JP2015206013A - Photosensitive adhesive composition, method for manufacturing semiconductor device using the same, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive adhesive composition that has photosensitivity characteristics (sensitivity and resolution) equivalent to those of a photosensitive resin composition used for a buffer coat layer, has little damages in a half-cured film state by dry etching or Oashing, allows continuous press-bonding in the manufacture of a semiconductor device by stacking a plurality of semiconductor chips, and has buffer coat characteristics with excellent wetting and spreading properties upon stacking chips, and a method for manufacturing a semiconductor device and a semiconductor device using the above composition.SOLUTION: The photosensitive adhesive composition comprises (A) a phenolic resin, (B) a compound that generates an acid by light, (C) a thermal crosslinking agent having three or more groups that crosslink with the (A) component, and (D) an acrylic resin having a structural unit represented by general formula (1) below.

Description

  The present invention relates to a photosensitive adhesive composition used for an adhesive layer or the like when stacking semiconductor devices, a method for manufacturing a semiconductor device using the same, and a semiconductor device.

In recent years, semiconductor devices having a multilayer structure in which a plurality of semiconductor chips are stacked are attracting attention. However, the thickness of a semiconductor device increases as the number of semiconductor chips increases, so there is a demand to reduce the thickness of the semiconductor device. It is getting stronger.
In response to the above requirement, the thickness of the semiconductor device is reduced by reducing the thickness of the semiconductor chip itself. However, reducing the thickness of the chip itself is approaching the limit.

  Therefore, in order to eliminate the thickness of the die attach film used to bond the semiconductor chips when laminating the semiconductor chips, and to reduce the thickness of the semiconductor device, the bonding function to the buffer coat layer formed on the surface of the semiconductor chip Has been proposed (see Patent Documents 1 and 2, for example). In the method described in the above-mentioned patent document, the photosensitive adhesive composition is required to have a low-temperature curing property of about 170 to 180 ° C. in order to avoid deterioration of characteristics due to heat of the semiconductor chip.

JP 2012-162676 A Japanese Patent No. 5077023

In the case where the photosensitive adhesive composition is used as a buffer coat / adhesive layer, it is necessary to have photosensitive characteristics, pressure-bonding properties, adhesiveness and reliability. In addition, since the photosensitive adhesive composition film needs to have a certain degree of wetting and spreading during the bonding process, the film is in a semi-cured state until the bonding process and needs to be cured after the bonding process. . Therefore, the photosensitive adhesive composition is required to have resistance to dry etching in an uncured state after pattern opening.
Furthermore, since the curing temperature of the photosensitive adhesive composition is 170 to 180 ° C. in order to avoid deterioration of characteristics due to heat of the semiconductor chip, low temperature curing characteristics are also required.
The present invention has been made in view of the above circumstances, has the same photosensitive characteristics (sensitivity and resolution) as the photosensitive resin composition used as the buffer coat layer, and the semi-cured film is subjected to dry etching and O ₂ ashing. A photosensitive adhesive composition having a buffer coating characteristic that has a small damage and can be continuously pressed when a semiconductor device is produced by laminating a plurality of semiconductor chips, and has excellent wetting and spreading properties when the chips are laminated. It is an object of the present invention to provide a method of manufacturing a semiconductor device and a semiconductor device used.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on a photosensitive adhesive composition having photosensitive characteristics, dry etching resistance, thermocompression bonding properties and adhesiveness. As a result, by improving the compatibility of the components in the photosensitive adhesive composition, a photosensitive adhesive composition having photosensitive characteristics, dry etching resistance, thermocompression bonding properties and adhesiveness is found, and the present invention is completed. It came to.

  The photosensitive adhesive composition according to the present invention includes (A) a phenol resin, (B) a compound that generates an acid by light, and (C) a thermal crosslinking agent having three or more groups that crosslink with the component (A). And (D) a photosensitive adhesive composition containing an acrylic resin having a structural unit represented by the following general formula (1).

[一般式（１）中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は炭素数２〜２０のヒドロキシアルキル基を示す。]

[In General Formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydroxyalkyl group having 2 to 20 carbon atoms. ]

  Since the sensitivity at the time of forming a pattern cured film improves, it is preferable that the said (B) component contains an o-quinonediazide compound. Further, from the viewpoint of further reducing the moisture absorption rate, the component (C) is preferably a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, or a compound having an epoxy group.

The present invention includes a step of applying the photosensitive adhesive composition to a circuit surface of a semiconductor wafer and drying to form a photosensitive adhesive composition film, and exposing a predetermined portion of the photosensitive adhesive composition film. A step of forming the pattern by developing the photosensitive adhesive composition film after the exposure and removing the predetermined portion; and heating the semiconductor wafer on which the pattern is formed to remove the residual solvent. A step of performing an ashing process after removing the predetermined portion of the insulating film by etching, a step of wafer thinning and chip separation, a step of stacking chips, and the photosensitive adhesive composition And a step of heat-curing the film.
According to this manufacturing method, a plurality of semiconductor chips can be continuously mounted, and a thin semiconductor device can be efficiently manufactured.
The present invention also relates to a semiconductor device obtained by the method for manufacturing a semiconductor device.

  According to the present invention, a photosensitive adhesive composition having photosensitive characteristics, dry etching resistance, thermocompression bonding, and adhesiveness, a method for manufacturing a semiconductor device obtained using the same, and a semiconductor device obtained by the manufacturing method are provided. can do. In addition, since the photosensitive adhesive composition having the buffer coating characteristics of the present invention can be cured at a low temperature, the semiconductor device can be prevented from being damaged by heat, and a thin and highly reliable semiconductor device can be obtained. It can be provided with good yield.

It is sectional drawing which shows an example of the semiconductor device produced using the photosensitive adhesive composition of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In this specification, “(meth) acrylate” means “acrylate” or “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” or “methacryl”. Moreover, unless otherwise indicated, the exemplary compound described below can be used individually by 1 type or in combination of 2 or more types.

[Photosensitive adhesive composition]
The photosensitive adhesive composition according to the present embodiment includes (A) a phenol resin, (B) a compound that generates an acid by light, and (C) a thermal crosslink having at least three groups that crosslink with the component (A). It is a photosensitive adhesive composition containing an agent and (D) an acrylic resin having a structural unit represented by the general formula (1).

<(A) component: phenol resin>
The phenol resin is a polycondensation product of phenol or a derivative thereof and aldehydes. Specific examples of the phenol resin include phenol / formaldehyde novolak resin, cresol / formaldehyde novolak resin, xylylenol / formaldehyde novolak resin, resorcinol / formaldehyde novolak resin, phenol-naphthol / formaldehyde novolak resin, and the like.

