JP2013030500A - Adhesive sheet for manufacturing semiconductor device, adhesive sheet for manufacturing semiconductor device integrated with dicing film, and semiconductor device containing adhesive sheet for manufacturing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive sheet for manufacturing a semiconductor device, capable of suppressing diffusion of cation in the adhesive sheet for manufacturing a semiconductor device.SOLUTION: The adhesive sheet for manufacturing a semiconductor device is used for pasting a second semiconductor chip on a first semiconductor chip where a bonding wire is connected to its upper surface, so that a part of the bonding wire is embedded in the adhesive sheet for manufacturing a semiconductor device. It contains an ion capturing agent, with a glass transition temperature after thermo-setting being 50°C or higher.

Description

  The present invention relates to an adhesive sheet for manufacturing a semiconductor device, an adhesive sheet for manufacturing a dicing film integrated semiconductor device, and a semiconductor device having an adhesive sheet for manufacturing a semiconductor device.

  In recent years, a stacked MCP (Multi Chip Package) in which memory package chips for mobile phones and portable audio devices are stacked in multiple stages has become widespread. In addition, with the increasing functionality of image processing technology and mobile phones, etc., higher density, higher integration, and thinner packages are being promoted.

  On the other hand, when cations (for example, copper ions or iron ions) are mixed into the crystal substrate of the wafer from the outside during the semiconductor manufacturing process, and these cations reach the circuit formation surface formed on the wafer, the electrical characteristics There has been a problem of lowering. In addition, there is a problem that cations are generated from circuits and wires during use of the product, resulting in deterioration of electrical characteristics.

  In order to solve the above-described problems, conventionally, an extrinsic gettering (hereinafter also referred to as “EG”) in which a back surface of a wafer is processed to form a crushed layer (strain) and a cation is captured and removed by the crushed layer. Intrinsic gettering (hereinafter also referred to as “IG”) in which oxygen precipitation defects are formed in the crystal substrate of the wafer and cations are captured and removed by the oxygen precipitation defects has been attempted.

  However, with the recent thinning of the wafer, the IG effect is reduced, and the backside distortion that causes the wafer to crack and warp is removed, so that the EG effect cannot be obtained and the gettering effect is improved. There was a problem that it could not be obtained sufficiently.

  Patent Document 1 describes a film adhesive provided with a copper ion adsorption layer containing a resin having a skeleton capable of complexing with copper ions. In addition, it is described that copper ions can be chemically adsorbed inside the resin of the copper ion adsorption layer, and the influence of copper ions generated from a member made of copper can be significantly reduced as compared with the conventional case. ing. Patent Documents 2 and 3 describe an adhesive composition containing an ion scavenger, and it is disclosed that this ion scavenger has an effect of capturing chlorine ions and the like. Patent Document 4 describes a film adhesive containing an ion trapping agent, and describes that the ion trapping agent captures a halogen element. Patent Document 5 describes an adhesive sheet containing an anion exchanger. Patent Document 6 describes a sheet-like adhesive containing a chelate-modified epoxy resin and capable of capturing internal ionic impurities.

JP 2011-52109 A JP 2009-203337 A JP 2009-203338 A JP 2010-116453 A JP 2009-256630 A JP 2011-105875 A

  The film adhesives of Patent Documents 2 to 5 do not disclose capturing cations. Therefore, it is difficult to prevent a decrease in electrical characteristics based on cations only by capturing chloride ions.

  Moreover, according to the film adhesive of patent document 1, and the sheet adhesive of patent document 6, a copper ion can be capture | acquired. However, when the temperature of the film adhesive increases according to the surrounding environment at the time of use, the cation easily moves in the film adhesive. Therefore, there is a problem that cations easily reach the circuit formation surface and cause malfunction. In particular, when a film adhesive is affixed to a semiconductor chip so that a part of the bonding wire is embedded in the film adhesive, it is also affected by cations generated from the bonding wire.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an adhesive sheet for manufacturing a semiconductor device capable of suppressing cation diffusion in the adhesive sheet for manufacturing a semiconductor device, and the semiconductor device. An object of the present invention is to provide an adhesive sheet for manufacturing a dicing film integrated semiconductor device in which an adhesive sheet for manufacturing is laminated on a dicing film, and a semiconductor device having the adhesive sheet for manufacturing the semiconductor device.

  The inventors of the present application have studied an adhesive sheet for manufacturing a semiconductor device in order to solve the conventional problems. As a result, the inventors have found that it is possible to suppress the diffusion of cations in the adhesive sheet for manufacturing a semiconductor device by adopting the following configuration, and have completed the present invention.

  That is, in the adhesive sheet for manufacturing a semiconductor device according to the present invention, a part of the bonding wire is embedded in the adhesive sheet for manufacturing a semiconductor device on the first semiconductor chip having the bonding wire connected to the upper surface. As described above, an adhesive sheet for manufacturing a semiconductor device for attaching a second semiconductor chip, which contains an ion scavenger and has a glass transition temperature after thermosetting of 50 ° C. or higher. To do.

  According to the said structure, since the ion capture | acquisition agent is contained, it can capture | acquire the cation mixed from the outside during the various processes in manufacture of a semiconductor device, and the cation generate | occur | produced from a bonding wire. As a result, cations mixed from the outside and cations generated from the bonding wire are difficult to reach the circuit forming surface formed on the wafer, and the deterioration of the electrical characteristics is suppressed and the product reliability is improved. Can do.

  Moreover, when a part of bonding wire is embedded in the adhesive sheet for semiconductor device manufacture, a cation not only mixes from the outside but a bonding wire is also generated. Therefore, there is a possibility that the cation cannot be sufficiently captured only by the ion scavenger. The adhesive sheet for manufacturing a semiconductor device of the present invention has a glass transition temperature after thermosetting of 50 ° C. or higher. This 50 ° C. is a temperature higher than a normal temperature at the time of use of the semiconductor device using the adhesive sheet for manufacturing the semiconductor device. Therefore, diffusion (movement) of cations in the adhesive sheet for manufacturing a semiconductor device can be suppressed. As a result, even when the cation cannot be completely captured by the ion scavenger, it is possible to suppress the cation from reaching the circuit formation surface and prevent malfunction.

  In the said structure, it is preferable that the melt viscosity in 140 degreeC before thermosetting is 10 Pa.s or more and 5000 Pa.s or less, and the tensile storage elastic modulus in 260 degreeC after thermosetting is 1 Mpa or more. When the melt viscosity at 140 ° C. before thermosetting is 10 Pa · s or more, the bonding wire can be suitably embedded in an adhesive sheet for manufacturing a semiconductor device. Further, when the melt viscosity at 140 ° C. before thermosetting is 5000 Pa · s or less, the bonding wire can be embedded in a state where the deformation of the bonding wire is small. Moreover, reflow resistance can be improved as the tensile storage elastic modulus in 260 degreeC after thermosetting is 1 Mpa or more. The tensile storage modulus and melt viscosity can be measured by the methods described in the examples.

