WO2020071391A1

WO2020071391A1 - Adhesive for semiconductors, method for producing semiconductor device, and semiconductor device

Info

Publication number: WO2020071391A1
Application number: PCT/JP2019/038821
Authority: WO
Inventors: 徹弥谷口; 慎佐藤; 幸一茶花
Original assignee: 日立化成株式会社
Priority date: 2018-10-02
Filing date: 2019-10-01
Publication date: 2020-04-09
Also published as: KR20210068412A; JPWO2020071391A1; CN112771659A; TW202033708A; JP7363798B2; KR102629861B1

Abstract

An adhesive for semiconductors, which contains (a) an inorganic filler, and which is configured such that the inorganic filler (a) contains 50% by mass or more of a surface-treated inorganic filler that has a glycidyl group based on the total amount of the inorganic filler (a).

Description

Semiconductor adhesive, method of manufacturing semiconductor device, and semiconductor device

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

Conventionally, a wire bonding method using a thin metal wire such as a gold wire has been widely applied for connecting a semiconductor chip and a substrate. On the other hand, in order to respond to demands for higher functionality, higher integration, higher speed, etc. for semiconductor devices, flip chips that directly connect the semiconductor chip and the substrate by forming conductive protrusions called bumps on the semiconductor chip or the substrate. The connection method (FC connection method) is spreading.

As the FC connection method, a method of bonding a connection to a metal using solder, tin, gold, silver, copper, etc., a method of bonding a connection to a metal by applying ultrasonic vibration, and a mechanical contact by a contraction force of a resin Are known. From the viewpoint of the reliability of the connection portion, a method of metal-joining the connection portion using solder, tin, gold, silver, copper, or the like is generally used.

For example, regarding the connection between the semiconductor chip and the substrate, a COB (Chip On Board) type connection system which is frequently used in BGA (Ball Grid Array), CSP (Chip Size Package) and the like also corresponds to the FC connection system. In the FC connection method, a connection section (bump or wiring) is formed on a semiconductor chip to connect between semiconductor chips, and a connection section (bump or wiring) is formed on a semiconductor wafer. Is widely used also in a COW (Chip \ On \ Wafer) type connection method for connecting a semiconductor chip and a semiconductor wafer (for example, see Patent Document 1).

Further, for packages that are strongly required to be further miniaturized, thinned, and highly functional, chip stack type packages in which the above-described connection methods are stacked and multi-staged, POP (Package On Package), TSV (Through-Silicon Via), and the like. Has also begun to spread widely. In such a stacking / multi-stage technique, since semiconductor chips and the like are arranged three-dimensionally, the size of the package can be reduced as compared with a technique of arranging two-dimensionally. In addition, such a stacking / multi-stage technology is effective in improving the performance of semiconductors, reducing noise, reducing the mounting area, and saving power, and thus has attracted attention as a next-generation semiconductor wiring technology.

JP 2016-102165 A

フ Flip-chip packages, which are becoming more sophisticated, highly integrated, and cost-effective, are expected to expand their applications and production volume in the future. Sustained mass production of flip-chip packages requires the continuous supply of semiconductor adhesives used for them. For this reason, semiconductor adhesives must have excellent stability over time. I have. If the stability over time of the adhesive for semiconductors is poor, the viscosity of the adhesive for semiconductors increases while being left at room temperature, and there is a concern that the mountability at the time of assembling the semiconductor device may deteriorate.

Therefore, the present disclosure is capable of suppressing an increase in viscosity after being left at room temperature, and is unlikely to cause deterioration in mountability when assembling a semiconductor device over time, and a method of manufacturing a semiconductor device using the same. It is an object to provide a semiconductor device.

In order to achieve the above object, the present disclosure provides (a) an inorganic filler, wherein the (a) inorganic filler is a surface-treated inorganic filler having a glycidyl group, and the (a) inorganic filler as a whole. And a semiconductor adhesive containing 50% by mass or more based on the above. According to the adhesive for semiconductors described above, (a) 50% by mass or more of the entire inorganic filler is a surface-treated inorganic filler having a glycidyl group. An increase in viscosity can be suppressed. For example, in the case of an inorganic filler that has been subjected to another surface treatment such as a surface treatment having a methacryl group, the surface treatment agent and moisture easily form a hydrogen bond to increase the viscosity, but the surface treatment having a glycidyl group is difficult. In the case of the applied inorganic filler, it is difficult for hydrogen bonds to be formed with water and the viscosity is unlikely to increase. According to the semiconductor adhesive, an increase in viscosity after standing at room temperature can be suppressed, so that it is possible to suppress the deterioration of the mountability when assembling the semiconductor device over time. In addition, since the inorganic filler is subjected to a surface treatment having a glycidyl group, the inorganic filler has excellent dispersibility in the adhesive for semiconductors, and the adhesive for semiconductors can obtain good adhesive strength and good insulation reliability. it can.

The semiconductor adhesive may further contain (b) an epoxy resin, (c) a curing agent, and (d) a high molecular weight component having a weight average molecular weight of 10,000 or more. Further, the semiconductor adhesive may further contain (e) a flux agent.

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

The present disclosure also provides a method of manufacturing a semiconductor device in which connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or a semiconductor device in which connection portions of a plurality of semiconductor chips are electrically connected to each other. A method for manufacturing a semiconductor device, comprising: a step of sealing at least a part of the connection portion with the semiconductor adhesive. According to the above-mentioned manufacturing method, since the adhesive for semiconductor used is hard to increase in viscosity with time, good mounting performance can be obtained stably.

The present disclosure further includes a connection structure in which connection portions of the semiconductor chip and the wiring circuit board are electrically connected to each other, or a connection structure in which connection portions of a plurality of semiconductor chips are electrically connected to each other, An adhesive material for sealing at least a part of the connection portion, wherein the adhesive material is made of a cured product of the semiconductor adhesive. The above-described semiconductor device has good mountability, and has excellent adhesion and reliability between the semiconductor chip and the printed circuit board or the semiconductor chip.

ADVANTAGE OF THE INVENTION According to this indication, the adhesive agent for semiconductors which can suppress the viscosity increase after leaving room temperature, and which hardly causes the deterioration of mountability at the time of assembling a semiconductor device over time, a method of manufacturing a semiconductor device using the same, and A semiconductor device can be provided.