Examples of the phenol derivative used for obtaining the phenol resin include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3 Alkylphenols such as 1,4,5-trimethylphenol;
Alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol; alkenylphenols such as vinylphenol and allylphenol; aralkylphenols such as benzylphenol; alkoxycarbonylphenols such as methoxycarbonylphenol; arylcarbonylphenols such as benzoyloxyphenol Halogenated phenols such as chlorophenol; polyhydroxybenzenes such as catechol, resorcinol, pyrogallol; bisphenols such as bisphenol A and bisphenol F; naphthol derivatives such as α- or β-naphthol; p-hydroxyphenyl-2-ethanol, p -Hydroxyalkylphenols such as hydroxyphenyl-3-propanol and p-hydroxyphenyl-4-butanol Hydroxyalkyl cresols such as hydroxyethyl cresol; monoethylene oxide adducts of bisphenol; alcoholic hydroxyl group-containing phenol derivatives such as monopropylene oxide adducts of bisphenol; p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxy Examples thereof include phenylbutanoic acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid, and carboxyl group-containing phenol derivatives such as diphenol. Further, methylolated products of the above-mentioned phenol derivatives such as bishydroxymethyl-p-cresol may be used as the phenol derivative.

  Furthermore, the phenol resin may be a product obtained by polycondensing the above-mentioned phenol or phenol derivative with an aldehyde together with a compound other than phenol such as m-xylene. In this case, the molar ratio of the compound other than phenol to the phenol derivative used for the condensation polymerization is preferably less than 0.5. Compounds other than the above-described phenol derivatives and phenol compounds are used singly or in combination of two or more.

  Aldehydes used to obtain phenolic resins include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, glyceraldehyde, glyoxylic acid , Methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate and the like. Also, formaldehyde precursors such as paraformaldehyde and trioxane, and ketones such as acetone, pyruvic acid, repric acid, 4-acetylbutyric acid, acetonedicarboxylic acid, and 3,3′-4,4′-benzophenonetetracarboxylic acid You may use for reaction.

  The weight average molecular weight of the component (A) is preferably from 500 to 150,000, preferably from 500 to 100,000 in consideration of the balance of solubility in an alkaline aqueous solution, photosensitive properties, and mechanical properties of the pattern cured film. Is more preferable, and it is more preferable that it is 1000-50,000. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

  The component (A) in the present invention may include both a phenol resin (A1) having no unsaturated hydrocarbon group and a modified phenol resin (A2) having an unsaturated hydrocarbon group. The component (A2) may be modified by a reaction between a phenolic hydroxyl group and a polybasic acid anhydride. By containing the component (A2), the adhesion and thermal shock resistance of the cured film can be improved.

  The component (A2) is generally a compound having phenol or a derivative thereof and an unsaturated hydrocarbon group (preferably having 4 to 100 carbon atoms) (hereinafter sometimes simply referred to as “unsaturated hydrocarbon group-containing compound”). Is a reaction product of a polycondensation product of aldehydes with a reaction product (hereinafter referred to as “unsaturated hydrocarbon group-modified phenol derivative”) or a reaction product of a phenol resin and an unsaturated hydrocarbon group-containing compound. . As the phenol derivative used for obtaining the component (A2), the same phenol derivatives and aldehydes used for obtaining the phenol resin can be used.

  The unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated bonds from the viewpoint of adhesion of the pattern cured film and thermal shock resistance, and preserves the photosensitive adhesive composition. From the viewpoint of stability, the number of unsaturated bonds is preferably 30 or less. In addition, from the viewpoint of compatibility when the photosensitive adhesive composition is used and the flexibility of the cured film, the unsaturated hydrocarbon group-containing compound preferably has 8 to 80 carbon atoms, and preferably has 10 to 60 carbon atoms. Those are more preferred.

  Examples of the unsaturated hydrocarbon group-containing compound include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linoleyl alcohol, oleyl alcohol, unsaturated fatty acid, or unsaturated fatty acid ester. Suitable unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, eleostearic acid, stearidone Examples include acids, arachidonic acid, eicosapentaenoic acid, sardine acid, or docosahexaenoic acid. Among these, vegetable oils that are unsaturated fatty acid esters are particularly preferred because of compatibility with phenolic resins and mechanical properties.

  Vegetable oils are generally esters of glycerin and unsaturated fatty acids, and are divided into non-drying oils having an iodine value of 100 or less, semi-drying oils exceeding 100 and less than 130, or drying oils of 130 or more. Examples of non-drying oils include olive oil, Asa seed oil, Japanese cabbage seed oil, potato oil, camellia oil, castor oil, and peanut oil. Semi-drying oils include corn oil, cottonseed oil, sesame oil and the like. Examples of the drying oil include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, camellia oil, coconut oil, and the like. Moreover, you may use the processed vegetable oil obtained by processing these vegetable oils.

  Among these vegetable oils, it is preferable to use a dry oil from the viewpoint of improving the adhesion, mechanical properties and thermal shock resistance of the pattern cured film. Among drying oils, tung oil, linseed oil, soybean oil, walnut oil, and safflower oil are more preferable, and tung oil and linseed oil are more preferable because the effects of the present invention can be more effectively and reliably exhibited.

  (A2) A phenolic resin that has been acid-modified by further reacting a polybasic acid anhydride with the phenolic hydroxyl group present in the component can also be used as the component (A2). Carboxy group is introduce | transduced by acid-modifying with a polybasic acid anhydride, and the solubility with respect to the aqueous alkali solution (developer) of (A2) component improves further.

  The component (A2) can be prepared by a known method described in, for example, International Publication No. 2010/026988.

  The acid value of the phenol resin further modified with polybasic acid anhydride is preferably 30 to 200 mgKOH / g, more preferably 40 to 170 mgKOH / g, and further preferably 50 to 150 mgKOH / g. . When the acid value is less than 30 mg KOH / g, it tends to require a longer time for alkali development than when the acid value is in the above range, and when it exceeds 200 mg KOH / g, the acid value is in the above range. In comparison with the above, the developer resistance of the unexposed portion tends to be lowered.

  The molecular weight of the component (A2) is preferably 1,000 to 500,000, more preferably 2,000 to 200,000 in terms of weight average molecular weight, considering the balance between solubility in an alkaline aqueous solution, photosensitive characteristics and cured film properties. Preferably, it is 2,000-100,000. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

  The photosensitive adhesive composition is used in terms of sensitivity and resolution when forming a patterned resin film, pattern shape after curing, change in opening size, adhesion of the patterned cured film, mechanical properties, and thermal shock resistance. When the modified phenolic resin (A2) having an unsaturated hydrocarbon group is used as a component (A), the phenolic resin (A1) having no unsaturated hydrocarbon group in the component (A), The mass ratio of the modified phenolic resin (A2) having a saturated hydrocarbon group is preferably 5:95 to 95: 5 in the former: the latter with the total amount of both being 100, and is preferably in the range 10:90 to 90:10. It is more preferable that 15:85 to 85:15 be included.

<(B) component: Compound that generates acid by light>
The photosensitive adhesive composition of this embodiment contains (B) the compound which produces | generates an acid by light. The component (B) is used as a photosensitive agent in the photosensitive adhesive composition. Such a component (B) has a function of generating acid upon irradiation with light and increasing the solubility of the irradiated portion in an alkaline aqueous solution.

