WO2015146714A1 - 保護膜形成用フィルム及び保護膜付き半導体チップの製造方法 - Google Patents
保護膜形成用フィルム及び保護膜付き半導体チップの製造方法 Download PDFInfo
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- WO2015146714A1 WO2015146714A1 PCT/JP2015/057887 JP2015057887W WO2015146714A1 WO 2015146714 A1 WO2015146714 A1 WO 2015146714A1 JP 2015057887 W JP2015057887 W JP 2015057887W WO 2015146714 A1 WO2015146714 A1 WO 2015146714A1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
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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
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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
- 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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- 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
- H01L21/022—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 the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides
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- 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
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
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- 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
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
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- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H01L2223/54406—Marks applied to semiconductor devices or parts comprising alphanumeric information
Definitions
- the present invention relates to a protective film forming film and a method of manufacturing a semiconductor chip with a protective film using the protective film forming film.
- a semiconductor device is manufactured using a mounting method called a face-down method.
- the semiconductor chip is bonded with the surface of the chip on which electrodes such as bumps are formed facing the substrate and the like, while the back surface of the chip is exposed, so that the back surface of the chip is protected by a protective film. Yes.
- a mark, a character, etc. are printed by the laser printing etc. on the protective film which protects the back surface of a semiconductor chip.
- the protective film has been formed by, for example, resin coating, but in recent years, it is formed by sticking a protective film-forming film for the purpose of ensuring the uniformity of the film thickness of the protective film.
- a protective film-forming film contains, for example, a thermosetting component made of an epoxy resin or the like and a binder resin component made of an acrylic resin or the like, and is provided on a support sheet.
- This protective film-forming film contains an epoxy thermosetting resin, an acrylic polymer, a resin having a functional group capable of reacting with an epoxy group and an unsaturated hydrocarbon group in one molecule, and a release sheet ( Support sheet).
- the target of pasting a film for forming a protective film was mainly a semiconductor material such as silicon on the back surface of the chip.
- a semiconductor material such as silicon on the back surface of the chip.
- devices with a metal film on the back surface Since the thickness of the chip is also reduced, it is required to protect the metal film on the back surface of the chip.
- the conventional protective film-forming film has a problem that it does not have sufficient adhesive strength when applied to a metal film, and is easily peeled off from the metal film particularly when exposed to high temperature conditions.
- the present invention has been made in view of the above circumstances, and a protective film that protects a metal film provided on the back surface of a semiconductor chip and suppresses peeling from the metal film even when it has undergone a history of temperature change. It is an object to provide a film for forming a protective film for forming.
- the present invention provides a protective film-forming film for forming a protective film for protecting a metal film provided on the back surface of a semiconductor chip, which has a thiol group or a protective thiol group.
- a film for forming a protective film which is formed from a composition for forming a protective film containing an agent.
- the coupling agent preferably has a protective thiol group.
- the protective film-forming composition has an inorganic filler in a ratio of the blending amount to the total blending amount of components other than the solvent in the protective film-forming composition. Those containing 75% by mass are preferred.
- the protective film-forming composition preferably further contains an acrylic resin having a glass transition temperature of ⁇ 3 ° C. or higher.
- the protective film-forming composition further contains an acrylic resin, and the acrylic resin adds glycidyl (meth) acrylate to the total amount of monomers constituting the acrylic resin. It is preferable to polymerize a monomer containing 8% by mass or less.
- the present invention is also a method for manufacturing a semiconductor chip with a protective film in which the metal film provided on the back surface of the semiconductor chip is protected by a protective film, wherein the protective film is formed on the metal film provided on the back surface of the semiconductor wafer.
- Dicing after forming a protective film from the protective film-forming film of the laminated body, or by dicing the laminated body after forming the protective film from the protective film-forming film, by a laminated body in which the forming film is laminated A method of manufacturing a semiconductor chip with a protective film is provided.
- a protective film-forming film according to the present invention is a protective film-forming film for forming a protective film for protecting a metal film provided on the back surface of a semiconductor chip, and is a thiol group (—SH) or a protective thiol group It is formed using the composition for protective film formation which mix
- Such a protective film-forming film is formed by using a coupling agent having a thiol group (-SH) or a protective thiol group, and affixing the protective film-forming film to a metal film and curing it. Can sufficiently enhance the adhesion to the metal film.
- this protective film has not only excellent initial adhesive strength, but also has high reliability because peeling from the metal film is suppressed even after a history of temperature change.
- the coupling agent (E) has at least one of a thiol group and a protected thiol group in one molecule, and further has a functional group capable of reacting (coupling) with another molecule.
- the “other molecules” include, for example, molecules constituting the filler when a filler described later is blended in the protective film-forming composition.
- the “protected thiol group” means a group in which the hydrogen atom of the thiol group (—SH) is replaced with a group other than a hydrogen atom (protecting group) and protected.
- Examples of the protecting group in the protected thiol group include trialkoxysilyl group, trialkylsilyl group, trialkylsiloxy group, carbamate group (carbamate group), carbonate group (carbonate group). ), And an acetyl group.
- the alkyl group constituting the protective group may be linear, branched or cyclic, and preferably has 1 to 10 carbon atoms.
- the total number of thiol groups and protected thiol groups that the coupling agent (E) has in one molecule is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2.
- the coupling agent (E) is preferably one in which a functional group capable of reacting with another molecule and a thiol group or a protected thiol group are linked by a divalent organic group having 2 or more carbon atoms.
- the divalent organic group is preferably an alkylene group, more preferably an alkylene group having 3 or more carbon atoms, and particularly preferably an alkylene group having 3 to 10 carbon atoms.
- Preferred examples of the coupling agent (E) include compounds represented by the following general formula (1).
- R 1 is an alkyl group, and three R 1 s may be the same or different from each other;
- X 1 is an alkylene group;
- Y 1 is a hydrogen atom, a trialkoxysilyl group, a trialkylsilyl group. , Trialkylsiloxy group, carbamate group or carbonate group.
- R 1 is an alkyl group, and this alkyl group may be linear, branched or cyclic, and when it is cyclic, the alkyl group is monocyclic or polycyclic. Either is acceptable.
- the linear or branched alkyl group in R 1 preferably has 1 to 10 carbon atoms.
- alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3 -Methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3- Dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl
- the cyclic alkyl group for R 1 preferably has 3 to 10 carbon atoms.
- the alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, Examples include cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group and tricyclodecyl group.
- examples of the cyclic alkyl group in R 1 include those in which one or more hydrogen atoms of these cyclic alkyl groups are substituted with a linear, branched or cyclic alkyl group.
- examples of the linear, branched, and cyclic alkyl groups for substituting a hydrogen atom include those described above as the alkyl group for R 1 .
- the compound represented by the general formula (1) represents that each of three sides of tetravalent Si is bonded to (R 1 O).
- the three R 1 s may be the same or different from each other, that is, all may be the same, all may be different, or only two may be the same.
- X 1 is an alkylene group, preferably having 3 or more carbon atoms, more preferably 3 to 10 carbon atoms, a propane-1,3-diyl group, etc. Examples thereof include a divalent group obtained by removing one hydrogen atom from the above alkyl group having 3 to 10 carbon atoms.
- Y 1 is a hydrogen atom, trialkoxysilyl group, trialkylsilyl group, trialkylsiloxy group, carbamate group or carbonate group, trialkoxysilyl group, trialkylsilyl group, trialkylsiloxy. group, the alkyl group constituting the carbamate group and carbonate group, linear, branched and may be any of circular, it is preferred that the 1 to 10 carbon atoms, and the alkyl group in the above R 1 The same thing can be illustrated. Among these, Y 1 is preferably a hydrogen atom or a trialkoxysilyl group.
- the coupling agent (E) having a protected thiol group is preferable to the coupling agent (E) having a thiol group in that it has little odor or no odor and is practically easy to handle.
- Examples of the coupling agent (E) having a protected thiol group include silane coupling agents such as (CH 3 O) 3 Si—C 3 H 6 —S—Si (OC 2 H 5 ) 3 ).
- Examples of the coupling agent (E) having a thiol group include silane coupling agents such as (CH 3 O) 3 Si—C 3 H 6 —SH).
- the ratio of the amount of the coupling agent (E) to the total amount of components other than the solvent is preferably 0.01 to 7% by mass, preferably 0.1 to 2% by mass. It is more preferable that When the ratio of the blending amount of the coupling agent (E) is equal to or higher than the lower limit, a higher effect of suppressing the peeling of the protective film from the metal film can be obtained even when a history of temperature change is passed. Moreover, when the ratio of the said compounding quantity of a coupling agent (E) is below the said upper limit, when the film for protective film formation contacts with a peeling film, reaction of a coupling agent (E) and a peeling agent This reduces the possibility that the peelability will fluctuate.
- the protective film protecting the metal film has a sulfur atom derived from the coupling agent (E) or the coupling agent (E).
- organic compounds organic sulfur compounds. It is presumed that the adhesive force between the protective film and the metal film is improved by the interaction between the sulfur atom in the compound and the metal atom in the metal film. As a result, it is presumed that the protective film not only has excellent initial adhesive strength to the metal film, but also suppresses peeling from the metal film even after a history of temperature change.
- Binder resin (A) A binder resin (A) can be exemplified as a preferable component other than the coupling agent (E) in the protective film-forming composition.
- the binder resin (A) is used, for example, to impart a good initial adhesive force to the metal film to the protective film-forming film, and to impart flexibility and film-forming properties to the protective film and the protective film-forming film.
