CN104137229B - Protective film for semiconductor wafer, and method for manufacturing semiconductor chip - Google Patents

Protective film for semiconductor wafer, and method for manufacturing semiconductor chip Download PDF

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Publication number
CN104137229B
CN104137229B CN201380009159.3A CN201380009159A CN104137229B CN 104137229 B CN104137229 B CN 104137229B CN 201380009159 A CN201380009159 A CN 201380009159A CN 104137229 B CN104137229 B CN 104137229B
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resin
mass parts
aforementioned
film
epoxy resin
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CN104137229A (en
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市六信広
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2433/00—Presence of (meth)acrylic polymer
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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    • C09J2463/00—Presence of epoxy resin
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding

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  • Adhesives Or Adhesive Processes (AREA)
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Abstract

The present invention provides a protective film for semiconductor wafers which is provided with a base film and a protective membrane formed on the upper side of the base film, wherein the protective film for a semiconductor wafer is characterized in that the protective membrane contains components (A)-(E) below. (A) 100 parts by mass of at least one type of resin selected from the group consisting of phenoxy resins, polyimide resins, and (meth)acrylic resins; (B) 5-200 parts by mass of an epoxy resin; (C) 100-400 parts by mass of a filler other than a fibrous inorganic filler; (D) a catalytic quantity of an epoxy resin curing catalyst; and (E) 25-5000 parts by mass of a fibrous inorganic filler. A semiconductor wafer protective film having excellent cutting properties, and a highly productive method for manufacturing semiconductor chips, are provided thereby.

Description

Semiconductor wafer protective film and the manufacture method of semiconductor chip
Technical field
The present invention relates to the manufacture method of a kind of semiconductor wafer protective film and semiconductor chip.
Background technology
Structure in order to reduce semiconductor chip (chip) fills area or carries out low back, is connected using flip-chip at present Method.In this connection method, cut the chip (wafer) that circuit and connection projection are formed with surface, thus obtaining quasiconductor Chip, by the surface of this chip towards after substrate connection, carries out resin seal etc., to protect semiconductor chip.
Known have a kind of chip protecting film formation sheet material, and it prevents terminating in above-mentioned cutting action, due to swivel knife Vibration etc. and cause chip damage (hereinafter referred to as " fragmentation "), and, replace resin seal, play a role as diaphragm seal (patent documentation 1, patent documentation 2).
Again it is known to prevent the technology (patent documentation of the torsion of ic card using the relatively low supporting material of linear expansion coefficient 3) and using supporting material prevent the technology (patent documentation 4) of the rupture of semiconductor chip in ic card.
Said chip protecting film is to be pasted on the back side of chip to use.Therefore, in cutting action, finally rotated The component of knife cut-out, is this protecting film.But, there is problems in that because the resinous principle included in this protecting film has Extensibility, therefore, it is difficult to cutting, also, causing blocking in swivel knife, makes swivel knife vibrate, thus damage wafers.
Using the relatively low supporting material of linear expansion coefficient prevent ic card reverse in the case of, when to ic card apply torsion or During bending stress, during overall no supporting material, no the part of the semiconductor chip of low elastic modulus can relax stress, but entirety adds In the case of entering supporting material, relatively thin semiconductor chip reversed or bending stress and rupture.
In the method for stick carbon fiber material on the semiconductor chip in ic card, because of plural number time curing process or sticker Spilling, the position skew of strengthening course or tilt and sticker caused reinforcement strength in uneven thickness inequality, and lead to Produce quality inequality or productivity ratio significantly reduces.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-280329 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2004-260190 publication
Patent documentation 3: Japanese Unexamined Patent Publication 10-24686 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2000-268152 publication
Content of the invention
Invent problem to be solved
The present invention completes in view of the foregoing, its object is to provide one kind practiced by dicer (dicer) The cut-out semiconductor wafer protective film of excellent and the higher semiconductor chip of productivity ratio manufacture method.
The method solving problem
For solve above-mentioned problem, according to the present invention, a kind of semiconductor wafer protective film is provided it is characterised in that its The protecting film possessing base film with the upside being formed at this base film, and, aforementioned protecting film contains following (a)～(e) Composition:
A () is selected from the group that phenoxy resin, polyimide resin and (methyl) acrylic resin are formed extremely Few one kind: 100 mass parts；
(b) epoxy resin: 5～200 mass parts；
Packing material beyond (c) threadiness inorganic filling material: 100～400 mass parts；
(d) Epoxy cure catalysts: catalytic amount；And
(e) threadiness inorganic filling material: 25～5000 mass parts.
The protecting film of this kind of semiconductor wafer protective film, by having fibrous inorganic filling material, can be in cutting Semiconductor wafer and obtain and during semiconductor chip, prevent fragmentation.Also, the anti-folding of the protecting film of this semiconductor wafer protective film is strong Degree is higher, can prevent terminating in the rupture of the chip causing when using on the market due to bending stress.
Also, being preferably: aforementioned protecting film is made up of with adhesion coating strengthening course,
And, aforementioned adhesion coating contains following (a)～(d) composition and forms, aforementioned strengthening course contain following (e) composition and Become:
A () is selected from the group that phenoxy resin, polyimide resin and (methyl) acrylic resin are formed extremely Few one kind: 100 mass parts；
(b) epoxy resin: 5～200 mass parts；
Packing material beyond (c) threadiness inorganic filling material: 100～400 mass parts；
(d) Epoxy cure catalysts: catalytic amount；And
(e) threadiness inorganic filling material: 1000～5000 mass parts.
If consequently, it is possible to protecting film is to be made up of with adhesion coating two-layer strengthening course, semiconductor core can be prevented further The fragmentation of piece simultaneously lifts rupture strength, thus realizing high production rate.
Also, being preferably: the phenoxy resin in aforementioned (a) composition is Bisphenol A Type phenoxy resin or Bisphenol-f phenoxy group Resin, the epoxy resin of aforementioned (b) composition is liquid bisphenol a type epoxy resin or liquid bisphenol f type epoxy resin.
If this kind of (a) composition and the combination of (b) composition, then semiconductor wafer protective film, it is real by dicer institute The cut-out characteristic of row is more excellent.
