JP7415536B2 - Resin composition, resin film, semiconductor laminate, method for manufacturing semiconductor laminate, semiconductor device, and method for manufacturing semiconductor device - Google Patents

Description

The present invention relates to a resin composition, a resin film, a semiconductor laminate, a method for manufacturing a semiconductor laminate, a semiconductor device, and a method for manufacturing a semiconductor device.

In recent years, the semiconductor industry has begun to pay attention to the dielectric properties of materials in order to support high frequency applications in mobile devices such as smartphones. In epoxy-phenol curing systems and epoxy-acid anhydride curing systems that have been commonly used in semiconductor encapsulating materials, hydroxyl groups are generated after crosslinking reactions, but these hydroxyl groups degrade dielectric properties. When the crosslinking density is lowered to reduce the number of hydroxyl groups, the adhesive strength required of the sealing material decreases, making it difficult to improve performance in a well-balanced manner. On the other hand, although it is known that introducing fluorine atoms improves dielectric properties, adhesive strength tends to decrease.

Therefore, a resin composition that maintains adhesive strength and has low dielectric loss, and a wafer molding material using the same that has good wafer protection performance have been desired.

The present invention has been made in view of the above problems, and includes a composition that provides a resin film with high adhesive strength, low dielectric loss, and low warpage, a resin film obtained from the composition, and a resin film obtained from the resin film. It is an object of the present invention to provide a semiconductor laminate including a cured product, a method for manufacturing the same, a semiconductor device in which the semiconductor laminate is cut into pieces, and a method for manufacturing the same.

As a result of intensive studies to achieve the above object, the present inventors found that (A) an epoxy resin having an epoxy equivalent of 140 to 5,000 g/eq, (B) a phenolic curing agent, and (C) curing. By combining an accelerator, (D) a modifier that is a compound with a specific structure, and (E) an inorganic filler, a composition that provides a resin film with high adhesive strength, low dielectric loss, and low warpage can be obtained. I found out that it can be done. Furthermore, the inventors have discovered that by forming the resin composition into a film, it becomes a wafer molding material that can be handled more easily, and the present invention has been completed.

（式中、Ｒは、炭素数１０～５０のヒドロカルビル基である。Ｑは、エーテル結合、エステル結合、カルボニル基又はチオエーテル結合である。Ｌは、酸素原子を含んでいてもよい炭素数１～２０のヒドロカルビレン基である。Ｔは、反応性官能基である。ｍは、１～３の整数である。ｍが２又は３のとき、各Ｌ及び各Ｔは、互いに同一であってもよく、異なっていてもよい。）
２．Ｔが、エポキシ基、オキセタン基又はアルコキシシリル基である１の樹脂組成物。
３．Ｑが、エーテル結合又はエステル結合である１又は２の樹脂組成物。
４．（Ａ）成分が、シルフェニレン及び／又はシリコーン変性エポキシ樹脂である１～３のいずれかの樹脂組成物。
５．前記シルフェニレン及び／又はシリコーン変性エポキシ樹脂が、下記式（Ａ）で表されるものである４の樹脂組成物。

［式中、Ｒ¹～Ｒ⁶は、それぞれ独立に、炭素数１～２０のヒドロカルビル基又はヒドロカルビルオキシ基である。ａ、ｂ、ｃ、ｄ及びｅは、各繰り返し単位の組成比を表し、０＜ａ＜１、０≦ｂ＜１、０≦ｃ＜１、０≦ｄ＜１、０≦ｅ＜１、０.６７≦(ｂ＋ｄ)／(ａ＋ｃ＋ｅ)≦１.６７、かつａ＋ｂ＋ｃ＋ｄ＋ｅ＝１を満たす数である。ｋは、０～３００の整数である。Ｘ¹は、下記式（Ｘ１）で表される２価の基である。Ｘ²は、下記式（Ｘ２）で表される２価の基である。Ｘ³は、下記式（Ｘ３）で表される２価の基である。

（式中、Ｘ¹¹は、単結合、メチレン基、プロパン－２,２－ジイル基、１,１,１,３,３,３－ヘキサフルオロプロパン－２,２－ジイル基又はフルオレン－９,９－ジイル基である。Ｒ¹¹及びＲ¹²は、それぞれ独立に、炭素数１～２０のヒドロカルビル基又はヒドロカルビルオキシ基である。ｘ¹及びｙ¹は、それぞれ独立に、０～２の整数である。）

