CN104937712A - Protective film-forming film and protective film-forming composite sheet - Google Patents

Protective film-forming film and protective film-forming composite sheet Download PDF

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Publication number
CN104937712A
CN104937712A CN201480004970.7A CN201480004970A CN104937712A CN 104937712 A CN104937712 A CN 104937712A CN 201480004970 A CN201480004970 A CN 201480004970A CN 104937712 A CN104937712 A CN 104937712A
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diaphragm formation
diaphragm
film
formation film
polymer
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CN104937712B (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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  • Chemical Kinetics & Catalysis (AREA)
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  • Adhesive Tapes (AREA)
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  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract

[Problem] To provide a protective film-forming film that minimizes warping of a wafer, and is capable of forming a highly-reliable protective film on a chip. [Solution] This protective film-forming film is thermally curable, has a glass transition temperature after being thermally cured of 150 to 300 DEG C, and has a modulus of elasticity at a temperature of 23 DEG C after being thermally cured of 0.5 to 10 GPa.

Description

Diaphragm formation film and diaphragm formation composite sheet
Technical field
The present invention relates to a kind of diaphragm formation film, it can form diaphragm on semiconductor crystal wafer or semiconductor chip, and can promote the manufacture efficiency of semiconductor chip.Particularly relate to what is called face down (face down) pattern structure dress the diaphragm formation film for semiconductor chip manufacture.
Background technology
In recent years, the structure dress method using what is called to be called as (face down) pattern that faces down is had to carry out the manufacture of semiconductor device.In the pattern of facing down, being used in semiconductor chip circuit face with electrodes such as projections (below, has the situation being only called " chip ".), this electrode engages with substrate.Therefore, expose with the face (chip back) of the circuit face opposition side of chip.
This chip back exposed, has the situation protected by organic film.In the past, there is the chip of the diaphragm be made up of this organic film, by aqueous resin is coated wafer rear with method of spin coating, dry, solidification and together with wafer tripping protection film and obtaining.But, insufficient due to the thickness and precision of diaphragm that formed like this, there is the situation reducing rate of finished products.
For solving the problem, disclose a kind of (patent documentation 1) with the curability diaphragm cambial chip diaphragm formation sheet comprising heat or energy ray-curable composition.
In the past, wafer itself abundant thick time, although wafer itself can't bend, along with wafer thinner, create following problem: the contraction rate variance of the crystal column surface being formed with circuit and the wafer rear that do not form circuit, the wafer that result in thinning produces bending.
Bending large wafer, has the possibility causing conveying bad in chip fabrication steps afterwards.In addition, the bending possibility being difficult to cutting crystal wafer because of wafer is had.
For eliminating the problem that this wafer bow causes, to the diaphragm formation film being pasted on wafer rear, require the performance of correcting wafer bow.
In patent documentation 2, cubical contraction in the scope of 23 DEG C to 165 DEG C when being used in hot curing is more than 100ppm/ DEG C less than 400ppm/ DEG C, stretching storage elastic modulus at 23 DEG C after hot curing is the film for flip chip type semiconductor back surface of more than 1GPa below 5GPa, suppresses or prevents the semiconductor element of semiconductor crystal wafer or semiconductor chip etc. from bending.
In addition, in patent documentation 3, the amount of contraction using hot curing to cause is the film for flip chip type semiconductor back surface of 2 more than volume % 30 volume below % relative to the full volumetric before hot curing, suppresses or prevents semiconductor element from bending.
Prior art document
Patent documentation
Patent documentation 1 ︰ Japanese Unexamined Patent Publication 2004-214288 publication
Patent documentation 2 ︰ Japanese Unexamined Patent Publication 2012-33554 publication
Patent documentation 3 ︰ Japanese Unexamined Patent Publication 2011-228499 publication
Summary of the invention
The technical problem to be solved in the present invention
In recent years, be formed at the circuit pattern variation of crystal column surface, the circuit that results from is formed and bending large wafer increases.Therefore, requirement can correct the diaphragm formation film of wafer bow more significantly, but in the film for flip chip type semiconductor back surface of patent documentation 2 or patent documentation 3, has the bending situation fully cannot eliminating wafer and chip.In addition, the present inventor etc. attentively attempt the result promoting detorsion function further, and obtained with in the chip of diaphragm, there is the situation occurring to peel off or crack at diaphragm at the junction surface of diaphragm and chip, and its reliability is also insufficient.
Problem of the present invention is to provide a kind of diaphragm formation film, and it can form the high diaphragm of reliability while can suppressing bending of wafer on chip.
The technological means of technical solution problem
Purport of the present invention is as follows.
(1) a diaphragm formation film, it has Thermocurable,
Glass transition temperature after hot curing is 150 ~ 300 DEG C,
Be 0.5 ~ 10GPa at the tensile modulus of elasticity of 23 DEG C after hot curing.
(2) the diaphragm formation film as described in (1), this film comprises the Thermocurable composition containing epoxy compounds and amine curing agent.
(3) diaphragm formation film as claimed in claim 2; its any one or both also containing component of polymer and Thermocurable component of polymer; relative to component of polymer and the Thermocurable component of polymer of total amount 100 mass parts, comprise the Thermocurable composition of below 135 mass parts.
(4) the diaphragm formation film as described in any one of (1) ~ (3), wherein diaphragm formation film comprises inorganic filler,
Form all solids composition of diaphragm formation film relative to 100 mass parts, the content of inorganic filler is 10 ~ 70 mass parts.
(5) the diaphragm formation film Gen Ju (4), wherein the average grain diameter of inorganic filler is 0.02 ~ 5 μm.
(6) according to the diaphragm formation film according to any one of (1) ~ (5), wherein diaphragm formation film comprises Thermocurable component of polymer,
Thermocurable component of polymer is comprise the acrylic polymer of the monomer containing epoxy radicals as the monomer formed.
(7) a diaphragm formation composite sheet, it is formed by a face of the diaphragm formation film described in any one in above-mentioned (1) ~ (6) forms strippable supporting slice.
Invention effect
According to the present invention; to resulting from the wafer bow that causes of contraction that the circuit of crystal column surface side formed; by diaphragm formation film is pasted on wafer rear; carry out hot curing; by resulting from the stress of cure shrinkage of diaphragm formation film; correct the bending of wafer, and obtain the high chip with diaphragm of reliability.
Accompanying drawing explanation
1st form of the diaphragm formation composite sheet that Fig. 1 uses the diaphragm formation film that the present invention relates to be formed for expression.
Fig. 2 is the 2nd form representing the diaphragm formation composite sheet using the diaphragm formation film that the present invention relates to be formed.
Fig. 3 is the 3rd form representing the diaphragm formation composite sheet using the diaphragm formation film that the present invention relates to be formed.
Fig. 4 is the 4th form representing the diaphragm formation composite sheet using the diaphragm formation film that the present invention relates to be formed.
Fig. 5 is the figure that " amount of bow " evaluated in embodiment is described.
Embodiment
Below, the details of diaphragm formation film of the present invention is described.
[diaphragm formation film]
Diaphragm formation film of the present invention has Thermocurable, and the glass transition temperature (Tg) after hot curing is 150 ~ 300 DEG C, is preferably 170 ~ 280 DEG C, is more preferably 220 ~ 270 DEG C.Glass transition temperature (Tg) after the hot curing of diaphragm formation film of the present invention is: in the Measurement of Dynamic Viscoelasticity of the diaphragm formation film (diaphragm) after the hot curing measured with frequency 11Hz, shows the temperature of maximum at the low-temperature region internal loss tangent tan δ of-50 ~ 30 DEG C.