  In the above configuration, the ion scavenger is preferably an organic complex-forming compound that forms a complex with a cation. When the ion scavenger is an organic complex-forming compound that forms a complex with a cation, since it is organic, damage to the bonding wire due to contact with the bonding wire can be suppressed.

  In the said structure, the copper ion density | concentration in the said aqueous solution after immersing the adhesive sheet for semiconductor device manufacture of 2.5 g in weight in 50 ml of aqueous solution which has a copper ion of 10 ppm, and leaving it to stand at 120 degreeC for 20 hours. 0 to 9.8 ppm is preferable. According to the said structure, the copper ion mixed from the outside in the various processes in manufacture of a semiconductor device and the copper ion generate | occur | produced from the bonding wire are captured more. As a result, it becomes difficult for copper ions to reach the circuit formation surface formed on the wafer.

  In the above-mentioned configuration, the chloride ion concentration in the aqueous solution after immersing an adhesive sheet for manufacturing a semiconductor device weighing 2.5 g in 50 ml of ion-exchanged water and leaving it at 120 ° C. for 20 hours is 0.00. It is preferable that it is 1 ppm or less. When chloride ions are present, the generation of cations is promoted. However, in the above configuration, the concentration of chloride ions in the aqueous solution after the operation is 0.1 ppm or less. Promotion is suppressed. That is, according to the configuration, since the promotion of the generation of cations is suppressed, the deterioration of the electrical characteristics of the semiconductor device manufactured using the adhesive sheet for manufacturing the semiconductor device is further suppressed, and the product reliability is improved. Can be improved.

  In the said structure, it is preferable that an inorganic filler is included. By including the inorganic filler, it is possible to suppress a decrease in the tensile storage elastic modulus at a high temperature (for example, 140 ° C.).

  In the said structure, it is preferable that an acrylic resin, an epoxy resin, a phenol resin, and an epoxy resin curing catalyst are included.

  In addition, an adhesive sheet for manufacturing a dicing film integrated semiconductor device according to the present invention is characterized in that the adhesive sheet for manufacturing a semiconductor device is laminated on a dicing film in order to solve the above problems. To do.

  The semiconductor device according to the present invention is a semiconductor device having the above-mentioned adhesive sheet for manufacturing a semiconductor device, wherein a part of a bonding wire is embedded in the adhesive sheet for manufacturing the semiconductor device. And According to the said structure, since it has the said adhesive sheet for semiconductor device manufacture, while catching the cation mixed from the outside and the cation generated from a bonding wire with an ion trapping agent, it is cation with an ion trapping agent. Even if it is not able to be trapped, it is possible to suppress the cation from reaching the circuit formation surface and prevent malfunction. As a result, a semiconductor device with improved product reliability can be obtained.

It is a cross-sectional schematic diagram which shows the adhesive sheet for dicing film integrated semiconductor device manufacture which concerns on this embodiment. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on this embodiment. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on this embodiment. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on this embodiment. It is a top view which shows typically the comb-type electrode used for HAST-proof evaluation.

  In the adhesive sheet for manufacturing a semiconductor device of the present invention (hereinafter also simply referred to as “adhesive sheet”), a part of the bonding wire is manufactured on the first semiconductor chip having the bonding wire connected to the upper surface. This is an adhesive sheet for attaching the second semiconductor chip so as to be embedded in the adhesive sheet for use.

  The adhesive sheet contains an ion scavenger. Since the ion scavenger is contained, it is possible to capture cations mixed from the outside during various processes in the manufacture of semiconductor devices and cations generated from bonding wires. As a result, cations mixed from the outside and cations generated from the bonding wire are difficult to reach the circuit forming surface formed on the wafer, and the deterioration of the electrical characteristics is suppressed and the product reliability is improved. Can do. The ion scavenger is preferably an additive that captures at least cations.

  Examples of the additive that captures at least a cation include a cation exchanger and a complex-forming compound. Among these, a cation exchanger is preferable from the viewpoint of excellent heat resistance, and a complex-forming compound is more preferable from the viewpoint that cations can be captured well.

  The cation exchanger is preferably an inorganic cation exchanger from the viewpoint that it can capture cations more suitably.

  In the present invention, the cation captured by the additive that captures at least the cation is not particularly limited as long as it is a cation. For example, Na, K, Ni, Cu, Cr, Co, Hf, Pt, Examples of the ions include Ca, Ba, Sr, Fe, Al, Ti, Zn, Mo, Mn, and V.

(Inorganic cation exchanger)
The inorganic cation exchanger is not particularly limited, and a conventionally known inorganic cation exchanger can be used.For example, from the viewpoint of capturing a cation more suitably, antimony, bismuth, zirconium, titanium, An oxide hydrate of an element selected from the group consisting of tin, magnesium and aluminum can be mentioned. These can be used alone or in combination of two or more. Of these, oxidized hydrates of magnesium and aluminum are preferable.

  As a commercial item of the said inorganic cation exchanger, Toa Gosei Co., Ltd. brand names: IXE-700F, IXE-770, IXE-770D, IXE-2116, IXE-100, IXE-300, IXE-500, IXE -600, IXE-633, IXE-6107, IXE-6136, and the like.

  The average particle size of the inorganic cation exchanger is preferably 0.05 to 20 μm, and more preferably 0.1 to 10 μm. By setting the average particle size of the inorganic cation exchanger to 20 μm or less, it is possible to suppress a decrease in adhesive force, and by setting the average particle size to 0.05 μm or more, it is possible to improve dispersibility.

(Complex-forming compound)
The complex-forming compound is not particularly limited as long as it forms a complex with a cation. From the viewpoint of suppressing damage to the bonding wire due to contact with the bonding wire, the organic complex It is preferably a forming compound, and among these, from the viewpoint that a cation can be suitably captured, it is preferably at least one selected from the group consisting of a nitrogen-containing compound, a hydroxyl group-containing compound, and a carboxylic acid group-containing compound.

(Nitrogen-containing compounds)
The nitrogen-containing compound is preferably in the form of fine powder, easily dissolved in an organic solvent, or liquid. Examples of such nitrogen-containing compounds include triazole compounds, tetrazole compounds, and bipyridyl compounds from the viewpoint of more suitably capturing cations, but the stability of complexes formed with copper ions. In view of the above, a triazole compound is more preferable. These can be used alone or in combination of two or more.

