JP7450697B2 - Resin composition, resin film, semiconductor laminate, method for manufacturing semiconductor laminate, and method for manufacturing semiconductor device - Google Patents

Description

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

In recent years, in order to respond to the miniaturization, higher functionality, and lower cost of mobile devices such as smartphones in the semiconductor industry, silicon wafers that serve as chip substrates have become thinner, and large CCL and BT substrates have been developed to improve manufacturing efficiency. etc., is in progress. However, with thin substrates, large CCL substrates, and BT substrates, warping becomes noticeable, which places a large load on the encapsulant and makes it easy for it to separate from the adhesive surface, making the adhesive strength of the encapsulant increasingly important. It has become to. Up to now, various studies have been carried out to improve the adhesive strength of sealing materials, but a sealing material with even higher adhesion is required (Patent Document 1).

In addition, in order to increase manufacturing efficiency, square substrates are often used for CCL and BT substrates, but when sealing these, liquid sealing material tends to cause unevenness between the inside and outside of the substrate, so it is easy to do this. A film type that could be uniformly sealed was desired.

Therefore, it has been desired to develop a highly adhesive resin composition that does not easily peel off even when it is distorted, a wafer mold material using the same that has good wafer protection performance, and to make it into a film.

Japanese Patent Application Publication No. 2001-332662

The present invention has been made in view of the above-mentioned problems, and includes a resin composition with low warpage and excellent adhesive strength, a highly adhesive resin composition film obtained by forming the composition into a film, and a film made of the film. It is an object of the present invention to provide a semiconductor laminate having 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.

（Ｒ’_１は加水分解性シリル基を含有する炭素数１～２０の１価の有機基、Ｒ’_２，Ｒ’_３はそれぞれ水素原子又は炭素数１～２０の１価の有機基、Ｘ’は酸素原子、もしくは硫黄原子、Ａｒは置換基を２つ持っていてもよい芳香環、もしくは複素環を示す。） In order to achieve the above object, the present invention provides a resin composition containing the following (A) to (D).
(A) a resin containing epoxy groups with an epoxy equivalent in the range of 140 to 5000 g/eq;
(B) phenolic curing agent,
(C) curing accelerator,
(D) At least one compound selected from the following formulas (0-1) to (0-5)

(R' ₁ is a monovalent organic group having 1 to 20 carbon atoms containing a hydrolyzable silyl group, R' ₂ and R' ₃ are each a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, ' represents an oxygen atom or a sulfur atom, and Ar represents an aromatic ring or a heterocycle that may have two substituents.)

Such a composition has small warpage and excellent adhesive strength.

The resin composition may further contain 0.1 to 80 parts by mass of (E) an epoxy compound other than the component (A) based on 100 parts by mass of the component (A).

Such a resin composition has less warpage and superior adhesive strength.

The resin composition may further include (F) an inorganic filler.

By containing an inorganic filler, such a resin composition can provide more preferable wafer protection, further improve heat resistance, moisture resistance, strength, etc., and increase the reliability of the cured product.

Further, the inorganic filler (F) may be silica, and may be contained in the resin composition in an amount of 20 to 96% by mass.

Such a resin composition can further improve the reliability of the cured product.

Furthermore, in the compounds represented by the general formulas (0-1) to (0-3), X' can be an oxygen atom.

Such compounds are more preferable from the viewpoint of easy availability of raw materials and storage stability of the composition.

Moreover, it is preferable that the component (A) is a silicone-modified epoxy resin.

By using such a resin, flexibility can be imparted to the resin composition before curing, making it easy to form a film, and furthermore, it can exhibit a sufficient elastic modulus after curing.

［式中、Ｒ^１～Ｒ^６は、それぞれ独立に、炭素数１～２０の１価炭化水素基又はアルコキシ基であり、互いに同一でも異なっていてもよい。また、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。ｇは、０～３００の整数である。Ｘは、下記式（５）で表される２価の有機基である。Ｙは、下記式（６）で表される２価のシロキサン骨格含有基である。Ｚは下記式（７）で表される２価の有機基である。］

（式中、Ｅは、単結合、又は下記式

から選ばれる２価の有機基である。Ｒ^７及びＲ^８は、炭素数１～２０の１価炭化水素基又はアルコキシ基であり、互いに同一でも異なっていてもよい。ｔ及びｕは、それぞれ独立に、０～２の整数である。）

（式中、ｖは、０～３００の整数である。）

（式中、Ｇは、単結合、又は下記式

から選ばれる２価の有機基である。Ｒ^９及びＲ^１０は、炭素数１～２０の１価炭化水素基又はアルコキシ基であり、互いに同一でも異なっていてもよい。ｗ及びｘは、それぞれ独立に、０～２の整数である。） Further, it is preferable that the silicone-modified epoxy resin contains a structural unit represented by the following formula (4) and has a weight average molecular weight of 3,000 to 500,000.