If the Tg after the hot curing of diaphragm formation film is less than 150 DEG C; then usual in the heat curing processes of about 120 ~ 150 DEG C diaphragm formation films carried out; the mobility of diaphragm formation film uprises, and results from the stress of cure shrinkage of diaphragm formation film and diminished by relaxing.Consequently, the rectification of wafer bow is become insufficient.
On the other hand, if the Tg after the hot curing of diaphragm formation film is more than 300 DEG C, then the possibility that the diaphragm having diaphragm formation film maybe this film hot curing to be obtained is peeled off from wafer or chip, consequently, can reduce the reliability of the chip with diaphragm.
By making the Tg after the hot curing of diaphragm formation film in above-mentioned scope; due in the thermal cure step of this film; diaphragm formation film has the rigidity of regulation; therefore can't relax and result from the stress of this film cure shrinkage, and the bending of the chip that this wafer sheet maybe obtains by wafer can be corrected.
In addition, diaphragm formation film is 0.5 ~ 10GPa at the tensile modulus of elasticity of 23 DEG C after hot curing, is preferably 1 ~ 10GPa, more preferably more than 5GPa and at below 8GPa.
If diaphragm formation film is less than 0.5GPa at the tensile modulus of elasticity of 23 DEG C after hot curing, then cannot maintain and result from the stress of cure shrinkage of diaphragm formation film, this stress is relaxed, and the rectification of wafer bow becomes insufficient.On the other hand, if diaphragm formation film after hot curing at the tensile modulus of elasticity of 23 DEG C more than 10GPa, then the diaphragm having diaphragm formation film maybe this film hot curing to be obtained from wafer or chip peel off may.
By make diaphragm formation film after hot curing at the tensile modulus of elasticity of 23 DEG C in above-mentioned scope, can correct wafer and chip bending while, promote the reliability of the chip having diaphragm.
In addition, the percent thermal shrinkage heated 2 hours at 130 DEG C of diaphragm formation film is preferably 0.1 ~ 10%, is more preferably 0.5 ~ 5%.At making 130 DEG C of diaphragm formation film, heat 2 little percent thermal shrinkages constantly in above-mentioned scope, the effect (detorsion performance) of correcting wafer bow can be promoted.In addition, being formed with membrane area by dropping into the diaphragm diaphragm formed before and after with film under 130 DEG C of environment, being tried to achieve the percent thermal shrinkage heating 2 little diaphragm formation films constantly at 130 DEG C by following formula.
Area × 100 of the diaphragm formation film before percent thermal shrinkage (%)={ (area of the diaphragm formation film before input)-(area of the diaphragm formation film after input) }/input
The function that diaphragm formation film at least requires, for: (1) plate shape maintenance; (2) initial bond; And (3) curability.In addition, diaphragm formation film of the present invention, though have Thermocurable as mentioned above, also can have the character of the means solidification beyond by heat.
Diaphragm formation film gives (1) plate shape maintenance and (3) curability by adding adhesive component; as adhesive component; the 1st adhesive component containing component of polymer (A) and Thermocurable composition (B) can be used, or containing having the 2nd adhesive component of Thermocurable component of polymer (AB) of character of (A) composition and (B) composition concurrently.
In addition, until (2) initial bond of the function for being temporarily adhered to to-be-adhered object of diaphragm formation film solidification, can be pressure-sensitive adhesiveness, also can be the character of being carried out softening bonding by heat.(2) initial bond, passes through the controls such as the adjustment of each characteristic of adhesive component or the addition of inorganic filler described later (C) usually.
(the 1st adhesive component)
1st adhesive component, by containing component of polymer (A) and Thermocurable composition (B), gives diaphragm formation film with plate shape dimension characteristic and Thermocurable.In addition, the 1st adhesive component is distinguished with the 2nd adhesive component convenient, not containing Thermocurable component of polymer (AB).
(A) component of polymer
Component of polymer (A), to give plate shape dimension characteristic to diaphragm formation film for main purpose, makes an addition in diaphragm formation film.
For achieving the above object, the weight average molecular weight (Mw) of component of polymer (A) is generally 20, more than 000, is preferably 20,000 ~ 3,000,000.The value of weight average molecular weight (Mw) is value when being measured by gel permeation chromatography (GPC) (polystyrene standard).Mensuration in this way can use such as, the high speed GPC device " HLC-8120GPC " of TOSO Inc., with by high speed post " TSK gurd column H xL-H ", " TSK Gel GMH xL", " TSK GelG2000H xL" device that the order of (more than, be TOSO Inc.) connects, pipe column temperature ︰ 40 DEG C, the condition that defeated liquid speed degree ︰ 1.0mL/ divides, carries out using Differential refractometer as detector.
In addition, for convenience of distinguishing with curable polymer described later (AB), component of polymer (A) does not have solidification function functional group described later.
As component of polymer (A), acrylic polymer, polyester, phenoxy resin can be used (for convenience of distinguishing with curable polymer described later (AB), to be limited to and not to have epoxy radicals.), Merlon, polyethers, polyurethane, polysiloxanes, rubber polymer etc.In addition, also can be these two or more material combined above-mentioned, such as, there is urethane prepolymer that the acrylic polyol of the acrylic polymers of hydroxyl and molecular end have a NCO and react and the acrylic acid urethane resin etc. that obtains.In addition, comprise the polymer that two or more combines, also these two or more above-mentioned can be combinationally used.
(A1) acrylic polymer
Acrylic polymer (A1) is preferably used as component of polymer (A).The glass transition temperature (Tg) of acrylic polymer (A1), is preferably-60 ~ 50 DEG C, is more preferably-50 ~ 40 DEG C, more preferably the scope of-40 ~ 30 DEG C.The glass transition temperature of acrylic polymer (A1) is high, then the initial bond of diaphragm formation film reduces, and has the situation that cannot be needed on to-be-adhered object.In addition, the glass transition temperature of acrylic polymer (A1) is low, then the peeling force of diaphragm formation film and supporting slice described later becomes greatly, and the situation having the transfer printing of generation diaphragm formation film bad.
In addition, the Tg of acrylic polymer is the value of being tried to achieve by FOX formula.
The weight average molecular weight (Mw) of acrylic polymer (A1) is preferably 100,000 ~ 1,500,000.Acrylic polymer (A1) weight average molecular weight is high, then the initial bond of diaphragm formation film reduces, and has the situation occurring to be needed on to-be-adhered object.In addition, acrylic polymer (A1) weight average molecular weight is low, then the adherence of diaphragm formation film and supporting slice uprises, and the situation having the transfer printing of generation diaphragm formation film bad.
Acrylic polymer (A1) at least comprises (methyl) acrylate in the monomer formed.
As (methyl) acrylate, alkyl (methyl) acrylate that atomic number of alkyl carbon is 1 ~ 18 can be exemplified out, specifically, (methyl) methyl acrylate can be exemplified out, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) dodecyl acrylate, (methyl) tetradecyl acrylate, (methyl) octadecyl acrylate, there is (methyl) acrylate of cyclic skeleton, specifically, (methyl) acrylate ester, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid bicyclopentyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl 2-ethoxyethyl acetate, acid imide (methyl) acrylate etc. can be exemplified out.In addition, the monomer, the monomer with carboxyl that there is hydroxyl exemplified as described later, have in the monomer of amido, (methyl) acrylate can be illustrated as.
In the present invention; diaphragm formation film, as the monomer forming acrylic polymer (A1), is easily controlled the scope in regulation at the tensile modulus of elasticity of 23 DEG C by (methyl) acrylate having acrylate by using (methyl) with hydroxyl, having (methyl) acrylate of carboxyl or having an amido after hot curing.
In addition, in this specification, (methyl) acrylic acid, to comprise acrylic acid and methacrylic acid two kinds of meanings and to use.
