TWI834852B - Adhesive for semiconductors, manufacturing method of semiconductor device, and semiconductor device - Google Patents

Abstract

An adhesive for semiconductors, containing a resin with a weight average molecular weight of less than 10,000, a hardener, an inorganic filler and a silicone rubber filler.

Description

Adhesive for semiconductors, manufacturing method of semiconductor device, and semiconductor device

The present disclosure relates to an adhesive for semiconductors, a manufacturing method of a semiconductor device, and a semiconductor device.

Previously, when connecting a semiconductor chip (chip) to a substrate, wire bonding using thin metal wires such as gold wires has been widely used. On the other hand, in order to meet the requirements for higher functionality, higher integration, and higher speed of semiconductor devices, conductive protrusions called bumps are formed on a semiconductor wafer or a substrate to directly connect the semiconductor wafer and the substrate. The flip-chip connection method (FC (flip chip) connection method) is being promoted.

Known FC connection methods include a method of metal-joining the connection parts using solder, tin, gold, silver, copper, etc., a method of metal-joining the connection parts by applying ultrasonic vibration, a method of maintaining mechanical contact using the shrinkage force of resin, etc. . From the viewpoint of the reliability of the connection part, a method of metal-joining the connection part using solder, tin, gold, silver, copper, etc. is usually used.

For example, regarding the connection between semiconductor chips and substrates, Chip On Board (COB) type connections are popularly used in Ball Grid Array (BGA), Chip Size Package (CSP), etc. The method is also equivalent to the FC connection method. In addition, the FC connection method is also widely used in a Chip On Chip (COC) type connection method that forms connection portions (bumps or wiring) on semiconductor wafers to connect semiconductor wafers (for example, see Patent Document 1) .

In addition, in packages that are strongly required to be further miniaturized, thinned, and highly functional, chip stack-type packages and package-on-package (POP) packages in which the connection method is multi-layered are being developed. , Through-Silicon Via (TSV), etc. have also begun to become widely popular. This layering-multi-segmentation technology arranges semiconductor wafers and the like in three dimensions, so the package can be reduced compared to the method of two-dimensional arrangement. In addition, the lamination-multi-segmentation technology is also effective in improving semiconductor performance, reducing noise, reducing mounting area, and saving power, and is therefore attracting attention as a next-generation semiconductor wiring technology.

In addition, from the viewpoint of improving productivity, a chip on wafer (COW) in which semiconductor wafers are pressed (connected) onto a semiconductor wafer and then singulated to produce a semiconductor package, the semiconductor wafers are pressed against each other. Wafer on wafer (WOW), which is connected (connected) and then monolithized to produce semiconductor packages, is also attracting attention. Furthermore, from the same point of view, after a plurality of semiconductor wafers are aligned and temporarily press-bonded on the semiconductor wafer or a mold array package (Mold Array Package, MAP) substrate, the plurality of semiconductor wafers are formally press-bonded together. The multi-terminal bonding (Gang bonding) method of using semiconductor chips to ensure connections is also attracting attention. [Prior Art Document] [Patent Document]

Patent Document 1: Japanese Patent Application Publication No. 2008-294382

[Problem to be solved by the invention] In flip-chip packages, stress may occur due to differences in thermal expansion coefficients between the semiconductor adhesive and the semiconductor wafer and between the semiconductor wafer and the substrate, causing warpage in the package. As semiconductor chips and semiconductor wafers become thinner, warpage of the package becomes more likely to occur.

In addition, in the multi-layered wafer stacked package, the warpage is likely to be greater compared to the one-stage wafer stacked package.

Due to the warpage of the package, problems such as overmold failure and poor connection of the package easily occur. Therefore, there is a strong demand for low package warpage.

Here, as a method for achieving low warpage of the package, it is considered to reduce the elasticity of the adhesive for semiconductors. As methods of reducing the elasticity of the adhesive for semiconductors, methods of lowering the glass transition temperature of the polymer component, methods of reducing the amount of added inorganic fillers, methods of increasing the amount of added organic fillers, and the like are considered. However, when these methods are used to reduce the elasticity of a semiconductor adhesive, it becomes difficult to deteriorate the handleability of the semiconductor adhesive or to adjust the melt viscosity appropriately, and it is difficult to achieve a balance between these characteristics and low warpage of the package. .

The present disclosure was made to solve the above problems, and aims to provide an adhesive for semiconductors that can achieve low warpage of the resulting package while suppressing reductions in adhesive strength and reliability, and an adhesive using the adhesive for semiconductors. A method of manufacturing a semiconductor device and a semiconductor device. [Means to solve the problem]

In order to achieve the above object, the present disclosure provides an adhesive for semiconductors, which contains a resin with a weight average molecular weight of less than 10,000, a hardener, an inorganic filler and a silicone rubber filler. According to the adhesive for semiconductors, by using an inorganic filler and a silicone rubber filler in combination as fillers, it is possible to achieve low warpage of the resulting package while suppressing reductions in adhesive strength and reliability. In particular, by using a silicone rubber filler as an organic filler in combination with an inorganic filler, the warpage of the resulting package can be significantly reduced.

The average particle size of the silicone rubber filler may be 30 μm or less. In this case, it is possible to further reduce the warpage of the resulting package while more fully suppressing the decrease in adhesive strength and reliability.

The inorganic filler may also contain silica filler. In this case, the adhesive force and reliability can be further improved. In addition, the inorganic filler and silicone rubber filler are more easily dispersed evenly, allowing a higher level of both good adhesion and reliability and low warpage of the resulting package.

The adhesive for semiconductors may further contain a polymer component having a weight average molecular weight of 10,000 or more. In this case, the heat resistance and film formability of the semiconductor adhesive can be improved.

The weight average molecular weight of the polymer component may be 30,000 or more. In addition, the glass transition temperature of the polymer component may be 100°C or lower. When the weight average molecular weight is 30,000 or more, film formability becomes good. When the glass transition temperature is 100° C. or lower, adhesion to the substrate and the semiconductor wafer becomes good.

The adhesive agent for semiconductors may be in a film form. In this case, the workability of the adhesive for semiconductors can be improved, and the workability and productivity during package manufacturing can be improved.

Based on the total solid content of the adhesive for semiconductors, the content of the silicone rubber filler in the adhesive for semiconductors may be 0.1% by mass to 20% by mass. In this case, it is possible to achieve both good adhesion and reliability and low warpage of the resulting package at a higher level.

In the adhesive for semiconductors, the mass ratio of the content of the silicone rubber filler to the content of the inorganic filler (mass of the silicone rubber filler/mass of the inorganic filler) may be 0.05 to 0.5. In this case, it is possible to achieve both good adhesion and reliability and low warpage of the resulting package at a higher level.

