TW202111069A - Adhesive composition, film-like adhesive, adhesive sheet, dicing/die-bonding integrated adhesive sheet, semiconductor apparatus, and method for manufacturing same - Google Patents

Abstract

Disclosed is an adhesive composition containing an epoxy resin, a curing agent, an elastomer, and a filler, wherein the elastomer comprises a polyurethane resin.

Description

Adhesive composition, film-like adhesive, adhesive sheet, dicing-bonding integrated adhesive sheet, semiconductor device and manufacturing method thereof

The present invention relates to an adhesive composition, a film-like adhesive, an adhesive sheet, a dicing-bonding integrated adhesive sheet, a semiconductor device and a manufacturing method thereof.

Previously, silver paste was mainly used for bonding of a semiconductor element and a support member for mounting a semiconductor element. However, in recent years, as semiconductor elements have increased in size, and semiconductor packages have increased in size and performance, the supporting members for mounting semiconductor elements have also been required to be reduced in size and density. With regard to such requirements, the use of silver paste cannot adequately cope with defects in wire bonding, difficulty in thickness control, generation of voids, etc. due to infiltration and diffusion, bleeding, tilting of semiconductor elements, and the like. Therefore, in recent years, instead of silver paste, an adhesive sheet including a film-like adhesive has begun to be used (for example, refer to Patent Document 1 and Patent Document 2). Such adhesive sheets are used in manufacturing methods of semiconductor devices such as the single-chip attachment method and the wafer backside attachment method.

In the case of manufacturing a semiconductor device by a single-chip bonding method, first, the roll-shaped adhesive sheet is cut into individual pieces by cutting or punching, and then the film-shaped adhesive is bonded Supporting member for mounting semiconductor elements. After that, the semiconductor element singulated by the dicing step is bonded to the support member for mounting a semiconductor element with a film-like adhesive. After that, through assembly steps such as wire bonding and sealing, a semiconductor device is manufactured (for example, refer to Patent Document 3). However, in the case of the single-chip attachment method, a dedicated assembly device for cutting out the adhesive sheet and attaching it to the support member for mounting the semiconductor element is required. Compared with the method using silver paste, there is a problem that the manufacturing cost becomes higher. .

On the other hand, in the case of manufacturing a semiconductor device by a wafer backside attachment method, first, a film-like adhesive is attached to the backside of the semiconductor wafer, and then a dicing sheet is attached to the other side of the film-like adhesive. After that, by dicing, the semiconductor wafer is singulated in a state where the film-like adhesive is attached to produce a semiconductor element. Then, the semiconductor element with the film-like adhesive is picked up, and it is joined to the support member for semiconductor element mounting. After that, through assembly steps such as wire bonding and sealing, a semiconductor device is manufactured (for example, refer to Patent Document 4). The wafer backside attachment method is different from the single-chip attachment method, and does not require a dedicated assembly device. The existing assembly device for silver paste can be used directly, or a hot plate can be added to partially improve the device. Therefore, in the manufacturing method of the semiconductor device using the adhesive sheet, the wafer backside attachment method tends to suppress the manufacturing cost comparatively.

However, the adhesive used in the wafer backside attachment method is required to have properties that are not prone to stress. In the semiconductor element, if stress derived from the adhesive is generated in the semiconductor wafer, peeling may occur between the semiconductor element mounting support member and the semiconductor element, and conduction failure of the semiconductor device may occur, for example.

The main factor that causes stress to the semiconductor wafer in the semiconductor element is the temperature dependence of the shrinkage rate between the semiconductor wafer, the cured product of the adhesive, and the substrate during the temperature cooling process from the heating and curing of the adhesive The difference in performance (linear expansion rate). Therefore, it is estimated that by reducing the linear expansion coefficient of the cured product of the adhesive, the stress on the semiconductor wafer in the semiconductor element can be suppressed. Conventionally, as a method of reducing the linear expansion coefficient of the cured product of the adhesive, for example, a method of adding a large amount of inorganic filler to the adhesive is known (for example, refer to Patent Document 5). [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 3-192178 Patent Document 2: Japanese Patent Laid-Open No. 4-234472 Patent Document 3: Japanese Patent Laid-Open No. 9-017810 Patent Document 4: Japanese Patent Laid-Open No. 4-196246 Patent Document 5: Japanese Patent Laid-Open No. 2004-172443

[The problem to be solved by the invention] However, if a large amount of inorganic filler is added to the adhesive, although the linear expansion rate of the cured product of the adhesive can be reduced, when this type of adhesive is used to form a film-like adhesive, the film-like adhesive itself becomes brittle and processed. There is a risk of deterioration in performance, or a decrease in adhesion to semiconductor wafers at low temperatures.

Therefore, the main object of the present invention is to provide an adhesive composition that is excellent in processability and low-temperature adhesion when forming a film-like adhesive, and can sufficiently reduce the linear expansion rate. [Means to solve the problem]

One aspect of the present invention provides an adhesive composition, which contains an epoxy resin, a hardener, an elastomer, and a filler, and the elastomer includes a polyurethane resin. According to such an adhesive composition, the processability and low-temperature adhesion when forming a film-like adhesive are excellent, and the linear expansion coefficient can be sufficiently reduced.

The hardener may also include a phenol resin.

Based on the total amount of the adhesive composition, the content of the elastomer may be 2% by mass to 20% by mass. If the content of the elastomer is in such a range, the processability when forming a film-like adhesive tends to be more excellent.

Based on the total amount of the adhesive composition, the content of the filler may be 50% by mass to 90% by mass. If the content of the filler is in such a range, there is a tendency that the coefficient of linear expansion can be reduced more sufficiently. The adhesive composition of one aspect of the present invention is more excellent in processability and low-temperature adhesion when forming a film-like adhesive even when the content of the filler is relatively large as described above.

The adhesive composition may further contain a hardening accelerator.