As the monomer forming acrylic polymer (A1), the monomer with hydroxyl can be used.There is the monomer of hydroxyl, (methyl) acrylate with hydroxyl of (methyl) dihydroxypropyl methyl esters, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl etc. can be listed; Vinyl alcohol, N-methylol (methyl) acrylamide etc.
As the monomer forming acrylic polymer (A1), the monomer with carboxyl also can be used.As the monomer with carboxyl, (methyl) acrylate with carboxyl of 2-(methyl) acrylyl oxy-ethyl phthalic acid ester, 2-(methyl) acryloxypropyl phthalic acid ester etc. can be listed; (methyl) acrylic acid, maleic acid, fumaric acid, itaconicacid etc.When using epoxies Thermocurable composition as curability composition (B) described later, because carboxyl can with the epoxy reaction in epoxies Thermocurable composition, therefore the use amount preferably with the monomer of carboxyl is few.
As the monomer forming acrylic polymer (A1), the monomer with amido also can be used.As the monomer monomer with amido, (methyl) acrylate etc. that monomethyl amido (methyl) acrylate, MEA base (methyl) acrylate, diethyl amido (methyl) acrylate etc. have amido can be listed.
As the monomer forming acrylic polymer (A1), other vinylacetate, styrene, ethene, alpha-olefin etc. also can be used.
Acrylic polymer (A1) also crosslinkable.Be cross-linked as acrylic polymer (A1) before crosslinking has the bridging property functional groups such as hydroxyl; by adding crosslinking agent in the composition for the formation of diaphragm formation film, the functional group that bridging property functional group and crosslinking agent are had reacts and carries out.By making acrylic polymer (A1) be cross-linked, the cohesiveness of adjustable protective film formation film.In addition, by the crosslink density of adjustment acrylic polymer (A1), the tensile modulus of elasticity at 23 DEG C after the glass transition temperature after the hot curing of diaphragm formation film or hot curing can be controlled.Crosslink density controls by the addition of crosslinking agent described later.
As crosslinking agent, organic polyvalent isocyanate compound, organic multivalence group with imine moiety etc. can be listed.
As organic polyvalent isocyanate compound, the trimer of aromatic series polyvalent isocyanate compound, aliphat polyvalent isocyanate compound, alicyclic multivalent isocyanate compound and these organic polyvalent isocyanate compound can be listed and make these organic polyvalent isocyanate compound and polyol compound react the terminal isocyanate urethane prepolymer etc. of gained.
As organic polyvalent isocyanate compound, specifically can list 2,4-toluene di-isocyanate(TDI), 2,6-toluene di-isocyanate(TDI), 1,3-XDI, 1,4-XDI, diphenyl methane-4,4'-vulcabond, diphenyl methane-2,4'-vulcabond, 3-MDPM vulcabond, hexamethylene diisocyanate, IPDI, dicyclohexyl methyl hydride-4,4'-vulcabond, dicyclohexyl methyl hydride-2,4'-vulcabond, lysine isocyanates and their polyalcohol addition product.
As organic polyvalent imide compound, specifically can list, N, N'-diphenyl methane-4,4'-two (1-aziridine carboxylic acid amides), trimethylolpropane-three-β-'-aziridino propionic ester, tetramethylol methane-three-β-'-aziridino propionic ester and N, N'-Toluene-2,4-diisocyanate, two (1-aziridine carboxylic acid amides) Persistols of 4-etc.
Acrylic polymer (A1) before crosslinking agent is cross-linked relative to 100 mass parts, usually with 0.01 ~ 20 mass parts, preferably with 0.1 ~ 10 mass parts, more preferably uses with the ratio of 0.5 ~ 5 mass parts.
In the present invention; about the form of the content of the composition of formation diaphragm formation film; when the content of component of polymer (A) is determined as benchmark; when component of polymer (A) is crosslinked acrylic polymer; as the content of its benchmark, be the content of the acrylic polymer before crosslinked.
(B) Thermocurable composition
Heat curable component (B) forms film Thermocurable for main purpose and making an addition in diaphragm formation film to give diaphragm.
The compound of Thermocurable composition (B) at least containing the functional group by adding thermal response.The functional group had by Thermocurable composition (B) is reacted to each other, and forms three dimensional network structure, thus realizes solidification.Thermocurable composition (B) is owing to combinationally using with component of polymer (A); therefore from the viscosity suppressed for the formation of the coating composition of diaphragm formation film; the viewpoint of lifting operation etc. is considered; usually its weight average molecular weight (Mw) is 10; less than 000; be preferably 100 ~ 10,000.
As Thermocurable composition (B), such as, preferred epoxies Thermocurable composition.
Epoxies Thermocurable composition comprises the compound (B11) with epoxy radicals and (below, is sometimes referred to as " epoxy compounds (B11) ".), preferably use the composition after being combined with thermal curing agents (B12) by the compound (B11) comprising epoxy radicals, preferably use combination to have the composition of curing accelerator (B13) further.
(B11) there is the compound of epoxy radicals
As epoxy compounds (B11), known material can be used.Specifically can list in multifunctional based epoxy resin, bisphenol A diglycidyl ether or its hydride, Study On O-cresol Epoxy Resin, dicyclopentadiene-type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenylene matrix type epoxy resin equimolecular there are 2 officials can above epoxy compounds.These materials can a kind be used singly or two or more kinds in combination.
(B12) thermal curing agents
Thermal curing agents (B12) works as the curing agent to epoxy compounds (B11).As preferred thermal curing agents, can enumerate for have in 1 molecule more than 2 can with the compound of the functional group of epoxy reaction.As this functional group, phenolic hydroxyl group, alcohol hydroxyl group, amido, carboxyl and acid anhydrides etc. can be listed.Among this, preferably can list phenolic hydroxyl group, amido, acid anhydrides etc., more preferably can list phenolic hydroxyl group, amido, be particularly preferably the amine curing agent with amido.Even if amine curing agent is with few addition, also easy glass transition temperature after the hot curing of diaphragm formation film to be adjusted in above-mentioned scope.On the other hand, the curing agent beyond amine curing agent, the situations such as such as phenols curing agent, if do not add more thermal curing agents, are then difficult to the glass transition temperature after by the hot curing of diaphragm formation film and adjust in above-mentioned scope.If the content of thermal curing agents (B12) is many, then has to all content of Thermocurable composition (B) is increased, and have the possibility making the content of Thermocurable composition (B) excessive.
As the concrete example of phenols curing agent, multifunctional class phenolic resins, bis-phenol, novolac type phenol resin, bicyclopentadiene class phenolic resins, new novolac type phenol resin, aralkyl-phenol resin can be listed.
As the concrete example of amine curing agent, DICY (dicyandiamide) can be listed.
These materials can a kind separately or mix two or more and use.
The content of thermal curing agents (B12), usually relative to 100 mass parts epoxy compoundss (B11), is about 0.1 ~ 500 mass parts.In the present invention, by the content of adjustment ring oxygen compound (B11), thermal curing agents (B12) and curing accelerator (B13), the glass transition temperature of diaphragm formation film after hot curing can be controlled.Particularly; when using amine curing agent as thermal curing agents (B12); the amount of the reactive hydrogen that the amount of the epoxy radicals that epoxy compounds (B11) has and amine curing agent have is in mol ratio (reactive hydrogen/epoxy radicals); be preferably 0.4 ~ 1.5; be more preferably 0.5 ~ 1.3; when being particularly preferably 0.6 ~ 1.1, easily the glass transition temperature after the hot curing of diaphragm formation film is controlled in above-mentioned scope.The viewpoint of the mol ratio (reactive hydrogen/epoxy radicals) of the amount of the reactive hydrogen that the amount of the epoxy radicals had from adjustment ring oxygen compound (B11) and amine curing agent have; in diaphragm formation film; relative to 100 mass parts epoxy compoundss (B11); preferably containing amine curing agent is 5 ~ 20 mass parts, is more preferably 5 ~ 15 mass parts.