  The triazole compound is not particularly limited, but 1,2,3-benzotriazole, 1- {N, N-bis (2-ethylhexyl) aminomethyl} benzotriazole, carboxybenzotriazole, 2- {2′-hydroxy -5'-methylphenyl} benzotriazole, 2- {2'-hydroxy-3 ', 5'-di-t-butylphenyl} -5-chlorobenzotriazole, 2- {2'-hydroxy-3'-t -Butyl-5'-methylphenyl} -5-chlorobenzotriazole, 2- {2'-hydroxy-3 ', 5'-di-t-amylphenyl} benzotriazole, 2- {2'-hydroxy-5' -T-octylphenyl} benzotriazole, 6- (2-benzotriazolyl) -4-t-octyl-6'-t-butyl-4 ' Methyl-2,2′-methylenebisphenol, 1- (2 ′, 3′-hydroxypropyl) benzotriazole, 1- (1 ′, 2′-dicarboxydiethyl) benzotriazole, 1- (2-ethylhexamino) Methyl) benzotriazole, 2,4-di-t-benzyl-6-{(H-benzotriazol-1-yl) methyl} phenol, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzo Triazole, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, octyl-3- [3-t-butyl-4-hydroxy-5- (5- Chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5 Chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3 3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4-t-butylphenol, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′- Hydroxy-5'-t-octylphenyl) -benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- 3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chloro -Benzotriazole, 2- [2'-hydroxy-3,5-di (1,1-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2'-methylenebis [6- (2H-benzotriazole-2- Yl) -4- (1,1,3,3-metramethylbutyl) phenol], (2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, And methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate.

  Although it does not restrict | limit especially as a commercial item of the said triazole compound, The brand name made from Johoku Chemical Co., Ltd .: BT-120, BT-LX, CBT-1, JF-77, JF-78, JF-79, JF- Product names of 80, JF83, JAST-500, BT-GL, BT-M, BT-260, BT-365, BASF: TINUVIN PS, TINUVIN P, TINUVIN P FL, TINUVIN 99-2, TINUVIN 109, TINUVIN 900 , TINUVIN 928, TINUVIN 234, TINUVIN 329, TINUVIN 329 FL, TINUVIN 326, TINUVIN 326 FL, TINUVIN 571, TINUVIN 213, Taiwan Yongkou Chemical Co., Ltd. Product names: EVESORB 81, EVES RB109, EVESORB 70, EVESORB 71, EVESORB 72, EVESORB 73, EVESORB 74, EVESORB 75, can be cited EVESORB 76, EVESORB 78, EVESORB 80 or the like. Triazole compounds are also used as rust inhibitors.

  Although it does not specifically limit as said tetrazole compound, 5-amino-1H-tetrazole etc. are mentioned.

  Although it does not specifically limit as said bipyridyl compound, 2,2'-bipyridyl, 1, 10-phenanthroline etc. are mentioned.

(Hydroxyl-containing compound)
Although it does not restrict | limit especially as said hydroxyl-containing compound, The thing of a fine powder form, the thing easy to melt | dissolve in an organic solvent, or a liquid thing is preferable. As such a hydroxyl group-containing compound, a quinol compound, a hydroxyanthraquinone compound, or a polyphenol compound can be exemplified from the viewpoint of more suitably capturing a cation, but the stability of a complex formed with a copper ion can be exemplified. From the viewpoint of properties, a polyphenol compound is more preferable. These can be used alone or in combination of two or more.

  Although it does not specifically limit as said quinol compound, 1, 2- benzenediol etc. are mentioned.

  Although it does not specifically limit as said hydroxyanthraquinone compound, Alizarin, anthralfin, etc. are mentioned.

  Although it does not specifically limit as said polyphenol compound, A tannin, a tannin derivative (gallic acid, methyl gallate, pyrogallol) etc. are mentioned.

(Carboxylic acid group-containing compound)
Although it does not specifically limit as said carboxylic acid group containing compound, A carboxyl group containing aromatic compound, a carboxyl group containing fatty acid compound, etc. are mentioned.

  The carboxyl group-containing aromatic compound is not particularly limited, and examples thereof include phthalic acid, picolinic acid, and pyrrole-2-carboxylic acid.

  The carboxyl group-containing fatty acid compound is not particularly limited, and examples thereof include higher fatty acids and carboxylic acid chelating reagents.

  Although it does not restrict | limit especially as a commercial item of the said carboxylic acid type | system | group chelating reagent, The product name made from Kyrest Co., Ltd .: Kyrest A, Kyrest 110, Kyrest B, Kyrest 200, Kyrest C, Kyrest D, Kyrest 400, Kyrest 40, Examples include Kirest 0D, Kirest NTA, Kirest 700, Kirest PA, Kirest HA, Kirest MZ-2, Kirest MZ-4A, and Kirest MZ-8.

  The content of the ion scavenger is preferably 0.1 to 80 parts by weight, and more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the resin component constituting the adhesive sheet. More preferably, it is 0.1 to 20 parts by weight. By setting the amount to 0.1 parts by weight or more, cations (particularly copper ions) can be effectively captured, and by setting the amount to 80 parts by weight or less, a decrease in heat resistance and an increase in cost are suppressed. Can do.

  The adhesive sheet has a glass transition temperature after thermosetting of 50 ° C. or higher, preferably 60 ° C. or higher and 200 ° C. or lower, and more preferably 70 ° C. or higher and 180 ° C. or lower. When a part of the bonding wire is embedded in the adhesive sheet, cations are not only mixed from the outside, but also a bonding wire is generated. Therefore, there is a possibility that the cation cannot be sufficiently captured only by the ion scavenger. The adhesive sheet has a glass transition temperature of 50 ° C. or higher after thermosetting. This 50 ° C. is a temperature higher than the normal temperature when using the semiconductor device using the adhesive sheet. Therefore, the diffusion (movement) of the cation in the adhesive sheet can be suppressed. As a result, even when the cation cannot be completely captured by the ion scavenger, it is possible to suppress the cation from reaching the circuit formation surface and prevent malfunction. As a method of setting the glass transition temperature after thermosetting to 50 ° C. or higher, the glass transition temperature can be adjusted by the amount of the epoxy resin and the epoxy resin curing catalyst. The glass transition temperature can be determined by the method described in the examples.

  The adhesive sheet preferably has a melt viscosity at 140 ° C. of 10 Pa · s or more and 5000 Pa · s or less, and more preferably 100 Pa · s or more and 3000 Pa · s or less before thermosetting. When the melt viscosity at 140 ° C. before thermosetting is 10 Pa · s or more, the bonding wire can be suitably embedded in an adhesive sheet for manufacturing a semiconductor device. Further, when the melt viscosity at 140 ° C. before thermosetting is 5000 Pa · s or less, the bonding wire can be embedded in a state where the deformation of the bonding wire is small. The melt viscosity at 140 ° C. before thermosetting can be controlled by the amount of acrylic resin.

