JP2013191761A - Adhesive agent composition for semiconductor device - Google Patents

Abstract

The present invention provides an adhesive composition for a semiconductor device that can provide an adhesive layer having high ion trapping properties and high elastic modulus at high temperature.
An adhesive composition for a semiconductor device containing an ion-trapping compound and a polyimide resin having a glass transition temperature of 10 to 80 ° C. and substantially free of an allyl-modified polyimide resin. The sheet 1 formed with the two-layer structure of the agent composition 1a and the base film 1b can be attached to a semiconductor wafer, and the base film 1b can be peeled off to be used as an adhesive for die bonding.
[Selection] Figure 1

Description

  The present invention relates to an adhesive composition for a semiconductor device, an adhesive sheet for a semiconductor device obtained from the adhesive composition for a semiconductor device, and a method for manufacturing a semiconductor device using the adhesive sheet.

  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 metal ions (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 reach the circuit formation surface formed on the wafer, the electrical characteristics There has been a problem of lowering. In addition, metal ions are generated from circuits and wires during use of the product, resulting in a problem that electrical characteristics are deteriorated.

  In order to solve the above-described problems, conventionally, an extrinsic gettering (hereinafter also referred to as “EG”) in which a rear surface of a wafer is processed to form a crushed layer (strain), and metal ions are 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 metal ions 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.

  As a method of capturing metal ions other than EG and IG, a method of adding an ion trapping agent or the like to an adhesive that fixes a semiconductor element to a substrate or the like has been proposed. Specifically, for example, a film adhesive having a copper ion adsorption layer containing a resin having a skeleton capable of complexing with copper ions (see, for example, Patent Document 1), ion exchange type or ion adsorption type ion trapping An adhesive sheet comprising an adhesive agent layer and a substrate (see, for example, Patent Documents 2 and 3), a film adhesive comprising an adhesive composition containing an ion trap agent comprising an inorganic compound (for example, a patent) Document 4), an adhesive sheet made of an adhesive composition containing an ion exchanger (for example, see Patent Document 5) and the like have been proposed.

  However, Patent Documents 1 to 4 do not use polyimide resin, and the elastic modulus at high temperature is not sufficient. Moreover, in patent document 5, it has not been examined about using the polyimide resin which has a specific glass transition temperature as a high molecular weight component.

JP 2011-052109 A JP 2009-203337 A JP 2009-203338 A JP 2010-116453 A JP 2009-256630 A

  In the present invention, there are provided an adhesive composition for a semiconductor device capable of providing an adhesive layer having a high ion scavenging property and a high elastic modulus at a high temperature, and an adhesive sheet for a semiconductor device comprising the composition. For the purpose.

  As a result of examining the adhesive composition for semiconductor devices in order to solve the above problems, the present inventors, as a result, contain a compound that traps ions and a specific polyimide resin, and substantially contain an allyl-modified polyimide resin. By not including it, it was found that an adhesive layer having high ion trapping property and high elastic modulus at high temperature could be provided, and the present invention was completed.

  That is, this invention relates to the adhesive composition for semiconductor devices characterized by including the compound which ion-captures, and the polyimide resin whose glass transition temperature is 10-80 degreeC, and does not contain an allyl modified polyimide resin substantially. .

  The compound that captures ions is preferably an organic low molecular weight compound, and more preferably one or more compounds selected from the group consisting of triazole compounds, tetrazole compounds, and bipyridyl compounds.

  The addition amount of the compound that traps ions is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the adhesive composition for a semiconductor device.

  The compound that traps ions is preferably an inorganic cation exchanger, and more preferably an oxide hydrate of an element selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, magnesium, and aluminum. preferable.

  The added amount of the inorganic cation exchanger is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the adhesive composition for a semiconductor device.

  The copper ion in the aqueous solution after immersing the adhesive composition for a semiconductor device having a weight of 2.5 g heated at 175 ° C. for 5 hours 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 concentration is preferably from 0 to 9.9 ppm.

  The present invention relates to an adhesive sheet for a semiconductor device comprising a base film, an adhesive layer comprising the adhesive composition for a semiconductor device, and a method for producing a semiconductor device using the adhesive sheet for a semiconductor device.

It is a cross-sectional schematic diagram of the adhesive sheet for semiconductor devices of this invention. It is a cross-sectional schematic diagram of the dicing die-bonding film which consists of an adhesive bond layer which consists of an adhesive composition for semiconductor devices of this invention, and a dicing film. It is a cross-sectional schematic diagram which shows the example which mounted the semiconductor chip through the adhesive bond layer which consists of an adhesive composition for semiconductor devices of this invention. 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.

1. Adhesive composition for semiconductor device The adhesive composition for semiconductor device of the present invention contains a compound that traps ions and a polyimide resin having a glass transition temperature of 10 to 80 ° C., and does not substantially contain an allyl-modified polyimide resin. It is characterized by this.

<Compound that traps ions>
The adhesive composition for a semiconductor device of the present invention contains a compound that traps ions (hereinafter, also referred to as an ion trapping agent), and an adhesive sheet obtained from the adhesive composition for a semiconductor device includes: Metal ions mixed from the outside during various processes in production can be captured. As a result, it is difficult for metal ions mixed from the outside to reach the circuit formation surface formed on the wafer, and a reduction in electrical characteristics can be suppressed to improve product reliability.