（式中、ｎは、０～３００の整数である。）

（式中、Ｘ¹²は、単結合、メチレン基、プロパン－２,２－ジイル基、１,１,１,３,３,３－ヘキサフルオロプロパン－２,２－ジイル基又はフルオレン－９,９－ジイル基である。Ｒ¹³及びＲ¹⁴は、それぞれ独立に、炭素数１～２０のヒドロカルビル基又はヒドロカルビルオキシ基である。ｘ²及びｙ²は、それぞれ独立に、０～２の整数である。）］
６．（Ｅ）無機充填剤が、シリカであり、前記樹脂組成物の固形分中２０～９６質量％含まれる１～５のいずれかの樹脂組成物。
７．更に、（Ｆ）エポキシ化合物を含む１～６のいずれかの樹脂組成物。
８．１～７のいずれかの樹脂組成物から得られる樹脂フィルム。
９．基板、及び該基板上に８の樹脂フィルムの硬化物を備える半導体積層体。
１０．９の半導体積層体が個片化されたものである半導体装置。
１１．８の樹脂フィルムを半導体ウエハに貼り付け、該半導体ウエハをモールドする工程と、前記樹脂フィルムを加熱し、硬化させる工程とを含む半導体積層体の製造方法。
１２．１１の半導体積層体の製造方法によって製造した半導体積層体を個片化する工程を含む半導体装置の製造方法。 Therefore, the present invention provides the following resin composition, resin film, semiconductor laminate, method for manufacturing a semiconductor laminate, semiconductor device, and method for manufacturing a semiconductor device.
1. (A) an epoxy resin having an epoxy equivalent of 140 to 5,000 g/eq;
(B) phenolic curing agent,
(C) curing accelerator,
(D) A resin composition containing a modifier that is a compound represented by the following formula (D), and (E) an inorganic filler.

(In the formula, R is a hydrocarbyl group having 10 to 50 carbon atoms. Q is an ether bond, ester bond, carbonyl group, or thioether bond. L is a carbon number 1 to 50 that may contain an oxygen atom. 20 hydrocarbylene groups.T is a reactive functional group.m is an integer from 1 to 3.When m is 2 or 3, each L and each T are the same as each other. may be different, but may be different.)
2. 1. The resin composition of 1, wherein T is an epoxy group, an oxetane group, or an alkoxysilyl group.
3. 1 or 2 resin compositions, wherein Q is an ether bond or an ester bond.
4. The resin composition according to any one of 1 to 3, wherein the component (A) is silphenylene and/or a silicone-modified epoxy resin.
5. The resin composition of 4, wherein the silphenylene and/or silicone-modified epoxy resin is represented by the following formula (A).

[In the formula, R ¹ to R ⁶ are each independently a hydrocarbyl group or a hydrocarbyloxy group having 1 to 20 carbon atoms. a, b, c, d and e represent the composition ratio of each repeating unit, 0<a<1, 0≦b<1, 0≦c<1, 0≦d<1, 0≦e<1, This is a number that satisfies 0.67≦(b+d)/(a+c+e)≦1.67 and a+b+c+d+e=1. k is an integer from 0 to 300. X ¹ is a divalent group represented by the following formula (X1). X ² is a divalent group represented by the following formula (X2). X ³ is a divalent group represented by the following formula (X3).

(Wherein, X ¹¹ is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, 9-diyl group. R ¹¹ and R ¹² are each independently a hydrocarbyl group or hydrocarbyloxy group having 1 to 20 carbon atoms. x ¹ and y ¹ are each independently an integer of 0 to 2. be.)

(In the formula, n is an integer from 0 to 300.)

(wherein, X ¹² is a single bond, methylene group, propane-2,2-diyl group, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, 9-diyl group. R ¹³ and R ¹⁴ are each independently a hydrocarbyl group or hydrocarbyloxy group having 1 to 20 carbon atoms. x ² and y ² are each independently an integer of 0 to 2. be.)]
6. (E) The resin composition according to any one of 1 to 5, wherein the inorganic filler is silica and is contained in an amount of 20 to 96% by mass based on the solid content of the resin composition.
7. Furthermore, (F) any one of the resin compositions 1 to 6 containing an epoxy compound.
8. A resin film obtained from the resin composition according to any one of 1 to 7.
9. A semiconductor laminate comprising a substrate and a cured resin film of No. 8 on the substrate.
10. A semiconductor device obtained by dividing the semiconductor laminate of 9 into individual pieces.
11. A method for manufacturing a semiconductor laminate, comprising the steps of attaching the resin film of 8 to a semiconductor wafer and molding the semiconductor wafer, and heating and curing the resin film.
12. A method for manufacturing a semiconductor device, including a step of dividing into pieces a semiconductor layered product manufactured by the method for manufacturing a semiconductor layered product according to item 11.

The resin composition of the present invention provides a film that has high adhesive strength, low dielectric loss, low warpage, and allows wafers to be molded all at once. By using this, wafers can be molded all at once, and it has good moldability especially for large-diameter and thin-film wafers.At the same time, it is difficult to peel off from the substrate, and has high adhesion and low It has warp resistance, allows for good molding process, and can be suitably used for wafer level packages. By using the resin composition of the present invention, it is possible to provide a high-quality semiconductor device with good yield.

[Resin composition]
The resin composition of the present invention comprises (A) an epoxy resin having an epoxy equivalent of 140 to 5,000 g/eq, (B) a phenolic curing agent, (C) a curing accelerator, (D) a modifier, and (E ) Contains an inorganic filler.

[(A) Epoxy resin]
The epoxy resin of component (A) has an epoxy equivalent of 140 to 5,000 g/eq. Note that the epoxy equivalent (g/eq) is a value calculated by dividing the mass (g) of the resin by the equivalent weight (eq) of the epoxy group contained in the resin. When the epoxy equivalent is within the above range, sufficient crosslinking can be achieved and chemical resistance and adhesive strength can be imparted to the cured product.

(A) The epoxy resin is preferably solid at room temperature (25°C). In this case, it becomes easy to form a film.

(A) Epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, phenol novolac epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, alicyclic epoxy resin, and glycidyl ester. epoxy resins, glycidylamine type epoxy resins, heterocyclic epoxy resins, diarylsulfone type epoxy resins, silphenylene and/or silicone modified epoxy resins, and the like.