- Component. Binder resin (A) may be used individually by 1 type, and may use 2 or more types together.
- binder resin As an acrylic resin, a phenoxy resin, a polyester resin, a urethane resin, an acrylic urethane resin, a silicone resin, a rubber-type polymer etc. as a preferable thing, an acrylic resin is illustrated. More preferred. That is, the protective film-forming composition (protective film-forming film) preferably contains an acrylic resin.
- a monomer constituting the acrylic resin does not contain an epoxy group-containing monomer, or contains an epoxy group-containing monomer in a proportion of 8% by mass or less based on the total amount of the monomers. Those are preferred.
- the monomer constituting the acrylic resin includes an epoxy group-containing monomer
- the monomer constituting the acrylic resin is an epoxy group-containing (meth) acrylic acid ester and a non-acrylic epoxy. From one or more epoxy group-containing monomers selected from the group consisting of group-containing monomers, and various (meth) acrylic acid esters and non-acrylic epoxy group-free monomers having no epoxy group Become.
- the epoxy group-containing monomer is composed only of a non-acrylic epoxy group-containing monomer
- the monomer constituting the acrylic resin includes various (meth) acrylic acid esters having no epoxy group.
- (meth) acrylic acid is a concept including both acrylic acid and methacrylic acid.
- the monomer constituting the acrylic resin constitutes the epoxy group-containing monomer and the acrylic resin.
- the compatibility between the acrylic resin and the cured product of the epoxy thermosetting resin (B) is lowered, and a phase separation structure described later This improves the reliability of a semiconductor chip with a protective film, which will be described later.
- the monomer constituting the acrylic resin preferably contains the epoxy group-containing monomer at a ratio of 6% by mass or less with respect to the total amount of monomers constituting the acrylic resin.
- Epoxy group-containing (meth) acrylic acid esters include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 3-epoxycyclo-2-hydroxypropyl.
- a (meth) acrylate etc. can be illustrated and a glycidyl (meth) acrylate is preferable.
- the non-acrylic epoxy group-containing monomer include glycidyl crotonate and allyl glycidyl ether. Among these, as the epoxy group-containing monomer, an epoxy group-containing (meth) acrylic acid ester is preferable.
- the monomer that constitutes the acrylic resin contains an epoxy group-containing monomer, so that it is easy to suppress a decrease in the gloss value of the protective film due to the progress of phase separation, and printing by laser printing. It becomes easy to improve the distinguishability of the part. Therefore, when the present invention is applied to an application that requires good print discrimination, the monomer constituting the acrylic resin preferably contains an epoxy group-containing monomer. And it is preferable that the monomer which comprises an acrylic resin contains an epoxy group containing monomer in the ratio of 0.1 mass% or more with respect to the total amount of the monomer which comprises an acrylic resin, 1 mass% More preferably, it is contained at a rate of 3% by mass or more.
- the monomer constituting the acrylic resin preferably contains the epoxy group-containing monomer in a range of 0.1 to 8% by mass with respect to the total amount of monomers constituting the acrylic resin. More preferably, it is contained in the range of ⁇ 6% by mass, particularly preferably in the range of 3 ⁇ 5% by mass.
- the monomer constituting the acrylic resin does not contain an epoxy group-containing monomer
- the monomer constituting the acrylic resin is specifically a hydroxyl group-containing (meth) acrylic acid ester or (meth) acrylic acid. It consists of (meth) acrylic acid ester having no various epoxy groups such as alkyl ester and non-acrylic epoxy group-free monomer such as styrene, ethylene, vinyl ether, vinyl acetate, etc., which are used in combination as appropriate.
- the monomer constituting the acrylic resin preferably contains a (meth) acrylic acid alkyl ester.
- the glass transition temperature (Tg) of the acrylic resin can be easily adjusted by increasing or decreasing the number of carbon atoms of the (meth) acrylic acid alkyl ester or by using a combination of (meth) acrylic acid alkyl esters having different carbon numbers.
- the monomer constituting the acrylic resin preferably contains the (meth) acrylic acid alkyl ester in a proportion of 50% by mass or more with respect to the total amount of monomers constituting the acrylic resin, More preferably, it is contained in a proportion.
- the monomer which comprises an acrylic resin contains the said (meth) acrylic-acid alkylester in the ratio of 92 mass% or less with respect to the total amount of the monomer which comprises an acrylic resin. That is, the monomer constituting the acrylic resin preferably contains (meth) acrylic acid alkyl ester in a range of 50 to 92% by mass with respect to the total amount of the monomers constituting the acrylic resin. More preferably, it is contained in the range of 92% by mass.
- Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic.
- 2-ethylhexyl acid isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate
- examples thereof include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 18 carbon atoms.
- the monomer constituting the acrylic resin is the total amount of the monomers constituting the acrylic resin of the (meth) acrylic acid alkyl ester, the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group. It is preferable to contain in the ratio of 12 mass% or less with respect to.
- the gloss value of the protective film can be easily adjusted to a good value while the glass transition temperature of the acrylic resin is set to ⁇ 3 ° C. or higher.
- This gloss value is an index representing gloss and gloss, and can be measured by a method based on JIS Z 8741.
- the monomer constituting the acrylic resin is an alkyl (meth) acrylate having an alkyl group with 4 or more carbon atoms.
- the ester is preferably contained in a proportion of 1 to 12% by mass, more preferably 5 to 12% by mass with respect to the total amount of monomers constituting the acrylic resin.
- the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group butyl (meth) acrylate is preferred.
- the monomer which comprises the said acrylic resin contains the (meth) acrylic-acid alkylester whose carbon number of an alkyl group is 3 or less among the said (meth) acrylic-acid alkylester.
- the monomer constituting the acrylic resin is a (meth) acrylic acid alkyl ester having an alkyl group with 3 or less carbon atoms, based on the total amount of monomers constituting the acrylic resin.
- the monomer which comprises the said acrylic resin is a ratio of 90 mass% or less with respect to the total amount of the monomer which comprises the (meth) acrylic-acid alkylester whose carbon number of an alkyl group is 3 or less. It is preferable to contain.
- a (meth) acrylic-acid alkylester whose carbon number of an alkyl group is 3 or less methyl (meth) acrylate or ethyl (meth) acrylate is preferable, and methyl (meth) acrylate is more preferable.
- the monomer which comprises the said acrylic resin is a (meth) acrylic-acid alkylester whose carbon number of an alkyl group among the said (meth) acrylic-acid alkylester is 4 or more, and carbon number of an alkyl group is 3 or less. It is good also as a structure which occupies the total amount of the monomer which comprises an acrylic resin with (meth) acrylic-acid alkylester.
- the monomer constituting the acrylic resin may contain a hydroxyl group-containing (meth) acrylic ester.
- the acrylic resin has a hydroxyl group, so that the adhesion of the protective film to the semiconductor chip and the adjustment of the adhesive property are facilitated.
- the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like.
- the monomer constituting the acrylic resin preferably contains a hydroxyl group-containing (meth) acrylic ester in a proportion of 1 to 30% by mass with respect to the total amount of monomers constituting the acrylic resin. More preferably, it is contained at a rate of 10% by mass, and particularly preferably at a rate of 10-20% by mass.
- the acrylic resin has a weight average molecular weight (Mw) of preferably 10,000 or more in order to more effectively impart flexibility and film-forming property to the protective film-forming film, and preferably 15,000 to 100 More preferably, it is more preferably 20,000 to 500,000.
- Mw weight average molecular weight
- the weight average molecular weight is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
- the acrylic resin preferably has a glass transition temperature of ⁇ 3 ° C. or higher.
- the glass transition temperature is ⁇ 3 ° C. or higher.
- the acrylic resin preferably has a glass transition temperature of 6 ° C. or lower.
- the glass transition temperature of the acrylic resin is 6 ° C. or less, the gloss value of the protective film described above is improved, and the recognizability of the printed part in which marks, characters, and the like are printed on the protective film becomes better. The reason is not necessarily clear, but it is presumed that the surface shape of the protective film after curing is smoothed because the acrylic resin has moderate mobility.
- the glass transition temperature of the acrylic resin is a theoretical value obtained from the Fox equation unless otherwise specified.
- the monomer constituting the acrylic resin does not contain an epoxy group-containing monomer at all, or the proportion of the epoxy group-containing monomer is small, so that a phase rich in acrylic resin in the protective film will be described later.
- the phase rich in the cured product of the epoxy thermosetting resin (B) is easily phase separated, and the reliability of the semiconductor chip with a protective film is improved. This is because even when a semiconductor chip with a protective film after mounting undergoes a temperature change, the stress caused by the deformation due to the temperature change is relaxed by the phase rich in the flexible acrylic resin. This is presumably because peeling is less likely to occur.
- the protective film-forming film after thermosetting that is phase-separated that is, the protective film
- it is preferable that the phase rich in acrylic resin forms a continuous phase. Thereby, the reliability improvement effect mentioned above becomes still higher.
- the phase rich in the acrylic resin and the phase rich in the cured product of the epoxy thermosetting resin (B) are, for example, any substance from a measurement chart of a certain phase obtained by Raman scattering spectrometry. It can be determined by specifying whether it is the main component of the phase.
- the harder one is an epoxy thermosetting resin with the hardness of tapping mode measurement of a scanning probe microscope (SPM) as an index.
