Classifications

• • C—CHEMISTRY; METALLURGY
  • 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
  • C09J135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J135/02—Homopolymers or copolymers of esters
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/12—Esters of phenols or saturated alcohols
  • C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5397—Phosphine oxides
• • C—CHEMISTRY; METALLURGY
  • 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
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • 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
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • C—CHEMISTRY; METALLURGY
  • 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
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/7402—Wafer tapes, e.g. grinding or dicing support tapes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
• • C—CHEMISTRY; METALLURGY
  • 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
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
• • C—CHEMISTRY; METALLURGY
  • 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
  • C09J2433/00—Presence of (meth)acrylic polymer
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/7412—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support the auxiliary support including means facilitating the separation of a device or wafer from the auxiliary support
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/7416—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/744—Details of chemical or physical process used for separating the auxiliary support from a device or a wafer

Definitions

• the present invention relates to a temporary fixing composition used for temporary fixing.
• An electronic device is obtained by using a substrate made of an inorganic material such as silicon as a main material, and performing processes such as forming an insulating film on the surface, forming a circuit, and thinning the substrate by grinding.
• a wafer-type substrate for processing it is often used with a thickness of about several hundred ⁇ m, but since many substrates are made of fragile and fragile materials, breakage prevention measures are taken especially when thinning by grinding. is required.
• a method of attaching a protective tape for temporary fixing which can be peeled off after the processing process is completed, to the surface opposite to the surface to be ground (also referred to as the back surface).
• This tape uses an organic resin film as a base material, and while it is flexible, it is insufficient in strength and heat resistance, and is not suitable for use in processes where high temperatures are applied.
• Necessary properties of the adhesive include (1) having a viscosity suitable for application and being a Newtonian fluid (or shear viscosity independent of shear rate), (2) grinding and polishing when thinning the substrate. (3) Similarly, when thinning the substrate, in order to avoid damage to the substrate due to local concentration of the load of the grindstone applied to the substrate during grinding and polishing, the load is distributed in the in-plane direction. Appropriate hardness to prevent local subsidence of the substrate and maintain flatness, (4) Heat resistance to withstand insulating film formation and solder reflow process, (5) Chemical resistance to withstand thinning and resist process, ( (7) cohesion properties such that no adhesive residue remains on the substrate after peeling;
• Patent Document 1 a technique for peeling the adhesive layer from the support by irradiating the adhesive containing a light-absorbing substance with high-intensity light to decompose the adhesive layer
• Patent Document 2 A technique has been proposed in which a hot-melt hydrocarbon-based compound is used as an adhesive and bonding/separation is performed in a heat-melted state (Patent Document 2).
• the former technique requires an expensive device such as a laser, and has problems such as a long processing time per substrate.
• the latter technique is simple because it can be controlled only by heating.
• Patent Document 3 a method for dismantling an adhesive body, which includes a step of irradiating an adhesive body formed by the method with excimer light having a central wavelength of 172 nm or 193 nm, wherein at least one base material exhibits transparency to the excimer light.
• Patent Document 3 does not describe the use of longer wavelength light.
• the present invention does not require the use of high-energy excimer light for ablation.
• Patent Document 4 A technique for an adhesive encapsulating composition for use in electronic devices, which contains a polyisobutene resin and a polyfunctional (meth)acrylate as a resin composition and does not contain a tackifier, has been disclosed (Patent Document 4). It also describes the use of a monofunctional (meth)acrylate as a monomer, but the glass transition temperature of the monofunctional (meth)acrylate is not described. There was a problem that the expression method of the flexibility required when applying was unclear.
• Patent Document 6 a resin composition for adhesion between different substrates containing monofunctional (meth)acrylate, polyfunctional (meth)acrylate, and isobutene/maleic anhydride copolymer as a resin composition, and a method of adhesion and dismantling.
• Patent Document 6 the type of polymer disclosed in Patent Document 6 is limited in that it contains a component derived from maleic anhydride, and the adhesion method is not described in detail.
• Patent Document 6 does not describe spin coating compatibility such as viscosity.
• Patent Document 7 A technique of a composite resin composition composed of a urethane (meth)acrylate resin containing an olefinic polymer structure and a polyisobutylene resin, which can be cured by active energy rays, has been disclosed (Patent Document 7).
• component (A) a (meth)acrylate compound having a polyisobutylene skeleton
• component (B) a (meth)acrylamide compound, and 0.1 to 15 parts of (B) per 100 parts by mass of component (A).
• Patent Document 8 A photocurable composition containing parts by weight has been disclosed (Patent Document 8).
• Patent Documents 7 and 8 do not describe temporary fixation applications.
• the present invention can provide the following aspects.
• a temporary fixing composition containing the following (A) to (C).
• (A) bifunctional (meth)acrylate containing no cyclic skeleton (B) bifunctional (meth)acrylate having a cyclic skeleton (C) photoradical polymerization initiator
• Component (C) is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis( ⁇ 5 -2,4-cyclopentadien-1-yl) )-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one , 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, 1-[4-(phenylthio)phenyl]-1,2- selected from the group consisting of octanedione 2-O-benzoyloxime and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone
• a temporary fixing adhesive comprising the temporary fixing composition according to any one of aspects 1-19.
• a first cured layer comprising a temporary fixing composition containing components (A), (B), and (C) but not containing component (D);
• a cured body having a second cured layer and having different component concentration distributions in the thickness direction.