The adhesive composition of one aspect of the present invention can be used in a semiconductor device formed by connecting a first semiconductor element to a substrate by wire bonding via a first wire, and crimping a second semiconductor element on the first semiconductor element , Used to crimp the second semiconductor element and embed at least a part of the first wire.

Furthermore, the present invention may also be related to the application (use) of the following composition as an adhesive or the application (use) for the manufacture of an adhesive, the composition containing: epoxy resin, hardener, filler, and elastomer , And the elastomer contains polyurethane resin. In the application (use), the composition is used to connect the first semiconductor element to the substrate by wire bonding via the first wire, and to the second In a semiconductor device formed by crimping a second semiconductor element on a semiconductor element, it is used to crimp the second semiconductor element and embed at least a part of the first wire.

Another aspect of the present invention provides a film-like adhesive, which is formed by forming the above-mentioned adhesive composition into a film.

Another aspect of the present invention provides an adhesive sheet, including: a substrate; and the above-mentioned film-like adhesive disposed on the substrate.

The substrate may be a dicing tape. The adhesive sheet whose base material is a dicing tape is sometimes referred to as a "dicing-bonding integrated adhesive sheet".

Another aspect of the present invention provides a dicing-bonding integrated adhesive sheet, including: a dicing tape; and the above-mentioned film-like adhesive disposed on the dicing tape.

Another aspect of the present invention provides a method of manufacturing a semiconductor device, which includes a wire bonding step, arranging a first semiconductor element on a support member having a substrate and a circuit pattern provided on the substrate, and connecting the circuit pattern and the first semiconductor device via a first wire. A semiconductor element is electrically connected; the laminating step is to attach the above-mentioned film-like adhesive to the single side of the second semiconductor element; and the die-attach step is to crimp and attach the film-like adhesive through the film-like adhesive The second semiconductor element of the first semiconductor element and the first wire, or at least a part of the first wire is embedded in the film-like adhesive.

Another aspect of the present invention provides a semiconductor device, including: a support member having a substrate and a circuit pattern provided on the substrate; a first semiconductor element provided on the support member; and a second semiconductor element via the above-mentioned film In the semiconductor device, the supporting member and the first semiconductor element are connected via the adhesive, the circuit pattern and the first semiconductor element are electrically connected via the first wire, and the first wire And at least a part of the first semiconductor element or the first wire is embedded with the film-like adhesive.

Here, the semiconductor device may be a semiconductor element (semiconductor wafer) embedded semiconductor device in which the first wire and the first semiconductor element are embedded in a film-like adhesive, or it may be a semiconductor device with at least a part of the first wire A wire-embedded semiconductor device embedded in a film-like adhesive. [Effects of the invention]

According to the present invention, it is possible to provide an adhesive composition that is excellent in processability and low-temperature adhesion when forming a film-like adhesive, and can sufficiently reduce the linear expansion rate. The film-like adhesive formed by forming the adhesive composition into a film can be effectively used as a film-on-die (FOD) embedded in a semiconductor element (semiconductor wafer) or as a wire Film Over Wire (FOW) of embedded film adhesive. In addition, according to the present invention, it is possible to provide an adhesive sheet using such a film-like adhesive and a method of manufacturing a semiconductor device.

Hereinafter, embodiments of the present invention will be described with appropriate reference to the drawings. However, the present invention is not limited to the following embodiments.

[Adhesive composition] The adhesive composition of one embodiment contains (A) epoxy resin, (B) hardener, (C) elastomer, and (D) filler. The adhesive composition is thermosetting, has undergone a semi-hardened (B-stage) state and can become a fully hardened (C-stage) state after the hardening treatment.

＜(A) component: epoxy resin＞ The component (A) has the property of forming a three-dimensional bond between molecules by heating or the like and hardening. After hardening, it shows the effect of the connection. (A) As long as a component has an epoxy group in a molecule|numerator, it can use without a restriction|limiting in particular. (A) The component may have two or more epoxy groups in the molecule.

(A) Component includes, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, and cresol novolak type epoxy resin. , Bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin, epoxy resin containing triazine skeleton, epoxy resin containing fluorene skeleton, triphenol methane type Epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, multifunctional phenols, Diglycidyl ether compounds of polycyclic aromatics such as anthracene. (A) The component may be these alkyl substituents, halides, or hydrides. These can be used individually by 1 type or in combination of 2 or more types. Among these, the (A) component may be a cresol novolak type epoxy resin or a bisphenol type epoxy resin.

(A) The epoxy equivalent of the component is not particularly limited, and it can be 90 g/eq to 600 g/eq, 100 g/eq to 500 g/eq, or 120 g/eq to 450 g/eq. When the epoxy equivalent of (A) component is such a range, there exists a tendency to obtain more favorable reactivity and fluidity.

Based on the total amount of the adhesive composition, the content of the component (A) may be 2% by mass to 25% by mass. Based on the total amount of the adhesive composition, the content of component (A) can be 4% by mass or more, 6% by mass or more, or 8% by mass or more, and can be 22% by mass or less, 20% by mass or less, or 18% by mass. Less than mass%.

＜(B)Component: Hardener＞ The component (B) is a component that can become a hardener for epoxy resin. As (B) component, a phenol resin, an active ester resin, etc. are mentioned, for example.

The phenol resin can be used without particular limitation as long as it has a phenolic hydroxyl group in the molecule. Examples of phenol resins include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and/or α- Novolac type phenol resin obtained by condensation or co-condensation of naphthols, β-naphthol, dihydroxynaphthalene and other naphthols with formaldehyde and other compounds having aldehyde groups under acidic catalysts; from allylated bisphenol A, Allylated bisphenol F, allylated naphthalenediol, phenol novolac, phenol and other phenols and/or naphthols and dimethoxy-para-xylene or bis(methoxymethyl) biphenyl Synthetic phenol aralkyl resin, naphthol aralkyl resin, biphenyl aralkyl type phenol resin, phenyl aralkyl type phenol resin, etc. These can be used individually by 1 type or in combination of 2 or more types. The phenol resin may be a novolak type phenol resin.