(A) The epoxy resin is preferably a silphenylene and/or silicone modified epoxy resin. The use of silphenylene and/or silicone modified epoxy resin increases the flexibility of the composition and makes it easier to form into a film.

The silphenylene and/or silicone-modified epoxy resin is preferably one represented by the following formula (A).

In formula (A), R ¹ to R ⁶ are each independently a hydrocarbyl group or a hydrocarbyloxy group having 1 to 20 carbon atoms. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group; aryl groups such as phenyl group; aralkyl groups such as benzyl group, phenethyl group; Examples include alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, and butenyl. Among these, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is preferred, and a methyl group and a phenyl group are more preferred from the viewpoint of easy availability of raw materials.

In formula (A), a, b, c, d and e represent the composition ratio of each repeating unit, 0<a<1, 0≦b<1, 0≦c<1, 0≦d<1, The number satisfies 0≦e<1, 0.67≦(b+d)/(a+c+e)≦1.67, and a+b+c+d+e=1.

In formula (A), k is an integer from 0 to 300. When k is an integer of 2 or more, each R ⁵ may be the same or different from each other, and each R ⁶ may be the same or different from each other. When k is an integer of 2 or more, the siloxane units indicated by the subscript k may be randomly bonded or alternately bonded, or may include a plurality of blocks of the same type of siloxane units.

In formula (A), X ¹ is a divalent group represented by the following formula (X1).

In formula (X1), X ¹¹ is a single bond, methylene group, propane-2,2-diyl group, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or fluorene- It is a 9,9-diyl group. R ¹¹ and R ¹² are each independently a hydrocarbyl group or a hydrocarbyloxy group having 1 to 20 carbon atoms. x ¹ and y ¹ are each independently an integer of 0 to 2, preferably 0.

In formula (A), X ² is a divalent group represented by formula (X2) below.

In formula (X2), n is an integer from 0 to 300, preferably an integer from 0 to 40.

In formula (A), X ³ is a divalent group represented by the following formula (X3).

In formula (X3), X ¹² is a single bond, methylene group, propane-2,2-diyl group, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or fluorene- It is a 9,9-diyl group. R ¹³ and R ¹⁴ are each independently a hydrocarbyl group or a hydrocarbyloxy group having 1 to 20 carbon atoms. x ² and y ² are each independently an integer of 0 to 2, preferably 0.

The hydrocarbyl moiety of the hydrocarbyl group and hydrocarbyloxy group represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl; benzyl and phenethyl groups; Aralkyl groups such as groups; examples include alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, and butenyl. Among these, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is preferred, and a methyl group, ethyl group, propyl group, tert-butyl group, methoxy group, and ethoxy group are more preferred.

The weight average molecular weight (Mw) of the silphenylene and/or silicone-modified epoxy resin represented by formula (A) is preferably 3,000 to 500,000, more preferably 5,000 to 200,000. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. The silphenylene and/or silicone-modified epoxy resin represented by formula (A) may be a random copolymer or a block polymer.

By using the silphenylene and/or silicone-modified epoxy resin represented by the formula (A), flexibility can be imparted to the resin composition before curing, facilitating film formation, and exhibiting a sufficient elastic modulus after curing. It is possible to provide a cured product with better chemical resistance, heat resistance, and pressure resistance.

(A) Epoxy resins may be used alone or in combination of two or more.

（式中、Ｒ¹～Ｒ⁶及びｋは、前記と同じ。） The silphenylene and/or silicone-modified epoxy resin represented by formula (A) contains at least one compound selected from a silphenylene compound represented by the following formula (A1) and an organohydrogensiloxane compound represented by the following formula (A2). 1 type and at least one type selected from a compound represented by the following formula (A3), a compound represented by the following formula (A4), and a compound represented by the following formula (A5), as shown below. It can be manufactured by a method.

(In the formula, R ¹ to R ⁶ and k are the same as above.)

（式中、Ｒ¹¹～Ｒ¹⁴、Ｘ¹¹、Ｘ¹²、ｎ、ｘ¹、ｘ²、ｙ¹及びｙ²は、前記と同じ。）

(In the formula, R ¹¹ to R ¹⁴ , X ¹¹ , X ¹² , n, x ¹ , x ² , y ¹ and y ² are the same as above.)

Silphenylene and/or silicone-modified epoxy resin represented by formula (A) can be synthesized by hydrosilylating raw materials. At that time, the reaction may be carried out with all the raw materials placed in the reaction container, or some of the raw materials may be reacted first and then the remaining raw materials may be reacted, or the raw materials may be reacted one by one. The reaction order can also be arbitrarily selected. The compounding ratio of each compound is expressed by formula (A1) with respect to the total of alkenyl groups possessed by the compound represented by formula (A3), the compound represented by formula (A4), and the compound represented by formula (A5). The sum of the hydrosilyl groups possessed by the compound represented by the formula (A2) and the compound represented by the formula (A2) is preferably from 0.67 to 1.67, more preferably from 0.83 to 1.25.