1 is a schematic cross-sectional view illustrating an embodiment of a semiconductor device according to the present disclosure. FIG. 4 is a schematic cross-sectional view illustrating another embodiment of the semiconductor device of the present disclosure. FIG. 4 is a schematic cross-sectional view illustrating another embodiment of the semiconductor device of the present disclosure. FIG. 4 is a schematic cross-sectional view illustrating another embodiment of the semiconductor device of the present disclosure.

Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the drawings as necessary. In the drawings, the same or corresponding parts have the same reference characters allotted, and overlapping description will be omitted. Unless otherwise specified, the positional relationship such as up, down, left, and right is based on the positional relationship shown in the drawings. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

において In this specification, a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as a minimum value and a maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit or the lower limit of a numerical range in one step can be arbitrarily combined with the upper limit or the lower limit of a numerical range in another step. In the numerical ranges described in this specification, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment. “A or B” may include one of A and B, and may include both. The materials exemplified in the present specification can be used alone or in combination of two or more, unless otherwise specified. In the present specification, “(meth) acryl” means acryl or methacryl corresponding thereto.

<Semiconductor adhesive>
The semiconductor adhesive according to the present embodiment contains (a) an inorganic filler (hereinafter sometimes referred to as “component (a)”). The (a) inorganic filler contains 50% by mass or more of an inorganic filler having a glycidyl group and subjected to a surface treatment, based on the total amount of the (a) inorganic filler. The semiconductor adhesive according to the present embodiment includes (b) an epoxy resin (hereinafter, sometimes referred to as “component (b)”) and (c) a curing agent (hereinafter, sometimes referred to as “component (c)”). ) And (d) one or more of high molecular weight components having a weight average molecular weight of 10,000 or more (hereinafter, sometimes referred to as “component (d)”). Furthermore, the semiconductor adhesive according to the present embodiment may contain (e) a fluxing agent (hereinafter, sometimes referred to as “component (e)”). Hereinafter, each component will be described.

((A) component: inorganic filler)
Examples of the inorganic filler as the component (a) include an insulating inorganic filler. Among them, an inorganic filler having an average particle diameter of 100 nm or less is more preferable. Examples of the material of the insulating inorganic filler include glass, silica, alumina, silica / alumina, titanium oxide, mica, and boron nitride, among which silica, alumina, silica / alumina, titanium oxide, and boron nitride are preferable. Silica, alumina and boron nitride are more preferred. The insulating inorganic filler may be a whisker, and examples of the material of the whisker include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride. The insulating inorganic filler can be used alone or in combination of two or more.

成分 From the viewpoint of improving dispersibility and adhesive strength, the component (a) is preferably a surface-treated filler. Examples of the surface treatment include glycidyl (epoxy), amine, phenyl, phenylamino, acryl, vinyl, and the like.

As the surface treatment, a silane treatment with a silane compound such as an epoxy silane type, an amino silane type or an acryl silane type is preferable from the viewpoint of easy surface treatment. As the surface treatment agent, glycidyl-based, phenylamino-based, and (meth) acryl-based compounds are preferable from the viewpoint of excellent dispersibility and fluidity and further improving the adhesive strength. As the surface treatment agent, a glycidyl-based compound is preferable from the viewpoint of suppressing an increase in the viscosity of the semiconductor adhesive after standing at room temperature.

In the present embodiment, the component (a) contains 50% by mass or more of a surface-treated inorganic filler having a glycidyl group, based on the total amount of the component (a). The surface treatment having a glycidyl group can be performed using a glycidyl-based compound having a structure represented by the following general formula (1) as a surface treatment agent. Thus, the surface of the inorganic filler has a structure represented by the following general formula (1).

In the formula, R represents a divalent organic group.

The content of the inorganic filler subjected to the surface treatment having a glycidyl group is 50% by mass or more based on the total amount of the component (a), and from the viewpoint of further suppressing the increase in the viscosity of the semiconductor adhesive after standing at room temperature, It is preferably at least 60% by mass, more preferably at least 80% by mass. The entire amount (100% by mass) of the component (a) may be a surface-treated inorganic filler having a glycidyl group.

From the viewpoint of improving the visibility (transparency), the average particle diameter of the component (a) is preferably 100 nm or less, and more preferably 60 nm or less. The average particle size of the component (a) can be measured by a laser diffraction type particle size distribution meter.

If the average particle size of the component (a) exceeds 100 nm, the viscosity of the semiconductor adhesive may become too low due to the large particle size, and the semiconductor adhesive may be mounted outside a chip called a fillet after mounting. Of the resin may easily occur. On the other hand, when the average particle size of the component (a) is 100 nm or less, the viscosity of the semiconductor adhesive is easily adjusted to a preferable range, and the generation of fillets is sufficiently suppressed, or the amount of fillets is sufficiently reduced. can do.

下限 The lower limit of the average particle diameter of the component (a) is not particularly limited, but may be 1 nm or more, 5 nm or more, or 10 nm or more from the viewpoint of suppressing aggregation of the component (a). When an inorganic filler that has not been subjected to a surface treatment is used, for example, aggregation may occur even if the average particle size is about 50 nm, but an inorganic filler that has been subjected to a surface treatment having a glycidyl group is used. In this case, even if the average particle size is about 50 nm or less, the occurrence of aggregation can be suppressed.

成分 The component (a) can be used alone or as a mixture of two or more. The shape of the component (a) is not particularly limited.

The content of the component (a) is preferably from 10 to 80% by mass, more preferably from 15 to 60% by mass, and more preferably from 20 to 50% by mass, based on the total solid content of the semiconductor adhesive. It is even more preferred. When the content is 10% by mass or more, the adhesive strength and the reflow resistance tend to be further improved. When the content is 80% by mass or less, the decrease in connection reliability due to thickening tends to be suppressed. .

半導体 The semiconductor adhesive according to the present embodiment may contain a resin filler. Examples of the resin filler include a filler made of a resin such as polyurethane and polyimide. The resin filler has a smaller coefficient of thermal expansion than other organic components (such as an epoxy resin and a curing agent), and thus has an excellent effect of improving connection reliability. Further, according to the resin filler, the viscosity of the semiconductor adhesive can be easily adjusted. Further, the resin filler has an excellent function of relieving stress as compared with the inorganic filler.