In addition, the present disclosure provides a method of manufacturing a semiconductor device, which is a method of manufacturing a semiconductor device in which connecting portions of a semiconductor wafer and a printed circuit board are electrically connected to each other, or a semiconductor device in which connecting portions of a plurality of semiconductor wafers are electrically connected to each other. The method of manufacturing a semiconductor device includes the step of sealing at least part of the connection portion using the semiconductor adhesive. According to the manufacturing method, a semiconductor device can be obtained that has excellent adhesion and reliability between the semiconductor wafer and the printed circuit board or the semiconductor wafer and has reduced warpage.

Furthermore, the present disclosure provides a semiconductor device including a connection structure in which connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or a connection structure in which connection portions of a plurality of semiconductor wafers are electrically connected to each other. A structure; and an adhesive material that seals at least part of the connection portion, the adhesive material including a cured product of the semiconductor adhesive. The semiconductor device has excellent adhesion and reliability between the semiconductor wafer and the printed circuit board or the semiconductor wafer, and has reduced warpage. [Effects of the invention]

According to the present disclosure, it is possible to provide an adhesive for semiconductors that can achieve low warpage of the resulting package while suppressing reductions in adhesive strength and reliability, as well as a method for manufacturing a semiconductor device using the adhesive for semiconductors, and a semiconductor. device.

Hereinafter, suitable embodiments of the present disclosure will be described in detail with reference to the drawings as appropriate. In addition, in the drawings, the same or equivalent parts are denoted by the same symbols, and repeated explanations are omitted. In addition, unless otherwise specified, positional relationships such as up, down, left, and right are regarded as based on the positional relationships shown in the drawings. Furthermore, the dimensional ratio of the drawings is not limited to the ratio shown in the drawings.

In this specification, the numerical range expressed using "～" means a range including the numerical values described before and after "～" as the minimum value and the maximum value, respectively. In the numerical ranges described in stages in this specification, the upper limit or lower limit of the numerical range in a certain stage can be arbitrarily combined with the upper limit or lower limit of the numerical range in other stages. In the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range can also be replaced by the value shown in the embodiment. The so-called "A or B" only needs to include either A or B, or both. Unless otherwise specified, one type of materials exemplified in this specification may be used alone or two or more types may be used in combination. In this specification, "(meth)acrylic acid" means acrylic acid or its corresponding methacrylic acid.

＜Adhesives for semiconductors＞ The adhesive for semiconductors of this embodiment contains a resin with a weight average molecular weight of less than 10,000 (hereinafter referred to as "(a) component" as the case may be), a hardener (hereinafter referred to as "(b) component" as the case may be), and an inorganic filler (hereinafter referred to as "(b) component" as the case may be). (hereinafter referred to as "(e) component" as appropriate) and organic fillers (hereinafter referred to as "(f) component" as appropriate). In addition, the adhesive agent for semiconductors of this embodiment contains a silicone rubber filler as an organic filler. Furthermore, the adhesive agent for semiconductors of this embodiment may contain a polymer compound with a weight average molecular weight of 10,000 or more (hereinafter referred to as "(c) component" as the case may be) and/or a flux (hereinafter referred to as "(d) as the case may be"). )Element"). Each component is explained below.

(a) Resins with a weight average molecular weight less than 10,000 The component (a) is not particularly limited, but from the viewpoint of heat resistance, a component that reacts with the curing agent of the component (b) is preferred. As component (a), one having two or more reactive groups in the molecule is preferred. Examples of the component (a) include epoxy resin, phenol resin, imide resin, urea resin, melamine resin, silicone resin, (meth)acrylic compound, and vinyl compound. Among these, from the viewpoint of excellent heat resistance and storage stability, epoxy resins, phenol resins, and amide imine resins are preferred, and epoxy resins and amide imine resins are more preferred. These (a) components may be used individually or as a mixture or copolymer of two or more types.

The epoxy resin is not particularly limited as long as it has two or more epoxy groups in the molecule. Examples thereof include: bisphenol A type, bisphenol F type, naphthalene type, phenol novolak type, and cresol novolac type. Varnish type, phenol aralkyl type, biphenyl type, triphenylmethane type and dicyclopentadiene type epoxy resins, as well as various multi-functional epoxy resins. Epoxy resin can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of heat resistance and workability, bisphenol F-type epoxy resin, phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, biphenyl-type epoxy resin, and Triphenylmethane type epoxy resin.

The acyl imine resin is not particularly limited as long as it has two or more acyl imine groups in the molecule. Examples thereof include: acyl imine-resistant resin, allyl acyl imine-resistant resin, cis-butyl imine resin, etc. Ethylenediimide resin, amideimine resin, amideimine acrylate resin, various multifunctional amideimine resins and various polyimide resins. The imine resin can be used individually by 1 type or in combination of 2 or more types.

From the viewpoint of suppressing decomposition and generation of volatile components during connection at high temperatures, when the temperature during connection is 250°C, component (a) preferably uses a thermogravimetric reduction coefficient of 5% at 250°C. For the following resins, when the temperature during connection is 300°C, it is preferable to use resins whose thermogravimetric reduction coefficient at 300°C is 5% or less.

When using epoxy resin as component (a), the 1% thermogravimetric loss temperature of bisphenol A type or bisphenol F type liquid epoxy resin is 250°C or less, so it may be decomposed when heated to high temperatures. Concerns about volatile components. Therefore, it is preferable to use an epoxy resin that is solid at room temperature (1 atmosphere, 25°C). When liquid epoxy resin is used, it is preferably used in combination with solid epoxy resin.

The weight average molecular weight of the component (a) is less than 10,000, preferably less than 10,000 from the viewpoint of film formation, and preferably 100 or more from the viewpoint of appropriate melt viscosity. Therefore, the weight average molecular weight of component (a) is preferably from 100 to 10,000, more preferably from 300 to 8,000, and even more preferably from 300 to 5,000.

Based on the total solid content of the semiconductor adhesive, the content of component (a) is, for example, 5% to 75% by mass, preferably 15% to 60% by mass, and more preferably 30% to 50% by mass. . By setting the content of component (a) to 5% by mass or more, adhesion and reliability are excellent, and if it is 75% by mass or less, the cured product is prevented from becoming too hard and warpage of the package is easily reduced.

(b) Hardener Examples of (b) the curing agent include a phenol resin curing agent, an acid anhydride curing agent, an amine curing agent, an imidazole curing agent, and a phosphine curing agent. If the component (b) contains phenolic hydroxyl groups, acid anhydrides, amines, or imidazoles, it exhibits fluxing activity that suppresses the formation of oxide films in the connection portion, thereby improving connection reliability and insulation reliability. Each hardener is explained below.

(b-i) Phenol resin hardener As the phenol resin hardener, if it has two or more phenolic hydroxyl groups in the molecule, it is not particularly limited, and can be used: phenol novolak resin, cresol novolac resin, phenol aralkyl resin, cresol naphthalene Phenol formaldehyde condensation polymer, triphenylmethane type multifunctional phenol resin and various multifunctional phenol resins, etc. These can be used individually or as a mixture of two or more types. In addition, liquid phenol resins may decompose when heated at high temperatures to produce volatile components, so it is ideal to use phenol resins that are solid at room temperature (1 atmosphere, 25°C).