  As the component (B), a compound generally called a photoacid generator can be used. Specific examples of the component (B) include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. (B) A component may consist only of 1 type in these compounds, and may be comprised including 2 or more types. Of these, o-quinonediazide compounds are preferred because of their high sensitivity.

  As the o-quinonediazide compound, for example, a compound obtained by subjecting o-quinonediazidesulfonyl chloride to a hydroxy compound and / or an amino compound in the presence of a dehydrochlorinating agent can be used.

  Examples of o-quinonediazidesulfonyl chloride used in the reaction include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-6-sulfonyl chloride. Etc.

  Examples of the hydroxy compound used in the reaction include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4- Hydroxyphenyl) -1-methylethyl} phenyl] ethane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4,3 ′, 4 ′, 5′-hexahydroxybenzophenone, Bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) Nyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, And tris (4-hydroxyphenyl) ethane.

  Examples of amino compounds used in the reaction include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diamino. Diphenyl sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis ( 3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, Bis (3-amino-4-hydroxyphenyl) hexaful Examples include oropropane and bis (4-amino-3-hydroxyphenyl) hexafluoropropane.

  Among these, from the absorption wavelength range and reactivity, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane and 1 -Compound obtained by condensation reaction of naphthoquinone-2-diazide-5-sulfonyl chloride, tris (4-hydroxyphenyl) methane or tris (4-hydroxyphenyl) ethane and 1-naphthoquinone-2-diazide-5 It is preferable to use a compound obtained by condensation reaction with sulfonyl chloride.

  Examples of the dehydrochlorinating agent used in the reaction include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, and pyridine. Moreover, as a reaction solvent, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran (THF), diethyl ether, N-methylpyrrolidone and the like are used.

  o-quinonediazidosulfonyl chloride and hydroxy compound and / or amino compound are blended so that the total number of moles of hydroxy group and amino group is 0.5 to 1 per mole of o-quinonediazidesulfonyl chloride. It is preferred that A preferred blending ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 molar equivalent to 1 / 0.95 molar equivalent. In addition, the preferable reaction temperature of the above-mentioned condensation reaction is 0-40 degreeC, and preferable reaction time is 1 to 10 hours.

  The content of the component (B) in the photosensitive adhesive composition is 3 with respect to 100 parts by mass of the component (A) because the difference in dissolution rate between the exposed part and the unexposed part increases and the sensitivity becomes better. -100 mass parts is preferable, 5-50 mass parts is more preferable, 5-30 mass parts is more preferable, It is especially preferable to set it as 10-30 mass parts, and 15-25 mass parts is very preferable.

<(C) component): (A) thermal crosslinking agent having three or more groups that crosslink with component>
The photosensitive adhesive composition of this embodiment contains a thermal crosslinking agent (C) having three or more groups that crosslink with the component (A). Thereby, brittleness of the film and melting of the film can be prevented. (C) The thermal crosslinking agent is preferably a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, or a compound having an epoxy group.

  The “compound having a phenolic hydroxyl group” here does not include the component (A). The compound having a phenolic hydroxyl group as a thermal crosslinking agent can increase the dissolution rate of the exposed area when developing with an alkaline aqueous solution as well as the thermal crosslinking agent, and improve the sensitivity. The molecular weight of such a compound having a phenolic hydroxyl group is preferably 2000 or less. Considering the solubility in an aqueous alkali solution and the balance between the photosensitive properties and the mechanical properties, the number average molecular weight is preferably 94 to 2000, more preferably 108 to 2000, and even more preferably 108 to 1500. The number average molecular weight of the “compound having a phenolic hydroxyl group” is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC).

  Conventionally known compounds can be used as the compound having a phenolic hydroxyl group, but the compound represented by the following general formula (2) prevents dissolution at the time of curing the resin film and the effect of promoting dissolution of the exposed portion. It is excellent in the balance of effects and is preferable.

（一般式（２）中、Ｘは単結合又は２価の有機基を示し、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又は１価の有機基を示し、ｓ及びｔはそれぞれ独立に１〜３の整数を示し、ｕ及びｖはそれぞれ独立に０〜４の整数を示す。）

(In General Formula (2), X represents a single bond or a divalent organic group, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and s and t Are each independently an integer of 1 to 3, and u and v are each independently an integer of 0 to 4.)

  In the general formula (2), examples of the compound in which X is a single bond include biphenol (dihydroxybiphenyl) derivatives. Examples of the divalent organic group represented by X include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group and propylene group; alkylidene groups having 2 to 10 carbon atoms such as ethylidene group and phenylene groups. An arylene group having 6 to 30 carbon atoms, such as a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond, an amide bond Etc.

  Examples of the compound having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N- And nitrogen-containing compounds obtained by alkyl etherifying all or part of active methylol groups such as hydroxymethyl) urea. Here, the alkyl group of the alkyl ether includes a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specific examples include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, and tetrakis (methoxymethyl) urea.

  A conventionally well-known thing can be used as a compound which has an epoxy group. Specific examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, alicyclic epoxy resins, glycidylamine type epoxy resins, heterocyclic epoxy resins, polyalkylene glycols. And epoxy-based epoxy crosslinking agents and polyalkylene-based epoxy crosslinking agents.

  As component (C), in addition to the compounds described above, hydroxymethyl groups such as bis [3,4-bis (hydroxymethyl) phenyl] ether and 1,3,5-tris (1-hydroxy-1-methylethyl) benzene , Aromatic compounds having a maleimide group, such as bis (4-maleimidophenyl) methane and 2,2-bis [4- (4′-maleimidophenoxy) phenyl] propane, compounds having a norbornene skeleton, polyfunctional acrylates A compound, a compound having an oxetanyl group, a compound having a vinyl group, a blocked isocyanate compound, or the like can be used.

  The component (C) is preferably used in combination with a bifunctional crosslinking agent from the viewpoint of thermocompression bonding. The type is preferably selected from the above-described compounds having a phenolic hydroxyl group, compounds having a hydroxymethylamino group, and compounds having an epoxy group, such as a polyalkylene glycol epoxy crosslinking agent and a polyalkylene epoxy crosslinking agent. It is more preferable to use a thermal crosslinking agent having a simple skeleton. 5-50 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of a bifunctional crosslinking agent, 10-45 mass parts is more preferable, and 15-40 mass parts is further more preferable.

  Moreover, as a process using the photosensitive adhesive composition which has a buffer coat characteristic, after performing pattern formation, it passes through a thermocompression bonding process. At this time, it is preferable to use at least two types of (C) thermal crosslinking agents having different reaction temperatures. These two types of thermal cross-linking agents are preferably used in combination with a thermal cross-linking agent whose reaction proceeds at a temperature lower than the pressure bonding temperature of 80 to 150 ° C. and two types of thermal cross-linking agents whose reaction proceeds at 150 to 230 ° C. .