Also, the present invention provides a kind of manufacture method of semiconductor chip, being cutting semiconductor chip to manufacture semiconductor core The method of piece is it is characterised in that aforesaid semiconductor chip protective film is pasted on aforesaid semiconductor chip for it and overall Cut, thus to manufacture the back side and there is the semiconductor chip with the protecting film of former semiconductor chip same size.
If the manufacture method of this kind of semiconductor chip, then fragmentation when cutting off is suppressed, and then, due to quasiconductor The rupture strength of the protecting film having on chip back is higher, therefore, the high production rate of achievable semiconductor chip.
The effect of invention
In the semiconductor chip protection film of the present invention, fibrous inorganic filling material is had by protecting film, can be easy to profit With dicer cut-out, prevent the fragmentation of semiconductor chip and lift rupture strength, thus realizing high production rate.
Brief description
Fig. 1 is the profile of an example of the semiconductor wafer protective film representing the present invention.
Fig. 2 is the profile of another example of semiconductor wafer protective film representing the present invention.
Fig. 3 is the profile of another example of semiconductor wafer protective film representing the present invention.
Specific embodiment
The present inventor, in order to reach above-mentioned purpose, is studied repeatedly, if it was found that following semiconductor wafer With protective film, then it cuts off excellent, and this semiconductor wafer protective film is characterised by, it possess base film with It is formed at the protecting film of the upside of this base film, and, aforementioned protecting film contains following (a)～(e) composition:
A () is selected from the group that phenoxy resin, polyimide resin and (methyl) acrylic resin are formed extremely Few one kind: 100 mass parts；
(b) epoxy resin: 5～200 mass parts；
Packing material beyond (c) threadiness inorganic filling material: 100～400 mass parts；
(d) Epoxy cure catalysts: catalytic amount；And
(e) threadiness inorganic filling material: 25～5000 mass parts.
[(a) is selected from the group that phenoxy resin, polyimide resin and (methyl) acrylic resin are formed At least one]
Phenoxy resin, is by epoxychloropropane and the derivative resin such as bis-phenol a or bis-phenol f.It is preferably, with gel The weight average molecular weight of the polystyrene conversion that permeable formation analyzer (gpc) measures is 10,000～200,000, more preferably 20,000 ～100,000, most preferably 30,000～80,000.Weight average molecular weight is more than above-mentioned lower limit, easily forms film, the opposing party Face, is below aforementioned higher limit, due to concavo-convex along the substrate surface with fine circuit pattern, can obtain sufficiently soft Softness, thus preferably.
As the example of phenoxy resin, can enumerate: with trade name pkhc, pkhh, pkhj commercially available (be all Japanese bar Learn industrial group (tomoe engineering co., ltd.) to manufacture)；Bis-phenol a and bis-phenol f mixed type with trade name What epikote4250, epikote4275, epikote1255hx30 were commercially available (is all Japanese chemical medicine company limited (nippon Kayaku co .ltd.) manufacture)；Epikote5580bpx40 using brominated epoxy resin (is all Japanese chemical medicine company limited Manufacture)；Bisphenol A Type with commercially available (being all Japanese Dongdu and be melted into limited public affairs of trade name yp-50, yp-50s, yp-55, yp-70 Department (tohto kasei co., ltd.) manufactures)；And with trade name jer e1256, e4250, e4275, yx6954bh30, Yl7290bh30 commercially available (being all Japanese epoxy resin company limited (japan epoxy resins co., ltd.) to manufacture) Deng.From have foresaid weight average molecular weight in terms of for, it is preferable to use jer e1256.The end of this phenoxy group based polymer There are epoxy radicals, it is reacted with aftermentioned (b) composition.
Polyimide resin can be used as using comprising following repetitives persons.
(in formula, x comprises aromatic ring or the quadrivalent organic radical of aliphatic ring, and y is divalent organic base, q be 1～300 whole Number.)
It is preferably, with the weight average molecular weight of the polystyrene conversion of gpc mensure for 10,000～200,000, more preferably 20,000～100,000, most preferably 30,000～80,000.Weight average molecular weight is more than aforementioned minimum value, then easily formed Film, on the other hand, is below aforementioned higher limit, due to concavo-convex along the substrate surface with fine circuit pattern, can obtain Obtain sufficient pliability, thus preferably.
Aforementioned polyimide resin, can will have the polyamic acid resin of following repetitives by using usual way Dehydration, cyclization and obtain.
(in formula, x, y and q are identical with aforementioned definitions.)
Polyamic acid resin represented by above formula can be by using usual way by following structural formula (3)
(wherein, x is as hereinbefore.)
Represented tetracarboxylic dianhydride and by following structural formula (4)
h2n-y-nh2(4)
(wherein, y is as hereinbefore.)
Represented diamidogen, is reacted in organic solvent with roughly equal mole, thus obtaining.
Wherein, as the example of the tetracarboxylic dianhydride represented by previously described formula (3), following substances can be enumerated, also can be by these It is applied in combination.
In diamidogen represented by previously described formula (4), preferably 1～80 mole %, and then preferably 1～60 mole of % by Diamino radical siloxane (diaminosiloxane) compound represented by following structural formula (5), from dissolving in organic solvent From the point of view of the aspect of property, the cohesiveness to base film, low elasticity and flexibility, ideal.
(in formula, r1The carbon number being separate is 3～9 divalent organic base, r2And r3It is separate unsubstituted Or the monovalent hydrocarbon that the carbon number replacing is 1～8, m is 1～200 integer.)
The r of the divalent organic base being 3～9 as aforementioned carbon number1, can enumerate for example ,-(ch2)3-、-(ch2)4-、- ch2ch(ch3)-、-(ch2)6- and-(ch2)8- wait and stretch alkyl；In following formula
What any one was represented stretch aryl, stretch alkyl/stretch aryl；-(ch2)3- o- and-(ch2)4The oxygen such as-o- stretch alkyl； Following formula
Any one of represented by oxygen stretch aryl；And by following formula
Represented oxygen stretches the bivalent hydrocarbon radical of the comprised ehter bond of alkyl/stretch aryl etc..