[In the formula, R ¹ to R ⁶ are each independently a monovalent hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, and may be the same or different from each other. In addition, 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, 0.67≦(b+d)/(a+c+e)≦1.67, and a+b+c+d+e=1. g is an integer from 0 to 300. X is a divalent organic group represented by the following formula (5). Y is a divalent siloxane skeleton-containing group represented by the following formula (6). Z is a divalent organic group represented by the following formula (7). ]

(In the formula, E is a single bond or the following formula

It is a divalent organic group selected from. R ⁷ and R ⁸ are a monovalent hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, and may be the same or different. t and u are each independently an integer of 0 to 2. )

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

(In the formula, G is a single bond or the following formula

It is a divalent organic group selected from. R ⁹ and R ¹⁰ are monovalent hydrocarbon groups or alkoxy groups having 1 to 20 carbon atoms, and may be the same or different. w and x are each independently an integer of 0 to 2. )

By using such a resin, the resin composition before curing can be given more flexibility, can be easily formed into a film, and can exhibit a better elastic modulus after curing.

The present invention also provides a resin film obtained by forming the resin composition into a film.

Since such a resin film has high adhesive strength, semiconductor wafers and the like can be sufficiently protected.

Further, the present invention provides a semiconductor laminate having a cured product of the resin film described above on a semiconductor wafer.

In such a semiconductor laminate, since the adhesive strength of the resin film is high, the semiconductor wafer is sufficiently protected by the resin film.

Further, the present invention provides a semiconductor device, characterized in that the semiconductor stack is separated into individual pieces.

Such a semiconductor device will be of high quality.

The present invention also provides a method for manufacturing a semiconductor laminate, which comprises the steps of attaching the resin film to a semiconductor wafer and molding the semiconductor wafer, and heating and curing the resin film. A method for manufacturing a semiconductor stack is provided.

With such a method for manufacturing a semiconductor laminate, it is possible to manufacture a semiconductor laminate in which the semiconductor wafer is sufficiently protected by the resin film.

Further, the present invention provides a method for manufacturing a semiconductor device, which includes a step of singulating a semiconductor stack manufactured by the above-described method for manufacturing a semiconductor stack.

With such a semiconductor device manufacturing method, a high quality semiconductor device can be manufactured.

The resin composition of the present invention can significantly increase the adhesive strength of the cured product, has excellent low warping properties, and forms a film that can be molded onto wafers all at once, making it suitable for wafer-level packaging. Can be used. By using these inventions, it is possible to provide high-quality semiconductor devices with good yield.

As mentioned above, a resin composition with small warpage and excellent adhesive strength, a high-strength resin film obtained by forming the composition into a film, a semiconductor laminate having a cured product of the resin film, and the production thereof There is a need for a method, a semiconductor device in which the semiconductor stack is singulated, and a method for manufacturing the same.

The present inventors conducted extensive studies in order to achieve the above object. As a result, by combining (A) a resin containing epoxy groups with an epoxy equivalent in the range of 140 to 5000 g/eq, (B) a phenolic curing agent, (C) a curing accelerator, and (D) a compound with a specific structure, It has been found that a resin composition with high adhesive strength and low warpage can be obtained. Furthermore, the inventors discovered that by forming the resin composition into a film, a wafer molding material that can be more easily handled could be obtained, and the present invention was completed.

（Ｒ’_１は加水分解性シリル基を含有する炭素数１～２０の１価の有機基、Ｒ’_２，Ｒ’_３はそれぞれ水素原子又は炭素数１～２０の１価の有機基、Ｘ’は酸素原子、もしくは硫黄原子、Ａｒは置換基を２つ持っていてもよい芳香環、もしくは複素環を示す。）
なお、上記式（０－１）～（０－５）で示される中から少なくとも１つ選択される化合物を、以下、「接着助剤」ともいう。 That is, the present invention is a resin composition containing the following (A) to (D).
(A) a resin containing epoxy groups with an epoxy equivalent in the range of 140 to 5000 g/eq;
(B) phenolic curing agent,
(C) curing accelerator,
(D) At least one compound selected from the following formulas (0-1) to (0-5)

(R' ₁ is a monovalent organic group having 1 to 20 carbon atoms containing a hydrolyzable silyl group, R' ₂ and R' ₃ are each a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, ' represents an oxygen atom or a sulfur atom, and Ar represents an aromatic ring or a heterocycle that may have two substituents.)
Note that at least one compound selected from the above formulas (0-1) to (0-5) is also referred to as an "adhesion aid" hereinafter.