  In the present invention, the metal ion captured by the ion scavenger is not particularly limited as long as it is a metal ion. For example, Na, K, Ni, Cu, Cr, Co, Hf, Pt, Ca, Ba, Sr, Ions such as Fe, Al, Ti, Zn, Mo, Mn, and V can be exemplified.

  Examples of the ion scavenger include cation exchangers and organic low-molecular compounds that form complexes with metal ions. Moreover, the organic low molecular weight compound that forms a complex with a metal ion used in the present invention is distinguished from a resin that can form a complex with a metal ion, and its molecular weight is preferably 1000 or less, More preferably, it is 500 or less. The lower limit of the molecular weight is not particularly limited, but is usually 50 or more. In the said resin, the ratio of the functional group which contributes to the capture | acquisition of the metal ion in resin is low, As a result, complex formation with a metal ion becomes difficult. Therefore, a resin capable of forming a complex with a metal ion is not sufficient in terms of ion trapping properties. On the other hand, organic low molecular weight compounds having a molecular weight of 1000 or less tend to form complexes with metal ions because of the high proportion of functional groups that contribute to the capture of metal ions in one molecule, resulting in high ion trapping properties. It is considered to be.

  The organic low molecular weight compound is not particularly limited as long as it forms a complex with a metal ion, but from the viewpoint of suitably capturing a metal ion, a nitrogen-containing compound, a hydroxyl group-containing compound, a carboxyl group-containing compound It is preferably at least one selected from the group consisting of compounds, and is at least one compound selected from the group consisting of nitrogen-containing heterocyclic compounds and compounds having two or more hydroxyl groups in one aromatic ring. It is more preferable.

(Nitrogen-containing compounds)
The nitrogen-containing compound is preferably in the form of fine powder, easily dissolved in an organic solvent, or liquid. Further, the nitrogen-containing compound may be a compound having one or more nitrogen atoms in one molecule, but is preferably a compound having two or more nitrogen atoms in one molecule. As such a nitrogen-containing compound, a nitrogen-containing heterocyclic compound is preferable from the viewpoint of suitably capturing a metal ion, and a heterocyclic compound having a tertiary nitrogen atom as a ring constituent atom is more preferable. Here, the tertiary atom refers to a nitrogen atom of a tertiary amine.

  Examples of the nitrogen-containing heterocyclic compound include a triazole compound, a tetrazole compound, and a bipyridyl compound. Among these, a triazole compound is more preferable from the viewpoint of the stability of a complex formed with a copper ion. . 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-pentyl-6-{(1H-benzotriazol-1-yl) methyl} phenol, 2- (2-hydroxy-5-t-butylphenyl) -2H- Benzotriazole, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, octyl-3- [3-tert-butyl-4-hydroxy-5- (5) -Chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-t-butyl-4-hydroxy-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 Rho-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-tetramethylbutyl) phenol], (2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole Methyl 3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate, 5-methyl-1H-benzotriazole and the like.

  Although it does not restrict | limit especially as a commercial item of the said triazole compound, Johoku Chemical Co., Ltd. brand name: BT-120, BT-LX, CBT-1, JF-77, JF-78, JF-79, JF -80, JF-83, JAST-500, BT-GL, BT-M, BT-260, BT-365, TT-LX, BASF trade names: 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, product name made by Yongkou Chemical Co., Taiwan: 81 EVESORB109, EVESORB 70, EVESORB 71, EVESORB 72, EVESORB 73, EVESORB 74, EVESORB 75, EVESORB 76, EVESORB 78, EVESORB 80, Daiwa Kasei Co., Ltd. trade name: VERZONE VT-120M and the like. Triazole compounds are also used as rust inhibitors.

  Although it does not specifically limit as said tetrazole compound, 5-amino-1H-tetrazole, 5-phenyl-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. Examples of such a hydroxyl group-containing compound include a quinol compound, a hydroxyanthraquinone compound, a polyphenol compound, and a higher alcohol from the viewpoint of more suitably capturing a metal ion, but a complex formed with a copper ion. From the viewpoint of stability, a compound having two or more hydroxyl groups in one aromatic ring is preferable, and 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.

  Examples of the polyphenol compound include, but are not limited to, tannin, tannin derivatives (gallic acid, methyl gallate, dodecyl gallate, pyrogallol) and the like.

  Examples of the higher alcohol include alcohols having a linear or branched alkyl group having 6 or more carbon atoms, particularly 6 to 18 carbon atoms.

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

  Although it does not specifically limit as said carboxyl group containing aromatic compound, A phthalic acid, picolinic acid, pyrrole-2-carboxylic acid, etc. are mentioned.

  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 Cylest Co., Ltd. | , Kirest 0D, Kirest NTA, Kirest 700, Kirest PA, Kirest HA, Kirest MZ-2, Kirest MZ-4A, Kirest MZ-8.

