JP6148430B2 - Adhesive sheet and its use - Google Patents

Description

  The present invention relates to an adhesive sheet and its use, and more specifically to an adhesive sheet, a dicing die bond film using the adhesive sheet, and a method for manufacturing a semiconductor device.

  In recent years, a stacked MCP (Multi Chip Package) in which memory package chips for mobile phones and portable audio devices are stacked in multiple stages has become widespread. In addition, with the increasing functionality of image processing technology and mobile phones, etc., higher density, higher integration, and thinner packages are being promoted. As a method for fixing a semiconductor chip to a substrate or the like, a method using a thermosetting paste resin or a method using an adhesive sheet in which a thermoplastic resin and a thermosetting resin are used in combination has been proposed.

  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 May decrease. In addition, metal ions may be generated from the circuit or bonding wire during use of the product, and the electrical characteristics may be similarly reduced.

  In contrast, extrinsic gettering (hereinafter also referred to as “EG”) in which the back surface of the wafer is processed to form a crush layer (strain), and metal ions are captured and removed by this crush layer, and the wafer Intrinsic gettering (hereinafter also referred to as “IG”) in which oxygen precipitation defects are formed in the crystal substrate and metal ions are captured and removed by the oxygen precipitation defects has been attempted.

  However, with the recent thinning of wafers for increasing the capacity of semiconductor devices, the effect of EG is reduced, and the effects of EG are reduced by removing back surface distortion that causes wafer cracking and warping. It is becoming impossible to obtain the gettering effect sufficiently.

  Therefore, various measures for complementing the gettering effect have been proposed. For example, Patent Document 1 discloses an adhesive sheet that contains an anion exchanger, captures chloride ions that cause wire corrosion, and improves connection reliability. Patent Document 2 discloses a film adhesive having a copper ion adsorbing layer containing a resin having a skeleton capable of complexing with copper ions. It is described that the influence of copper ions generated from a member made of copper can be significantly reduced as compared with the conventional case.

JP 2009-256630 A JP 2011-52109 A

  However, even if the adhesive sheet contains a component that adsorbs metal ions, for example, if the adhesive sheet is peeled off from the semiconductor chip, the complementary action of the gettering effect is reduced by the amount of the peeled area. Along with the recent increase in capacity of semiconductor devices, multi-layer stacking of thinned semiconductor chips and adhesive sheets is required for packages of the same standard, and as the stacking progresses, heat history due to heat treatment accumulates in the adhesive sheets. . As a result, the adhesive property of the adhesive sheet is lowered, and the adhesive sheet may be peeled off from the semiconductor chip during the sealing process or the reflow process, and the tendency for the complementary action of the gettering effect to decrease is increasing. Such a peeling phenomenon cannot be solved by the above conventional technique.

  Accordingly, an object of the present invention is to prevent the peeling from the semiconductor chip even when a high temperature treatment is performed, and to capture the metal ions mixed in the semiconductor chip in the manufacturing process of the semiconductor device, thereby reducing the electrical characteristics of the semiconductor device. It is to provide an adhesive sheet that can be prevented.

  The inventors of the present invention intensively studied to solve the above-described conventional problems, and as a result of paying attention to the storage elastic modulus at a high temperature of the adhesive sheet capable of capturing metal ions, the present invention has been completed.

That is, the adhesive sheet according to the present invention is composed of an adhesive composition containing an ion scavenger,
The tensile storage elastic modulus at 260 ° C. after being cured at 175 ° C. for 5 hours is 0.5 MPa or more and 1000 MPa or less.

  In the adhesive sheet, the tensile storage elastic modulus at 260 ° C. (hereinafter sometimes simply referred to as “elastic modulus”) after thermosetting under a predetermined condition is 0.5 MPa or more and 1000 MPa or less. The elasticity modulus (for example, 175 ° C. to 260 ° C.) can be maintained, and peeling of the adhesive sheet from the semiconductor chip can be prevented in the sealing process and the reflow process. Moreover, since it is possible to prevent the adhesive sheet from being peeled and maintain the adhesive state between the adhesive sheet and the semiconductor chip, it is possible to prevent a decrease in the capture efficiency of metal ions mixed in or possibly mixed into the semiconductor chip. It is possible to prevent deterioration of electrical characteristics of the obtained semiconductor device. In addition, the measuring method of the tensile storage elastic modulus of an adhesive sheet is based on description of an Example.

  It is preferable that the adhesive composition constituting the adhesive sheet further includes a thermoplastic resin and a thermosetting resin. By employing both components, the elastic modulus of the adhesive sheet can be suitably set within a predetermined range.