  The adhesive sheet preferably has a tensile storage modulus at 260 ° C. of 1 MPa or more after heat curing, and more preferably 1 MPa or more and 500 MPa or less. Reflow resistance can be improved as the tensile storage elastic modulus in 260 degreeC after thermosetting is 1 Mpa or more.

  The adhesive sheet has a copper ion concentration of 0-9. After immersing an adhesive sheet having a weight of 2.5 g in 50 ml of an aqueous solution containing 10 ppm of copper ions and leaving it at 120 ° C. for 20 hours. 8 ppm is preferred, 0 to 9.5 ppm is more preferred, and 0 to 9.0 ppm is even more preferred. The adhesive sheet has a copper ion concentration of 0 to 9.9 ppm after immersing an adhesive sheet having a weight of 2.5 g in 50 ml of an aqueous solution containing 10 ppm of copper ions and leaving it at 120 ° C. for 20 hours. In this case, cations mixed from the outside during various processes in manufacturing the semiconductor device are more easily captured. As a result, it becomes difficult for cations mixed from the outside to reach the circuit forming surface formed on the wafer, and the deterioration of the electrical characteristics is suppressed, and the product reliability can be further improved.

  The adhesive sheet is prepared by immersing an adhesive sheet for manufacturing a semiconductor device having a weight of 2.5 g in 50 ml of ion-exchanged water and leaving it at 120 ° C. for 20 hours. It is preferable that it is 1 ppm or less. When chloride ions are present, the generation of cations is promoted. However, when the chloride ion concentration in the aqueous solution after the operation is 0.1 ppm or less, the promotion of the generation of cations is suppressed. The That is, when the chloride ion concentration is 0.1 ppm or less, since the promotion of cation generation is suppressed, the electrical characteristics of the semiconductor device manufactured using the adhesive sheet for manufacturing the semiconductor device are deteriorated. Can be further suppressed and product reliability can be improved.

  Although the said adhesive sheet is not specifically limited, It is preferable that a film thickness is 5-100 micrometers, and it is more preferable that it is 10-80 micrometers. By setting the film thickness of the adhesive sheet to 5 μm or more, cations can be captured more favorably.

  The adhesive sheet preferably contains a thermoplastic resin. Moreover, it is preferable that the said adhesive sheet contains a thermoplastic resin and a thermosetting resin. Examples of the thermosetting resin include phenol resin, amino resin, unsaturated polyester resin, epoxy resin, polyurethane resin, silicone resin, and thermosetting polyimide resin. These resins can be used alone or in combination of two or more, and it is particularly preferable to use at least one of an epoxy resin and a phenol resin. Among these, it is preferable to use an epoxy resin. When an epoxy resin is contained as a curing agent, a high adhesive force between the adhesive sheet and the wafer can be obtained at a high temperature. As a result, it is difficult for water to enter the adhesive interface between the adhesive sheet and the wafer, making it difficult for ions to move. Thereby, reliability is improved.

  The epoxy resin is not particularly limited as long as it is generally used as an adhesive composition, 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 novolak type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type, etc., bifunctional epoxy resin or polyfunctional epoxy resin, or hydantoin type, trisglycidyl isocyanurate Type or glycidylamine type epoxy resin is used. These can be used alone or in combination of two or more. 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 and the like. Moreover, it is preferable to employ | adopt what has little content of chloride ion as an epoxy resin. If such an epoxy resin is employed, an adhesive sheet for manufacturing a semiconductor device having a weight of 2.5 g is immersed in 50 ml of ion exchange water even when an ion scavenger that cannot trap chloride ions is used. The chloride ion concentration in the aqueous solution after being left at 120 ° C. for 20 hours can be made 0.1 ppm or less.

  When using an epoxy resin, it is preferable to use an epoxy resin curing catalyst. As an epoxy resin curing catalyst of an imidazole compound, 2MZ, C11Z, C17Z, 1.2DMZ, 2E4MZ, 2PZ, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CNS, 2PZCNS-PW, 2MZ-A, C11Z-A, 2E4MZ-A, 2MA-OK, 2PHZ-PW, 2P4MHZ-PW (manufactured by Shikoku Chemicals) and the like. Examples of the epoxy resin curing catalyst having a triphenylphosphine skeleton include TPP-PB, TPP-MB, TPP-MC, TPP-MOC, and TPP-ZC (made by Hokuko Chemical Co., Ltd.). Examples of the thermosetting acceleration catalyst that is a salt composed of a triphenylphosphine skeleton and a triphenylborane skeleton include TPP-K, TPP-MK, TPP-ZK, and TPP-S (manufactured by Hokuko Chemical Co., Ltd.). it can. By using an epoxy resin curing catalyst, curing with an epoxy resin and an epoxy resin curing agent can be promoted at a high temperature. As an addition amount of an epoxy resin curing catalyst, it can be 0.1-10 weight part with respect to 100 weight part of resin components which comprise the said adhesive sheet.

  Further, the phenol resin acts as a curing agent for the epoxy resin, for example, a novolac type phenol resin such as a phenol novolac resin, a phenol aralkyl resin, a cresol novolac resin, a tert-butylphenol novolac resin, a nonylphenol novolac resin, Examples include resol-type phenolic resins and polyoxystyrenes such as polyparaoxystyrene. These can be used alone or in combination of two or more. 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 mixing ratio of the epoxy resin and the phenol resin is preferably such that, for example, the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per 1 equivalent of the 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 the above range, sufficient curing reaction does not proceed and the properties of the cured epoxy resin are likely to deteriorate.

  Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, heat Examples thereof include plastic polyimide resins, polyamide resins such as 6-nylon and 6,6-nylon, phenoxy resins, acrylic resins, saturated polyester resins such as PET and PBT, polyamideimide resins, and fluorine resins. These thermoplastic resins can be used alone or in combination of two or more. Of these thermoplastic resins, an acrylic resin that has few ionic impurities and high heat resistance and can ensure the reliability of the semiconductor element is particularly preferable.

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

  In addition, the other monomer forming the polymer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Carboxyl group-containing monomers such as acid anhydride monomers such as maleic anhydride or itaconic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- (meth) acrylic acid 4- Hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4-hydroxymethylcyclohexyl) -Methyla Hydroxyl group-containing monomers such as relate, styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate or (meth) Examples thereof include sulfonic acid group-containing monomers such as acryloyloxynaphthalene sulfonic acid, and phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate. These can be used alone or in combination of two or more.

  The blending ratio of the thermosetting resin is not particularly limited as long as the adhesive sheet exhibits a function as a thermosetting mold when heated under predetermined conditions, but is in the range of 5 to 60% by weight. It is preferable that it is in the range of 10 to 50% by weight.