As r2Or r3, can enumerate for example: methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, hexyl, ring The alkyl such as hexyl, 2- ethylhexyl, octyl group；The alkene such as pi-allyl, acrylic, isopropenyl, cyclobutenyl, isobutenyl, hexenyl Base；The aryl such as phenyl, tolyl, xylyl；The aralkyl such as benzyl, phenethyl；And with the carbon atom bonding of these alkyl The part or all of base being replaced by halogen atoms such as fluorine, bromine, chlorine etc. of hydrogen atom, for example, chloromethyl, bromoethyl and 3,3, Halogen-substituted alkyls such as 3- trifluoro propyl etc.；Wherein, preferably methyl and phenyl.Also two or more diamino radical siloxanes can be used The combination of compound.
As represented by previously described formula (4) two beyond the diaminourea silicone compounds represented by previously described formula (5) Amine, can enumerate for example, p-phenylenediamine, m-diaminobenzene., 4,4 '-MDA, 4,4 '-diaminodiphenyl ether, 2,2 '-bis- (4- aminophenyl) propane, 4,4 '-diaminourea hexichol maple, 4,4 '-diaminodiphenyl sulfide, 1,4- are double (3- amino-benzene oxygen) Double (4- amino-benzene oxygen) benzene of benzene, 1,4-, double (p-aminophenyl sulfonyl) benzene of 1,4-, 1,4- are double (m-aminophenyl base sulfonyl) Double (p-aminophenyl thioether) benzene of benzene, 1,4-, double (the m-aminophenyl base thioether) benzene of 1,4-, the double [4- (4- amino-benzene oxygen) of 2,2- Phenyl] propane, double [3- methyl -4- (4- amino-benzene oxygen) phenyl] propane of 2,2-, double [the chloro- 4- of 3- (the 4- aminobenzene oxygen of 2,2- Base) phenyl] propane, double [4- (4- amino-benzene oxygen) phenyl] ethane of 1,1-, the double [3- methyl -4- (4- amino-benzene oxygen) of 1,1- Phenyl] ethane, double [the chloro- 4- of 3- (4- amino-benzene oxygen) phenyl] ethane of 1,1-, double [3,5- dimethyl -4- (the 4- aminobenzene of 1,1- Epoxide) phenyl] ethane, double [4- (4- amino-benzene oxygen) phenyl] methane, double [3- methyl -4- (4- amino-benzene oxygen) phenyl] first Alkane, double [the chloro- 4- of 3- (4- amino-benzene oxygen) phenyl] methane, double [3,5- dimethyl -4- (4- amino-benzene oxygen) phenyl] methane, Double [4- (4- amino-benzene oxygen) phenyl] maples and double [4- (4- amino-benzene oxygen) phenyl] perfluoropropane of 2,2- etc. contain aromatic series Diamidogen of ring etc., preferably p-phenylenediamine, m-diaminobenzene., 4,4 '-MDA, 4,4 '-diaminodiphenyl ether, Isosorbide-5-Nitrae- Double [4- (4- amino-benzene oxygen) phenyl] propane of double (3- amino-benzene oxygen) benzene, Isosorbide-5-Nitrae-bis- (4- amino-benzene oxygen) benzene, 2,2- and Double [3- methyl -4- (4- amino-benzene oxygen) phenyl] propane of 2,2- etc..
From the point of view of in terms of adhesive, polyimide resin preferably has phenolic hydroxyl group.Can be by using having phenol Hydroxyl person is used as diamine compound, thus possessing this phenolic hydroxyl group, as this kind of diamidogen, can enumerate for example, following structures Diamidogen.
In formula, a is following arbitrary group,
In formula, b is following arbitrary group,
(in formula, r4Separate for the halogen atom such as hydrogen atom or fluorine, bromine and iodine, or alkyl, thiazolinyl, alkynyl, trifluoro Methyl and phenyl etc. unsubstituted or replace carbon number be 1～8 monovalent hydrocarbon, be attached to the substituent group of each aromatic rings Also can be different, n is 0～5 integer.A, b can be respectively individually a kind of, alternatively two or more combination.R is hydrogen atom, halogen Plain atom or monovalent hydrocarbon that is unsubstituted or replacing).
As aforementioned r4Unsubstituted or replace carbon number be 1～8 monovalent hydrocarbon, can enumerate for example: with front State r2And r3The identical person of illustrated person；And the alkynyl such as acetenyl, propinyl, butynyl and hexin base etc..
Also, as the diamidogen with other phenolic hydroxyl group, can be listed below.
(in above formula, r ' is the halogen atoms such as hydrogen atom, fluorine, bromine and iodine, or alkyl that carbon number is 1～8, thiazolinyl, alkynyl, Trifluoromethyl and phenyl etc. be unsubstituted or the monovalent hydrocarbon of halogen substiuted, and the substituent group being attached to each aromatic rings also can be different, X is singly-bound, methylene or acrylic.N is identical with defined above.)
Have in the diamine compound of aforementioned phenolic hydroxyl group, be particularly preferably the diamine compound represented by following formula (6).
(in formula, r4It is identical with defined above.)
As the allotment amount of the diamine compound with aforementioned phenolic hydroxyl group, preferably the 5～60 of diamine compound entirety Quality %, particularly preferably for 10～40 mass %.If the use of this allotment amount being the polyimides silicones in the range of this, adhesion strength Higher, and the compositionss forming soft adhesion coating can be obtained.
Furthermore, it is possible to use the monoamine with phenolic hydroxyl group, to import phenolic hydroxyl group, as its example, can be enumerated and have The monoamine of following structures.
(in formula, r4As hereinbefore, the substituent group being attached to each aromatic rings can be difference.D can be used alone one kind, Can and with two or more.Also, p is 1～3 integer.)
Using have phenolic hydroxyl group monoamine when, as its allotment amount, overall with respect to diamine compound, preferably 1 ～10 moles of %.
By being dissolved in solvent aforementioned each initiation material under inert environments, and in usual less than 80 DEG C, preferably It is made to react at 0～40 DEG C, can synthesizing polyamides acid resin.By the polyamic acid resin being obtained is warming up to generally 100～200 DEG C, preferably 150～200 DEG C, make the amide moieties dehydration condensation of polyamic acid resin, the polyamides of target can be synthesized Imide resin.