から From the viewpoint of insulation reliability, the filler contained in the semiconductor adhesive is preferably insulating. It is preferable that the semiconductor adhesive does not contain a conductive metal filler such as a silver filler and a solder filler. An adhesive for semiconductors (circuit connecting material) that does not contain conductive fillers (conductive particles) is sometimes called NCF (Non-Conductive-FILM) or NCP (Non-Conductive-Paste). The semiconductor adhesive according to the present embodiment can be suitably used as NCF or NCP.

((B) component: epoxy resin)
Examples of the epoxy resin (b) include an epoxy resin having two or more epoxy groups in a molecule, such as a bisphenol A epoxy resin, a bisphenol F epoxy resin, a naphthalene epoxy resin, a phenol novolak epoxy resin, Cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, various polyfunctional epoxy resins and the like can be used. As the component (b), one type can be used alone, or two or more types can be used in combination.

Among the epoxy resins, the bisphenol A type or the bisphenol F type liquid epoxy resin has a 1% thermal weight loss temperature of 250 ° C. or less, and thus may be decomposed when heated at a high temperature to generate volatile components. Therefore, it is preferable to use an epoxy resin that is solid at room temperature (1 atm, 25 ° C.). When using a liquid epoxy resin, it is preferable to use it in combination with a solid epoxy resin.

重量 The weight average molecular weight of the component (b) may be less than 10,000, and from the viewpoint of heat resistance, is preferably 100 or more and less than 10,000, more preferably 300 or more and 8000 or less, and further preferably 300 or more and 5000 or less.

The content of the component (b) is preferably from 10 to 50% by mass, more preferably from 20 to 45% by mass, and still more preferably from 30 to 40% by mass, based on the total solid content of the semiconductor adhesive. It is. When the content of the component (b) is 10% by mass or more, it is easy to sufficiently control the flow of the cured resin. When the content is 50% by mass or less, the resin component of the cured product does not become too large, and Easy to reduce warpage.

半導体 The semiconductor adhesive according to the present embodiment may further contain a thermosetting resin other than the epoxy resin (b). Examples of other thermosetting resins include phenolic resins, imide resins, (meth) acrylic compounds, and the like.

(Component (c): curing agent)
(C) Examples of the curing agent include a phenol resin-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, an imidazole-based curing agent, and a phosphine-based curing agent. When the component (c) contains a phenolic hydroxyl group, an acid anhydride, an amine or an imidazole, it is easy to exhibit a flux activity for suppressing the formation of an oxide film at the connection portion, thereby easily improving connection reliability and insulation reliability. Can be done. Hereinafter, each curing agent will be described.

(Ci) Phenolic resin-based curing agent Examples of the phenolic resin-based curing agent include curing agents having two or more phenolic hydroxyl groups in a molecule, such as phenol novolak resin, cresol novolak resin, phenol aralkyl resin, and cresol naphthol. Formaldehyde polycondensates, triphenylmethane-type polyfunctional phenol resins, various polyfunctional phenol resins, and the like can be used. The phenolic resin-based curing agents can be used alone or in combination of two or more.

The equivalent ratio of the phenolic resin-based curing agent to the component (b) (phenolic hydroxyl group / epoxy group, molar ratio) is preferably from 0.3 to 1.5 from the viewpoint of excellent curability, adhesiveness and storage stability. , 0.4 to 1.0, more preferably 0.5 to 1.0. When the equivalent ratio is 0.3 or more, the curability tends to be improved and the adhesive strength tends to be improved. When the equivalent ratio is 1.5 or less, unreacted phenolic hydroxyl groups do not remain excessively, and the water absorption Is kept low, and the insulation reliability tends to be further improved.

(C-ii) Acid anhydride-based curing agent Examples of the acid anhydride-based curing agent include methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and ethylene glycol bis. Anhydrotrimellitate or the like can be used. The acid anhydride-based curing agent can be used alone or in combination of two or more.

The equivalent ratio of the acid anhydride-based curing agent to the component (b) (acid anhydride group / epoxy group, molar ratio) is from 0.3 to 1.5 from the viewpoint of excellent curability, adhesiveness and storage stability. Is preferably, 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is more preferable. When the equivalent ratio is 0.3 or more, the curability tends to be improved and the adhesive strength tends to be improved. When the equivalent ratio is 1.5 or less, the unreacted acid anhydride does not remain excessively, and the water absorption Is kept low, and the insulation reliability tends to be further improved.

(C-iii) Amine-based curing agent As the amine-based curing agent, dicyandiamide, various amine compounds, and the like can be used.

The equivalent ratio of the amine-based curing agent to the component (b) (amine / epoxy group, molar ratio) is preferably from 0.3 to 1.5 from the viewpoint of excellent curability, adhesion and storage stability. -1.0 is more preferable, and 0.5-1.0 is more preferable. When the equivalent ratio is 0.3 or more, the curability tends to be improved and the adhesive strength tends to be improved. When the equivalent ratio is 1.5 or less, unreacted amine does not remain excessively, and insulation reliability is improved. There is a tendency to further improve.

(C-iv) Imidazole curing agent Examples of the imidazole curing agent include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, Cyanoethyl-2-undecylimidazole, 1-cyano-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-to Azine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5- Examples include dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, adducts of epoxy resins and imidazoles, and the like. Among these, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellit, from the viewpoint of further improving curability, storage stability and connection reliability. Tate, 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 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenylimidazole Preferred is phenyl-4-methyl-5-hydroxymethylimidazole. The imidazole-based curing agents can be used alone or in combination of two or more. Further, these may be used as a latent curing agent obtained by microencapsulation.

The content of the imidazole-based curing agent is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the component (b). When the content of the imidazole-based curing agent is 0.1 part by mass or more, the curability tends to be improved, and when the content is 20 parts by mass or less, the adhesive composition is cured before metal bonding is formed. And there is a tendency that poor connection hardly occurs.

(Cv) Phosphine-based curing agent Examples of the phosphine-based curing agent include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (4-methylphenyl) borate, and tetraphenylphosphonium (4-fluorophenyl) borate. Is mentioned.

