CN104937712B - Diaphragm formation is with film and diaphragm formation composite sheet - Google Patents

Diaphragm formation is with film and diaphragm formation composite sheet Download PDF

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Publication number
CN104937712B
CN104937712B CN201480004970.7A CN201480004970A CN104937712B CN 104937712 B CN104937712 B CN 104937712B CN 201480004970 A CN201480004970 A CN 201480004970A CN 104937712 B CN104937712 B CN 104937712B
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film
diaphragm
diaphragm formation
polymer
thermocurable
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CN104937712A (en
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佐伯尚哉
山本大辅
高野健
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Lintec Corp
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Lintec Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/14—Semiconductor wafers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/10—Epoxy resins modified by unsaturated compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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  • Health & Medical Sciences (AREA)
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  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
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  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

The present invention provides a kind of diaphragm formation film, and it can form the high diaphragm of reliability while can suppress the bending of wafer.The diaphragm formation film of the present invention has Thermocurable, and the glass transition temperature after heat cure is 150~300 DEG C, and the tensile modulus of elasticity after heat cure at 23 DEG C is 0.5~10GPa.

Description

Diaphragm formation is with film and diaphragm formation composite sheet
Technical field
The present invention relates to a kind of diaphragm formation film, and it can form protection on semiconductor crystal wafer or semiconductor chip Film, and the manufacture efficiency of semiconductor chip can be lifted.More particularly to the use of the so-called dress of (face down) pattern structure down In the diaphragm formation film of semiconductor chip manufacture.
Background technology
In recent years, there is the system that semiconductor device is carried out using the so-called structure dress method for being referred to as face-down (face down) pattern Make.In face-down pattern, (below, have using the semiconductor chip in circuit face with electrodes such as projections and be only called " core The situation of piece ".), the electrode engages with substrate.Therefore, the face (chip back) of side opposite with the circuit face of chip is exposed.
The chip back exposed, there is the situation protected by organic film.Conventional, there is the guarantor being made up of the organic film The chip of cuticula, by the way that the resin of liquid is coated on into wafer rear with method of spin coating, dries, solidify and cut together with wafer Disconnected diaphragm and obtain.But the thickness and precision of the diaphragm due to so being formed and insufficient, there are the feelings for reducing yield rate Shape.
To solve the above problems, disclose a kind of curability diaphragm shape having comprising heat or energy ray-curable composition The chip of stratification is with (patent document 1) of diaphragm formation piece.
Conventional, when wafer is fully thick in itself, although wafer can't be bent in itself, with wafer thinner, generate Problems with：The shrinkage factor of wafer rear of the crystal column surface formed with circuit with not forming circuit is poor, result in thinning Wafer produces bending.
Big wafer is bent, there is the possibility for causing conveying bad in chip fabrication steps afterwards.In addition, have because of wafer Bending be difficult to the possibility of cutting crystal wafer.
To eliminate the problem of wafer bow causes, the diaphragm formation film to being pasted on wafer rear, it is desirable to correct The performance of wafer bow.
In patent document 2, it is using the cubical contraction in the range of 23 DEG C to 165 DEG C in heat cure Less than more than 100ppm/ DEG C 400ppm/ DEG C, the stretching storage elastic modulus after heat cure at 23 DEG C be more than 1GPa below 5GPa Film for flip chip type semiconductor back surface, suppress or prevent semiconductor crystal wafer or the semiconductor element of semiconductor chip etc. occurs Bending.
The use of the amount of contraction caused by heat cure relative to the full volumetric before heat cure is 2 in addition, in patent document 3 Below the volume % of more than volume % 30 film for flip chip type semiconductor back surface, suppress or prevent that semiconductor element generation is curved It is bent.
Prior art literature
Patent document
The ︰ Japanese Unexamined Patent Publication 2004-214288 publications of patent document 1
The ︰ Japanese Unexamined Patent Publication 2012-33554 publications of patent document 2
The ︰ Japanese Unexamined Patent Publication 2011-228499 publications of patent document 3
The content of the invention
The technical problem to be solved in the present invention
In recent years, the circuit pattern variation of crystal column surface is formed at, big wafer is bent due to circuit is formed and increases. It is therefore desirable to the diaphragm formation film of wafer bow can be corrected significantly more, but falling in patent document 2 or patent document 3 In cartridge chip type semiconductor back surface film, there is the situation for the bending that can not fully eliminate wafer and chip.In addition, the present inventor etc. The wholwe-hearted result for attempting further lifting detorsion function, in the resulting chip with diaphragm, in diaphragm and There is situation that is peeling-off or being cracked in diaphragm on the junction surface of chip, its reliability is simultaneously insufficient.
The problem of the present invention is to provide a kind of diaphragm formation film, can be while it can suppress the bending of wafer The high diaphragm of reliability is formed on chip.
Solves the technological means of technical problem
The purport of the present invention is as follows.
(1) a kind of diaphragm formation film, it has Thermocurable,
Glass transition temperature after heat cure is 150~300 DEG C,
Tensile modulus of elasticity after heat cure at 23 DEG C is 0.5~10GPa.
(2) the diaphragm formation film as described in (1), the film include what is formed containing epoxide and amine curing agent Thermocurable composition.
(3) diaphragm formation film as claimed in claim 2, it also contains component of polymer and Thermocurable polymer Any one of composition or both, relative to the component of polymer and Thermocurable component of polymer of the mass parts of total amount 100, comprising Thermocurable composition below 135 mass parts.
(4) the diaphragm formation film as described in any one of (1)~(3), wherein diaphragm formation include nothing with film Machine filler,
The all solids composition of diaphragm formation film is formed relative to 100 mass parts, the content of inorganic filler is 10 ~70 mass parts.
(5) the diaphragm formation film according to (4), the wherein average grain diameter of inorganic filler are 0.02~5 μm.
(6) the diaphragm formation film according to any one of (1)~(5), wherein diaphragm formation include heat with film Curable polymer composition,
Thermocurable component of polymer is comprising the acrylic polymer monomer for containing epoxy radicals as the monomer formed.
(7) a kind of diaphragm formation composite sheet, its diaphragm described in by any one in above-mentioned (1)~(6) Formation is formed with strippable supporting slice is formed on a face of film.
Invention effect
According to the present invention, to the wafer bow caused by the contraction of the circuit formation due to crystal column surface side, pass through by Diaphragm formation is pasted on wafer rear with film, carries out heat cure, can pass through the cure shrinkage due to diaphragm formation film Stress, correct the bending of wafer, and obtain the high chip with diaphragm of reliability.
Brief description of the drawings
Fig. 1 by expression using diaphragm of the present invention formed the diaphragm formed with film formed with composite sheet 1 form.
Fig. 2 is represent to use the diaphragm formation composite sheet of diaphragm formation film of the present invention formation the 2 Form.
Fig. 3 is represent to use the diaphragm formation composite sheet of diaphragm formation film of the present invention formation the 3 Form.
Fig. 4 is represent to use the diaphragm formation composite sheet of diaphragm formation film of the present invention formation the 4 Form.
Fig. 5 is the figure of " amount of bow " for illustrating to evaluate in embodiment.
Embodiment
Hereinafter, the details of the diaphragm formation film of the present invention is illustrated.
[diaphragm formation film]
The diaphragm formation film of the present invention has Thermocurable, and the glass transition temperature (Tg) after heat cure is 150 ~300 DEG C, preferably 170~280 DEG C, more preferably 220~270 DEG C.After the heat cure of the diaphragm formation film of the present invention Glass transition temperature (Tg) be：Diaphragm formation moving with film (diaphragm) after the heat cure determined with frequency 11Hz In state determination of viscoelasticity, the temperature of maximum is shown in -50~30 DEG C of low-temperature region internal loss tangent tan δ.