  The compounding amount of the organic low molecular compound that forms a complex with the metal ion is preferably 0.1 to 5 parts by weight, and 0.3 to 5 parts by weight with respect to 100 parts by weight of the adhesive composition for a semiconductor device. More preferably, it is 0.5-3 weight part. By setting the amount to 0.1 parts by weight or more, metal ions (particularly copper ions) can be effectively captured, and by setting the amount to 5 parts by weight or less, a decrease in heat resistance and an increase in cost are suppressed. Can do. Here, the reference "adhesive composition for semiconductor device" of "100 parts by weight of the adhesive composition for semiconductor device" refers to the total solid content contained in the adhesive composition for semiconductor device, Solvents such as N-methyl-2-pyrrolidone are not included.

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

(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. product names: IXE-700F, IXE-770, IXE-770D, IXE-2116, IXE-100, IXE-300, IXE-600, IXE-633, IXE-6107, IXE-6136, etc. can be mentioned.

  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.

  The amount of the inorganic cation exchanger is preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the adhesive composition for semiconductor devices. The amount is more preferably 10 parts by weight, and particularly preferably 2 to 5 parts by weight. By setting it as 1 weight part or more, a metal ion (especially copper ion) can be capture | acquired effectively, and a heat resistance fall and the increase in cost can be suppressed by setting it as 20 weight part or less. . The reference “100 parts by weight of the adhesive composition for semiconductor devices” is as described above.

<Polyimide resin>
The polyimide resin that can be used in the present invention is only required to have a glass transition temperature (Tg) of 10 to 80 ° C. For example, it is obtained by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. The polyimide resin which can be mentioned can be mentioned. In addition, as described above, the adhesive composition for a semiconductor device of the present invention does not substantially contain an allyl-modified polyimide resin, and of course, the “polyimide resin having a glass transition temperature of 10 to 80 ° C.” Allyl-modified polyimide resin is not included. Further, “substantially free” means that the allyl-modified polyimide resin is less than 1 part by weight with respect to 100 parts by weight of the adhesive composition for semiconductor devices, and is not included at all (0 part by weight). Is preferred. Note that the reference “100 parts by weight of the adhesive composition for a semiconductor device” is as described above.

  As the known method, for example, a polyamic acid obtained by mixing approximately equimolar amounts of tetracarboxylic dianhydride and diamine in an organic solvent and reacting at a reaction temperature of 80 ° C. or less is subjected to dehydration and cyclization. A resin is obtained. Here, “substantially equimolar” means that the molar ratio of tetracarboxylic dianhydride and diamine is close to 1: 1. If necessary, the composition ratio of tetracarboxylic dianhydride and diamine is 0.5 to 2.0 mol of diamine with respect to 1.0 mol of tetracarboxylic dianhydride. You may adjust as follows. By adjusting the composition ratio of tetracarboxylic dianhydride and diamine within the above range, the weight average molecular weight of the polyimide resin can be adjusted. The weight average molecular weight (Mw) of the polyimide resin is preferably 10,000 to 1,000,000, and more preferably 20,000 to 100,000.

  The tetracarboxylic dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane Dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, Screw 3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2, 3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2, 6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- Tetrachloronaphthalene -1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, Thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride Anhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane Dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4 - Carboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid Dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5 , 6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3 , 4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2,2] -oct-7-ene -2,3 5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2, -bis [4- (3,4-dicarboxyphenyl) phenyl] Propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2, -bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane Anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3 -Bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl -3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 4,4 ',-oxydiphthalic dianhydride, 1,2- (ethylene ) Bis (trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride) ), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9 -(Nonamethylene) bis (trimellitate anhydride), 1,10- (decamethylene) bis (trimellitate anhydride), 1,12- (dodecame) Tylene) bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride), and the like. It can use individually or in combination of 2 or more types. Among these, 4,4 ',-oxydiphthalic dianhydride and 1,10- (decamethylene) bis (trimellitate anhydride) are preferable.

  The diamine is not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3 , 3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, 3,3′- Diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl Sulfon, , 3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diamino Diphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 '-(3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3- Aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) Noxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′ -(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl ) Hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminoenoxy) phenyl) sulfide, bis (4- (4-aminoenoxy) phenyl) sulfide Bis (4- (3-aminoenoxy) phenyl) sulfone, bis (4- (4-aminoenoxy) phenyl) sulfone , 3,3′-dihydroxy-4,4′-diaminobiphenyl, aromatic diamines such as 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4-amino) Phenoxyphenyl) propane, aliphatic ether diamine represented by the following general formula (1), and the like.

(In the formula, R ¹ , R ² , and R ³ each independently represents a linear or branched alkylene group having 1 to 10 carbon atoms, and m represents an integer of 2 to 80)

  As what is shown by the said General formula (1), polyoxypropylene diamine etc. can be mentioned, for example. Examples of the aliphatic ether diamine other than the aliphatic ether diamine represented by the general formula (1) include 4,9-dioxadecane-1,12-diamine and 4,9,14-trioxaheptadecane-1,17. -A diamine etc. are mentioned. Although the molecular weight of aliphatic diamine is not specifically limited, For example, it is 50-1,000,000.

  Furthermore, the following general formula (2):

(In the formula, n represents an integer of 5 to 20)
The aliphatic diamine represented by these is mentioned.

  Specifically, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8- Examples include aliphatic diamines such as diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and 1,2-diaminocyclohexane.

  Furthermore, the following general formula (3):

(Wherein R ⁴ and R ⁹ each independently represents an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently A hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and p represents an integer of 1 to 5)
Specific examples include 1,3-bis (3-aminopropyl) tetramethyldisiloxane.