• LTHC light-to-heat conversion
• a structure comprising the cured body according to any one of aspects 30 to 33 and an adherend.
• Aspect 36 a step of applying a temporary fixing composition containing components (A), (B), and (C) but not containing component (D) onto the wafer, and partially curing the composition as necessary; a step of applying the temporary fixing composition according to aspect 2 onto a transparent substrate and partially curing the composition, if necessary;
• a method for manufacturing a structure comprising a step of bonding the surfaces of the wafer and the transparent substrate on which the temporary fixing composition is applied to each other by photocuring after the surfaces thereof are brought into close contact with each other.
• FIG. 37 a step of applying the temporary fixing composition according to aspect 1, which contains components (A), (B), and (C) but does not contain component (D), onto a wafer, and partially cures as necessary; , applying, drying and curing a light-to-heat conversion (LTHC) layer on a transparent substrate;
• a method for manufacturing a structure comprising a step of bringing the surface of the wafer coated with the temporary fixing composition and the surface of the transparent substrate coated with the LTHC layer into close contact with each other and then bonding them by photocuring.
• a composition that is excellent in curing speed, spin coating process compatibility, heat resistance, low outgassing under a heated nitrogen atmosphere and under reduced pressure, and peeling speed can be obtained.
• a temporary fixing composition is obtained which is compatible with UV laser stripping processes, etc.).
• a monofunctional (meth)acrylate refers to a compound having one (meth)acryloyl group in one molecule.
• Bifunctional (meth)acrylate refers to a compound having two (meth)acryloyl groups in one molecule, and in the present specification, it is distinguished from other polyfunctional (meth)acrylates and monofunctional (meth)acrylates. be done.
• polyfunctional (meth) acrylate refers to a compound having two or more (meth) acryloyl groups in one molecule, but depending on the context, difunctional (meth) acrylates may be excluded. Please note.
• a polymerizable compound such as (meth)acrylate means a monomer, and a product obtained by polymerizing them is called a polymer.
• a temporary fixing composition (hereinafter sometimes simply referred to as "composition") according to an embodiment of the present invention is characterized by containing the following components (A) to (C).
• the composition preferably does not contain (meth)acrylates other than components (A) and (B).
• a composition according to an embodiment may be free of (meth)acrylates other than difunctional (meth)acrylates.
• the composition according to another embodiment contains (meth)acrylates other than bifunctional (meth)acrylates (for example, monofunctional (meth)acrylates or trifunctional (meth)acrylates) as long as the effects of the present invention are not impaired. It may be contained, and its amount may be more than 0 parts by mass and 50 parts by mass or less when the total of components (A) and (B) is 100 parts by mass.
• the bifunctional (meth)acrylate having no cyclic skeleton which is the component (A), refers to those having neither an alicyclic skeleton nor an aromatic ring skeleton.
• component (A) a bifunctional (meth)acrylate having a linear alkyl group or a branched alkyl group is preferred.
• the alkyl group may have a substituent, such as a hydroxyalkyl group.
• component (A) examples include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol.
• HPHPAH hydroxypivalyl hydroxypivalate bis[6-(acryloyloxy)hexanoate
• di(meth) of ⁇ -caprolactone adduct of neopentylglycol hydroxypivalate examples thereof include compounds having
• the molecular weight of component (A) may be 250 or more, more preferably 300 or more, and even more preferably 500 or more, from the viewpoint of moderately increasing the viscosity of the resulting composition.
• the upper limit of the molecular weight of component (A) is not particularly limited, it may be, for example, 2,000 or less, preferably 1,000 or less, from the viewpoint of not excessively increasing the viscosity of the composition.
• Component (A) preferably has 18 to 40 carbon atoms, more preferably 18 to 32 carbon atoms, such as isostearyl group, isotetracosanyl group (2-decyl-1-tetradecanyl group, etc.), isotriacontane group, etc.
• It may have a structure derived from a branched chain alkyl group such as a nyl group (2-tetradecyl-1-octadecanyl group, etc.).
• a branched chain alkyl group such as a nyl group (2-tetradecyl-1-octadecanyl group, etc.).
• component (A) may be a polyhydric alcohol (more preferably a dihydric or trihydric alcohol) or a di(meth)acrylate derived from an alkyl ester. More specifically, the component (A) has an aliphatic hydrocarbon skeleton or has an aliphatic hydrocarbon skeleton having a hydroxy group (preferably a linear or branched chain having (meth)acryloyl groups at both ends). (consisting of an aliphatic hydrocarbon), having an ester skeleton (preferably consisting of an aliphatic ester having (meth)acryloyl groups at both ends), or having both characteristics.
• component (A) may have a structure having no alkyl ether skeleton.
• the bifunctional (meth)acrylate having a cyclic skeleton as component (B) is a compound having one or more ring structures, and the ring may be carbocyclic or heterocyclic. It may be a combination.
• component (B) may have one or more aromatic rings, more preferably a plurality of aromatic rings, and a condensed aromatic ring (for example, fluorene skeleton, naphthalene skeleton, indene skeleton, anthracene skeleton, etc.) is more preferable.
• the component (B) has a spiro ring structure, so that a remarkable effect is obtained in which excellent outgassing property and heat resistance are compatible with each other while obtaining excellent viscosity in the composition.
• component (B) include bisphenolfluorene derivatives (e.g., 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate), biscresolfluorene derivatives, cycloalkane derivatives (cyclodecane derivatives, cyclooctane derivatives, etc.).