If the Tg after the heat cure of diaphragm formation film is less than 150 DEG C, generally carried out at 120~150 DEG C or so In the heat curing processes of diaphragm formation film, diaphragm formation is uprised with the mobility of film, and is formed and used due to diaphragm The stress of the cure shrinkage of film is alleviated and diminished.As a result, the correction to wafer bow becomes insufficient.
On the other hand, if the Tg after the heat cure of diaphragm formation film is more than 300 DEG C, have diaphragm formation film or The possibility that diaphragm obtained by the film heat cure is peeled off from wafer or chip, as a result, the core with diaphragm can be reduced The reliability of piece.
The Tg after heat cure by making diaphragm formation film is in above range, due to the thermal cure step in the film In, diaphragm formation film has defined rigidity, therefore can't relax the stress due to the film cure shrinkage, and can rectify Positive wafer or the bending by chip obtained from the wafer piece.
In addition, diaphragm formation film, the tensile modulus of elasticity after heat cure at 23 DEG C is 0.5~10GPa, preferably 1 ~10GPa, more preferably more than 5GPa and in below 8GPa.
If diaphragm formation film is less than 0.5GPa after heat cure in 23 DEG C of tensile modulus of elasticity, it has been unable to maintain that Because of the stress of the cure shrinkage in diaphragm formation film, the stress is alleviated, and the correction of wafer bow becomes insufficient.It is another Aspect, if diaphragm formation film after heat cure in 23 DEG C of tensile modulus of elasticity more than 10GPa, there is diaphragm to be formed and use Film or the possibility for peeling off diaphragm obtained by the film heat cure from wafer or chip.
By make diaphragm formation film after heat cure in 23 DEG C of tensile modulus of elasticity in above range, can correct While the bending of wafer and chip, the reliability of chip of the lifting with diaphragm.
In addition, diaphragm formation is preferably 0.1~10% with the percent thermal shrinkage heated 2 hours at 130 DEG C of film, more preferably For 0.5~5%.Percent thermal shrinkage when being heated 2 hours at 130 DEG C by making diaphragm formation film can be carried in above range Rise the effect (detorsion performance) of correction wafer bow.In addition, formed by putting into diaphragm under 130 DEG C of environment with before and after film Diaphragm formation membrane area, the thermal contraction of diaphragm formation film when being heated 2 hours at 130 DEG C is tried to achieve by following formula Rate.
Percent thermal shrinkage (%)={ (area of the diaphragm formation film before input)-(diaphragm formation film after input Area)/input before diaphragm formation film area × 100
The function that diaphragm formation is at least required with film, it is：(1) plate shape maintenance；(2) initial bond；And (3) are solid The property changed.In addition, the diaphragm formation film of the present invention, though having Thermocurable as described above, can also have by beyond heat The property of means solidification.
Diaphragm formation film can assign (1) plate shape maintenance and (3) curability by adding adhesive component, as Adhesive component, can be used the 1st adhesive component containing component of polymer (A) and Thermocurable composition (B), or containing having concurrently (A) the 2nd adhesive component of the Thermocurable component of polymer (AB) of the property of composition and (B) composition.
In addition, at (2) initial stage for being used to temporarily be adhered to the function of to-be-adhered object solidified until diaphragm formation with film It cohesive, can be pressure-sensitive cohesive, or by heat soften the property of bonding.(2) initial bond, glue is generally passed through Each characteristic of stick composition or the adjustment of addition of inorganic filler described later (C) etc. control.
(the 1st adhesive component)
1st adhesive component is by containing component of polymer (A) and Thermocurable composition (B), assigning diaphragm and forming use Film ties up characteristic and Thermocurable with plate shape.In addition, the 1st adhesive component is distinguished convenient with the 2nd adhesive component, no Contain Thermocurable component of polymer (AB).
(A) component of polymer
Component of polymer (A) ties up characteristic as main purpose to assign plate shape to diaphragm formation film, makes an addition to protection In film formation film.
To achieve the above object, the weight average molecular weight (Mw) of component of polymer (A) is usually 20, more than 000, is preferably 20,000~3,000,000.The value of weight average molecular weight (Mw) is to be entered by gel permeation chromatography (GPC) (polystyrene standard) Value during row measure.Measure in this way can be used for example, the high speed GPC devices " HLC-8120GPC " of TOSO company systems, with By high speed post " TSK gurd column HXL-H”、“TSK Gel GMHXL”、“TSK Gel G2000HXL" (more than, it is TOSO company systems) order connection device, 40 DEG C of pipe column temperature ︰, defeated liquid speed degree ︰ 1.0mL/ point condition, with differential refractive It is counted as carrying out for detector.
In addition, for convenience of being distinguished with curable polymer described later (AB), component of polymer (A) is without described later Solidify function functional group.
As component of polymer (A), can be used acrylic polymer, polyester, phenoxy resin (for convenience of with it is described later Curable polymer (AB) is distinguished, and is limited to without epoxy radicals.), makrolon, polyethers, polyurethane, polysiloxanes, rubber Birds of the same feather flock together compound etc..In addition, or the material that combines of these above-mentioned two or more, for example, acrylic polymers with hydroxyl Acrylic polyol has acrylic acid urethane resin etc. obtained by the urethane prepolymer reaction of NCO with molecular end.This Outside, the polymer of two or more combination is included, these above-mentioned two or more can also be applied in combination.
(A1) acrylic polymer
Acrylic polymer (A1) is preferably used as component of polymer (A).The glass of acrylic polymer (A1) Change transition temperature (Tg), be preferably -60~50 DEG C, more preferably -50~40 DEG C, more preferably -40~30 DEG C of scope. The glass transition temperature of acrylic polymer (A1) is high, then the initial bond of diaphragm formation film reduces, and whether there is Method is needed on the situation of to-be-adhered object.In addition, the glass transition temperature of acrylic polymer (A1) is low, then diaphragm is formed Become big with the peeling force of film and supporting slice described later, and have the bad situation of the transfer that diaphragm formation film occurs.
In addition, the Tg of acrylic polymer is the value tried to achieve by FOX formulas.
The weight average molecular weight (Mw) of acrylic polymer (A1) is preferably 100,000~1,500,000.Acrylic polymer Compound (A1) weight average molecular weight is high, then the initial bond of diaphragm formation film reduces, and has generation not to be needed on and glued The situation of body.In addition, acrylic polymer (A1) weight average molecular weight is low, then the adherence of diaphragm formation film and supporting slice Property uprise, and have the bad situation of transfer that diaphragm formation film occurs.
Acrylic polymer (A1) includes (methyl) acrylate at least in the monomer of composition.
As (methyl) acrylate, alkyl (methyl) acrylate that atomic number of alkyl carbon is 1~18, tool can be included For body, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) propylene can be included Acid butyl ester, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (methyl) dodecyl acrylate, (methyl) tetradecyl acrylate, (methyl) octadecyl acrylate；(methyl) acrylate with cyclic skeleton, specifically, (methyl) acrylate ester, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid can be included Bicyclopentyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl 2-ethoxyethyl acetate, acid imide (methyl) propylene Acid esters etc..In addition, exemplified as in the monomer described later with hydroxyl, the monomer with carboxyl, the monomer with amido, can example It is shown as (methyl) acrylate.
In the present invention, acrylate, (methyl) acrylic acid with carboxyl are had by using (methyl) with hydroxyl Ester or monomer of (methyl) acrylate as composition acrylic polymer (A1) with amido, easily form diaphragm Controlled with tensile modulus of elasticity of the film at 23 DEG C after heat cure in defined scope.
In addition, in this specification, (methyl) acrylic acid, to be used comprising two kinds of meanings of acrylic acid and methacrylic acid.
As the monomer for forming acrylic polymer (A1), the monomer with hydroxyl can be used.Monomer with hydroxyl, Can include (methyl) dihydroxypropyl methyl esters, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylate with hydroxyl of (methyl) acrylic acid 2- hydroxybutyls etc.；Vinyl alcohol, N- methylols (methyl) third Acrylamide etc..