If the polyamic acid being obtained is inertia, as aforementioned solvents, alternatively cannot be completely dissolved aforementioned initial former The solvent of material.Can enumerate for example, oxolane, Isosorbide-5-Nitrae-dioxanes, Ketocyclopentane, cyclohexanone, gamma-butyrolacton, n- methylpyrrole pyridine Ketone, n, n- dimethyl acetylamide and n, n- dimethylformamide and dimethyl sulfoxide, preferably aprotic polar solvent, special excellent Elect n- methylpyrrole pyridine ketone, cyclohexanone and gamma-butyrolacton as.These solvents can be used alone one kind, also can be combined two or more Use.
Ideal is using azeotropy dehydrants such as toluene and dimethylbenzene, easily to carry out aforementioned dehydration condensation.Also, also may be used Carry out dehydration condensation using acetic anhydride/pyridine mixed solution under low temperature.
Furthermore, for the molecular weight of adjustment polyamic acid and polyimide resin, maleic anhydride, acid phthalic anhydride etc. two also can be added Carboxylic acid anhydrides and/or aniline, n-butylamine, and the monoamine with phenolic hydroxyl group of aforementioned list.Wherein, every 100 mass parts tetracarboxylic acids Acid dianhydride, generally adds 0～2 mass parts dicarboxylic anhydride, every 100 mass parts diamidogen, generally adds 0～2 mass parts monoamine.
As (methyl) acrylic resin, can enumerate for example, (methyl) acrylate monomer and derive from (methyl) propylene (methyl) acrylate copolymer that the Component units of acid derivative are formed.Wherein, as (methyl) acrylate monomer, excellent Elect (methyl) alkyl acrylate that the carbon number using alkyl is 1～18, for example, (methyl) acrylic acid methyl ester., (methyl) third as Olefin(e) acid ethyl ester, (methyl) propyl acrylate and (methyl) butyl acrylate etc..Also, as (methyl) acrylic acid derivative, can arrange Illustrate such as: (methyl) acrylic acid, (methyl) glycidyl acrylate and (methyl) hydroxyethyl acrylate etc..
By making the copolymerization such as glycidyl methacrylate, and glycidyl is imported (methyl) acrylic resin, The intermiscibility with the epoxy resin as aftermentioned thermohardening type adhesion composition can be lifted, also, the glass transition temperature after solidification (tg) increase, and thermostability is also lifted.Also, hydroxyl is imported acrylic based polymer by using hydroxyl ethyl acrylate etc., It is readily able to control the sealing to chip or adhesion physical property.
The weight average molecular weight of (methyl) acrylic resin is preferably 100, more than 000, more preferably 150,000～1,000, 000.Also, the glass transition temperature of (methyl) acrylic resin is preferably less than 20 DEG C, more preferably -70～0 DEG C about, and in Under room temperature (23 DEG C), there is cohesiveness.
[(b) epoxy resin]
Epoxy resin is the resins different from aforementioned (a) composition, and, preferably epoxide equivalent is 50～5000g/eq, More preferably 100～500g/eq.
As this kind of epoxy resin, can enumerate: as Bisphenol-a Epoxy Resin, Bisphenol-f epoxy resin, (especially, liquid is double Phenol a type epoxy resin or liquid bisphenol f type epoxy resin)；The phenols glycidyl ether such as resorcinol, phenolic aldehyde, cresol-novolak；Fourth two The alcohols glycidyl ether such as alcohol, Polyethylene Glycol, polypropylene glycol；The glycidyl ether of the carboxylic acids such as phthalandione, isophathalic acid, tetrahydrochysene phthalandione； Aniline chlorinated isocyanurates (aniline isocyanurate) etc. is replaced and the reactive hydrogen of nitrogen atom bonding with glycidyl (+)-2,3-Epoxy-1-propanol type or alkyl glycidyl type epoxy resin；Vinyl cyclohexene dioxide (vinylcyclohexene Diepoxide), 3,4- epoxycyclohexyl-methyl -3,4- dicyclohexyl formic acid esters, 2- (3,4- epoxy radicals) cyclohexyl -5,5- spiral shell (3,4- epoxy radicals) hexamethylene-dioxanes etc., by for example intramolecular carbon-to-carbon double bond being aoxidized to import epoxy radicals, I.e. alicyclic ring type epoxide.In addition, can use and there is biphenyl backbone, two cyclohexadiene (dicyclohexadiene) bone Frame and the epoxy resin of naphthalene skeleton.
In these, it is preferable to use Bisphenol-a Epoxy Resin, Bisphenol-f epoxy resin (especially, liquid bisphenol a type epoxy Resin or liquid bisphenol f type epoxy resin), o-cresol formaldehyde type epoxy resin and phenol novolak type epoxy.Also this can be combined The two or more uses of a little epoxy resin.
With respect to (a) composition 100 mass parts, allocate 5～200 mass parts, be preferably 10～200 mass parts, be more preferably The epoxy resin of 50～150 mass parts (b).If to allocate (a) composition and (b) composition with this kind of ratio, show before solidification The viscosity of appropriateness, thus the sticking operation to chip can stably be carried out, also, can obtain the protecting film of excellent strength after solidification.
A () composition is combined with (b) composition, preferably, the phenoxy resin in (a) composition is Bisphenol A Type phenoxy group tree Fat or Bisphenol-f phenoxy resin, the epoxy resin of aforementioned (b) composition is liquid bisphenol a type epoxy resin or liquid bisphenol f type Epoxy resin.
[packing material beyond (c) threadiness inorganic filling material]
As the packing material of (c) composition, can be using inorganic filling material (the non-fibre beyond fibrous inorganic filling material Dimension shape inorganic filling material), for example, the electroconductive particle such as silicon dioxide, aluminium oxide, titanium oxide, white carbon black and silver particles and silicon Toner, for example, has the cross-linking type spherical dimethyl polysiloxane micropowder of the crosslinked structure of dimethyl polysiloxane (Japanese Unexamined Patent Publication 3-93834 publication), cross-linking type spherical poly methyl silsesquioxane micropowder (Japanese Unexamined Patent Publication 3-47848 Number publication), micropowder (Japan of being coated to poly methyl silsesquioxane particle of cross-linking type spherical polysiloxane rubber surface Unexamined Patent 7-196815 publication, Japanese Unexamined Patent Publication 9-20631 publication).