  By using the crosslinking agent in combination, semi-curing can be performed once after pattern formation, pattern deformation in the process up to pressure bonding can be prevented, and sufficient flexibility for pressure bonding can be maintained. Furthermore, the adhesive strength with the adherend can be enhanced by proceeding with the curing after the pressure bonding. As the component (C), it is desirable to use a compound having a hydroxymethylamino group and a compound having an epoxy group in combination.

  The content of the component (C) is preferably 12 to 50 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of alkali developability, moisture absorption after moisture reflow, and adhesive strength. A mass part is more preferable, and 20-30 mass parts is further more preferable.

<(D): Acrylic resin having a structural unit represented by the following general formula (1)>
The photosensitive adhesive composition of this embodiment contains the acrylic resin (D) which has a structural unit represented by following General formula (1). Thereby, the compatibility of the components in the photosensitive adhesive composition is improved, and the photosensitive properties, dry process resistance, and thermocompression bonding properties are improved.

[一般式（１）中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は炭素数２〜２０のヒドロキシアルキル基を示す。]

[In General Formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydroxyalkyl group having 2 to 20 carbon atoms. ]

Monomers represented by the general formula (1) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, and (meth) acrylic. Hydroxyhexyl acid, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxynonyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxyundecyl (meth) acrylate, (meth) acrylic acid Hydroxydodecyl (sometimes called hydroxylauryl (meth) acrylate), hydroxytridecyl (meth) acrylate, hydroxytetradecyl (meth) acrylate, hydroxypentadecyl (meth) acrylate, hydroxy (meth) acrylate Heki Decyl, (meth) acrylic acid hydroxy heptadecyl, a (meth) acrylic acid hydroxy octadecyl, a (meth) acrylic acid hydroxy nonadecyl, and (meth) hydroxy eicosyl acrylic acid. In addition, R ¹ may include a branch such as a methyl group or an ethyl group.

  Among these, from the viewpoint of further improving the compatibility with the component (A) and the elongation at break, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylic Hydroxypentyl acid, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxynonyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxy (meth) acrylate It is preferable to use undecyl or hydroxydodecyl (meth) acrylate.

  The component (D) may be an acrylic resin composed only of the structural unit represented by the general formula (1), or an acrylic resin having a structural unit other than the structural unit represented by the general formula (1). Also good. When the acrylic resin has a structural unit other than the structural unit represented by the general formula (1), the proportion of the structural unit represented by the general formula (1) in the acrylic resin is based on the total amount of the component (D). The content is preferably 0.1 to 30 mol%, more preferably 0.3 to 25 mol%, and still more preferably 0.5 to 20 mol%. When the composition ratio of the structural unit represented by the general formula (1) is 0.1 to 30 mol%, the compatibility with the component (A) and the thermal shock resistance of the pattern cured film can be further improved. it can.

  In addition, the component (D) contains a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4) from the viewpoints of alkali developability and cured film properties. An acrylic resin is preferable. When the photosensitive adhesive composition contains the acrylic resin, the thermal shock resistance can be improved while maintaining good photosensitive characteristics.

［一般式（３）及び（４）中、Ｒ^７又はＲ^９は水素原子又はメチル基を表し、Ｒ^８は炭素数４〜２０のアルキル基を表す。］

[In General Formulas (3) and (4), R ⁷ or R ⁹ represents a hydrogen atom or a methyl group, and R ⁸ represents an alkyl group having 4 to 20 carbon atoms. ]

In the general formula (3), R ⁸ is preferably an alkyl group having 4 to 16 carbon atoms, and more preferably an alkyl group having 4 carbon atoms from the viewpoint of improving sensitivity, resolution, and thermal shock. Examples of the polymerizable monomer that gives the structural unit represented by the general formula (3) include (meth) acrylic acid alkyl esters.

  Moreover, (meth) acrylic acid is mentioned as a polymerizable monomer which gives the structural unit represented by General formula (4).

  In the acrylic resin as the component (D), the composition ratio of the structural unit represented by the general formula (3) is preferably 50 to 95 mol% with respect to the total amount of the component (D), More preferably, it is 90 mol%, and it is further more preferable that it is 70-85 mol%. When the composition ratio of the structural unit represented by the general formula (3) is 50 to 95 mol%, the thermal shock resistance of the cured film of the photosensitive adhesive composition can be further improved.

  In the acrylic resin as the component (D), the composition ratio of the structural unit represented by the general formula (4) is preferably 5 to 35 mol% with respect to the total amount of the component (D). More preferably, it is 10-30 mol%, and it is further more preferable that it is 15-25 mol%. When the composition ratio of the structural unit represented by the general formula (4) is 5 to 35 mol%, the compatibility with the component (A) and the developability of the photosensitive adhesive composition can be further improved. it can.

  In addition, from the viewpoint of further improving the compatibility with the component (A), the adhesion of the resist pattern to the substrate, the mechanical properties, and the thermal shock resistance, the component (D) is a structure represented by the following general formula (5). It is more preferable to contain an acrylic resin having units. When (D) component is the said acrylic resin, interaction with (D) component and (A) phenol resin becomes favorable, and compatibility improves more.

［一般式（５）中、Ｒ^１０は水素原子又はメチル基を表し、Ｒ^１１は１級、２級又は３級アミノ基を有する１価の有機基を表す。］

[In General Formula (5), R ¹⁰ represents a hydrogen atom or a methyl group, and R ¹¹ represents a monovalent organic group having a primary, secondary, or tertiary amino group. ]

Examples of the polymerizable monomer that gives the structural unit represented by the general formula (5) include aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N-ethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, aminoethyl (meth) acrylamide, N-methylaminoethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N-ethylaminoe (Meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, aminopropyl (meth) acrylamide, N-methylaminopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-ethylamino Propyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, piperidin-4-yl (meth) acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2,6,6-tetramethyl Piperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate, 2- (piperidine- 4-yl) ethyl (meth) acrylate And the like. Among these, from the viewpoint of further improving the adhesion of the resist pattern to the substrate, mechanical properties, and thermal shock resistance, in the general formula (5), R ¹¹ is a monovalent group represented by the following general formula (6). Particularly preferred is an organic group.

［一般式（６）中、Ｘは炭素数１〜５のアルキレン基を表し、Ｒ^１２〜Ｒ^１６はそれぞれ独立に水素原子又は炭素数１〜２０のアルキル基を表し、ｎは０〜１０の整数である］

In [formula (6), X represents an alkylene group having 1 to 5 carbon ^atoms, R 12 ^{to R 16} each independently represent a hydrogen atom or an alkyl group having a carbon number 1 to 20, n is of 0 Is an integer]

In the general formula (5), R ¹¹ is a polymerizable monomer giving a structural unit represented by a monovalent organic group represented by the general formula (6). Piperidin-4-yl (meth) acrylate 1-methylpiperidin-4-yl (meth) acrylate, 2,2,6,6-tetramethylpiperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4- Il (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate, 2- (piperidin-4-yl) ethyl (meth) acrylate and the like. Among these, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate is FA-711MM, and 2,2,6,6-tetramethylpiperidin-4-yl methacrylate is FA-712HM. (Both manufactured by Hitachi Chemical Co., Ltd.) are commercially available.