As the monomer for forming acrylic polymer (A1), it is possible to use have the monomer of carboxyl.As with carboxyl Monomer, 2- (methyl) acrylyl oxy-ethyls phthalic acid ester, 2- (methyl) acryloxypropyl O-phthalic can be included (methyl) acrylate with carboxyl of acid esters etc.；(methyl) acrylic acid, maleic acid, fumaric acid, itaconicacid etc..Use epoxy When class Thermocurable composition is as curability composition described later (B), because carboxyl can be with the ring in epoxies Thermocurable composition Epoxide is reacted, therefore it is preferred that the usage amount of the monomer with carboxyl is few.
As the monomer for forming acrylic polymer (A1), it is possible to use have the monomer of amido.As with amido Monomer, monomethyl amido (methyl) acrylate, MEA base (methyl) acrylate, diethyl amido can be included (methyl) acrylate etc. has (methyl) acrylate of amido etc..
As the monomer for forming acrylic polymer (A1), it is possible to use other vinylacetates, styrene, second Alkene, alpha-olefin etc..
Acrylic polymer (A1) is also cross-linking.Be crosslinked has hydroxyl for acrylic polymer (A1) before crosslinking Deng bridging property functional group, by for forming diaphragm formation with crosslinking agent is added in the composition of film, making bridging property function Base reacts and carried out with functional group possessed by crosslinking agent.By being crosslinked acrylic polymer (A1), adjustable protective film The cohesiveness of formation film.In addition, the crosslink density by adjusting acrylic polymer (A1), can control diaphragm to be formed and uses In 23 DEG C of tensile modulus of elasticity after glass transition temperature or heat cure after the heat cure of film.Crosslink density can be by aftermentioned Crosslinking agent addition control.
As crosslinking agent, organic polyvalent isocyanate compound, organic multivalence group with imine moiety etc. can be included.
As organic polyvalent isocyanate compound, it is more that aromatic series polyvalent isocyanate compound, aliphatic can be included The trimerization of valency isocyanate compound, alicyclic multivalent isocyanate compound and such organic polyvalent isocyanate compound Thing and the terminal isocyanate urethane pre-polymerization for making these organic polyvalent isocyanate compounds and polyol compound reaction gained Thing etc..
As organic polyvalent isocyanate compound, 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene two can be specifically included Isocyanates, 1,3- XDIs, 1,4- XDIs, the isocyanic acids of diphenyl methane -4,4'- two Ester, diphenyl methane -2,4'- diisocyanate, 3- Dimethyl diphenylmethanes diisocyanate, hexamethylene diisocyanate, IPDI, dicyclohexyl methyl hydride -4,4'- diisocyanate, dicyclohexyl methyl hydride -2,4'- diisocyanate, Lysine isocyanates and their polyalcohol addition product.
As organic polyvalent imide compound, it can specifically include, N, double (the 1- nitrogen third of N'- diphenyl methanes -4,4'- Pyridine carboxylic acid amides) ,-β of trimethylolpropane-three-'-aziridino propionic ester ,-the β of tetramethylol methane-three-'-aziridino propionic ester and N, N'- Toluene-2,4-diisocyanate, double (the 1- aziridine carboxylic acid amides) Persistols of 4- etc..
Crosslinking agent be crosslinked relative to 100 mass parts before acrylic polymer (A1), generally with 0.01~20 mass parts, It is preferred that with 0.1~10 mass parts, more preferably used with the ratio of 0.5~5 mass parts.
In the present invention, on form diaphragm formation film composition content form, by component of polymer (A) When content is as benchmark decision, when component of polymer (A) is the acrylic polymer of crosslinking, as the content of its benchmark, it is The content of acrylic polymer before crosslinking.
(B) Thermocurable composition
Heat curable component (B) makes an addition to diaphragm formation use to assign diaphragm formation film Thermocurable as main purpose In film.
Thermocurable composition (B), which at least contains, can pass through the compound of the functional group of heating response.By Thermocurable into Divide functional group possessed by (B) to react to each other, form three dimensional network structure, so as to realize solidification.Thermocurable composition (B) due to It is applied in combination with component of polymer (A), therefore from the viscosity for suppressing to be used to be formed the coating composition of diaphragm formation film, carry From the viewpoint of lift operations etc., its usual weight average molecular weight (Mw) is 10, less than 000, preferably 100~10,000.
As Thermocurable composition (B), for example, it is preferable to epoxies Thermocurable composition.
Epoxies Thermocurable composition includes the compound (B11) with epoxy radicals and (below, is sometimes referred to as " epoxy compound Thing (B11) ".), the composition after being combined the compound (B11) comprising epoxy radicals and thermal curing agents (B12) is preferably used, Further preferably there is curing accelerator (B13) composition using combination.
(B11) there is the compound of epoxy radicals
As epoxide (B11), known material can be used.Multifunctional class asphalt mixtures modified by epoxy resin can specifically be included Fat, bisphenol A diglycidyl ether or its hydride, Study On O-cresol Epoxy Resin, dicyclopentadiene-type epoxy resin, biphenyl type There are 2 officials in epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenylene matrix type epoxy resin equimolecular Epoxide more than energy.These materials can be used singly or two or more kinds in combination with a kind.
(B12) thermal curing agents
Thermal curing agents (B12) work as the curing agent to epoxide (B11).As preferable heat cure Agent, can enumerate in 1 molecule have more than 2 can be with the compound of the functional group of epoxy reaction., can as the functional group Include phenolic hydroxyl group, alcohol hydroxyl group, amido, carboxyl and acid anhydrides etc..Can preferably be included among this phenolic hydroxyl group, amido, Acid anhydrides etc., it can more preferably include phenolic hydroxyl group, amido, the particularly preferably amine curing agent with amido.Amine curing agent Even if with few addition, also easily diaphragm formation is adjusted in above-mentioned model with the glass transition temperature after the heat cure of film Enclose.On the other hand, the curing agent beyond amine curing agent, such as situations such as phenols curing agent, if not adding more thermosetting Agent, then it is difficult to the glass transition temperature after the heat cure of film adjust diaphragm formation in above range.If heat cure The content of agent (B12) is more, if it has to which the content for making Thermocurable composition (B) all increases, and having makes Thermocurable composition (B) The excessive possibility of content.
As the concrete example of phenols curing agent, multifunctional class phenolic resin, bis-phenol, novolac type phenol resin, two can be included Cyclopentadiene phenolic resin, new novolac type phenol resin, aralkyl-phenol resin.
As the concrete example of amine curing agent, DICY (dicyandiamide) can be included.
These materials individually or can mix two or more use with a kind.
The content of thermal curing agents (B12) is commonly angled relative to 100 mass parts epoxides (B11), is 0.1~500 mass Part or so.In the present invention, by adjusting epoxide (B11), thermal curing agents (B12) and curing accelerator (B13) contain Amount, it can control glass transition temperature of the diaphragm formation film after heat cure.Particularly, amine curing agent conduct is being used During thermal curing agents (B12), reactive hydrogen possessed by the amount of epoxy radicals possessed by epoxide (B11) and amine curing agent Amount is in terms of mol ratio (reactive hydrogen/epoxy radicals), preferably 0.4~1.5, more preferably 0.5~1.3, particularly preferably 0.6~ When 1.1, easily the glass transition temperature after the heat cure of diaphragm formation film is controlled in above range.From adjustment epoxy Mol ratio (the reactive hydrogen/ring of the amount of reactive hydrogen possessed by the amount of epoxy radicals possessed by compound (B11) and amine curing agent Epoxide) from the viewpoint of, in diaphragm formation film, relative to 100 mass parts epoxides (B11), preferably comprise amine Class curing agent is 5~20 mass parts, more preferably 5~15 mass parts.