(B13) curing accelerator
Also curing accelerator (B13) can be used to adjust the hot curing speed of diaphragm formation film.Curing accelerator (B13), is particularly preferred for the situation using epoxies Thermocurable composition as Thermocurable composition (B).
As preferred curing accelerator, the tertiary amines of triethylenediamine, benzyl dimethyl amine, triethanolamine, dimethyl amido ethanol, three (dimethylaminomethyl) phenol etc. can be listed; The imidazoles of glyoxal ethyline, 2-phenylimidazole, 2-phenyl 4-methylimidazole, 2-phenyl-4,5-bishydroxymethyl imidazoles, 2-phenyl 4-methyl 5-hydroxymethylimidazole etc.; The organic phosphine class of three fourth phosphines, diphenyl phosphine, triphenyl phasphine etc.; The tetraphenylborate etc. of tetraphenylphosphoniphenolate tetraphenylborate, triphenyl phasphine tetraphenylborate etc.These materials can a kind separately or mix two or more and use.
Relative to total amount 100 mass parts of epoxy compounds (B11) and thermal curing agents (B12), curing accelerator (B13) is preferably 1 ~ 10 mass parts, the more preferably amount of 5 ~ 10 mass parts.By containing curing accelerator (B13) with the amount of above-mentioned scope, even if also there is excellent adhesiveness under being exposed to high-temperature high humility, even if also very high reliability can be reached when being exposed to harsh tempered condition.By adding curing accelerator (B13), diaphragm formation film adhesiveness after hardening can be promoted.The content of curing accelerator (B13) is more, and this effect is stronger.
(the 2nd adhesive component)
2nd adhesive component, by containing Thermocurable component of polymer (AB), gives diaphragm formation film with plate shape dimension characteristic and Thermocurable.
(AB) Thermocurable component of polymer
Thermocurable component of polymer is the polymer with solidification function functional group.Solidification function functional group interreaction can form the functional group that three-dimensional grid constructs, and can list the functional group by adding thermal response.
Solidification function functional group can add in the unit of the continuous structure being formed in the skeleton becoming Thermocurable polymer (AB), also can add and be formed in end.When solidification function functional group adds in the unit of the continuous structure being formed in the skeleton becoming Thermocurable component of polymer (AB), solidification function functional group can add and is formed in side chain, also directly can add and be formed in main chain.The weight average molecular weight (Mw) of Thermocurable component of polymer (AB), to realize giving diaphragm formation film with the viewpoint of the object of plate shape dimension characteristic, is generally 20, more than 000.
As the functional group by adding thermal response, epoxy radicals can be listed.As the Thermocurable component of polymer (AB) with epoxy radicals, the phenoxy resin with epoxy radicals can be listed.
In addition, can be the polymer same with aforesaid propylene acids polymers (A1), use the monomer polymerization person (acrylic polymer containing epoxy radicals) with epoxy radicals as monomer.As such monomer, (methyl) acrylate containing epoxy radicals or the monomer containing non-acrylic compounds epoxy radicals can be listed, as (methyl) acrylate containing epoxy radicals, such as (methyl) glycidyl acrylate, (methyl) senecioate-methylglycidyl esters, (methyl) acrylic acid (3,4-expoxycyclohexyl) methyl esters, (methyl) acrylic acid 3-epoxy basic ring-2-hydroxy propyl ester etc. can be listed; As the monomer containing non-acrylic compounds epoxy radicals, such as butenoic acid ethylene oxidic ester, allyl glycidyl ether etc. can be listed.As the monomer containing epoxy radicals, (methyl) acrylate preferably containing epoxy radicals, wherein, preferably (methyl) glycidyl acrylate.
When using the acrylic polymer containing epoxy radicals, its preferred configuration is identical with acrylic polymer (A1).
Use the acrylic polymer containing epoxy radicals; when the aftermentioned thermal curing agents being contained in the 2nd adhesive component is amine curing agent; by the reactive with active hydrogen that epoxy radicals and amine curing agent have; contribute to the glass transition temperature of diaphragm formation film after hot curing, easily this glass transition temperature is controlled in above-mentioned scope.In addition, diaphragm formation film also becomes easy in the control of the tensile modulus of elasticity of 23 DEG C after hot curing.
When use has Thermocurable component of polymer (AB) of epoxy radicals, identical with when being used as the epoxies Thermocurable composition of Thermocurable composition (B), preferably and with thermal curing agents (B12) or curing accelerator (B13).
2nd adhesive component, also can with Thermocurable component of polymer (AB) in the lump, containing above-mentioned component of polymer (A) or Thermocurable composition (B).
Diaphragm formation film contain in Thermocurable composition (B) and Thermocurable component of polymer (AB) arbitrary separately or both time, diaphragm formation film has Thermocurable.For giving Thermocurable more fully to diaphragm formation film, and promote the detorsion function to to-be-adhered object, preferred diaphragm formation film is at least containing Thermocurable composition (B).But, when diaphragm formation only contains Thermocurable composition (B) with film, have the plate shape of diaphragm formation film to tie up the poor situation of characteristic.Therefore, diaphragm formation film is preferably containing independent any one or both in Thermocurable composition (B) and component of polymer (A) and Thermocurable component of polymer (AB).
In this situation; in diaphragm formation film; relative to total amount 100 mass parts of component of polymer (A) and Thermocurable component of polymer (AB), Thermocurable composition (B) preferably containing being greater than 70 mass parts, more preferably containing being greater than 85 mass parts.Thermocurable composition (B) if content lower limit in this scope, then easily to adjust in above-mentioned scope by the glass transition temperature after the hot curing of diaphragm formation film or after hot curing at the tensile modulus of elasticity of 23 DEG C.
In addition; in the present invention; about the form of the content of the composition of formation diaphragm formation film; when the content of Thermocurable component of polymer (AB) is determined as benchmark; when Thermocurable component of polymer (AB) is for the crosslinked acrylic polymer containing epoxy radicals, as the content of its benchmark be crosslinked before the content of the acrylic polymer containing epoxy radicals.
In addition, as the upper limit of content, relative to total amount 100 mass parts of component of polymer (A) and Thermocurable component of polymer (AB), preferably containing below Thermocurable composition (B) 135 mass parts.By making the upper content limit of Thermocurable composition (B) in this scope, there are the plate shape dimension characteristic or flexual tendency that can keep diaphragm formation film well.Particularly; when diaphragm formation film contains inorganic filler described later (C); if inorganic filler (C) content is many, then plate shape dimension characteristic and the pliability of diaphragm formation film reduce, relative to the patience bent or operability reduction.Therefore, particularly preferably the upper content limit of Thermocurable composition (B) in above-mentioned scope.
In addition; when Thermocurable composition (B) is for epoxies Thermocurable composition; in diaphragm formation film; relative to total amount 100 mass parts of component of polymer (A) and Thermocurable component of polymer (AB); preferably comprise the above epoxy compounds of 70 mass parts (B11); more preferably comprise 85 ~ 130 mass parts, preferably comprise 85 ~ 120 mass parts further.Thus, easily adjust in above-mentioned scope by the glass transition temperature after the hot curing of diaphragm formation film or after hot curing at the tensile modulus of elasticity of 23 DEG C.
In diaphragm formation film except adhesive component, also can containing following composition.
(C) inorganic filler
Diaphragm formation film, preferably containing inorganic filler (C).By adding inorganic filler (C) in diaphragm formation film, easily the tensile modulus of elasticity at 23 DEG C after the hot curing of diaphragm formation film is adjusted in above-mentioned scope.