  In the case where the component (D) is an acrylic resin having the structural unit represented by the general formula (5), the content ratio of the structural unit represented by the general formula (5) is included in the component (D). It is preferably 0.3 to 10 mol%, more preferably 0.4 to 6 mol%, particularly 0.5 to 5 mol% based on the total amount of structural units of the acrylic resin. preferable.

In addition, the polymerizable monomer used for the synthesis of the acrylic resin constituting the component (D) is a polymerization that gives each structural unit represented by the general formulas (1), (3), (4), and (5). A polymerizable monomer other than the polymerizable monomer may further be included.
Examples of such polymerizable monomers include styrene, α-methylstyrene, (meth) acrylic acid benzyl ester, (meth) acrylic acid 4-methylbenzyl ester, (meth) acrylic acid 2-hydroxyethyl ester, (meta ) Acrylic acid 2-hydroxypropyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl ester, acrylonitrile, vinyl alcohol esters such as vinyl-n-butyl ether, (meth) acrylic Acid tetrahydrofurfuryl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, α-bromo (meth) Acrylic acid, α-chloro (meth) Maleic acid monoesters such as crylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid Cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like.

The weight average molecular weight of component (D) is preferably from 2,000 to 100,000, more preferably from 3,000 to 60,000, and even more preferably from 5,000 to 50,000. It is especially preferable that it is 10,000-40,000. If the weight average molecular weight is less than 2,000, the thermal shock resistance of the cured film tends to decrease, and if it exceeds 100,000, the compatibility with the component (A) and the developability tend to decrease.
The blending amount of the component (D) is preferably 1 to 60 parts by weight, and 3 to 50 parts by weight with respect to 100 parts by weight of the total amount of the component (A) from the viewpoints of adhesion, mechanical properties and thermal shock resistance, and photosensitive properties. Part is more preferable, and 5 to 40 parts by mass is particularly preferable.

<Other ingredients>
The photosensitive adhesive composition of the present invention can contain other components such as a silane compound, a solvent, an elastomer, a dissolution accelerator, a dissolution inhibitor, a surfactant, or a leveling agent, if necessary.

<(E): Silane compound>
The photosensitive adhesive composition of this invention may contain the silane compound as (E) component from a viewpoint of improving adhesiveness with a board | substrate. Examples of such silane compounds include ureidopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltriethoxysilane, and methylphenylsilanediol. , Ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethyl Phenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol Tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyl Diphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene 1,4-bis (ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxy) Ryl) benzene, 1,4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) ) Benzene, 1,4-bis (dibutylhydroxysilyl) benzene, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane. Of these, ureidopropyltriethoxysilane, vinyltriethoxysilane, and γ-glycidoxypropyltriethoxysilane are reacted with the components (A) and (C) to improve adhesion and elongation at break of the cured product. Γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane are preferable.

  In the case where the component (E) is used, the content of the component (E) and the component (E) with respect to 100 parts by mass of the component (A) from the viewpoint of adhesiveness to wiring and storage stability of the photosensitive adhesive composition The total amount of silane compounds other than the components is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass.

<Other components (F): Solvent>
The photosensitive adhesive composition of this invention may contain the (F) solvent from a viewpoint that the applicability | paintability on a board | substrate and the resin film of uniform thickness can be formed. Specific examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene Examples include glycol monobutyl ether and dipropylene glycol monomethyl ether. (F) Although content in the case of containing a component is not specifically limited, It is preferable to adjust so that the ratio of the solvent in a photosensitive adhesive composition may be 20-90 mass%.

<Method for Manufacturing Semiconductor Device>
Next, a method for manufacturing a semiconductor device using the above-described photosensitive adhesive composition will be described. The manufacturing method according to this embodiment mainly includes the following steps.
Step 1: A photosensitive adhesive composition is applied to a circuit surface of a semiconductor wafer and dried to form a photosensitive adhesive composition film.
Step 2: The exposed photosensitive adhesive composition film is exposed.
Step 3: The photosensitive adhesive composition film after exposure is developed to form a pattern by dissolving and removing the exposed portions of the photosensitive adhesive layer.
Step 4: The semiconductor wafer on which the pattern is formed is heated to remove the remaining solvent.
Step 5: After removing the insulating film in the opening of the photosensitive adhesive composition film in the predetermined portion by etching, ashing is performed.
Step 6: Thinn wafer and separate chips.
Step 7: Stack chips.
Step 8: Heat-curing the photosensitive adhesive composition film.
Hereinafter, each step will be described.

<Step 1: Application and drying>
A photosensitive adhesive composition is applied to the circuit surface of the semiconductor wafer. The application is selected from a printing method, a spin coating method, a spray coating method, a jet dispensing method, an ink jet method and the like. Among these, the spin coat method is preferable from the viewpoint of thinning and film thickness uniformity. Application by spin coating is preferably performed at a rotational speed of 500 to 5000 min ⁻¹ , and more preferably 600 to 4000 min ⁻¹ in order to prevent wafer undulation and edge swelling. From the viewpoint of the dissolution rate of the exposed area in the developer, the remaining film ratio of the unexposed area and the sensitivity, the drying is preferably 80 to 150 ° C, more preferably 100 to 130 ° C.

  When a photosensitive adhesive composition is applied to a semiconductor wafer by, for example, a spin coating method, an unnecessary photosensitive adhesive composition may adhere to the edge portion of the semiconductor wafer. Such unnecessary adhesive can be removed by washing with a solvent after spin coating. The cleaning method is not particularly limited, but a method of discharging a solvent from a nozzle to a portion where an unnecessary adhesive is attached while spinning a semiconductor wafer is preferable. The solvent used for cleaning is not particularly limited as long as it dissolves the adhesive, and low-boiling solvents such as methyl ethyl ketone, acetone, isopropyl alcohol, and methanol, DMF (N, N-dimethylformamide), NMP (N-methyl-2- High boiling solvents such as pyrrolidone) are used.

  After applying the photosensitive adhesive composition to the semiconductor wafer, the photosensitive adhesive composition film is formed by drying using a hot plate or an oven.

<Step 2: Exposure>
The applied photosensitive adhesive composition film is irradiated with actinic rays (typically ultraviolet rays) by an exposure apparatus to expose the photosensitive adhesive composition film. The exposure is performed for the purpose of patterning the photosensitive adhesive composition film. In the present embodiment, the dicing line portion when the semiconductor wafer is divided into a plurality of semiconductor chips and the photosensitive adhesive composition film of the bonding pad portion for wire bonding are removed by development so as to be removed. Exposure is performed through a mask having a pattern. The exposure can be performed under an atmosphere such as vacuum, nitrogen, air, or the like. The exposure amount is preferably 50 to 2000 mJ / cm ² .

  The film thickness of the photosensitive adhesive composition film is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less.