The active ester resin is a component that has an active ester bond in the epoxy group in the molecule and functions as an epoxy resin hardener. In the active ester resin, the ester bond can react with the epoxy group of component (A) to form a three-dimensional bond between molecules. By using active ester resin as the component (B), the dielectric loss tangent can be reduced in the cured product of the adhesive composition. The active ester resin is not particularly limited as long as it has an ester bond in the molecule. Examples include aliphatic or aromatic carboxylic acid compounds, and aliphatic hydroxy compounds, aromatic hydroxy compounds (phenol compounds), and aromatic Group thiol compounds (thiophenol compounds), N-hydroxy amine compounds, ester compounds of heterocyclic hydroxy compounds, etc. These can be used individually by 1 type or in combination of 2 or more types. Since the ester compound obtained from an aliphatic carboxylic acid compound or an aliphatic hydroxy compound contains an aliphatic chain, there is a tendency that solubility in an organic solvent and compatibility with an epoxy resin can be improved. Since the ester compound obtained from an aromatic carboxylic acid compound or an aromatic hydroxy compound (phenol compound) has an aromatic ring, it tends to improve heat resistance. Among these, the active ester resin may be an ester compound obtained from an aromatic carboxylic acid compound and an aromatic hydroxy compound (phenol compound).

Examples of commercially available active ester resins include: EXB9451, EXB9460, EXB9460S, HPC-8000-65T (all manufactured by DIC Co., Ltd., trade names) having a dicyclopentadiene-type bisphenol structure ); EXB9416-70BK with a naphthalene structure (manufactured by DIC Co., Ltd., trade name); DC808 (manufactured by Mitsubishi Chemical Co., Ltd., trade name) with an acetyl structure of phenol novolac; benzyl with phenol novolac YLH1026 (manufactured by Mitsubishi Chemical Co., Ltd., trade name) with an acyl structure, etc.

From the viewpoint of heat resistance, the (B) component may contain a phenol resin. The hydroxyl equivalent of the phenol resin is not particularly limited, and may be 80 g/eq to 400 g/eq, 90 g/eq to 350 g/eq, or 100 g/eq to 300 g/eq. If the hydroxyl equivalent of the phenol resin is in this range, there is a tendency that better reactivity and fluidity can be obtained.

From the viewpoint of curability, the ratio of the epoxy equivalent of (A) component to the hydroxyl equivalent of (B) component (phenol resin) (the epoxy equivalent of (A) component / the hydroxyl equivalent of (B) component (phenol resin)) Equivalent) can be 0.30/0.70~0.70/0.30, 0.35/0.65~0.65/0.35, 0.40/0.60~0.60/0.40, or 0.45/0.55~0.55/0.45. If the equivalent ratio is 0.30/0.70 or more, there is a tendency that more sufficient curability can be obtained. If the equivalent ratio is 0.70/0.30 or less, the viscosity can be prevented from becoming too high, and more sufficient fluidity can be obtained.

Based on the total amount of the adhesive composition, the content of the component (B) may be 2% by mass to 20% by mass. Based on the total amount of the adhesive composition, the content of component (B) may be 3% by mass or more, 4% by mass or more, or 5% by mass or more, and may be 18% by mass or less, 15% by mass or less, or 12% by mass or less.

＜(C)Component: Elastomer＞ (C) Component contains polyurethane resin. The (C) component can impart flexibility to the adhesive composition by containing a polyurethane resin, and the adhesive composition will be excellent in processability and low-temperature adhesion when forming a film-like adhesive.

The polyurethane resin can be used without particular limitation as long as it has a urethane bond in the molecule. The polyurethane resin may have a structural unit derived from a polyol and a structural unit derived from a polyisocyanate. That is, the polyurethane resin may be a reaction product (or condensation polymer) of a polyol and a polyisocyanate. Polyurethane resin can be used individually by 1 type or in combination of 2 or more types.

The polyol can be used without particular limitation as long as it is a compound having more than one, preferably two or more hydroxyl groups. Examples of polyols include polyester polyols, polyether polyols, polyether ester polyols, polyurethane polyols, polycarbonate polyols, and polyolefin polyols. The polyol may be used alone or in combination of two or more. The polyol may also include a compound having two hydroxyl groups (diol) or a compound having three hydroxyl groups (triol).

The polyisocyanate can be used without particular limitation as long as it is a compound having more than one isocyanate group, preferably two or more. Examples of polyisocyanates include aromatic isocyanates such as diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, and p-phenylene diisocyanate; dicyclohexylmethane diisocyanate, Alicyclic isocyanates such as isophorone diisocyanate; aliphatic isocyanates such as hexamethylene diisocyanate, etc. The polyisocyanate may be used singly or in combination of two or more kinds. The polyisocyanate may also include a compound having two isocyanate groups (diisocyanate).

As commercially available products of polyurethane resins, for example, PANDEX (registered trademark) series, Desmopan (registered trademark) series, Texin (registered trademark) ) Series (DIC Covestro Polymer (DIC Covestro Polymer) Co., Ltd.), etc.

Based on the total amount of the component (C), the content of the polyurethane resin may be 50% by mass to 100% by mass, 70% by mass to 100% by mass, or 90% by mass to 100% by mass.

In addition to containing the polyurethane resin, the (C) component may contain elastomers other than the polyurethane resin. Examples of elastomers other than polyurethane resins include polyimide resins, acrylic resins, polyphenylene ether resins, polyetherimide resins, phenoxy resins, modified polyphenylene ether resins, etc. .

Based on the total amount of component (C), the content of elastomers other than polyurethane resin can be 0% by mass to 50% by mass, 0% by mass to 30% by mass, or 0% by mass to 10% by mass .