The present invention will be described in detail below, but the present invention is not limited thereto.

[Resin composition]
The resin composition of the present invention contains the following components (A) to (D).
(A) Resin containing epoxy groups with an epoxy equivalent in the range of 140 to 5000 g/eq (B) Phenolic curing agent (C) Curing accelerator (D) Adhesion aid Each component will be explained in detail below.

[(A) Component]
Component (A) is a resin containing epoxy groups at an epoxy equivalent in the range of 140 to 5000 g/eq (hereinafter also referred to as "epoxy resin").
The resin (epoxy resin) includes 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. Examples include, but are not limited to, ester-type epoxy resins, glycidylamine-type epoxy resins, heterocyclic epoxy resins, diarylsulfone-type epoxy resins, and silicone-modified epoxy resins. If the component (A) is solid at room temperature, it can be easily formed into a film. In the case of a solid, it is easy to mold into a film, and the cover film is also easy to peel off. Further, an epoxy resin having an epoxy group with an epoxy equivalent in the range of 140 to 5000 g/eq can form sufficient crosslinking, and can impart chemical resistance and adhesive strength to the cured product. If the amount is less than this, curing will be insufficient, resulting in poor chemical resistance and adhesive strength, and if it is more than this, warping will become large.
Note that the epoxy equivalent [g/eq] is calculated by dividing the resin amount [g] by the equivalent weight [eq] of the epoxy group contained in the resin. Epoxy equivalent measurement is based on JIS K 7236.

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

［式中、Ｒ^１～Ｒ^６は、それぞれ独立に、炭素数１～２０の１価炭化水素基又はアルコキシ基であり、互いに同一でも異なっていてもよい。また、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。ｇは、０～３００の整数である。Ｘは、下記式（５）で表される２価の有機基である。Ｙは、下記式（６）で表される２価のシロキサン骨格含有基である。Ｚは下記式（７）で表される２価の有機基である。］

（式中、Ｅは、単結合、又は下記式

から選ばれる２価の有機基である。Ｒ^７及びＲ^８は、炭素数１～２０の１価炭化水素基又はアルコキシ基であり、互いに同一でも異なっていてもよい。ｔ及びｕは、それぞれ独立に、０～２の整数である。） Furthermore, it is preferable that the silicone-modified epoxy resin has a structural unit represented by the following formula (4) and has a weight average molecular weight of 3,000 to 500,000.

[In the formula, R ¹ to R ⁶ are each independently a monovalent hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, and may be the same or different from each other. In addition, 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, 0.67≦(b+d)/(a+c+e)≦1.67, and a+b+c+d+e=1. g is an integer from 0 to 300. X is a divalent organic group represented by the following formula (5). Y is a divalent siloxane skeleton-containing group represented by the following formula (6). Z is a divalent organic group represented by the following formula (7). ]

(In the formula, E is a single bond or the following formula

It is a divalent organic group selected from. R ⁷ and R ⁸ are monovalent hydrocarbon groups or alkoxy groups having 1 to 20 carbon atoms, and may be the same or different. t and u are each independently an integer of 0 to 2. )

（式中、ｖは、０～３００の整数である。）

（式中、Ｇは、単結合、又は下記式

から選ばれる２価の有機基である。Ｒ^９及びＲ^１０は、炭素数１～２０の１価炭化水素基又はアルコキシ基であり、互いに同一でも異なっていてもよい。ｗ及びｘは、それぞれ独立に、０～２の整数である。）

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

(In the formula, G is a single bond or the following formula

It is a divalent organic group selected from. R ⁹ and R ¹⁰ are monovalent hydrocarbon groups or alkoxy groups having 1 to 20 carbon atoms, and may be the same or different. w and x are each independently an integer of 0 to 2. )

R ¹ to R ⁶ each independently represent a monovalent hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, and may be the same or different from each other. In addition, 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, 0.67≦(b+d)/(a+c+e)≦1.67, and a+b+c+d+e=1.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include alkyl groups, cycloalkyl groups, and aryl groups having 1 to 20 carbon atoms, such as methyl group, ethyl group, propyl group, hexyl group, Examples include cyclohexyl group and phenyl group. Among them, methyl group and phenyl group are preferred because of easy availability of raw materials. Examples of the alkoxy group include groups in which an oxygen atom is bonded to the monovalent hydrocarbon group, such as a methoxy group, an ethoxy group, a propoxyl group, and a phenoxy group. a to e are not particularly limited as long as they satisfy the above conditions.