The content of the phosphine-based curing agent is preferably from 0.1 to 10 parts by mass, more preferably from 0.1 to 5 parts by mass, per 100 parts by mass of the component (b). When the content of the phosphine-based curing agent is 0.1 part by mass or more, the curability tends to be improved, and when the content is 10 parts by mass or less, the semiconductor adhesive is cured before metal bonding is formed. And there is a tendency that poor connection hardly occurs.

The phenolic resin-based curing agent, acid anhydride-based curing agent, and amine-based curing agent can be used alone or in combination of two or more. The imidazole-based curing agent and the phosphine-based curing agent may be used alone, but may be used together with a phenolic resin-based curing agent, an acid anhydride-based curing agent, or an amine-based curing agent.

As the component (c), from the viewpoint of excellent curability, a combined use of a phenolic resin-based curing agent and an imidazole-based curing agent, a combined use of an acid anhydride-based curing agent and an imidazole-based curing agent, an amine-based curing agent and an imidazole-based curing agent And the use of an imidazole-based curing agent alone is preferred. Since the productivity is improved when the connection is made in a short time, it is more preferable to use an imidazole-based curing agent having excellent quick-curing properties alone. In this case, when cured in a short time, volatile components such as low molecular components can be suppressed, so that the generation of voids can be easily suppressed.

(Component (d): high molecular weight component having a weight average molecular weight of 10,000 or more)
(D) The high molecular weight component having a weight average molecular weight of 10,000 or more (excluding the compound corresponding to the component (b)) includes phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, (meth) acrylic resin, Polyester resin, polyethylene resin, polyether sulfone resin, polyetherimide resin, polyvinyl acetal resin, polyurethane resin, acrylic rubber, and the like, among which, from the viewpoint of excellent heat resistance and film formability, phenoxy resin, polyimide resin, (Meth) acrylic resin, acrylic rubber, cyanate ester resin and polycarbodiimide resin are preferred, phenoxy resin, polyimide resin, (meth) acrylic resin and acrylic rubber are more preferred, and phenoxy resin is even more preferred. The component (d) may be used alone or as a mixture or copolymer of two or more.

The mass ratio of the component (d) to the component (b) is not particularly limited, but from the viewpoint of maintaining a good film shape, the content of the component (b) is 1 part by mass of the component (d). The amount is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and even more preferably 0.1 to 3 parts by mass. When the content of the component (b) is 0.01 parts by mass or more, the curability does not decrease, and the adhesive strength does not decrease. When the content is 5 parts by mass or less, the film formability and the film are reduced. The formability does not decrease.

The weight average molecular weight of the component (d) is 10,000 or more in terms of polystyrene, but is preferably 30,000 or more, more preferably 40,000 or more, and still more preferably 50,000 or more, in order to show good film-forming properties by itself. When the weight average molecular weight is 10,000 or more, there is no possibility that the film forming property is reduced. In the present specification, the weight-average molecular weight means a weight-average molecular weight measured by high-performance liquid chromatography (Shimadzu Corporation, CR4A) in terms of polystyrene.

(Component (e): flux agent)
The semiconductor adhesive may further contain (e) a flux agent which is a compound exhibiting flux activity (activity for removing oxides, impurities, and the like). Examples of the flux agent include nitrogen-containing compounds having an unshared electron pair (imidazoles, amines, etc., except those contained in the component (c)), carboxylic acids, phenols, alcohols, and the like. Note that carboxylic acids exhibit stronger flux activity than alcohols, and are more likely to improve connectivity.

From the viewpoint of solder wettability, the content of the component (e) is preferably from 0.2 to 3% by mass, and more preferably from 0.4 to 1.8% by mass, based on the total solid content of the semiconductor adhesive. Is more preferable.

接着 The semiconductor adhesive may further contain an ion trapper, an antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, and the like. These may be used alone or in combination of two or more. What is necessary is just to adjust suitably these compounding quantities so that the effect of each additive may be exhibited.

The shear viscosity at 80 ° C. when the semiconductor adhesive is formed into a film is preferably 4500 to 14000 Pa · s, more preferably 5000 to 13000 Pa · s, and more preferably 5000 to 10000 Pa · s. More preferred. When the shear viscosity is 4500 Pa · s or more, generation of fillets can be sufficiently suppressed, or the amount of fillets can be sufficiently reduced. When the shear viscosity is 14000 Pa · s or less, the mountability at the time of assembling the semiconductor device can be improved. The shear viscosity of the film-form semiconductor adhesive can be measured, for example, by using a dynamic shear viscoelasticity measuring device (trade name “ARES-G2” manufactured by TA Instruments Japan Co., Ltd.). It can be measured under the conditions of 10 ° C./min, a measurement temperature range of 30 ° C. to 145 ° C., and a frequency of 10 Hz. The value of the viscosity at 80 ° C. of the viscosity value measured by the above method can be determined as the shear viscosity at 80 ° C. when the adhesive for a semiconductor is formed into a film.

<Production method of semiconductor adhesive>
The adhesive for semiconductors according to the present embodiment is preferably in the form of a film (film-like adhesive) from the viewpoint of improving productivity. The method for producing the film adhesive will be described below.

First, (a) component, (b) component, (c) component, (d) component, and other components as necessary are added to an organic solvent, and then dissolved or dispersed by stirring, mixing, kneading, or the like. Prepare a resin varnish. Then, after applying a resin varnish using a knife coater, a roll coater, an applicator, a die coater, a comma coater, or the like on the release-treated base film, the organic solvent is reduced by heating, and the base film is removed. Form a film adhesive on top. In addition, before the organic solvent is reduced by heating, a film adhesive may be formed on the wafer by a method of spin-coating a resin varnish on a wafer or the like to form a film, and then drying the solvent.

As the organic solvent used for preparing the resin varnish, those having properties capable of uniformly dissolving or dispersing each component are preferable, for example, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, diethylene glycol dimethyl ether, Examples include 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. The stirring, mixing and kneading at the time of preparing the resin varnish can be performed using, for example, a stirrer, a raker, a three-roll, a ball mill, a bead mill or a homodisper.