In addition, by imposing laser labelling to diaphragm, inorganic filler (C) exposes the part of pruning at laser, presents connect subalbous color because reverberation is diffused.Thus, when diaphragm formation film contains colouring agent described later (D), the contrast differences of laser labelling part and other part can be obtained, make marking become obvious effect.
As preferred inorganic filler, the powder such as silicon dioxide, aluminium oxide, talcum powder, calcium carbonate, titanium oxide, iron oxide, carborundum, boron nitride can be listed, by the pearl of above-mentioned substance spheroidization, mono-crystlling fibre and glass fibre etc.In these materials, preferably silica-filled dose and alumina filled dose.Above-mentioned inorganic filler (C) separately or can mix two or more and use.
For more really obtaining above-mentioned effect; as the scope of the content of inorganic filler (C), relative to the ratio of all solids composition 100 mass parts of formation diaphragm formation film, be preferably 10 ~ 70 mass parts; be more preferably 40 ~ 70 mass parts, be particularly preferably 55 ~ 65 mass parts.By making the content of inorganic filler (C) in above-mentioned scope, can easilier adjust in above-mentioned scope by after hot curing at the tensile modulus of elasticity of 23 DEG C, curvature correction function can be promoted, obtain the chip with diaphragm that reliability is high.
In addition, the average grain diameter of inorganic filler (C), is preferably 0.02 ~ 5 μm, is more preferably 0.05 ~ 4.5 μm, is particularly preferably 0.1 ~ 4 μm.By making the average grain diameter of inorganic filler (C) in above-mentioned scope, detorsion function can be promoted.The average grain diameter of inorganic filler (C) is: the major axis footpath arbitrarily choosing 20 inorganic fillers (C) with determination of electron microscopy, using its arithmetic mean as the number average grain diameter calculated.
(D) colouring agent
Colouring agent (D) can be added in diaphragm formation film.By adding colouring agent, when semiconductor device group is entered machine, the infrared ray that can prevent semiconductor device from producing because of the device of surrounding etc. and the breakdown that causes.In addition, by the means of laser labelling etc. to when diaphragm marks, the mark making word, mark etc. is had to become the effect being easier to identification.Namely; on the semiconductor device being formed with diaphragm or semiconductor chip; usual with laser labelling method (carrying out the method for lettering by laser diaphragm surface of pruning) lettering Article Number etc. on the surface of the protective film; and contain colouring agent (D) by diaphragm; and fully can obtain diaphragm by the contrast differences of the laser part of pruning and the part of not pruning, and promote visibility.
As colouring agent, pigment and the dyestuff of organic or inorganic can be used.Wherein, by the aspect of electromagnetic wave or infrared ray shielding, preferred black pigment.As black pigment, carbon black, iron oxide, manganese dioxide, nigrosine, active carbon etc. can be used, but be not limited in these.By the viewpoint of the reliability of raising semiconductor device, particularly preferably carbon black.Colouring agent (D) can a kind be used alone, also capable of being combined two or more use.
The addition of colouring agent (D), forms all solids composition of diaphragm formation film relative to 100 mass parts, be preferably 0.1 ~ 35 mass parts, more preferably 0.5 ~ 25 mass parts, be particularly preferably 1 ~ 15 mass parts.
(E) coupling agent
Can will have the coupling agent (E) of the functional group that reacts with inorganic matter and the functional group with organic functional radical reaction, for promoting the coherency of diaphragm formation film to the adhesiveness of to-be-adhered object, adherence and/or diaphragm.In addition, by using coupling agent (E), solidification diaphragm formation film can not be undermined and the thermal endurance of diaphragm that obtains, and promoting its resistance to water.As such coupling agent, titante coupling agent, aluminate coupling agent, silane coupler etc. can be listed.Among this, preferred silane coupler.
As silane coupler, the silane coupler of the group preferably using the functional group had with the functional group of this organic functional radical reaction and component of polymer (A), Thermocurable composition (B) or curable polymer composition (AB) etc. to react.
As such silane coupler, γ-glycidoxypropyltrime,hoxysilane can be listed, γ-glycidoxypropyl diethoxy silane, β-(3, 4-expoxycyclohexyl) ethyl trimethoxy silane, γ-(methacryloxypropyl) trimethoxy silane, γ-aminocarbonyl propyl trimethoxy silane, N-6-(amido ethyl)-γ-aminocarbonyl propyl trimethoxy 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 dimethoxysilane, two (the silica-based propyl group of 3-triethoxy) tetrasulfide, methyltrimethoxy silane, methyl triethoxysilane, vinyltrimethoxy silane, vinyltriacetoxy silane, imidizole silane etc.These materials can a kind separately or mix two or more and use.
Silane coupler, relative to total amount 100 mass parts of component of polymer (A), curability composition (B) and curable polymer composition (AB), be generally 0.1 ~ 20 mass parts, be preferably 0.2 ~ 10 mass parts, more preferably comprise with the ratio of 0.3 ~ 5 mass parts.If the content of silane coupler is less than 0.1 mass parts, then there is the possibility that cannot obtain above-mentioned effect, if more than 20 mass parts, then have the possibility of the reason becoming degassed.
(F) universal additive
Except adding except above-mentioned substance in diaphragm formation film, also various additive can be added as required.As various additive, levelling agent, plasticizer, antistatic agent, antioxidant, ion capturing agent, gas agent for capturing, chain-transferring agent, remover etc. can be listed.
Diaphragm formation film, has initial bond and Thermocurable, by easily bonding by signature semiconductor crystal wafer or chip etc. in its uncured state.In addition, also diaphragm formation film can be heated by during signature.Then, finally can give resistance to impact very high diaphragm via hot curing, bonding strength is excellent, under harsh high-temperature high humidity, also can keep sufficient defencive function.In addition, diaphragm formation film can be monolayer constructions will, also can be multi-ply construction.
Diaphragm formation film such as obtains by using the composition (diaphragm formation composition) that is obtained by mixing with suitable proportion by above-mentioned each composition.Diaphragm formation composition in advance with solvent dilution, also can add solvent when mixing.In addition, also can when using diaphragm formation composition with solvent dilution.
As this solvent, can enumerate as ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, acetone, methylethylketone, acetonitrile, hexane, cyclohexane, toluene, heptane etc.
The thickness of diaphragm formation film is not particularly limited, and is preferably 3 ~ 300 μm, is more preferably 5 ~ 250 μm, is particularly preferably 7 ~ 200 μm.
Represent the maximum transmission rate of the wavelength 300 ~ 1200nm of luminous ray and/or infrared ray and ultraviolet radioparent yardstick in diaphragm formation film; be preferably less than 20%; be more preferably 0 ~ 15%, more preferably more than 0% and less than 10%, be particularly preferably 0.001 ~ 8%.By making the maximum transmission rate of the diaphragm formation film under wavelength 300 ~ 1200nm in above-mentioned scope; reduce the transmittance of visible wavelength region and/or infrared wavelength region; the operation that can prevent the infrared ray of semiconductor device from causing is malfunctioning, maybe can promote the effect of the visibility of lettering.The maximum transmission rate of the diaphragm formation film under wavelength 300 ~ 1200nm adjusts by above-mentioned colouring agent (D).In addition; the maximum transmission rate of diaphragm formation film is: use UV-vis spectrum detection device ((Co., Ltd.) Shimadzu Seisakusho Ltd. system), measures the diaphragm formation film (thickness 25 μm) after solidification in the highest value (maximum transmission rate) of the transmissivity of the full light transmittance of 300 ~ 1200nm.
Diaphragm formation film of the present invention is, using silicon and GaAs etc. as the semiconductor crystal wafer of material and chip as to-be-adhered object, as they diaphragm and use.
