluminum deposited on one side. The dicing wafer was attached to an adhesive sheet with a dicing sheet and then diced into 2 mm squares to obtain a chip with an adhesive sheet. A chip with an adhesive sheet was die-attached on a Cu lead frame at 120 ° C., 0.1 MPa, and 1 sec. The adhesive sheet was cured by heating at 175 ° C. for 30 minutes. Using a wire bonding apparatus (Maxum Plus manufactured by K & S), five Cu wires having a wire diameter of 20 μm were bonded to one chip. A Cu wire was struck onto a Cu lead frame under the conditions of an output of 80 Amp, a time of 10 ms, and a load of 50 g. Cu wire was struck onto the chip under the conditions of 200 ° C., output 125 Amp, time 10 ms, and load 80 g. The case where one or more of the five Cu wires could not be bonded to the chip was determined as x, and the case where five of the five Cu wires could be bonded to the chip was determined as ◯.

DESCRIPTION OF SYMBOLS 10 Adhesive sheet with dicing sheet 1 Dicing sheet 11 Base material 12 Adhesive layer 3 Adhesive sheet 4 Semiconductor wafer 5 Semiconductor chip 501 Pad 502 Chip body part 41 Die-bonding chip 6 Substrate 601 Terminal part 602 Body part 61 Semiconductor chip-attached object Kimono 7 Bonding wire 8 Sealing resin

Claims (9)

In the DSC curve drawn by DSC measurement under the condition that the temperature is raised from 25 ° C. to 175 ° C. in 3 minutes and then maintained at 175 ° C. for 3 hours, the time from reaching 175 ° C. until the reaction peak disappears is 30 minutes Is less than
The tensile storage elastic modulus at 200 ° C. obtained by measuring the viscoelasticity of the cured product obtained by heating at 175 ° C. for 30 minutes at 10 Hz is 100 MPa or more.
An adhesive sheet used in the manufacture of semiconductor devices.   2. The adhesive sheet according to claim 1, wherein a reaction heat obtained by DSC measurement under a condition in which a temperature is raised in a range of 25 ° C. to 300 ° C. at 10 ° C. per minute is 80 mJ / mg or more.   The adhesive sheet according to claim 1 or 2, wherein the Tg of the cured product obtained by curing at 175 ° C for 30 minutes is 150 ° C or higher. Including a silica filler having a BET specific surface area of 4 m ² / g or more,
The adhesive sheet according to claim 1, wherein the content of the silica filler is 50% by weight or more.   Hydroxyl equivalent weight is 120 g / eq. The adhesive sheet in any one of Claims 1-4 containing the following phenol resins. Including resin components,
The resin component includes an epoxy resin, a phenol resin, and an acrylic resin,
The adhesive sheet according to any one of claims 1 to 4, wherein a content of the acrylic resin in 100% by weight of the resin component is 14% by weight or less.   The phenol resin has a hydroxyl group equivalent of 120 g / eq. The adhesive sheet according to claim 6, which is as follows. A dicing sheet comprising a base material and an adhesive layer disposed on the base material;
The adhesive sheet with a dicing sheet provided with the adhesive sheet in any one of Claims 1-7 arrange | positioned on the said adhesive layer. Preparing an adhesive sheet with a dicing sheet according to claim 8;
Crimping a semiconductor wafer to the adhesive sheet;
Forming a die bonding chip including a semiconductor chip including a pad and an adhesive film disposed on the semiconductor chip by dicing the semiconductor wafer disposed on the adhesive sheet; and
Forming a chip-attached adherend by crimping the die-bonding chip to an adherend having a terminal portion;
Curing the adhesive film by heating the adherend with a chip; and
A method of manufacturing a semiconductor device, comprising: a step of bonding one end of a wire containing copper and the pad; and a step of bonding the other end of the wire and the terminal portion;

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