The substrate film is not particularly limited as long as it has heat resistance enough to withstand the heating conditions when the organic solvent is volatilized, and polyester film, polypropylene film, polyethylene terephthalate film, polyimide film, polyetherimide film, polyether Ether naphthalate film, methylpentene film and the like can be mentioned. The base film is not limited to a single layer made of one of these films, and may be a multilayer film made of two or more films.

(4) As conditions for evaporating the organic solvent from the resin varnish after application, specifically, it is preferable to perform heating at 50 to 200 ° C. for 0.1 to 90 minutes. It is preferable that the organic solvent is volatilized to 1.5% by mass or less as long as there is no effect on the voids, viscosity adjustment, and the like after mounting.

フィルム The thickness of the film in the film adhesive according to the present embodiment is preferably from 10 to 100 μm, and more preferably from 20 to 50 μm, from the viewpoint of visibility, fluidity, and filling property.

<Semiconductor device>
The semiconductor adhesive according to the present embodiment is preferably used for a semiconductor device, and a semiconductor device in which electrodes of respective connection portions of a semiconductor chip and a wiring circuit board are electrically connected to each other, or a plurality of semiconductor chips. In a semiconductor device in which electrodes of respective connection portions are electrically connected to each other, it is particularly suitably used for sealing the connection portions. Hereinafter, a semiconductor device using the semiconductor adhesive according to the present embodiment will be described. The electrodes of the connection portion in the semiconductor device may be either a metal joint between the bump and the wiring or a metal joint between the bump and the bump. In a semiconductor device, for example, flip-chip connection for obtaining electrical connection via a semiconductor adhesive may be used.

FIG. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device (COB-type connection between a semiconductor chip and a substrate). As shown in FIG. 1A, the first semiconductor device 100 is arranged on a semiconductor chip 10 and a substrate (wiring circuit board) 20 facing each other, and on a surface of the semiconductor chip 10 and the substrate 20 facing each other. Wiring 15, connecting bumps 30 for connecting the wiring 15 of the semiconductor chip 10 and the wiring 20 of the substrate 20 to each other, and an adhesive material 40 that fills the gap between the semiconductor chip 10 and the substrate 20 without gaps. The semiconductor chip 10 and the substrate 20 are flip-chip connected by the wiring 15 and the connection bump 30. The wiring 15 and the connection bump 30 are sealed with an adhesive material 40 and are shielded from an external environment. The adhesive material 40 is a cured product of the semiconductor adhesive of the present embodiment.

As shown in FIG. 1B, the second semiconductor device 200 is disposed on the semiconductor chip 10 and the substrate (wiring circuit substrate) 20 facing each other, and on the surfaces of the semiconductor chip 10 and the substrate 20 facing each other. And a bonding material 40 that fills the gap between the semiconductor chip 10 and the substrate 20 without any gap. The semiconductor chip 10 and the substrate 20 are flip-chip connected by connecting the opposing bumps 32 to each other. The bump 32 is sealed with an adhesive material 40 and is shielded from an external environment.

FIG. 2 is a schematic sectional view showing another embodiment of the semiconductor device (COC type connection between semiconductor chips). As shown in FIG. 2A, the third semiconductor device 300 is the same as the first semiconductor device 100 except that two semiconductor chips 10 are flip-chip connected by wirings 15 and connection bumps 30. It is. As shown in FIG. 2B, the fourth semiconductor device 400 is similar to the second semiconductor device 200 except that two semiconductor chips 10 are flip-chip connected by bumps 32.

The semiconductor chip 10 is not particularly limited, and various semiconductors such as element semiconductors composed of the same kind of elements such as silicon and germanium, and compound semiconductors such as gallium / arsenic and indium / phosphorus can be used.

The substrate 20 is not particularly limited as long as it is a printed circuit board, and is formed on the surface of an insulating substrate mainly composed of glass epoxy resin, polyimide resin, polyester resin, ceramic, epoxy resin, bismaleimide triazine resin and the like. A circuit board having wiring (wiring pattern) formed by removing unnecessary portions of the metal layer by etching, a circuit board having wiring (wiring pattern) formed on the surface of the insulating substrate by metal plating or the like, and a surface of the insulating substrate. A circuit board or the like on which a conductive material is printed to form a wiring (wiring pattern) can be used.

Connections such as the wiring 15 and the bumps 32 are mainly composed of gold, silver, copper, solder (for example, tin-silver, tin-lead, tin-bismuth, tin-copper), nickel, tin, lead, etc. And may contain a plurality of metals.

On the surface of the wiring (wiring pattern), gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc. are main components. A metal layer may be formed. This metal layer may be composed of only a single component, or may be composed of a plurality of components. Further, a structure in which a plurality of metal layers are stacked may be employed. Copper and solder are generally used because they are inexpensive. Since copper and solder contain oxides and impurities, the semiconductor adhesive preferably has flux activity.

The material of the conductive protrusions called bumps is mainly composed of gold, silver, copper, solder (for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc. And may be composed of only a single component, or may be composed of a plurality of components. Further, these metals may be formed so as to form a laminated structure. The bump may be formed on a semiconductor chip or a substrate. Copper and solder are generally used because they are inexpensive. Since copper and solder contain oxides and impurities, the semiconductor adhesive preferably has flux activity.

Further, a semiconductor device (package) as shown in FIG. 1 or FIG. 2 is laminated, and gold, silver, copper, solder (for example, tin-silver, tin-lead, tin-bismuth, tin-copper), You may electrically connect with tin, nickel, etc. For example, as in the case of the TSV technology, an adhesive may be flip-chip connected or laminated between semiconductor chips to form a hole penetrating the semiconductor chip and connect to the electrode on the pattern surface.

FIG. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device (semiconductor chip stacked type (TSV)). As shown in FIG. 3, in the fifth semiconductor device 500, the wiring 15 formed on the interposer 50 is connected to the wiring 15 of the semiconductor chip 10 via the connection bumps 30, so that the semiconductor chip 10 and the interposer 50 are connected. Is flip-chip connected. The gap between the semiconductor chip 10 and the interposer 50 is filled with the adhesive material 40 without any gap. On the surface of the semiconductor chip 10 opposite to the interposer 50, the semiconductor chip 10 is repeatedly laminated via the wiring 15, the connection bump 30, and the adhesive material 40. The wirings 15 on the pattern surface on the front and back sides of the semiconductor chip 10 are connected to each other by through electrodes 34 filled in holes passing through the inside of the semiconductor chip 10. The material of the through electrode 34 may be copper, aluminum, or the like.