(C) The glass transition temperature (Tg) of the component can be -50°C to 50°C or -30°C to 20°C. If the Tg of the acrylic resin is -50°C or higher, the viscosity after the adhesive composition is formed on the film becomes low, and therefore, the workability tends to be further improved. If the Tg of the acrylic resin is 50°C or less, there is a tendency that the fluidity of the adhesive composition can be more sufficiently ensured. Here, the glass transition temperature (Tg) of component (C) refers to the measurement measured using a differential scanning calorimeter (Differential Scanning Calorimeter, DSC) (for example, manufactured by Rigaku Co., Ltd., trade name: Thermo Plus 2) value.

(C) The weight average molecular weight (Mw) of the component can be 10,000 to 1.2 million or 50,000 to 1 million. If the Mw of the component (C) is 10,000 or more, the film-forming properties tend to be more excellent. If the Mw of the component (C) is 1.2 million or less, the fluidity tends to be more excellent. In addition, Mw is a value measured by Gel Permeation Chromatography (GPC) and converted using a calibration curve based on standard polystyrene.

(C) The measuring device and measuring conditions of the Mw of the component are as follows. Pump: L-6000 (manufactured by Hitachi, Ltd.) Column: Gelpack GL-R440 (manufactured by Hitachi Chemical Co., Ltd.), gelpack GL-R450 (manufactured by Hitachi Chemical Co., Ltd.), and gel pack GL-R400M (manufactured by Hitachi Chemical Co., Ltd.) Manufactured by Co., Ltd.) (each 10.7 mm (diameter) × 300 mm) pipe string connected in this order Eluent: tetrahydrofuran (tetrahydrofuran, THF) Sample: A solution made by dissolving 120 mg of the sample in 5 mL of THF Flow rate: 1.75 mL/min

From the viewpoint of obtaining more excellent processability, the content of the (C) component may be 2% by mass to 20% by mass based on the total amount of the adhesive composition. Based on the total amount of the adhesive composition, the content of component (C) can be 3% by mass or more, 4% by mass or more, or 5% by mass or more, and can be 18% by mass or less, 16% by mass or less, or 14% by mass. Less than mass%. In addition, when the (C) component consists only of a polyurethane resin, the description of "(C) component" can be replaced with the description of "polyurethane resin" for application.

＜（D）Component: Filler＞ (D) The component may be an inorganic filler. As the (D) component, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, Boron nitride, crystalline silicon dioxide, amorphous silicon dioxide, etc. These can be used individually by 1 type or in combination of 2 or more types. Among these, the component (D) may include silicon dioxide.

From the viewpoint of further improvement in adhesiveness, the average particle size of the component (D) may be 0.005 μm to 2.0 μm, 0.005 μm to 1.5 μm, or 0.005 μm to 1.0 μm. Here, the average particle size refers to a value obtained by conversion based on the Brunauer-Emmett-Teller (BET) specific surface area.

From the viewpoint of the compatibility of the surface with solvents, other components, and adhesive strength, the component (D) may be surface-treated with a surface treatment agent. As a surface treatment agent, a silane coupling agent etc. are mentioned, for example. Examples of the functional group of the silane coupling agent include vinyl groups, (meth)acrylic groups, epoxy groups, mercapto groups, amino groups, diamino groups, alkoxy groups, and ethoxy groups.

From the viewpoint of reducing the linear expansion rate more sufficiently, the content of the (D) component may be 50% by mass to 90% by mass based on the total amount of the adhesive composition. Based on the total amount of the adhesive composition, the content of component (D) can be 52% by mass or more, 55% by mass or more, 58% by mass or more, or 60% by mass or more, and can be 88% by mass or less and 85 mass% % Or less, 82% by mass or less, or 80% by mass or less.

The adhesive composition may further contain (E) a hardening accelerator and/or (F) a coupling agent.

＜(E) component: hardening accelerator＞ By containing the (E) component, the adhesive composition tends to have both the adhesiveness and connection reliability of the adhesive composition. As the (E) component, for example, imidazoles and derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, etc. may be mentioned. These can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of reactivity, the component (E) may be imidazoles and derivatives thereof.

Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole. Wait. These can be used individually by 1 type or in combination of 2 or more types.

Based on the total amount of the adhesive composition, the content of the (E) component may be 0.01% by mass to 1.0% by mass. If the content of the (E) component is in such a range, there is a tendency that adhesiveness and connection reliability can be further combined.

＜(F) component: coupling agent＞ By containing the component (F) in the adhesive composition, there is a tendency to further increase the interfacial bonding between dissimilar components of the adhesive composition. As (F) component, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc. are mentioned, for example. These can be used individually by 1 type or in combination of 2 or more types. Among these, the component (F) may be a silane coupling agent.

As the silane coupling agent, for example, vinyl trichlorosilane, vinyl triethoxy silane, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxy propyl trimethyl Oxysilane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxy propyl trimethoxy silane, γ-glycidoxy propyl methyl dimethoxy Silane, vinyl triacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-amino Propyl triethoxysilane, γ-aminopropylmethyl diethoxysilane, γ-anilinopropyl trimethoxysilane, γ-anilinopropyl triethoxysilane, γ-(N, N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyl Trimethoxysilane, γ-(N-methyl)anilinopropyl trimethoxysilane, γ-(N-ethyl)anilinopropyl trimethoxysilane, γ-(N,N-dimethyl) Aminopropyltriethoxysilane, γ-(N,N-diethyl)aminopropyltriethoxysilane, γ-(N,N-dibutyl)aminopropyltriethoxy Silane, γ-(N-methyl)anilinopropyltriethoxysilane, γ-(N-ethyl)anilinopropyltriethoxysilane, γ-(N,N-dimethyl)amine Propylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N,N-dibutyl)aminopropylmethyl Dimethoxysilane, γ-(N-methyl)anilinopropylmethyldimethoxysilane, γ-(N-ethyl)anilinopropylmethyldimethoxysilane, N-( Trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltri Ethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-ureidopropyltriethoxy Base silane and so on.