From the viewpoint of improving curability, adhesion, storage stability, etc., the equivalent ratio (phenolic hydroxyl group/reactive group of the component (a)) of the (b-i) phenolic resin-based curing agent to the component (a) molar ratio) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, still more preferably 0.5 to 1.0. If the equivalent ratio is 0.3 or more, the hardening properties tend to be improved and the adhesion force will be improved. If it is 1.5 or less, unreacted phenolic hydroxyl groups will not remain excessively, the water absorption rate will be suppressed to a low value, and the insulation reliability will be improved. tendency. Phenolic hydroxyl groups show fluxing activity that removes oxide films. Therefore, when a semiconductor adhesive contains a phenolic resin-based hardener, connectivity and reliability can be improved.

(b-ii) Acid anhydride hardener Examples of acid anhydride-based hardeners that can be used include: methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, and ethylene glycol bis-trimellitic anhydride. Ester etc. These can be used individually or as a mixture of two or more types. In addition, liquid acid anhydrides may decompose when heated at high temperatures to produce volatile components, so it is ideal to use acid anhydrides that are solid at room temperature (1 atmosphere, 25°C).

From the viewpoint of improving the curability, adhesion, storage stability, etc., the equivalent ratio (acid anhydride group/reactive group of the component (a)) of the acid anhydride-based curing agent (b-ii) to the component (a) molar ratio) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, still more preferably 0.5 to 1.0. If the equivalent ratio is 0.3 or more, the hardenability and adhesion force tend to be improved. If it is 1.5 or less, unreacted acid anhydride will not remain excessively, the water absorption rate will be suppressed to a low value, and the insulation reliability will tend to be improved. . Acid anhydrides exhibit fluxing activity that removes oxide films. Therefore, when a semiconductor adhesive contains an acid anhydride-based hardener, connectivity and reliability can be improved.

(b-iii) Amine hardener As the amine-based hardener, dicyandiamide or the like can be used. In addition, liquid amines may decompose during high-temperature heating to produce volatile components, so it is ideal to use amines that are solid at room temperature (1 atmosphere, 25°C).

From the viewpoint of improving curability, adhesion, storage stability, etc., the equivalent ratio of (b-iii) the amine-based curing agent to the component (a) (the molar ratio of the reactive group of the amine/component (a) ear ratio) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, further preferably 0.5 to 1.0. If the equivalent ratio is 0.3 or more, the hardenability will be improved and the adhesive force will tend to be improved. If it is 1.5 or less, unreacted amine will not remain excessively, the water absorption rate will be suppressed to a low value, and the insulation reliability will tend to be improved. . Amines exhibit fluxing activity that removes oxide films. Therefore, when a semiconductor adhesive contains an amine-based hardener, connectivity and reliability can be improved.

(b-iv) Imidazole hardener (the nitrogen atoms contained are tertiary nitrogen atoms) Examples of imidazole-based hardeners include: 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyano Ethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine Azine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isotripolymer Cyanic acid adducts, adducts of epoxy resin and imidazoles, etc. Among these, from the viewpoint of improving hardenability, adhesion, storage stability, etc., 1-cyanoethyl-2-undecylimidazole and 1-cyanoethyl-2-benzene are preferred. imidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino- 6-[2'-Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-( 1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid addition substance, 2-phenylimidazole isocyanuric acid adduct. These can be used individually or in combination of 2 or more types. In addition, a latent hardening agent that can be microencapsulated to improve the potency can also be used.

The content of the (b-iv) imidazole hardener is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the component (a). If the content is 0.1 parts by mass or more, the curability tends to be improved. If the content is 20 parts by mass or less, the semiconductor adhesive does not harden before metal bonding is formed, and connection defects tend to be less likely to occur. The imidazole-based hardening agent may be used alone as the hardening agent (b) or may be used as a hardening accelerator together with the hardening agents (b-i) to (b-iii) described above.

(b-v) Phosphine hardener Examples of phosphine-based hardeners include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrakis(4-methylphenyl)borate, tetraphenylphosphonium(4-fluorophenyl) ) borate, etc.

The content of the (b-v) phosphine-based hardener is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the component (a). If the content of the phosphine-based curing agent is 0.1 parts by mass or more, the curability tends to be improved. If it is 10 parts by mass or less, the film-like adhesive does not harden before metal bonding is formed, and connection failures tend to be less likely to occur.

Each of the phenolic resin-based hardener, the acid anhydride-based hardener, and the amine-based hardener can be used individually by one type or as a mixture of two or more types. The imidazole-based hardener and the phosphine-based hardener can be used alone or together with a phenol resin-based hardener, an acid anhydride-based hardener, or an amine-based hardener.

(c) Polymer components with a weight average molecular weight of more than 10,000 (c) Polymer components having a weight average molecular weight of 10,000 or more include: phenoxy resin, polyamide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyamide resin, Ester resin, polyethylene resin, polyether resin, polyetherimide resin, polyvinyl acetal resin, urethane resin, acrylic rubber, etc. Among these, phenoxy resin, polyimide resin, acrylic rubber, cyanate ester resin, polycarbodiimide resin, etc. are preferable from the viewpoint of excellent heat resistance and film formation properties, and more preferred They are phenoxy resin, polyimide resin, and acrylic rubber, and phenoxy resin is more preferred. These polymer components can be used alone or as a mixture or copolymer of two or more types.

The mass ratio of component (c), component (a), and component (b) is not particularly limited. From the viewpoint of improving film-forming properties and film-forming properties by spin coating, etc., 1 mass of component (c) parts, the total mass of component (a) and component (b) is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and still more preferably 0.1 to 3 parts by mass. If the mass ratio is 0.01 parts by mass or more, the decrease in the curability of the semiconductor adhesive and the decrease in the adhesive force tend to be suppressed. If the mass ratio is 5 parts by mass or less, the film formability and film formation tend to be improved. Good sexual tendencies.

The polyimide resin used as component (c) can be obtained by condensing tetracarboxylic dianhydride and diamine by a known method, for example. More specifically, in an organic solvent, tetracarboxylic dianhydride and diamine are mixed in equimolar or approximately equimolar amounts (the order of addition of each component is arbitrary), and the reaction temperature is 80°C or lower, preferably 0°C. The addition reaction proceeds at ~60°C. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is the precursor of polyimide, is generated. Furthermore, in order to suppress deterioration in various characteristics of the semiconductor adhesive, it is preferable that the tetracarboxylic dianhydride is subjected to recrystallization purification treatment using acetic anhydride.

The molecular weight of the polyamide can also be adjusted by depolymerizing it by heating at a temperature of 50°C to 80°C.