• component (B) has a phenol ether skeleton, so that heat resistance can be improved in combination with component (A) described above.
• the molecular weight of component (B) is not particularly limited, it may be, for example, 200 or more, more preferably 300 or more, and even more preferably 500 or more from the viewpoint of moderately increasing the viscosity of the composition.
• the upper limit of the molecular weight of component (B) is not particularly limited, it may be, for example, 2,000 or less, preferably 1,000 or less, from the viewpoint of not excessively increasing the viscosity of the composition.
• Component (B) is preferably liquid with a viscosity of 500 mPa ⁇ s or more at 23°C, or solid at 23°C.
• the component (B) has an aromatic ring and the number of carbon atoms in the alkyl chain portion is relatively small (that is, the ratio of the aliphatic portion to the aromatic ring is relatively small) from the viewpoint of improving the outgassing property.
• the number of carbon atoms in the alkyl chain portion of component (B) may be 20 or less, preferably 10 or less, and even more preferably 5 or less.
• component (B) examples include 1,3-di(meth)acryloyloxyadamantane, dicyclopentanyl di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, 2,2-bis(4- (Meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloxytetraethoxyphenyl)propane, isocyanuric acid
• examples thereof include ethylene oxide-modified di(meth)acrylates and di(meth)acrylates having a fluorene skeleton (eg, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene di(meth)acrylate).
• di(meth)acrylates having a fluorene skeleton are commercially available as A-BPEF-2 manufactured by Shin-Nakamura Chemical Co., Ltd., and OGSOL GA-5060P, EA-0300, GA-5060P, and GA-2800 manufactured by Osaka Gas Chemicals. things are available.
• component (B) includes ethoxylated bisphenol A di(meth)acrylate represented by the following formula (1).
• the compounding ratio of component (A) and component (B) is preferably in the range of 5 to 95:5 to 95 by mass with respect to a total of 100 parts by mass, from the viewpoint of suitability for the spin coating process.
• the range of 25-75:25-75 is more preferred, and the range of 33-67:33-67 is even more preferred.
• the photoradical polymerization initiator which is the component (C) is, for example, ultraviolet light or visible light (for example, wavelength 350 nm to 700 nm, preferably 385 nm to 700 nm, more preferably 385 nm to 500 nm, still more preferably 385 nm to 450 nm).
• ultraviolet light or visible light for example, wavelength 350 nm to 700 nm, preferably 385 nm to 700 nm, more preferably 385 nm to 500 nm, still more preferably 385 nm to 450 nm.
• the reaction speed, heat resistance after curing, low outgassing, the wavelength of the UV laser used for UV laser peeling described later, and the absorption wavelength range of the UV absorber used for the UV laser peeling At least one selected from acylphosphine oxide-based compounds, titanocene-based compounds, and ⁇ -aminoalkylphenone-based compounds is preferable in terms of having absorption characteristics in different regions.
• the temporary fixing composition having a structure described later it is not a layer for responding to the UV laser peeling process, but is used for temporary fixing to prevent breakage from joining the base material to be processed with the support base material to the heating process.
• an oxime ester compound can also be selected as the photoradical polymerization initiator for the resin composition for.
• acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Among these, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is particularly preferred.
• Titanocene compounds include bis( ⁇ 5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.
• ⁇ -Aminoalkylphenone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1 -(4-morpholin-4-ylphenyl)-butan-1-one and the like.
• Oxime ester compounds include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]ethanone 1-(O-acetyloxime) and the like. Among these, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) is preferred.
• Photoradical polymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis( ⁇ 5 -2,4-cyclo Pentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)- Butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, 1-[4-(phenylthio)phenyl] -1,2-octanedione 2-O-benzoyloxime and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetylox
• the most preferred radical photopolymerization initiator is an acylphosphine oxide compound.
• Preferred acylphosphine oxide compounds are bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and/or 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• These photo-radical polymerization initiators are highly sensitive and have photofading properties, so they are excellent in deep-part curability.
• the absorption wavelength range for generating radicals extends to a relatively long wavelength range.
• bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide has a wavelength range of up to about 440 nm, which is significantly different from the absorption wavelength range of the UV absorber used in the UV laser peeling process described later.
• radical polymerization can be initiated with light having a longer wavelength where the degree of inhibition of UV curing by the added UV absorber is small. Therefore, even in the coexistence of a UV absorber, radical polymerization can be initiated and cured at a relatively high speed and with high efficiency.
• the photoradical polymerization initiator can be selected from the absorbance.
• a solvent eg, acetonitrile, toluene, etc.
• the absorbance at a wavelength of 365 nm is 0.1%. 5 or more, an absorbance of 0.5 or more at a wavelength of 385 nm, and an absorbance of 0.5 or more at a wavelength of 405 nm.
• a photoradical polymerization initiator can be selected from.
• An example of a compound that satisfies such conditions is 1-[9-ethyl, which has an absorbance of 0.5 or more at a wavelength of 365 nm when dissolved in acetonitrile as a solvent at a concentration of 0.1% by mass.
• bis( ⁇ 5 -2,4-cyclopentadien-1-yl)- which has an absorption wavelength region in the range of 400 to 500 nm
• Bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium can also be used as a photoradical polymerization initiator.