This polymerization reaction is carried out in the presence of a catalyst. The catalyst is not particularly limited as long as it allows hydrosilylation to proceed. Specifically, palladium complexes, rhodium complexes, platinum complexes, etc. are used, but are not limited to these. The catalyst is preferably added in an amount of about 0.01 to 10.0 mol per 1 mol in total of the hydrosilyl groups possessed by the compound represented by formula (A1) and the compound represented by formula (A2). If it is 0.01 mol or more, the reaction will not slow down and the reaction will proceed sufficiently, and if it is 10.0 mol or less, the dehydrogenation reaction will be difficult to proceed and there is a possibility that the addition reaction will inhibit the progress. There is no.

As the solvent used in the polymerization reaction, a wide range of organic solvents that do not inhibit hydrosilylation can be used. Specific examples include, but are not limited to, octane, toluene, tetrahydrofuran, dioxane, and the like. The solvent is preferably used so that the solute content is 10 to 70% by mass. If it is 10% by mass or more, the reaction system will not become thin and the progress of the reaction will not be slowed down. Further, if it is 70% by mass or less, the viscosity will not increase and there is no risk that the system will not be sufficiently stirred during the reaction.

The reaction is usually carried out at a temperature of 40 to 150°C, preferably 60 to 120°C, particularly preferably 70 to 100°C. If the reaction temperature is 150°C or lower, side reactions such as decomposition are less likely to occur, and if it is 40°C or higher, the progress of the reaction will not be slowed down. The reaction time is usually 0.5 to 60 hours, preferably 3 to 24 hours, particularly preferably 5 to 12 hours.

[(B) Phenolic curing agent]
As the component (B), a wide variety of known phenolic curing agents can be used. The structure of the curing agent is preferably a compound having at least two or more phenolic hydroxy groups, and examples thereof include, but are not limited to, those shown below.

The content of component (B) is preferably such that the phenolic hydroxy group in component (B) is 0.6 to 1.4 moles per mole of epoxy group in component (A), and is preferably 0.9 More preferably, the amount is between 1.1 mol and 1.1 mol. Within the above range, the curing reaction proceeds favorably, epoxy groups and phenolic hydroxy groups do not accumulate excessively, and reliability is unlikely to deteriorate.

[(C) Curing accelerator]
The curing accelerator of component (C) can be widely used as long as it is used for ring-opening of epoxy groups. Examples of the curing accelerator include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 2-phenyl. Imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl Imidazole such as imidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; 2-ethyl-4-methylimidazole; Tertiary amines such as 2-(dimethylaminomethyl)phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo[5.4.0]undecene-7, tris(dimethylaminomethyl)phenol; diphenylphosphine, Organic phosphines such as triphenylphosphine and tributylphosphine; tetra-substituted phosphoniums and tetra-substituted borates such as tetraphenylphosphonium/tetraphenylborate and tetraphenylphosphonium/ethyltriphenylborate; metal compounds such as tin octylate, and the like.

The content of component (C) is preferably 0.01 to 20.0 parts by mass, more preferably 0.1 to 5.0 parts by mass, per 100 parts by mass of component (A). Within the above range, the curing reaction will proceed in just the right amount.

[(D) Modifier]
The modifier of component (D) is a compound represented by the following formula (D).

In formula (D), R is a hydrocarbyl group having 10 to 50 carbon atoms. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. The hydrocarbyl group preferably has 10 to 30 carbon atoms, and includes decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, triacontyl group, and diphenyl group. Methyl group, triphenylmethyl group, phenylbutyl group, 1-(3-dimethyl-1-methylbutyl)-6-methyl-4-methylheptyl group, n-butylphenyl group, sec-butylphenyl group, isobutylphenyl group, Preferable examples include tert-butylphenyl group and 1-pentylhexyl group.

In formula (D), Q is an ether bond, an ester bond, a carbonyl group, or a thioether bond, and is preferably an ether bond or an ester bond from the viewpoint of availability of raw materials.

In formula (D), L is a hydrocarbylene group having 1 to 20 carbon atoms and which may contain an oxygen atom. The hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. The hydrocarbylene group preferably has 1 to 5 carbon atoms, and particularly includes a methylene group and a propylene group.

In formula (D), T is a reactive functional group. Here, the term "reactive functional group" refers to a functional group that can react with a functional group contained in a compound in the resin composition of the present invention under the temperature and pressure to which the resin composition of the present invention is normally exposed. means. Examples of the reactive functional group include an epoxy group, an oxetane group, an alkoxysilyl group, etc., and an epoxy group is preferable from the viewpoint of easy availability of raw materials and storage stability of the composition.

In formula (D), m is an integer from 1 to 3. When m is 2 or 3, each L and each T may be the same or different.

Examples of the compound represented by formula (D) include, but are not limited to, those shown below.

The content of component (D) is preferably 0.1 to 40 parts by weight, more preferably 1.0 to 15 parts by weight, per 100 parts by weight of component (A). Within the above range, the adhesive strength is improved without inhibiting the curing reaction. Component (D) may be used alone or in combination of two or more.

[(E) Inorganic filler]
The resin composition of the present invention contains an inorganic filler as component (E) in order to provide wafer protection, improve low dielectric loss, heat resistance, moisture resistance, strength, etc., and increase the reliability of the cured product. include. Examples of the inorganic filler include oxides such as titanium oxide, alumina, fused silica (fused spherical silica, fused crushed silica), and crystalline silica powder; silicates such as talc, glass, and calcined clay; aluminum nitride, boron nitride, Nitride such as silicon nitride; carbonate such as calcium carbonate and magnesium carbonate; hydroxide such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide; sulfate such as barium sulfate and calcium sulfate; sulfite such as calcium sulfite etc. Among these, oxides are preferred, and silica such as fused silica and crystalline silica powder is preferred.