In formulas (5) and (7), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are monovalent hydrocarbon groups or alkoxy groups having 1 to 20 carbon atoms, and may be the same or different from each other. R ⁷ to R ¹⁰ are preferably an alkyl group or an alkoxy group having 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and specifically include a methyl group, an ethyl group, a propyl group, and a tert-butyl group. group, methoxy group, ethoxy group, etc. are preferred.

In formulas (5) and (7), t, u, w and x are each independently an integer of 0 to 2, with 0 being preferred.

The weight average molecular weight (Mw) of the silicone-modified epoxy resin represented by formula (4) is 3,000 to 500,000, preferably 5,000 to 200,000. The silicone-modified epoxy resin represented by formula (4) may be a random copolymer or a block polymer.

The epoxy resins may be used alone or in combination of two or more.

The silicone-modified epoxy resin represented by the formula (4) is prepared by using a compound selected from the silphenylene compound represented by the following formula (8) and the compounds represented by the following formulas (9) to (12), It can be manufactured by the method shown below.

（式中、Ｒ^１～Ｒ^１０、Ｅ、Ｇ、ｇ、ｔ、ｕ、ｖ、ｗ及びｘは、前記と同じ。）

(In the formula, R ¹ to R ¹⁰ , E, G, g, t, u, v, w and x are the same as above.)

The silicone-modified epoxy resin represented by formula (4) 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 the above formula (8) and formula (9) relative to the total number of moles of alkenyl groups possessed by the compounds represented by the above formula (10), formula (11), and formula (12). The total number of moles of hydrosilyl groups contained in the compound is preferably 0.67 to 1.67, preferably 0.83 to 1.25.

This polymerization reaction is carried out in the presence of a catalyst. As the catalyst, catalysts that are widely known to cause hydrosilylation to proceed can be used. 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 % based on the Si--H bond. 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 the addition reaction will be inhibited. There is no risk of it happening.

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 able to be stirred sufficiently 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.

By using such a resin, the resin composition before curing can be made flexible and easily formed into a film, and can also exhibit sufficient elastic modulus after curing, as well as chemical resistance, heat resistance, A cured product with better pressure resistance can be provided.

[(B) Component]
As the component (B), a wide variety of known phenolic curing agents can be used. The structure of the curing agent is preferably a polyhydric alcohol having 2 to 10 OH groups, and examples thereof include, but are not limited to, those shown below.

The content of component (B) is preferably blended so that the phenolic hydroxyl equivalent in component (B) is 60 mol% to 140 mol%, and 90 mol% to 110 mol%, based on the epoxy equivalent in the composition. More preferred. Within the above range, the curing reaction proceeds favorably, epoxy groups and phenolic hydroxyl groups do not accumulate excessively, and reliability is unlikely to deteriorate.

[(C) Component]
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, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and other imidazoles, 2-ethyl-4-methylimidazole 2 - Tertiary amines such as (dimethylaminomethyl)phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo[5.4.0]undecene-7, tris(dimethylaminomethyl)phenol, diphenylphosphine, triethanolamine, etc. Examples include organic phosphines such as phenylphosphine and tributylphosphine, tetra-substituted phosphonium and tetra-substituted borates such as tetraphenylphosphonium/tetraphenylborate and tetraphenylphosphonium/ethyltriphenylborate, and metal compounds such as tin octylate.

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 proceeds in just the right amount, the cured product does not become brittle, and reliability is improved.

（Ｒ’_１は加水分解性シリル基を含有する炭素数１～２０の１価の有機基、Ｒ’_２，Ｒ’_３はそれぞれ水素原子又は炭素数１～２０の１価の有機基、Ｘ’は酸素原子、もしくは硫黄原子、Ａｒは置換基を２つ持っていてもよい芳香環、もしくは複素環を示す。） [(D) Component]
Component (D) is an essential component of the present invention and is an effective component (adhesive aid) for improving adhesive strength. Component (D) is a compound selected from at least one compound represented by the following formulas (0-1) to (0-5).

(R' ₁ is a monovalent organic group having 1 to 20 carbon atoms containing a hydrolyzable silyl group, R' ₂ and R' ₃ are each a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, ' represents an oxygen atom or a sulfur atom, and Ar represents an aromatic ring or a heterocycle that may have two substituents.)