- SPM scanning probe microscope
- Whether or not the protective film-forming film forms a phase separation structure is determined by using a protective film-forming composition that does not contain a filler (F) and a colorant (G) described later. It is preferable to carry out by observing a protective film obtained by preparing a film for use, laminating the film on a silicon wafer, and thermosetting. This is because it is difficult to determine the presence or absence of the phase separation structure in the protective film-forming film containing the filler (F) and the colorant (G).
- the ratio of the content of the acrylic resin to the total mass in terms of solid content in the protective film-forming film is The content is preferably 10 to 80% by mass, and more preferably 15 to 50% by mass.
- the protective film-forming film (or the protective film-forming composition for forming the protective film-forming film) contains an acrylic resin, and the acrylic resin has a glass transition temperature of ⁇ 3 ° C. or higher. Some are particularly preferred.
- the protective film-forming film (or the protective film-forming composition for forming the protective film-forming film) contains an acrylic resin, and the acrylic resin contains glycidyl (meth) acrylate and acrylic resin. Particularly preferred is one obtained by polymerizing a monomer containing 8% by mass or less with respect to the total amount of the constituent monomers.
- thermosetting resin (B) [Thermosetting agent (C)]
- examples of preferable components other than the coupling agent (E) of the composition for forming a protective film further include an epoxy thermosetting resin (B) and a thermosetting agent (C).
- the epoxy thermosetting resin (B) is a component that hardens the protective film by curing.
- the thermosetting agent (C) functions as a curing agent for the epoxy thermosetting resin (B).
- the epoxy thermosetting resin (B) may be used without using the thermosetting agent (C), but it is easy to adjust the rate of the curing reaction and the elastic modulus of the protective film.
- thermosetting resin (B) and the thermosetting agent (C) in combination from the viewpoint that the physical properties such as the above can be easily adjusted within a preferable range.
- an epoxy-type thermosetting resin (B) and a thermosetting agent (C) all may be used individually by 1 type, and may use 2 or more types together.
- the epoxy-based thermosetting resin (B) may be a known one, and preferable ones include biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, biphenyl types.
- Bifunctional or higher functional epoxy compounds having two or more polymerizable groups in the molecule such as epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin can be exemplified.
- the thermosetting agent (C) may be a known one, and a preferable example is a compound having two or more functional groups (structures) capable of reacting with an epoxy group in one molecule.
- the functional group capable of reacting with an epoxy group include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxy groups, and groups in which acid groups are anhydrided, and phenolic hydroxyl groups, amino groups, and acid groups are condensed.
- An anhydride group is preferred, and a phenolic hydroxyl group and an amino group are more preferred.
- phenolic curing agent having a phenolic hydroxyl group examples include polyfunctional phenolic resins, biphenols, novolac type phenolic resins, dicyclopentadiene type phenolic resins, zyloc type phenolic resins, aralkylphenolic resins and the like.
- amine curing agent having an amino group examples include dicyandiamide.
- the content of the thermosetting agent (C) in the protective film-forming film (the amount of the thermosetting agent (C) in the protective film-forming composition) is 100 parts by mass of the epoxy thermosetting resin (B).
- the content is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, and particularly preferably 1 to 20 parts by mass.
- the content of the thermosetting agent (C) is equal to or more than the lower limit value, the curing of the epoxy thermosetting resin (B) is sufficiently facilitated, and the protective film adheres to the metal film of the semiconductor chip. Power improves more.
- the raise of the moisture absorption rate of the film for protective film formation is suppressed because content of a thermosetting agent (C) is below the said upper limit, and the reliability of the semiconductor chip with a protective film improves.
- Total content of epoxy-based thermosetting resin (B) and thermosetting agent (C) in protective film-forming film Is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and particularly preferably 100 parts by mass or less with respect to 100 parts by mass of the binder resin (A). .
- the total content of the epoxy thermosetting resin (B) and the thermosetting agent (C) in the protective film forming film (the epoxy thermosetting resin (B) and the thermosetting agent in the protective film forming composition ( The total blending amount of C) is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, and 60 parts by mass or more with respect to 100 parts by mass of the binder resin (A). Particularly preferred. That is, the total content of the epoxy thermosetting resin (B) and the thermosetting agent (C) in the protective film-forming film is 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin (A). It is preferably 40 to 150 parts by weight, more preferably 60 to 100 parts by weight.
- the adhesion of the protective film to the metal film of the semiconductor chip is further improved.
- the peeling force from the support sheet described later becomes a more appropriate range, and the suppression effect such as poor peeling when the support sheet is peeled from the protective film is enhanced.
- the total content of the epoxy-based thermosetting resin (B) and the thermosetting agent (C) is not more than the upper limit value, the above-described acrylic resin-rich phase is likely to be a continuous phase and has a protective film. The reliability of the semiconductor chip is improved.
- the ratio of the total amount of the epoxy thermosetting resin (B) and the thermosetting agent (C) to the total amount is preferably 5 to 60% by mass, more preferably 10 to 40% by mass. preferable.
- a curing accelerator (D) As a preferable component other than the coupling agent (E) in the composition for forming a protective film, a curing accelerator (D) can be further exemplified.
- a hardening accelerator (D) is a component which adjusts the hardening rate of the film for protective film formation.
- Preferred curing accelerators (D) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2 -Imidazoles such as phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (groups in which one or more hydrogen atoms are other than hydrogen atoms) Substituted imidazole); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphine in which one or more hydrogen atoms are substituted with organic groups); tetraphenylphosphonium tetraphenylborate, trif Tetraphenyl boron salts such as sulfon
- the content of the curing accelerator (D) in the protective film-forming film is the epoxy thermosetting resin (B) and the thermosetting agent (C ) Is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total.
- the protective film has excellent adhesive properties even under high temperature and high humidity conditions, and the semiconductor chip with the protective film is exposed to severe conditions. Even if it is done, it has high reliability.
- a filler (F) can be further exemplified as a preferable component other than the coupling agent (E) in the protective film-forming composition.
- the filler (F) is a component that imparts moisture resistance, dimensional stability (elastic modulus) and the like to the protective film, and specific examples thereof include inorganic fillers.
- the filler (F) is exposed at the part (printed part) scraped off with the laser light and reflected light is emitted. Because of the diffusion, the contrast with the non-printing portion is increased and the discrimination is improved.
- the inorganic filler include powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride and the like; beads formed by spheroidizing these silicas; single crystal fibers such as silica; glass A fiber etc. can be illustrated and a silica filler and an alumina filler are especially preferable.
- the average particle size of these inorganic fillers is, for example, preferably 0.005 to 20 ⁇ m, more preferably 0.01 to 15 ⁇ m, and particularly preferably 0.1 to 12 ⁇ m.
- said average particle diameter means the average value of the outer diameter in one particle.
- a filler (F) may be used individually by 1 type, and may use 2 or more types together.
- the content of the filler (F) in the protective film-forming film increases to some extent, the linear expansion coefficient of the protective film decreases, and the shear stress at the interface between the protective film and the metal film of the semiconductor chip increases.
- the reliability (adhesion reliability) of the semiconductor chip with the protective film is improved.
- the content of the filler (F) in the protective film-forming film is reduced to some extent, the initial adhesive force of the protective film is increased and process suitability is improved.
- the ratio of the content of the filler (F) to the total mass in terms of solid content in the protective film-forming film (in the protective film-forming composition is particularly preferably 55 to 75% by mass.
- the filler (F) with respect to the total mass in terms of solid content in the protective film-forming film is preferably 50 to 80% by mass, and 55 to 75%.
- the mass is more preferably 60% to 70% by mass.
- Examples of preferable components other than the coupling agent (E) in the composition for forming a protective film further include the colorant (G).
- the colorant (G) may be used as a component that prevents malfunction of the semiconductor chip by shielding infrared rays or the like generated from surrounding devices when the semiconductor chip with a protective film is incorporated into the device.
- the colorant (G) may be used as a component that improves character identification when a product number, a mark, or the like is printed on the protective film. That is, the product number or the like may be printed on the protective film attached to the semiconductor chip by the laser marking method.
- the protective film contains the coloring agent (G),
- the contrast with the non-printing portion is increased, and the distinguishability is improved.
- a coloring agent (G) may be used as a component which provides designability by making it difficult to see the grinding trace of a semiconductor wafer.
- the colorant (G) examples include organic pigments, inorganic pigments, organic dyes, and inorganic dyes.
- the dye is not particularly limited, and may be any dye such as an acid dye, a reactive dye, a direct dye, a disperse dye, and a cationic dye.
- the pigment is not particularly limited, and a known pigment can be used.
- the colorant (G) it is preferable to use a black pigment because it has good shielding properties against electromagnetic waves and infrared rays, and further improves discrimination by the laser marking method.
- the black pigment include, but are not limited to, carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like. From the viewpoint of improving the reliability of the semiconductor chip with a protective film, the black pigment is particularly preferably carbon black.
- Coloring agent (G) may be used alone or in combination of two or more.
- the ratio of the content of the colorant (G) to the total mass in terms of solid content in the protective film-forming film (the amount of the colorant (G) relative to the total amount of components other than the solvent in the protective film-forming composition) Is preferably 0.01 to 25% by mass, more preferably 0.03 to 15% by mass.
- the composition for forming a protective film comprises a coupling agent (E), a binder resin (A), an epoxy thermosetting resin (B), a thermosetting agent (C), a curing accelerator (D), and a filler (F).
- a coupling agent E
- a binder resin A
- an epoxy thermosetting resin B
- a thermosetting agent C
- a curing accelerator D
- a filler F
- other additives that do not fall under these may be blended within the range not impairing the effects of the present invention.