Polyimide resin can be obtained by dehydrating and ring-closing the reaction product (polyamide acid). Dehydration loop closure can be performed by a thermal loop closure method using heat treatment or a chemical loop closure method using a dehydrating agent.

From the viewpoint of improving the adhesion to the substrate and the semiconductor wafer, the glass transition temperature (Tg) of the component (c) is preferably 100°C or lower, more preferably 75°C or lower. If Tg is 100°C or less, bumps formed on a semiconductor wafer or irregularities such as electrodes or wiring patterns formed on a substrate can be easily filled with the semiconductor adhesive, thereby preventing bubbles from remaining and suppressing voids. ) the tendency to produce. In addition, the Tg was measured using a differential scanning calorimeter (DSC-7 model manufactured by PerkinElmer) under the conditions of sample amount 10 mg, temperature rise rate 5°C/min, and measurement environment: air. Tg at the time of measurement.

The weight average molecular weight of the component (c) is 10,000 or more in terms of polystyrene. In order to exhibit good film-forming properties alone, it is preferably 20,000 or more, more preferably 30,000 or more, and still more preferably 40,000 or more. When the weight average molecular weight is less than 10,000, film formation properties may be reduced. In addition, taking fluidity into consideration, the weight average molecular weight of component (c) is, for example, 1 million or less, preferably 500,000 or less.

In this specification, the weight average molecular weight refers to the weight average molecular weight when measured in terms of polystyrene using high performance liquid chromatography (C-R4A manufactured by Shimadzu Corporation).

The ratio of the content of component (c) to component (a) is not particularly limited, but from the viewpoint of maintaining a good film shape, it is preferably 0.01 part by mass of component (a) relative to 1 part by mass of component (c). ~5 parts by mass, more preferably 0.1-2 parts by mass. If the ratio of the content is 0.01 parts by mass or more, the decrease in the curability of the semiconductor adhesive and the decrease in the adhesive force tend to be suppressed. If the ratio is 5 parts by mass or less, the film formability and composition may be reduced. Good film properties.

(d) Flux The adhesive for semiconductors may contain (d) a flux, that is, a flux activator that is a compound showing fluxing activity (activity for removing oxides and impurities). Examples of the flux include nitrogen-containing compounds having non-covalent electron pairs such as imidazoles and amines, carboxylic acids, phenols and alcohols. In addition, organic acids such as carboxylic acids exhibit fluxing activity more strongly than alcohols and can easily improve connectivity.

From the viewpoint of exhibiting fluxing activity and improving connectivity, the content of component (d) is preferably 0.1 mass % to 5 mass %, more preferably 1 mass %, based on the total solid content of the semiconductor adhesive. %~5 mass%.

(e) Inorganic filler The adhesive agent for semiconductors of this embodiment contains an inorganic filler as (e) component. By containing the component (e), the viscosity of the semiconductor adhesive and the physical properties of the cured product can be controlled, and the generation of voids and the moisture absorption rate when connecting the semiconductor wafer and the substrate can be suppressed. In addition, by containing the component (e), the adhesive agent for semiconductors can obtain excellent adhesive strength, and can improve reliability such as reflow resistance and moisture resistance.

Examples of the component (e) include insulating inorganic fillers and whiskers. Examples of materials for the insulating inorganic filler include glass, silica, alumina, silica-alumina, titanium oxide, mica, boron nitride, and the like. Among them, silica, alumina, and boron nitride are preferred. Silicon - aluminum oxide, titanium oxide, boron nitride, etc., more preferably silicon dioxide, aluminum oxide, boron nitride, and still more preferably silicon dioxide. Examples of whisker materials include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, boron nitride, and the like.

From the viewpoint of improving dispersion and adhesion, component (e) is preferably a surface treatment filler. Examples of surface treatments include glycidyl-based (epoxy-based), amine-based, phenyl-based, phenylamino-based, acrylic-based, vinyl-based, and the like.

As surface treatment, in terms of ease of surface treatment, silane treatment using silane compounds such as epoxy silane type, amino silane type, and acrylic silane type is preferred. As the surface treatment agent, glycidyl-based, phenylamino-based, or (meth)acrylic-based compounds are preferred from the viewpoint of excellent dispersion and fluidity and further improvement in adhesive strength. As the surface treatment agent, from the viewpoint of storage stability, phenyl-based or (meth)acrylic-based compounds are preferred.

Regarding the particle diameter of component (e), from the viewpoint of preventing inclusion during flip-chip connection, the average particle diameter is preferably 1.5 μm or less, and from the viewpoint of visibility (transparency), the average particle diameter is even more preferable. is less than 1.0 μm. (e) The average particle diameter of the component can be measured, for example, with a wet-dry particle size distribution measuring device (LS13 320, manufactured by Beckman-Coulter).

These (e) components may be used individually or as a mixture of two or more types. The shape of component (e) is not particularly limited.

Based on the total solid content of the semiconductor adhesive, the content of component (e) is preferably 20 to 60 mass%, more preferably 30 to 50 mass%. If the content is 20% by mass or more, especially 30% by mass or more, the generation of voids and the moisture absorption rate tend to be further suppressed, and reliability such as adhesive strength, reflow resistance, and moisture resistance tend to be further improved. On the other hand, if the content is 60% by mass or less, especially 50% by mass or less, the warpage of the resulting package tends to be easily reduced and inclusion during flip-chip connection tends to be easily prevented.

(f) Organic filler The adhesive agent for semiconductors of this embodiment contains an organic filler as (f) component. By containing the component (f), the viscosity of the semiconductor adhesive and the physical properties of the cured product can be controlled, and the generation of voids and the moisture absorption rate when connecting the semiconductor wafer and the substrate can be suppressed.

Examples of organic filler materials include polyurethane, polyimide, silicone, methyl methacrylate resin, and methyl methacrylate-butadiene-styrene copolymer resin (Methylmethacrylate Butadiene Styrene, MBS). Compared with the component (e), the component (f) can impart flexibility to the semiconductor adhesive and its cured product at high temperatures such as 260°C, and is therefore suitable for improving reflow resistance and temperature cycle resistance. In addition, since it imparts flexibility, it is also effective in improving film formability.

These (f) components may be used individually or as a mixture of 2 or more types. The shape of component (f) is not particularly limited.

The adhesive agent for semiconductors of this embodiment contains a silicone rubber filler as the (f) component. When the adhesive for semiconductors contains a silicone rubber filler, the resulting package can have low warpage.