R' ₁ is a monovalent organic group having 1 to 20 carbon atoms and containing a hydrolyzable silyl group. The organic group may be a hydrocarbon group having a hydrolyzable silyl group. Examples of the hydrolyzable silyl group include an alkoxysilyl group, an acyloxysilyl group, an alkenyloxysilyl group, an aryloxysilyl group, a halogenated silyl group, and a silyl group having an amide group, an amino group, an aminooxy group, and a ketoximate group. Examples of the hydrocarbon group include alkylene groups such as methylene group, ethylene group, propylene group, butylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, and phenylene group. Examples include arylene groups such as naphthylene groups, phenethylene groups, and aralkylene groups such as xylylene groups. Examples of the alkoxy group in the alkoxysilyl group include methoxy group, ethoxy group, propoxyl group, and phenoxy group.

R' ₂ and R' ₃ are each a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Examples of monovalent organic groups having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and cyclohexyl group, and aryl groups such as phenyl group and naphthyl group. , aralkyl groups such as phenethyl groups, and the like.

Ar is an aromatic ring or a heterocycle which may have two substituents. Examples include phenyl group, tolyl group, xylyl group, naphthyl group, pyridyl group, quinolyl group, pyrrolyl group, imidazolyl group, and pyrimidyl group.

X' is an oxygen atom or a sulfur atom. In the compounds represented by the general formulas (0-1) to (0-3), it is preferable when X' is an oxygen atom from the viewpoint of easy availability of raw materials and storage stability of the composition.

Examples of component (D) (adhesive aid) include the following compounds.

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) component]
Moreover, an epoxy compound (E) other than the component (A) can be added to this resin composition. When adding, it can be added in an amount of 0.1 to 80 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight, per 100 parts by weight of the epoxy group-containing resin of component (A). can. Within this range, the effect of the epoxy compound appears and the amount of warpage does not increase.

The epoxy compound (E) preferably has 2 to 10 epoxy groups, preferably 2 to 5 epoxy groups, and examples thereof include, but are not limited to, the following. One type may be used alone, or two or more types may be used in combination.

[(F) component]
The resin composition of the present invention may contain an inorganic filler as component (F) in order to provide wafer protection, further improve heat resistance, moisture resistance, strength, etc., and increase reliability of the cured product. . Examples of inorganic fillers include titanium oxide, alumina, fused silica (fused spherical silica, fused crushed silica), oxides such as crystalline silica powder, silicates such as talc, glass, and fired clay, aluminum nitride, and boron nitride. , nitrides such as silicon nitride, carbonates such as calcium carbonate and magnesium carbonate, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite. etc. These inorganic fillers may be used alone or in combination of two or more.

The average particle size 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 will be easier to fill the filler and the strength of the cured product will be more likely to increase, and if it is 30 μm or less, the filling properties between the chips will be good. .

Among these, silica powders such as fused silica and crystalline silica are preferred. The content of component (F) is preferably 14 to 96% by mass, more preferably 20 to 96% by mass, even more preferably 50 to 95% by mass, and even more preferably 60 to 93% by mass based on the solid content of the resin composition. Particularly preferred. If the content of the inorganic filler is 96% by mass or less, the filling properties of the inorganic filler and the processability of the composition will be better, and if the content is 14% by mass or more, preferably 20% by mass or more, the inorganic filler The effect is fully realized. Note that the solid content refers to components other than the organic solvent.

[Other ingredients]
Moreover, the resin composition of the present invention may further contain components other than those described above. Examples include organic solvents, flame retardants, antioxidants, pigments, dyes, and the like.

(Organic solvent)
The resin composition of the present invention may be used after being dissolved in an organic solvent in order to uniformly mix these 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, propylene glycol monomethyl ether, Examples include propylene glycol monomethyl ether acetate, toluene, xylene, etc., and methyl ethyl ketone, cyclopentanone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are particularly preferred, but not limited thereto. 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.

(Flame retardants)
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).

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

With the composition of the present invention, wafers can be molded all at once (wafer molding), and it has good moldability, especially for large-diameter and thin-film wafers, and at the same time, it does not peel off from the substrate. It has high adhesion and low warping properties, allows for good molding processes, and can be suitably used for wafer level packages.