Relate to the manufacture method of diaphragm formation film of the present invention, be not particularly limited.
Such as, by diaphragm formation by film masking on engineering film.Masking is: by the composition for forming diaphragm formation film on engineering film by generally well-known method coating, dryings such as blade coating machine, gravure coater, die coater, inverse knife over roll coating machines, carry out thus.
Engineering film can directly use supporting slice described later and coverlay.In addition, also after this masking, diaphragm formation film can be carried out transfer printing by engineering film to supporting slice or coverlay.Engineering film is any one of supporting slice or coverlay, and the material of transfer printing can be supporting slice or coverlay another.
[diaphragm formation composite sheet]
Supporting slice can be formed at the one side of diaphragm formation film and obtain by diaphragm formation composite sheet in a releasable manner.It is lobate that the shape of diaphragm formation composite sheet is not limited to sheet, also can be bar-shape, also can be furled.As supporting slice, can stripping film be listed, in addition, bonding sheet described later can be used.
Diaphragm formation composite sheet is pasted on various to-be-adhered object, according to circumstances in diaphragm formation composite sheet, to-be-adhered object is imposed to the required processing such as cutting.Then, the set of diaphragm formation film is made to remain in to-be-adhered object and peel off supporting slice.That is, the operation comprising step diaphragm formation film being needed on to-be-adhered object by supporting slice is used in.
Diaphragm formation film can be made the shape identical with supporting slice.In addition, diaphragm formation composite sheet also can be shape diaphragm formation film being modulated into shape roughly the same with wafer or intactly can comprising wafer, and lamination is being formed than the prior shaping of diaphragm formation on the larger sized supporting slice of film.
As stripping film, can use such as, polyethylene film, polypropylene screen, polybutene film, polybutadiene film, polymethylpentene film, polychloroethylene film, vinyl chloride copolymer film, PETG film, poly-naphthalenedicarboxylic acid acid glycol ester film, polybutylene terephthalate (PBT) film, polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethene (methyl) acrylic copolymer film, ethene (methyl) acrylate copolymer film, polystyrene film, polycarbonate membrane, polyimide film, fluororesin film etc.In addition, their cross linking membrane can also be used.In addition, also can be their laminated film.
The surface tension being connected to the face of the diaphragm formation film of stripping film is preferably below 40mN/m, and more preferably below 37mN/m, is particularly preferably below 35mN/m.Lower limit is generally about 25mN/m.The stripping film that such surface tension is lower, can be suitable for selecting material and obtaining, and in addition, also can obtain by imposing lift-off processing to the surface coating remover of stripping film.
As the remover for lift-off processing, alcohol acids, silicone, fluorine class, unsaturated polyester (UP) class, TPO, wax class etc. can be used, particularly with the remover of alcohol acids, silicone, fluorine class, there is thermal endurance, so preferably.
In order to lift-off processing being carried out on the surface becoming the film of stripping film matrix etc. to the above-mentioned remover of use, can by remover directly with solvent-free or with solvent dilution or latex, by coatings such as gravure coater, metering rod coater, Kohler coater, running roller coating machines, by the base material of coating remover under normal temperature or under heating, or make to solidify to form peeling agent layer with electric wire.
In addition, by wet type lamination or dry lamination, heat fusing lamination, the lamination that film is carried out in lamination, coextrusion processing etc. is melt extruded, the surface tension of adjustment stripping film.Namely; the surface tension at least one surface can be in as the film in the preferable range in the face of the diaphragm formation film being connected to above-mentioned stripping film; be connected to the mode in the face of diaphragm formation film to make this face become, manufacture the laminate long-pending with other rete, as stripping film.
Diaphragm formation composite sheet imposes the required processing such as cutting to to-be-adhered object, be preferably used in base material is formed with bond layer adhesive sheet as supporting slice.In this form, diaphragm formation film, lamination is on the bond layer being located at supporting slice.As the base material of adhesive sheet, the above-mentioned film exemplified as stripping film can be listed.Bond layer can use the weak cementability layer of the bonding force of the degree with peelable protective film formation film, also can use and irradiate by energy line the energy ray-curable layer that bonding force is reduced.
Adhesive phase is formed by known various bonding agent (such as, the general bonding agent of rubber-like, acrylic compounds, silicone, urethanes, vinyl ethers etc., the irregular bonding agent of surperficial tool, energy-line solidifying type bonding agent, bonding agent etc. containing thermal expansion composition).
If this formation of formation of diaphragm formation composite sheet; then in diaphragm formation composite sheet as when working for supporting the cutting blade of to-be-adhered object at cutting step; supporting slice and diaphragm can be kept to be formed with intermembranous cementability, there is the effect suppressing the chip with diaphragm formation film to peel off from supporting slice at cutting step.Diaphragm formation composite sheet working for supporting the cutting blade of to-be-adhered object in as cutting step, cutting blade need not be pasted in addition to the wafer with diaphragm formation film at cutting step, the manufacturing step of semiconductor device can be simplified.
When diaphragm formation composite sheet is taked to be shaped formation in advance, diaphragm formation composite sheet can be formed as the following the 1st, the 2nd or the 3rd.Below, use 1st ~ 3 figure that each formation of diaphragm formation composite sheet 100 is described.
1st is formed as shown in Figure 1, and in the one side of diaphragm formation film 10, shape forms the formation of the adhesive sheet 3 of bond layer 2 on base material 1 in a releasable manner.When adopting the 1st to form, this bond layer can be formed with energy-line solidifying type bonding agent, in advance energy line irradiation is carried out to the region of lamination diaphragm formation film; lower cementability; on the other hand, also can not carry out energy line irradiation to other region, maintain high bonding force.Only have and energy line irradiation is not carried out to other region, such as, to the region in other regions corresponding to supporting slice, energy line shielding layer can be set by printing etc., carry out energy line by supporting slice side and irradiate.
2nd is formed as shown in Figure 2, on the adhesive phase 2 of diaphragm formation composite sheet 100, in not overlapping with diaphragm formation film 10 region, arranges the formation of fixture adhesive layer 4 in addition.As fixture adhesive layer, the double-sided adhesive sheet with core or the layer be made up of individual layer bonding agent can be adopted.
3rd is formed as shown in Figure 3, and between diaphragm formation film 10 and adhesive phase 2, arranging further can by the formation of the surface adhesive adjustment layer 5 of whole for the shape of the diaphragm formation film shape comprised.Surface adhesive adjustment layer can be the film of regulation, also can be surface adhesive adjustment bond layer.Preferably carry out energy line in advance to the bonding agent of energy ray-curable irradiates the layer making it solidify to surface adhesive adjustment bond layer.
Forming by diaphragm formation composite sheet being formed as the above-mentioned 1st to the 3rd, surrounding the region of diaphragm formation film, by the abundant adhesiveness of bond layer or fixture adhesive layer, diaphragm formation composite sheet can be bonded on fixture.Meanwhile, the adhesiveness on the surface of diaphragm formation film and bond layer or surface adhesive adjustment layer can be controlled, the chip being bonded to diaphragm formation film or diaphragm is easily picked up.
When diaphragm formation composite sheet is not taked to be shaped in advance and is formed; namely; as shown in Figure 4; diaphragm formation film 10 is made with supporting slice (in Fig. 4; base material 1 is formed the adhesive sheet 3 of bond layer 2) same shape time; in the peripheral part on diaphragm formation film 10 surface, fixture adhesive layer 4 can be set.As fixture adhesive layer, can use and above-mentioned identical person.
The thickness of supporting slice is generally 10 ~ 500 μm, is preferably 15 ~ 300 μm, is particularly preferably with 20 ~ 250 μm.When supporting slice is adhesive sheet base material being formed bond layer, 3 ~ 50 μm in supporting slice is the thickness of bond layer.