  The thermoplastic resin preferably includes an acrylic resin having a weight average molecular weight of 100,000 or more. Thereby, the cohesive force due to the acrylic resin is sufficiently exerted, an adhesive force at a low temperature (for example, 60 ° C.) can be obtained, and a decrease in the elastic modulus at a high temperature can be prevented.

  In the adhesive sheet, the acrylic resin preferably contains an epoxy group or a carboxyl group. By adopting an epoxy group-containing acrylic resin or a carboxyl group-containing acrylic resin, a crosslinking reaction with a thermosetting resin is possible, and an elastic modulus at a high temperature can be secured.

  In the adhesive sheet, the weight-based content of the thermoplastic resin in the adhesive composition is preferably 0.5 to 20 times the weight-based content of the thermosetting resin. By setting the ratio of the content of the thermoplastic resin and the content of the thermosetting resin in such a range, it is possible to efficiently achieve both low temperature adhesiveness and high temperature elastic modulus.

  In the said adhesive sheet, the copper ion density | concentration in the said aqueous solution after immersing a 2.5-g adhesive sheet in 50 ml of aqueous solution which has a copper ion of 10 ppm, and leaving it to stand at 120 degreeC for 20 hours is 0-9. It is preferably 9 ppm. When the adhesive sheet has such a copper ion trapping property, metal ions mixed in the semiconductor chip or the like in the semiconductor device manufacturing process can be captured. As a result, it becomes difficult for metal ions mixed from the outside to reach the circuit formation surface formed on the wafer, the deterioration of electrical characteristics is suppressed, and the product reliability can be improved.

In the present invention, a dicing film having a substrate and an adhesive layer formed on the substrate,
A dicing die-bonding film comprising the adhesive film laminated on the pressure-sensitive adhesive layer is also included.

  Thus, the said adhesive sheet can be used suitably as a die-bonding film which comprises a dicing die-bonding film.

In the present invention, the step of bonding the adhesive sheet of the dicing die bond film and the semiconductor wafer,
Forming a semiconductor chip by dicing the semiconductor wafer;
Picking up the semiconductor chip together with the adhesive sheet;
Fixing the picked-up semiconductor chip on the adherend via the adhesive sheet;
Also included is a method of manufacturing a semiconductor device including a step of electrically connecting the semiconductor chip and the adherend with a bonding wire and a step of sealing the semiconductor chip with a sealing resin.

  By manufacturing a semiconductor device with a dicing die bond film using the adhesive sheet as a die bond film, it is possible to prevent peeling of the adhesive sheet from the semiconductor chip in a sealing process or a reflow process. The yield can be improved and a semiconductor device having excellent electrical characteristics can be manufactured by efficiently capturing metal ions that can be mixed into the semiconductor chip.

It is a cross-sectional schematic diagram which shows the dicing die-bonding film which used the adhesive sheet which concerns on one Embodiment of this invention as a die-bonding film. 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.

  An adhesive sheet according to an embodiment of the present invention, a dicing die-bonding film using the adhesive sheet, a semiconductor device obtained using the dicing die-bonding film, and a manufacturing method thereof will be described with reference to the drawings as necessary.

<Adhesive sheet>
The adhesive sheet according to the present invention is composed of an adhesive composition containing an ion scavenger,
The tensile storage elastic modulus at 260 ° C. after being cured at 175 ° C. for 5 hours is 0.5 MPa or more and 1000 MPa or less.

  In the above adhesive sheet, the tensile storage elastic modulus at 260 ° C. after thermosetting under a predetermined condition is 0.5 MPa or more and 1000 MPa or less, so that the elastic modulus at a high temperature can be maintained, and a sealing process or In the reflow process, the peeling of the adhesive sheet from the semiconductor chip can be prevented. Moreover, since peeling of the adhesive sheet can be prevented and adhesion between the adhesive sheet and the semiconductor chip can be maintained, it is possible to prevent a reduction in the capture efficiency of metal ions mixed in or possibly mixed into the semiconductor chip. .

  The adhesive sheet preferably has a film thickness of 3 to 150 μm, more preferably 5 to 120 μm, and still more preferably 5 to 60 μm. By setting the film thickness of the adhesive sheet to 3 μm or more, metal ions can be captured better. On the other hand, when the film thickness of the adhesive sheet is 150 μm or less, the film thickness can be easily controlled.