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 to 30 μm, more preferably 0.03 to 14 μm. If the average particle size of the inorganic filler is 0.01 μm or more, it becomes easier to fill with the filler and the strength of the cured product becomes high, and if it is 30 μm or less, the fillability between the chips becomes good. In the present invention, the average particle diameter can be determined by a particle size distribution measuring device using a laser beam diffraction method, and is expressed as the mass average value D ₅₀ (i.e., the particle diameter or median diameter when the cumulative mass is 50%). can be measured.

The content of component (E) is preferably 20 to 96% by weight, more preferably 50 to 95% by weight, particularly preferably 60 to 93% by weight based on the solid content of the resin composition. If the content of the inorganic filler is 20% by mass or more, the effect of the inorganic filler can be sufficiently obtained, and if the content is 96% by mass or less, the filling properties of the inorganic filler and the processability of the composition will be good. . Note that the solid content refers to components other than the organic solvent described below. (E) Inorganic fillers may be used alone or in combination of two or more.

[(F) Epoxy compound]
The resin composition of the present invention may further contain (F) an epoxy compound. The epoxy compound (F) is a compound different from the components (A) and (D), preferably a compound containing at least two epoxy groups, and more preferably a compound containing 2 to 10 epoxy groups. (F) By including the epoxy compound, reliability can be further increased and various physical properties such as elastic modulus and elongation can be improved.

(F) Epoxy compounds include, but are not limited to, those shown below.

（式中、ｐ及びｑは、それぞれ独立に、１～１０の整数である。）

(In the formula, p and q are each independently an integer of 1 to 10.)

When the resin composition of the present invention contains (F) an epoxy compound, its content is preferably 0.1 to 80 parts by weight per 100 parts by weight of component (A). Within this range, the effect of the epoxy compound can be obtained and the amount of warpage will not increase. (F) The epoxy compound may be used alone or in combination of two or more.

[Other ingredients]
The resin composition of the present invention may contain components other than those described above (hereinafter also referred to as other components) as necessary. Examples of other components include flame retardants, antioxidants, pigments, dyes, and organic solvents.

The resin composition of the present invention may contain a flame retardant for the purpose of improving flame retardancy. Examples of flame retardants include phosphorus-based flame retardants, which impart flame retardancy without containing halogen atoms, such as phosphazene compounds, phosphate ester compounds, phosphate ester amide compounds, etc. Can be mentioned. Since phosphazene compounds and phosphoric acid ester amide compounds contain phosphorus atoms and nitrogen atoms in their molecules, particularly high flame retardance can be obtained. The content of the flame retardant is preferably 3 to 40 parts by weight per 100 parts by weight of component (A).

Furthermore, in order to improve the compatibility of each component and various properties such as storage stability and workability of the resin composition, internal mold release agents such as fatty acid ester, glyceric acid ester, zinc stearate, calcium stearate, etc. , phenol-based, phosphorus-based or sulfur-based antioxidants, etc. may be added. The composition can also be colored using pigments or dyes such as carbon black.

The resin composition of the present invention may be dissolved in an organic solvent in order to uniformly mix the above-mentioned components. Examples of the organic solvent include N,N-dimethylacetamide, methyl ethyl ketone, N,N-dimethylformamide, cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, acetone, and propylene glycol monomethyl ether. , propylene glycol monomethyl ether acetate, toluene, xylene and the like. Among these, methyl ethyl ketone, cyclopentanone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are preferred. These organic solvents may be used alone or in combination of two or more. The amount of organic solvent used is preferably such that the solid content concentration in the resin composition is 40 to 90% by mass.

Since the resin composition of the present invention contains the modifier (D), it maintains high adhesive strength and has small dielectric loss. Specifically, the dielectric loss tangent of the cured resin film described below at 10 GHz is preferably 0 to 0.015, more preferably 0 to 0.014.

[Resin film]
The resin film of the present invention is obtained by processing the resin composition into a film shape. Processed into a film, it has good molding performance for large-diameter, thin-film wafers, and since there is no need to pour resin when molding wafers all at once, there is no problem with filling defects on the wafer surface. This will not cause any problems. Furthermore, a resin film formed using the resin composition is less likely to warp and has high adhesive strength, making it a wafer molding material that is less prone to various defects.

The thickness of the resin film of the present invention is not particularly limited, but is preferably 2 mm or less, more preferably 50 to 1,200 μm, and even more preferably 80 to 850 μm. Such a thickness is preferable as a semiconductor encapsulant because it provides excellent protection.

The resin film of the present invention may be a resin film laminate in which a protective film is laminated on a resin film obtained from the resin composition. The protective film is not particularly limited as long as it can be peeled off without damaging the form of the resin film made of the resin composition of the present invention, but it functions as a protective film and a release film for wafers, and is usually made of polyethylene. Examples include plastic films such as (PE) film, polypropylene (PP) film, polymethylpentene (TPX) film, and polyester film subjected to mold release treatment. Further, the peeling force of the protective film from the resin film is preferably 50 to 300 mN/50 mm. The peeling force was measured when polyester adhesive tape Nitto No. 31B tape (manufactured by Nitto Denko Corporation) was applied to the protective film, cut into strips with a width of 50 mm, and peeled off at 180° at 0.3 m/min. The peeling force is The thickness of the protective film is preferably 25 to 150 μm, more preferably 38 to 125 μm.