On the opposing face that the supporting being pasted on diaphragm formation film is unilateral, coverlay can be pasted with temporarily.Coverlay can supporting slice non-adhesive sheet time bond layer or fixture adhesive layer cover.Coverlay can use person identical with above-mentioned stripping film.
The thickness of coverlay, is generally 5 ~ 300 μm, preferably 10 ~ 200 μm, is particularly preferably about 20 ~ 150 μm.
The diaphragm formation film of such diaphragm formation composite sheet, can be used as the diaphragm of to-be-adhered object.Diaphragm formation film, is pasted on the chip semiconductor crystal wafer of the pattern of facing down or the back side of semiconductor chip, by the solidification of suitable means, has the function replacing sealing resin protection semiconductor crystal wafer or semiconductor chip.Be pasted on semiconductor die bowlder, because diaphragm has the function of reinforcement wafer, therefore the breakage etc. of wafer can be prevented.
[manufacture method of semiconductor device]
Then, about the Application way of diaphragm formation film of the present invention, said protection film formation composite sheet being used in the situation manufacturing semiconductor device is example explanation.
In the manufacture method of semiconductor device of the present invention, preferably comprise and the diaphragm formation film of said protection film formation composite sheet is pasted on semiconductor crystal wafer, obtain the step of the semiconductor chip with diaphragm.
Specifically, be formed with the back side of the semiconductor crystal wafer of circuit on surface, the diaphragm formation film of bonding protective film formation composite sheet, then, the semiconductor chip that the back side has diaphragm must be arrived.This diaphragm is preferably the diaphragm of semiconductor crystal wafer or semiconductor chip.In addition; be the manufacture method of semiconductor device of the present invention; preferably comprise following step (1) ~ (3) further; for playing the detorsion function of the wafer that diaphragm formation film has, more first carry out step (2) than step (3).In addition; as mentioned above; when making it produce effect as the cutting blade at cutting step supporting to-be-adhered object diaphragm formation composite sheet, by the viewpoint of the manufacturing step of simplification semiconductor device, preferably before step (1), carry out step (3).
Step (1): peel off diaphragm formation film or diaphragm and supporting slice;
Step (2): solidification diaphragm formation film obtains diaphragm;
Step (3): cutting semiconductor wafer and diaphragm formation film or diaphragm.
In addition, in the manufacture method of semiconductor device of the present invention, except above-mentioned steps (1) ~ (3), following step (4) can be comprised further.
Step (4): carry out laser beam marking 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 is formed, and is undertaken by the various methods comprising the in the past general method such as etching method, lift-off method.Then, by opposition face (back side) grinding of the circuit face of semiconductor crystal wafer.Grinding method is not particularly limited, and carries out grinding by using the known approaches of grinder etc.During the grinding of the back side, for protecting the circuit on surface, be pasted with the adhesive sheet being called as surface protective plate in circuit face.The circuit face side (i.e. surface protective plate side) of wafer is fixed by sucker etc. by back side grinding, will not form the rear side of circuit with grinder grinding.Thickness after the grinding of wafer is not particularly limited, and is generally about 50 ~ 500 μm.
Then as required, the crushable layer produced when removing back side grinding.Remove crushable layer to be undertaken by chemical etching or electric paste etching etc.
Then, the diaphragm formation film of said protection film formation composite sheet is pasted at the back side of semiconductor crystal wafer.Then, by step (1) ~ (3), with step (1), (2), (3) sequentially, any one order of the order of the order of step (2), (1), (3) or step (2), (3), (1) is carried out.About the details of this processing procedure, be specified in Japanese Unexamined Patent Publication 2002-280329 publication.As an example, the situation of carrying out with the order of step (1), (2), (3) is described.
First, be formed with the back side of the semiconductor crystal wafer of circuit on surface, paste the diaphragm formation film of said protection film formation composite sheet.Then, formed by diaphragm and peel off supporting slice with film, obtain the laminate of semiconductor crystal wafer and diaphragm formation film.Then, diaphragm formation film is solidified, at comprehensive formation diaphragm of wafer.Specifically, by hot curing, diaphragm formation film is solidified.Consequently, forming the diaphragm be made up of cured resin at the back side of wafer, due to compared to the situation strength enhancing independent compared with wafer, therefore the damage of thinning wafer when processing can being reduced.In addition, directly carry out being coated with and overlay film at the back side of wafer and chip compared to by the coating fluid of diaphragm, the excellent in uniformity of diaphragm thickness.
Then, the laminate of semiconductor crystal wafer and diaphragm is cut into each circuit being formed at crystal column surface.Cutting is carried out in the mode cut off together with diaphragm by wafer.Cutting through of wafer uses the conventional method of cutting blade to carry out.Consequently, that obtain a sheet on cutting blade, that there is diaphragm overleaf semiconductor chip groups.
Then, preferably laser beam marking is carried out on diaphragm.Laser beam marking is undertaken by laser labelling method, is reamed the surface of diaphragm, diaphragm marks Article Number etc. by the irradiation of laser.
Finally, the semiconductor chip (chip with the diaphragm) back side with diaphragm picks up with the universal means of chuck etc., obtains with diaphragm chip.Then, the chip with diaphragm is loaded on set base station with the pattern structure that faces down, can semiconductor device be manufactured thus.In addition, the semiconductor chip by the back side being had diaphragm is bonded on other the component such as crystal grain pad portion or other semiconductor chips (in chip carrying portion), manufactures semiconductor device.According to the present invention, the back side at chip that can be easy forms the high diaphragm of thickness evenness, after cutting step or encapsulation, be full of cracks is less likely to occur.
In addition; after the diaphragm formation film of said protection film formation composite sheet is pasted at the back side of semiconductor crystal wafer; when carrying out step (3) before step (1); (situation of carrying out with the order of step (2), (3), (1)); diaphragm formation composite sheet, can be used as cutting blade and plays a role.That is, can be used for as during cutting step for the sheet of bearing semiconductor wafer.This kind of situation; semiconductor crystal wafer is pasted via diaphragm formation film in the inner peripheral portion of diaphragm formation composite sheet; engaged with other fixtures of ring frame etc. by the peripheral part of diaphragm formation composite sheet; the diaphragm formation composite sheet being pasted on semiconductor crystal wafer is fixed on device, cuts.
Use diaphragm formation film of the present invention or use the diaphragm formation composite sheet of this film, except using method as above, also can be used for the protection of semiconducting compound, glass, pottery, metal etc.
Embodiment
Below, by embodiment, the present invention will be described, but the present invention is not limited to these embodiments.In addition, in following embodiment or comparative example, following measure and after glass transition temperature >, < hot curing after assessment < hot curing at tensile modulus of elasticity >, < detorsion Performance Evaluation >, < Reliability assessment > of 23 DEG C and < wafer bow assessment >.
Glass transition temperature > after < hot curing
The diaphragm formation film of lamination 4 thickness 45 μm, carries out hot curing (130 DEG C 2 hours) with air atmosphere in baking oven, makes the strip test film cutting into width 4.5mm, length 20.0mm, thickness 0.18mm.
Use determination of viscoelasticity device (TA instruments company DMA Q800), with stretch mode, with frequency 11Hz, programming rate 3 DEG C/minute, with the tan δ of 0 ~ 300 DEG C of determination test sheet (ratio of loss elastic modulus and storage elastic modulus) under air atmosphere.In this temperature range, read the temperature that tan δ shows maximum, it can be used as the glass transition temperature (Tg) after the hot curing of diaphragm formation film.
At the tensile modulus of elasticity > of 23 DEG C after < hot curing
Read in determination data that the glass transition temperature > after above-mentioned < hot curing records at the storage elastic modulus of 23 DEG C, as diaphragm formation film after hot curing at the tensile modulus of elasticity of 23 DEG C.