  The adhesive sheet preferably has a water absorption of 3% by weight or less, more preferably 2% by weight or less, and more preferably 1% by weight or less when left for 120 hours in an atmosphere of 85 ° C. and 85% RH. More preferably it is. When the water absorption is 3% by weight or less, the movement of metal ions in the adhesive sheet is suppressed in the semiconductor package, and the metal ions can be captured more suitably.

  The adhesive sheet preferably has a shear adhesive force after thermal curing to a silicon wafer of 0.1 MPa or more and 20 MPa or less, more preferably 0.15 MPa or more and 15 MPa or less under the condition of 175 ° C. More preferably, it is 2 MPa or more and 10 MPa or less. When the shear adhesive force is 0.1 MPa or more under the condition of 175 ° C., the metal ions easily diffuse from the support member (for example, a wafer) to the adhesive sheet in the semiconductor package, and the metal ions It can capture more suitably.

  In the said adhesive sheet, the copper ion density | concentration in the said aqueous solution after immersing a 2.5-g adhesive sheet in 50 ml of aqueous solution which has a copper ion of 10 ppm, and leaving it to stand at 120 degreeC for 20 hours is 0-9. It is preferably 9 ppm. When the adhesive sheet has such a copper ion trapping property, metal ions mixed in the semiconductor chip or the like in the semiconductor device manufacturing process 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, as described above, the method for setting the copper ion concentration after capturing copper ions to 0 to 9.9 ppm is not limited to the method of containing an ion capturing agent in the adhesive sheet, as described above, and the resin component used is a carboxylic acid group. For example, a method of introducing a functional group that captures a metal ion such as a method of ion-implanting boron or an n-type dopant may be employed.

[Adhesive composition]
The adhesive composition constituting the adhesive sheet contains an ion scavenger, preferably contains a thermoplastic resin or a thermosetting resin, and contains other components as necessary.

(Ion scavenger)
When an ion-trapping agent that captures metal ions is included in the adhesive sheet, metal ions mixed in or possibly mixed into the semiconductor wafer or the semiconductor chip from the outside during various processes in the manufacture of the semiconductor device are more preferably captured. be able to.

  Examples of the ion scavenger include cation exchangers and complex-forming compounds. Especially, a cation exchanger is preferable at the point which is excellent in heat resistance, and a complex formation compound is more preferable at the point which can capture | acquire a metal ion favorably.

  The cation exchanger is preferably an inorganic cation exchanger from the viewpoint that metal ions can be captured more suitably.

  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.

(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 metal ions more preferably, antimony, bismuth, zirconium, titanium, An oxide hydrate of an element selected from the group consisting of tin, magnesium and aluminum can be mentioned. These can be used alone or in combination of two or more. Of these, oxidized hydrates of magnesium and aluminum are preferable.

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

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

(Complex-forming compound)
The complex-forming compound is not particularly limited as long as it forms a complex with a metal ion. However, the complex-forming compound is preferably an organic complex-forming compound, and nitrogen can be suitably captured from the viewpoint of capturing a metal ion. It is preferably at least one selected from the group consisting of a containing compound, a hydroxyl group-containing compound, and a carboxylic acid group-containing compound.

(Nitrogen-containing compounds)
The nitrogen-containing compound is preferably a fine powder, easily dissolved in an organic solvent, or liquid. As such a nitrogen-containing compound, a heterocyclic compound having a tertiary nitrogen atom is preferable from the viewpoint of more suitably capturing a metal ion, and a triazole compound, a tetrazole compound, or a bipyridyl compound can be exemplified. From the viewpoint of the stability of the complex formed with the copper ion, a triazole compound is more preferable. These can be used alone or in combination of two or more.

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

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

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

  The bipyridyl compound is not particularly limited, and examples thereof include 2,2'-bipyridyl and 1,10-phenanthroline.

(Hydroxyl-containing compound)
Although it does not restrict | limit especially as said hydroxyl-containing compound, The thing of a fine powder form, the thing easy to melt | dissolve in an organic solvent, or a liquid thing is preferable. As such a hydroxyl group-containing compound, a compound having two or more hydroxyl groups on one aromatic ring is preferable from the viewpoint of more suitably capturing a metal ion. Specifically, a quinol compound, a hydroxyanthraquinone compound, or a polyphenol is preferred. Although a compound can be mentioned, a polyphenol compound is more preferable from a viewpoint of the stability of the complex formed between copper ions. These can be used alone or in combination of two or more. The aromatic ring refers to a conjugated ring structure in which the π-electron system is delocalized, and not only a non-condensed aromatic ring (for example, a benzene ring) but also a condensed aromatic ring (for example, a naphthalene ring, Anthracene ring, phenanthrene ring, naphthacene ring, pentacene ring, pyrene ring, etc.), anthraquinone ring and the like.