[Resin film]
Furthermore, the present invention provides a resin film characterized in that the resin composition of the present invention is formed into a film. The resin film of the present invention is obtained by processing the resin composition into a film shape. By being formed into a film, it has good molding performance for large-diameter, thin-film wafers, and when molding wafers all at once, there is no need to pour resin, which eliminates the possibility of filling defects on the wafer surface. This will not cause any problems such as Furthermore, a resin film formed using the resin composition is less likely to warp and has high adhesive strength, resulting in a wafer molding material that is less prone to various errors.

The resin film of the present invention may be obtained by laminating a protective film on a resin film obtained from the resin composition. An example of the method for manufacturing the resin film of the present invention in this case will be described.

A resin composition is prepared by mixing the above (A), (B), (C), (D) components, and if necessary, the (F) component, an epoxy compound (E) other than the (A) component, and other components. A solution is prepared, and the resin composition solution is applied to a protective film to a desired thickness using a reverse roll coater, a comma coater, or the like. The protective film coated with the resin composition solution 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 bonded to another protective film using a roll laminator. By laminating them, a laminate film in which a resin film is formed can be obtained. When this laminate film is used as a wafer molding material, it provides good moldability.

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

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 is preferably 50 to 300 mN/min. The thickness of the protective film is preferably 25 to 150 μm, more preferably 38 to 125 μm.

[Semiconductor laminate and method for manufacturing the same]
The semiconductor laminate of the present invention has a cured product of the resin film of the present invention on a semiconductor wafer. The method for manufacturing a semiconductor laminate of the present invention is a method including the steps of attaching the resin film to a semiconductor wafer and molding the semiconductor wafer, and heating and curing the 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.

Note that the resin film of the present invention can also be used to produce a semiconductor laminate having a cured product of the resin film of the present invention on a square substrate.
The square substrate may have a semiconductor element (chip) mounted on its surface, or may have a semiconductor element fabricated on its surface. The resin film of the present invention can be suitably used as a molding material regardless of the substrate size, such as 10 cm square or 50 cm square, larger substrates, rectangular or trapezoidal shapes, and regardless of the thickness of the substrate.

The method for 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), the degree of vacuum in the vacuum chamber is set to 50 to 1,000 Pa, preferably 50 to 500 Pa, for example 100 Pa, and the other protective layer is heated to 80 to 200°C, preferably 80 to 130°C, for example 100°C. This can be done by closely adhering the resin film pasted to the wafer all at once, returning the pressure to normal pressure, cooling the wafer to room temperature, taking it out of the vacuum laminator, and peeling off the other protective layer. .

Furthermore, for wafers on which semiconductor chips are stacked, 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 example, as a compression molding device, a device manufactured by Apic Yamada Co., Ltd. (product name: MZ-824-01) can be used, and when molding a 300mm silicon wafer on which semiconductor chips are stacked, ℃, molding pressure of 100 to 300 kN, clamp time of 30 to 90 seconds, and molding time of 5 to 20 minutes.

In addition, as a device equipped with a vacuum diaphragm laminator and a metal plate press for flattening, a device manufactured by Nichigo Morton Co., Ltd. (product name: CVP-300) can be used, and the lamination temperature is 100 to 180. ℃, degree of vacuum 50-500 Pa, pressure 0.1-0.9 MPa, lamination time 30-300 seconds, then upper and lower hot plate temperature 100-180 ℃, pressure 0.1-3.0 MPa, pressurization time 30 It is possible to flatten the resin molding surface in ~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.

In such a semiconductor laminate, since the resin film has high strength and adhesive strength, the semiconductor wafer is sufficiently protected by the resin film.

Moreover, with the method for manufacturing a semiconductor laminate as described above, it is possible to manufacture a semiconductor laminate in which the semiconductor wafer is sufficiently protected by the resin film.

[Semiconductor device and its manufacturing method]
The semiconductor device of the present invention is obtained by dividing the semiconductor laminate of the present invention into individual pieces. The method for manufacturing a semiconductor device of the present invention is a method including the step of singulating the semiconductor stack produced by the method for manufacturing a semiconductor stack of the present invention. In this way, by dividing the semiconductor wafer molded with a resin film into individual pieces, a semiconductor device having a heat-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 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 selected as appropriate, but usually 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.

[Epoxy compound (S-7) synthesis example]
In a 5 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 617 g (2.0 mol) of compound S-1, 256 g (8.0 mol) of methanol, and 852 g of epichlorohydrin ( 8.0 mol) was added thereto, and 768 g (19.2 mol) of sodium hydroxide was added over 2 hours, and then the temperature was raised to 60°C and the reaction was carried out for 3 hours. After the reaction, 500 mL of toluene was added, and after washing 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.