• the amount of photoradical polymerization initiator used is 0.01 to 5 parts per 100 parts by mass of (A) to (B) in terms of reaction speed, heat resistance after curing, and low outgassing. Part by weight is preferred, and 0.1 to 1 part by weight is more preferred. If the amount of component (C) is 0.01 parts by mass or more, sufficient curability will be obtained, and if it is 5 parts by mass or less, low outgassing properties and heat resistance will not be impaired.
• the UV absorber that can be used as the component (D) that may be contained in the present composition is, for example, a molecule that is decomposed/vaporized by irradiation with an ultraviolet or visible laser, and the decomposition/vaporization is a support group. A compound that occurs at the interface between the material (or support) and the temporary fixing agent, thereby losing the adhesive strength between the temporary fixing agent and the support substrate (or support) that had been maintained until just before the peeling process.
• UV absorbers include benzotriazole-based compounds and hydroxyphenyltriazines in terms of the degree of overlap of the UV absorption wavelength region with the UV laser wavelength, UV absorption characteristics at the same wavelength, low outgassing, and heat resistance. One or more selected from the group compounds are preferred.
• benzotriazole compounds include 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2,2′-methylenebis[6-(2H-benzo triazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl) -4-(1,1,3,3-tetramethylbutyl)phenol and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriazole
• One or more selected from the group consisting of is particularly preferable from the viewpoint of compatibility with the resin component, UV absorption properties, low outgassing properties, and heat resistance.
• Hydroxyphenyltriazine compounds include 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl )-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and At least one selected from the group consisting of 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine has compatibility with the resin component, UV It is particularly preferred in terms of absorption properties, low outgassing properties, and heat resistance.
• the most preferred UV absorber is 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1, 3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, or 2,2' -methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol].
• components (A) and (B) have excellent compatibility with components (A) and (B), have a high melting point, and have a relatively low vapor pressure under temperature conditions of about 300°C or less, so they can be selected within a wide range of usage amounts. Also, it can contribute to the reduction of outgassing from the temporary fixing composition after curing under this temperature condition.
• the following absorbers selected from the viewpoint of UV transmittance are most preferably used.
• the component (D) having such a UV transmittance provides an effect of being able to appropriately control the curing and peeling of the composition.
• the transmittance is 50% or less at a wavelength of 355 nm at an optical path length of 1 cm. , and a transmission of greater than 50% at wavelengths between 385 and 420 nm. More preferably, it has a transmittance of 40% or less at a wavelength of 355 nm and a transmittance of 60% or more at a wavelength of 385 to 420 nm.
• Examples of the most preferred (D) UV absorbers include the following.
• the transmittance at a wavelength of 355 nm at an optical path length of 1 cm is 20% or less, and the transmittance is 60% or more at a wavelength of 385 to 420 nm.
• 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (BASF Tinuvin 900, Adeka Adastave LA-24, Everlight Chemical EVERSORB 76, EVERSORB 234, molecular weight 447).
• the transmittance at a wavelength of 355 nm at an optical path length of 1 cm is 30% or less, and the transmittance is 70% or more at a wavelength of 385 to 420 nm.
• 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (BASF Tinuvin 928 , Everlight Chemical EVERSORB 89/89FD, molecular weight 442).
• the transmittance at a wavelength of 355 nm at an optical path length of 1 cm is 40% or less, and the transmittance at a wavelength of 385 to 420 nm is 90% or more.
• 2-[4-[(2-hydroxy-3-(2′-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3, 5-triazine BASF Tinuvin 405, molecular weight 584).
• the transmittance at a wavelength of 355 nm at an optical path length of 1 cm is 10% or less, and the transmittance is 80% or more at a wavelength of 385 to 420 nm 2 ,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine (BASF Tinuvin 460, molecular weight 630).
• the UV transmittance of the cured product herein is a value obtained by reflectometric spectroscopy. Specifically, the transmittance was measured using a cured film having a thickness of about 50 ⁇ m sandwiched between PET resin sheets under the following conditions, using a reflectance spectrometer (V-650 manufactured by JASCO Corporation). ).
• the amount of the UV absorber used as component (D) is preferably 0.01 to 5 parts by mass, more preferably 0.5 to 2.5 parts by mass, based on 100 parts by mass of (A) to (B) in total. .
• the amount is 0.01 parts by mass or more, a sufficient UV laser peeling speed can be obtained, and when it is 5 parts by mass or less, there is no risk of impairing low outgassing properties and heat resistance.
• a composition having such properties can be suitably used in processes including high-temperature vacuum processes such as electrode formation by ion implantation, annealing, and sputtering, particularly in the backside process after thinning.
• the viscosity of the composition according to the embodiment of the present invention is preferably in the range of 100 to 10000 mPa s at 23 ° C. (under atmospheric pressure), more preferably in the range of 560 to 9200 mPa s. More preferably, it is in the range of up to 6400 mPa ⁇ s.
• the outgassing property of the cured body of the composition according to the embodiment of the present invention can be evaluated by the 2% mass loss temperature.
• the 2% mass loss temperature of the cured product in a nitrogen atmosphere is preferably 250° C. or higher, more preferably 270° C. or higher, and even more preferably 300° C. or higher.
• the 2% mass loss temperature of the cured product in an environment reduced to 30 to 100 Pa is preferably 150° C. or higher, more preferably 200° C. or higher, and even more preferably 250° C. or higher.