信号 With such TSV technology, signals can be obtained even from the back surface of a semiconductor chip that is not normally used. Furthermore, since the penetrating electrodes 34 pass vertically through the semiconductor chip 10, the distance between the opposing semiconductor chips 10 or the distance between the semiconductor chip 10 and the interposer 50 can be shortened, and flexible connection is possible. In such TSV technology, the semiconductor adhesive according to the present embodiment is suitably used as a sealing material between the opposing semiconductor chips 10 or between the semiconductor chip 10 and the interposer 50.

<Semiconductor device manufacturing method>
In the method for manufacturing a semiconductor device according to the present embodiment, a semiconductor chip and a wiring circuit board or a plurality of semiconductor chips are connected to each other using the semiconductor adhesive according to the present embodiment. The method of manufacturing a semiconductor device according to the present embodiment includes, for example, connecting a semiconductor chip and a wiring circuit board to each other via a semiconductor adhesive and electrically connecting respective connection portions of the semiconductor chip and the wiring circuit board to each other. Obtaining a semiconductor device by connecting the plurality of semiconductor chips to each other via a semiconductor adhesive and electrically connecting respective connection portions of the plurality of semiconductor chips to each other to obtain a semiconductor device.

In the method for manufacturing a semiconductor device according to the present embodiment, the connection portions can be connected to each other by metal bonding. That is, the connection portions of the semiconductor chip and the printed circuit board are connected to each other by metal bonding, or the connection portions of the plurality of semiconductor chips are connected to each other by metal bonding.

として As an example of the method of manufacturing the semiconductor device according to the present embodiment, a method of manufacturing the sixth semiconductor device 600 shown in FIG. 4 will be described. In the sixth semiconductor device 600, a substrate (for example, a glass epoxy substrate) 60 having a wiring (copper wiring) 15 and a semiconductor chip 10 having a wiring (for example, copper pillar, copper post) 15 are bonded to each other via an adhesive material 40. It is connected. The wiring 15 of the semiconductor chip 10 and the wiring 15 of the substrate 60 are electrically connected by connection bumps (solder bumps) 30. The solder resist 70 is arranged on the surface of the substrate 60 where the wiring 15 is formed, except for the position where the connection bump 30 is formed.

In the method of manufacturing the sixth semiconductor device 600, first, a semiconductor adhesive (such as a film adhesive) is attached to the substrate 60 on which the solder resist 70 is formed. The sticking can be performed by heating press, roll lamination, vacuum lamination, or the like. The supply area and the thickness of the semiconductor adhesive are appropriately set according to the size of the semiconductor chip 10 or the substrate 60, the bump height, and the like. The semiconductor adhesive may be adhered to the semiconductor chip 10. The semiconductor adhesive may be adhered to the semiconductor wafer, and the semiconductor chip 10 may be diced into individual semiconductor chips 10. May be produced. In this case, if a semiconductor adhesive having a high light transmittance is used, the visibility can be ensured even when the alignment mark is covered, so that the adhesive can be applied not only on the semiconductor wafer (semiconductor chip) but also on the substrate. It is not restricted and has excellent handling properties.

After the semiconductor adhesive is attached to the substrate 60 or the semiconductor chip 10, the connection bumps 30 on the wiring 15 of the semiconductor chip 10 and the wiring 15 of the substrate 60 are aligned using a connection device such as a flip chip bonder. . Then, the semiconductor chip 10 and the substrate 60 are pressed while being heated at a temperature equal to or higher than the melting point of the connection bump 30 (when solder is used for the connection portion, it is preferably applied to the solder portion at 240 ° C. or higher). At the same time, the semiconductor adhesive is cured, and the gap between the semiconductor chip 10 and the substrate 60 is sealed and filled with the adhesive material 40 made of a cured product of the semiconductor adhesive. The connection load depends on the number of bumps, but is set in consideration of bump height variation absorption, control of the amount of bump deformation, and the like. The connection time is preferably short from the viewpoint of improving productivity. It is preferable that the solder is melted, an oxide film, impurities on the surface and the like are removed, and a metal joint is formed at the connection portion.

The short connection time (crimping time) means that the time required for the connection portion to be 240 ° C. or more (for example, the time when solder is used) is 10 seconds or less during the connection formation (final pressure bonding). The connection time is preferably 5 seconds or less, more preferably 3 seconds or less.

In the method of manufacturing a semiconductor device according to the present embodiment, the semiconductor chip and the substrate are temporarily fixed after alignment (in a state in which the semiconductor adhesive is interposed), and are heated in a reflow furnace to melt the solder bumps, thereby bonding the semiconductor chip and the substrate. The semiconductor device may be manufactured by connecting. Temporary fixing does not require a significant need to form a metal bond, so that a lower load, a shorter time, and a lower temperature may be used as compared to the above-described full pressure bonding, and advantages such as improved productivity and prevention of deterioration of the connection portion are generated. . After connecting the semiconductor chip and the substrate, heat treatment may be performed in an oven or the like to further cure the semiconductor adhesive. The heating temperature is a temperature at which the curing of the semiconductor adhesive proceeds, and is preferably substantially complete. The heating temperature and the heating time may be set as appropriate.

The method for manufacturing a semiconductor device according to this embodiment includes a semiconductor chip, a substrate, another semiconductor chip, or a semiconductor wafer including a portion corresponding to another semiconductor chip, and a semiconductor adhesive disposed therebetween. (Film adhesive), and sandwiching the laminate, in which the connection portion of the semiconductor chip and the connection portion of the substrate or another semiconductor chip are arranged to face each other, between a pair of opposing temporary pressure-pressing pressing members. Heating and pressurizing, thereby temporarily bonding a substrate, another semiconductor chip or a semiconductor wafer to the semiconductor chip (temporary pressure bonding step), and connecting a connection portion of the semiconductor chip and a connection portion of the substrate or another semiconductor chip to a metal. And a step of electrically connecting by bonding (final pressure bonding step).