(B13) curing accelerator
Curing accelerator (B13) can also be used to adjust the heat cure speed of diaphragm formation film.Curing accelerator (B13), particularly preferred for the situation that epoxies Thermocurable composition is used as Thermocurable composition (B).
As preferable curing accelerator, triethylenediamine, benzyldimethylamine, 2,4, triethanolamine, diformazan can be included The tertiary amines of base aminoethanol, three (dimethylaminomethyl) phenol etc.；2-methylimidazole, 2- phenylimidazoles, 2- phenyl 4- first The imidazoles of base imidazoles, 2- phenyl -4,5- bishydroxymethyls imidazoles, 2- phenyl 4- methyl 5- hydroxymethylimidazoles etc.；Three fourth phosphines, Organic phosphine of diphenyl phosphine, triphenyl phasphine etc.；The tetraphenyl boron of tetraphenylphosphoniphenolate tetraphenylborate, triphenyl phasphine tetraphenylborate etc. Acid esters etc..These materials individually or can mix two or more use with a kind.
It is excellent relative to the mass parts of total amount 100 of epoxide (B11) and thermal curing agents (B12), curing accelerator (B13) Elect the amount of 1~10 mass parts, more preferably 5~10 mass parts as.By containing curing accelerator with the amount of above range (B13), if exposed to also having excellent cohesive under high-temperature high humility, during if exposed to harsh tempered condition It may achieve very high reliability.By adding curing accelerator (B13), the bonding of diaphragm formation film after hardening can be lifted Property.The content of curing accelerator (B13) is more, and the effect is stronger.
(the 2nd adhesive component)
2nd adhesive component is by containing Thermocurable component of polymer (AB), assigning diaphragm formation film with piece shape Shape ties up characteristic and Thermocurable.
(AB) Thermocurable component of polymer
Thermocurable component of polymer is the polymer with solidification function functional group.Solidification function functional group is can be mutual Reaction forms the functional group of three-dimensional grid construction, can include the functional group by heating response.
Solidify function functional group can addition in the unit as the continuous structure of the skeleton of Thermocurable polymer (AB), Also can addition in end.Solidify function functional group addition in the continuous structure of the skeleton as Thermocurable component of polymer (AB) Unit in when, solidification function functional group can addition in side chain, also can directly addition in main chain.Thermocurable component of polymer (AB) weight average molecular weight (Mw), from the viewpoint of realizing imparting diaphragm formation film with the purpose of plate shape dimension characteristic, Usually more than 20,000.
As the functional group by heating response, epoxy radicals can be included.As the Thermocurable polymerization with epoxy radicals Thing composition (AB), can include the phenoxy resin with epoxy radicals.
Furthermore, it is possible to be the polymer same with aforesaid propylene acids polymers (A1), the monomer with epoxy radicals is used Polymerization person's (acrylic polymer containing epoxy radicals) is used as monomer.As such monomer, can include containing epoxy radicals (methyl) acrylate or monomer containing non-acrylic compounds epoxy radicals, as (methyl) acrylate containing epoxy radicals, Such as (methyl) glycidyl acrylate, (methyl) senecioate-methylglycidyl esters, (methyl) propylene can be included Sour (3,4- expoxycyclohexyls) methyl esters, (methyl) acrylic acid 3- epoxy basic ring -2- hydroxy propyl esters etc.；As containing non-acrylic acid The monomer of class epoxy radicals, it can include such as butylene acid glycidyl ester, allyl glycidyl ether.As containing epoxy radicals Monomer, preferably comprise (methyl) acrylate of epoxy radicals, wherein, preferred (methyl) glycidyl acrylate.
During using acrylic polymer containing epoxy radicals, its preferred configuration is identical with acrylic polymer (A1).
Using the acrylic polymer containing epoxy radicals, the aftermentioned thermal curing agents for being contained in the 2nd adhesive component are amine During class curing agent, by reactive with active hydrogen possessed by epoxy radicals and amine curing agent, contribute to diaphragm formation film in heat Glass transition temperature after solidification, the glass transition temperature is easily controlled in above range.Used in addition, diaphragm is formed Film also becomes easy after heat cure in the control of 23 DEG C of tensile modulus of elasticity.
During using Thermocurable component of polymer (AB) with epoxy radicals, with using as Thermocurable composition (B) It is identical during epoxies Thermocurable composition, preferably and with thermal curing agents (B12) or curing accelerator (B13).
2nd adhesive component, it can also contain above-mentioned component of polymer (A) with Thermocurable component of polymer (AB) in the lump Or Thermocurable composition (B).
Diaphragm formation film contain in Thermocurable composition (B) and Thermocurable component of polymer (AB) it is any individually or Both when, diaphragm formation film has Thermocurable.To assign more fully Thermocurable to diaphragm formation film, and The detorsion function to to-be-adhered object is lifted, preferably diaphragm formation film at least contains Thermocurable composition (B).But When diaphragm formation only contains Thermocurable composition (B) with film, there are the poor feelings of the plate shape dimension characteristic of diaphragm formation film Condition.Therefore, diaphragm formation preferably comprises Thermocurable composition (B) and component of polymer (A) and Thermocurable polymer with film In composition (AB) it is independent either or both.
In the situation, in diaphragm formation film, relative to component of polymer (A) and Thermocurable component of polymer (AB) the mass parts of total amount 100, Thermocurable composition (B) are preferably comprised more than 70 mass parts, preferably more than 85 mass Part.Thermocurable composition (B) if content lower limit in the scope, easily by the glass after the heat cure of diaphragm formation film Change transition temperature or the tensile modulus of elasticity at 23 DEG C after heat cure is adjusted in above range.
In addition, in the present invention, the form of the content of the composition on forming diaphragm formation film, being thermally cured property is gathered When the content of polymer component (AB) is as benchmark decision, Thermocurable component of polymer (AB) is third containing epoxy radicals of crosslinking During alkene acids polymers, the content as its benchmark is the content of the acrylic polymer containing epoxy radicals before crosslinking.
In addition, the upper limit as content, relative to the total amount of component of polymer (A) and Thermocurable component of polymer (AB) 100 mass parts, preferably comprise below the mass parts of Thermocurable composition (B) 135.In content by making Thermocurable composition (B) The plate shape that limiting in the scope, has the tendency of that diaphragm formation film can be kept well ties up characteristic or pliability.Particularly, protect When cuticula formation film contains inorganic filler described later (C), if inorganic filler (C) content is more, diaphragm formation film Plate shape dimension characteristic and pliability reduce, reduced relative to the patience or operability of bending.It is therefore especially preferred that Thermocurable The upper content limit of composition (B) is in above range.
In addition, when Thermocurable composition (B) is epoxies Thermocurable composition, in diaphragm formation film, relative to The mass parts of total amount 100 of component of polymer (A) and Thermocurable component of polymer (AB), preferably comprise 70 mass parts above epoxies Compound (B11), more preferably comprising 85~130 mass parts, further preferably comprising 85~120 mass parts.Thus, will easily protect Cuticula formation with the glass transition temperature after the heat cure of film or after heat cure 23 DEG C of tensile modulus of elasticity adjust in Above range.
In diaphragm formation film in addition to adhesive component, also contain following composition.
(C) inorganic filler
Diaphragm formation film, preferably comprise inorganic filler (C).By to diaphragm formation with adding inorganic fill out in film Agent (C) is filled, easily adjusts diaphragm formation in above range with the tensile modulus of elasticity after film heat cure at 23 DEG C.
In addition, by imposing laser labelling to diaphragm, inorganic filler (C) exposes in the part that laser is pruned, due to The color close to white is presented by diffusion for reflected light.Thus, can when diaphragm formation film contains colouring agent described later (D) The contrast differences of laser labelling part and other parts are obtained, having makes marking become obvious effect.