An example of a method for manufacturing the resin film laminate will be described. A resin composition is prepared by mixing the above-mentioned components (A) to (E) and, if necessary, the epoxy compound (F) and other components, and the resin composition is coated using a reverse roll coater, a comma coater, etc. Apply to the protective film to the desired thickness. The protective film coated with the resin composition is passed through an in-line dryer and dried by removing the organic solvent at 80 to 160°C for 2 to 20 minutes, and then pressure-bonded to the protective film using a roll laminator. , a film laminate in which a protective film is laminated on a resin film is obtained.

[Semiconductor laminate and method for manufacturing the same]
The semiconductor laminate of the present invention includes a cured product of the resin film on a substrate such as a semiconductor wafer or a square substrate. Since the cured resin film has high strength and adhesive strength, the semiconductor wafer is sufficiently protected by the cured resin film.

The semiconductor wafer may be a wafer on which semiconductor elements (chips) are mounted, or a semiconductor wafer on which semiconductor elements are fabricated. The resin film of the present invention has good filling properties on the wafer surface before molding, and has high strength and high adhesiveness after molding, and is excellent in protecting the wafer. Further, the resin film of the present invention can be suitably used for molding large diameter wafers or thin film wafers with a diameter of 8 inches or more, for example, 8 inches (200 mm), 12 inches (300 mm) or more in diameter. . The thin wafer is preferably a wafer processed to have a thickness of 5 to 400 μm.

The square substrate may have a semiconductor element (chip) mounted on its surface, or may have a semiconductor element fabricated on its surface. The size of the square substrate may be 10 cm square, 50 cm square, etc., and may be even larger. The resin film of the present invention can be suitably used as a molding material regardless of the shape, such as a rectangle or trapezoid, or the thickness of the substrate.

The method for manufacturing a semiconductor laminate of the present invention includes a step of attaching the resin film to a substrate and molding the substrate, and a step of heating and curing the resin film.

The method of molding a wafer using the resin film of the present invention is not particularly limited, but for example, one protective layer pasted on the resin film is peeled off, and a vacuum laminator manufactured by Takatori Co., Ltd. (product name: TEAM-300) is used. ), set the inside of the vacuum chamber at a vacuum level of 50 to 1,000 Pa, preferably 50 to 500 Pa, for example 100 Pa, and heat the other protective layer at 80 to 200°C, preferably 80 to 130°C, for example 100°C. A method may be used in which the applied resin film is brought into close contact with the wafer at once, the pressure is returned to normal, the wafer is cooled to room temperature, the wafer is taken out from the vacuum laminator, and the other protective layer is peeled off.

Furthermore, a compression molding device, a device equipped with a vacuum diaphragm laminator, a metal plate press for flattening, or the like can be suitably used for wafers on which semiconductor chips are stacked. As a compression molding device, for example, a device manufactured by Apic Yamada Co., Ltd. (product name: WCM-300 manual system) can be used. When molding a 300 mm silicon wafer on which semiconductor chips are stacked, the molding temperature is 100~ Molding is possible at 180°C, molding pressure of 100 to 300 kN, clamp time of 30 to 90 seconds, and molding time of 5 to 20 minutes. Furthermore, as a device equipped with a vacuum diaphragm laminator and a metal plate press for flattening, for example, a device manufactured by Nikko Materials Co., Ltd. (product name: CVP-300) can be used, and the lamination temperature is 100 After laminating at ~180℃, vacuum level 50~500Pa, pressure 0.1~0.9MPa, lamination time 30~300 seconds, upper and lower hot plate temperature 100~180℃, pressure 0.1~3.0MPa, and pressurization. It is possible to flatten the resin molding surface in 30 to 300 seconds.

After molding, the resin film can be cured by heating it at 120 to 220°C for 15 to 360 minutes. Thereby, a semiconductor laminate is obtained.

[Semiconductor device and its manufacturing method]
The semiconductor device of the present invention is obtained by dividing the semiconductor stack into individual pieces. The method for manufacturing a semiconductor device of the present invention includes a step of dividing the semiconductor stack into individual pieces. In this way, by dividing the semiconductor wafer molded with a resin film into individual pieces, semiconductor devices having a cured film can be obtained. The molded wafer is attached to a protective tape for semiconductor processing such as dicing tape so that the mold resin surface or the wafer surface is in contact with it, and is placed on the suction table of a dicer. It is cut using a saw (for example, DFD6361 manufactured by DISCO Co., Ltd.). The spindle rotation speed and cutting speed during dicing may be set as appropriate, but it is usually preferable that the spindle rotation speed is 25,000 to 45,000 rpm and the cutting speed is 10 to 50 mm/sec. Further, the size of the individual pieces depends on the design of the semiconductor package, but is approximately 2 mm x 2 mm to 30 mm x 30 mm.

In this way, semiconductor wafers molded with the resin film are sufficiently protected due to the resin film's high strength and adhesive strength. High quality semiconductor devices can be manufactured.

Hereinafter, the present invention will be explained in more detail by showing synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples.