In the above manufacturing method, at least one of the pair of temporary pressing members used in the temporary pressing step, when heating and pressing the laminate, is formed of a metal material forming a surface of a connection portion of the semiconductor chip. The substrate is heated to a temperature lower than the melting point and the melting point of the metal material forming the surface of the connection portion of the substrate or other semiconductor chip.

On the other hand, in the final pressure bonding step, the laminate has a melting point of the metal material forming the surface of the connection portion of the semiconductor chip or the melting point of the metal material forming the surface of the connection portion of the substrate or another semiconductor chip. Heating is performed to at least one of the melting points or more. Here, the final pressure bonding step can be performed, for example, by the following method.

(First method)
The laminated body is heated and pressed by sandwiching it between a pair of opposing pressing members, which are prepared separately from the temporary pressing member, thereby connecting the connection portion of the semiconductor chip to the substrate or another semiconductor chip. The parts are electrically connected by metal bonding. In this case, at least one of the pair of pressure-bonding pressing members, when heating and pressing the laminate, the melting point of the metal material forming the surface of the connection portion of the semiconductor chip, or the substrate or other semiconductor chip. The heating is performed to a temperature equal to or higher than at least one of the melting points of the metal material forming the surface of the connection portion.

According to the above method, the step of temporarily press-bonding at a temperature lower than the melting point of the metal material forming the surface of the connection portion, and the final press-bonding at a temperature equal to or higher than the melting point of the metal material forming the surface of the connection portion By performing the process and the pressing using different pressing members for pressing, the time required for heating and cooling each pressing member for pressing can be reduced. Therefore, a semiconductor device can be manufactured with higher productivity in a shorter time than when crimping is performed with one crimping pressing member. As a result, many highly reliable semiconductor devices can be manufactured in a short time. Connections can be made collectively in the final pressure bonding step. In the case of performing the collective connection, in the final press bonding, a larger number of semiconductor chips are pressed than in the temporary press, so that a pressing member having a larger pressing head with a larger area can be used. When the plurality of semiconductor chips can be permanently pressed together to secure the connection, the productivity of the semiconductor device is improved.

(Second method)
A pressure bonding head facing a stage and a batch connection sheet arranged so as to cover the plurality of laminates or a plurality of semiconductor chips, a semiconductor wafer, and a laminate having an adhesive disposed on the stage By heating and pressurizing the plurality of stacked bodies at once, the connection portion of the semiconductor chip and the connection portion of the substrate or another semiconductor chip are electrically connected by metal bonding. In this case, at least one of the stage and the pressure bonding head is formed of the melting point of the metal material forming the surface of the connection portion of the semiconductor chip, or of the metal material forming the surface of the connection portion of the substrate or another semiconductor chip. The heating is performed to a temperature equal to or higher than at least one of the melting points.

According to the above method, in the case where a plurality of semiconductor chips and a plurality of substrates, a plurality of other semiconductor chips, or a semiconductor wafer are collectively press-bonded together, the ratio of semiconductor devices having poor connection can be reduced.

The raw material of the sheet for collective connection is not particularly limited, for example, polytetrafluoroethylene resin, polyimide resin, phenoxy resin, epoxy resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, polyethylene resin, poly Examples include an ether sulfone resin, a polyetherimide resin, a polyvinyl acetal resin, a urethane resin, and an acrylic rubber. The sheet for collective connection is selected from a polytetrafluoroethylene resin, a polyimide resin, an epoxy resin, a phenoxy resin, an acrylic resin, an acrylic rubber, a cyanate ester resin, and a polycarbodiimide resin from the viewpoint of excellent heat resistance and film formability. It may be a sheet containing at least one resin. The resin for the sheet for collective connection is a sheet containing at least one resin selected from polytetrafluoroethylene resin, polyimide resin, phenoxy resin, acrylic resin and acrylic rubber, from the viewpoint of particularly excellent heat resistance and film formability. There may be. These resins can be used alone or in combination of two or more.

(Third method)
The laminated body is heated in a heating furnace or on a hot plate, and the melting point of the metal material forming the surface of the connection portion of the semiconductor chip, or the melting point of the metal material forming the surface of the connection portion of the substrate or another semiconductor chip. Heat to a temperature that is at least one of the melting points.

も Also in the case of the above method, the time required for heating and cooling of the pressing member for provisional pressure bonding can be reduced by separately performing the provisional pressure bonding step and the main pressure bonding step. Therefore, a semiconductor device can be manufactured with higher productivity in a shorter time than when crimping is performed with one crimping pressing member. As a result, many highly reliable semiconductor devices can be manufactured in a short time. Further, in the above method, a plurality of laminates may be heated collectively in a heating furnace or on a hot plate. Thereby, a semiconductor device can be manufactured with higher productivity.

In such a manufacturing method in which the temporary press-bonding step and the main press-bonding step are separately performed, after the plurality of laminates are temporarily press-bonded, the plurality of temporarily-pressed laminates can be fully press-bonded collectively. In addition, it is required that, for example, of the plurality of laminates, the one subjected to temporary compression bonding first and the one subjected to temporary compression bonding last do not vary in quality after the final compression bonding. That is, since the first pre-compressed product is held in the pre-compressed state longer than the last pre-compressed product, the semiconductor adhesive used has a viscosity from the beginning to the end of the pre-compression process. It is required that the increase hardly occurs. The adhesive for semiconductors (film-like adhesive) according to the present embodiment can suppress the increase in viscosity over time, and thus can satisfy the above requirements and can be suitably used in the above manufacturing method.

Hereinafter, the present disclosure will be described more specifically with reference to examples. However, the present disclosure is not limited to these examples.

The compounds used in each of the examples and comparative examples are as follows.
(A) Inorganic filler / epoxy surface treated nano-silica filler (inorganic filler having a glycidyl group and surface treatment, manufactured by Admatex Co., Ltd., trade name "50 nm SE-AH1", average particle size: about 50 nm, hereinafter referred to as "SE" It is called nano-silica.)
-Methacryl surface-treated nano silica filler (trade name "50 nm YA050C-HGF", manufactured by Admatechs Co., Ltd., average particle size: about 50 nm, hereinafter referred to as "YA nano silica")

(B) Epoxy resin / triphenolmethane skeleton-containing polyfunctional solid epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name “EP1032H60”, hereinafter referred to as “EP1032”)
-Flexible epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "YL7175", hereinafter referred to as "YL7175")

(C) Curing agent • 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct (trade name “2MAOK-PW manufactured by Shikoku Chemical Industry Co., Ltd.) , "Hereinafter referred to as" 2MAOK ".)

