JP2013026566A - Adhesive sheet for manufacturing semiconductor device, semiconductor device containing adhesive sheet for manufacturing semiconductor device, and method of manufacturing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive sheet for manufacturing a semiconductor device, capable of suppressing cracking or chipping of a semiconductor wafer or the like, with chemical stability and easy physical property control.SOLUTION: The adhesive sheet for manufacturing a semiconductor device includes a thermoplastic resin which contains epoxy group but does not contain carboxyl group, a thermosetting resin, and an organic complex formation compound which contains a heterocyclic compound in which a ring atom contains a tertiary nitrogen atom, to form a complex with cation.

Description

  The present invention relates to an adhesive sheet for manufacturing a conductor device, a semiconductor device having an adhesive sheet for manufacturing a semiconductor device, and a method for manufacturing the 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, the ion trapping agent, the ion trapping agent, and the anion exchanger disclosed in Patent Documents 2 to 5 are inorganic compounds. For this reason, the ion trapping property varies depending on the dispersion state in the resin such as a film adhesive, or when the inorganic compound is bonded to the wafer, the inorganic compound comes into contact with the wafer and cracks or chips occur. There is a problem. In particular, in recent years, there is a demand for thinning the adhesive sheet, and it is necessary to suppress cracking and chipping of the wafer due to the inorganic compound.

  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. In addition, since the resin has a skeleton capable of complexing with copper ions, the problem that the inorganic compound comes into contact with the wafer and cracks and chips do not easily occur. However, the skeleton capable of complexing with copper ions in the resin may react with other resins constituting the film adhesive or the like. For this reason, there are problems that the chemical stability of the film adhesive or the like is lowered, and it is difficult to control the physical properties of the film adhesive or the like, and the necessary characteristics cannot be obtained.

  The present invention has been made in view of the above-mentioned problems, and its purpose is to suppress the cracking and chipping of a semiconductor wafer and the like, and has chemical stability and adhesion for manufacturing a semiconductor device with easy physical property control. A semiconductor device having a sheet, an adhesive sheet for manufacturing the semiconductor device, and a method for manufacturing a semiconductor device using 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, it was found that by adopting the following configuration, cracking and chipping of a semiconductor wafer or the like was suppressed, chemical stability was achieved, and physical property control could be facilitated, and the present invention was completed. I came to let you.

  That is, the adhesive sheet for manufacturing a semiconductor device according to the present invention includes a thermoplastic resin having an epoxy group and no carboxyl group, a thermosetting resin, and a tertiary nitrogen atom in a ring atom. It has a heterocyclic compound and has an organic complex-forming compound that forms a complex with a cation.

  According to the said structure, since it has the organic type complex formation compound which forms a complex with a cation, the cation mixed from the outside during the various processes in manufacture of a semiconductor device can be capture | acquired. As a result, it becomes difficult for cations mixed from the outside to reach the circuit formation surface formed on the wafer, and the deterioration of electrical characteristics can be suppressed to improve product reliability. Moreover, since it is an organic complex-forming compound, even if it contacts a semiconductor wafer or the like during bonding, it is possible to suppress the occurrence of cracks and chips.

  Further, when the semiconductor wafer is bonded to the adherend via the adhesive sheet, since the adherend is generally uneven, air bubbles are mixed therein. The bubbles are usually diffused into the sealing resin or the like by pressure or the like during resin sealing, and the influence thereof is reduced. However, when a compound having a heterocyclic compound containing a tertiary nitrogen atom as a ring atom is used as the organic complex-forming compound, if a carboxyl group is present in the thermoplastic resin, steps such as wire bonding before resin sealing Due to the thermal history at, the curing reaction proceeds abruptly, and bubbles cannot be diffused into the sealing resin in the resin sealing step. As a result, peeling due to bubbles occurs at the bonding interface. In particular, when semiconductor chips are stacked in multiple layers, the thermal history is increased, and the influence of air bubbles on peeling becomes large. According to the present invention, since the thermoplastic resin does not have a carboxyl group, the reaction with a heterocyclic compound containing a tertiary nitrogen atom in the ring atom is suppressed. Therefore, the chemical stability of the adhesive sheet can be improved. In addition, since the reaction with a heterocyclic compound containing a tertiary nitrogen atom in the ring atom is suppressed, it is possible to suppress the rapid progress of the curing reaction before the molding step, and the bubbles at the adhesive interface are used as a sealing resin. It becomes possible to diffuse. Thereby, peeling at the adhesion interface can be prevented.