- the other additives include crosslinking agents, compatibilizers, leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, gettering agents, chain transfer agents, energy beam polymerizable compounds, and photopolymerization initiation. An agent etc. can be illustrated.
- the protective film-forming film has a phase rich in the acrylic resin (binder resin (A)) and a phase rich in a cured product of the epoxy thermosetting resin (B).
- the solubility can be adjusted as appropriate, and an appropriate phase separation structure can be designed.
- At least one surface of the protective film formed by curing the protective film-forming film preferably has a gloss value of 20 or more measured according to JIS Z 8741.
- the protective film-forming film has a surface opposite to the surface having a gloss value of 20 or more by curing, and is adhered to the semiconductor wafer and cured, so that the surface to be printed by laser marking of the protective film
- the gloss value is 20 or more. Therefore, the laser-printed surface becomes smooth, the contrast between the printed part and the non-printed part is improved, and the distinguishability of the printed part is improved.
- the gloss value is more preferably 27 or more from the viewpoint that the contrast between the printed portion and the non-printed portion is further improved and the distinguishability of the printed portion is further improved.
- the upper limit of the gloss value is not particularly limited, but is preferably 45.
- the gloss value is the amount of monomers such as an epoxy group-containing monomer constituting the acrylic resin (binder resin (A)) or a (meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms.
- the composition for forming a protective film is preferably one in which a solvent for dilution is further blended in addition to the above-described components.
- the solvent is not particularly limited, and preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; Examples include esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
- the said solvent may be used individually by 1 type, and may use 2 or more types together.
- the ratio of the amount of the solvent to the total amount of all the components is preferably 25 to 75% by mass, and more preferably 35 to 65% by mass.
- the thickness of the protective film-forming film is not particularly limited, but is preferably 3 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, and particularly preferably 7 to 80 ⁇ m.
- the thickness of the protective film-forming film can be measured by a measuring instrument and a measuring method that are generally used conventionally.
- the film for forming a protective film according to the present invention is usually detachably provided on a support sheet and used as a composite sheet for forming a protective film that is a laminate.
- the surface facing the support sheet of the protective film-forming film is the same shape and size as the surface facing the protective film-forming film of the support sheet, or more than the surface facing the protective film-forming film of the support sheet Small size.
- the surface of the protective film-forming film facing the semiconductor wafer is substantially the same shape and size as the surface of the semiconductor wafer facing the protective film-forming film, or the surface of the semiconductor wafer facing the protective film-forming film
- the shape and size can cover the entire facing surface.
- FIG. 1 is a cross-sectional view schematically illustrating a protective film-forming composite sheet using the protective film-forming film according to the present invention.
- the protective sheet-forming composite sheet 1 is formed by laminating a protective film-forming film 12 on the surface 11a of the support sheet 11, and the surface of the protective film-forming film 12 facing the support sheet 11 is The shape and size are the same as the surface of the support sheet 11 facing the protective film-forming film 12 (the surface 11a).
- the protective film-forming composite sheet 1 shown here is merely an example of an embodiment using the protective film-forming film according to the present invention. It is not limited to.
- the material of the support sheet polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyurethane, ethylene vinyl acetate copolymer, An ionomer resin, an ethylene / (meth) acrylic acid copolymer, an ethylene / (meth) acrylic acid ester copolymer, polystyrene, polycarbonate, polyimide, a fluororesin, and the like can be exemplified, and those obtained by crosslinking these can also be exemplified.
- the support sheet may be a colored film.
- the thickness of the support sheet is preferably 5 to 200 ⁇ m, and more preferably 10 to 160 ⁇ m.
- the thickness of this support sheet can be measured by a measuring instrument and a measuring method method that are generally used conventionally.
- the support sheet may be composed of a single layer, or may be composed of two or more layers.
- the plurality of layers may be the same as or different from each other. That is, all the layers may be the same, all the layers may be different, or only some of the layers may be different. And when several layers differ from each other, the combination of these several layers is not specifically limited.
- the plurality of layers being different from each other means that at least one of the material and the thickness of each layer is different from each other.
- a support sheet consists of two or more layers, it is good to make it the total thickness of each layer be the thickness of said preferable support sheet.
- the surface facing the protective film-forming film in the support sheet may be appropriately subjected to a peeling treatment.
- This release treatment can be performed by a known method, and examples of the release agent used in the release treatment include various release agents such as alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax. In view of heat resistance, alkyd, silicone or fluorine release agents are preferred.
- an adhesive sheet in which an adhesive layer is formed on a release film may be used as a support sheet.
- the protective film-forming film is laminated on the pressure-sensitive adhesive layer provided on the support sheet.
- the releasable pressure-sensitive adhesive layer As the releasable pressure-sensitive adhesive layer, a weakly-adhesive layer having an adhesive strength that can peel the protective film-forming film may be used. Things may be used.
- the re-peelable pressure-sensitive adhesive layer is made of various conventionally known pressure-sensitive adhesives (for example, rubber-based, acrylic-based, silicone-based, urethane-based, vinyl ether-based general-purpose pressure-sensitive adhesives, pressure-sensitive adhesives with surface irregularities, Energy ray-curable pressure-sensitive adhesive, thermal expansion component-containing pressure-sensitive adhesive, etc.).
- the protective film-forming film may be protected by attaching a lightly peelable release film to the surface opposite to the surface facing the support sheet.
- the protective film-forming composition includes a coupling agent (E), and a binder resin (A), an epoxy thermosetting resin (B), a thermosetting agent (C), a curing accelerator (D), as appropriate. It is obtained by blending at least one selected from the group consisting of a filler (F), a colorant (G), other additives and a solvent so as to be 100% in total. At this time, for example, by mixing and stirring each of the above components in appropriate amounts, and further controlling the temperature so that the temperature of the mixture is about 25 ° C., the mixture is diluted with methyl ethyl ketone or the like to dilute the protective film.
- a forming composition can be prepared.
- each component is not particularly limited, and two or more components may be added simultaneously.
- the method of mixing each component at the time of blending is not particularly limited, and is a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, etc. What is necessary is just to select suitably from the method.
- the temperature and time during addition and mixing of each component are not particularly limited as long as each component does not deteriorate, and may be adjusted as appropriate. For example, the temperature is preferably 15 to 30 ° C.
- the protective film-forming film according to the present invention (or the protective film-forming composite sheet) is obtained, for example, by applying the protective film-forming composition to the surface of the support sheet (the surface 11a of the support sheet 11 in FIG. 1). This can be produced by drying.
- the protective film-forming film formed by applying the composition for forming a protective film on the surface of the process film different from the support sheet and drying is bonded to the surface of the support sheet, and the process film is removed.
- a protective film-forming film (or a protective film-forming composite sheet) can be produced.
- the forming surface of the protective film-forming film in the process film may be appropriately subjected to a peeling treatment as in the case of the above support sheet.
- the process film after bonding the protective film-forming film to the surface of the support sheet may be the above-described release film without being removed.
- the drying conditions for the composition for forming a protective film may be selected according to the type of the ingredients, and are not particularly limited. For example, it is preferable to dry at 60 to 120 ° C. for 1 to 30 minutes.
- Application of the protective film-forming composition to the surface of the support sheet or the surface of the process film may be carried out by a known method.
- the method include using various coaters such as a coater, a die coater, a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.
- the film for forming a protective film according to the present invention can be used for manufacturing a semiconductor chip with a protective film in which a metal film provided on the back surface of the semiconductor chip is protected by a protective film.
- dicing is performed after forming a protective film from the protective film-forming film of the laminated body by a laminated body in which the protective film-forming film is laminated on a metal film provided on the back surface of the semiconductor wafer.
- the semiconductor chip with the protective film can be manufactured. Details are as follows.
- the protective film-forming composite sheet is attached to a semiconductor film by attaching the protective film-forming film of the protective film-forming composite sheet to a metal film provided on the back surface of the semiconductor wafer.
- the protective film-forming film is protected with a release film, the release film is removed and the exposed protective film-forming film is bonded to the metal film. Thereby, the said laminated body of the state provided with the support sheet is obtained.
- species of the metal film used as the sticking object of the film for protective film formation is not specifically limited, It is preferable that it is gold, silver, or copper, and it is more preferable that it is gold or silver.
- the metal film may be composed of a single layer, or may be composed of two or more layers. When the metal film is composed of a plurality of layers, these layers may be the same as or different from each other.
- the thickness of the metal film to be applied with the protective film-forming film is usually 50 to 300 nm. preferable.
- the semiconductor wafer may be, for example, a silicon wafer or a compound semiconductor wafer such as gallium / arsenic.
- a typical semiconductor wafer has a circuit formed on the front surface side thereof, and is appropriately ground on the opposite back surface side, and has a thickness of about 50 to 500 ⁇ m.
- the support sheet is peeled off from the protective film-forming film, and the protective film-forming film attached to the metal film of the semiconductor wafer is cured by heat curing or the like to form a protective film on the entire surface of the metal film.
- the protective film-forming film was applied to the surface of the metal film while being heated to about 70 ° C., and the release film was further removed, and then at 130 ° C. for about 2 hours. By heating, the protective film can be formed by curing the protective film-forming film.
- the semiconductor wafer provided with this protective film is diced for each circuit formed on the wafer surface.
- Dicing is performed so that the semiconductor wafer and the protective film are cut together, and the semiconductor wafer with the protective film is divided into semiconductor chips having a plurality of protective films by dicing.
- the dicing can be performed by attaching a dicing tape to the surface of the protective film and dicing the silicon wafer having the protective film attached thereto into an appropriate size using a commercially available dicing apparatus.