Based on the total amount of the adhesive composition, the content of the component (F) may be 0.1% by mass to 5.0% by mass. If the content of the (F) component is in such a range, there is a tendency that the interfacial bonding between dissimilar components can be further increased.

＜Other ingredients＞ The adhesive composition may further contain antioxidants, rheology control agents, leveling agents, etc. as other ingredients. Based on the total amount of the adhesive composition, the content of these components may be 0.01% by mass to 3% by mass.

The adhesive composition can be used as a varnish of the adhesive composition diluted with a solvent. The solvent is not particularly limited as long as it can dissolve components other than the (D) component. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cymene; aliphatic hydrocarbons such as hexane and heptane; cyclic alkanes such as methylcyclohexane; Cyclic ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc.; acetic acid Methyl, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone and other esters; ethylene carbonate, propylene carbonate and other carbonates; N,N-dimethylformamide , N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amides. These can be used individually by 1 type or in combination of 2 or more types. Among these, in terms of solubility and boiling point, the solvent may be toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone.

Based on the total amount of the varnish of the adhesive composition, the solid content concentration in the varnish of the adhesive composition may be 10% by mass to 80% by mass.

The varnish of the adhesive composition can be prepared by mixing and kneading the components (A) to (F), a solvent, and other components. In addition, the order of mixing and kneading of each component is not particularly limited, and can be set appropriately. Mixing and kneading can be performed by appropriately combining a disperser such as a general mixer, a crusher, a three-rod roll mill, a ball mill, and a bead mill. After preparing the varnish of the adhesive composition, the bubbles in the varnish can be removed by vacuum degassing or the like.

[Film Adhesive] Fig. 1 is a schematic cross-sectional view showing a film adhesive according to an embodiment. The film adhesive 10 is obtained by forming the above-mentioned adhesive composition into a film. The film-like adhesive 10 may be in a semi-cured (B-stage) state. Such a film-like adhesive 10 can be formed by applying an adhesive composition to a support film. In the case of using the varnish of the adhesive composition, the varnish of the adhesive composition may be applied to a support film and heated and dried to remove the solvent, thereby forming the film-like adhesive 10.

Examples of the supporting film include films of polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, and polyimide. The thickness of the support film may be, for example, 10 μm to 200 μm or 20 μm to 170 μm.

As a method of applying the varnish of the adhesive composition to the support film, a known method can be used, for example, a knife coating method, a roll coating method, a spray method, a gravure coating method, a bar coating method, a curtain coating method, etc. . The conditions for heating and drying are not particularly limited as long as the solvent used is sufficiently volatilized. For example, they may be from 0.1 to 90 minutes at 50°C to 200°C.

The thickness of the film adhesive can be appropriately adjusted according to the application. The thickness of the film adhesive can be 5 μm to 200 μm, 10 μm to 110 μm, or 15 μm from the viewpoint of fully embedding the unevenness of semiconductor elements (semiconductor wafers), wires, wiring circuits of the substrate, etc. ~80 μm.

The cured product of the film adhesive obtained by heating the film adhesive at 170°C for 1 hour has a linear expansion rate below the glass transition temperature of 45 ppm/°C or less, 40 ppm/°C or less, 35 ppm/ Below ℃, or below 30 ppm/℃. If the cured product of the film-like adhesive has a coefficient of linear expansion of 45 ppm/°C or less at the glass transition temperature or less, there is a tendency that the stress to the semiconductor wafer in the semiconductor element can be further suppressed. The lower limit of the linear expansion coefficient of the cured product of the film adhesive at a glass transition temperature or lower is not particularly limited, and it may be, for example, 1 ppm/°C or higher. In addition, in this specification, the "linear expansion coefficient (the linear expansion coefficient of the cured product of the film-like adhesive below the glass transition temperature)" refers to the value measured by the method described in the examples.

[Continue film] Fig. 2 is a schematic cross-sectional view showing an adhesive sheet according to an embodiment. The adhesive sheet 100 includes a substrate 20 and the above-mentioned film-like adhesive 10 provided on the substrate.

The substrate 20 is not particularly limited, and may be a substrate film. Examples of the base film include those exemplified in the support films described above.

The substrate 20 may also be a dicing tape. This adhesive sheet can be used as a cutting-bonding integrated adhesive sheet. That is, the dicing-bonding integrated adhesive sheet includes a dicing tape and the above-mentioned film-like adhesive 10 provided on the dicing tape. Since such a dicing-bonding integrated adhesive sheet is laminated to a semiconductor wafer once, the efficiency of the work can be achieved.

Examples of the dicing tape include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. In addition, the dicing tape can be subjected to surface treatments such as primer coating, UV treatment, corona discharge treatment, grinding treatment, and etching treatment, if necessary. The cutting tape can also be adhesive. The cutting tape can be one that imparts adhesiveness to the plastic film, or one that is provided with an adhesive layer on one side of the plastic film.

The adhesive sheet 100 can be formed by applying an adhesive composition or a varnish to a base film in the same manner as the method of forming the film-like adhesive described above. The method of applying the adhesive composition or the varnish to the substrate 20 may be the same as the method of applying the adhesive composition or the varnish to the support film described above.

The adhesive sheet 100 can be formed using a film-like adhesive produced in advance. In this case, the adhesive sheet 100 can be formed by laminating under a predetermined condition (for example, room temperature (20° C.) or heating state) using a roll laminator or a vacuum laminator. The subsequent sheet 100 can be manufactured continuously, and in terms of efficiency, it can be formed by using a roll laminator in a heated state.