  Among these diamines, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, polyoxypropylenediamine, 2,2-bis (4-aminophenoxyphenyl) propane, 4,9-dioxadecane-1,12 -It is preferably one or more selected from the group consisting of diamine, 1,6-diaminohexane, and 4,9,14-trioxaheptadecane-1,17-diamine, and preferably two or more. More preferred.

  Examples of the organic solvent used in the reaction of the tetracarboxylic dianhydride and diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N, N-dimethylformamide. In order to adjust the solubility of raw materials and the like, a nonpolar solvent (for example, toluene or xylene) may be used in combination.

  The reaction temperature of the tetracarboxylic dianhydride and the diamine is preferably less than 100 ° C, more preferably less than 90 ° C. Moreover, imidation of polyamic acid is typically performed by heat treatment under an inert atmosphere (typically a vacuum or nitrogen atmosphere). The heat treatment temperature is preferably 150 ° C. or higher, more preferably 180 to 450 ° C.

  Moreover, the said polyimide may be mixed (blended) individually or as needed.

  The glass transition temperature (Tg) of the polyimide resin is 10 to 80 ° C, preferably 30 to 75 ° C, and more preferably 40 to 75 ° C. By using a polyimide resin having such a glass transition temperature, the elastic modulus at a high temperature is high, and movement of copper ions from the lead frame to the semiconductor element can be prevented.

  The blending amount of the polyimide resin is preferably 30 parts by weight or more, more preferably 30 to 90 parts by weight, and 40 to 80 parts by weight with respect to 100 parts by weight of the adhesive composition for a semiconductor device. More preferably, it is particularly preferably 40 to 70 parts by weight. The reference “100 parts by weight of the adhesive composition for semiconductor devices” is as described above.

<Thermoplastic resin or thermosetting resin>
Moreover, it is preferable that the adhesive composition for semiconductor devices of this invention contains a thermoplastic resin or a thermosetting resin, and it is more preferable to contain a thermosetting resin.

  Examples of the thermosetting resin include phenol resin, amino resin, unsaturated polyester resin, epoxy resin, polyurethane resin, and silicone 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.

  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 An isocyanurate type or glycidylamine type epoxy resin is used. These can be used alone or in combination of two or more. Among these epoxy resins, novolac type epoxy resins, biphenyl type epoxy resins, trishydroxyphenylmethane type resins, or tetraphenylolethane type epoxy resins are particularly preferable.

  When the epoxy resin is included in the adhesive composition for a semiconductor device, it is preferable to use a hydroxyl group or carboxyl group-containing resin in combination, and from the viewpoint of heat resistance, it is preferable to use a phenol resin in combination. Moreover, when the adhesive composition for semiconductor devices contains a thermoplastic tree having an epoxy group, which will be described later, the phenol resin can react with the thermoplastic resin having the epoxy group. Examples of the phenol resin include phenol novolak resin, phenol aralkyl resin, cresol novolak resin, tert-butylphenol novolak resin, nonyl phenol novolak resin and other novolak type phenol resins, resol type phenol resin, and polyhydroxystyrene such as polyparahydroxystyrene. Etc. These can be used alone or in combination of two or more. Among these phenol resins, a phenol novolac resin and a phenol aralkyl resin are particularly preferable because the connection reliability of the semiconductor device can be improved.

  Further, the mixing ratio of the epoxy resin, the thermoplastic resin having an epoxy group, the hydroxyl group or carboxyl group-containing resin is not particularly limited. For example, the epoxy resin component or the thermoplastic resin component having an epoxy group It is preferable to blend so that the hydroxyl group in the hydroxyl group-containing resin component or the carboxyl group in the carboxyl group-containing resin component is 0.5 to 2.0 equivalents per equivalent of epoxy group in the group, 0.8 to 1.2 The equivalent is more preferable. It is preferable for the blending ratio to be within the above range since a sufficient reaction proceeds.

  The blending ratio of the thermosetting resin is preferably in the range of 1 to 40 parts by weight and more preferably in the range of 1 to 30 parts by weight in 100 parts by weight of the adhesive composition for semiconductor devices. .

  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 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 -Ethylhexyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, stearyl group, octadecyl group, or dodecyl group.

  Further, the other monomer that forms 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, maleic anhydride or acid anhydride monomers such as itaconic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4-hydroxymethylcyclohexyl) -methyl acrylate Hydroxyl group-containing monomers such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate or (meth) acryloyloxy Examples include sulfonic acid group-containing monomers such as naphthalenesulfonic acid, or phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate, and epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether. . These can be used alone or in combination of two or more. The (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  In the present invention, the thermoplastic resin and the thermosetting resin are suitably cross-linked, and from the viewpoint of obtaining good reliability, a thermoplastic tree having an epoxy group or a carboxyl group (for example, having an epoxy group) An acrylic resin or an acrylic resin having a carboxyl group) can be used. Examples of the acrylic resin having an epoxy group include a copolymer of an acrylic acid or methacrylic acid ester having an alkyl group and an epoxy group-containing monomer. Examples of the epoxy group-containing monomer include the same ones as described above. As a commercial item of the acrylic resin which has an epoxy group, Nagase ChemteX Co., Ltd. brand name: SG-P3 etc. can be mentioned. Moreover, as an acrylic resin which has a carboxyl group, the copolymer of the ester of acrylic acid or methacrylic acid which has the above-mentioned alkyl group, and carboxyl group-containing monomers, such as (meth) acrylic acid, is mentioned. As a commercial item of the acrylic resin which has a carboxyl group, Nagase ChemteX Co., Ltd. brand name: SG-708-6 etc. can be mentioned.