- the obtained semiconductor chip is picked up by a general-purpose means such as a collet to obtain a semiconductor chip (semiconductor chip with a protective film) in which the metal film on the back surface is protected by a protective film.
- the removal of the support sheet may be performed after curing (after formation of the protective film), not after curing of the protective film-forming film, or after dicing.
- the support sheet When removing the support sheet after dicing, the support sheet also serves as the dicing sheet. Moreover, you may perform hardening of the film for protective film formation after dicing instead of before dicing.
- the semiconductor chip with a protective film in which the metal film on the back surface of the semiconductor chip is protected by the protective film formed from the protective film-forming film according to the present invention has a sufficiently high adhesive force to the metal film of the protective film.
- the initial adhesive strength to the metal film excellent, but even when a history of temperature change is passed, the peeling from the metal film is suppressed, so that the reliability is high.
- the above-described reliability for example, when a thermal history is given to a semiconductor chip with a protective film, a test sample in which a floating / peeling at a joint portion between the semiconductor chip and the protective film and a crack in the protective film have occurred.
- evaluation of an odor is also mentioned as an evaluation item of the film for forming a protective film.
- This odor is evaluated by, for example, sensory evaluation based on the presence or absence of odor when the protective film-forming film is cut into a size of 20 cm ⁇ 20 cm and the release film is peeled off at 25 ° C. from the cut test piece. can do.
- Example 1 Manufacture of protective film-forming film (composite sheet for forming protective film)>
- the following components were mixed and stirred in the amounts shown in Table 1 below, and 700 parts by mass of methyl ethyl ketone was further mixed and diluted to prepare a protective film forming composition. During this time, the temperature of the mixture was adjusted to 25 ° C.
- Binder resin (A) (1) Acrylic resin (A-1): butyl acrylate (10 parts by mass), methyl acrylate (70 parts by mass), glycidyl methacrylate (5 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) Copolymerized copolymer having a weight average molecular weight of 350,000 and a glass transition temperature of ⁇ 1 ° C. (2) Acrylic resin (A-2): butyl acrylate (15 parts by mass), methyl acrylate (65 parts by mass) , A copolymer having a weight average molecular weight of 350,000 and a glass transition temperature of ⁇ 4 ° C.
- Epoxy thermosetting resin (B) bisphenol A type epoxy resin (epoxy resin equivalent 220 to 240 g / mol) (2) Epoxy thermosetting resin (B-2): dicyclopentadiene type epoxy resin (“Epiclon HP-7200HH” manufactured by DIC) (epoxy equivalent: 274 to 286 g / mol) [Thermosetting agent (C)] (1) Thermosetting agent (C-1): Dicyandiamide (“ADEKA HARDNER 3636AS” manufactured by ADEKA) [Curing accelerator (D)] (1) Curing accelerator (D-1): 2-Phenyl-4,5-dihydroxymethylimidazole (“Curesol 2PHZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.) [Coupling agent having a thiol group
- the protective film forming composition obtained above is applied to the release-treated surface of a polyethylene terephthalate (PET) film (“SP-PET3811” manufactured by Lintec Co., Ltd.) whose one side has been subjected to a release treatment.
- PET polyethylene terephthalate
- the film for forming the protective film was applied to a thickness of 25 ⁇ m and dried at 100 ° C. for 3 minutes to produce a film for forming the protective film on the PET film (a composite sheet for forming the protective film was produced).
- a release film was further bonded to the protective film-forming film.
- Titanium, nickel, and gold were deposited on the polished surface of a # 2000 polished silicon wafer (200 mm diameter, 200 ⁇ m thick) in this order so as to have a thickness of 100 nm.
- the release film is peeled from the protective film-forming composite sheet obtained above, and the protective film-forming film is heated to 70 ° C. using a tape mounter (“Adwill RAD-3600 F / 12” manufactured by Lintec Corporation).
- the other release film PET film was also removed and heated at 130 ° C. for 2 hours to cure the protective film-forming film, and the gold on the back side of the silicon wafer.
- a protective film was formed on the surface of the film.
- a dicing tape (“Adwill D-686H” manufactured by Lintec Co., Ltd.) is attached to the surface of the protective film, and a silicon wafer to which the protective film is applied is attached using a dicing apparatus (“DFD651” manufactured by Disco Corporation). Dicing to a size of 3 mm ⁇ 3 mm gave a semiconductor chip with a protective film.
- the semiconductor chip with a protective film obtained by the above procedure was processed under conditions (preconditions) imitating the process of actually mounting the semiconductor chip. That is, first, a semiconductor chip with a protective film is baked at 125 ° C. for 24 hours in a thermostatic chamber, and further, left in a constant temperature and humidity chamber at 85 ° C. and a relative humidity of 85% for 168 hours to absorb moisture. After taking out from the humidity chamber, it was immediately passed through an IR reflow furnace three times under the conditions of preheating 160 ° C., peak temperature 260 ° C., and heating time 30 seconds.