The compounds (S-1) to (S-6) used are as follows.

[1] Synthesis of epoxy compound [Synthesis Example 1] Synthesis of epoxy compound (S-7) Into a 5 L flask equipped with a stirrer, a thermometer, a nitrogen purge device, and a reflux condenser, 617 g (2. 0 mol), 256 g (8.0 mol) of methanol and 852 g (8.0 mol) of epichlorohydrin were added, and 768 g (19.2 mol) of sodium hydroxide was added over 2 hours, and then heated to 60°C. The temperature was raised and the reaction was continued for 3 hours. After the reaction, 500 mL of toluene was added and washed with pure water until the aqueous layer became neutral. The solvent in the organic layer was removed under reduced pressure, and 757 g (1.8 mol) of epoxy compound (S-7) was added. Obtained.

[2] Synthesis of epoxy resin In the following synthesis examples, Mw is determined using a GPC column (TSKgel Super HZM-H (manufactured by Tosoh Corporation)), a flow rate of 0.6 mL/min, an elution solvent of tetrahydrofuran, and a column temperature of 40°C. This is a value measured by GPC using monodisperse polystyrene as a standard under the following analysis conditions.

[Synthesis Example 2] Synthesis of Epoxy Resin 1 After adding 420.5 g (1.0 mol) of compound (S-7) to a 3 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, toluene 1,400g was added and heated to 70°C. Thereafter, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 194.4 g (1.0 mol) of compound (S-3) was added dropwise over 1 hour (total of hydrosilyl groups). /total of alkenyl groups = 1.0/1.0 = 1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain 1,570 g of a solid epoxy resin represented by the following formula. The Mw of epoxy resin 1 was 53,200, and the epoxy equivalent was 307 g/eq.

[Synthesis Example 3] Synthesis of epoxy resin 2 After adding 133.5 g (0.227 mol) of compound (S-2) to a 3 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, toluene was added. 1,500g was added and heated to 70°C. Then, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 525.6 g (0.182 mol) of compound (S-4) and 8.8 g (0.0 mol) of compound (S-3) were added. 0.045 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups = 0.5/0.5 = 1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and toluene was distilled off from the reaction solution under reduced pressure to obtain 605 g of solid epoxy resin 2 represented by the following formula. The Mw of epoxy resin 2 was 51,100, and the epoxy equivalent was 1,471 g/eq.

[Synthesis Example 4] Synthesis of Epoxy Resin 3 Into a 3L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser, 104.9 g (0.179 mol) of compound (S-2) and compound (S-5) were added. ) and 6.6 g (0.036 mol) of compound (S-6) were added, followed by 1,600 g of toluene and heated to 70°C. Thereafter, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 516.3 g (0.179 mol) of compound (S-4) and 34.7 g (0.0 mol) of compound (S-3) were added. .179 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups = 0.5/0.5 = 1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain 680 g of solid epoxy resin 3 represented by the following formula. The Mw of epoxy resin 3 was 46,800, and the epoxy equivalent was 2,022 g/eq.

[3] Production of resin film and evaluation thereof [Examples 1 to 20 and Comparative Examples 1 to 9]
With the compositions listed in Tables 1 to 3 below, (A) epoxy resin, (B) phenolic curing agent, (C) curing accelerator, (D) modifier, (E) inorganic filler, and (F) epoxy. Compounds were blended. Further, cyclopentanone was added in an amount such that the solid component concentration was 80% by mass, and the mixture was stirred using a stirrer to mix and disperse, thereby preparing a dispersion of the resin composition. A phenolic curing agent was added so that the epoxy group and phenol equivalent matched.
Each resin composition was applied onto the protective film using a die coater as a film coater and E7304 (trade name, polyester manufactured by Toyobo Co., Ltd., thickness 75 μm, peeling force 200 mN/50 mm) as the protective film. Next, the solvent was completely evaporated by placing it in an oven set at 100° C. for 20 minutes, and a resin film with a thickness of 100 μm was formed on the protective film.

In Tables 1 to 3, each component is as follows.
・YL983U: Bisphenol type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 172 g/eq, viscosity 30 to 60 P (Gardner-Holt method, 25°C)

・Phenol curing agent 1, 2:

・Curing accelerator: Curesol 2P4MHZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2-phenyl-4-methyl-5-hydroxymethylimidazole)

・Modifier 1 to 4:

・Silica 1: Manufactured by Admatex Co., Ltd., average particle size 5.0 μm
・Silica 2: Manufactured by Admatex Co., Ltd., average particle size 10.0 μm

・Epoxy compounds 1 to 3:

The obtained resin film was evaluated by the following method. The results are also listed in Tables 1 to 3.
(1) Adhesive force measurement test The prepared film was attached to a 20 mm square silicon wafer at 110°C and 0.5 MPa using a laminator V-130 manufactured by Nikko Materials, and cut into 2 mm square pieces from above. A silicon chip was pressed against it and the film was cured by heating at 180° C. for 4 hours. Then, using an adhesion measuring device (Universal Bond Tester Series 4000 (DS-100) manufactured by Nordson Advanced Technologies), the chip was pushed from the side at a test speed of 200 μm/sec at 23°C, and the chip was pressed against the substrate. The adhesive strength was measured when it was peeled off (die shear test).