  Moreover, according to the said structure, since a thermoplastic resin has an epoxy group, a thermoplastic resin bridge | crosslinks to some extent or more by the post-curing process after resin sealing, for example, and can prevent peeling in an adhesion interface.

  That is, according to the said structure, it has a heterocyclic compound which has an epoxy group and does not have a carboxyl group, a thermosetting resin, and a tertiary nitrogen atom in a ring atom, Since it has an organic complex-forming compound that forms a complex with a cation, the product reliability of a semiconductor device manufactured using the adhesive sheet for manufacturing the semiconductor device can be improved.

  In the above configuration, the thermoplastic resin is 5 to 95 parts by weight, the thermosetting resin is 5 to 50 parts by weight, and the filler is 0 to 60 parts by weight with respect to 100 parts by weight of the total amount of the adhesive sheet for manufacturing the semiconductor device. Part of the organic complex-forming compound is preferably contained in a proportion of 0.1 to 5 parts by weight. By setting each of the above components within the above numerical range, it is possible to further suppress cracking and chipping of a semiconductor wafer and the like, to further increase chemical stability, and to facilitate physical property control.

  In the above configuration, the copper ion concentration in the aqueous solution 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 at 120 ° C. for 20 hours, It is preferably 0 to 9.9 ppm. According to the said structure, the copper ion mixed from the outside during the various processes in manufacture of a semiconductor device is trapped more. As a result, it becomes difficult for copper ions mixed from the outside to reach the circuit forming surface formed on the wafer.

  A semiconductor device according to the present invention includes the adhesive sheet for manufacturing a semiconductor device described above. According to the said structure, since it has the adhesive sheet for semiconductor device manufacture as described above, it can be set as the semiconductor device which product reliability improved.

  A method for manufacturing a semiconductor device according to the present invention includes a step of attaching a semiconductor chip to an adherend via the adhesive sheet for manufacturing a semiconductor device described above. According to the said structure, since the semiconductor device which has the adhesive sheet for semiconductor device manufacture as described above is manufactured, it can be set as the semiconductor device which product reliability improved.

It is a cross-sectional schematic diagram which shows the dicing die-bonding film which concerns on this embodiment. It is a cross-sectional schematic diagram which shows the example which mounted the semiconductor chip through the die-bonding film in the said dicing die-bonding film. It is a cross-sectional schematic diagram which shows the example which mounted the semiconductor chip three-dimensionally through the die-bonding film in the said dicing die-bonding film.

  The adhesive sheet for manufacturing a semiconductor device of the present invention (hereinafter also simply referred to as “adhesive sheet”) has an epoxy group and a thermoplastic resin having no carboxyl group, a thermosetting resin, and a tertiary grade. And an organic complex-forming compound that forms a complex with a cation.

  Since the adhesive sheet has an organic complex-forming compound that forms a complex with a cation, the cation mixed from the outside can be captured during various processes in manufacturing a semiconductor device. As a result, it becomes difficult for cations mixed from the outside to reach the circuit formation surface formed on the wafer, and the deterioration of electrical characteristics can be suppressed to improve product reliability. Moreover, since it is an organic complex-forming compound, even if it contacts a semiconductor wafer or the like during bonding, it is possible to suppress the occurrence of cracks and chips.