The silicone rubber filler only needs to be a filler containing silicone rubber as a constituent component of the filler, and may be a filler containing only silicone rubber or a filler compounded with other components. The silicone rubber filler may be particles with a core-shell structure. Examples of a core-shell type structure include a structure having a core layer (core material) and a shell layer (surface layer) provided to cover the core layer. The compositions of the core layer and the shell layer may be the same or different. Furthermore, the core layer and the shell layer may not have a clear boundary line. As the silicone rubber filler, for example, composite particles in which the core layer is composed of silicone rubber particles and the shell layer is composed of components other than silicone rubber particles can be used. Preferable examples of such composite particles include a silicone composite powder in which the core layer is composed of silicone rubber particles and the shell layer is composed of a silicone resin having a higher glass transition temperature and elastic coefficient than the silicone rubber particles of the core layer. . The shell layer of this silicone composite powder can prevent the silicone rubber particles in the core layer from swelling due to the solvent or the constituent material of the semiconductor adhesive, thereby preventing the formation of agglomerates between the silicone rubber particles.

The average particle size of the silicone rubber filler is preferably 0.1 μm to 50 μm, more preferably 0.1 μm to 30 μm, and further preferably 0.1 μm to 10 μm. When the average particle diameter is 50 μm or less, the connectivity during mounting tends to be good. The average particle size of the silicone rubber filler can be measured, for example, by a wet-dry particle size distribution measuring device (LS13 320 manufactured by Beckman-Coulter).

Based on the total solid content of the semiconductor adhesive, the content of the silicone rubber filler is preferably 0.1% to 20% by mass, more preferably 1% to 18% by mass, and further preferably 3% to 15% by mass. Mass %. If the content is 0.1% by mass or more, the elasticity tends to be low, and if it is 20% by mass or less, the melt viscosity tends to be appropriately adjusted.

From the viewpoint of obtaining the effects of the present disclosure more fully, the proportion of the content of the silicone rubber filler in component (f) is preferably 50 mass % or more based on the total amount of component (f), and more preferably It is more than 80 mass%. Furthermore, the content ratio of the silicone rubber filler may also be 100% by mass.

The mass ratio of the content of the silicone rubber filler to the content of the component (e) (mass of the silicone rubber filler/mass of the inorganic filler) is preferably 0.05 to 0.5, more preferably 0.08 to 0.4, and still more preferably 0.1 to 0.1. 0.3. By setting the mass ratio within the above range, it is possible to achieve both good adhesion and reliability and low warpage of the resulting package at a higher level.

Based on the solid content of the entire semiconductor adhesive, the total content of component (e) and component (f) is preferably 30% by mass to 90% by mass, more preferably 40% by mass to 80% by mass. If the content is 30% by mass or more, the adhesive force tends to be more fully improved. If the content is 90% by mass or less, it is possible to suppress the decrease in fluidity of the semiconductor adhesive due to an increase in viscosity and the inclusion (trapping) of the filler into the connection part, thereby tending to obtain good connection reliability. .

From the viewpoint of insulation reliability, the filler is preferably insulating. The adhesive for semiconductors preferably does not contain conductive metal fillers such as silver fillers and solder fillers. Semiconductor adhesives (circuit connection materials) that do not contain conductive fillers (conductive particles) are sometimes called non-conductive film (Non-Conductive-FILM, NCF) or non-conductive paste (Non-Conductive-Paste, NCP) ). The adhesive agent for semiconductors of this embodiment can be suitably used as NCF or NCP.

An ion trap, an antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, etc. may also be further blended into the adhesive for semiconductors. These may be used individually by 1 type, and may be used in combination of 2 or more types. The blending amounts may be appropriately adjusted to express the effects of each additive.

The adhesive agent for semiconductors of this embodiment can be formed into a film shape. An example of a method for producing a film-like adhesive using the semiconductor adhesive of this embodiment is shown below.

First, necessary components among components (a) to (f) and additives are added to an organic solvent, and are dissolved or dispersed by stirring, mixing, kneading, etc. to prepare a resin varnish. Thereafter, the resin varnish is applied to the base film that has been subjected to the release treatment using a blade coater, a roll coater, an applicator, etc., and then the organic solvent is removed by heating, whereby the organic solvent can be applied to the base film. A film-like adhesive is formed on the material film.

The thickness of the film adhesive is not particularly limited, but for example, it is preferably 0.5 to 1.5 times the height of the bump before connection, more preferably 0.6 to 1.3 times, and still more preferably 0.7 to 1.2 times.

If the thickness of the film-like adhesive is 0.5 times or more the height of the bump, the generation of voids caused by insufficient filling of the adhesive can be sufficiently suppressed, thereby further improving connection reliability. In addition, if the thickness is 1.5 times or less, the amount of adhesive extruded from the wafer connection area during connection can be sufficiently suppressed, and therefore adhesion of the adhesive to unnecessary parts can be sufficiently prevented. If the thickness of the film adhesive is greater than 1.5 times, a large amount of adhesive must be removed from the bump, which may easily cause poor conduction. In addition, regarding the weakening of the bumps (miniaturization of the bump diameter) caused by narrowing the pitch and increasing the number of pins, excluding a large amount of resin will increase damage to the bumps, which is not preferable.

Generally, the height of the bumps is 5 μm to 100 μm. Accordingly, the thickness of the film adhesive is preferably 2.5 μm to 150 μm, and more preferably 3.5 μm to 120 μm.

The organic solvent used in the preparation of the resin varnish is preferably one that has the characteristics of uniformly dissolving or dispersing each component. Examples thereof include dimethylformamide, dimethylacetamide, and N-methyl. -2-pyrrolidinone, dimethylsyanin, diglyme, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate , butyl cellosolve, dioxane, cyclohexanone, and ethyl acetate. These organic solvents can be used alone or in combination of two or more. Stirring, mixing, and kneading when preparing a resin varnish can be performed using a mixer, a grinder, a three-roller, a ball mill, a bead mill, or a homogenizer, for example.

The base film is not particularly limited as long as it has heat resistance that can withstand the heating conditions for volatilizing the organic solvent. Examples include polyolefin films such as polypropylene films and polymethylpentene films; polyparaphenylene films. Polyester films such as ethylene dicarboxylate film and polyethylene naphthalate film; polyimide film and polyetherimide film. The base film is not limited to a single layer including these films, and may be a multilayer film including two or more materials.

The drying conditions for volatilizing the organic solvent from the resin varnish applied to the base film are preferably conditions in which the organic solvent is fully volatilized. Specifically, it is preferable to perform heating at 50°C to 200°C for 0.1 to 90 minutes. . The organic solvent is preferably removed to 1.5% by mass or less relative to the total amount of the film adhesive.

In addition, the adhesive agent for semiconductors of this embodiment can be formed directly on a wafer. Specifically, for example, the resin varnish can be directly spin-coated on the wafer to form a film, and then the organic solvent can be removed to form the semiconductor adhesive directly on the wafer.