  The blending ratio of the thermoplastic resin is not particularly limited as long as the adhesive sheet exhibits a function as a thermosetting type when heated under predetermined conditions, but in 100 parts by weight of the adhesive composition for a semiconductor device. It is preferably 95 parts by weight or less, more preferably in the range of 30 to 95 parts by weight, and still more preferably in the range of 50 to 60 parts by weight.

  A crosslinking agent can be added to the adhesive composition for a semiconductor device. A conventionally well-known thing can be employ | adopted as a 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 not particularly limited, but for example, it is preferably 7 parts by weight or less with respect to 100 parts by weight of the polymer having a crosslinkable functional group, and 0.05 to 7 More preferred are parts by weight. When the amount of the cross-linking agent is more than 7 parts by weight, the adhesive force is lowered, 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 hardening accelerator can be added to the adhesive composition for semiconductor devices. In particular, when an epoxy resin is used as the thermosetting resin, it is preferable to use a phosphorus-based curing accelerator such as tetraphenylphosphonium tetraphenylborate (TPPK) as the curing accelerator. Although it does not specifically limit as addition amount of a hardening accelerator, For example, it is preferable to set it as 5 weight part or less with respect to 100 weight part of epoxy resins, and it shall be 0.05-5 weight part. More preferred.

  Moreover, the adhesive composition for semiconductor devices of this invention can be mix | blended suitably with a filler according to the use. The blending of the filler makes it possible to impart conductivity to the adhesive sheet including the adhesive layer obtained from the adhesive composition for semiconductor devices, improve thermal conductivity, adjust 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 0.005 to 10 μm. Adhesiveness can be made favorable by the average particle diameter of the said filler being 0.005 micrometer or more. Moreover, by setting it as 10 micrometers 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 above, other additives can be appropriately blended in the adhesive composition for a semiconductor device of the present invention as necessary. Examples of other additives include a dispersant, an antioxidant, and a silane coupling agent. These can be used alone or in combination of two or more.

  The method for producing the adhesive composition for a semiconductor device is not particularly limited. For example, an ion scavenger and a polyimide resin, and if necessary, a thermosetting resin, a thermoplastic resin, and other additives are put into a container. And it can obtain as an adhesive composition solution for semiconductor devices by dissolving in an organic solvent and stirring uniformly.

  The organic solvent is not particularly limited as long as it can uniformly dissolve, knead or disperse the components constituting the adhesive composition for semiconductor devices, and a conventionally known organic solvent 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.

2. Adhesive Sheet As shown in FIG. 1, the adhesive sheet for a semiconductor device 1 of the present invention comprises an adhesive layer 1a made of the adhesive composition for a semiconductor device and a base film 1b.

  The adhesive sheet 1 for a semiconductor device of the present invention may have a two-layer structure composed of an adhesive layer 1a composed of the adhesive composition for a semiconductor device and a base film 1b, and within a range not impairing the effects of the present invention. Furthermore, another layer such as an adhesive layer may be included.

  The adhesive sheet 1 for a semiconductor device of the present invention is produced as follows, for example. First, the adhesive composition solution for a semiconductor device is prepared. Next, an adhesive composition solution for a semiconductor device is applied on a base film 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, polyethylene terephthalate (PET), polyethylene, polypropylene, a plastic film or paper surface-coated with a release agent such as a fluorine-type release agent or a long-chain alkyl acrylate 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 bond layer 1a of the adhesive sheet 1 for semiconductor devices of the present invention is obtained.

  Although the film thickness of the adhesive bond layer 1a is not specifically limited, It is preferable that it is 5-100 micrometers, and it is more preferable that it is 5-25 micrometers. A film thickness larger than 5 μm is preferable because it can be adhered to the adherend without voids.

  Since the adhesive sheet 1 for a semiconductor device of the present invention has an adhesive layer 1a composed of an adhesive composition for a semiconductor device containing a compound for ion trapping and a specific polyimide resin, the adhesive sheet 1a is externally used during various processes in the manufacture of the semiconductor device. Metal ions can be captured from the substrate, and as a result, the mixed metal ions can hardly reach the circuit forming surface formed on the wafer, and the deterioration of electrical characteristics can be suppressed to improve product reliability. Can do.

  The adhesive layer 1a of the adhesive sheet 1 for a semiconductor device of the present invention can be suitably used for manufacturing a semiconductor device. Specifically, a die bond film for fixing the semiconductor chip to an adherend such as a lead frame, a protective film for protecting the back surface of the semiconductor chip of the flip chip type semiconductor device, and a seal for sealing the semiconductor chip. What is used as a stop sheet is mentioned.

  When the adhesive layer 1a of the adhesive sheet 1 for semiconductor devices of the present invention is used as a die bond film, a semiconductor wafer (semiconductor chip) is laminated on the adhesive layer 1a (FIG. 1) side, and then the base film is peeled off. Then, it is preferable to laminate a dicing film (or adherend).