  In addition, since the thermoplastic resin does not have a carboxyl group, the reaction with a heterocyclic compound containing a tertiary nitrogen atom in the ring atom is suppressed. Therefore, the chemical stability of the adhesive sheet can be improved. In addition, since the reaction with a heterocyclic compound containing a tertiary nitrogen atom in the ring atom is suppressed, it is possible to suppress the rapid progress of the curing reaction before the molding step, and the bubbles at the adhesive interface are used as a sealing resin. It becomes possible to diffuse. Thereby, peeling at the adhesion interface can be prevented.

  In addition, since the thermoplastic resin has an epoxy group, the thermoplastic resin is crosslinked to some extent by a post-curing step after resin sealing, for example, and peeling at the adhesive interface can be prevented.

  That is, the adhesive sheet has a thermoplastic resin having an epoxy group and not having a carboxyl group, a thermosetting resin, and a heterocyclic compound containing a tertiary nitrogen atom as a ring atom. Since it has an organic complex-forming compound that forms a complex with a cation, the product reliability of a semiconductor device manufactured using the adhesive sheet for manufacturing the semiconductor device can be improved.

  The organic complex-forming compound is preferably soluble in an organic solvent. If the organic complex-forming compound is soluble in an organic solvent, it can be easily and suitably dispersed in the resin. In the present invention, an organic complex-forming compound is soluble in an organic solvent. For example, 1 part by weight of an organic complex-forming compound causes suspension or the like with respect to 100 parts by weight of methyl ethyl ketone as an organic solvent. It can be dissolved without any problems.

  In the present invention, the cation that forms a complex with the organic complex-forming compound is not particularly limited as long as it is a cation. For example, Na, K, Ni, Cu, Cr, Co, Hf, Pt, Ca, Examples of the ions include Ba, Sr, Fe, Al, Ti, Zn, Mo, Mn, and V.

(Organic complex forming compounds)
The organic complex-forming compound is not particularly limited as long as it has a heterocyclic compound containing a tertiary nitrogen atom as a ring atom and forms a complex with a cation. And a triazole compound, a tetrazole compound, or a bipyridyl compound can be exemplified from the viewpoint of suppressing the reaction with the epoxy group of the thermoplastic resin. Among these, a triazole compound is more preferable from the viewpoint of the stability of a complex formed with copper ions. These can be used alone or in combination of two or more. The organic complex-forming compound is preferably a fine powder, easily dissolved in an organic solvent, or liquid.

  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-t-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, TT-LX, 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, TINUVIN 213, Taiwan Eiko Chemical Co., Ltd. Product names: EVESORB 8 , It may be mentioned EVESORB109, EVESORB 70, EVESORB 71, EVESORB 72, EVESORB 73, EVESORB 74, EVESORB 75, 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 tetraazole 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.

  The adhesive sheet contains a thermoplastic resin having an epoxy group and no carboxyl group, 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. In particular, when an epoxy resin is used, a high adhesive force at a high temperature (for example, 175 to 260 ° C.) can be obtained. Therefore, by using a combination of an organic complex-forming compound and an epoxy resin, an adhesive sheet having high adhesive strength at high temperatures can be obtained.

  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.

  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.

  The thermoplastic resin is not particularly limited as long as it has an epoxy group and does not have a carboxyl group, but butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic. Acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin, phenoxy resin, acrylic resin, saturated polyester resin such as PET and PBT, polyamideimide resin, or fluorine resin Etc. 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 as long as it has an epoxy group and does not have a carboxyl group. For example, the acrylic resin has a carbon number of 30 or less, particularly a straight chain having 4 to 18 carbon atoms, or Examples thereof include a copolymer of an acrylic acid or methacrylic acid ester having a branched alkyl group and an epoxy group-containing monomer. 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 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. Examples of the epoxy group-containing monomer include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and the like.

  Among the adhesive sheets, the thermoplastic resin is 5 to 95 parts by weight (more preferably 10 to 90 parts by weight) and the thermosetting resin is 5 to 55 parts by weight with respect to 100 parts by weight of the adhesive sheet. (More preferably 10 to 50 parts by weight), 0 to 60 parts by weight (more preferably 0 to 50 parts by weight) filler, and 0.1 to 5 parts by weight (more preferably 0.5 parts by weight) of the organic complex-forming compound. It is preferably contained in a ratio of ˜3 parts by weight. By setting each of the above components within the above numerical range, it is possible to further suppress cracking and chipping of a semiconductor wafer and the like, to further increase chemical stability, and to facilitate physical property control.