  Among the adhesive sheets, an epoxy resin, a phenol resin, and an acrylic resin are contained, and the total amount of the epoxy resin and the phenol resin with respect to 100 parts by weight of the acrylic resin is preferably 10 to 2000 parts by weight. It is more preferably ˜1500 parts by weight, and further preferably 10 to 1000 parts by weight. By making the total amount of the epoxy resin and the phenol resin with respect to 100 parts by weight of the acrylic resin 10 parts by weight or more, an adhesive effect due to curing can be obtained, and peeling can be suppressed. It is possible to suppress the workability from being deteriorated due to the weakening of the film.

  When the adhesive sheet is previously crosslinked to some extent, it is preferable to add a polyfunctional compound that reacts with a functional group at the molecular chain end of the polymer as a crosslinking agent. Thereby, the adhesive property under high temperature can be improved and heat resistance can be improved.

  A conventionally well-known thing can be employ | adopted as said crosslinking agent. In particular, polyisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, adducts of polyhydric alcohol and diisocyanate are more preferable. The addition amount of the crosslinking agent is usually preferably 0.05 to 7 parts by weight with respect to 100 parts by weight of the polymer. When the amount of the cross-linking agent is more than 7 parts by weight, the adhesive force is lowered, which is not preferable. On the other hand, if it is less than 0.05 parts by weight, the cohesive force is insufficient, which is not preferable. Moreover, you may make it include other polyfunctional compounds, such as an epoxy resin, together with such a polyisocyanate compound as needed.

  Moreover, a filler can be appropriately blended in the adhesive sheet according to its use. The blending of the filler enables imparting electrical conductivity to the adhesive sheet, improving thermal conductivity, adjusting the elastic modulus, and the like. Examples of the filler include inorganic fillers and organic fillers. Improvement in handling properties, improvement in thermal conductivity, adjustment of melt viscosity, adjustment of tensile storage modulus at high temperature (eg, 140 ° C.), thixo In view of characteristics such as imparting tropic properties, inorganic fillers are preferred. The inorganic filler is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, and aluminum borate whisker. , Boron nitride, crystalline silica, amorphous silica and the like. These can be used alone or in combination of two or more. From the viewpoint of improving thermal conductivity, aluminum oxide, aluminum nitride, boron nitride, crystalline silica, and amorphous silica are preferable. Further, from the viewpoint that the above properties are well balanced, crystalline silica or amorphous silica is preferable. In addition, a conductive substance (conductive filler) may be used as the inorganic filler for the purpose of imparting conductivity and improving thermal conductivity. Examples of the conductive filler include metal powder in which silver, aluminum, gold, cylinder, nickel, conductive alloy and the like are made into a spherical shape, needle shape and flake shape, metal oxide such as alumina, amorphous carbon black, graphite and the like.

  The filler may have an average particle size of 0.01 to 1.0 μm. By setting the average particle size of the filler to 0.01 μm or more, the wettability to the adherend and the adhesiveness can be improved. Moreover, by setting it as 1.0 micrometer or less, while being able to make the effect of the filler added for provision of said each characteristic sufficient, heat resistance can be ensured. In addition, the average particle diameter of a filler is the value calculated | required, for example with the photometric type particle size distribution analyzer (The product made from HORIBA, apparatus name; LA-910).

  In addition to the ion scavenger, other additives can be appropriately blended in the adhesive sheet as necessary. Examples of other additives include an anion scavenger, a dispersant, an antioxidant, a silane coupling agent, and a curing accelerator. These can be used alone or in combination of two or more.

  The production method of the adhesive composition for forming the adhesive sheet is not particularly limited, and for example, the thermosetting resin, the thermoplastic resin, and the ion scavenger, and other, if necessary. Can be obtained as an adhesive composition solution by adding the above additives and the like into a container, dissolving them in an organic solvent, and stirring them uniformly.

  The organic solvent is not particularly limited as long as it can uniformly dissolve, knead or disperse the components constituting the adhesive sheet, and a conventionally known one can be used. Examples of such a solvent include ketone solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, and cyclohexanone, toluene, xylene, and the like. Methyl ethyl ketone, cyclohexanone, and the like are preferably used because they have a high drying rate and can be obtained at low cost.

  The adhesive sheet according to the present embodiment is produced, for example, as follows. First, the adhesive composition solution is prepared. Next, the adhesive composition solution is applied on the base separator so as to have a predetermined thickness to form a coating film, and then the coating film is dried under predetermined conditions. As the base material separator, polyethylene terephthalate (PET), polyethylene, polypropylene, or a plastic film or paper surface-coated with a release agent such as a fluorine-type release agent or a long-chain alkyl acrylate-type release agent can be used. Moreover, it does not specifically limit as a coating method, For example, roll coating, screen coating, gravure coating, etc. are mentioned. As drying conditions, for example, the drying temperature is 70 to 160 ° C. and the drying time is 1 to 5 minutes. Thereby, the adhesive sheet which concerns on this embodiment is obtained.

(Method for manufacturing semiconductor device)
Next, an embodiment of a method for manufacturing a semiconductor device will be described. Hereinafter, an adhesive sheet 10 for manufacturing a dicing film integrated semiconductor device (hereinafter, also referred to as a dicing film integrated adhesive sheet 10) in which the adhesive sheet 3 according to this embodiment is laminated on a conventionally known dicing film is used. A method for manufacturing a semiconductor device will be described. The dicing film according to the present embodiment has a structure in which the pressure-sensitive adhesive layer 2 is laminated on the substrate 1. FIG. 1 is a schematic cross-sectional view showing an adhesive sheet for manufacturing a dicing film integrated semiconductor device according to this embodiment. 2 to 4 are schematic cross-sectional views for explaining the method for manufacturing a semiconductor device according to this embodiment.

  First, as shown in FIG. 1, the semiconductor wafer 4 is pressure-bonded onto the semiconductor wafer attaching portion 3a of the adhesive sheet 3 in the dicing film integrated adhesive sheet 10, and this is adhered and held and fixed (mounting process). . This step is performed while pressing with a pressing means such as a pressure roll.

  Next, dicing of the semiconductor wafer 4 is performed. Thereby, the semiconductor wafer 4 is cut into a predetermined size and separated into individual pieces, and the semiconductor chip 5 is manufactured. The semiconductor chip 5 corresponds to the first semiconductor chip of the present invention. Dicing is performed according to a conventional method from the circuit surface side of the semiconductor wafer 4, for example. Further, in this step, for example, a cutting method called full cut for cutting up to the dicing film integrated adhesive sheet 10 can be adopted. It does not specifically limit as a dicing apparatus used at this process, A conventionally well-known thing can be used. Further, since the semiconductor wafer is bonded and fixed by the dicing film integrated adhesive sheet 10, chip chipping and chip jump can be suppressed, and damage to the semiconductor wafer 4 can be suppressed.