  The adhesive composition for a semiconductor device of the present invention heated at 175 ° C. for 5 hours (weight 2.5 g) was immersed in 50 mL of an aqueous solution containing 10 ppm of Cu (II) ions and left at 120 ° C. for 20 hours. The copper ion concentration in the later aqueous solution is preferably 0 to 9.9 ppm, more preferably 0 to 9.5 ppm, and even more preferably 0 to 9 ppm. By being in the said range, the metal ion mixed from the outside during the various processes in manufacture of a semiconductor device is caught more easily. As a result, metal ions mixed from the outside are less likely to reach the circuit forming surface formed on the wafer, and the deterioration of the electrical characteristics can be suppressed and the product reliability can be further improved.

  Moreover, you may provide adhesive layers other than the said adhesive bond layer 1a in the adhesive sheet 1 for semiconductor devices of this invention. The adhesive layer is not particularly limited, and any adhesive layer made of an adhesive or the like used in this field can be used.

3. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device in which chips are stacked on an adherend via an adhesive layer 1a of the adhesive sheet 1 for semiconductor devices, and a chip using the adhesive sheet 1 for semiconductor devices. The present invention relates to a method for manufacturing a semiconductor device including a step of laminating a substrate on an adherend. Hereinafter, an embodiment of a semiconductor device and a method for manufacturing the semiconductor device when the adhesive layer 1a of the adhesive sheet 1 for a semiconductor device according to the present invention is used as a die bond film will be specifically described with reference to the drawings. In the description, the adhesive layer 1a may be referred to as a die bond film 1a.

  Below, the dicing die bond film 2 which bonded together the adhesive layer 1a of the adhesive sheet 1 for semiconductor devices of this invention to a conventionally well-known dicing film, and peeled the base film 1b on the adhesive layer 1a after that is used. A method of manufacturing the semiconductor device will be described (FIG. 2). The dicing film according to the present embodiment has a structure in which the pressure-sensitive adhesive layer 3 is laminated on the base material 4.

  First, as shown in FIG. 2, the semiconductor wafer 5 is pressure-bonded onto the semiconductor wafer attaching portion 1c on the adhesive layer 1a side of the die bond film 1 in the dicing die bond film 2, 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 5 is performed. Thereby, the semiconductor wafer 5 is cut into a predetermined size and separated into individual pieces, and the semiconductor chip 6 is manufactured. Dicing is performed according to a conventional method from the circuit surface side of the semiconductor wafer 5, for example. Further, in this step, for example, a cutting method called full cut for cutting up to the dicing die-bonding film 2 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 5 is bonded and fixed by the dicing die-bonding film 2, chip chipping and chip jumping can be suppressed, and damage to the semiconductor wafer 5 can also be suppressed.

  In order to peel off the semiconductor chip adhered and fixed to the dicing die bond film 2, the semiconductor chip 6 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 individual semiconductor chips 6 from the dicing die-bonding film 2 side with a needle and picking up the pushed-up semiconductor chips 6 with a pick-up device can be mentioned.

  Here, when the pressure-sensitive adhesive layer 3 is an ultraviolet curable type, the pickup is performed after the pressure-sensitive adhesive layer 3 is irradiated with ultraviolet rays. Thereby, the adhesive force with respect to the die-bonding film 1a of the adhesive layer 3 falls, and peeling of the semiconductor chip 6 becomes easy. As a result, the pickup can be performed without damaging the semiconductor chip.

  Next, as shown in FIG. 3, the semiconductor chip 6 formed by dicing is die-bonded to the adherend 8 via the die-bonding film 1a (semiconductor wafer bonding portion 1c). Die bonding is performed by pressure bonding. The conditions for die bonding are not particularly limited, and can be set as necessary. Here, examples of the adherend 8 include a resin substrate, a lead frame, and a Si wafer.

  Next, a wire bonding step of electrically connecting the tip of the terminal portion (inner lead) of the adherend 8 and an electrode pad (not shown) on the semiconductor chip 6 with the bonding wire 9 is performed. As the bonding wire 9, 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 1a by heat processing.

  Subsequently, a sealing process for sealing the semiconductor chip 6 with the sealing resin 7 is performed. This step is performed to protect the semiconductor chip 6 and the bonding wire 9 mounted on the adherend 8. This step is performed by molding a sealing resin with a mold. As the sealing resin 7, for example, an epoxy resin is used.

  In the mounting process, air bubbles are generally mixed in the interface between the adherend 8 and the adhesive layer 1b of the die bond film 1a. In the main sealing step, the bubbles are diffused into the sealing resin 7 or the like by the pressure at the time of resin sealing or the like, and the influence is reduced.

  Next, in the post-curing process, the sealing resin 7 that is insufficiently cured in the sealing process is completely cured. Even in the case where the die bond film 1a is not thermally cured in the sealing process, the die bond film 1a is thermally cured together with the curing of the sealing resin 7 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 minute-8 hours.