  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. It is preferably 9 ppm, more preferably 0 to 9.5 ppm, and even more preferably 0 to 8 ppm. 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.

  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, and inorganic fillers are preferable from the viewpoints of characteristics such as improvement in handleability, improvement in thermal conductivity, adjustment of melt viscosity, and imparting thixotropic properties. 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 0.001 to 1 μm. By setting the average particle size of the filler to 0.001 μm or more, the wettability to the adherend and the adhesiveness can be improved. Moreover, by setting it as 1 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, the said adhesive sheet can mix | blend suitably other additives other than the said organic type complex formation compound as needed. 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.

  It does not specifically limit as a manufacturing method of the adhesive composition for forming the said adhesive sheet, For example, the said thermosetting resin, the said thermoplastic resin, and the said organic type complex formation compound, and as needed Other additives and the like are charged into a container, dissolved in an organic solvent, and stirred uniformly to obtain an adhesive composition solution.

  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. Among these, methyl ethyl ketone that can dissolve the organic complex-forming compound is more preferable.

  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 when the adhesive sheet is used as a die bond film will be described. Below, the manufacturing method of the semiconductor device using the dicing die-bonding film 10 by which the adhesive sheet 3 (henceforth the die-bonding film 3) based on this embodiment was laminated | stacked on the conventionally well-known dicing film is demonstrated. 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 a dicing die-bonding film according to this embodiment. FIG. 2 is a schematic cross-sectional view showing an example in which a semiconductor chip is mounted via a die bond film in the dicing die bond film.

  First, as shown in FIG. 1, the semiconductor wafer 4 is pressure-bonded onto the semiconductor wafer attachment portion 3a of the die-bonding film 3 in the dicing die-bonding film 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. 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 in which cutting is performed up to the dicing die bond film 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 die-bonding film 10, chip chipping and chip jumping can be suppressed, and damage to the semiconductor wafer 4 can also be suppressed.

  In order to peel off the semiconductor chip adhered and fixed to the dicing die bond film 10, the semiconductor chip 5 is picked up. 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 die bond film 10 side with a needle and picking up the pushed-up semiconductor chips 5 with a pickup device may 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 die-bonding film 3 of the adhesive layer 2 falls, and peeling of the semiconductor chip 5 becomes easy. As a result, the pickup can be performed without damaging the semiconductor chip.

  Next, as shown in FIG. 2, the semiconductor chip 5 formed by dicing is die-bonded to the adherend 6 through the die-bonding film 3. 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.

  Next, 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 the bonding wire 7 is performed. As the bonding wire 7, for example, a gold wire, an aluminum wire, a copper wire or the like is used. 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.

  In addition, a wire bonding process is performed without thermosetting the die-bonding film 3 by heat processing. In this case, the shear bond strength of the die bond film 3 at 25 ° C. is preferably 0.2 MPa or more, more preferably 0.2 to 10 MPa, with respect to the adherend 6. Even if the wire bonding step is performed without thermosetting the die bond film 3 by setting the shear adhesive force to 0.2 MPa or more, the die bond film 3 and the semiconductor chip 5 are caused by ultrasonic vibration or heating in the step. Alternatively, shear deformation does not occur on the adhesion surface with the adherend 6. That is, the semiconductor element does not move due to ultrasonic vibration during wire bonding, thereby preventing the success rate of wire bonding from decreasing.

  The die bond film 3 includes a thermoplastic resin having an epoxy group and not having a carboxyl group, a thermosetting resin, and a heterocyclic compound containing a tertiary nitrogen atom as a ring atom, and a cation. And an organic complex-forming compound that forms a complex. Therefore, the thermoplastic resin having no carboxyl group and the organic complex-forming compound hardly react even by the thermal history in the wire bonding step. As a result, the rapid progress of the curing reaction of the die bond film 3 is suppressed.