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

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

  The polyphenol compound is not particularly limited, but tannin, tannin derivatives (gallic acid, gallic acid alkyl ester (alkyl groups such as methyl group, ethyl group, propyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl group, decyl group, undecyl group, dodecyl group, etc.), pyrogallol) and the like.

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

  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 .: Cylest A, Cylest 110, Cylest B, Cylest 200, Cylest C, Cylest D, Crest 400, Cylest 40, Examples include Kirest 0D, Kirest NTA, Kirest 700, Kirest PA, Kirest HA, Kirest MZ-2, Kirest MZ-4A, and Kirest MZ-8.

  The content of the additive for capturing the metal ions is preferably 0.1 to 80 parts by weight, and 0.1 to 50 parts by weight with respect to 100 parts by weight of the resin component constituting the adhesive sheet. More preferably, the amount is 0.1 to 20 parts by weight. 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 80 parts by weight or less, a decrease in heat resistance and an increase in cost are suppressed. Can do.

(Thermoplastic resin)
The adhesive composition used for forming the adhesive sheet preferably contains a thermoplastic resin. 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 more esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms. Examples thereof include a polymer (acrylic copolymer) as a component. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, cyclohexyl, 2- Examples include an ethylhexyl group, an octyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a lauryl group, a tridecyl group, a tetradecyl group, a stearyl group, an octadecyl group, and a dodecyl group.

  In the said adhesive sheet, it is preferable that the said thermoplastic component and the thermosetting component mentioned later are mutually crosslinkable. By cross-linking the thermoplastic component and the thermosetting component, the adhesive force at a high temperature (for example, 175 to 260 ° C.) is further increased, and peeling in a reflow process or the like can be prevented. As a result, the semiconductor device The production yield can be improved. As a means for allowing the thermoplastic component and the thermosetting component to be cross-linked with each other, for example, introduction of functional groups capable of cross-linking with each other can be mentioned. Examples of combinations of functional groups that can crosslink each other include an epoxy group and a hydroxyl group, an epoxy group and a carboxyl group, and an epoxy group and an amino group. One of these functional group combinations is introduced into the thermoplastic component, and the remaining functional groups are introduced into the thermosetting component so that the thermoplastic component and the thermosetting component can be cross-linked with each other. Can do.

  In order to crosslink the thermoplastic component and the thermosetting component, when the thermoplastic component specifically has an epoxy group or a carboxyl group, the crosslinking reaction with the thermosetting component can be suitably advanced. . When the thermoplastic component has an epoxy group, the adhesive sheet preferably contains a phenol resin as a thermosetting component. Moreover, when a thermoplastic component has a carboxyl group, it is preferable that the said adhesive sheet contains an epoxy resin as a thermosetting component. A crosslinking reaction can be suitably performed between the epoxy group of the thermoplastic component and the hydroxyl group of the phenol resin of the thermosetting component, or between the carboxyl group of the thermoplastic component and the epoxy group of the epoxy resin of the thermosetting component. . In order to introduce an epoxy group into the thermoplastic component, an epoxy group-containing monomer can be employed as a constituent monomer of the acrylic copolymer. The epoxy group-containing monomer is not particularly limited as long as it has an epoxy group, and examples thereof include glycidyl acrylate and glycidyl methacrylate. In order to introduce a carboxyl group into the thermoplastic component, a carboxyl group-containing monomer can be employed as a constituent monomer of the acrylic copolymer. The carboxyl group-containing monomer is not particularly limited as long as it has a carboxyl group, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

  In addition, the other monomer that forms the polymer is not particularly limited. For example, an acid anhydride monomer such as maleic anhydride or 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, ( Hydroxyl group-containing monomers such as meth) acrylic acid 12-hydroxylauryl or (4-hydroxymethylcyclohexyl) -methyl acrylate, styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (Meth) acrylamide propanesulfur Phosphate, sulfopropyl (meth) acrylate or (meth) acryloyl such sulfonic acid group-containing monomers such as sulfopropyl acid, or 2-hydroxyethyl acryloyl phosphate phosphoric acid group-containing monomers such as sulfates, and the like. These can be used alone or in combination of two or more.

(Thermosetting resin)
Moreover, it is preferable that the said adhesive composition contains a thermosetting resin with the said thermoplastic 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. Thereby, it becomes difficult for water to enter the bonding interface between the adhesive sheet and the wafer, and ions are difficult to move. As a result, the reliability of the semiconductor device is improved.