  Next, the semiconductor chip 5 is picked up in order to peel off the semiconductor chip adhered and fixed to the dicing film integrated adhesive sheet 10. The pickup method is not particularly limited, and various conventionally known methods can be employed. For example, a method of pushing up the individual semiconductor chips 5 from the dicing film integrated adhesive sheet 10 side with a needle and picking up the pushed-up semiconductor chips 5 with a pickup device or the like can be mentioned.

  Here, when the pressure-sensitive adhesive layer 2 is an ultraviolet curable type, the pickup is performed after the pressure-sensitive adhesive layer 2 is irradiated with ultraviolet rays. Thereby, the adhesive force with respect to the adhesive sheet 3 of the adhesive layer 2 falls, and peeling of the semiconductor chip 5 becomes easy. As a result, the semiconductor chip 5 with the adhesive sheet 3 can be picked up without damaging the semiconductor chip.

  On the other hand, as shown in FIG. 2, a member 30 is prepared in which another semiconductor chip 16 is die-bonded on the adherend 6 via the die-bonding film 13. The semiconductor chip 16 corresponds to the second semiconductor chip of the present invention. The tip of the terminal portion (inner lead) of the adherend 6 and an electrode pad (not shown) on the semiconductor chip 16 are electrically connected (wire bonded) by a bonding wire 7. As the die bond film 13 and the bonding wire 7, conventionally known ones can be used. Examples of the adherend 6 include a lead frame, a TAB film, a substrate, and a separately manufactured semiconductor chip. The adherend 6 may be, for example, a deformable adherend that can be easily deformed or a non-deformable adherend (such as a semiconductor wafer) that is difficult to deform. The member 30 shown in FIG. 2 can be manufactured by a conventionally known method. For example, the die bonding is performed by pressure bonding. The conditions for die bonding are not particularly limited, and can be set as necessary. Specifically, for example, it can be performed within a die bonding temperature of 80 to 160 ° C., a bonding pressure of 5 N to 15 N, and a bonding time of 1 to 10 seconds. Moreover, the temperature at the time of performing the said wire bonding is 80-250 degreeC, Preferably it is performed within the range of 80-220 degreeC. The heating time is several seconds to several minutes. The connection is performed by a combination of vibration energy by ultrasonic waves and pressure energy by pressurization while being heated so as to be within the temperature range.

  Next, as shown in FIG. 3, the semiconductor chip 5 with the adhesive sheet 3 is laminated on the upper surface of another semiconductor chip 16 so that a part of the bonding wire 7 is embedded in the adhesive sheet 3. Thereby, the connection part with the other semiconductor chip 16 of the bonding wire 7 is embedded in the adhesive sheet 3. As temperature at the time of this lamination | stacking, 100-150 degreeC is preferable and 110-140 degreeC is more preferable. In addition, the pressure at this time can be in the range of 0.05 MPa to 1.0 MPa, and the time can be in the range of 0.5 to 1 second. By setting the temperature at the time of lamination within the above range, the viscosity of the adhesive sheet 3 can be set to a viscosity at which the bonding wire 7 can be suitably embedded.

  Next, as shown in FIG. 4, a wire bonding step of electrically connecting the tip of the terminal portion (inner lead) of the adherend 6 and an electrode pad (not shown) on the semiconductor chip 5 with a bonding wire 7 is performed. Do. The temperature at the time of wire bonding is 80 to 250 ° C, preferably 80 to 220 ° C. The heating time is several seconds to several minutes. The connection is performed by a combination of vibration energy by ultrasonic waves and pressure energy by pressurization while being heated so as to be within the temperature range.

  Next, as shown in FIG. 4, a sealing process for sealing the semiconductor chip 5 and the other semiconductor chip 16 with the sealing resin 8 is performed. This step is performed to protect the semiconductor chip 5 mounted on the adherend 6, the other semiconductor chips 16, and the bonding wires 7. This step is performed by molding a sealing resin with a mold. As the sealing resin 8, for example, an epoxy resin is used. Although the heating temperature at the time of resin sealing is normally performed at 175 degreeC for 60 to 90 second, this invention is not limited to this, For example, it can cure at 165 to 185 degreeC for several minutes.

  Next, in the post-curing step, the sealing resin 8 that is insufficiently cured in the sealing step is completely cured. Even when the die bond film 13 and the adhesive sheet 3 are not thermally cured in the sealing process, the die bond film 13 and the adhesive sheet 3 are thermally cured together with the curing of the sealing resin 8 in this process, thereby allowing the adhesive fixing. . Although the heating temperature in this process changes with kinds of sealing resin, it exists in the range of 165-185 degreeC, for example, and heating time is about 0.5 to 8 hours.

  In the above-described embodiment, the case where the adhesive sheet 3 is laminated on the dicing film has been described. However, the support member is not the adhesive sheet for manufacturing the dicing film integrated semiconductor device, and the bonding wire is connected to the upper surface. The adhesive sheet may be directly attached to (for example, a semiconductor chip) so that a part of the bonding wire is embedded in the adhesive sheet.

  Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, blending amounts, and the like described in this example are not intended to limit the gist of the present invention only to those unless otherwise limited. In the following, “parts” means parts by weight.

Example 1
The following (a) to (g) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 40% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-70L) 100 parts (b) Epoxy resin 1 (manufactured by Nippon Steel Chemical Co., Ltd., YD-825GS) 233.8 parts (c) Epoxy resin 2 ( Nippon Steel Chemical Co., Ltd., YDCN-700-3) 217.1 parts (d) Phenolic resin (Maywa Kasei Co., Ltd., MEH-7851SS) 450.9 parts (e) Silica filler (Admatechs Co., Ltd.) Manufactured by SC-2050MC, average particle size 0.5 μm) 334 parts (f) epoxy resin curing catalyst (product name: TPP-MK, manufactured by Hokuko Chemical Co., Ltd.) 3.3 parts (g) ion scavenger 1 ( Toa Gosei Co., Ltd., IXE-770, inorganic cation exchanger)
334 parts

  The adhesive composition solution was applied on a release treatment film made of a polyethylene terephthalate film having a thickness of 50 μm after the silicone release treatment, and then dried at 130 ° C. for 2 minutes. As a result, an adhesive sheet according to Example 1 having a thickness of 20 μm was produced.