  Subsequently, a sealing step 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. 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.

  In the mounting process, since the semiconductor wafer 4 generally has fine irregularities, bubbles are mixed in the interface between the semiconductor 4 and the die bond film 3. In the main sealing step, the bubbles are diffused into the sealing resin 8 and the like by the pressure at the time of resin sealing and the influence is reduced. In addition, as above-mentioned, the progress of rapid hardening reaction by the die-bonding film 3 by the heat history in a wire bonding process is suppressed. As a result, bubbles can be easily diffused in the sealing step, and peeling due to bubbles at the bonding interface can be prevented.

  Next, in the post-curing step, the sealing resin 8 that is insufficiently cured in the sealing step is completely cured. Even if the die bond film 3 is not thermally cured in the sealing process, the die bond film 3 is 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.

  Moreover, as shown in FIG. 3, the adhesive sheet (die bond film) can be suitably used also when a plurality of semiconductor chips are stacked and three-dimensionally mounted. FIG. 3 is a schematic cross-sectional view showing an example in which a semiconductor chip is three-dimensionally mounted through a die bond film. In the case of the three-dimensional mounting shown in FIG. 3, first, at least one die bond film 3 cut out so as to have the same size as the semiconductor chip is pasted on the adherend 6, and then the semiconductor chip 5 is attached via the die bond film 3. , Paste the wire bond side up. Next, the die bond film 13 is pasted while avoiding the electrode pad portion of the semiconductor chip 5. Further, another semiconductor chip 15 is die-bonded on the die-bonding film 13 so that the wire-bonding surface is on the upper side.

  Next, a wire bonding process is performed. Thereby, each electrode pad in the semiconductor chip 5 and the other semiconductor chip 15 and the adherend 6 are electrically connected by the bonding wire 7. In addition, this process is implemented without passing through the heating process of the die bond films 3 and 13.

  Subsequently, a sealing process for sealing the semiconductor chip 5 and the like with the sealing resin 8 is performed, and the sealing resin is cured. Next, in the post-curing step, the sealing resin 8 that is insufficiently cured in the sealing step is completely cured.

  When the semiconductor chips are stacked in multiple layers, the thermal history of the wire bonding process and the like increases, and the influence on the peeling due to the bubbles present at the interface between the die bond film and the semiconductor chip becomes large. However, the thermoplastic resin having no carboxyl group hardly reacts with the organic complex-forming compound. As a result, the rapid progress of the curing reaction of the die bond films 3 and 13 is suppressed. Accordingly, the bubbles can be easily diffused in the sealing step, and peeling due to the bubbles at the adhesion interface can be prevented.

  In the embodiment described above, the case where the adhesive sheet is a die bond film has been described. However, the adhesive sheet is not particularly limited as long as it is used for manufacturing a semiconductor device. It may be a protective film for protecting the back surface of the semiconductor chip of the flip chip type semiconductor device, or a sealing sheet for sealing between the surface of the semiconductor chip of the flip chip type semiconductor device and the adherend. The said adhesive sheet is used for the manufacturing method of the semiconductor device which comprises the process of affixing a semiconductor chip on a to-be-adhered body via the said adhesive sheet. As a process of attaching the semiconductor chip to the adherend via the adhesive sheet, a conventionally known attaching process can be adopted. Moreover, the semiconductor device manufactured by the manufacturing method of the semiconductor device becomes a semiconductor device having 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 (e) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin having an epoxy group as a functional group (manufactured by Nagase ChemteX Corporation, SG-P3, weight average molecular weight 850,000) 29.91 parts (b) Epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd.) YDF-8170C) 4.985 parts (c) phenol resin (Maywa Kasei Co., Ltd., MEH-7851H) 4.985 parts (d) silica filler (manufactured by Admatechs Co., Ltd., SC-2050, average particle size) 0.5μm)
59.82 parts (e) Organic complex forming compound (Johoku Chemical Co., Ltd., TT-LX, triazole compound)
0.3 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 Example 1 having a thickness of 20 μm was produced.