• the 2% mass loss temperature can be evaluated by a combination of multiple conditions. It is known in the art that 2% mass loss temperatures measured under different environments are generally not interchangeable. That is, it is known that from the 2% mass loss temperature in one environment, the value in another environment cannot be easily inferred.
• a cured film having a thickness of 50 ⁇ m is produced using the temporary fixing composition of the present invention, one or more of the following conditions are preferably satisfied, and more preferably all of them are satisfied.
• the following conditions can be satisfied by using, for example, the above-described UV absorbers and photoradical polymerization initiators.
• the light transmittance of the cured film the light transmittance in the wavelength range of 395 nm or more among the wavelengths of the light source used for curing should be 70% or more.
• the light transmittance of the cured film the light transmittance in the wavelength region of 350 nm or more and less than 395 nm, preferably 385 nm or more and less than 395 nm, of the wavelengths of the light source used for curing is 20% or more.
• the light transmittance at the wavelength (355 nm) of the UV laser used for UV laser peeling should be 1% or less.
• a temporary fixing agent having such properties can be suitably used in a process including a high-temperature vacuum process such as electrode formation by ion implantation, annealing, or sputtering, particularly in the back surface process after thinning.
• compositions of the present invention may employ antioxidants to maintain strippability after exposure to elevated temperatures.
• Antioxidants include methylhydroquinone, hydroquinone, 2,2-methylene-bis(4-methyl-6-tertiarybutylphenol), catechol, hydroquinone monomethyl ether, monotertiarybutylhydroquinone, 2,5-ditertiarybutylhydroquinone.
• the amount of the antioxidant used is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass in total of (A) to (D).
• the amount is 0.001 parts by mass or more, the peelability after exposure to high temperatures can be maintained, and when the amount is 3 parts by mass or less, good adhesiveness can be obtained and uncured state does not occur.
• a monofunctional (meth)acrylate may be further added as component (E), and the amount added is based on a total of 100 parts by mass of components (A) to (B).
• (E) component may be more than 0 mass parts and 50 mass parts or less.
• Component (E) is preferably a (meth)acrylate having a linear or branched alkyl group.
• Such compounds include, for example, ethyl (meth)acrylate, butyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicodecyl (meth)acrylate, behenyl (meth)acrylate, 2 -decyl-1-tetradecanyl (meth)acrylate, 2-tetradecyl-1-octadecanyl (meth)acrylate and the like.
• a polymer may be added as component (F), and the amount of component (F) added is 100 parts by mass in total of components (A) to (B). It may be more than 0 parts by mass and 50 parts by mass or less.
• Component (F) desirably has properties that do not impair the light transmittance of the cured product of the composition.
• Component (F) includes polymers made from polyvinyl chloride, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, vinyl acetate, modified vinyl acetate, etc., vinyl acetate-(meth)acrylic copolymer, styrene-(meth) ) acrylic copolymer, vinyl acetate-(meth)acrylic acid ester copolymer, (meth)acrylic-silicon copolymer, (meth)acrylic-urethane copolymer, natural rubber, synthetic rubber, etc. From the viewpoint of improving heat resistance, it is preferable to add only a small amount of those having a glass transition temperature of 300° C. or lower (polyisobutene, etc.) part or less), it is more preferable not to add.
• the viscosity of the composition of the present invention is preferably 100 mPa ⁇ s or more, more preferably 1000 mPa ⁇ s or more, and most preferably 2000 mPa ⁇ s or more, from the viewpoint of coatability and workability.
• the viscosity of the composition of the present invention is preferably 10,000 mPa ⁇ s or less, more preferably 5,000 mPa ⁇ s or less, and most preferably 4,000 mPa ⁇ s or less, from the viewpoint of applicability and workability. If it is 100 mPa ⁇ s or more, the coatability, especially the coatability by spin coating, is excellent. If it is 10000 mPa ⁇ s or less, workability is excellent.
• Spin coating is, for example, a method of dropping a liquid composition onto a substrate and rotating the substrate at a predetermined number of revolutions to apply the composition onto the surface of the substrate.
• Spin coating enables efficient production of high-quality coating films.
• the composition of the present invention can be used as a temporary fixing resin composition, a temporary fixing adhesive, an adhesive sheet, or a temporary fixing adhesive for manufacturing electronic devices.
• the temporary fixing composition, the temporary fixing resin composition, and the temporary fixing adhesive may be collectively referred to as a temporary fixing agent.
• the energy amount is 1 in visible light or ultraviolet light (wavelength or center wavelength 365 to 405 nm). It is preferable to irradiate up to 20000 mJ/cm 2 .
• the energy amount is 1 mJ/cm 2 or more, sufficient adhesiveness is obtained, and when the energy amount is 20000 mJ/cm 2 or less, the productivity is excellent, decomposition products from the photoradical polymerization initiator are less likely to occur, and outgassing is suppressed. be done. It is preferably 1000 to 10000 mJ/cm 2 from the viewpoints of productivity, adhesiveness, low outgassing and easy peeling.
• the substrates to be bonded by the composition of the present invention are not particularly limited, but at least one of the substrates is preferably a transparent substrate that transmits light.
• transparent substrates include inorganic substrates such as crystal, glass, quartz, calcium fluoride and magnesium fluoride, and organic substrates such as plastics.
• inorganic substrates are preferred in that they have versatility and provide great effects.
• the inorganic substrates one or more selected from glass and quartz are preferable.
• the composition of the present invention is photocurable, and the cured product provided thereby has excellent heat resistance and peelability.