With respect to (a) composition 100 mass parts, the allotment amount of this packing material is 100～400 mass parts, preferably 150～ 350 mass parts.This allotment amount be aforementioned minimum value more than when, can fully reach packing material the low water absorbable of allotment purpose, Low linear expansion etc..When cannot reach low water absorbable, semiconductor subassembly is unqualified it is impossible to reach in moisture absorption reliability test During low linear expansion coefficient, when solidification, linear expansion coefficient mismatches the complex of semiconductor wafer protective film and silicon wafer, And produce larger warpage, thus cannot be carried out follow-up cutting.On the other hand, when being below aforementioned higher limit, chip can be prevented There is larger warpage with the complex of semiconductor wafer protective film, and there is not the viscosity mistake of protective layer formation compositionss It is deteriorated higher than mobility when smearing on base film and protecting film is difficult to be pasted on the probability of silicon wafer under low temperature.Fill out The containing ratio filling material is preferably 30～80 mass % of protecting film.
Using dissolving silicon dioxide, crystalline silica is used as silicon dioxide.The mean diameter of silicon dioxide is preferably 0.1～10 μm, more preferably 0.5～7 μm.If the mean diameter of silicon dioxide is in such range, the protecting film being coated with is (viscous Layer) surface, good flatness can be obtained.Also, in recent years, as the thickness of adhesion coating, require 15～50 μm more, if two The mean diameter of silicon oxide is in aforementioned range, even if then there is the particle of 2 coagulations, also readily satisfies this requirement.
Surface can utilize foregoing publication (Japanese Unexamined Patent Publication with the resin-coated silicone rubber micropartical of organic poly sesquisiloxane 7-196815 publication, Japanese Unexamined Patent Publication 9-20631 publication) described in method make, or can be used as silicon composite powder Last kmp600 series (Japanese Shin-Estu Chemical Co., Ltd (shin-etsu chemical co., ltd.) manufactures) and Commercially available material.From the point of view of in terms of the particle diameter, it is preferable to use kmp600.
C () packing material, it is preferable to use inorganic filling material, more preferably using silicon dioxide, most preferably uses The silicon dioxide being manufactured using detonation method.This silicon dioxide is easily wetted because of resinous principle, carries out surface according to universal method Process.As surface conditioning agent, from the point of view of its versatility and cost advantages etc., preferably silane system (silane coupling agent).As Silane coupling agent, this alkoxy silane is preferably with glycidyl oxy methyl trimethoxy silane, glycidyl oxy methyl three Ethoxysilane, α-glycidoxyethyl trimethoxy silane, α-glycidoxyethyl triethoxysilane, beta epoxide third Epoxide ethyl trimethoxy silane, beta epoxide Among triethoxysilane, α-glycidoxypropyl group trimethoxy silicon Alkane, α-glycidoxypropyl group triethoxysilane, beta epoxide propoxypropyl trimethoxy silane, beta epoxide propoxyl group third Base-glycidoxypropyl group triethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group Methyldiethoxysilane, α-glycidoxy butyl trimethoxy silane, α-glycidoxy butyl triethoxysilane, β- Glycidoxy butyl trimethoxy silane, beta epoxide propyloxybutyl triethoxysilane, γ-glycidoxy butyl front three TMOS, γ-glycidoxy butyl triethoxysilane, δ-glycidoxy butyl trimethoxy silane, δ-epoxy third Epoxide butyl triethoxysilane, (3,4- epoxycyclohexyl) MTMS, (3,4- epoxycyclohexyl) methyl three Ethoxysilane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, β-(3,4- epoxycyclohexyl) ethyl triethoxy Silane, β-(3,4- epoxycyclohexyl) ethyl tripropoxy silane, β-(3,4- epoxycyclohexyl) ethyl three butoxy silane, β- (3,4- epoxycyclohexyl) ethyl triple phenoxyl silane, γ-(3,4- epoxycyclohexyl) propyl trimethoxy silicane, γ-(3,4- Epoxycyclohexyl) propyl-triethoxysilicane, δ-(3,4- epoxycyclohexyl) butyl trimethoxy silane, δ-(3,4- epoxide ring Hexyl) trialkoxy silane, n- β-(amino-ethyl) gamma-amino propyl trimethoxy silicane, the n- such as butyl triethoxysilane β-(amino-ethyl) gamma-amino hydroxypropyl methyl diethoxy silane, gamma-amino propyl trimethoxy silicane, n- phenyl-γ-ammonia Base propyl trimethoxy silicane, trimethoxysilylpropyl carbic anhydride etc., γ mercaptopropyitrimethoxy silane and γ-Mercaptopropyltriethoxysilane.
[(d) Epoxy cure catalysts]
Solid as Epoxy cure catalysts, preferably heating curing type namely hot activation type potentiality epoxy resin Agent.Can enumerate for example: dicyanodiamine, imidazolium compoundss, all kinds of salt and binary acid dihydrazide (dibasic acid Dihydrazide) compound etc., can be combined these two or more uses.The amount of this curing catalysts is, having as catalyst Effect dosage (catalytic amount), generally, with respect to epoxy resin 100 mass parts, using 0.1～20 mass parts, preferably makes With 1～12 mass parts.
[(e) threadiness inorganic filling material]
As fibrous inorganic filling material, can enumerate: glass fibre, ca silicate fibre, potassium titanate fibre, carbon fiber, The ceramic whiskers such as silicon nitride, potassium titanate or ceramic fibre and metallic fiber etc..In these, most preferably glass fibre.Also, glass The form of glass fiber is simultaneously not specially provided, referred to as the pulverizing of the wire harness of rove, wire harness, chopped strand, milled fiber and glass dust Product etc. all may be used.
E there is no particular restriction for shape of fibrous inorganic filling material of () composition etc., for example, glass fibre and carbon fiber In the case of, preferably fibre diameter is 10～100 μm, and then preferably 15～60 μm.Also, in formed body, preferably length and width It is more than 3 than (ratio of fibre length/fibre diameter), and then preferably more than 5.