- Example 2-5 A protective film-forming film and a semiconductor chip with a protective film were produced in the same manner as in Example 1, except that the types and amounts of the blending components during preparation of the protective film-forming composition were as shown in Table 1 below. evaluated. The results are shown in Table 1 below.
- the semiconductor chip with a protective film of Examples 1 to 5 using the coupling agent (E) having a thiol group or a protected thiol group has a float / junction at the junction between the semiconductor chip and the protective film. Peeling and generation of cracks in the protective film were suppressed, and the reliability was high when a history of temperature changes was passed.
- the semiconductor chip with a protective film of Examples 1, 4 and 5 was particularly excellent in reliability.
- the reliability when Example 2 undergoes a history of temperature change compared to Examples 1, 4 and 5 is that the acrylic resin (A-2) having a glass transition temperature of less than ⁇ 3 ° C. as the binder resin (A). ).
- Example 3 undergoes a history of temperature change as compared with Examples 1, 4 and 5 is that the filler relative to the total amount of components other than the solvent in the protective film forming composition It is estimated that the ratio of the blending amount of (F) was less than 55% by mass.
- the protective film-forming films of Examples 1 to 4 using the coupling agent (E-1) having a protective thiol group generation of odor was suppressed.
- the semiconductor chip with a protective film of Comparative Examples 1 and 2 using a coupling agent (H) having no thiol group and a protective thiol group floats and peels off at the joint between the semiconductor chip and the protective film, Or the generation
- the present invention can be used for protecting a metal film such as the back surface of a semiconductor chip.
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Abstract
Description
本出願は、2014年3月28日に日本に出願された特願2014-67468号に基づき、優先権を主張し、その内容をここに援用する。
本発明の保護膜形成用フィルムは、前記カップリング剤が保護チオール基を有するものが好ましい。
本発明の保護膜形成用フィルムは、前記保護膜形成用組成物が、無機充填剤を、前記保護膜形成用組成物における、溶媒以外の成分の総配合量に対する配合量の割合で、55~75質量%の含有量で含有するものが好ましい。
本発明の保護膜形成用フィルムは、前記保護膜形成用組成物が、さらにアクリル樹脂を含有し、前記アクリル樹脂が、グリシジル(メタ)アクリレートを、前記アクリル樹脂を構成する単量体の総量に対して8質量%以下の割合で含む単量体を重合してなるものであるものが好ましい。
また、本発明は、半導体チップの裏面に設けられた金属膜が保護膜で保護された保護膜付き半導体チップの製造方法であって、半導体ウエハの裏面に設けられた金属膜に、前記保護膜形成用フィルムが積層されてなる積層体により、前記積層体の保護膜形成用フィルムから保護膜を形成した後にダイシングするか、又は、前記積層体をダイシングした後に保護膜形成用フィルムから保護膜を形成することを特徴とする保護膜付き半導体チップの製造方法を提供する。
本発明に係る保護膜形成用フィルムは、半導体チップの裏面に設けられた金属膜を保護する保護膜を形成するための保護膜形成用フィルムであって、チオール基(-SH)又は保護チオール基を有するカップリング剤(以下、「カップリング剤(E)」と略記することがある)が配合されてなる保護膜形成用組成物を用いて形成されたことを特徴とする。
かかる保護膜形成用フィルムは、チオール基(-SH)又は保護チオール基を有するカップリング剤を用いたことにより、この保護膜形成用フィルムを金属膜へ貼付して硬化させることで形成した保護膜は、金属膜への接着力が十分に高められる。また、この保護膜は、初期接着力に優れるだけでなく、温度変化の履歴を経た場合でも金属膜からの剥離が抑制され、高い信頼性を有する。
カップリング剤(E)は、一分子中にチオール基及び保護チオール基の少なくとも一方を有し、さらに他の分子と反応(カップリング)可能な官能基を有する。ここで、「他の分子」には、例えば、後述する充填材が保護膜形成用組成物中に配合されている場合には、この充填材を構成している分子も包含される。なお、本明細書において「保護チオール基」とは、チオール基(-SH)の水素原子が水素原子以外の基(保護基)によって置換され、保護された基を意味する。
カップリング剤(E)が一分子中に有するチオール基及び保護チオール基の総数は、特に限定されないが、1~3個であることが好ましく、1又は2個であることがより好ましい。
また、カップリング剤(E)は、他の分子と反応可能な官能基とチオール基又は保護チオール基とが、炭素数が2以上の2価の有機基で連結されているものが好ましい。また、前記2価の有機基はアルキレン基であることが好ましく、炭素数が3以上のアルキレン基であることがより好ましく、炭素数が3~10のアルキレン基であることが特に好ましい。
(R1O)3-Si-X1-S-Y1 ・・・・(1)
(式中、R1はアルキル基であり、3個のR1は互いに同一でも異なっていてもよく;X1はアルキレン基であり;Y1は水素原子、トリアルコキシシリル基、トリアルキルシリル基、トリアルキルシロキシ基、カルバメート基又はカーボネート基である。)
上記のR1における直鎖状又は分岐鎖状のアルキル基は、炭素数が1~10であることが好ましく、このアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、ネオペンチル基、tert-ペンチル基、1-メチルブチル基、n-ヘキシル基、2-メチルペンチル基、3-メチルペンチル基、2,2-ジメチルブチル基、2,3-ジメチルブチル基、n-ヘプチル基、2-メチルヘキシル基、3-メチルヘキシル基、2,2-ジメチルペンチル基、2,3-ジメチルペンチル基、2,4-ジメチルペンチル基、3,3-ジメチルペンチル基、3-エチルペンチル基、2,2,3-トリメチルブチル基、n-オクチル基、イソオクチル基、ノニル基、デシル基が例示できる。
上記のR1における環状のアルキル基は、炭素数が3~10であることが好ましく、前記アルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、ノルボルニル基、イソボルニル基、1-アダマンチル基、2-アダマンチル基、トリシクロデシル基が例示できる。さらに、R1における環状のアルキル基は、これら環状のアルキル基の1個以上の水素原子が、直鎖状、分岐鎖状又は環状のアルキル基で置換されたものが例示できる。ここで、水素原子を置換する直鎖状、分岐鎖状及び環状のアルキル基としては、R1におけるアルキル基として例示した上記のものが挙げられる。
なお、上記一般式(1)で示した化合物は、4価のSiの三方の各々が(R1O)と結合していることを表している。
また、3個のR1は互いに同一でも異なっていてもよく、すなわち、すべて同一であってもよいし、すべて異なっていてもよく、2個のみ同一であってもよい。
これらの中でも、上記のY1は、水素原子又はトリアルコキシシリル基であることが好ましい。
保護膜形成用組成物における、カップリング剤(E)以外の配合成分で好ましいものとしては、バインダー樹脂(A)が例示できる。バインダー樹脂(A)は、例えば、保護膜形成用フィルムに金属膜への良好な初期接着力を付与し、保護膜及び保護膜形成用フィルムに可撓性及び造膜性を付与するために用いられる成分である。
バインダー樹脂(A)は、1種を単独で用いてもよいし、2種以上を併用してもよい。
なお、本明細書において「(メタ)アクリル酸」とは、アクリル酸及びメタクリル酸の両方を含む概念とする。
非アクリル系エポキシ基含有単量体としては、グリシジルクロトネート、アリルグリシジルエーテル等が例示できる。
これらの中でも、エポキシ基含有単量体としては、エポキシ基含有(メタ)アクリル酸エステルが好ましい。
なお、前記アクリル樹脂を構成する単量体は、エポキシ基含有単量体を含むことにより、相分離の進行に起因して進行する保護膜のグロス値の低下を抑制し易く、レーザー印字による印字部分の識別性を向上させ易くなる。したがって、良好な印字識別性を要求される用途に本発明を適用する場合には、アクリル樹脂を構成する単量体は、エポキシ基含有単量体を含むことが好ましい。そして、アクリル樹脂を構成する単量体は、エポキシ基含有単量体を、アクリル樹脂を構成する単量体の総量に対して0.1質量%以上の割合で含むことが好ましく、1質量%以上の割合で含むことがより好ましく、3質量%以上の割合で含むことが特に好ましい。即ち、アクリル樹脂を構成する単量体は、エポキシ基含有単量体を、アクリル樹脂を構成する単量体の総量に対して、0.1~8質量%の範囲で含むことが好ましく、1~6質量%の範囲で含むことがより好ましく、3~5質量%の範囲で含むことが特に好ましい。