  Moreover, as shown in FIG. 4, the adhesive sheet (die bond film) of this invention can be used suitably also when laminating | stacking a some semiconductor chip and carrying out three-dimensional mounting. In the case of the three-dimensional mounting shown in FIG. 4, first, at least one die bond film 1a cut out to be the same size as the semiconductor chip is attached on the adherend 8, and then the semiconductor chip 6 is attached via the die bond film 1a. , Paste the wire bond side up. Next, the die bond film 1a (which may be the adhesive layer 1a of the present invention or another die bond film) is pasted while avoiding the electrode pad portion of the semiconductor chip 6. Furthermore, another semiconductor chip 10 is die-bonded on the die-bonding film 1a 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 6 and the other semiconductor chip 10 and the adherend 8 are electrically connected by the bonding wire 9. In addition, this process is implemented without passing through the heating process of the die-bonding film 1a.

  Subsequently, a sealing step of sealing the semiconductor chip 6 and the like with the sealing resin 7 is performed, and the sealing resin is cured. Next, in the post-curing process, the sealing resin 7 that is insufficiently cured in the sealing process is completely cured.

  In the above-described embodiment, the case where the adhesive sheet of the present invention 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.

  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.

<Synthesis of polyimide resin (PI-1)>
In a 300 mL flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inflow tube, 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: LP-7100) ) 12.4 g, polyoxypropylenediamine (manufactured by BASF Corp., trade name: D400, molecular weight: 452.4) 22.6 g and N-methyl-2-pyrrolidone 140 g were added, and the reaction solution was stirred. . After the diamine was dissolved, 32.6 g of 4,4′-oxydiphthalic dianhydride previously purified by recrystallization from acetic anhydride was added little by little while the flask was cooled in an ice bath. After reacting at room temperature (25 ° C.) for 8 hours, 80.5 g of xylene was added and heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene together with water to obtain a polyimide resin (PI-1) varnish. Got. When GPC of the obtained polyimide resin was measured, it was number average molecular weight (Mn) 13900 and weight average molecular weight (Mw) 35100 in terms of polystyrene. Moreover, Tg of the obtained polyimide resin was 42 degreeC.

<Synthesis of polyimide resin (PI-2)>
In a 300 mL flask equipped with a thermometer, stirrer, condenser, and nitrogen inlet tube, 20.5 g of 2,2-bis (4-aminophenoxyphenyl) propane as a monomer and 4,9-dioxadecane-1,12- 10.3 g of diamine and 194 g of N-methyl-2-pyrrolidone as an organic solvent were charged and stirred to obtain a reaction solution in which each diamine was dissolved in the organic solvent. Next, 52.20 g of decamethylene bistrimellitate dianhydride was added to the reaction solution little by little, and the reaction was allowed to proceed by heating at 180 ° C. for 5 hours while blowing nitrogen gas to remove the generated water out of the system. By doing this, a polyimide resin (PI-2) varnish was obtained. When the molecular weight of the obtained polyimide resin was measured by GPC, it was number average molecular weight (Mn) 29000 and weight average molecular weight (Mw) 87000 in terms of polystyrene. Moreover, Tg of the obtained polyimide resin was 71 degreeC.

<Synthesis of polyimide resin (PI-3)>
In a 300 mL flask equipped with a thermometer, stirrer, condenser, and nitrogen inlet tube, 20.5 g of 2,2-bis (4-aminophenoxyphenyl) propane as a monomer and 6.96 g of 1,6-diaminohexane, In addition, 194 g of N-methyl-2-pyrrolidone as an organic solvent was charged and stirred to obtain a reaction solution in which each diamine was dissolved in the organic solvent. Next, 52.20 g of decamethylene bistrimellitate dianhydride was added to the reaction solution little by little, and the reaction was allowed to proceed by heating at 180 ° C. for 5 hours while blowing nitrogen gas to remove the generated water out of the system. By doing this, a polyimide resin (PI-2) varnish was obtained. When the molecular weight of the obtained polyimide resin was measured by GPC, it was number average molecular weight (Mn) 21000 and weight average molecular weight (Mw) 72000 in terms of polystyrene. Moreover, Tg of the obtained polyimide resin was 8 degreeC.

<Synthesis of polyimide resin (PI-4)>
In a 300 mL flask equipped with a thermometer, stirrer, condenser, and nitrogen inlet tube, 20.5 g of 2,2-bis (4-aminophenoxyphenyl) propane as a monomer and 4,9,14-trioxaheptadecane- By adding 16.9 g of 1,17-diamine and 194 g of N-methyl-2-pyrrolidone as an organic solvent and stirring, a reaction solution in which each diamine was dissolved in the organic solvent was obtained. Next, 52.20 g of decamethylene bistrimellitate dianhydride was added to the reaction solution little by little, and the reaction was allowed to proceed by heating at 180 ° C. for 5 hours while blowing nitrogen gas to remove the generated water out of the system. By doing this, a polyimide resin (PI-4) varnish was obtained. When the molecular weight of the obtained polyimide resin was measured by GPC, it was number average molecular weight (Mn) 31000 and weight average molecular weight (Mw) 81000 in terms of polystyrene. Moreover, Tg of the obtained polyimide resin was 86 degreeC.