If fibre diameter is more than 10 μm, there is no difficult to manufacture, if less than 100 μm, then do not exist The probability that the engineering propertiess of formed body, especially impact strength reduce, thus preferably.If also, length-width ratio is more than 3, can fill Separately win to obtain reinforcing effect, thus preferably.
As the method for the reinforcing effect of lifting protecting film, it is randomly distributed about protection with fibrous inorganic filling material Compare in film, it is preferable to use glass non-woven fabric (Japanese Bao Ling company (the japan vilene of plane random distribution Company, ltd.) manufacture glass non-woven fabric cumulus), or by the long fibre person that is woven to mesh-shape (Japanese day east spin limited public affairs Department (nitto boseki co., ltd.) manufactures ipc specification 3313 glass cloth etc.).Because protecting film contains epoxy resin conduct B () composition, therefore preferably with epoxy resin, polyamide and phenol resin etc. as its matrix resin.
Fibrous inorganic filler can be dispersed randomly in protecting film, preferably, protection membrane system adhesion coating and strengthening course Double-decker, and fibrous inorganic filler is only scattered in strengthening course.Also strengthening course can be used as using the resin of adhesion coating Matrix resin.
When being scattered in protecting film, with respect to selected from the phenoxy resin of aforementioned (a) composition, polyimide resin and At least one in the group that (methyl) acrylic resin is formed is 100 mass parts, and fibrous inorganic filler is preferably 25 To 5000 mass parts.More preferably 40 to 3000 mass parts.If this allotment amount is more than aforementioned minimum value, there is not protecting film Become high linear expansion coefficient thus producing the probability of larger warpage, and cause fragmentation when there is not cutting, thus causing anti-folding The probability of intensity decreases, thus preferably.Also, when this allotment amount is below aforementioned higher limit, there is not protecting film with respect to silicon The probability that the flatness of the bonding plane of chip reduces, and not there is a possibility that to cause adhesion strength to reduce, thus rupture strength Higher.
[other composition]
The protecting film of the present invention, in addition to aforesaid ingredients, can comprise firming agent and the various additives of epoxy resin.As Firming agent, can use phenol resin, for example, condensation substance of the phenols such as alkyl phenol, polyhydric phenols and naphthols and aldehydes etc., preferably make With phenol novolacs, orthoresol resin, paracresol resin (p-cresol novolak resin), chemical amplification resist, Bicyclopentadiene cresol resin (dicyclopentadiene cresol resin), poly- 4-Vinyl phenol resin, Bisphenol A Type Phenolic resin, Bisphenol-f phenolic resin or these modifier etc..
As additive, pigment and dyestuff etc. being enumerated, if allocating these, and the protecting film in the present invention being coloured, then By improving laser labeling properties.And then, for lifting protecting film and the purpose of the cohesiveness/sealing of chip back, also can add Plus silane coupling agent.In addition, also adjustable fire retardant and antistatic additive etc..
As the modulus of elasticity after protective film solidification for the semiconductor wafer of the present invention, preferably 10～100gpa.If Modulus of elasticity after solidification is more than 10gpa, then semiconductor wafer protective film can fully bear bending stress during anti-folding, Not there is a possibility that to cause rupture strength to reduce.Also, when modulus of elasticity is below 100gpa, using when there is not semiconductor wafer During the composite solid compound warpage of protective film and silicon wafer, produce larger stress in silicon wafer side, thus producing fragmentation more Probability, and not there is a possibility that to lead to rupture strength to reduce.
[semiconductor wafer protective film]
Semiconductor wafer in present invention protective film as shown in FIG. 1 to 3, is to possess base film 1 and be formed at The semiconductor wafer protective film 10 of the protecting film 2 of the upside of this base film 1.And, protecting film 2 contain aforementioned (a)～ (e) composition.
Fig. 1 is that the fibrous inorganic filling material 3 of (e) composition is dispersed randomly in the semiconductor die of the form in protecting film 2 Piece protective film 10.
The protecting film 2 of Fig. 2 is made up of with adhesion coating 4 strengthening course 3 ', and adhesion coating 4 is containing (a)～(d) composition Become, strengthening course 3 ' is to form containing (e) composition.As strengthening course 3 ', preferably glass cloth etc..Now, preferably, with respect to A () composition 100 mass parts, the content of fibrous inorganic filling material is 25～1000 mass parts.
The protecting film 2 of Fig. 3 is by strengthening course 3 " formed with adhesion coating 4, adhesion coating 4 is containing (a)～(d) composition Become, strengthening course 3 " it is to form containing (e) composition.As strengthening course 3 ", preferably prepreg (is for example impregnated with the glass of epoxy resin Glass cloth etc.).Now, preferably, with respect to (a) composition 100 mass parts, the content of fibrous inorganic filling material is 1000～ 5000 mass parts.As the configuration to semiconductor wafer, for preventing warpage, the collocation method that preferably linear expansion coefficient diminishes, And preferably semiconductor wafer (not making icon), adhesion coating 4 and strengthening course 3 ".
As the manufacture method of the semiconductor wafer protective film of the present invention, following (method 1)～(method can be enumerated 3), but be not limited to these methods.
(method 1) utilizes usual way, and by fibrous inorganic filler ((e) composition), mixing is scattered in and utilizes solvent And in the scattered adhesion layer composition comprising aforementioned (a)～(d) composition, and coat on base film 1 using following methods, To form protecting film 2, thus making the semiconductor wafer protective film 10 (Fig. 1) that adhesion coating is integrally formed with strengthening course.
(method 2) configures the benefit being made up of cancellous threadiness inorganic filler ((e) composition) on base film 1 Strong layer 3 ', and it is coated with the scattered adhesion layer composition comprising aforementioned (a)～(d) composition using solvent from above it, thus Make semiconductor wafer protective film 10, this semiconductor wafer protective film 10 has obliquely configuration adhesion coating 4 and benefit The double-deck protecting film 2 (Fig. 2) of strong layer 3 '.