<Step 3: pattern formation>
The photosensitive adhesive composition film after exposure is developed, and the dicing line part and the photosensitive adhesive composition film in the part (bonding pad part) to be electrically connected are removed to form individual pieces. The formed photosensitive adhesive composition film (adhesive pattern) is formed. Development is performed using an alkali developer or an organic solvent. Examples of the alkaline developer include alkaline aqueous solutions such as alkali metal carbonates, alkali metal hydroxides, and tetraammonium hydroxide (tetramethylammonium hydride). Examples of the organic solvent include DMF and NMP. In this way, by removing the photosensitive adhesive composition film from the dicing line part and bonding pad part in advance, the generation of chips during dicing and the connection failure during wire bonding are suppressed. Effect is obtained.

<Step 4: Half cure>
The substrate on which the photosensitive adhesive composition film has been formed is heated to remove the remaining solvent, and the reaction of the crosslinking agent proceeds partially. The heating temperature at this time is usually preferably 70 to 200 ° C, more preferably 75 to 190 ° C. The heating time is preferably 1 to 60 minutes, more preferably 5 to 50 minutes. By removing the solvent remaining by this heating, gas generation at the time of pressure bonding and curing described later can be suppressed, and good pressure bonding properties can be obtained. Further, by causing the reaction of the crosslinking agent to partially proceed by this heating, damage to the photosensitive adhesive composition film during the etching and ashing in step 5 can be suppressed.

<Step 5: Etching and ashing>
Etching is performed using the pattern of the photosensitive adhesive composition film as a mask. Examples of the insulating film to be etched include SiO ₂ and SiN. Thereby, after forming a pattern using a resist on the upper part of a conventionally used adhesive layer, etching is performed using the resist as a mask, and the process of peeling the resist can be simplified. For the etching, dry etching means using a gas such as oxygen or carbon tetrafluoride can be used.
In the ashing treatment, oxygen gas is converted into plasma by non-ionizing radiation such as visible light and microwave, and when the pattern resin film of the photosensitive adhesive composition film is placed in oxygen plasma, it bonds with oxygen radicals in the plasma, and carbon dioxide. And the surface is cleaned.

<Step 6: wafer thinning and chip separation>
When the substrate having the photosensitive adhesive composition film is singulated, a “first dicing method” in which the substrate is half-cut and then polished (back grind) to a desired substrate thickness, or the substrate is first formed to a desired thickness. There is a method of dicing after polishing (back grinding). When dicing is performed, dicing is performed with the photosensitive adhesive composition film as a surface, and therefore, it is exposed to cooling water during the dicing process. For this reason, the photosensitive adhesive composition film is preferably a material having a low water absorption rate. If the photosensitive adhesive composition film absorbs water during the dicing process, it becomes a degassing factor in the press-bonding process and the curing process described later.

<Step 7: Step of laminating chips (crimping)>
The adherend is pressure-bonded to the surface of the photosensitive adhesive composition film of the substrate having the patterned photosensitive adhesive composition film. The treatment temperature in the crimping step is preferably 100 to 200 ° C. The pressure is preferably from 0.01 to 5 MPa, and the treatment time is preferably from 0.5 to 120 seconds.

  The tack strength (surface tack force) at a pressure treatment temperature of 100 to 200 ° C. on the surface of the photosensitive adhesive composition film after exposure and development is preferably 100 gf or less. Thereby, it can fully suppress that a photosensitive adhesive composition film adheres to a collet at the time of pick-up, and when a semiconductor device is produced by laminating a plurality of semiconductor chips, continuous pressure bonding is possible. The tack strength is more preferably 100 gf or less, and even more preferably 80 gf or less, because the above-described effects can be obtained more sufficiently. Moreover, since it becomes easy to laminate | stack a several semiconductor chip, it is preferable that tack intensity | strength is 5 gf or more.

  The tack strength of the surface of the photosensitive adhesive composition film is measured as follows. First, a photosensitive adhesive composition film is formed on a silicon wafer to a thickness of 10 μm using a spin coater. Then, after heating at 150 ° C. for 10 minutes using a hot plate, the tack strength of the surface of the photosensitive adhesive composition film at a predetermined temperature (for example, 120 ° C.) is measured with a probe tacking tester (manufactured by Reska Co., Ltd.). Is used under the specified conditions (probe diameter: 5.1 mm, peeling speed: 5 mm / s, contact load: 0.2 MPa, contact time: 1 s).

  The tack strength (surface tack force) at 120 to 180 ° C. on the surface of the photosensitive adhesive composition film is preferably 80 gf or less, and more preferably 50 gf or less. If this tack strength is higher than 80 gf, collet adhesion may occur during thermocompression bonding.

<Step 8: Heat curing>
After pressure-bonding the adherend to the photosensitive adhesive composition film, heat treatment is performed at 150 to 200 ° C. for 1 to 9 hours.

FIG. 1 shows an example of a semiconductor device 120 formed using the photosensitive adhesive composition of the present invention.
In the semiconductor device 120 shown in FIG. 1, the semiconductor chip 2 separated into a support member (semiconductor element mounting support member) 13 for a semiconductor device is stacked via an adhesive member 30, and the semiconductor chip 2 is further stacked on the semiconductor chip 2. The semiconductor chip 2 is repeatedly laminated via the photosensitive adhesive composition film 5 of the present invention to form a multilayer structure in which a plurality of semiconductor chips are laminated, and the photosensitive adhesive composition film 5 is cured. Then, the bonding pads 17 exposed in the openings 51 of the semiconductor chip 2 and the external connection terminals 16 of the semiconductor device support member (semiconductor element mounting support member) 13 are electrically connected via the wires 14. Thereafter, the semiconductor chip 2 is sealed with the sealing material 15 to obtain the semiconductor device 120.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

First, the materials used in this example are shown below.
[(A) component]
A1: Cresol novolak resin (cresol / formaldehyde novolak resin, m-cresol / p-cresol (molar ratio) = 60/40, polystyrene-equivalent weight average molecular weight = 13,000, manufactured by Asahi Organic Materials Co., Ltd., trade name “EP4020G”) Prepared.
A2: Copolymer consisting of p-hydroxystyrene / styrene = 85/15 (mol), polystyrene equivalent weight average molecular weight = 10000, manufactured by Toho Chemical Co., Ltd., trade name “C100A15”
A3: Prepared by the method described in Synthesis Example 1 below.

Synthesis Example 1: Synthesis of phenol resin (A3) modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms 100 parts by mass of phenol, 43 parts by mass of linseed oil and 0.1 part by mass of trifluoromethanesulfonic acid Were mixed and stirred at 120 ° C. for 2 hours to obtain a vegetable oil-modified phenol derivative (a). Next, 130 g of the vegetable oil-modified phenol derivative (a), 16.3 g of paraformaldehyde and 1.0 g of oxalic acid were mixed and stirred at 90 ° C. for 3 hours. Subsequently, after heating up to 120 degreeC and stirring under reduced pressure for 3 hours, 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction liquid, and it stirred at 100 degreeC under atmospheric pressure for 1 hour. The reaction solution was cooled to room temperature (25 ° C., the same applies hereinafter) to obtain a phenol resin (hereinafter referred to as A3) modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms, which is a reaction product. (Acid value 120 mg KOH / g). The weight average molecular weight determined by standard polystyrene conversion of this A3 GPC method was about 25,000.