(2) Warp stress measurement test The prepared film was laminated onto a silicon wafer using a film laminator (TEAM-100 manufactured by Takatori Co., Ltd.), heated at 180°C for 4 hours to harden the film, and then formed into a thin film. Warpage stress (25° C.) was measured using a stress measuring device (FLX-2320-S manufactured by Toho Technology Co., Ltd.).

(3) Dielectric loss tangent measurement test The produced film was cured by heating at 180°C for 4 hours, and the dielectric loss tangent of the cured product at 10 GHz was measured at 25°C using a vector network analyzer (MS46122A manufactured by Anritsu Corporation). .

(4) Reliability test A 10 mm square 400 μm thick silicon chip was mounted on a silicon wafer using an epoxy adhesive (SINR-DF3770 manufactured by Shin-Etsu Chemical Co., Ltd.) and bonded by heating at 190°C for 2 hours. The agent was cured. Then, using a film laminator (TEAM-100 manufactured by Takatori Co., Ltd.), the produced film was laminated onto a silicon wafer, heated at 180°C for 4 hours to cure, and then 3 cm on each side centered on the chip. diced into squares. It was placed in a thermal shock tester manufactured by ESPEC Co., Ltd., and subjected to 1,000 thermal shock tests at -55 to 125 degrees Celsius, and the state of the interface between the chip and the mold was confirmed by cross-sectional observation using an electron microscope. did. Those with peeling or cracks were marked as ×, and those without these were marked as ○.

From the above results, the resin film obtained from the resin composition of the present invention maintains high adhesive strength and has lower dielectric loss than the resin film of the comparative example obtained from the composition containing no modifier. It was shown that there was no impact on the reliability of the package. Due to these characteristics, when the resin composition of the present invention is used in a semiconductor encapsulation film, there is no current loss, the electrical characteristics of high-frequency compatible devices are improved, and problems such as peeling are less likely to occur even after long-term use. It can be said. As a result, when the resin composition of the present invention is used for molding purposes, it exhibits good low warping properties and difficult peeling properties for chip-mounted wafers.

Claims (11)

(A) an epoxy resin modified with silphenylene or epoxy resin modified with silphenylene and silicone, the epoxy resin having an epoxy equivalent of 140 to 5,000 g/eq;
(B) phenolic curing agent,
(C) curing accelerator,
(D) a modifier that is one or more selected from a compound represented by the following formula (D), a compound represented by the following formula (D1), and a compound represented by the following formula (D2) ; and (E) a resin composition containing an inorganic filler.

(In the formula, R is a hydrocarbyl group having 10 to 50 carbon atoms. Q is an ether bond, ester bond, carbonyl group, or thioether bond. L is a carbon number 1 to 50 that may contain an oxygen atom. 20 hydrocarbylene group.T is an epoxy group, oxetane group or alkoxysilyl group.m is 1. )

The resin composition according to claim 1, wherein Q is an ether bond or an ester bond. The resin composition according to claim 1 or 2, wherein the silphenylene-modified epoxy resin or the silphenylene and silicone-modified epoxy resin is represented by the following formula (A).

[In the formula, R ¹ to R ⁶ are each independently a hydrocarbyl group or a hydrocarbyloxy group having 1 to 20 carbon atoms. a, b, c, d and e represent the composition ratio of each repeating unit, 0<a<1, 0<b<1, 0≦c<1, 0≦d<1, 0≦e<1, This is a number that satisfies 0.67≦(b+d)/(a+c+e)≦1.67 and a+b+c+d+e=1. k is an integer from 0 to 300. X ¹ is a divalent group represented by the following formula (X1). X ² is a divalent group represented by the following formula (X2). X ³ is a divalent group represented by the following formula (X3).

(Wherein, X ¹¹ is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, 9-diyl group. R ¹¹ and R ¹² are each independently a hydrocarbyl group or hydrocarbyloxy group having 1 to 20 carbon atoms. x ¹ and y ¹ are each independently an integer of 0 to 2. be.)

(In the formula, n is an integer from 0 to 300.)

(wherein, X ¹² is a single bond, methylene group, propane-2,2-diyl group, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, 9-diyl group. R ¹³ and R ¹⁴ are each independently a hydrocarbyl group or hydrocarbyloxy group having 1 to 20 carbon atoms. x ² and y ² are each independently an integer of 0 to 2. be.)] The resin composition according to any one of claims 1 to 3, wherein the modifier (D) is a compound represented by any of the following formulas.

The resin composition according to any one of claims 1 to 4, wherein the inorganic filler (E) is silica and is contained in an amount of 20 to 96% by mass based on the solid content of the resin composition. The resin composition according to any one of claims 1 to 5, further comprising (F) an epoxy compound different from the components (A) and (D). A resin film obtained from the resin composition according to any one of claims 1 to 6 . A semiconductor laminate comprising a substrate and a cured product of the resin film according to claim 7 on the substrate. A semiconductor device, which is obtained by dividing the semiconductor laminate according to claim 8 into individual pieces. A method for manufacturing a semiconductor laminate, comprising the steps of attaching the resin film according to claim 7 to a semiconductor wafer and molding the semiconductor wafer, and heating and curing the resin film. A method for manufacturing a semiconductor device, comprising the step of dividing the semiconductor layered product manufactured by the method for manufacturing a semiconductor layered product according to claim 10 into individual pieces.