[1] Synthesis of resin The resin (epoxy resin) of component (A) was synthesized as follows.
In the synthesis example, the weight average molecular weight (Mw) was determined using a GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) under the analysis conditions of 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 gel permeation chromatography (GPC) using dispersed polystyrene as a standard.

[Resin synthesis example 1]
After adding 420.5 g (1.000 mol) of compound S-7 into a 3 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 1,400 g of toluene was added, and the mixture was heated to 70°C. Warmed. Thereafter, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 194.4 g (1.000 mol) of S-3 was added dropwise over 1 hour to each solution (total mole of hydrosilyl groups). number/total number of moles of alkenyl groups = 1.000/1.000 = 1.00). After the dropwise addition was completed, 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 570 g of Epoxy Resin 1. Mw of epoxy resin 1 was 53,200. Epoxy equivalent weight is 307 g/eq. (Epoxy equivalent measurement; JIS K 7236)

[Resin synthesis example 2]
After adding 133.5 g (0.227 mol) of compound S-2 into a 3 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 1,500 g of toluene was added, and the mixture was heated to 70°C. Warmed. Thereafter, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 525.6g (0.182 mol) of compound S-4 and 8.8g (0.182 mol) of compound S-3 were added. 045 mol) were added dropwise over a period of 1 hour (total number of moles of hydrosilyl groups/total number of moles of alkenyl groups = 0.500/0.500 = 1). 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 605 g of epoxy resin 2 represented by the following formula. Mw of epoxy resin 2 was 51,100. The epoxy equivalent weight is 1471 g/eq.

[Resin synthesis example 3]
Into a 3L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 104.9 g (0.179 mol) of compound S-2 and 61.5 g (0.143 mol) of compound S-5 were added. ), and 6.6 g (0.036 mol) of Compound S-6 were added, and then 1,600 g of toluene was added and the mixture was heated to 70°C. Thereafter, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 516.3g (0.179 mol) of Compound S-4 and 34.7g (0.179 mol) of Compound S-3 were added. 179 mol) were added dropwise over 1 hour (total number of moles of hydrosilyl groups/total number of moles of alkenyl groups = 0.500/0.500 = 1.00). 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 epoxy resin 3. Mw of epoxy resin 3 was 46,800. Epoxy equivalent weight is 2022 g/eq.

[2] Production of resin film [Examples 1 to 21 and Comparative Examples 1 to 7]
With the compositions of Examples 1 to 21 and Comparative Examples 1 to 7 listed in Tables 1 to 2 below, (A) epoxy resin, (B) phenolic curing agent, (C) curing accelerator, and (D) adhesion aid. , (E) an epoxy compound, and (F) an inorganic filler. 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 to prepare a dispersion of the resin composition. A phenolic curing agent was added so that the epoxy groups and phenol equivalents matched.
Each resin composition was applied onto the base 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 base film. . Next, the solvent was completely evaporated by placing it in an oven set at 100° C. for 20 minutes to form a resin film with a thickness of 100 μm on the base film.

In addition to the above, each component used in the preparation of the resin composition is shown below.
[Component (A): Epoxy resin]
・YL983U (epoxy equivalent 172g/eq; manufactured by Mitsubishi Chemical Corporation)

[Component (B): Phenolic curing agent]

[Component (C): Curing accelerator]
・Curezol 2P4MHZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2-phenyl-4-methyl-5-hydroxymethylimidazole)

[Component (D): Adhesive aid]

[Component (E): Epoxy compound]

[Component (F): Inorganic filler]
・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)

[3] Evaluation of resin film The obtained resin film was evaluated by the following method. The results are shown in Tables 1 and 2.
<Adhesion test method>
The produced film was pasted on a 20 mm square silicon wafer, a silicon chip cut into 2 mm square pieces was pressed onto it, and the film was cured by heating (180°C x 4 hours). - Using a universal bond tester series 4000 (DS-100) manufactured by Technology Co., Ltd., the adhesive strength was measured when the chip was flipped from the side (die shear test).

<Warp stress measurement test method>
The produced film was laminated onto a silicon wafer using a film laminator (TAKATORI TEAM-100), heated and cured (180°C x 4 hours), and then measured using a thin film stress measuring device (FLX-2320-) manufactured by Toho Technology Co., Ltd. S) was used to measure warping stress.