(method 3) makes semiconductor wafer protective film 10, and this semiconductor wafer protective film 10 has thin film The double-deck protecting film 2 that shape strengthening course 3 " is fitted with film like adhesion coating 4, wherein, film like strengthening course 3 " is by being impregnated with Cancellous threadiness inorganic filling material ((e) composition) of matrix resin is constituted, and film like adhesion coating 4 is to use following methods To make (Fig. 3) using adhesion layer composition ((a)～(d) composition).
Protecting film 2 in (method 1) or the adhesion coating 4 in (method 2) and (method 3), available intaglio plate coating etc. is known Method, will mix the compositionss that aforementioned tie element is obtained, with thickness for 5～100 μm, preferably 10～60 μm of mode, Coat on base film 1, thus obtaining.Furthermore, foregoing can be scattered in solvent as desired, for example, be scattered in In cyclohexanone, then it is coated.
As base film 1, can use: polyethylene film, polypropylene film, polyvinyl chloride film, poly terephthalic acid Second two ester film and Kapton etc..After solidification protecting film 2, during peeling base thin film 1, it is preferable to use thermostability Excellent polyethylene phthalic acid thin film and Kapton.Also, now, also can be coated with the surface of this base film Silicones etc. simultaneously implement demoulding process, or, form the layer of fissility between base film 1 and protecting film 2.
The thickness of base film 1 is 5～200 μm, preferably 10～150 μm, particularly preferably for 20～100 μm about.
Semiconductor wafer protective film, for example, made using following methods including following operation.
(1) it is formed with the back side of the semiconductor wafer of circuit in surface, paste the semiconductor wafer protection in the present invention The protecting film of thin film；
(2) base film of stripping semiconductor chip protective film；
(3) heat and protecting film is solidified；And
(4) cutting semiconductor chip and protecting film.
Wherein, operation (3) and (4) also can overturn order.
The cutting action of aforementioned (4), can use cutting sheet, and carry out according to universal method.By cutting, the back side can be obtained There is the semiconductor chip of protecting film.Pick up this chip by universal means such as chucks, and be configured on substrate.By using this The semiconductor wafer protective film of invention, is not likely to produce small damage in chip section, such that it is able to high yield manufacture Semiconductor device.
[embodiment]
Hereinafter, the present invention is illustrated by embodiment, but the present invention is not limited to following embodiments.
[preparing protective layer formation compositionss]
(a) composition of mass parts shown in table 1 is dissolved in about 50 mass parts cyclohexanones.By the solution being obtained and table 1 Other composition mixing of amount shown, thus obtain the compositionss that solid constituent is about 70 mass %.
Each composition shown in table 1 and composition used below are as follows.
(a) composition
Phenoxy resin: mw about 60,000, jer1256 (Japanese epoxy resin company limited manufactures)
Polyimide resin 1: synthetic method is as be described hereinafter.
Acrylic resin 1: butyl acrylate 55 mass parts, methyl methacrylate 15 mass parts, Glycidyl methacrylate (weight average molecular weight is the transfer of 900,000, glass to the copolymer of glyceride 20 mass parts and acrylic acid 2- hydroxyethyl ester 15 mass parts Temperature is -28 DEG C)
(b) composition
Epoxy resin: re310s (Japanese chemical medicine company limited manufacture), the viscosity at 25 DEG C are 15pa.s
(c) composition
Silicon dioxide: sc2050, mean diameter be 0.5 μm, maximum particle diameter be 5 μm, kbm-403 item for disposal, Japan Admatechs company manufactures
(d) composition
Dicyanodiamine (dicy-7): Japanese epoxy resin company limited manufactures
(e) composition
Epoxy impregnation glass cloth eg adhesive tape model s: Japan have pool make institute (arisawa manufacturing co., Ltd.) manufacture
Glass cloth: Japanese Dong Fang company limited manufactures ipc specification 3313 glass cloth
Glass fibre: NEG company limited (nippon electric glass co., ltd.) manufactures and grinds Fiber gp-10ma (fibre diameter is 10 μm, average fiber length is 70 μm, length-width ratio is 7)
[synthesis of polyimides resin 1]
(possess 25ml water and basis weight receptor, the temperature of the subsidiary valve linking reflux cooler to 1 liter of removable flask Degree meter and agitator) in, (kf-8010, Japanese SHIN-ETSU HANTOTAI chemistry have to load the diamino radical siloxane represented by following structural formula Limit company (shin-etsu chemical co., ltd.) manufactures) 49.01 mass parts and the 2- methyl pyrrole as reaction dissolvent Cough up pyridine ketone 100 mass parts, stir at 80 DEG C, diamidogen is disperseed.Instill the 6fda (double (3,4- of 2,2- as anhydride thereto Phthalate anhydride) hexafluoropropylene oxide) 42.68 mass parts and 2- methylpyrrole pyridine ketone 100 mass parts solution, stir at room temperature Mix 2 hours and reacted, thus the oligoamic acid rich in anhydride for the synthesis.
Then, will be by following formula:
The represented diamidogen with phenolic hydroxyl group (refine industrial group (seika by hab, Japanese Wakayama Corporation) manufacturing) the 2- methylpyrrole pyridine ketone of 8.31 mass parts and 100 mass parts loads 1 liter of removable flask (tool The standby 25ml water and basis weight receptor of subsidiary valve linking reflux cooler, thermometer and agitator) in so as to dispersion, drip Enter aforementioned rich in the oligoamic acid of anhydride after, stir 16 hours at room temperature, thus synthesizing polyamides acid solution.Afterwards, After putting into dimethylbenzene 25ml, rise high-temperature, so that it is flowed back 2 hours with about 180 DEG C.Confirm to contain spy in water and basis weight receptor Quantitative water, and do not find that water flows out, side removes the effluent accumulating in water and basis weight receptor, while with 180 DEG C of removal diformazans Benzene.After the completion of reaction, instilling the reactant liquor obtained in excessive methanol, and separate out polymer, carrying out drying under reduced pressure, thus obtaining Obtain the polyimide resin in skeleton with phenolic hydroxyl group.