＜Semiconductor Device＞ The semiconductor device of this embodiment will be described below using FIGS. 1 and 2 . FIG. 1 is a schematic cross-sectional view showing an embodiment of the semiconductor device of the present disclosure. As shown in (a) of FIG. 1 , the semiconductor device 100 includes a semiconductor chip 10 and a substrate (wired circuit board) 20 facing each other, wiring 15 respectively arranged on the surfaces of the semiconductor chip 10 and the substrate 20 facing each other. The connection bumps 30 that connect the semiconductor wafer 10 and the wiring 15 of the substrate 20 to each other, and the adhesive material 40 that fills the gap between the semiconductor wafer 10 and the substrate 20 without any gap. The semiconductor chip 10 and the substrate 20 are flip-chip connected via wiring 15 and connection bumps 30 . The wiring 15 and the connection bump 30 are sealed by the adhesive material 40 and isolated from the external environment.

As shown in FIG. 1( b ), the semiconductor device 200 includes a semiconductor wafer 10 and a substrate 20 facing each other, bumps 32 respectively arranged on the mutually facing surfaces of the semiconductor wafer 10 and the substrate 20 , and a gap-free filling device. The adhesive material 40 is in the gap between the semiconductor chip 10 and the substrate 20 . The semiconductor chip 10 and the substrate 20 are connected to each other through opposite bumps 32 and are flip-chip connected. The bump 32 is sealed from the external environment by the adhesive material 40 . The subsequent material 40 is a cured product of the semiconductor adhesive of this embodiment.

2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present disclosure. As shown in FIG. 2( a ), the semiconductor device 300 is the same as the semiconductor device 100 except that two semiconductor chips 10 are flip-chip connected through the wiring 15 and the connection bump 30 . As shown in FIG. 2( b ), the semiconductor device 400 is the same as the semiconductor device 200 except that the two semiconductor chips 10 are flip-chip connected through the bumps 32 .

The semiconductor wafer 10 is not particularly limited, and may be an elemental semiconductor composed of one type of element such as silicon or germanium; or a compound semiconductor such as gallium arsenide or indium phosphide.

As the substrate 20, if it is a circuit substrate, there is no particular limitation. It can use glass epoxy, polyimide, polyester, ceramic, epoxy, bismaleimide triazine, etc. as the main component. A circuit board with wiring (wiring pattern) 15 formed by etching and removing unnecessary parts of a metal film on the surface of an insulating substrate; and a circuit board with wiring 15 formed on the surface of the insulating substrate by metal plating or the like. Circuit board: a circuit board on which wiring 15 is formed by printing a conductive material on the surface of the insulating substrate.

The connection parts such as the wiring 15 and the bump 32 contain gold, silver, copper, solder (the main component is, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper), nickel, tin, and lead etc. as the main component, and may also contain a variety of metals.

Among the above-mentioned metals, from the viewpoint of forming a package with excellent electrical conductivity and thermal conductivity of the connection portion, gold, silver, and copper are preferred, and silver and copper are more preferred. From the viewpoint of forming a cost-reduced package, silver, copper and solder are preferable due to low cost, copper and solder are more preferable, and solder is still more preferable. If an oxide film is formed on the surface of a metal at room temperature, productivity may decrease and costs may increase. Therefore, from the viewpoint of suppressing the formation of an oxide film, gold, silver, copper and solder are preferred. Gold, silver, and solder are more preferred, and gold and silver are even more preferred.

The surface of the wiring 15 and the bump 32 may also be formed with gold, silver, copper, solder (main components such as tin-silver, tin-lead, tin-bismuth, tin- Copper), tin, nickel and other metal layers as main components. The metal layer may contain only a single component or may contain multiple components. In addition, the metal layer may also have a structure in which a single layer or a plurality of metal layers are laminated.

In FIG. 1( b ), the bump 32 provided on the surface of the semiconductor chip 10 may also have a multi-layer structure including a copper pillar part and a solder part. In this case, it is preferable that the copper pillar portion is disposed on the semiconductor chip 10 side, and the solder portion is provided at the end of the copper pillar portion.

In addition, in the semiconductor device of this embodiment, a plurality of structures (packages) shown in the semiconductor device 100 to the semiconductor device 400 may be laminated. In this case, the semiconductor device 100 to the semiconductor device 400 may also be made of gold, silver, copper, and solder (the main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, and tin-silver-copper). , tin, nickel, etc. bumps or wiring to electrically connect each other.

As a method of stacking a plurality of semiconductor devices, as shown in FIG. 3 , for example, TSV (Through-Silicon Via) technology can be used. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present disclosure, and is a semiconductor device using TSV technology. In the semiconductor device 500 shown in FIG. 3 , the wiring 15 formed on the interposer 50 is connected to the wiring 15 of the semiconductor chip 10 through the connection bumps 30 , thereby flip-chip the semiconductor chip 10 and the interposer 50 connection. The gap between the semiconductor wafer 10 and the interposer 50 is filled with the adhesive material 40 without any gap. On the surface of the semiconductor wafer 10 opposite to the interposer 50 , the semiconductor wafer 10 is repeatedly laminated via the wiring 15 , the connection bump 30 and the adhesive material 40 . The wirings 15 on the pattern surfaces on the front and back of the semiconductor wafer 10 are connected to each other by through-electrodes 34 filled in holes penetrating the inside of the semiconductor wafer 10 . In addition, as the material of the through-electrode 34, copper, aluminum, etc. can be used.

With this TSV technology, signals can be obtained from the backside of a semiconductor chip that is not normally used. Furthermore, since the through-electrodes 34 are vertically inserted into the semiconductor wafer 10 , the distance between the opposing semiconductor wafers 10 or between the semiconductor wafer 10 and the interposer 50 can be shortened to achieve a flexible connection. In such TSV technology, the semiconductor adhesive of this embodiment can be applied as a semiconductor adhesive between opposing semiconductor wafers 10 or between the semiconductor wafer 10 and the interposer 50 .

In addition, in a bump formation method with a high degree of freedom such as area bump wafer technology, the semiconductor chip can be directly packaged on a mother board without an interposer. The adhesive agent for semiconductors of this embodiment is also applicable to the case where a semiconductor chip is directly packaged on a motherboard. Furthermore, when two printed circuit boards are laminated, the adhesive agent for semiconductors of this embodiment can also be applied when sealing the gap between the board|substrates.

＜Manufacturing method of semiconductor device＞ Next, a method for manufacturing a semiconductor device according to this embodiment will be described.

First, a film-like adhesive is attached to the substrate or semiconductor wafer. The film adhesive can be attached by heat pressing, roller lamination, vacuum lamination, etc. The supply area and thickness of the film-like adhesive are appropriately set according to the size of the semiconductor wafer or substrate and the height of the connection bump. The film adhesive can be attached to the semiconductor wafer, or it can be separated into semiconductor wafers by dicing after being attached to the semiconductor wafer, thereby producing a semiconductor wafer to which the film adhesive is attached.