• the cured product of the composition of the present invention has a small amount of outgassing even when exposed to high temperatures, and is suitable for joining, encapsulating, and coating various optical parts, optical devices, and electronic parts.
• the composition of the present invention is suitable for applications requiring a wide range of durability such as solvent resistance, heat resistance, adhesiveness, etc., especially semiconductor manufacturing process applications.
• the cured body of the composition of the present invention can be used in processes over a wide temperature range from room temperature to elevated temperatures.
• the heating temperature during the process is preferably 350° C. or lower, more preferably 300° C. or lower, most preferably 250° C. or lower.
• An adhesive body adhered with the temporary fixing adhesive of the present invention has a high shear adhesive strength, so it can withstand a thinning process and the like, and can be easily peeled off after a heating process such as the formation of an insulating film.
• the cured body of the composition of the present invention can be used in high temperature processes, for example, preferably 200° C. or higher, more preferably 250° C. or higher.
• an adhesive body is obtained by bonding a base material with a temporary fixing adhesive, and an effect that the adhesive body can be peeled off by applying an external force to the adhesive body is obtained.
• peeling can be achieved by inserting a knife, sheet or wire into the joint.
• a bonded body is obtained by bonding a substrate with a temporary fixing adhesive, and the entire surface of the bonded body is scanned with a UV laser or an IR laser from the optically transparent substrate side. The effect of being able to peel off is obtained by irradiation.
• Embodiments of the present invention can also provide a method for manufacturing thin wafers.
• the manufacturing method uses the above-described temporary fixing composition or temporary fixing adhesive (hereinafter sometimes simply referred to as adhesive or temporary fixing agent) as an adhesive layer between a wafer having a semiconductor circuit or the like and a support.
• adhesive or temporary fixing agent used as an adhesive layer between a wafer having a semiconductor circuit or the like and a support.
• the thin wafer manufacturing method of the present invention includes the following steps (a) to (e).
• step (a) when bonding the circuit-formed surface of a wafer having a circuit-formed surface on its front surface and a circuit-non-formed surface on its back surface to a support via an adhesive, the substrate or the circuit is
• an adhesive is applied onto the wafer with the attached substrate by spin coating, and the adhesive is bonded to the other substrate or the wafer with the circuit attached under vacuum.
• a wafer having a circuit-formed surface and a circuit-non-formed surface is a wafer in which one surface is a circuit-formed surface and the other surface is a circuit-unformed surface.
• Wafers to which the present invention can be applied are typically semiconductor wafers.
• the semiconductor wafers include not only silicon wafers, but also gallium nitride wafers, lithium tantalate wafers, lithium niobate wafers, silicon carbide wafers, germanium wafers, gallium-arsenide wafers, gallium-phosphorus wafers, gallium-arsenide-aluminum wafers, and the like. mentioned.
• the thickness of the wafer is not particularly limited, but is preferably 600-800 ⁇ m, more preferably 625-775 ⁇ m.
• As the support for example, a transparent substrate that transmits light is used.
• Step (b) is a step of photocuring the adhesive.
• the wafer processed body laminate substrate
• the energy amount is 1 mJ/cm 2 or more, sufficient adhesiveness is obtained, and when the energy amount is 20000 mJ/cm 2 or less, the productivity is excellent, decomposition products from the photoradical polymerization initiator are less likely to occur, and outgassing is suppressed. be done. 1000 to 10000 mJ/cm 2 is more preferable from the viewpoints of productivity, adhesiveness, low outgassing and easy peeling.
• a black light, UV-LED, or visible light-LED can be used as a light source.
• the following light sources can be used.
• the black light light containing a component with a wavelength of 350 nm or more, preferably 385 nm or more, is preferably used regardless of its central wavelength.
• ⁇ Black light (center wavelength 365 nm, illuminance 10 mW/cm 2 , TUV-8271 manufactured by Toyo Adtec Co., Ltd.)
• ⁇ UV-LED (wavelength 385 ⁇ 5 nm, illuminance 350 mW/cm 2 (conditions: working distance 20 mm from the tip of the mirror unit), HOYA H-4MLH200-V2-1S19 + specially designed mirror unit)
• ⁇ UV-LEDz (wavelength 395 ⁇ 5 nm, illuminance 375 mW/cm 2 (conditions: work distance 20 mm from the tip of the mirror unit), HOYA H-4MLH200-V3-1S19 + specially designed mirror unit)
• ⁇ UV-LED (wavelength 405 ⁇ 5 nm, illuminance 400 mW/cm 2 (conditions: work distance 20 mm from the tip of the mirror unit), HOYA H-4MLH200-V4-1S19 + specially designed mirror unit)
• ⁇ UV-LED
• the integrated light amount is large and the irradiation time tends to be long.
• the step (c) is a step of grinding and/or polishing the circuit non-formed surface of the wafer bonded to the support, that is, grinding the wafer rear surface side of the wafer processed body obtained by bonding in the step (a). It is a step of thinning the thickness of the wafer.
• the thickness of the thinned wafer is preferably 10-300 ⁇ m, more preferably 30-100 ⁇ m.
• the method of grinding/polishing the back surface of the wafer is not particularly limited, and a known grinding/polishing method is employed. Grinding is preferably carried out while cooling the wafer and the whetstone (a whetstone with a diamond edge, etc.) with water.