[Component (B)]
B1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane 1-naphthoquinone-2-diazide-5-sulfonic acid Esters (Esterification rate of about 90%, manufactured by AZ Electronic Materials, trade name “TPPA528”)

[Component (C)]
C1: Glycidylamine type epoxy crosslinking agent (manufactured by ADEKA Corporation, trade name “EP-3950s”)
C2: Isocyanuric acid type epoxy resin (manufactured by Nissan Chemical Industries, Ltd., trade name “TEPIC-VL”)
C3: Bisphenol A type epoxy resin (manufactured by Printec Co., Ltd., trade name “VG-3101”)
C4: Multifunctional epoxy resin (trade name “1032H60” manufactured by Mitsubishi Chemical Corporation)
C5: Aliphatic polyglycidyl ether type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name “ZX-1542”)
C6: 1,6-hexanediol diglycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., trade name “SR-16HL”)
C7: Hexakis (methoxymethyl) melamine (manufactured by Sanwa Chemical Co., Ltd., trade name “MW-30HM”)

[(D) component]
As the component (D), acrylic resins (D1 to D3) were prepared by the method described in Synthesis Example 2 below.
Synthesis Example 2: Synthesis of acrylic resin D1 In a 100 ml three-necked flask equipped with a stirrer, a nitrogen introduction tube and a thermometer, 25 g of ethyl lactate was weighed and stirred at a rotation speed of about 200 rotations / minute (rpm) at room temperature. While stirring, nitrogen gas was passed at a flow rate of 400 ml / min for 30 minutes to remove dissolved oxygen. Then separately 17 g of butyl acrylate (BA), 2.9 g of hydroxybutyl acrylate (HBA), 2.9 g of acrylic acid (AA), and 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (Product name: FA-711MM, manufactured by Hitachi Chemical Co., Ltd.) 2.9 g of polymerizable monomer was weighed, 0.08 g of azobisisobutyronitrile (AIBN) was dissolved, and 1 ml / ml was added to the three-necked flask. The solution was dropped at a rate of min. A polymerization reaction was carried out while maintaining the same temperature for 4 hours to obtain an acrylic resin D1. The polymerization rate at this time was 98%. Further, Table 1 shows the weight average molecular weight (Mw) determined by standard polystyrene conversion of the GPC method of D1. In the same manner, D2 to D3 were synthesized with the formulations shown in Table 1.

BA: n-butyl acrylate HBA: hydroxybutyl acrylate AA: acrylic acid FA-711MM: 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)

In addition, the weight average molecular weight of (D) component was specifically measured with the apparatus and conditions shown below.
Measuring device: Detector L-3300 RI manufactured by Hitachi, Ltd.
Pump: L-6000 manufactured by Hitachi, Ltd.
Measurement conditions: Column manufactured by Tosoh Corporation (trade name “GMH _XL- L”) x 2 Solvent: THF
Flow rate: 1.0 ml / min
It measured using the solution of 1 ml of solvent with respect to 0.5 mg of samples to measure.

[(E) component]
As the component (E), a silane compound E1 was prepared.
E1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”)

<Adjustment of photosensitive adhesive composition>
(Examples 1-8 and Comparative Examples 1-4)
Ingredients (A) to (E) (unit: part by mass) of the blending amounts shown in Table 2 and 120 parts by mass of ethyl lactate as a solvent were blended, and this was used using a PTFE (polytetrafluoroethylene) filter with a 3 μm pore. It filtered under pressure and the photosensitive adhesive composition of Examples 1-8 and Comparative Examples 1-4 was prepared.

<Compatibility evaluation (haze value)>
The photosensitive adhesive composition was spin-coated on a glass plate and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of about 10 to 12 μm. Then, the haze value of the film | membrane was measured using the haze meter (The Nippon Denshoku Industries Co., Ltd. make, brand name "NDH5000", a light source uses white LED). The haze value is a numerical value indicating the degree of cloudiness, and indicates the ratio of diffused light to total reflected light. The formula for calculating the haze value is as follows.
Haze = diffusivity / total light transmittance × 100
The lower the haze value, the lower the haze (white turbidity) and the higher the compatibility of the resin component in the coating film.

<Evaluation of thermocompression bonding>
A solution of the photosensitive adhesive composition is spin-coated on a silicon substrate, heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 12 to 14 μm, and then heated on a hot plate at 150 ° C. for 10 minutes. A silicon wafer with a photosensitive adhesive composition film was obtained. A dicing tape (thickness: 80 μm) was laminated to the silicon wafer on the surface of the silicon wafer opposite to the photosensitive adhesive composition film to prepare a dicing sample. Then, the said dicing sample which laminated | stacked the photosensitive adhesive composition film | membrane, the silicon wafer, and the dicing tape was cut | disconnected using the full auto dicer (The product made from DISCO Corporation, brand name "DFD-6361"). Cutting is performed using a single cutting method in which processing is completed with one blade (manufactured by DISCO Corporation, trade name “Dicing Blade NBC-ZH104F-SE 27HEDD”), blade rotation speed 45000 min ⁻¹ , cutting speed 20 mm / s. I went there. The blade height at the time of cutting was set to leave 10 μm of dicing tape. The size for cutting the semiconductor wafer was set to 3.0 mm × 3.0 mm. Next, using a thermocompression bonding machine (manufactured by Hitachi Chemical Co., Ltd.), a photosensitive adhesive composition of a silicon wafer with a photosensitive adhesive composition film diced on a silicon chip of 10 mm length × 10 mm width × 400 μm thickness. Lamination was performed such that the material film was on the silicon chip side, and pressure bonding was performed under conditions of 120 ° C., 1 s, 5N. After that, the shear adhesive strength measurement at room temperature was performed 10 times on one sample with a shear adhesive strength measuring device (trade name “DAGE-4000” manufactured by Dage), and a value of 0.8 MPa or more was shown. The numbers are shown in Table 2.

<Evaluation of photosensitive characteristics (sensitivity and resolution)>
A solution of the photosensitive adhesive composition was spin-coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 12 to 14 μm. Subsequently, reduction projection exposure with i-line (365 nm) was performed through a mask using an i-line stepper (trade name “FPA-3000i” manufactured by Canon Inc.). After the exposure, development was performed using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH), and development was performed so that the remaining film thickness was about 80 to 95% of the initial film thickness. Then, it rinsed with water and calculated | required the magnitude | size of the minimum exposure amount required for pattern formation, and the size of the minimum square hole pattern opened. The minimum exposure amount was used as sensitivity, and the size of the smallest square hole pattern opened was evaluated as resolution. Sensitivity and resolution indicate that the smaller the value, the better.