Examples 1-4
Using polyimide resins (PI-1 to 4), each component was blended at a composition ratio shown in Table 1 below to obtain an adhesive composition (varnish for forming an adhesive layer). This adhesive composition solution was applied onto a release-treated film comprising a polyethylene release film (thickness: 50 μm) subjected to silicone release treatment as a release liner. Furthermore, by drying at 175 ° C. for 5 hours, an adhesive sheet having a thickness of 20 μm was produced. In addition, the weight part of the polyimide resin in Table 1 indicates the solid content.

In addition, the symbol of each component in Table 1 means the following.
Phenol resin: Meiwa Kasei Co., Ltd., (trade name) MEH-7851H
Epoxy resin: manufactured by Nippon Steel Chemical Co., Ltd. (trade name) YDF-8170C
TPPK: manufactured by Tokyo Chemical Industry Co., Ltd., tetraphenylphosphonium tetraphenylborate BT-LX: manufactured by Johoku Chemical Co., Ltd., rust inhibitor IXE-100: inorganic cation exchanger NMP manufactured by Toagosei Co., Ltd .: Kanto N-methyl-2-pyrrolidone, manufactured by Chemical Co., Ltd.

(Evaluation method)
<Ion trapping ability>
An adhesive sheet (thickness: 20 μm) is cut into a size of 240 mm × 300 mm (about 2.5 g) and bent to a size of 37.5 mm × 60 mm, and is a cylindrical sealed type with a diameter of 58 mm and a height of 37 mm It put into the container made from a Teflon (trademark), and 50 mL of 10 ppm Cu (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 Cu ions in the aqueous solution was measured using ICP-AES (manufactured by SII Nanotechnology, Inc., SPS-1700HVR). Table 2 shows values obtained by subtracting the measured Cu ion concentration in the aqueous solution from the initial concentration of 10 ppm (that is, the amount of trapped ions).

<Wafer bondability>
The adhesive sheet obtained above was cut into a width of 10 mm and a length of 40 mm to obtain a film adhesive with a substrate. This film-like adhesive with a substrate is placed on the back surface (surface opposite to the support table) of the silicon wafer (6 inch diameter, thickness 400 μm) placed on the support table. Then, the film was laminated by pressing with a roll (temperature 100 ° C., linear pressure 4 kgf / cm, feed rate 0.5 m / min), and evaluated according to the following evaluation criteria. The results are shown in Table 2.
◯: No voids are visually observed at the wafer and film adhesive interface after bonding.
X: A void is visually observed on the wafer and the film-like adhesive interface after bonding.

<Measurement of glass transition temperature Tg of polyimide>
Using the adhesive sheet obtained above, a strip-shaped sample having a width of 10 mm, a length of 40 mm, and a thickness of 200 μm was prepared. Using a fixed viscoelasticity measuring device (RSA (III), manufactured by Rheometric Scientific), the tensile storage elastic modulus of the sample at −50 to 300 ° C. is the distance between chucks of 22.5 mm, the frequency of 1 Hz, and the heating rate. The measurement was performed under the condition of 10 ° C./min. The inflection point of the curve when the tensile storage modulus is plotted against the measurement temperature is shown in Table 2 as the glass transition temperature Tg.

DESCRIPTION OF SYMBOLS 1: Adhesive sheet for semiconductor devices 1a: Adhesive layer which consists of adhesive composition for semiconductor devices 1b: Base film 1c: Semiconductor wafer sticking part 2: Dicing die-bonding film 3: Adhesive layer 4: Base material 5: Semiconductor wafer 6: Semiconductor chip 7: Sealing resin 8: Substrate 9: Bonding wire 10: Other semiconductor chip

Claims (10)

  An adhesive composition for a semiconductor device, comprising an ion-trapping compound and a polyimide resin having a glass transition temperature of 10 to 80 ° C. and substantially free of an allyl-modified polyimide resin.   The adhesive composition for a semiconductor device according to claim 1, wherein the compound that traps ions is an organic low-molecular compound.   The adhesive composition for a semiconductor device according to claim 2, wherein the organic low molecular weight compound is one or more compounds selected from the group consisting of a triazole compound, a tetrazole compound, and a bipyridyl compound.   The adhesive for a semiconductor device according to claim 2 or 3, wherein the addition amount of the organic low molecular weight compound is 0.1 to 5 parts by weight with respect to 100 parts by weight of the adhesive composition for a semiconductor device. Composition.   The adhesive composition for a semiconductor device according to claim 1, wherein the compound that traps ions is an inorganic cation exchanger.   The adhesive composition for a semiconductor device according to claim 5, wherein the inorganic cation exchanger is an oxidized hydrate of an element selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, magnesium, and aluminum.   The adhesive composition for a semiconductor device according to claim 5 or 6, wherein the addition amount of the inorganic cation exchanger is 1 to 20 parts by weight with respect to 100 parts by weight of the adhesive composition for a semiconductor device. object.   The copper ion in the aqueous solution after immersing the adhesive composition for a semiconductor device having a weight of 2.5 g heated at 175 ° C. for 5 hours 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 adhesive composition for semiconductor devices according to claim 1, wherein the concentration is from 0 to 9.9 ppm.   The adhesive sheet for semiconductor devices containing the base material film and the adhesive bond layer which consists of an adhesive composition for semiconductor devices in any one of Claims 1-8.   The manufacturing method of the semiconductor device using the adhesive sheet for semiconductor devices of Claim 9.