After the film-like adhesive is attached to the substrate or semiconductor wafer, a connection device such as a flip-chip bonding machine is used to align the connection bumps (solder bumps, etc.) of the semiconductor wafer with the wiring (copper wiring, etc.) of the substrate. Then, the semiconductor wafer and the substrate are pressure-bonded while being heated at a temperature above the melting point of the connection bumps, thereby connecting the semiconductor wafer and the substrate, and the gap between the semiconductor wafer and the substrate is sealed and filled with a film-like adhesive. . A semiconductor device is obtained as described above.

The connection load can be set taking into account variations in the number and height of the connection bumps, and the amount of deformation of the connection bumps or the wiring receiving the bumps in the connection portion due to pressurization. Regarding the connection temperature, the temperature of the connection portion is preferably not less than the melting point of the connection bump, but it may be a temperature at which metal bonding of each connection portion (bump or wiring) can be formed. When the connection bumps are solder bumps, the connection temperature can also be about 220°C or above.

The connection time during connection varies depending on the constituent metal of the connection part, but from the viewpoint of improving productivity, the shorter the time, the better. When the connection bumps are solder bumps, the connection time is preferably 20 seconds or less, more preferably 10 seconds or less, and still more preferably 5 seconds or less. In the case of short-time connection using solder bumps, the connection time is preferably 4 seconds or less, more preferably 3 seconds or less, and still more preferably 2 seconds or less. By making connections in a short time in this manner, more high-reliability packages can be manufactured. Here, the connection time refers to the time the connection temperature takes to reach the connection bump. In the case of copper-copper or copper-gold metal connection, the connection time is preferably 60 seconds or less. When the connection bumps are solder bumps, it is preferable to melt the solder during connection to remove the oxide film and surface impurities to form a metal joint at the connection portion.

In the method of manufacturing a semiconductor device according to this embodiment, the connection bumps may be melted by temporarily fixing (with a semiconductor adhesive interposed therebetween) after alignment and performing heat treatment in a reflow furnace. Connect the semiconductor wafer to the substrate. Since it is not necessary to form a metal joint in the temporary fixation stage, compared with the above-mentioned method of performing pressure bonding while heating, pressure bonding can be performed with a low load, a short time, and a low temperature, thereby improving productivity and enabling Suppresses deterioration of connection parts.

In addition, after the semiconductor chip is connected to the substrate, heat treatment may be performed using an oven or the like, thereby further improving connection reliability and insulation reliability. The heating temperature is preferably a temperature at which the film-like adhesive is hardened, and more preferably a temperature at which it is completely hardened. The heating temperature and heating time can be set appropriately.

In the method of manufacturing a semiconductor device according to this embodiment, a paste-like semiconductor adhesive may be supplied on the substrate or semiconductor wafer instead of the film-like adhesive. The adhesive for semiconductors can be supplied by a coating method such as spin coating.

The preferred embodiments of the present disclosure have been described above, but the present disclosure is not limited to the embodiments. [Example]

Hereinafter, the present disclosure will be explained in more detail using examples, but the present disclosure is not limited to the examples.

The compounds used in each Example and Comparative Example are as follows. (a) Ingredient: Resin with weight average molecular weight less than 10,000 (a-1): Multifunctional epoxy resin containing trisphenolmethane skeleton (manufactured by Mitsubishi Chemical Co., Ltd., trade name "EP1032H60", weight average molecular weight: 800 to 2000) (a-2): Bisphenol F-type liquid epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "YL983U", weight average molecular weight: approximately 340) (a-3): Flexible semi-solid epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "YX7110B60", weight average molecular weight: about 1000 to 5000)

(b) Ingredients: Hardener: 2,4-diamino-6-[2'-methylimidazole-(1')]-ethyl-s-triazine isocyanuric acid adduct (manufactured by Shikoku Chemical Co., Ltd., trade name "2MAOK-PW")

(c) Ingredients: Polymer compound with a weight average molecular weight of 10,000 or more: Phenoxy resin (manufactured by Toto Chemical Co., Ltd., trade name "ZX1356", Tg: about 71°C, weight average molecular weight: about 63,000)

(d) Ingredients: Flux (carboxylic acid): glutaric acid (melting point: about 95°C)

(e) Ingredients: Inorganic filler (e-1) Silica filler (manufactured by Admatechs Co., Ltd., trade name "SE2050", average particle size: 0.5 μm) (e-2) Methacrylic surface-treated nanosilica filler (manufactured by Admatechs Co., Ltd., trade name "YA050C-SM", average particle size: about 50 nm)

(f) Ingredients: organic fillers (f-1): Silicone composite powder (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "KMP-602", average particle diameter: 30 μm, spherical silicone rubber powder whose surface is coated with silicone resin) powder) (f-2): Silicone composite powder (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "KMP-600", average particle diameter: 5 μm, spherical silicone rubber powder whose surface is coated with silicone resin) powder) (f-3): Silicone composite powder (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "KMP-605", average particle diameter: 2 μm, spherical silicone rubber powder whose surface is coated with silicone resin) powder) (f-4): Silicone composite powder (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "X-52-7030", average particle diameter: 0.8 μm, spherical silicone rubber powder whose surface is coated with silicone resin spherical powder) (f-5): Core-shell type organic fine particles (manufactured by Rohm and Haas Japan Co., Ltd., trade name "EXL-2655", core part: butadiene/styrene copolymer, shell part : PMMA/styrene copolymer)

(Example 1 to Example 4 and Comparative Example 1 to Comparative Example 2) ＜Preparation of film adhesive＞ The (a) component, (b) component, (c) component, (d) component, (e) component, and (f) component were prepared in the preparation amounts (unit: parts by mass) shown in Table 1 and calculated as the NV value ([dry It is added to the organic solvent (methyl ethyl ketone) so that the mass of the paint component after drying/[the mass of the paint component before drying] × 100) becomes 60 mass %. Thereafter, zirconium dioxide beads having the same mass of ϕ1.0 mm as the total amount of components (a) to (f) and the organic solvent were added, and the mixture was milled using a ball mill (Fritsch Japan Co., Ltd. Manufactured by the company, planetary micro-pulverizer P-7) stir for 30 minutes. After stirring, the zirconium dioxide beads are removed by filtration to produce a coating varnish.

The obtained coating varnish was applied with a desktop coater (manufactured by HIRANO KINZOKU Co., Ltd.) and dried at 80° C. for 5 minutes to obtain a film-like adhesive with a film thickness of 20 μm.

The following evaluation methods were used to evaluate the adhesive strength and reliability of the film adhesives obtained in the Examples and Comparative Examples, and the warpage of the semiconductor devices produced using them. The evaluation results are shown in Table 1.