Fig. 3 is a schematic cross-sectional view showing an adhesive sheet of another embodiment. The adhesive sheet 110 further includes a protective film 30 laminated on the surface of the film-like adhesive 10 on the opposite side to the substrate 20. Examples of the protective film 30 include those exemplified in the support films described above. The thickness of the protective film 30 may be, for example, 10 μm to 200 μm or 20 μm to 170 μm.

[Semiconductor Device] Fig. 4 is a schematic cross-sectional view showing a semiconductor device according to an embodiment. The semiconductor device 200 includes: a semiconductor element mounting support member 14 having a substrate 90, a circuit pattern 84 and the circuit pattern 94 provided on the substrate 90; a first semiconductor element Wa provided on the semiconductor element mounting support member 14; and The film-like adhesive 10 is the second semiconductor element Waa that adheres to the first semiconductor element Wa. The support member 14 for mounting a semiconductor element and the first semiconductor element Wa are bonded via an adhesive 41. The circuit pattern 84 and the first semiconductor element Wa are electrically connected via a first wire 88. The first wire 88 and the first semiconductor element Wa, or at least a part of the first wire 88 is embedded (sealed) with the film-like adhesive 10. Here, the semiconductor device may be a semiconductor element (semiconductor wafer) embedded type semiconductor device in which the first wire 88 and the first semiconductor element Wa are buried, or may be a semiconductor device with at least a part of the first wire 88 buried in. It is a semiconductor device with embedded wires. In addition, in the semiconductor device 200, the semiconductor element mounting support member 14 and the second semiconductor element Waa are further electrically connected via the second wire 98, and the second semiconductor element Waa is sealed by the sealing material 42.

The thickness of the first semiconductor element Wa may be 10 μm to 170 μm, and the thickness of the second semiconductor element Waa may be 20 μm to 400 μm. The first semiconductor element Wa embedded in the film adhesive 10 may be a controller chip for driving the semiconductor device 200.

The support member 14 for mounting a semiconductor element includes a substrate 90 in which a circuit pattern 84 and a circuit pattern 94 are respectively formed at two places on the surface. The substrate 90 may be an organic substrate. The first semiconductor element Wa is adhered to the circuit pattern 94 via the adhesive 41. The second semiconductor element Waa is attached to the semiconductor element mounting support member via the film-like adhesive 10 so as to cover a part of the circuit pattern 94 to which the first semiconductor element Wa is not attached, the first semiconductor element Wa, and the circuit pattern 84 14. The film-like adhesive 10 is embedded in the level difference of the unevenness caused by the circuit pattern 84 and the circuit pattern 94 on the semiconductor element mounting support member 14. Then, the second semiconductor element Waa, the circuit pattern 84, and the second wire 98 are sealed with the sealing material 42 made of resin.

[Method of Manufacturing Semiconductor Device] The manufacturing method of the semiconductor device of this embodiment includes a wire bonding step, arranging a first semiconductor element on a support member having a substrate and a circuit pattern provided on the substrate, and connecting the circuit pattern and the first semiconductor element via a first wire Electrical connection; lamination step, attaching the above-mentioned film-like adhesive on one side of the second semiconductor element; and die bonding step, crimping and attaching the second film-like adhesive through the film-like adhesive For the semiconductor element, at least a part of the first wire and the first semiconductor element, or the first wire is embedded in the film-like adhesive.

5, FIG. 6, FIG. 7, FIG. 8, and FIG. 9 are schematic cross-sectional views showing a series of steps in a method of manufacturing a semiconductor device according to an embodiment. Here, a semiconductor device (semiconductor wafer) embedded type semiconductor device in which the first wire 88 and the first semiconductor element Wa are embedded will be described. First, as shown in FIG. 5, the first semiconductor element Wa having the adhesive 41 is attached (crimped) to the circuit pattern 94 on the semiconductor element mounting support member 14, and the semiconductor element is mounted via the first wire 88. The circuit pattern 84 on the support member 14 is electrically connected to the first semiconductor element Wa (first wire bonding step).

Next, the adhesive sheet 100 is laminated on one side of the semiconductor wafer (for example, the thickness is 100 μm, the size is 8 inches), and the substrate 20 is peeled off, thereby attaching the film-like adhesive 10 on the single side of the semiconductor wafer (For example, the thickness is 110 μm). Then, after attaching the dicing tape to the film-like adhesive 10, it is cut into a predetermined size (for example, 7.5 mm square), as shown in FIG. 6, thereby obtaining a second semiconductor element with the film-like adhesive 10 attached. Waa (laminating step).

The temperature condition of the lamination step may be 50°C to 100°C or 60°C to 80°C. If the temperature of the lamination step is 50°C or higher, good adhesion to the semiconductor wafer can be obtained. If the temperature of the lamination step is 100° C. or less, the film-like adhesive 10 can be prevented from flowing excessively during the lamination step, and thus it is possible to prevent changes in thickness and the like.

As the dicing method, for example, a blade dicing using a rotating blade, a method of cutting both the film-like adhesive or the wafer and the film-like adhesive by laser, and the like can be cited.

Then, the second semiconductor element Waa to which the film-like adhesive 10 is attached is crimp-bonded to the semiconductor element mounting support member 14 to which the first semiconductor element Wa is bonded and connected via the first wire 88. Specifically, as shown in FIG. 7, the second semiconductor element Waa to which the film adhesive 10 is attached is placed so that the first wire 88 and the first semiconductor element Wa are covered by the film adhesive 10, and then As shown in FIG. 8, the second semiconductor element Waa is fixed to the semiconductor element mounting support member 14 by crimping the second semiconductor element Waa to the semiconductor element mounting support member 14 (die bonding step). The crystal bonding step may be a step of crimping the film adhesive 10 at 80° C. to 180° C. and 0.01 MPa to 0.50 MPa for 0.5 seconds to 3.0 seconds. After the crystal bonding step, the film adhesive 10 can be heated and pressurized for more than 5 minutes under the conditions of 60°C to 175°C and 0.3 MPa to 0.7 MPa, and the film adhesive 10 can also be (completely) hardened.