As preferable inorganic filler, silica, aluminum oxide, talcum powder, calcium carbonate, titanium oxide, oxygen can be included Change iron, carborundum, the powder such as boron nitride, by the pearl of above-mentioned substance spheroidization, mono-crystlling fibre and glass fibre etc..These materials In, preferably silica-filled dose and alumina filled dose.Above-mentioned inorganic filler (C) individually or can mix two or more and make With.
To obtain the effect above more really, as the scope of the content of inorganic filler (C), relative to composition diaphragm shape Into the ratio of the mass parts of all solids composition 100 with film, preferably 10~70 mass parts, more preferably 40~70 mass parts, Particularly preferably 55~65 mass parts.By making the content of inorganic filler (C) within the above range, can be easier will be in thermosetting Tensile modulus of elasticity after change at 23 DEG C is adjusted in above range, can lift curvature correction function, obtains high attached of reliability There is the chip of diaphragm.
In addition, the average grain diameter of inorganic filler (C), preferably 0.02~5 μm, more preferably 0.05~4.5 μm, especially Preferably 0.1~4 μm.Average grain diameter by making inorganic filler (C) can lift detorsion function within the above range. The average grain diameter of inorganic filler (C) is：The long diameter of axle of 20 inorganic fillers (C) is arbitrarily chosen with determination of electron microscopy, The number average grain diameter calculated is used as using its arithmetic mean of instantaneous value.
(D) colouring agent
Colouring agent (D) can be added in diaphragm formation film.By adding colouring agent, semiconductor device group is being entered into machine During device, semiconductor device breakdown caused by infrared ray caused by the device of surrounding etc. can be prevented.In addition, by swashing When the means of signal etc. on diaphragm to marking, having makes the mark of word, mark etc. become to be easier to the effect of identification. That is, on the semiconductor device or semiconductor chip formed with diaphragm, on the surface of the protective film generally with laser labelling method (method that progress lettering in diaphragm surface is pruned by laser) lettering Article Number etc., and colouring agent (D) is contained by diaphragm, and Film can be sufficiently protected by the part that laser is pruned and the contrast differences for the part do not pruned, and lift visibility.
As colouring agent, the pigment and dyestuff of organic or inorganic can be used.Wherein, by electromagnetic wave or infrared ray shielding Aspect is set out, preferably black pigment.As black pigment, carbon black, iron oxide, manganese dioxide, nigrosine, activated carbon can be used Deng, it is not limited to these.From the viewpoint of reliability by raising semiconductor device, particularly preferred carbon black.Colouring agent (D) Two or more use can also can be combined with a kind of exclusive use.
The addition of colouring agent (D), all solids composition of diaphragm formation film is formed relative to 100 mass parts, it is excellent Elect 0.1~35 mass parts, more preferably 0.5~25 mass parts, particularly preferably 1~15 mass parts as.
(E) coupling agent
Coupling agent (E) with the functional group reacted with inorganic matter and with the functional group of organic functional base reaction can be used Coherency in lifting diaphragm formation film to the cohesive of to-be-adhered object, adherence and/or diaphragm.In addition, by making With coupling agent (E), the heat resistance of diaphragm obtained by solidification diaphragm formation film can not be undermined, and lifts its water resistance.Make For such coupling agent, titante coupling agent, aluminate coupling agent, silane coupler etc. can be included.It is excellent among this Select silane coupler.
As silane coupler, preferably use and the functional group of organic functional base reaction and component of polymer (A), thermosetting The silane coupler of the group of functional group's reaction possessed by the property changed composition (B) or curable polymer composition (AB) etc..
As such silane coupler, γ-glycidoxypropyltrime,hoxysilane, γ-epoxy third can be included Epoxide hydroxypropyl methyl diethoxy silane, β-(3,4- expoxycyclohexyls) ethyl trimethoxy silane, γ-(methacryl Oxygen propyl group) trimethoxy silane, γ-aminocarbonyl propyl trimethoxy silane, N-6- (amido ethyl)-γ-aminocarbonyl propyl trimethoxy Base silane, N-6- (amido ethyl)-γ-aminocarbonyl propyl methyldiethoxysilane, N- phenyl-γ-aminocarbonyl propyl trimethoxy Silane, γ-urine base propyl-triethoxysilicane, γ mercaptopropyitrimethoxy silane, γ-mercaptopropyi methyl dimethoxy epoxide Silane, double (3- triethoxy silicon substrates propyl group) tetrasulfides, MTMS, MTES, vinyl Trimethoxy silane, vinyltriacetoxy silane, imidizole silane etc..These materials can with a kind individually or mix two or more Use.
Silane coupler, relative to component of polymer (A), curability composition (B) and curable polymer composition (AB) The mass parts of total amount 100, usually 0.1~20 mass parts, preferably 0.2~10 mass parts, more preferably with 0.3~5 mass parts Ratio includes.If the content of silane coupler is less than 0.1 mass parts, there is the possibility that can not obtain the effect above, if more than 20 Mass parts, then have as possibility the reason for degassing.
(F) universal additive
In addition to adding above-mentioned substance in diaphragm formation film, various additives can be also added as required.Make For various additives, levelling agent, plasticizer, antistatic agent, antioxidant, ion capturing agent, gas agent for capturing, chain can be included Transfer agent, remover etc..
Diaphragm formation film, there is initial bond and Thermocurable, can by its uncured state to semiconductor die Circle or chip etc. are easily bonded by signature.In addition, diaphragm formation can also be heated with film by when giving as security.Then, via thermosetting Change can finally assign impact resistance very high diaphragm, and bonding strength is excellent, under harsh high-temperature high humidity, also may be used Keep sufficient defencive function.In addition, diaphragm formation film can be monolayer constructions, or multi-ply construction.
Diaphragm formation (can for example be protected with film by using the composition for being obtained by mixing above-mentioned each composition with suitable proportion Cuticula formation composition) and obtain.Diaphragm formation can be diluted with solvent in advance with composition, can also be added in mixing molten Agent.In addition it is also possible to diluted when using diaphragm formation with composition with solvent.
As the solvent, can enumerate as ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, acetone, MEK, acetonitrile, Hexane, hexamethylene, toluene, heptane etc..
Diaphragm formation is not particularly limited with the thickness of film, preferably 3~300 μm, more preferably 5~250 μm, especially Preferably 7~200 μm.
Represent the wavelength of the radioparent yardstick of luminous ray and/or infrared ray and ultraviolet in diaphragm formation film 300~1200nm maximum transmission rate, preferably less than 20%, more preferably 0~15%, more preferably more than 0% and Less than 10%, particularly preferably 0.001~8%.By making the maximum of the diaphragm formation film under 300~1200nm of wavelength thoroughly Rate is penetrated in above range, the transmittance of visible wavelength region and/or infrared wavelength region is reduced, semiconductor device can be prevented Operation failure caused by infrared ray, or can must lift the effect of the visibility of lettering.Diaphragm under 300~1200nm of wavelength The maximum transmission rate of formation film can be adjusted by above-mentioned colouring agent (D).In addition, the maximum transmission rate of diaphragm formation film For：Using UV-vis spectrum detection devices ((Co., Ltd.) Shimadzu Seisakusho Ltd. system), the diaphragm formation film after measure solidification The transmissivity highest value (maximum transmission rate) of (25 μm of thickness) in 300~1200nm full light transmittance.
The diaphragm formation of the present invention is with film, using silicon and GaAs etc. as the semiconductor crystal wafer of material and chip as To-be-adhered object, used as their diaphragm.
It is related to the manufacture method of the diaphragm formation film of the present invention, is not particularly limited.
For example, diaphragm formation is film-made on engineering film with film.It is film-made and is：It will be used to form diaphragm on engineering film The composition of formation film is generally public by knife type coater, gravure coater, die coater, inverse roller blade coating machine etc. The method known is coated with, dried, and thus carries out.
Supporting slice and cover layer described later can be used directly in engineering film.In addition, diaphragm can also be formed after the film Transferred with film from engineering film to supporting slice or cover layer.Engineering film is any one of supporting slice or cover layer, and is transferred Material can be supporting slice or cover layer another.