• Step (d) is a step of processing the non-circuit-formed surface of the processed wafer whose circuit-non-formed surface has been ground/polished, that is, the circuit-non-formed surface of the wafer processed body thinned by backside grinding/polishing.
• This step includes various processes used at the wafer level. Examples include electrode formation, metal wiring formation, and protective film formation.
• metal sputtering for forming electrodes and the like wet etching for etching a metal sputtering layer, application of a resist to serve as a mask for forming metal wiring, exposure, and pattern formation by development, resist , dry etching, formation of metal plating, silicon etching for TSV formation, formation of an oxide film on the silicon surface, and other conventionally known processes.
• Step (e) is a peeling step.
• This step is a step of separating the wafer processed in the step (d) from the wafer processing body. For example, after subjecting a thinned wafer to various processing, the wafer is peeled off from the wafer processing body before dicing. At this time, a dicing tape can be pasted on the surface that has been thinned and processed in advance.
• This peeling process is generally carried out under relatively low temperature conditions from room temperature to about 60.degree.
• any known UV laser peeling process, IR laser peeling process, or mechanical peeling process can be adopted.
• a UV laser stripping process can be used.
• the UV laser detachment step is, for example, a UV laser that irradiates the entire surface so as to reciprocate in a straight line in the tangential direction from the end of the wafer processing body on the side of the optically transparent support, and bonds with the energy of the laser.
• the agent layer is decomposed and peeled off.
• Such a peeling process is described in, for example, Japanese Patent Publication No. 2019-501790 and Japanese Patent Publication No. 2016-500918.
• the temporary fixing composition of the present invention is particularly suitable for the UV laser peeling process by including the component (D) and satisfying the preferred requirements of the component (C) and/or the component (D).
• IR laser peeling process for example, an IR laser is irradiated to the entire surface so as to reciprocate in a straight line in the tangential direction from the end of the wafer processing body on the side of the optically transparent support, and the laser energy is used for bonding.
• the agent layer is heated and decomposed to be peeled off.
• a peeling process is described, for example, in Japanese Patent No. 4565804.
• a light-to-heat conversion layer for example, 3M's LTHC; release coating
• LTHC When using 3M's LTHC, for example, LTHC is spin-coated on a glass support and cured, and the temporary fixing agent layer is spin-coated on a wafer and then bonded to the glass support on which the LTHC layer is formed. can be UV cured.
• a method of performing an IR laser stripping process using 3M LTHC is described, for example, in the same US Pat. No. 4,565,804.
• the mechanical peeling process includes, for example, inserting a blade into the edge of the interface of the wafer processing body and horizontally fixing the wafer processing body with the wafer facing downward in order to cause a split between the wafer and the support, After inserting the blade, an upward stress is applied to the upper support and/or the blade to promote the cleavage and separate the wafer and the support.
• a peeling process is described, for example, in Japanese Patent No. 6377956 and Japanese Patent Application Laid-Open No. 2016-106404.
• any of these stripping methods can be used to strip the compositions according to embodiments of the present invention.
• a blade or a solvent for example, pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene, etc.
• These peeling methods are usually carried out at room temperature, but heating at an upper limit of about 90° C. is also preferable.
• a laser it is preferable to use a YAG laser or a YVO4 laser.
• the step of peeling off the processed wafer from the support in the above step (e) further includes: (f) a step of bonding a dicing tape to the wafer surface of the processed wafer; (g) a step of vacuum-sucking the dicing tape surface to the suction surface; (h) peeling the support from the processed wafer at a temperature of the adsorption surface of 10 to 100° C.; is preferably included.
• the support can be easily separated from the processed wafer, and the subsequent dicing process can be easily performed.
• the manufacturing method further includes, for example, (i) placing/fixing the processed wafer, optically transparent support side up, on a horizontal surface, preferably via dicing tape; (j) a step of irradiating the entire surface of the processed wafer so as to scan the laser from the support side; is preferably included.
• the support can be easily separated from the processed wafer, and the subsequent dicing process can be easily performed.
• step (k) removing the temporary fixing agent remaining on the surface of the wafer; should be implemented.
• the thinned surface is vacuum-adsorbed to the adsorption surface, and an adhesive tape such as a dicing tape is pasted on the entire surface of the other side where the temporary fixing agent remains.
• a method of peeling off the temporary fixing agent together with the tape, and a wafer with a solvent for example, pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene, or other aliphatic or aromatic hydrocarbons) solvent
• a solvent for example, pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene, or other aliphatic or aromatic hydrocarbons
• the tape peeling method is preferable in terms of the small number of steps and short required time.
• the wafer from which the temporary fixing agent has been removed can also proceed to the next step as it is without cleaning the surface.
• a solvent e.g., a fat such as pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene, etc.
• a solvent e.g., a fat such as pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene, etc.
• Part of the adhesive may remain on the circuit forming surface of the wafer from which the temporary fixing agent has been removed in step (k). Moreover, it is preferable to wash and reuse the peeled support, but there are cases where the adhesive residue adheres to the surface of this support.
• Solvents for example, aliphatic or aromatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, and mesitylene
• solvents for example, aliphatic or aromatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, and mesitylene
• solvents for example, aliphatic or aromatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonan
• the following various methods can be employed in curing the composition to obtain a cured product.
• a second layer made of a temporary fixing composition containing the component (D) is prepared and cured to obtain a cured body having an integrated single layer or multiple layers (multiple layers).