アクリル樹脂を構成する単量体は、前記(メタ)アクリル酸アルキルエステルを、アクリル樹脂を構成する単量体の総量に対して50質量%以上の割合で含むことが好ましく、70質量%以上の割合で含むことがより好ましい。また、アクリル樹脂を構成する単量体は、前記(メタ)アクリル酸アルキルエステルを、アクリル樹脂を構成する単量体の総量に対して92質量%以下の割合で含むことが好ましい。即ち、アクリル樹脂を構成する単量体は、(メタ)アクリル酸アルキルエステルを、アクリル樹脂を構成する単量体の総量に対して、50~92質量%の範囲で含むことが好ましく、70~92質量%の範囲で含むことがより好ましい。
前記(メタ)アクリル酸アルキルエステルとしては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸n-ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ラウリル等の、アルキル基の炭素数が1~18の(メタ)アクリル酸アルキルエステルが例示できる。
そして、保護膜の信頼性を維持しつつ、保護膜のグロス値を向上させるためには、前記アクリル樹脂を構成する単量体は、アルキル基の炭素数が4以上の(メタ)アクリル酸アルキルエステルを、アクリル樹脂を構成する単量体の総量に対して1~12質量%の割合で含むことが好ましく、5~12質量%の割合で含むことがより好ましい。
アルキル基の炭素数が4以上の(メタ)アクリル酸アルキルエステルとしては、(メタ)アクリル酸ブチルが好ましい。
そして、前記アクリル樹脂を構成する単量体は、アルキル基の炭素数が3以下の(メタ)アクリル酸アルキルエステルを、アクリル樹脂を構成する単量体の総量に対して90質量%以下の割合で含むことが好ましい。
アルキル基の炭素数が3以下の(メタ)アクリル酸アルキルエステルとしては、(メタ)アクリル酸メチル又は(メタ)アクリル酸エチルが好ましく、(メタ)アクリル酸メチルがより好ましい。
さらに、前記アクリル樹脂を構成する単量体は、前記(メタ)アクリル酸アルキルエステルのうち、アルキル基の炭素数が4以上の(メタ)アクリル酸アルキルエステルと、アルキル基の炭素数が3以下の(メタ)アクリル酸アルキルエステルとで、アクリル樹脂を構成する単量体の総量を占める構成としてもよい。
前記水酸基含有(メタ)アクリル酸エステルとしては、(メタ)アクリル酸ヒドロキシメチル、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル等が例示できる。
前記アクリル樹脂を構成する単量体は、水酸基含有(メタ)アクリル酸エステルを、アクリル樹脂を構成する単量体の総量に対して1~30質量%の割合で含むことが好ましく、5~25質量%の割合で含むことがより好ましく、10~20質量%の割合で含むことが特に好ましい。
なお、本明細書において、重量平均分子量とは、特に断りのない限り、ゲル・パーミエーション・クロマトグラフィー(GPC)法により測定されるポリスチレン換算値である。
また、前記アクリル樹脂は、ガラス転移温度が6℃以下であることが好ましい。前記アクリル樹脂のガラス転移温度が6℃以下であることで、上述した保護膜のグロス値が向上し、この保護膜にマークや文字等が印字された印字部の認識性がより良好となる。その理由は、必ずしも明らかではないが、前記アクリル樹脂が適度に運動性を有することに起因して、硬化後の保護膜の表面形状が平滑化するためであると推測される。
なお、本明細書において、アクリル樹脂のガラス転移温度は、特に断りのない限り、Foxの式から求められる理論値である。
また、保護膜形成用フィルム(または、保護膜形成用フィルムを形成するための保護膜形成用組成物)は、アクリル樹脂を含有し、前記アクリル樹脂が、グリシジル(メタ)アクリレートを、アクリル樹脂を構成する単量体の総量に対して8質量%以下の割合で含む単量体を重合してなるものが特に好ましい。
保護膜形成用組成物のカップリング剤(E)以外の配合成分で好ましいものとしては、さらに、エポキシ系熱硬化性樹脂(B)及び熱硬化剤(C)が例示できる。エポキシ系熱硬化性樹脂(B)は、硬化により前記保護膜を硬質のものとする成分である。また、熱硬化剤(C)は、エポキシ系熱硬化性樹脂(B)に対する硬化剤として機能するものである。本発明においては、熱硬化剤(C)を用いずにエポキシ系熱硬化性樹脂(B)を用いてもよいが、硬化反応の速度の調節が容易となる点と、前記保護膜の弾性率等の物性を好ましい範囲に容易に調節できる点から、エポキシ系熱硬化性樹脂(B)及び熱硬化剤(C)を併用することが好ましい。
エポキシ系熱硬化性樹脂(B)及び熱硬化剤(C)は、いずれも1種を単独で用いてもよいし、2種以上を併用してもよい。
アミノ基を有するアミン系硬化剤としては、ジシアンジアミドが例示できる。
熱硬化剤(C)の含有量が前記下限値以上であることで、エポキシ系熱硬化性樹脂(B)の硬化が十分に進行し易くなり、保護膜の、半導体チップの前記金属膜に対する接着力がより向上する。また、熱硬化剤(C)の含有量が前記上限値以下であることで、保護膜形成用フィルムの吸湿率の上昇が抑制され、保護膜付き半導体チップの信頼性が向上する。
また、保護膜形成用フィルムにおけるエポキシ系熱硬化性樹脂(B)及び熱硬化剤(C)の総含有量(保護膜形成用組成物におけるエポキシ系熱硬化性樹脂(B)及び熱硬化剤(C)の総配合量)は、バインダー樹脂(A)100質量部に対して、20質量部以上であることが好ましく、40質量部以上であることがより好ましく、60質量部以上であることが特に好ましい。
即ち、保護膜形成用フィルムにおけるエポキシ系熱硬化性樹脂(B)及び熱硬化剤(C)の総含有量は、バインダー樹脂(A)100質量部に対して、20~200質量部であることが好ましく、40~150質量部であることがより好ましく、60~100質量部であることが特に好ましい。
エポキシ系熱硬化性樹脂(B)及び熱硬化剤(C)の前記総含有量がこのような範囲であることで、保護膜の、半導体チップの前記金属膜に対する接着力がより向上し、また、後述する支持シートからの剥離力がより適切な範囲となって、支持シートを保護膜から剥離するときの剥離不良等の抑制効果が高くなる。
さらに、エポキシ系熱硬化性樹脂(B)及び熱硬化剤(C)の前記総含有量が前記上限値以下であることで、上述した前記アクリル樹脂に富む相が連続相となり易く、保護膜付き半導体チップの信頼性が向上する。
保護膜形成用組成物における、カップリング剤(E)以外の配合成分で好ましいものとしては、さらに、硬化促進剤(D)が例示できる。
硬化促進剤(D)は、保護膜形成用フィルムの硬化速度を調整する成分である。
好ましい硬化促進剤(D)としては、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス(ジメチルアミノメチル)フェノール等の第3級アミン;2-メチルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール等のイミダゾール類(1個以上の水素原子が水素原子以外の基で置換されたイミダゾール);トリブチルホスフィン、ジフェニルホスフィン、トリフェニルホスフィン等の有機ホスフィン類(1個以上の水素原子が有機基で置換されたホスフィン);テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート等のテトラフェニルボロン塩等が例示できる。
硬化促進剤(D)は、1種を単独で用いてもよいし、2種以上を併用してもよい。
硬化促進剤(D)の含有量がこのような範囲であることで、保護膜が、高温・高湿度条件下においても優れた接着特性を有し、保護膜付き半導体チップが、厳しい条件に曝された場合でも高い信頼性を有する。
保護膜形成用組成物における、カップリング剤(E)以外の配合成分で好ましいものとしては、さらに、充填剤(F)が例示できる。
充填剤(F)は、保護膜に耐湿性、寸法安定性(弾性率)等を付与する成分であり、具体的には無機充填剤等が例示できる。また、保護膜にレーザーマーキング(レーザー光により保護膜表面を削り取り印字を行うこと)を施す場合、レーザー光により削り取られた部分(印字部分)は、充填剤(F)が露出して反射光を拡散させるため、非印字部分とのコントラストが大きくなって、識別性が向上する。
好ましい前記無機充填剤としては、シリカ、アルミナ、タルク、炭酸カルシウム、酸化チタン、酸化鉄、炭化珪素、窒化ホウ素等の粉末;これらシリカ等を球形化したビーズ;これらシリカ等の単結晶繊維;ガラス繊維等が例示でき、シリカフィラー及びアルミナフィラーが特に好ましい。
また、これら無機充填剤の平均粒子径としては、例えば、0.005~20μmが好ましく、0.01~15μmがより好ましく、0.1~12μmが特に好ましい。ここで、上記の平均粒子径とは、1個の粒子における外径の平均値のことをいう。また、無機充填剤としては、できるだけ平均粒子径の大きなものを用いることが、保護膜の信頼性が向上する観点から好ましい。
充填剤(F)は、1種を単独で用いてもよいし、2種以上を併用してもよい。
このような観点から、本発明において、無機充填剤を用いる場合、保護膜形成用フィルムにおける固形分換算の全質量に対する、充填剤(F)の含有量の割合(保護膜形成用組成物における、溶媒以外の成分の総配合量に対する充填剤(F)の配合量の割合)は、55~75質量%であることが特に好ましい。
保護膜形成用組成物における、カップリング剤(E)以外の配合成分で好ましいものとしては、さらに、着色剤(G)が例示できる。
着色剤(G)は、保護膜付き半導体チップを機器に組み込んだ際に、周囲の装置から発生する赤外線等を遮蔽することで、半導体チップの誤作動を防止する成分として用いられることがある。また、着色剤(G)は、保護膜に製品番号やマーク等を印字した際の文字の識別性を向上させる成分として用いられることがある。すなわち、半導体チップに貼付された保護膜には、レーザーマーキング法により品番等が印字されることがあるが、この場合、保護膜が着色剤(G)を含有していることで、印字部分と非印字部分とのコントラストが大きくななって、識別性が向上する。また、着色剤(G)は、半導体ウエハの研削跡を見難くすることで、意匠性を付与する成分として用いられることがある。
前記染料としては、特に限定されず、酸性染料、反応染料、直接染料、分散染料、カチオン染料等のいずれの染料であってもよい。前記顔料としても、特に限定されず、公知のものを用いることができる。
これらの中でも、着色剤(G)としては、電磁波や赤外線の遮蔽性が良好で、かつレーザーマーキング法による識別性がより向上する点から、黒色顔料を用いることが好ましい。
前記黒色顔料としては、カーボンブラック、酸化鉄、二酸化マンガン、アニリンブラック、活性炭等が例示できるが、これらに限定されない。保護膜付き半導体チップの信頼性を向上させるという観点からは、前記黒色顔料はカーボンブラックが特に好ましい。
保護膜形成用組成物は、カップリング剤(E)、バインダー樹脂(A)、エポキシ系熱硬化性樹脂(B)、熱硬化剤(C)、硬化促進剤(D)、充填剤(F)及び着色剤(G)以外に、本発明の効果を損なわない範囲内において、さらに、これらに該当しないその他の添加剤が配合されてなるものでもよい。
前記その他の添加剤としては、架橋剤、相溶化剤、レベリング剤、可塑剤、帯電防止剤、酸化防止剤、イオン捕捉剤、ゲッタリング剤、連鎖移動剤、エネルギー線重合性化合物、光重合開始剤等が例示できる。例えば、相溶化剤を用いることにより、保護膜形成用フィルムは、前記アクリル樹脂(バインダー樹脂(A))に富む相と、エポキシ系熱硬化性樹脂(B)の硬化物に富む相との相溶性が適宜調整可能となり、適切な相分離構造を設計できる。
前記グロス値は、印字部と非印字部とのコントラストがより向上して、印字部分の識別性がより向上する点から、27以上であることがより好ましい。
一方、前記グロス値の上限値は、特に限定されないが、45であることが好ましい。
保護膜形成用組成物は、上述の各成分以外に、さらに希釈用の溶媒が配合されてなるものが好ましい。
前記溶媒は、特に限定されないが、好ましいものとしては、トルエン、キシレン等の炭化水素;メタノール、エタノール、2-プロパノール、イソブチルアルコール(2-メチルプロパン-1-オール)、1-ブタノール等のアルコール;酢酸エチル等のエステル;アセトン、メチルエチルケトン等のケトン;テトラヒドロフラン等のエーテル;ジメチルホルムアミド、N-メチルピロリドン等のアミド(アミド結合を有する化合物)等が例示できる。