[diaphragm formation composite sheet]
Supporting slice can be formed at the one of diaphragm formation film in a releasable manner by diaphragm formation with composite sheet Face and obtain.Diaphragm formation is not limited to that piece is lobate or bar-shape with the shape of composite sheet, can also be rolled up Receive.As supporting slice, stripping film can be included, in addition, bonding sheet described later can be used.
Diaphragm formation is pasted on various to-be-adhered objects with composite sheet, according to circumstances in diaphragm formation composite sheet, Processing needed for cutting etc. is imposed to to-be-adhered object.Then, diaphragm formation is made to remain in to-be-adhered object with film set and peel off branch Hold piece.That is, it is used in the process for including the step of diaphragm formation is needed on to-be-adhered object with film by supporting slice.
Diaphragm formation film can be made and supporting slice identical shape.In addition, diaphragm formation composite sheet can also It is that diaphragm formation is modulated into shape roughly the same with wafer with film or can intactly include the shape of wafer, lamination is than protecting Prior shaping on the larger sized supporting slice of cuticula formation film is formed.
As stripping film, can be used for example, polyethylene film, polypropylene screen, polybutene film, polybutadiene film, poly- methylpent Alkene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, poly- naphthalenedicarboxylic acid acid glycol ester film, Polybutylene terephthalate (PBT) film, polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethene (first Base) acrylic copolymer film, ethene (methyl) acrylate copolymer film, polystyrene film, polycarbonate membrane, polyimides Film, fluororesin film etc..In addition, it is possible to use their cross linking membrane.In addition it is also possible to it is their laminated film.
It is preferably below 40mN/m that the diaphragm formation of stripping film, which is connected to, with the surface tension in the face of film, more preferably Below 37mN/m, particularly preferably below 35mN/m.Lower limit is usually 25mN/m or so.The relatively low stripping of such surface tension From piece, can suitably select material and obtain, in addition it is also possible to by the surface of stripping film is coated with remover impose lift-off processing and .
As the remover for lift-off processing, alcohol acids, silicone, fluorine class, unsaturated polyester (UP) class, polyolefin can be used Class, wax class etc., particularly there is heat resistance with the remover of alcohol acids, silicone, fluorine class, so it is preferred that.
In order to using above-mentioned remover lift-off processing will be carried out as the surface of the film for peeling off sheet matrix etc., will peel off Agent directly with it is solvent-free or with solvent dilution or latex, by gravure coater, metering rod coater, Kohler coater, Disk roller coating machine etc. is coated with, and will be coated with the base material of remover under normal temperature or under heating, or with electric wire make to be formed by curing Peeling agent layer.
In addition, it can enter by the way that wet type lamination or dry lamination, heat fusing are laminated, melting extrusion is laminated, are coextruded processing etc. The lamination of row film, adjust the surface tension of stripping film.I.e., it is possible to the surface tension at least one surface is on as being connected to The film in the preferred scope in the face of the diaphragm formation film of stripping film is stated, so that the face, which turns into, is connected to diaphragm formation film The mode in face, manufacture and the laminate of other film layers product, as stripping film.
Diaphragm formation with to-be-adhered object is imposed in composite sheet cutting etc. needed for processing in the case of, be preferably used in The adhesive sheet formed with bond layer is as supporting slice on base material.In the form, diaphragm formation film, lamination is located at branch Hold on the bond layer of piece.As the base material of adhesive sheet, the above-mentioned film exemplified as stripping film can be included.Bond layer can make With the weak cementability layer of the bonding force of the degree with peelable protective film formation film, it is possible to use made by energy line irradiation The energy ray-curable layer that bonding force reduces.
Adhesive phase can be by known various bonding agents (for example, rubber-like, acrylic compounds, silicone, urethane The general bonding agent of class, vinyl ethers etc., surface have irregular bonding agent, energy-line solidifying type bonding agent, containing hot swollen Bonding agent being expanded into point etc.) formed.
The composition of diaphragm formation composite sheet then walks if this composition in diaphragm formation by the use of composite sheet as in cutting It is rapid to be used to supporting the cutting sheet of to-be-adhered object in the case of working, supporting slice can be kept to be formed with diaphragm and glued with intermembranous Connecing property, there is the effect peeled off in chip of the cutting step suppression with diaphragm formation film from supporting slice.Diaphragm is formed By the use of composite sheet as be used in cutting step supporting the cutting sheet of to-be-adhered object and in the case of working, cutting step without It must can simplify the manufacturing step of semiconductor device to pasting cutting sheet in addition with the wafer of film with diaphragm formation.
, can be using diaphragm formation by the use of composite sheet as follows when diaphragm forms and shapes composition in advance with compound piece collection The 1st, the 2nd or the 3rd form.Hereinafter, each composition of diaphragm formation composite sheet 100 is illustrated using the 1st~3 figure.
1st is formed as shown in figure 1, in the one side of diaphragm formation film 10, shape is in base material 1 in a releasable manner The composition of the upper adhesive sheet 3 for forming bond layer 2.When being formed using the 1st, the bond layer can be bonded with energy-line solidifying type Agent is formed, and is carried out energy line irradiation in advance with the region of film to the formation of lamination diaphragm, is lowered cementability, on the other hand, also may be used To be irradiated to other regions without energy line, high bonding force is maintained.Only other regions are irradiated without energy line, For example, energy line shielding layer can be set by printing etc. to the region in other regions corresponding to supporting slice, entered by supporting slice side Row energy line irradiates.
2nd is formed as shown in Fig. 2 on the adhesive phase 2 of diaphragm formation composite sheet 100, not with diaphragm Form the composition with the overlapping region of film 10, in addition setting fixture adhesive layer 4.As fixture adhesive layer, can use has core Double-sided adhesive sheet or the layer that is made up of individual layer bonding agent.
3rd is formed as shown in figure 3, between diaphragm formation film 10 and adhesive phase 2, further setting will protect The composition of the surface bonding adjustment layer 5 for the shape that cuticula formation is entirely included with the shape of film.Surface bonding adjustment layer can be rule Fixed film, or surface bonding adjustment bond layer.Surface bonding adjustment bond layer is preferably to energy ray-curable Bonding agent carries out the layer that energy line irradiation solidifies it in advance.
Formed by the way that diaphragm formation composite sheet is formed as into the above-mentioned 1st to the 3rd, surrounding diaphragm formation film Region, by the abundant cohesive of bond layer or fixture adhesive layer, diaphragm formation can be bonded on fixture with composite sheet. At the same time, diaphragm formation film and bond layer or the cohesive on the surface of surface bonding adjustment layer are can control, makes set Easily picked up in diaphragm formation with the chip of film or diaphragm.
When diaphragm formation does not take that shaping is formed in advance with composite sheet, i.e. as shown in figure 4, by diaphragm formation film 10 be made with supporting slice (in Fig. 4, on base material 1 formed bond layer 2 adhesive sheet 3) same shape when, can be formed in diaphragm With the peripheral part on the surface of film 10, fixture adhesive layer 4 is set.As fixture adhesive layer, person same as described above can be used.
The thickness of supporting slice is usually 10~500 μm, preferably 15~300 μm, particularly preferably with 20~250 μm.Branch When holding piece to form the adhesive sheet of bond layer on base material, 3~50 μm of thickness for bond layer in supporting slice.
On the unilateral opposing face of the supporting for being pasted on diaphragm formation film, cover layer can be temporarily pasted with.Cover layer can Bond layer or the covering of fixture adhesive layer during the non-adhesive sheet of supporting slice.Person identical with above-mentioned stripping film can be used in cover layer.
The thickness of cover layer, particularly preferably usually 5~300 μm, preferably 10~200 μm, 20~150 μm or so.