  The epoxy resin is not particularly limited as long as it is generally used as an adhesive composition. For example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type. Biphenyl type, naphthalene type, fluorene type, phenol novolac 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 an epoxy group. For example, a novolak such as a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a biphenyl type phenol resin, a tert-butylphenol novolak resin, or a nonylphenol novolak resin. And polyoxystyrene such as polyphenol styrene, resol type phenol resin, and polyparaoxystyrene. These can be used alone or in combination of two or more. Of these phenol resins, phenol novolac resins, biphenyl type phenol resins, and phenol aralkyl resins are particularly preferable. This is because the connection reliability of the semiconductor device can be improved.

  The blending ratio of the thermosetting resin is not particularly limited as long as it exhibits a function as a thermosetting adhesive sheet when the adhesive sheet is heated under predetermined conditions, but the total amount of the adhesive composition The content is preferably in the range of 1 to 80% by weight, more preferably in the range of 3 to 70% by weight.

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

  In the adhesive sheet, the thermoplastic resin content in the adhesive composition is preferably 0.5 to 20 times the content of the thermosetting resin on a weight basis, and is 1 to 15 times. More preferably. By making the ratio of the content of the thermoplastic resin and the content of the thermosetting resin in such a range, the adhesiveness at low temperature and the elastic modulus at high temperature of the above-mentioned adhesive sheet can be efficiently made compatible. it can.

(Crosslinking agent)
When the adhesive sheet prepared using the adhesive composition is previously crosslinked to some extent, a polyfunctional compound that reacts with a functional group at the molecular chain end of the polymer is added as a crosslinking agent. Is good. 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.

(Filler)
Moreover, a filler can be suitably mix | blended with the said adhesive composition according to the use. The blending of the filler enables imparting conductivity to the adhesive sheet obtained from the adhesive composition, 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 improved handleability, improved 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 average particle diameter of the filler can be 0.005 to 10 μm. By setting the average particle size of the filler to 0.005 μm or more, the wettability to the adherend and the adhesiveness can be improved. 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 with the photometric type particle size distribution meter (The product made from HORIBA, apparatus name; LA-910).

(Other additives)
In addition to the said component, another additive can be suitably mix | blended with the said adhesive composition 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.

  In the above embodiment, the case where a thermosetting resin or a thermoplastic resin is used as the main component of the adhesive contained in the adhesive composition has been described. However, in the present invention, the adhesive mainly contained in the adhesive composition is used. As a component, instead of or in addition to the thermosetting resin and thermoplastic resin as described above, an inorganic material such as ceramic, cement, or solder may be included.

[Method for Preparing Adhesive Composition]
The method for preparing the adhesive composition is not particularly limited. For example, an ion scavenger and, if necessary, a thermosetting resin, a thermoplastic resin, or other additives are put into a container, and an organic solvent is added. It can be obtained as an adhesive composition solution by being dissolved in and stirred to be uniform.

  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 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.

[Production method of adhesive sheet]
The adhesive sheet according to the present embodiment is produced, for example, as follows. First, the adhesive composition solution prepared as described above is applied on a base separator to 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.

  The application of the adhesive sheet is not particularly limited and can be suitably used for manufacturing a semiconductor device. For example, a die bond film for fixing a semiconductor chip to an adherend such as a lead frame or a flip chip type semiconductor device The protective film which protects the back surface of this semiconductor chip, and what is used as a sealing sheet for sealing a semiconductor chip are mentioned.

  The adhesive sheet preferably has a tensile storage modulus at 60 ° C. before thermosetting of 0.01 MPa or more and 1000 MPa or less, more preferably 0.05 MPa or more and 100 MPa or less, and 0.1 MPa or more and 50 MPa or less. More preferably. By setting the tensile storage modulus at 60 ° C. before thermosetting to 0.01 MPa or more, the shape as a film can be maintained and good workability can be imparted. Moreover, the favorable wettability with respect to a to-be-adhered body can be provided by making the tensile storage elastic modulus in 60 degreeC before thermosetting into 1000 Mpa or less.

[Semiconductor device]
The semiconductor device according to this embodiment will be described with reference to FIG. The semiconductor device includes an adherend 6, the adhesive sheet 3 stacked on the adherend 6, and a semiconductor chip 5 disposed on the adhesive sheet 3. The adherend 6 may be a substrate or another semiconductor chip. In FIG. 2, the substrate is used as an adherend. In the semiconductor device shown in FIG. 2, the bonding wire 7 responsible for electrical connection between the semiconductor chip 5 and the adherend 6 further includes the tip of the terminal portion (inner lead) of the adherend 6 and the electrode on the semiconductor chip 5. A semiconductor chip 5 including a bonding wire 7 is covered with a sealing resin 8 so as to connect to a pad (not shown).