前記溶媒は、1種を単独で用いてもよいし、2種以上を併用してもよい。
保護膜形成用フィルムの支持シートへの対向面は、支持シートの保護膜形成用フィルムへの対向面と同じ形状及びサイズであるか、又は支持シートの保護膜形成用フィルムへの対向面よりも小さいサイズである。また、保護膜形成用フィルムの半導体ウエハへの対向面は、半導体ウエハの保護膜形成用フィルムへの対向面と略同等の形状及びサイズであるか、又は半導体ウエハの保護膜形成用フィルムへの対向面全面を被覆できる形状及びサイズである。
ここに示す保護膜形成用複合シート1は、支持シート11の表面11a上に保護膜形成用フィルム12が積層されてなるものであり、保護膜形成用フィルム12の支持シート11への対向面は、支持シート11の保護膜形成用フィルム12への対向面(前記表面11a)と同じ形状及びサイズである。ただし、上述のように、ここに示す保護膜形成用複合シート1は、本発明に係る保護膜形成用フィルムを用いたものの一実施形態を例示するに過ぎず、保護膜形成用複合シートはこれに限定されない。
また、支持シートは着色フィルムであってもよい。
なお、支持シートが複数層からなる場合には、各層の合計の厚さが、上記の好ましい支持シートの厚さとなるようにするとよい。
各成分の配合時における添加順序は特に限定されず、2種以上の成分を同時に添加してもよい。
配合時に各成分を混合する方法についても、特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法;ミキサーを用いて混合する方法;超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
各成分の添加及び混合時の温度並びに時間は、各成分が劣化しない限り特に限定されず、適宜調節すればよいが、例えば、温度は15~30℃であることが好ましい。
本発明に係る保護膜形成用フィルムは、半導体チップの裏面に設けられた金属膜が保護膜で保護された保護膜付き半導体チップの製造に利用できる。具体的には、半導体ウエハの裏面に設けられた金属膜に、前記保護膜形成用フィルムが積層されてなる積層体により、前記積層体の保護膜形成用フィルムから保護膜を形成した後にダイシングするか、又は、前記積層体をダイシングした後に保護膜形成用フィルムから保護膜を形成することにより、前記保護膜付き半導体チップを製造できる。詳細は以下のとおりである。
金属膜は単層からなるものでもよいし、二層以上の複数層からなるものでもよく、複数層からなる場合、これら複数層は、互いに同一でも、異なっていてもよい。
保護膜形成用フィルムの貼付対象となる金属膜(複数層からなる金属膜の場合には、保護膜形成用フィルムが貼付される金属膜)の厚さは、通常、50~300nmであることが好ましい。
次いで、この保護膜を備えた半導体ウエハ(保護膜付き半導体ウエハ)を、ウエハ表面に形成された回路毎にダイシングする。ダイシングは、半導体ウエハ及び保護膜を共に切断するように行われ、ダイシングによって保護膜付き半導体ウエハは、複数の保護膜を備えた半導体チップに分割される。このダイシングは、例えば、保護膜の表面にダイシングテープを貼付し、市販のダイシング装置を用いて、上記の保護膜が貼付されたシリコンウエハを適宜の寸法にダイシングする方法とすることができる。
次いで、得られた半導体チップを、コレット等の汎用手段によりピックアップすることで、裏面の金属膜が保護膜で保護された半導体チップ(保護膜付き半導体チップ)が得られる。
また、保護膜形成用フィルムの硬化は、ダイシング前ではなくダイシング後に行ってもよい。
ここで、上述した信頼性としては、例えば、保護膜付き半導体チップに熱履歴を付与した際、半導体チップと保護膜との接合部における浮き・剥がれ、及び保護膜におけるクラックが発生した試験サンプルが、サンプル数=25個において0~3個程度である場合に、信頼性が高いということができる。
また、保護膜形成用フィルムの評価項目としては、臭気の評価も挙げられる。この臭気の評価は、例えば、保護膜形成用フィルムを20cm×20cmの大きさに切り出し、切り出した試験片から、25℃の温度条件下で剥離フィルムを剥離させた際の臭気の有無で官能評価することができる。
[実施例1]
下記成分を下記表1に示す量で混合及び撹拌し、さらにメチルエチルケトン700質量部を混合して希釈することで、保護膜形成用組成物を調製した。この間、混合物の温度は25℃となるように調整した。
(1)アクリル樹脂(A-1):アクリル酸ブチル(10質量部)、アクリル酸メチル(70質量部)、メタクリル酸グリシジル(5質量部)及びアクリル酸2-ヒドロキシエチル(15質量部)を共重合してなる、重量平均分子量35万、ガラス転移温度-1℃の共重合体
(2)アクリル樹脂(A-2):アクリル酸ブチル(15質量部)、アクリル酸メチル(65質量部)、メタクリル酸グリシジル(5質量部)及びアクリル酸2-ヒドロキシエチル(15質量部)を共重合してなる、重量平均分子量35万、ガラス転移温度-4℃の共重合体
[エポキシ系熱硬化性樹脂(B)]
(1)エポキシ系熱硬化性樹脂(B-1):ビスフェノールA型エポキシ樹脂(エポキシ樹脂当量220~240g/mol)
(2)エポキシ系熱硬化性樹脂(B-2):ジシクロペンタジエン型エポキシ樹脂(DIC社製「エピクロンHP-7200HH)(エポキシ当量274~286g/mol)
[熱硬化剤(C)]
(1)熱硬化剤(C-1):ジシアンジアミド(ADEKA社製「アデカハードナー3636AS」)
[硬化促進剤(D)]
(1)硬化促進剤(D-1):2-フェニル-4,5-ジヒドロキシメチルイミダゾール(四国化成工業社製「キュアゾール2PHZ)
[チオール基又は保護チオール基を有するカップリング剤(E)]
(1)カップリング剤(E-1):保護チオール基を有するシランカップリング剤(信越化学工業社製「X-12-1056ES」、(CH3O)3Si-C3H6-S-Si(OC2H5)3)
(2)カップリング剤(E-2):チオール基を有するシランカップリング剤(信越化学工業社製「KBM-803」、(CH3O)3Si-C3H6-SH)
[充填剤(F)]
(1)無機充填剤(F-1):溶融石英フィラー(平均粒径10μm)
[着色剤(G)]
(1)着色剤(G-1):カーボンブラック(三菱化学社製「MA600」、平均粒径20nm)
[チオール基及び保護チオール基を有しないカップリング剤(H)]
(1)カップリング剤(H-1):チオール基及び保護チオール基をいずれも有しないオリゴマータイプシランカップリング剤(信越化学工業社製「X-41-1056」)
(2)カップリング剤(H-2):チオール基及び保護チオール基をいずれも有しないモノマータイプシランカップリング剤(信越化学工業社製「KBM-403」)
#2000研磨したシリコンウエハ(200mm径、厚さ200μm)の研磨面に、チタン、ニッケル及び金を、この順で、それぞれ厚さが100nmとなるように蒸着して成膜した。そして、上記で得られた保護膜形成用複合シートから剥離フィルムを剥離させ、テープマウンター(リンテック社製「Adwill RAD-3600 F/12)を用いて、保護膜形成用フィルムを70℃に加熱しながら金膜の表面に貼付した。次いで、もう一方の剥離フィルム(PETフィルム)も除去し、130℃で2時間加熱することにより、保護膜形成用フィルムを硬化させ、シリコンウエハの裏面側における金膜の表面に保護膜を形成した。
次いで、前記保護膜の表面にダイシングテープ(リンテック社製「Adwill D-686H」)を貼付し、ダイシング装置 (ディスコ社製「DFD651」)を用いて、上記の保護膜が貼付されたシリコンウエハを3mm×3mmのサイズにダイシングして、保護膜付き半導体チップを得た。
(信頼性の評価)
上記手順で得られた保護膜付き半導体チップを、半導体チップが実際に実装されるプロセスを模倣した条件(プレコンディション)で処理した。すなわち、まず、恒温器中において保護膜付き半導体チップを125℃で24時間ベイキングし、さらに、恒温恒湿器中において85℃、相対湿度85%の条件下で168時間放置して吸湿させ、恒温恒湿器内から取り出した後、直ちにプレヒート160℃、ピーク温度260℃、加熱時間30秒間の条件でIRリフロー炉に3回通した。これらプレコンディションで処理した保護膜付き半導体チップ25個を、冷熱衝撃装置(ESPEC社製「TSE-11-A」)内に設置し、-65℃で10分間保持してから150℃で10分間保持するサイクルを1000回繰り返した。
次いで、走査型超音波探傷装置(日立建機ファインテック社「Hi-focus ST120」)を用いた、140MHzの周波数による反射法での測定により、冷熱衝撃装置から取り出した25個の保護膜付き半導体チップについて、半導体チップと保護膜との接合部における浮き・剥がれ、及び保護膜におけるクラックの有無を確認した。そして、浮き・剥がれ及びクラックの少なくとも一方が認められた保護膜付き半導体チップの個数が0個の場合を「a」、1~3個の場合を「b」、4個以上の場合を「c」として評価した。結果を下記表1に示す。
(臭気の評価)
上記手順で得られた保護膜形成用フィルムを20cm×20cmの大きさに切り出し、得られた試験片について、25℃の温度条件下で剥離フィルムを剥離させ、このときの臭気の有無を官能評価し、臭気を感じなかった場合を「a」、臭気を感じた場合を「c」として評価した。結果を下記表1に示す。
[実施例2~5、比較例1~2]
保護膜形成用組成物調製時の配合成分の種類及び量を下記表1に示すとおりとした点以外は、実施例1と同様に、保護膜形成用フィルム及び保護膜付き半導体チップを製造し、評価した。結果を下記表1に示す。
これに対して、チオール基及び保護チオール基を有しないカップリング剤(H)を用いた比較例1~2の保護膜付き半導体チップは、半導体チップと保護膜との接合部における浮き・剥がれ、又は保護膜におけるクラックの発生が認められ、温度変化の履歴を経た場合の信頼性が低かった。
Claims (6)
- 半導体チップの裏面に設けられた金属膜を保護する保護膜を形成するための保護膜形成用フィルムであって、
チオール基又は保護チオール基を有するカップリング剤が配合されてなる保護膜形成用組成物から形成されたことを特徴とする保護膜形成用フィルム。 - 前記カップリング剤が保護チオール基を有することを特徴とする請求項1に記載の保護膜形成用フィルム。
- 前記保護膜形成用組成物は、無機充填剤を、前記保護膜形成用組成物における、溶媒以外の成分の総配合量に対する配合量の割合で、55~75質量%の含有量で含有することを特徴とする請求項1又は2に記載の保護膜形成用フィルム。
- 前記保護膜形成用組成物は、ガラス転移温度が-3℃以上であるアクリル樹脂を含有することを特徴とする請求項1又は2に記載の保護膜形成用フィルム。
- 前記保護膜形成用組成物は、アクリル樹脂を含有し、前記アクリル樹脂が、グリシジル(メタ)アクリレートを、前記アクリル樹脂を構成する単量体の総量に対して8質量%以下の割合で含む単量体を重合してなるものであることを特徴とする請求項1又は2に記載の保護膜形成用フィルム。
- 半導体チップの裏面に設けられた金属膜が保護膜で保護された保護膜付き半導体チップの製造方法であって、
半導体ウエハの裏面に設けられた金属膜に、請求項1又は2に記載の保護膜形成用フィルムが積層されてなる積層体により、前記積層体の保護膜形成用フィルムから保護膜を形成した後にダイシングするか、又は、前記積層体をダイシングした後に保護膜形成用フィルムから保護膜を形成することを特徴とする保護膜付き半導体チップの製造方法。
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JP6458290B2 (ja) | 2019-01-30 |
KR102355113B1 (ko) | 2022-01-24 |
CN106030763A (zh) | 2016-10-12 |
SG11201606984PA (en) | 2016-09-29 |
TW201541578A (zh) | 2015-11-01 |
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