The diaphragm formation film of such diaphragm formation composite sheet, can be as the diaphragm of to-be-adhered object.Protection Film formation film, chip semiconductor crystal wafer or the back side of semiconductor chip of face-down pattern are pasted on, passes through appropriate hand Section solidification, there is the function of replacing sealing resin protection semiconductor crystal wafer or semiconductor chip.Semiconductor die bowlder is pasted on, by There is the function of reinforcement wafer in diaphragm, therefore the breakage of wafer can be prevented etc..
[manufacture method of semiconductor device]
Then, the Application way on diaphragm formation film of the invention, said protection film formation is made with composite sheet Illustrate in case of for manufacturing semiconductor device.
In the manufacture method of the semiconductor device of the present invention, preferably comprise the protection of said protection film formation composite sheet Film formation is pasted on semiconductor crystal wafer with film, the step of obtaining the semiconductor chip with diaphragm.
Specifically, at the back side of semiconductor crystal wafer of the surface formed with circuit, bonding protective film formation composite sheet Diaphragm formation film, then, obtaining the back side has the semiconductor chip of diaphragm.The diaphragm be preferably semiconductor crystal wafer or The diaphragm of semiconductor chip.In addition, it is the manufacture method of the semiconductor device of the present invention, preferably further comprising following Step (1)~(3), to play the detorsion function of wafer possessed by diaphragm formation film, more first carried out than step (3) Step (2).In addition, as described above, diaphragm formation is being used as to the cutting in cutting step supporting to-be-adhered object by the use of composite sheet Piece and make in the case that it acts, from the viewpoint of the manufacturing step by simplifying semiconductor device, preferably step (1) it Preceding progress step (3).
Step (1)：Peel off diaphragm formation film or diaphragm and supporting slice；
Step (2)：Solidification diaphragm formation obtains diaphragm with film；
Step (3)：Cutting semiconductor wafer and diaphragm formation film or diaphragm.
In addition, in the manufacture method of the semiconductor device of the present invention, in addition to above-mentioned steps (1)~(3), one can be entered Step includes following step (4).
Step (4)：Laser beam marking is carried out on diaphragm.
Semiconductor crystal wafer can be Silicon Wafer, or can be the compound semiconductor wafers such as GaAs.The circuit of crystal column surface Formed, can be carried out by the various methods comprising the in the past general method such as etching method, lift-off method.Then, by semiconductor crystal wafer Circuit face opposition face (back side) grinding.Grinding method is not particularly limited, and can be entered by using the known approaches of grinder etc. Row grinding.During the grinding of the back side, to protect the circuit on surface, the adhesive sheet for being referred to as surface protective plate is pasted with circuit face.The back of the body Face grinding is fixed by sucker etc. by the circuit surface side (i.e. surface protective plate side) of wafer, by the rear side for not forming circuit with Grinder grinding.Thickness after the grinding of wafer is not particularly limited, usually 50~500 μm or so.
Then as needed, caused crushable layer when removing back side grinding.Remove crushable layer can by chemical etching or Electric paste etching etc. is carried out.
Then, diaphragm formation film of the said protection film formation with composite sheet is pasted at the back side of semiconductor crystal wafer.So Afterwards, by step (1)~(3), with step (1), (2), (3) order, step (2), (1), the order of (3) or step (2), (3), (1) any one order of order is carried out.On the details of the processing procedure, Japanese Unexamined Patent Publication 2002-280329 is specified in Publication.As one, the situation of the order progress with step (1), (2), (3) is illustrated.
First, at the back side of semiconductor crystal wafer of the surface formed with circuit, said protection film formation composite sheet is pasted Diaphragm formation film.Then, formed by diaphragm and peel off supporting slice with film, obtain semiconductor crystal wafer and diaphragm formation film Laminate.Then, diaphragm formation is made to be solidified with film, in comprehensive formation diaphragm of wafer.Specifically, heat cure is passed through Diaphragm formation is set to be solidified with film.As a result, the diaphragm being made up of solidified resin is formed at the back side of wafer, due to comparing In compared with the single situation strength enhancing of wafer, therefore damage of the thinning wafer in processing can be reduced.In addition, compared to will protection The coating fluid of film is directly coated at the back side of wafer and chip and overlay film, protects the excellent in uniformity of film thickness.
Then, the laminate of semiconductor crystal wafer and diaphragm is cut into each circuit for being formed at crystal column surface.Cutting By by wafer with being carried out in a manner of being cut off together with diaphragm.Cutting through for wafer is carried out using the conventional method of cutting sheet.Its As a result, in obtained in cutting sheet piece, overleaf there are the semiconductor chip groups of diaphragm.
Then, laser beam marking is carried out on preferred pair diaphragm.Laser beam marking is carried out by laser labelling method, passes through laser Irradiation reams the surface of diaphragm, and Article Number etc. is marked on diaphragm.
Finally, the back side had into the semiconductor chip (chip for having diaphragm) of diaphragm with the universal means of chuck etc. Pickup, obtain with protection membrane DNA chip.Then, the chip with diaphragm is loaded on set base station with face-down pattern structure On, it thus can manufacture semiconductor device.In addition, can be by the back side being had the semiconductor chip of diaphragm be bonded in crystal grain pad portion Or on other components such as other semiconductor chips (in chip carrying portion), manufacture semiconductor device., can be easy according to the present invention Form the high diaphragm of thickness evenness at the back side of chip, be less likely to occur to be cracked after cutting step or encapsulation.
In addition, semiconductor crystal wafer the back side paste said protection film formation composite sheet diaphragm formation with film it Afterwards, when step (3) are carried out before step (1), (situation about being carried out with the order of step (2), (3), (1)), diaphragm is formed With composite sheet, can be played a role as cutting sheet.That is, for supporting semiconductor crystal wafer when being used as cutting step Piece.Such a situation, semiconductor crystal wafer is pasted with film via diaphragm formation in the inner peripheral portion of diaphragm formation composite sheet, is passed through The peripheral part of diaphragm formation composite sheet engages with other fixtures of ring frame etc., will be pasted on the diaphragm of semiconductor crystal wafer Formation is fixed on device with composite sheet, is cut.
Diaphragm formation film using the present invention or the diaphragm formation composite sheet using the film, except as described above Application method beyond, it may also be used for the protection of semiconducting compound, glass, ceramics, metal etc..
Embodiment
Hereinafter, by embodiment, the present invention will be described, but the present invention is not limited to these embodiments.In addition, with Under embodiment or comparative example in, following measure and assess<Glass transition temperature after heat cure>、<At 23 DEG C after heat cure Tensile modulus of elasticity>、<Detorsion Performance Evaluation>、<Reliability assessment>And<Wafer bow is assessed>.
<Glass transition temperature after heat cure>
The diaphragm formation film of 45 μm of the thickness of lamination 4, with (130 DEG C 2 of heat cure of progress under air atmosphere in baking oven Hour), make the strip test film for cutting into width 4.5mm, length 20.0mm, thickness 0.18mm.
Using determination of viscoelasticity device (TA instruments companies DMA Q800), with stretch mode, with frequency 11Hz, 3 DEG C/minute of programming rate, with tan δ (loss elastic modulus and the storage elasticity of 0~300 DEG C of determination test piece under air atmosphere The ratio of modulus).The temperature that tan δ show maximum is read in the temperature range, as the thermosetting of diaphragm formation film Glass transition temperature (Tg) after change.
<In 23 DEG C of tensile modulus of elasticity after heat cure>
Read above-mentioned<Glass transition temperature after heat cure>Storage elasticity of the determination data measured at 23 DEG C Modulus, as diaphragm formation film after heat cure in 23 DEG C of tensile modulus of elasticity.
<Detorsion Performance Evaluation>
By the diaphragm formation of 45 μm of thickness with film be pasted on 30 μm of thickness copper foil test film (Chi Cun ︰ 100mm × 100mm), heat cure (130 DEG C 2 hours) is carried out under air atmosphere in baking oven.