< detorsion Performance Evaluation >
The diaphragm formation film of thickness 45 μm is pasted on the test film (chi cun ︰ 100mm × 100mm) of the Copper Foil of thickness 30 μm, in baking oven, under air atmosphere, carries out hot curing (130 DEG C 2 hours).
Then, by the contraction of hot curing with diaphragm formation film, with the shape of the face of bonding protective film formation film for the curling Copper Foil in inner side, get 2 points that the distances connecting these points become maximum, measure this distance.Bending of the less expression Copper Foil of this distance is comparatively large, can judge that the stress that the thermal contraction of diaphragm formation film causes is comparatively large, and detorsion ability is higher.
< Reliability assessment >
1. with the manufacture of the chip of diaphragm
Use and paste mould machine (Lintec Inc.; Adwill RAD-3600F/12); the diaphragm formation film limit of diaphragm formation composite sheet is heated to 70 DEG C; while be pasted on Silicon Wafer (the diameter 200mm of No. 2000 grindings; thick 350 μm) abradant surface on, then peel off supporting slice.Then, within 2 hours, make diaphragm formation film solidify with 130 DEG C of heating, obtain the laminate of Silicon Wafer and diaphragm.
The diaphragm side of above-mentioned gained laminate is pasted on cutting film (Lintec Inc.; Adwill D-686H) on; cut into the size of 3mm × 3mm with cutter sweep (DISCO Inc. DFD651), obtain the chip with diaphragm of Reliability assessment.
2. Reliability assessment
By the chip of gained with diaphragm; with 85 DEG C, place under the condition of relative humidity 85% and make its moisture absorption in 168 hours after, carry out the IR tempering (returning fiery stove ︰ phase mould science and engineering WL-15-20DNX type) of 3 maximum temperatures 260 DEG C, 1 minute heating time.In addition, the chip that this has diaphragm is arranged in thermal shock device (ESPEC Inc. TSE-11A), after repeating to keep 10 minutes at-40 DEG C 1000 times, keeps the process of 10 minutes at 125 DEG C.
Then; for the chip with diaphragm taken out from thermal shock device; observed by scan-type ultrasonic waves failure detector (Jian Ji FINTEC Inc. of Hitachi Hye-Focus) and section, observe the stripping at junction surface with or without semiconductor chip and diaphragm or the be full of cracks of diaphragm.
Carrying out above-mentioned assessment to 25 chips with diaphragm, there is the number (umber of defectives) of the stripping at junction surface or the moire of diaphragm in counting.Umber of defectives is fewer, represents that the reliability of diaphragm formation film is higher.
< wafer bow assessment >
Prepare the thickness with 200 μm, produce 8 cun of wafers with circuit (with reference to Fig. 5) of concave shape bending (bending Liang ︰ 10mm) in circuit face side (face side).
Then, at the back side bonding protective film formation film of wafer, with 130 DEG C of hot curings 2 hours.
Then, the amount of bow of gained wafer be evaluated as " well " when below 2mm, the amount of bow of wafer is evaluated as " bad " more than during 2mm.As long as the amount of bow of wafer is at below 2mm, then can be carried by general wafer chip mounter.
[diaphragm formation composition]
The each composition forming diaphragm formation composition is expressed as follows.
(A1-1) polymer becomes point ︰ by the acrylic polymer (heavy average molecular weight ︰ 900,000, vitrifying turns alternating temperature degree ︰-28 DEG C) of 55 mass parts n-butyl acrylates, 15 mass parts methyl acrylates, 20 mass parts glycidyl methacrylate and 10 mass parts acrylic acid 2-hydroxy methacrylate combined polymerizations
(A1-2) polymer becomes point ︰ by the acrylic polymer (heavy average molecular weight ︰ 900,000, vitrifying turns alternating temperature degree ︰-31 DEG C) of 55 mass parts n-butyl acrylates, 35 mass parts methyl acrylates and 10 mass parts acrylic acid 2-hydroxy methacrylate combined polymerizations
(B11-1) bisphenol A type epoxy resin (Mitsubishi Chemical jER828, epoxide equivalent 184 ~ 194g/eq)
(B11-2) bisphenol A type epoxy resin (Mitsubishi Chemical jER1055, epoxide equivalent 800 ~ 900g/eq)
(B11-3) dicyclopentadiene-type epoxy resin (large Japanese ink chemical industry (stock) system, EPICRONE HP-7200HH, epoxide equivalent 255 ~ 260g/eq)
(B11-4) orthoresol phenol aldehyde type epoxy resin (Japanese chemical drug EOCN-104S, epoxide equivalent 213 ~ 223g/eq)
(B12) thermal activities potentiality epoxy curing agent (dicyandiamide (ADEKA ADEKAHARDNER EH-3636AS, active hydrogen amount 21g/eq))
(B13) Cu Jin Ji ︰ 2-phenyl-4,5-hydroxymethyl-imidazole (four countries change into industrial group Cuazole 2PHZ) is solidified
(C-1) silica-filled dose (ADMATEX SC2050MA, average grain diameter 0.5 μm)
(C-2) silica-filled dose (average grain diameter 3 μm)
(C-3) silica-filled dose (TATSUMORI SV-10, average grain diameter 8 μm)
(D) Se Ji ︰ carbon black (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.Represent at the addition of each composition of table 1 mass parts that solid constituent converts, 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; being diluted to solid component concentration by methylethylketone is 61 quality %; in the mode that thickness after drying is 45 μm; coating is dry (120 DEG C, dry condition ︰ baking oven also; 2 minutes) in supporting slice (Lintec Inc. SP-PET3811; thickness 38 μm) lift-off processing face on, supporting slice is formed diaphragm formation film, obtains diaphragm formation composite sheet.Then, by diaphragm formation film and stripping film, (fitting in the lift-off processing face of PETG film (Lintec Inc. SP-PET381031, thickness 38 μm), obtains the diaphragm formation composite sheet posting stripping film.Each assessment result is shown in table 2.
The explanation of Reference numeral
1 is base material; 2 is adhesive phase; 3 is bonding sheet (supporting slice); 4 is fixture adhesive layer; 5 is surface adhesive adjustment layer; 10 is diaphragm formation film; 100 is diaphragm formation composite sheet.

Claims (7)

1. a diaphragm formation film, it has Thermocurable,
Glass transition temperature after its hot curing is 150 ~ 300 DEG C,
Be 0.5 ~ 10GPa at the tensile modulus of elasticity of 23 DEG C after its hot curing.
2. diaphragm formation film as claimed in claim 1, this film comprises the Thermocurable composition containing epoxy compounds and amine curing agent.
3. diaphragm formation film as claimed in claim 2; its also containing in component of polymer and Thermocurable component of polymer arbitrarily separately one or both; relative to component of polymer and the Thermocurable component of polymer of total amount 100 mass parts, comprise the Thermocurable composition of below 135 mass parts.
4. the diaphragm formation film as described in any one of claims 1 to 3, wherein diaphragm formation film comprises inorganic filler,
Form all solids composition of diaphragm formation film relative to 100 mass parts, the content of inorganic filler is 10 ~ 70 mass parts.
5. diaphragm formation film as claimed in claim 4, wherein the average grain diameter of inorganic filler is 0.02 ~ 5 μm.
6. the diaphragm formation film as described in any one of Claims 1 to 5, wherein diaphragm formation film comprises Thermocurable component of polymer,
Thermocurable component of polymer is the acrylic polymer comprising the monomer containing epoxy radicals as the monomer formed.
7. a diaphragm formation composite sheet, it on a face of the diaphragm formation film described in any one of claim 1 ~ 6, strippingly forms supporting slice form.
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