(Example 2)
The following (a) to (e) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin having an epoxy group as a functional group (manufactured by Nagase ChemteX Corporation, SG-P3, weight average molecular weight 850,000) 29.7 parts (b) Epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd.) YDF-8170C) 4.95 parts (c) phenol resin (Maywa Kasei Co., Ltd., MEH-7851H) 4.95 parts (d) silica filler (manufactured by Admatechs Co., Ltd., SC-2050, average particle size) 0.5μm)
59.4 parts (e) organic complex forming compound (Johoku Chemical Co., Ltd., TT-LX, triazole compound)
1 copy

  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 (e) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin having an epoxy group as a functional group (manufactured by Nagase ChemteX Corporation, SG-P3, weight average molecular weight 850,000) 28.5 parts (b) Epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd.) YDF-8170C) 4.75 parts (c) phenol resin (Maywa Kasei Co., Ltd., MEH-7851H) 4.75 parts (d) silica filler (manufactured by Admatechs Co., Ltd., SC-2050, average particle size) 0.5μm)
57 parts (e) organic complex-forming compound (Johoku Chemical Co., Ltd., TT-LX, triazole compound)
5 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 3 having a thickness of 20 μm was produced.

(Comparative Example 1)
The following (a) to (e) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin having a carboxyl group and a hydroxyl group as functional groups (manufactured by Nagase ChemteX Corporation, SG-708-6, weight average molecular weight 700,000) 29.7 parts (b) Epoxy resin (Nippon Steel 4.95 parts (c) phenolic resin (Maywa Kasei Co., Ltd., MEH-7851H) 4.95 parts (d) silica filler (manufactured by Admatechs, SC) -2050, average particle size 0.5 μm)
59.4 parts (e) organic complex forming compound (Johoku Chemical Co., Ltd., TT-LX, triazole compound)
1 copy

  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 (e) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin having a hydroxyl group as a functional group (manufactured by Nagase ChemteX Corporation, SG-600TEA, weight average molecular weight 1,200,000) 29.7 parts (b) Epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YDF-8170C) 4.95 parts (c) phenol resin (Maywa Kasei Co., Ltd., MEH-7851H) 4.95 parts (d) silica filler (manufactured by Admatechs Co., Ltd., SC-2050, average particle size 0) .5μm)
59.4 parts (e) organic complex forming compound (Johoku Chemical Co., Ltd., TT-LX, triazole compound)
1 copy

  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.

(Comparative Example 3)
The following (a) to (e) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin having an epoxy group as a functional group (manufactured by Nagase ChemteX Corporation, SG-P3, weight average molecular weight 850,000) 29.7 parts (b) Epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd.) YDF-8170C) 4.95 parts (c) phenol resin (Maywa Kasei Co., Ltd., MEH-7851H) 4.95 parts (d) silica filler (manufactured by Admatechs Co., Ltd., SC-2050, average particle size) 0.5μm)
59.4 parts (e) Organic complex-forming compound (Tokyo Chemical Industry Co., Ltd., dodecyl gallate) 1 part

  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 3 having a thickness of 20 μm was produced.

(Comparative Example 4)
The following (a) to (d) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin having an epoxy group as a functional group (manufactured by Nagase ChemteX Corporation, SG-P3, weight average molecular weight 850,000) 30 parts (b) epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YDF -8170C) 5 parts (c) phenol resin (Maywa Kasei Co., Ltd., MEH-7851H) 5 parts (d) silica filler (manufactured by Admatechs, SC-2050, average particle size 0.5 μm)
60 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. This produced the adhesive sheet which concerns on the comparative example 4 of thickness 20 micrometers.

(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.