Next, as shown in FIG. 9, after the semiconductor element mounting support member 14 and the second semiconductor element Waa are electrically connected via the second wire 98 (the second wire bonding step), the circuit pattern 84, The second wire 98 and the second semiconductor element Waa are sealed. By passing through such steps, a semiconductor device 200 of embedded semiconductor element (semiconductor wafer) can be manufactured.

As another embodiment, the semiconductor device may be a wire-embedded semiconductor device in which at least a part of the first wire 88 is buried. [Example]

Hereinafter, examples are given to explain the present invention more specifically. However, the present invention is not limited to these embodiments.

(Example 1-1 to Example 1-3 and Comparative Example 1-1, Comparative Example 1-2, Comparative Example 2-1, Comparative Example 2-2) ＜Production of Adhesive Film＞ With each component and its content shown in Table 1 and Table 2, the varnish of the adhesive composition was prepared by the following procedure. First, mix (A) epoxy resin, (B) hardener and (D) filler, add cyclohexanone and stir, then add (C) elastomer, (E) hardening accelerator and (F) The coupling agent is stirred until each component becomes uniform, thereby obtaining a varnish of an adhesive composition having a solid content of 40% by mass.

In addition, each component in Table 1 and Table 2 is as follows.

(A) Ingredient: Epoxy resin (A-1) Cresol novolac epoxy resin (manufactured by DIC Co., Ltd., trade name: N-500P-10, epoxy equivalent: 204 g/eq) (A-2) Bisphenol A epoxy resin (manufactured by DIC Co., Ltd., trade name: EXA-830CRP, epoxy equivalent: 159 g/eq)

(B) Ingredient: Hardener (B-1) Phenolic novolac type phenol resin (manufactured by Qunrong Chemical Industry Co., Ltd., trade name: Resttop PSM-4326, softening point: 126°C, hydroxyl equivalent: 105 g/eq)

(C) Ingredient: Elastomer (C-1) Polyurethane resin (manufactured by DIC Covestro Polymer Co., Ltd., trade name: T-8175N, weight average molecular weight: 80,000, glass transition temperature: -23°C) (C-2) Acrylic rubber (manufactured by Nagase ChemteX Co., Ltd., trade name: HTR-860P-3CSP, weight average molecular weight: 800,000, glass transition temperature: -7°C) (C-3) Acrylic rubber (manufactured by Nagase Chemical Co., Ltd., trade name: HTR-860P-30B, weight average molecular weight: 230,000, glass transition temperature: -7°C)

(D) Ingredients: filler (D-1) Silica filler (manufactured by Admatechs Co., Ltd., trade name: SC2050-HLG, average particle size: 0.500 μm)

(E) Ingredient: Hardening accelerator (E-1) 1-Cyanoethyl-2-phenylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., trade name: Curezol 2PZ-CN)

(F) Ingredient: Coupling agent (F-1) γ-Mercaptopropyl trimethoxysilane (manufactured by Unika Co., Ltd., trade name: NUC A-189) (F-2) γ-ureidopropyltriethoxysilane (manufactured by Unika Co., Ltd., Japan, trade name: NUC A-1160)

Next, apply the obtained varnish to a 38 μm thick polyethylene terephthalate (PET) film as a base film that has been subjected to a mold release treatment, and heat and dry it at 140°C for 5 minutes . In this way, Example 1-1 to Example 1-3 and Comparative Example 1-1 in which a film-like adhesive with a thickness of 20 μm in a semi-cured (B-stage) state was provided on the base film Adhesive sheets of Comparative Example 1-2, Comparative Example 2-1, and Comparative Example 2-2.

＜Evaluation of workability＞ Each adhesive sheet of the Examples and Comparative Examples was cut into a width of 20 mm and a length of 100 mm, and a 5 mm cut was made from the end at a position of 50 mm from the end of the cut adhesive sheet as a test piece. Using an Autograph (manufactured by Shimadzu Corporation, trade name: Autograph AGS-H100N), a tensile test was performed at a speed of 100 mm/min to measure the breaking distance. In the measurement of the breaking distance, the distance between the chucks is set to 40 mm. The case where the breaking distance was 10 mm or more was regarded as excellent in workability and was evaluated as "A", and the case where the distance was less than 10 mm was evaluated as "B". The results are shown in Table 1.

＜Evaluation of low-temperature adhesion＞ The adhesive sheets of the Examples and Comparative Examples were cut into 50 mm in width and 100 mm in length, and these were used as test pieces. With the film-like adhesive facing the silicon wafer side, the test piece was laminated on the surface of the silicon wafer (8 inches in diameter, 400 μm thick) placed on the support table on the opposite side of the support table. Laminating is performed while applying pressure with a roller at a temperature of 70°C, a linear pressure of 39.2 N/cm (4 kgf/cm), and a feed speed of 0.5 m/min. At this time, the case where the generation of voids (voids) is not observed between the silicon wafer and the adhesive sheet is considered to be excellent in low-temperature adhesion and is evaluated as "A", and the case where the generation of voids (voids) is observed is evaluated Is "B". The results are shown in Table 1 and Table 2.

＜Measurement of linear expansion rate＞ Regarding the adhesive sheets of Examples 1-1 to 1-3, Comparative Example 1-1, and Comparative Example 2-1, which are excellent in workability and low-temperature adhesiveness, the linear expansion coefficient was measured. In such a way that the film-like adhesive becomes fully cured (C stage), each adhesive sheet is heat-cured at 170°C for 1 hour, and the heat-cured adhesive sheet is cut into a width of 40 mm and a length of 3.5 mm, and this is used as a test piece . Using a thermomechanical analysis device (manufactured by Hitachi High-technologies Co., Ltd., trade name: TMA7100), the linear expansion rate of the test piece was measured in a tensile mode. A quartz tensile probe was used for the measurement, and the distance between the chucks was set to 10 mm. The measurement was performed in the temperature range of -60°C to 260°C, and the linear expansion coefficient (α1) of the cured product of the film-like adhesive of the test piece below the glass transition temperature was calculated. The results are shown in Table 1 and Table 2.