(Example 2)
The following (a) to (h) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 40% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-70L) 100 parts (b) Epoxy resin 1 (manufactured by Nippon Steel Chemical Co., Ltd., YD-825GS) 144.4 parts (c) Epoxy resin 2 ( Nippon Steel Chemical Co., Ltd., YDCN-700-3) 133.2 parts (d) Phenolic resin (Maywa Kasei Co., Ltd., MEH-7851SS) 288.6 parts (e) Silica filler (Admatechs Co., Ltd.) Manufactured by SC-2050MC, average particle size 0.5 μm) 222 parts (f) epoxy curing catalyst (product name: TPP-MK, manufactured by Hokuko Chemical Co., Ltd.) 3.3 parts (g) ion scavenger 2 (Toa (IXE-100, inorganic cation exchanger, manufactured by Synthesis Co., Ltd.)
111.0 parts (h) ion scavenger 3 (manufactured by Toa Gosei Co., Ltd., IXE-500, inorganic cation exchanger)
111.0 parts

  The adhesive composition solution was applied on a release treatment film made of a polyethylene terephthalate film having a thickness of 50 μm after the silicone release treatment, and then dried at 130 ° C. for 2 minutes. As a result, an adhesive sheet according to Example 2 having a thickness of 20 μm was produced.

(Example 3)
The following (a) to (h) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 40% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-70L) 100 parts (b) Epoxy resin 1 (manufactured by Nippon Steel Chemical Co., Ltd., YD-825GS) 33.3 parts (c) Epoxy resin 2 ( Nippon Steel Chemical Co., Ltd., YDCN-700-3) 83.3 parts (d) Phenolic resin (Maywa Kasei Co., Ltd., MEH-7851SS) 115.5 parts (e) Silica filler (Admatechs Co., Ltd.) Manufactured by SC-2050MC, average particle size 0.5 μm) 110.0 parts (f) Epoxy curing catalyst (manufactured by Hokuko Chemical Co., Ltd., product name: TPP-MK) 3.3 parts (g) ion scavenger 2 (Toa Gosei Co., Ltd., IXE-100, inorganic cation exchanger)
55.0 parts (h) ion scavenger 3 (manufactured by Toa Gosei Co., Ltd., IXE-500, inorganic cation exchanger)
55.0 parts

  The adhesive composition solution was applied on a release treatment film made of a polyethylene terephthalate film having a thickness of 50 μm after the silicone release treatment, and then dried at 130 ° C. for 2 minutes. As a result, an adhesive sheet according to Example 3 having a thickness of 20 μm was produced.

Example 4
The following (a) to (h) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 40% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-70L) 100 parts (b) Epoxy resin 1 (manufactured by Nippon Steel Chemical Co., Ltd., YD-825GS) 144.4 parts (c) Epoxy resin 2 ( Nippon Steel Chemical Co., Ltd., YDCN-700-3) 133.2 parts (d) Phenolic resin (Maywa Kasei Co., Ltd., MEH-7851SS) 288.6 parts (e) Silica filler (Admatechs Co., Ltd.) Manufactured by SC-2050MC, average particle size 0.5 μm) 333.0 parts (f) Epoxy curing catalyst (manufactured by Hokuko Chemical Co., Ltd., product name: TPP-MK) 3.3 parts (g) ion scavenger 3 (Toa Gosei Co., Ltd., IXE-500, inorganic cation exchanger)
111.0 parts (h) ion scavenger 4 (manufactured by Johoku Chemical Co., Ltd., BT-120, triazole compound)
30 copies

  The adhesive composition solution was applied on a release treatment film made of a polyethylene terephthalate film having a thickness of 50 μm after the silicone release treatment, and then dried at 130 ° C. for 2 minutes. As a result, an adhesive sheet according to Example 4 having a thickness of 20 μm was produced.

(Comparative Example 1)
The following (a) to (f) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 40% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-70L) 100 parts (b) Epoxy resin 1 (manufactured by Nippon Steel Chemical Co., Ltd., YD-825GS) 144.4 parts (c) Epoxy resin 2 ( Nippon Steel Chemical Co., Ltd., YDCN-700-3) 133.2 parts (d) Phenolic resin (Maywa Kasei Co., Ltd., MEH-7851SS) 288.6 parts (e) Silica filler (Admatechs Co., Ltd.) SC-2050MC, average particle size 0.5 μm) 444.0 parts (f) Epoxy curing catalyst (manufactured by Hokuko Chemical Co., Ltd., product name: TPP-MK) 3.3 parts

  The adhesive composition solution was applied on a release treatment film made of a polyethylene terephthalate film having a thickness of 50 μm after the silicone release treatment, and then dried at 130 ° C. for 2 minutes. As a result, an adhesive sheet according to Comparative Example 1 having a thickness of 20 μm was produced.

(Comparative Example 2)
The following (a) to (g) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 40% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-70L) 100 parts (b) Epoxy resin 1 (manufactured by Nippon Steel Chemical Co., Ltd., YD-825GS) 19.2 parts (c) Epoxy resin 2 ( Nippon Steel Chemical Co., Ltd., YDCN-700-3) 72.0 parts (d) Phenolic resin (Maywa Kasei Co., Ltd., MEH-7851SS) 96.0 parts (e) Silica filler (Admatechs Co., Ltd.) Manufactured by SC-2050MC, average particle size 0.5 μm) 96.0 parts (f) Epoxy curing catalyst (manufactured by Hokuko Chemical Co., Ltd., product name: TPP-MK) 3.3 parts (g) ion scavenger 1 (Toa Gosei Co., Ltd., IXE-770, inorganic cation exchanger)
96.0 parts

  The adhesive composition solution was applied on a release treatment film made of a polyethylene terephthalate film having a thickness of 50 μm after the silicone release treatment, and then dried at 130 ° C. for 2 minutes. Thereby, an adhesive sheet according to Comparative Example 2 having a thickness of 20 μm was produced.

(Measurement of glass transition temperature after thermosetting and measurement of tensile storage modulus at 260 ° C. after thermosetting)
The adhesive sheet was thermally cured by heat treatment at 175 ° C. for 1 hour, and then cut into a strip shape having a thickness of 200 μm, a length of 400 mm (measured length), and a width of 10 mm with a cutter knife, and a solid viscoelasticity measuring device (RSAIII, Leo The storage elastic modulus at −50 to 300 ° C. was measured using metric scientific). The measurement conditions were a frequency of 1 Hz and a heating rate of 10 ° C./min. Furthermore, the glass transition temperature was obtained by calculating the value of tan δ (G ″ (loss elastic modulus) / G ′ (storage elastic modulus)).

(Measurement of melt viscosity at 140 ° C before thermosetting)
Using a rheometer (manufactured by HAAKE, trade name: RS-1), the melt viscosity at 140 ° C. before thermosetting was measured by a parallel plate method. Specifically, 0.1 g of an adhesive sheet was placed on a plate heated to 140 ° C., and measurement was started. The average value after 240 seconds from the start of measurement was taken as the melt viscosity. The gap between the plates was 0.1 mm. The results are shown in Table 1.