When measuring the obtained infrared absorption spectroscopy of polyimide resin, do not manifest the absorption based on polyamic acid, should Polyamic acid represents there is unreacted functional group, is identified in 1780cm-1And 1720cm-1In absorption based on imide, and It is identified in 3500cm-1In absorption based on phenolic hydroxyl group.The weight average molecular weight of the polystyrene conversion of the resin being obtained is 55, 000, functional group's equivalent is 760g/eq.
[making semiconductor wafer protective film]
(embodiment 1～embodiment 5 and comparative example 1)
Make the adhesion layer composition liquid (coating liquid 1～coating liquid 5) shown in table 1, in an embodiment, in 115 μm of ring On oxygen tree fat prepreg strengthening course, in the way of 20 μm of thickness, it is coated with adhesion coating, and in a comparative example, in 50 μm of rustless steel On (model sus304) strengthening course, in the way of 20 μm of thickness, it is coated with adhesion coating, and with 110 DEG C of heat dryings 10 minutes, from And form the protecting film of 135 μm and 70 μm.
(embodiment 6)
75 μm of glass cloth ipc specification 3313 is configured on the pet thin film of 38 μm being surface-treated with silicon, from it The coating liquid 1 of top coating table 1 in the way of the thickness that adhesion coating is 15 μm, and with 110 DEG C of heat dryings 10 minutes, thus shape Become 90 μm of protecting film.
(embodiment 7)
By the coating liquid 6 of the addition glass fibre of table 2, in the way of the thickness that protecting film becomes 50 μm, coat with silicon On the pet thin film of 38 μm being surface-treated, and with 110 DEG C of heat dryings 10 minutes, thus forming 50 μm of protecting film.
Furthermore (, coating liquid 6 is the composition adding glass fibre in coating liquid 1.)
(comparative example 2, comparative example 3)
In addition to using coating liquid 4, coating liquid 5, form 135 μm of protecting film using method same as Example 7.
[modulus of elasticity in direct stress]
By the protecting film being obtained after 175 DEG C of solidifications 4 hours, make 5mm width, the strip sample of 40mm length, to make For mensure sample.Using NSK Electronics Co., Ltd. (seiko instruments inc.) dma6100, with 1hz, askew 10 μm and using 3 DEG C/min 25 DEG C when being warming up to 200 DEG C for 0 DEG C data as the modulus of elasticity in direct stress.
[cutting test]
Using Japanese technovision company (technovision, inc.) fm-114, by the protecting film being obtained with 50 DEG C are pasted on the silicon wafer that thickness is 75 μm and (are manufactured using limited company of enlightening Cisco (disco corporation) Dag-810,8 inches of non-grinding wafers light is ground, makes the chip of 5 μ m thick) on.Will in 175 DEG C using drying machine The silicon wafer of subsidiary protecting film solidifies 4 hours, thus solidifying protecting film.With following conditions, the silicon wafer of this subsidiary protecting film is cut It is slit into the foursquare chip of 10mm × 10mm, observe 40 cut-out end faces of obtained chip, during no more than 50 μm of fragmentation, be Qualified.
Cutting condition
Device: disco dicer dad-341
Cutting-off method: single cutting
Cutting blade: zh05-sd3500-n1-70ee
Rotating speed of flail: 30000rpm
Blade speed: 30mm/sec
The thickness of cutting thin film is 110 μm, the otch in thin film is cut in incision: 50 μm
[rupture strength determination test]
Measure the foursquare chip of 10mm × 10mm 40 obtained in previous cutting test using following conditions Rupture strength, using meansigma methodss as measurement result.Result is shown in table 3.
Rupture strength condition determination
Device: Japanese Shimadzu Corporation (shimadzu corporation) autograph
Anti- folding tool: 4mm wide wedge shape
Distance between the fulcrum: 6mm
Wedge shape tool speed: 0.01m/min
Table 1
Table 2
Table 3
The protecting film of embodiment 1～embodiment 7 comprises the quasiconductor protective film of fibrous inorganic filling material, and it draws Stretch that modulus of elasticity, cutting performance and rupture strength are higher, thus can achieve the high production rate of semiconductor chip.On the other hand, than Relatively low compared with the cutting performance of the quasiconductor protective film not comprising fibrous inorganic filling material of example 1～comparative example 3, also, Rupture strength is also poor.
Furthermore, the present invention is not limited to aforementioned embodiments.Aforementioned embodiments are to illustrate, and every have and the present invention Substantially the same structure of the technological thought described in claim and play the same role the technical scheme of effect, all wrap It is contained in the technical scope of the present invention.

Claims (3)

1. a kind of semiconductor wafer protective film is it is characterised in that it possesses base film and is formed at this base film The protecting film of upside,
And, aforementioned protecting film is made up of with adhesion coating strengthening course,
Aforementioned adhesion coating contains following a～d compositions and forms, and aforementioned strengthening course contains following e compositions and forms, and aforementioned strengthening course inclines Tiltedly configured:
A. it is selected from least in the group that phenoxy resin, polyimide resin and (methyl) acrylic resin are formed Kind: 100 mass parts；
B. epoxy resin: 5～200 mass parts；
C. the packing material beyond fibrous inorganic filling material: 100～400 mass parts；
D. Epoxy cure catalysts: with respect to b composition described in 100 mass parts epoxy resin be 0.1～20 mass parts；
E. cancellous threadiness inorganic filling material: 25～5000 mass parts.
2. semiconductor wafer protective film as claimed in claim 1, wherein, the phenoxy resin in aforementioned a composition is double Phenol a type phenoxy resin or Bisphenol-f phenoxy resin, the epoxy resin of aforementioned b composition be liquid bisphenol a type epoxy resin or Liquid bisphenol f type epoxy resin.
3. a kind of manufacture method of semiconductor chip, it is the method to manufacture semiconductor chip for the cutting semiconductor chip, and it is special Levy and be, semiconductor wafer protective film described in claim 1 or 2 is pasted on aforesaid semiconductor chip for it, and whole Body is cut, and thus to manufacture the back side and to have the semiconductor chip with the protecting film of former semiconductor chip same size.
CN201380009159.3A 2012-02-13 2013-01-24 Protective film for semiconductor wafer, and method for manufacturing semiconductor chip Expired - Fee Related CN104137229B (en)

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