<Reliability test method>
A 10 mm square 400 um thick silicon chip was mounted on a silicon wafer using an epoxy adhesive (SINR-DF3770; manufactured by Shin-Etsu Chemical Co., Ltd.), and the adhesive was cured by heating (190° C. x 2 hr). Thereafter, the produced film was laminated onto a silicon wafer using a film laminator (TAKATORI TEAM-100), heated and cured (180° C. for 4 hours), and then diced into squares of 3 cm on each side with the chip as the center. It was placed in a thermal shock tester manufactured by ESPEC, and subjected to 1000 thermal shock tests at -55°C to 125°C, and the state of the interface between the chip and the mold was confirmed by cross-sectional observation. If there is peeling or cracking, it is marked as ×, and if there is no problem, it is marked as ○.

Table 1 shows Examples, and Table 2 shows Comparative Examples.

As a result, the resin films obtained from the resin compositions of the present invention (Examples 1 to 21) were superior to those obtained from the compositions not containing component (D) (Comparative Examples 1 to 7). , it was shown that the adhesive strength was improved and significantly contributed to the reliability of the package. From this feature, it can be said that when the resin composition of the present invention is used in a film for semiconductor encapsulation, peeling is difficult to occur.
As a result, when the resin composition of the present invention is used, for example, in a film-like mold application, it is possible to exhibit good low warping properties and difficult peeling properties for chip-mounted wafers.

Note that the present invention is not limited to the above embodiments. The above-mentioned embodiments are illustrative, and any embodiment that has substantially the same configuration as the technical idea stated in the claims of the present invention and has similar effects is the present invention. covered within the technical scope of

Claims (11)

A resin composition for semiconductor encapsulation comprising the following (A) to (D).
(A) a silicone-modified epoxy resin containing epoxy groups with an epoxy equivalent in the range of 140 to 5000 g/eq;
(B) phenolic curing agent,
(C) curing accelerator,
(D) At least one adhesion aid selected from the following formulas (0-4) to ( 0-7 ) (provided that 3-methacryloxypropyltriethoxysilane, N-phenyl-3-aminopropyl (Excluding trimethoxysilane )

( _R'1 is a monovalent organic group having 1 to 20 carbon atoms containing a hydrolyzable silyl group, _R'2 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and Ar is a substituent. Indicates an aromatic ring or a heterocycle that may have two.) Furthermore, the epoxy compound (E) other than the component (A) is contained in an amount of 0.1 to 80 parts by mass based on 100 parts by mass of the component (A). Resin composition for semiconductor encapsulation. The resin composition for semiconductor encapsulation according to claim 1 or 2, further comprising (F) an inorganic filler. The resin composition for semiconductor encapsulation according to claim 3, wherein the inorganic filler (F) is silica and is contained in the resin composition in an amount of 20 to 96% by mass. R' in the above formula (0-5) ₂ The resin composition for semiconductor encapsulation according to any one of claims 1 to 4, wherein is a monovalent organic group having 1 to 20 carbon atoms. Any one of claims 1 to 5, wherein the silicone-modified epoxy resin contains a structural unit represented by the following formula (4) and has a weight average molecular weight of 3,000 to 500,000. The resin composition for semiconductor encapsulation as described in 1 .

[In the formula, R ¹ to R ⁶ are each independently a monovalent hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, and may be the same or different from each other. In addition, 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, 0.67≦(b+d)/(a+c+e)≦1.67, and a+b+c+d+e=1. g is an integer from 0 to 300. X is a divalent organic group represented by the following formula (5). Y is a divalent siloxane skeleton-containing group represented by the following formula (6). Z is a divalent organic group represented by the following formula (7). ]

(In the formula, E is a single bond or the following formula

It is a divalent organic group selected from. R ⁷ and R ⁸ are a monovalent hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, and may be the same or different. t and u are each independently an integer of 0 to 2. )

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

(In the formula, G is a single bond or the following formula

It is a divalent organic group selected from. R ⁹ and R ¹⁰ are monovalent hydrocarbon groups or alkoxy groups having 1 to 20 carbon atoms, and may be the same or different. w and x are each independently an integer of 0 to 2. ) A resin film, characterized in that the resin composition for semiconductor encapsulation according to any one of claims 1 to 6 is formed into a film. A semiconductor laminate comprising a cured product of the resin film according to claim 7 on a semiconductor wafer. A semiconductor device,
A semiconductor device, characterized in that the semiconductor laminate according to claim 8 is singulated. A method for manufacturing a semiconductor laminate, the method comprising:
A method for manufacturing a semiconductor laminate, comprising the steps of attaching the resin film according to claim 7 to a semiconductor wafer, molding the semiconductor wafer, and heating and curing the resin film. A method for manufacturing a semiconductor device, the method comprising:
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.