  In the semiconductor device according to the present embodiment, since the adhesive sheet is used for fixing the semiconductor chip to the adherend, the adhesion between the adhesive sheet and the semiconductor chip even after a high-temperature treatment such as a sealing process or a reflow process. While maintaining the above, it is possible to efficiently capture metal ions mixed in in the manufacturing process, and as a result, excellent product reliability can be ensured.

[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. The method for manufacturing a semiconductor device according to the present invention includes a step of bonding a dicing die bond film adhesive sheet and a semiconductor wafer, a step of dicing the semiconductor wafer to form a semiconductor chip, and picking up the semiconductor chip together with the adhesive sheet. And a step of fixing the picked-up semiconductor chip on the adherend via the adhesive sheet.

(Dicing die bond film)
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 bond film using an adhesive sheet according to an embodiment of the present invention as a die bond film. 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.

(Method for manufacturing semiconductor device)
First, as shown in FIG. 1, the semiconductor wafer 4 is pressure-bonded onto the semiconductor wafer attaching 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 using vibration energy by ultrasonic waves and pressure bonding energy by applying pressure in a heated state so as to be within the above temperature range.

  In addition, a wire bonding process is performed without heat-hardening 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 or the coated substrate are subjected to ultrasonic vibration or heating in the step. Shear deformation does not occur on the adhesive surface with the body 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.

  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. Even when the die-bonding film 3 is not thermally cured in the following post-curing process, the die-bonding film 3 is thermally cured together with the curing of the sealing resin 8 in this process, thereby allowing the adhesive fixing.

  Next, in the post-curing process, the sealing resin 8 that is insufficiently cured in the sealing process is completely cured. Even when the die-bonding film 3 is not thermally cured in the sealing process, the die-bonding film 3 is thermally cured together with the curing of the sealing resin 8 in this process, so that the adhesive fixing can be performed. 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. Thereby, a semiconductor package is obtained.

  Next, the semiconductor package is surface-mounted on a printed wiring board. Examples of the surface mounting method include reflow soldering in which solder is supplied on a printed wiring board in advance and then heated and melted with warm air to perform soldering. Examples of the heating method include hot air reflow and infrared reflow. Moreover, any system of whole heating or local heating may be used. The heating temperature is preferably 240 to 265 ° C., and the heating time is preferably in the range of 1 to 60 seconds.

  According to the above adhesive sheet, the tensile storage elastic modulus at 260 ° C. after being cured at 175 ° C. for 5 hours is 0.5 MPa or more and 1000 MPa or less, so that the elastic modulus at a high temperature (for example, 175 ° C. to 260 ° C.) is maintained. It is possible to prevent peeling of the adhesive sheet from the semiconductor chip in the sealing process and the reflow process.

  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 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, if the sealing resin 8 is insufficiently cured in the sealing step, it is completely cured. The semiconductor package thus obtained is then surface-mounted on a printed wiring board through the reflow process as described above.

  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 the examples are not intended to limit the gist of the present invention only to those unless otherwise specified. In the following, “parts” means parts by weight.

Example 1
25 parts of ion scavenger (Toa Gosei Co., Ltd., IXE-100), 80 parts of acrylic resin (Nagase Chemtex Co., Ltd., SG-80H, epoxy group-containing, weight average molecular weight 350,000), epoxy 10 parts of resin (Mitsubishi Chemical Co., Ltd., JER828), 10 parts of phenolic resin (Maywa Kasei Co., Ltd., MEH7800), 125 parts of spherical silica (manufactured by Admatechs Co., Ltd., SO-25R) in methyl ethyl ketone The concentration was adjusted to 23.6 wt% by dissolution.

  The adhesive composition solution was applied onto a release film made of a polyethylene terephthalate film having a thickness of 50 μm and subjected to a silicone release treatment as a release liner, and then dried at 130 ° C. for 2 minutes to obtain a thickness of 25 μm. An adhesive sheet was prepared.

(Example 2)
As an ion scavenger (Johoku Chemical Co., Ltd., BT-120) 5 parts, as an acrylic resin (Nagase ChemteX Co., Ltd., SG-80H, epoxy group-containing, weight average molecular weight 350,000) 50 parts, epoxy 25 parts of resin (Mitsubishi Chemical Co., Ltd., JER828), 25 parts of phenolic resin (Maywa Kasei Co., Ltd., MEH7800), 50 parts of spherical silica (manufactured by Admatechs Co., Ltd., SO-25R) in methyl ethyl ketone The concentration was adjusted to 23.6 wt% by dissolution.