[Table 1] Example 1-1 Comparative example 1-1 Comparative example 2-1 (A) Ingredient A-1 4.3 4.3 4.3 A-2 12.8 12.8 12.8 (B) Ingredients B-1 10.5 10.5 10.5 (C) Ingredients C-1 12.0 - - C-2 - 12.0 - C-3 - - 12.0 (D) Ingredients D-1 60.0 60.0 60.0 (E) Ingredients E-1 0.1 0.1 0.1 (F) Ingredients F-1 0.1 0.1 0.1 F-2 0.2 0.2 0.2 Processability A B B Low temperature adhesion A A A Linear expansion rate (ppm/℃) 40 47 50

[Table 2] Example 1-2 Example 1-3 Comparative example 1-2 Comparative example 2-2 (A) Ingredient A-1 3.2 2.1 3.2 3.2 A-2 9.7 6.4 9.7 9.7 (B) Ingredients B-1 8.0 5.2 8.0 8.0 (C) Ingredients C-1 9.0 5.8 - - C-2 - - 9.0 - C-3 - - - 9.0 (D) Ingredients D-1 70.0 80.0 70.0 70.0 (E) Ingredients E-1 0.1 0.1 0.1 0.1 (F) Ingredients F-1 0.1 0.1 0.1 0.1 F-2 0.2 0.2 0.2 0.2 Processability A A B B Low temperature adhesion A A B B Linear expansion rate (ppm/℃) 29 twenty three - -

According to Table 1, compared with the adhesive sheets of Comparative Example 1-1 and Comparative Example 2-1, the adhesive sheet of Example 1-1 is superior in processability, and the linear expansion coefficient of the cured product of the film-like adhesive is low. In addition, according to Table 2, the adhesive sheets of Example 1-2 and Example 1-3 are superior in processability and low-temperature adhesion properties compared to the adhesive sheets of Comparative Example 1-2 and Comparative Example 2-2. The linear expansion rate of the cured product of the film-like adhesive of the adhesive sheet of Example 1-2 and Example 1-3 was also sufficiently low. From these results, it was confirmed that the adhesive composition of the present invention has excellent processability and low-temperature adhesion when forming a film-like adhesive, and can sufficiently reduce the linear expansion rate.

10: Film adhesive 14: Support member for mounting semiconductor elements 20: Substrate 30: Protective film 41: Adhesive 42: Sealing material 84, 94: Circuit pattern 88: first wire 90: substrate 98: second wire 100, 110: follow the film 200: Semiconductor device Wa: The first semiconductor element Waa: second semiconductor element

Fig. 1 is a schematic cross-sectional view showing a film adhesive according to an embodiment. Fig. 2 is a schematic cross-sectional view showing an adhesive sheet according to an embodiment. Fig. 3 is a schematic cross-sectional view showing an adhesive sheet of another embodiment. Fig. 4 is a schematic cross-sectional view showing a semiconductor device according to an embodiment. 5 is a schematic cross-sectional view showing a series of steps in a method of manufacturing a semiconductor device according to an embodiment. 6 is a schematic cross-sectional view showing a series of steps in a method of manufacturing a semiconductor device according to an embodiment. FIG. 7 is a schematic cross-sectional view showing a series of steps in a method of manufacturing a semiconductor device according to an embodiment. FIG. 8 is a schematic cross-sectional view showing a series of steps in a method of manufacturing a semiconductor device according to an embodiment. 9 is a schematic cross-sectional view showing a series of steps in a method of manufacturing a semiconductor device according to an embodiment.

Claims (11)

An adhesive composition containing: epoxy resin, hardener, elastomer and filler, and The elastomer includes a polyurethane resin. The adhesive composition according to claim 1, wherein the hardener contains a phenol resin. The adhesive composition according to claim 1 or 2, wherein the content of the elastomer is 2% by mass to 20% by mass based on the total amount of the adhesive composition. The adhesive composition according to any one of claims 1 to 3, wherein the content of the filler is 50% by mass to 90% by mass based on the total amount of the adhesive composition. The adhesive composition according to any one of claims 1 to 4 further contains a hardening accelerator. A film-like adhesive formed by forming the adhesive composition according to any one of claims 1 to 5 into a film. An adhesive sheet, comprising: a substrate; and the film-like adhesive according to claim 6 provided on the substrate. The adhesive sheet according to claim 7, wherein the substrate is a dicing tape. A cutting-bonding integrated adhesive sheet, comprising: a cutting tape; and the film-like adhesive according to claim 6 arranged on the cutting tape. A method for manufacturing a semiconductor device includes: In the wire bonding step, a first semiconductor element is arranged on a support member having a substrate and a circuit pattern provided on the substrate, and the circuit pattern is electrically connected to the first semiconductor element via a first wire; In the lamination step, the film-like adhesive as described in claim 6 is attached to one side of the second semiconductor element; and In the die bonding step, the second semiconductor element to which the film adhesive is attached is crimped through the film adhesive, and the first wire and the first semiconductor element, or the first wire At least a part is embedded in the film-like adhesive. A semiconductor device including: A supporting member having a substrate and a circuit pattern arranged on the substrate; The first semiconductor element is disposed on the supporting member; and The second semiconductor element is bonded to the first semiconductor element via the film-like adhesive as described in claim 6, In the semiconductor device, The supporting member and the first semiconductor element are connected via an adhesive, The circuit pattern and the first semiconductor element are electrically connected via a first wire, and The first wire and the first semiconductor element, or at least a part of the first wire is buried in the film-like adhesive.

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