Then, by the contraction of the heat cure with diaphragm formation film, using bonding protective film formation with the face of film as The shape of the copper foil of inner side curling, the distance of these points of connection is taken to determine the distance into 2 points of maximum.This is apart from smaller table Show that the bending of copper foil is larger, the stress caused by can determine whether the thermal contraction of diaphragm formation film is larger, and detorsion ability It is higher.
<Reliability assessment>
1. the manufacture of the chip with diaphragm
Using patch mould machine (Lintec company systems, Adwill RAD-3600F/12), by the guarantor of diaphragm formation composite sheet Cuticula formation is heated to 70 DEG C with film side, while being pasted on the grinding of the Silicon Wafer (diameter 200mm, thick 350 μm) of No. 2000 grindings On face, supporting slice is then peeled off.Then, diaphragm formation is solidified with film within 2 hours with 130 DEG C of heating, obtain Silicon Wafer with protecting The laminate of cuticula.
The diaphragm side of above-mentioned obtained laminate is pasted in cutting film (Lintec company systems, Adwill D-686H), 3mm × 3mm size is cut into cutter device (DISCO company system DFD651), obtain Reliability assessment has protection The chip of film.
2. Reliability assessment
Gained is had to the chip of diaphragm, makes its moisture absorption to be placed 168 hours under conditions of 85 DEG C, relative humidity 85% Afterwards, 3 260 DEG C of maximum temperatures, the IR of 1 minute heat time tempering (Hui Huo Lu ︰ phase mould science and engineerings WL-15-20DNX are carried out Type).In addition, the chip with diaphragm is arranged in thermal shock device (ESPEC company system TSE-11A), repeat After being kept for 10 minutes at -40 DEG C for 1000 times the process of 10 minutes is kept at 125 DEG C.
Then, for the chip with diaphragm taken out from thermal shock device, filled by scan-type Supersonic wave inspection Put (Hitachi builds machine FINTEC company system Hye-Focus) and section observation, observation whether there is the engagement of semiconductor chip and diaphragm The stripping in portion or the cracking of diaphragm.
Above-mentioned assessment is carried out to 25 chips with diaphragm, counts the moire of the stripping that junction surface occurs or diaphragm Number (umber of defectives).Umber of defectives is fewer, represents that the reliability of diaphragm formation film is higher.
<Wafer bow is assessed>
Prepare with 200 μm of thickness, the 8 of spill sigmoid (bending amount ︰ 10mm) are produced in circuit surface side (face side) The very little wafer (reference picture 5) with circuit.
Then, in the back side bonding protective film formation film of wafer, with 130 DEG C of heat cures 2 hours.
Then, the amount of bow of gained wafer is evaluated as " good " in below 2mm, when the amount of bow of wafer is more than 2mm It is evaluated as " bad ".As long as the amount of bow of wafer in below 2mm, then can be conveyed by general wafer chip mounter.
[diaphragm formation composition]
Diaphragm formation will be formed and represent as follows with each composition of composition.
(A1-1) polymer Cheng Fen ︰ are by 55 mass parts n-butyl acrylates, 15 mass parts methyl acrylates, 20 mass parts first The acrylic polymer that base glycidyl acrylate and 10 mass parts acrylic acid 2- hydroxy methacrylate combined polymerizations form (is divided equally again Son amount ︰ 900,000, vitrifying turn to become ︰ -28 DEG C of temperature)
(A1-2) polymer Cheng Fen ︰ are by 55 mass parts n-butyl acrylates, 35 mass parts methyl acrylates and 10 mass parts (the equal molecular weight ︰ 900,000 of weight, vitrifying turn to become temperature ︰ -31 acrylic polymer that acrylic acid 2- hydroxy methacrylate combined polymerizations form ℃)
(B11-1) bisphenol A type epoxy resin (Mitsubishi Chemical jER828,184~194g/eq of epoxide equivalent)
(B11-2) bisphenol A type epoxy resin (Mitsubishi Chemical jER1055,800~900g/eq of epoxide equivalent)
(B11-3) dicyclopentadiene-type epoxy resin (big Japanese ink chemical industry (stock) system, EPICRONE HP- 7200HH, 255~260g/eq of epoxide equivalent)
(B11-4) orthoresol phenol aldehyde type epoxy resin (Japanese chemical drug EOCN-104S, 213~223g/eq of epoxide equivalent)
(B12) thermal activities potentiality epoxy curing agent (dicyandiamide (ADEKA ADEKA HARDNER EH- 3636AS, active hydrogen amount 21g/eq))
(B13) Cu Jin Ji ︰ 2 pheny1 4,5 dihydroxymethyl imidazoles (four countries chemical conversion industry company system Cuazole is solidified 2PHZ)
(C-1) silica-filled dose (ADMATEX SC2050MA, 0.5 μm of average grain diameter)
(C-2) silica-filled dose (3 μm of average grain diameter)
(C-3) silica-filled dose (TATSUMORI SV-10,8 μm of average grain diameter)
(D) Se Ji ︰ carbon blacks (Mitsubishi Chemical Ind #MA650, average grain diameter 28nm)
(E) silane coupler (Japanese UNICAR A-1110)
(embodiment and comparative example)
Mentioned component is added with the addition described in table 1, obtains diaphragm formation composition.Table 1 it is each into Point addition represent the mass parts of solid constituent conversion, the solid constituent in the present invention refers to all the components beyond solvent.
The diaphragm formation composition of the composition of table 1 will be recorded in, solid component concentration is diluted to as 61 with MEK Quality %, in a manner of thickness after drying is 45 μm, coated and dried (120 DEG C, 2 minutes of dried strip Jian ︰ baking ovens) is in supporting slice On the lift-off processing face of (Lintec company system SP-PET3811,38 μm of thickness), diaphragm formation film is formed on supporting slice, Obtain diaphragm formation composite sheet.Then, by diaphragm formation film and stripping film (polyethylene terephthalate film The lift-off processing face fitting of (Lintec company system SP-PET381031,38 μm of thickness), obtain posting the diaphragm shape of stripping film Into with composite sheet.Each assessment result is shown in table 2.
The explanation of reference
1 is base material；2 be adhesive phase；3 be bonding sheet (supporting slice)；4 be fixture adhesive layer；5 be that surface bonding adjusts Layer；10 be diaphragm formation film；100 be diaphragm formation composite sheet.

Claims (7)

1. a kind of diaphragm formation film, it has Thermocurable,
Glass transition temperature after its heat cure is 150~260 DEG C,
Tensile modulus of elasticity after its heat cure at 23 DEG C is 2.9~7.9GPa.
2. diaphragm formation film as claimed in claim 1, the film includes to be formed containing epoxide and amine curing agent Thermocurable composition.
3. diaphragm formation film as claimed in claim 2, it also contains component of polymer and Thermocurable component of polymer In it is any individually one or two kinds of, relative to the component of polymer and Thermocurable component of polymer of the mass parts of total amount 100, bag Containing the Thermocurable composition below 135 mass parts.
4. diaphragm formation film as claimed in claim 1 or 2, wherein diaphragm formation include inorganic filler with film,
The all solids composition of diaphragm formation film is formed relative to 100 mass parts, the content of inorganic filler is 10~70 Mass parts.
5. diaphragm formation film as claimed in claim 4, the wherein average grain diameter of inorganic filler are 0.02~5 μm.
6. diaphragm formation film as claimed in claim 1 or 2, wherein diaphragm formation include Thermocurable polymer with film Composition,
Thermocurable component of polymer is the acrylic polymer for including the monomer containing epoxy radicals as the monomer formed.
7. a kind of diaphragm formation composite sheet, it is the diaphragm formation film described in any one in claim 1~6 A face on strippingly form supporting slice and form.
CN201480004970.7A 2013-03-22 2014-03-24 Diaphragm formation is with film and diaphragm formation composite sheet Active CN104937712B (en)

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