  The adhesive composition solution was applied onto a release film made of a polyethylene terephthalate film having a thickness of 50 μm and subjected to a silicone release treatment as a release liner, and then dried at 130 ° C. for 2 minutes to obtain a thickness of 25 μm. An adhesive sheet was prepared.

(Example 3)
25 parts as ion scavenger (Toa Gosei Co., Ltd., IXE-100), 80 parts as acrylic resin (Nagase ChemteX Corporation, SG-708-6, carboxyl group-containing, weight average molecular weight 800,000) 10 parts of epoxy resin (Mitsubishi Chemical Co., Ltd., JER828), 10 parts of phenolic resin (Maywa Kasei Co., Ltd., MEH7800), 80 parts of spherical silica (manufactured by Admatex Co., Ltd., SO-25R) The concentration was adjusted to 23.6% by weight by dissolving in methyl ethyl ketone.

  The adhesive composition solution was applied onto a release film made of a polyethylene terephthalate film having a thickness of 50 μm and subjected to a silicone release treatment as a release liner, and then dried at 130 ° C. for 2 minutes to obtain a thickness of 25 μm. An adhesive sheet was prepared.

Example 4
25 parts as ion scavenger (manufactured by Toa Gosei Co., Ltd., IXE-100), 50 parts as acrylic resin (manufactured by Nagase ChemteX Corporation, SG-708-6, carboxyl group-containing, weight average molecular weight 350,000) 30 parts of epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER828), 30 parts of phenolic resin (manufactured by Meiwa Kasei Co., Ltd., MEH7800), 110 parts of spherical silica (manufactured by Admatechs Co., Ltd., SO-25R) The concentration was adjusted to 23.6% by weight by dissolving in methyl ethyl ketone.

  The adhesive composition solution was applied onto a release film made of a polyethylene terephthalate film having a thickness of 50 μm and subjected to a silicone release treatment as a release liner, and then dried at 130 ° C. for 2 minutes to obtain a thickness of 25 μm. An adhesive sheet was prepared.

(Comparative Example 1)
As an ion scavenger (Toa Gosei Co., Ltd., IXE-100) 25 parts, As an acrylic resin (Toa Gosei Co., Ltd., UH2000, weight average molecular weight. 12,000) 80 parts, As an epoxy resin (DIC) 10 parts by product, HP-7200), 10 parts by phenol resin (Maywa Kasei Co., Ltd., MEH7800), 100 parts spherical silica (manufactured by Admatechs, SO-25R) are dissolved in methyl ethyl ketone. The concentration was adjusted to 23.6% by weight.

  The adhesive composition solution was applied onto a release film made of a polyethylene terephthalate film having a thickness of 50 μm and subjected to a silicone release treatment as a release liner, and then dried at 130 ° C. for 2 minutes to obtain a thickness of 25 μm. An adhesive sheet was prepared.

(Comparative Example 2)
80 parts as an acrylic resin (manufactured by Nagase ChemteX Corporation, SG-80H, weight average molecular weight 350,000), 10 parts as an epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER828), as a phenol resin (Maywa Kasei Co., Ltd.) 10 parts manufactured by MEH7800 and 100 parts spherical silica (manufactured by Admatechs Co., Ltd., SO-25R) were dissolved in methyl ethyl ketone and adjusted to a concentration of 23.6% by weight.

  The adhesive composition solution was applied onto a release film made of a polyethylene terephthalate film having a thickness of 50 μm and subjected to a silicone release treatment as a release liner, and then dried at 130 ° C. for 2 minutes to obtain a thickness of 25 μm. An adhesive sheet was prepared.

(Measurement of tensile storage modulus at 260 ° C after thermosetting)
After leaving the adhesive sheets of each Example and Comparative Example in an oven at 175 ° C. for 5 hours, the tensile storage elasticity at 260 ° C. after thermosetting using a viscoelasticity measuring device (RSA-II, manufactured by Rheometric). The rate was measured. For the measurement, a plurality of the prepared adhesive sheets were bonded together, and a measurement sample cut out to have a length of 30 mm, a width of 10 mm, and a thickness of 0.20 mm was used. The tensile storage modulus was measured in the temperature range of −40 to 300 ° C. at a frequency of 1 Hz, a strain amount of 0.1%, and a temperature increase rate of 10 ° C./min. The measured values at 260 ° C. at that time are shown in Table 1.