<Dry process resistance evaluation>
A solution of the photosensitive adhesive composition was spin-coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 12 to 14 μm. Subsequently, reduction projection exposure with i-line (365 nm) was performed through a mask using an i-line stepper (trade name “FPA-3000i” manufactured by Canon Inc.). After the exposure, development was performed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) and rinsed with water to form a pattern. Thereafter, etching is performed using a dry etching apparatus (product name “e-Max” manufactured by Applied Materials (AMAT)) (used gas: CF ₄ / O ₂ = 90/10 sccm, Press: 8 Pa, Power: 500 W, Temp: 15 ° C., Time: 400 sec.), SEM (scanning electron microscope) was used to confirm the surface state of the photosensitive adhesive composition. In Table 2, the case where unevenness occurred on the coating film surface after etching was evaluated as “×”, and the case where the surface was not formed was evaluated as “◯”.

<Evaluation of moisture absorption rate>
A photosensitive adhesive composition solution was spin-coated on a silicon substrate whose mass was measured, and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 12 to 14 μm. Thereafter, it was put into an inert gas oven (trade name “INH-9SD-S” manufactured by Koyo Thermo System Co., Ltd.) and heated at 175 ° C. for 4 hours in a nitrogen atmosphere. Subsequently, the mass was measured, and the mass of the cured film was calculated. After measuring the mass, it was put into a constant temperature and humidity chamber (trade name “LHL-113”, manufactured by ESPEC CORP.) At 85 ° C. and 85% RH, and allowed to stand for 24 hours. Thereafter, the mass was measured again, and the moisture absorption and moisture absorption were calculated.

<Adhesive evaluation after moisture absorption reflow>
A solution of the photosensitive adhesive composition is spin-coated on a silicon substrate, heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 12 to 14 μm, and then heated on a hot plate at 150 ° C. for 10 minutes. And a photosensitive adhesive composition film was obtained. A dicing sample (thickness: 80 μm) was laminated to a silicon wafer with a photosensitive adhesive composition film on the surface of the silicon wafer opposite to the photosensitive adhesive composition film at room temperature to prepare a dicing sample. Then, the said dicing sample which laminated | stacked the photosensitive adhesive composition film | membrane, the silicon wafer, and the dicing tape was cut | disconnected using the full auto dicer (The product made from DISCO Corporation, brand name "DFD-6361"). Cutting is performed using a single cutting method in which processing is completed with one blade (manufactured by DISCO Corporation, trade name “Dicing Blade NBC-ZH104F-SE 27HEDD”), blade rotation speed 45000 min ⁻¹ , cutting speed 20 mm / s. I went there. The blade height at the time of cutting was set to leave 10 μm of dicing tape. The size for cutting the semiconductor wafer was set to 3.0 mm × 3.0 mm. Then, using a thermocompression bonding machine (manufactured by Hitachi Chemical Co., Ltd.), the photosensitive adhesive composition film of the silicon wafer with the adhesive layer diced on the silicon chip having a length of 10 mm × width 10 mm × thickness 400 μm is on the silicon chip side. The layers were laminated so as to come in contact with each other, and pressure bonding was performed under the conditions of 120 ° C., 1 s, and 5N. Then, it pressurized at 180 degreeC, 90 s, and 36N, and hardened | cured at 175 degreeC for 4 hours. The chip | tip which hardened | cured was thrown into 85 degreeC and 85% RH constant temperature and humidity tank (The product name "LHL-113" by ESPEC CORP.), And left still for 24 hours. Thereafter, shear adhesive strength measurement at 260 ° C. was performed 10 times on one sample with a shear adhesive strength measuring device (trade name “DAGE-4000” manufactured by Dage), and a value of 1.5 MPa or more was shown. The number of the seeds is shown in Table 2.

When the D3 component which does not contain the hydroxybutyl acrylate which is a structural unit containing the hydroxyalkyl group represented by General formula (1) is used for the acrylic resin of (D) component from the comparative example 1, (A) component and Since the compatibility was not sufficient, phase separation caused haze value after coating to increase. Furthermore, since the phases were separated, portions having different etching rates were generated on the surface of the coating film, and when etching was performed, irregularities were generated on the surface of the coating film. From Comparative Example 2, when A2 was used for the phenol resin of the component (A), the sensitivity was lowered. In Comparative Examples 3 and 4, which did not contain a trifunctional crosslinking agent as the thermal crosslinking agent of component (C), the moisture absorption rate was high, and peeling occurred after moisture absorption reflow.
In contrast, the D1 and D2 components containing hydroxybutyl acrylate are used for the acrylic resin of the (D) component, the A1 component which is a cresol novolac resin is used for the phenolic resin of the (A) component, and the heat of the (C) component Examples 1 to 8 containing a trifunctional cross-linking agent as a cross-linking agent have good sensitivity, dry etching resistance, resolution, thermocompression bonding, moisture absorption rate, and moisture absorption after reflow adhesion.

  According to the present invention, it is excellent in photosensitive characteristics and dry etching resistance, can form a thin and high-definition adhesive pattern, and can be continuously pressed when a semiconductor device is manufactured by stacking a plurality of semiconductor chips. It is possible to provide a photosensitive adhesive composition, a method for producing a semiconductor device using the same, and a semiconductor device having a photosensitive adhesive layer obtained thereby. Furthermore, since the photosensitive adhesive of the present invention can be cured at a low temperature, it is possible to prevent damage to the electronic component due to heat, and furthermore, since the moisture absorption is low, the electronic component is highly reliable. Can be provided with a high yield, and an electronic component having a patterned cured film made of the photosensitive adhesive of the present invention as an interlayer insulating layer can be provided.

2: Semiconductor chip separated, 5: Photosensitive adhesive composition film, 13: Support member for semiconductor device (support member for mounting semiconductor element), 14: Wire, 15: Sealing material, 16: External connection Terminal: 17: Bonding pad; 30: Adhesive member; 51: Opening; 120: Semiconductor device.

Claims (5)

(A) a phenolic resin;
(B) a compound that generates an acid by light;
(C) a thermal crosslinking agent having three or more groups capable of crosslinking with the component (A);
(D) an acrylic resin having a structural unit represented by the following general formula (1);
A photosensitive adhesive composition containing:

[In General Formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydroxyalkyl group having 2 to 20 carbon atoms. ]   (B) The photosensitive adhesive composition of Claim 1 in which a component contains an o-quinonediazide compound.   The photosensitive adhesive composition according to claim 1 or 2, wherein the component (C) includes a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, or a compound having an epoxy group. Applying and drying the photosensitive adhesive composition according to any one of claims 1 to 3 on a circuit surface of a semiconductor wafer to form a photosensitive adhesive composition film;
Exposing a predetermined portion of the photosensitive adhesive composition film; and
Developing the photosensitive adhesive composition film after the exposure to form a pattern by removing the predetermined portion;
Heating the semiconductor wafer on which the pattern is formed to remove residual solvent;
Removing the predetermined portion of the insulating film by etching, and then performing an ashing process;
A process of wafer thinning and chip separation;
A step of stacking chips;
And a step of heat-curing the photosensitive adhesive composition film.   A semiconductor device obtained by the method for manufacturing a semiconductor device according to claim 4.

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