(Void disappearance)
The adhesive sheets (thickness 20 μm) of Examples and Comparative Examples were each attached to a 10 mm square semiconductor chip under a temperature of 40 ° C., and the semiconductor chip was mounted on a BGA substrate via each adhesive sheet. The mounting conditions were a temperature of 120 ° C., a pressure of 0.1 MPa, and 1 second. Next, the BGA substrate on which the semiconductor chip was mounted was heat-treated at 175 ° C. for 30 minutes with a dryer, and then packaged with a sealing resin (manufactured by Nitto Denko Corporation, GE-100). The sealing conditions were a heating temperature of 175 ° C. and 90 seconds. Subsequently, the sealed semiconductor device was cut with a glass cutter, and the cross section was observed with an ultrasonic microscope to measure the void area on the bonding surface of each adhesive sheet and the BGA substrate. The case where the void area was less than 50% with respect to the bonded area was rated as ◯, and the case where the void area was 50% or more was marked as x. The results are shown in Table 1 below.

(Moisture reflow resistance)
The adhesive sheets (thickness 20 μm) of Examples and Comparative Examples were each attached to a 10 mm square semiconductor chip under a temperature of 40 ° C., and the semiconductor chip was mounted on a BGA substrate via each adhesive sheet. The mounting conditions were a temperature of 120 ° C., a pressure of 0.1 MPa, and 1 second. Next, the BGA substrate on which the semiconductor chip was mounted was heat-treated at 175 ° C. for 30 minutes with a dryer, and then packaged with a sealing resin (manufactured by Nitto Denko Corporation, GE-100). The sealing conditions were a heating temperature of 175 ° C. and 90 seconds. Thereafter, the BGA substrate mounted with the semiconductor chip was placed in an IR reflow furnace set so as to absorb moisture under conditions of 85 ° C., 60% Rh and 168 hours, and further hold at 260 ° C. or higher for 10 seconds. Then, the semiconductor device after sealing was cut with a glass cutter, and the cross section was observed with an ultrasonic microscope to confirm the presence or absence of peeling at the boundary between each thermosetting die bond film and the BGA substrate. The confirmation was performed on nine semiconductor chips, and the case where three or less semiconductor chips were peeled off was marked as ◯, and the case where there were four or more semiconductor chips was marked as x. The results are shown in Table 1 below.

(result)
In the examples, good results were shown for copper ion scavenging properties, void disappearance properties, and moisture reflow resistance properties. On the other hand, in Comparative Example 1, TT-LX worked as a basic catalyst, the reaction between the carboxyl group of the acrylic resin and the epoxy resin was promoted, the curing proceeded rapidly, and the void disappearance during molding decreased. In Comparative Example 2, since the acrylic resin does not have a functional group that reacts with the curable resin or the organic complex-forming compound (triazole compound), the void disappearance at the time of molding can be ensured. However, since the acrylic resin was not cross-linked, it could not withstand the reflow test, and peeling occurred at the adhesive interface, resulting in voids. Moreover, in Comparative Example 3, since dodecyl gallate reacts with the epoxy group of the acrylic resin, curing rapidly progressed and void disappearance at the time of molding decreased. Moreover, in the comparative example 4, since the organic type complex formation compound which forms a complex with a cation was not contained, the metal ion could not be captured.

Claims (5)

A thermoplastic resin having an epoxy group and no carboxyl group;
A thermosetting resin;
An adhesive sheet for manufacturing a semiconductor device, comprising: a heterocyclic compound containing a tertiary nitrogen atom as a ring atom, and an organic complex-forming compound that forms a complex with a cation.   The thermoplastic resin is 5 to 95 parts by weight, the thermosetting resin is 5 to 50 parts by weight, the filler is 0 to 60 parts by weight, and the organic system is 100 parts by weight of the total amount of the adhesive sheet for manufacturing a semiconductor device. The adhesive sheet for manufacturing a semiconductor device according to claim 1, wherein the complex-forming compound is contained in a proportion of 0.1 to 5 parts by weight.   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 9 ppm.   A semiconductor device comprising the adhesive sheet for manufacturing a semiconductor device according to claim 1. A method for manufacturing a semiconductor device, comprising a step of attaching a semiconductor chip to an adherend through the adhesive sheet for manufacturing a semiconductor device according to claim 1.

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