(Evaluation of copper ion scavenging properties)
Each of the adhesive sheets of Examples and Comparative Examples was cut out so as to have a weight of about 2.5 g, and the cut out sample was put in a cylindrical sealed Teflon (registered trademark) container having a diameter of 58 mm and a height of 37 mm, and 10 ppm. 50 ml of an aqueous copper (II) ion 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 9.9 ppm was designated as “◯”, and the case where it was greater than 9.9 ppm was designated as “x”. The results are shown in Table 1. In addition, the difference between the initial copper ion concentration (10 ppm) and the copper ion concentration measured after the test is shown in Table 1 as the ion trapping amount (ppm).

(Data retention test)
The test was performed according to JESD22-A117B, which is a standard defined by JEDEC. Specifically, data was written to a semiconductor package manufactured by the following procedure, and the data retention error of the sample after the acceleration test that was left in a dryer at 150 ° C. for 1000 hours was confirmed, causing a data retention error. When the number of packages was 5 or less in 20 packages, the evaluation was “◯”, and when the number was more than 6, the evaluation was “X”. The results are shown in Table 1.

[Production of semiconductor packages]
The wafer on which the circuit was formed was polished to a thickness of 50 μm. After bonding this wafer and each adhesive sheet of an Example and a comparative example at 60 degreeC, dicing was performed (dicing apparatus: Co., Ltd. product DISCO, DFD6361), and the adhesive sheet was bonded 10 mm x 10 mm. A chip was produced. The produced chip with an adhesive sheet was die-bonded on a lead frame (Alloy 42). The die bonding was performed using a die bonder (SPA-300 manufactured by Shinkawa Co., Ltd.) under the condition of applying a load (0.1 MPa) at a temperature of 120 ° C. and heating for 1 second. Next, wire bonding was performed at 175 ° C. using an Au wire having a wire diameter of 23 μm, and sealing was performed at 175 ° C. for 2 minutes with a sealing resin (manufactured by Nitto Denko Corporation, GE-100). Thereafter, the sealing resin was heated and cured at 175 ° C. for 5 hours to produce a semiconductor package.

  From the results of Table 1, in the adhesive sheet according to the example, all of the tensile storage elastic modulus at 260 ° C., the copper ion scavengeability, and the data retention after thermosetting were good results. On the other hand, in the adhesive sheet of Comparative Example 1, although the copper ion scavenging property was good, the data retention property caused a data retention error in many samples. This is because the tensile storage modulus at 260 ° C. after heat curing is a low value of 0.4 MPa, so that peeling occurs between the adhesive sheet and the semiconductor chip during the acceleration test, and metal ions are captured by the adhesive sheet. This is thought to be due to the reduction in action. Further, since the ion scavenger was not added to the adhesive sheet of Comparative Example 2, the copper ion scavenging property was hardly exhibited, and as a result, a data retention error occurred in all samples in the data retention test.

Claims (4)

Consists of an adhesive composition containing a metal ion scavenger,
The tensile storage elastic modulus at 260 ° C. after being cured at 175 ° C. for 5 hours is 0.5 MPa or more and 1000 MPa or less,
The adhesive composition further includes a thermoplastic resin and a thermosetting resin,
The thermoplastic resin includes an acrylic resin having a weight average molecular weight of 100,000 or more,
The acrylic resin contains an epoxy group or a carboxyl group,
The water absorption when left for 120 hours in an atmosphere of 85 ° C. and 85% RH is 3% by weight or less,
The content of the metal ion capturing agent, an adhesive sheet Ru 5-80 parts by der per 100 parts by weight of the resin component,
An adhesive sheet having 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 allowing to stand at 120 ° C. for 20 hours. .   The adhesive sheet according to claim 1, wherein the thermoplastic resin in the adhesive composition has a weight-based content of 0.5 to 20 times the weight-based content of the thermosetting resin. A dicing film having a substrate and an adhesive layer formed on the substrate;
A dicing die-bonding film comprising: the adhesive sheet according to claim 1 or 2 laminated on the pressure-sensitive adhesive layer. A step of bonding the dicing die-bonding film adhesive sheet according to claim 3 and a semiconductor wafer;
Forming a semiconductor chip by dicing the semiconductor wafer;
Picking up the semiconductor chip together with the adhesive sheet;
Fixing the picked-up semiconductor chip on the adherend via the adhesive sheet;
A method for manufacturing a semiconductor device, comprising: a step of electrically connecting the semiconductor chip and the adherend with a bonding wire; and a step of sealing the semiconductor chip with a sealing resin.

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