(D) A high molecular weight component / acrylic resin having a weight average molecular weight of 10,000 or more (trade name “Clarity LA4285”, manufactured by Kuraray Co., Ltd., Mw / Mn = 1.28, weight average molecular weight Mw: 80000, hereinafter referred to as “LA4285”)

(E) Flux agent / glutaric acid (manufactured by Sigma-Aldrich Japan G.K., melting point: about 97 ° C)

<Preparation of film adhesive>
(Example 1)
12.4 g of epoxy resin “EP1032”, 0.72 g of “YL7175”, 0.9 g of curing agent “2MAOK”, 1.2 g of glutaric acid, 33.9 g of inorganic filler “SE nanosilica”, 6.0 g of acrylic resin “LA4285”, And cyclohexanone (the amount of the solid content in the resin varnish becomes 49% by mass) is charged, and zirconia beads having a diameter of 1.0 mm are added in the same mass as the solid content, and a bead mill (Fritsch Japan K.K. The mixture was stirred for 30 minutes at P-7). Thereafter, the zirconia beads used for stirring were removed by filtration to obtain a resin varnish.

The obtained resin varnish is coated on a base film (manufactured by Teijin Dupont Film Co., Ltd., trade name "Purex A54") using a small precision coating apparatus (manufactured by Yasui Seiki Co., Ltd.), and the coated resin is coated. The varnish was dried (100 ° C./5 minutes) in a clean oven (manufactured by Espec Corporation) to obtain a film adhesive. The thickness was made 0.02 mm.

(Example 2)
A film-like adhesive was produced in the same manner as in Example 1, except that the amount of the inorganic filler “SE nanosilica” was reduced to 17 g and the amount of the inorganic filler “YA nanosilica” was added 17 g.

(Comparative Example 1)
A film-like adhesive was produced in the same manner as in Example 1 except that the inorganic filler “SE nanosilica” was eliminated and 33.9 g of the inorganic filler “YA nanosilica” was added.

Table 1 shows the compositions (unit: g) of Examples 1 and 2 and Comparative Example 1 collectively.

<Evaluation>
Hereinafter, evaluation methods of the film adhesives obtained in Examples and Comparative Examples will be described.

(1) Preparation of Shear Viscosity Measurement Sample The prepared film-like adhesive was applied to a desktop laminator (trade name “Hot Dog GK-13DX” manufactured by Mirror Corporation) until the total thickness became 0.4 mm (400 μm). A plurality of sheets were laminated (laminated) and cut out into a size of 7.3 mm in length and 7.3 mm in width to obtain a measurement sample.

(2) Measurement of Shear Viscosity The shear viscosity of the obtained measurement sample was measured by a dynamic shear viscoelasticity measuring device (trade name “ARES-G2” manufactured by TA Instruments Japan Co., Ltd.). . The measurement was performed at a heating rate of 10 ° C./min, a measuring temperature range of 30 ° C. to 145 ° C., and a frequency of 10 Hz, and the viscosity at 80 ° C. was read. In the same manner, the shear viscosity of the measurement sample left at room temperature (23 ° C., 50% RH) for 4 weeks was measured. Table 2 shows the measurement results of shear viscosity before and after standing at room temperature and the rate of increase in viscosity before and after standing at room temperature.

According to the evaluation results in Table 2, the viscosity of the film adhesives of Examples 1 and 2 in which the surface-treated inorganic filler having a glycidyl group accounts for 50% by mass or more of the entire inorganic filler is increased before and after being left at room temperature. The rate was 20% or less, and it was confirmed that the increase in viscosity over time was suppressed. In the film-like adhesives of Examples 1 and 2, the increase in viscosity with time is suppressed, and therefore, the mounting property at the time of assembling the semiconductor device hardly deteriorates with time. On the other hand, in the case of the film adhesive of Comparative Example 1 in which the surface-treated inorganic filler having a glycidyl group is less than 50% by mass of the entire inorganic filler, the viscosity increase before and after standing at room temperature is 80% or more, and It was found that the viscosity easily increased.

DESCRIPTION OF SYMBOLS 10 ... Semiconductor chip, 15 ... Wiring, 20, 60 ... Substrate, 30 ... Connection bump, 32 ... Bump, 34 ... Through electrode, 40 ... Adhesive material, 50 ... Interposer, 70 ... Solder resist, 100, 200, 300, 400 , 500, 600 ... semiconductor devices.

Claims

(A) an adhesive for semiconductors, comprising an inorganic filler, wherein the (a) inorganic filler contains a glycidyl group-treated surface-treated inorganic filler in an amount of 50% by mass or more based on the total amount of the (a) inorganic filler. Agent.
The adhesive for semiconductors according to claim 1, further comprising: (b) an epoxy resin, (c) a curing agent, and (d) a high molecular weight component having a weight average molecular weight of 10,000 or more.
The adhesive for semiconductors according to claim 1 or 2, further comprising (e) a flux agent.
接着 The semiconductor adhesive according to any one of claims 1 to 3, which is in the form of a film.
A method of manufacturing a semiconductor device in which connection portions of a semiconductor chip and a wiring circuit board are electrically connected to each other, or a semiconductor device in which connection portions of a plurality of semiconductor chips are electrically connected to each other,
A method for manufacturing a semiconductor device, comprising a step of sealing at least a part of the connection portion with the semiconductor adhesive according to any one of claims 1 to 4.
A connection structure in which connection portions of the semiconductor chip and the wiring circuit board are electrically connected to each other, or a connection structure in which connection portions of the plurality of semiconductor chips are electrically connected to each other;
An adhesive material for sealing at least a part of the connection portion,
A semiconductor device, wherein the adhesive material comprises a cured product of the semiconductor adhesive according to any one of claims 1 to 4.