(Evaluation of copper ion scavenging properties)
The adhesive sheets (thickness 20 μm) of Examples and Comparative Examples were cut into 240 mm × 300 mm sizes (about 2.5 g), respectively, and folded in half to a size of 37.5 mm × 60 mm. Into a cylindrical sealed Teflon (registered trademark) container having a diameter of 58 mm and a height of 37 mm, 50 mL of a 10 ppm copper (II) ion aqueous solution was added. Then, it was left to stand at 120 degreeC for 20 hours in the constant temperature dryer (Espec Co., Ltd. product, PV-231). After taking out the film, the concentration of copper ions in the aqueous solution was measured using ICP-AES (manufactured by SII Nanotechnology, Inc., SPS-1700HVR). The case where the concentration of the copper ion in the aqueous solution was 0 to 9.8 ppm was evaluated as ◯, and the case where it was higher than 9.8 ppm was evaluated as x. The results are shown in Table 1.

(Evaluation of chloride ion scavenging properties)
The adhesive sheets (thickness 20 μm) of Examples and Comparative Examples were cut into 240 mm × 300 mm sizes (about 2.5 g), respectively, and folded in half to a size of 37.5 mm × 60 mm. Into a cylindrical sealed Teflon (registered trademark) container having a diameter of 58 mm and a height of 37 mm, 50 ml of ion-exchanged water was added. Then, it was left to stand at 120 degreeC for 20 hours in the constant temperature dryer (Espec Co., Ltd. product, PV-231). After taking out the film, the concentration of chloride ions in the aqueous solution was measured using ion chromatography (product name ICS-2000, manufactured by Nippon Dionex Co., Ltd.). The case where the concentration of the chloride ion in the aqueous solution was 0.1 ppm or less was rated as ◯, and the case where it was larger than 0.1 ppm was rated as x. The results are shown in Table 1.

(Evaluation of wire embedment)
The adhesive sheets (thickness: 60 μm) of Examples and Comparative Examples were attached to the first semiconductor element (5 × 5 × 0.5 mm) with a laminator at 50 ° C., 10 mm / sec, and pressure of 0.15 MPa. I attached. Next, a second semiconductor element (5 × 5 × 0.5 mm, wire loop height: 40 μm) which was die-attached on the substrate and connected with bonding wires was prepared. Next, the first semiconductor element with an adhesive sheet is heated to 140 ° C., pressure 0.1 MPa, time using a die bonder (SPIN300 SPA300) on the surface of the second semiconductor element to which the bonding wires are connected. Affixed vertically under the condition of 1 sec. The pasting was performed so that the adhesive sheet surface of the first semiconductor element with the adhesive sheet and the surface of the second semiconductor element on the side to which the bonding wire was connected were opposed to each other. Then, it was confirmed using the scanning electron microscope (HITACHI S-3400N) whether the bonding wire of the 2nd semiconductor element was embedded in the adhesive sheet without generating a void. The case where no void was found was evaluated as ◯, and the case where a void was seen was evaluated as x. The results are shown in Table 1.

(HAST resistance evaluation)
The resistance to HAST (High Accelerated Stress Test) was confirmed by the following method. First, as shown in FIG. 5, a substrate 21 in which a copper comb electrode pattern 15 was provided on the surface of a polyimide substrate 14 was prepared. The comb-shaped electrode pattern 15 includes a plus electrode 15a and a minus electrode 15b, and is formed so that the line width / space width is 20 μm / 20 μm. Next, a semiconductor chip to which the adhesive sheets of Examples and Comparative Examples were attached was prepared. The surface of the semiconductor chip on which the adhesive sheet was affixed was laminated on the comb-shaped electrode pattern 15 of the substrate 21 under the conditions of 120 ° C., 0.2 MPa, 10 mm / sec seconds to obtain a sample. Thereafter, the obtained sample was cured in a pressure oven at 150 ° C. for 1 hour in a nitrogen atmosphere at a pressure of 5N. Thereafter, the adhesive sheet layer was cured by heating at 175 ° C. for 5 hours. The positive electrode and negative electrode of the obtained sample were each connected to the wiring of the HAST test with solder, and the test was performed under the conditions of 50 ° C., 85% RH, and 5V. The electrical resistance is monitored, and those that can be maintained without declining rapidly even after 196 hours are regarded as non-defective products, and those that cause a rapid decrease in electrical resistance are regarded as defective products (electrical fault occurrence). . Five samples were prepared and tested in the same manner. When the number of defective samples was 2 or less, ◯, and when more than 2, the sample was rated as x. The results are shown in Table 1.

Claims (9)

A semiconductor device for attaching a second semiconductor chip on a first semiconductor chip having a bonding wire connected to the upper surface so that a part of the bonding wire is embedded in an adhesive sheet for manufacturing a semiconductor device An adhesive sheet for manufacturing,
Contains an ion scavenger,
An adhesive sheet for producing a semiconductor device, wherein the glass transition temperature after thermosetting is 50 ° C. or higher.   2. The melt viscosity at 140 ° C. before thermosetting is 10 Pa · s or more and 5000 Pa · s or less, and the tensile storage modulus at 260 ° C. after thermosetting is 1 MPa or more. Adhesive sheet for manufacturing semiconductor devices.   The adhesive sheet for manufacturing a semiconductor device according to claim 1, wherein the ion scavenger is an organic complex-forming compound that forms a complex with a cation.   After immersing an adhesive sheet for manufacturing a semiconductor device having a weight of 2.5 g in 50 ml of an aqueous solution containing 10 ppm of copper ions and leaving it to stand at 120 ° C. for 20 hours, the copper ion concentration in the aqueous solution is 0 to 9. The adhesive sheet for manufacturing a semiconductor device according to claim 1, wherein the adhesive sheet is 8 ppm.   The concentration of chloride ions in the aqueous solution after immersion of an adhesive sheet for manufacturing a semiconductor device weighing 2.5 g in 50 ml of ion-exchanged water and left at 120 ° C. for 20 hours is 0.1 ppm or less. The adhesive sheet for manufacturing a semiconductor device according to any one of claims 1 to 4.   The adhesive sheet for manufacturing a semiconductor device according to claim 1, comprising an inorganic filler.   The adhesive sheet for manufacturing a semiconductor device according to claim 1, comprising an acrylic resin, an epoxy resin, a phenol resin, and an epoxy resin curing catalyst.   8. An adhesive sheet for manufacturing a dicing film integrated semiconductor device, wherein the adhesive sheet for manufacturing a semiconductor device according to claim 1 is laminated on a dicing film. A semiconductor device comprising the adhesive sheet for manufacturing a semiconductor device according to claim 1,
A part of the bonding wire is embedded in the adhesive sheet for manufacturing the semiconductor device.

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