＜Measurement of adhesive force＞ Cut the film adhesive into a predetermined size (length 3.2 mm × width 3.2 mm × thickness 0.02 mm), attach it to the silicon wafer (length 3 mm × width 3 mm × thickness 0.725 mm) at 70°C, and use Thermocompression bonding testing machine (manufactured by Hitachi Chemical Electronics Factory Co., Ltd.), crimping (crimping conditions: crimping for 5 seconds at a crimping head temperature of 190°C, then crimping for 5 seconds at a crimping head temperature of 240°C, load 0.5 MPa) to another silicon wafer (length 5 mm × width 5 mm × thickness 0.725 mm). Thereafter, hardening (175° C., 2 hours) was performed in a clean oven (manufactured by ESPEC Co., Ltd.) to obtain a test sample.

The test sample was placed in a constant temperature and humidity chamber (manufactured by ESPEC) at 85°C and 85% relative humidity for 24 hours, and after being taken out, the adhesion force was measured on a hot plate at 250°C. The device (manufactured by DAGE) measures the adhesion force (adhesion force at 250°C after moisture absorption) at a tool height of 0.05 mm from the upper surface of the lower silicon wafer and a tool speed of 0.05 mm/s. ).

<Evaluation of reflow resistance> The film adhesive was cut into a predetermined size (7.3 mm in height × 7.3 mm in width × 0.04 mm in thickness), attached to the bump side of a semiconductor chip with solder bumps (chip size: 7.3 mm in height × 7.3 mm in width × 0.15 mm in thickness, metal of the connection part: copper pillar + solder, bump height (total height of copper pillar + solder): about 45 μm), and mounted using the flip chip mounting device "FCB3" (mounting conditions: after temporary compression bonding at 100℃/0.5 MPa/1 s, the temperature was raised to 180℃/0.5 MPa/2 s, and then at 260℃/0.5 MPa/5 s) on a glass epoxy substrate (thickness of the glass epoxy substrate: 0.42 mm, thickness of the copper wiring: 9 μm) to obtain a semiconductor device. The film adhesive was made 40 μm thick by laminating two sheets of 20 μm thick film. The stage temperature on which the substrate was placed during the press bonding was 80°C. Using a sealing material (manufactured by Hitachi Chemical Co., Ltd., trade name "CEL9750ZHF10"), the semiconductor device was molded under the conditions of 180°C, 6.75 MPa, and 90 seconds, and hardened (175°C, 2 hours) in a clean oven (manufactured by ESPEC) to obtain a test sample.

Next, after processing the test sample under the conditions of Joint Electron Device Engineering Council (JEDEC) Level 2, it was passed through a reflow furnace (Tamura Manufacturing Co., Ltd., with a maximum temperature of 260°C) three times. manufacturing). Use a multimeter (manufactured by CUSTOM) to measure the connection resistance value of the package before and after reflow soldering. When the change in the connection resistance value before and after reflow is 5 Ω or less, the evaluation is "A", and when the change exceeds 5 Ω or the connection is poor, the evaluation is "B".

＜Warp evaluation＞ A semiconductor device was produced using the same method as for the evaluation of reflow resistance and used as a test sample. For the test sample, a non-contact shape measuring device (manufactured by Sony Corporation) was used to measure the shape of both sides in the diagonal direction when the wafer was viewed from above. The difference between the maximum value and the minimum value of the unevenness on each side was defined as the amount of warpage (μm), and the amount of warpage was evaluated using the average value of both sides. The case where the amount of warpage is 70 μm or less is evaluated as "A", and the case where the amount of warpage exceeds 70 μm is evaluated as "B".

[Table 1] Embodiment Comparison Example 1 2 3 4 1 2 (a) Ingredients (a-1) 45 45 45 45 45 45 (a-2) 15 15 15 15 15 15 (a-3) 5 5 5 5 5 5 (b) Ingredients 2 2 2 2 2 2 (c) Ingredients 30 30 30 30 30 30 (d) Ingredients 4 4 4 4 4 4 (e) Ingredients (e-1) 30 30 30 30 30 - (e-2) 45 45 45 45 45 - (f) Ingredients (f-1) 10 - - - - - (f-2) - 10 - - - - (f-3) - - 10 - - - (f-4) - - - 10 - - (f-5) - - - - 10 85 Adhesion force (MPa) 10 10 10 9 10 3 Reflow resistance A A A A A B Curve A A A A B A

From the results shown in Table 1, it was clearly confirmed that the adhesives for semiconductors of Examples 1 to 4 containing inorganic fillers and silicone rubber fillers were more adhesive than the adhesives for semiconductors of Comparative Examples 1 to 2. It has excellent strength and reflow resistance and can achieve low warpage.

10:Semiconductor wafer 15: Wiring (connection part) 20:Substrate (wiring circuit board) 30:Connection bumps 32: Bump (connection part) 34:Through electrode 40:Add materials 50:Intermediate layer 100, 200, 300, 400, 500: semiconductor device

FIG. 1 is a schematic cross-sectional view showing an embodiment of the semiconductor device of the present disclosure. 2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present disclosure. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present disclosure.

10:Semiconductor wafer

15: Wiring (connection part)

20:Substrate (wiring circuit board)

30:Connection bumps

32: Bump (connection part)

40:Add materials

100, 200: Semiconductor devices

Claims (9)

An adhesive for semiconductors, containing a resin with a weight average molecular weight of less than 10,000, a hardener, an inorganic filler and a silicone rubber filler, wherein based on the total solid content of the adhesive for semiconductors, the resin with a weight average molecular weight of less than 10,000 The content is 5% to 75% by mass, the content of the inorganic filler is 20% to 50% by mass, and the content of the silicone rubber filler is 0.1% to 20% by mass. The adhesive for semiconductors according to claim 1, wherein the silicone rubber filler has an average particle size of 30 μm or less. The adhesive for semiconductors according to claim 1 or 2, wherein the inorganic filler contains a silica filler. The adhesive for semiconductors according to claim 1 or 2 further contains a polymer component having a weight average molecular weight of 10,000 or more. The adhesive for semiconductors according to claim 4, wherein the weight average molecular weight of the polymer component is 30,000 or more, and the glass transition temperature of the polymer component is 100°C or less. The adhesive for semiconductors according to claim 1 or 2 is in a film form. The adhesive for semiconductors according to claim 1 or 2, wherein the mass ratio of the content of the silicone rubber filler to the content of the inorganic filler is 0.05 to 0.5. A method of manufacturing a semiconductor device, which is to manufacture semiconductor wafers and components A method of manufacturing a semiconductor device in which connecting portions of line circuit substrates are electrically connected to each other, or a semiconductor device in which connecting portions of a plurality of semiconductor wafers are electrically connected to each other. The method of manufacturing the semiconductor device includes: using the method of claims 1 to 7 The step of sealing at least part of the connection portion with the semiconductor adhesive according to any one of the above. A semiconductor device including: a connection structure in which connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or a connection structure in which connection portions of a plurality of semiconductor wafers are electrically connected to each other; and An adhesive material for sealing at least part of the connection portion, the adhesive material including a cured product of the semiconductor adhesive according to any one of claims 1 to 7.

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