• the concentration distribution of the component is different in the thickness direction, or the concentration distribution of the component is different between the upper surface and the lower surface in the thickness direction of the cured body.
• the different concentration distributions of the components can be confirmed by quantifying the UV transmittance for both sides of the cured body by reflectometric spectroscopy as described above.
• a black light or UV-LED can be used as a light source (the same applies to the method described below).
• An example of the black light is TUV-8271 manufactured by Toyo Adtec Co., Ltd. (center wavelength: 365 nm, illuminance: 10 mW/cm 2 ).
• HOYA Corporation H-4MLH200-V2-1S19 + specially designed mirror unit (wavelength 385 ⁇ 5 nm, illuminance 350 mW/cm 2 , conditions: scan pitch 20 mm from mirror unit tip), HOYA Corporation H-4MLH200-V3-1S19+ specially designed mirror unit (wavelength 395 ⁇ 5 nm, illuminance 375 mW/cm 2 , condition: work distance 20 mm from tip of mirror unit), H-4MLH200-V4-1S19+ specially designed mirror unit manufactured by HOYA Corporation (wavelength 405 ⁇ 5 nm, illuminance 400 mW/cm 2 , condition: work distance 20 mm from the tip of the mirror unit).
• the component (D) is applied (for example, by spin coating) onto the cured layer composed of the temporary fixing composition containing the components (A), (B), and (C).
• the concentration distribution of the component differs in the thickness direction of the cured product.
• the concentration distribution of the components can be quantified by reflectometry spectroscopy for each target layer as described above. This technique has the effect of enabling precise control of UV absorption characteristics.
• a layer of a commercially available LTHC agent (light-to-heat conversion agent) is placed on a layer of a temporary fixing composition containing components (A), (B), and (C) and cured.
• a multi-layered cured product may be obtained by allowing the Thereby, an effect of easily obtaining a cured product can be obtained.
• the cured body obtained by the method described above can be combined with an adherend to provide a structure.
• a first temporary fixing composition containing components (A), (B), and (C) but not containing component (D) is applied onto a wafer and partially cured.
• applying a second temporary fixing composition containing components (A) to (D) on the partially cured temporary fixing composition applying the applied second temporary fixing composition and further placing a transparent substrate on top of and photocuring.
• a first temporary fixing composition containing components (A), (B), and (C) but not containing component (D) is applied onto a wafer.
• a temporary fixing composition containing components (A), (B), and (C) but not containing component (D) is applied onto a wafer, and if necessary applying the LTHC layer on the transparent substrate, drying and curing, the side of the wafer on which the temporary fixing composition is applied, and the side of the transparent substrate on which the LTHC layer is applied. and then bonding by photocuring.
• the same composition as used in the temporary fixing composition of the present invention is a photothermal conversion (LTHC) that absorbs IR laser light and converts it into heat, described in Japanese Patent No. 4565804. It can also be used as a raw material for layers. By adding this composition as a component of the light-to-heat conversion (LTHC) layer, it becomes possible to improve the heat resistance thereof.
• LTHC photothermal conversion
• a laser beam preferably a laser beam with a wavelength of 200 nm or more and less than 385 nm
• the cured temporary fixing adhesive may form a single layer in the adhesive body. By doing so, it is preferable for the simplification of the process and the shortening of the tact time (cycle time).
• the composition contains both the above-mentioned preferred (C) photoradical polymerization initiator component and (D) UV absorber component, so that even a single-layer temporary fixing adhesive can be cured quickly. It is possible to achieve both speed and high peel speed. In addition, it is possible to significantly reduce the amount of uncured UV-curable monomer components remaining in the cured body when the temporary fixing adhesive is UV-cured, thereby reducing the heat resistance of the cured body and the volatile matter under vacuum. It is possible to That is, for example, it is possible to increase the 2% heating mass loss temperature in Tg/DTA measurement of the cured product. Temporary fixing adhesives with high heat resistance of cured products and reduced volatile content under vacuum are extremely useful for recent semiconductor manufacturing processes.
• Curable resin compositions (hereinafter also referred to as liquid resin compositions) having compositions (unit: parts by mass) shown in Tables 1a, 1b, and 2 were prepared and evaluated. The following compounds were selected as each component in the curable resin composition described in Experimental Examples.
• composition (composition) (A) The following compounds were selected as bifunctional (meth)acrylates containing no cyclic skeleton.
• Diacrylate of ⁇ -caprolactone adduct of neopentylglycol hydroxypivalate (“KAYARAD HX-220” manufactured by Nippon Kayaku Co., Ltd., hereinafter abbreviated as “HX-220”, molecular weight 541, carbon number 28)
• Diacrylate of ⁇ -caprolactone adduct of neopentylglycol hydroxypivalate (“KAYARAD HX-620” manufactured by Nippon Kayaku Co., Ltd., hereinafter abbreviated as “HX-620”, molecular weight 783, carbon number 40) 1,4-but
• Preparation process of a test piece for UV laser peeling process compatibility evaluation The prepared liquid resin composition is placed on an 8-inch silicon wafer (diameter 200 mm x thickness 0.725 mm) in an automatic wafer bonder. and then bonded to an 8-inch glass wafer (diameter 201 mm ⁇ thickness 0.7 mm) under a reduced pressure condition of 10 Pa in the same apparatus. After bonding, the liquid resin compound was cured from the glass wafer side using any of the above UV light sources to obtain an adhesive body. Next, the silicon wafer surface of the resulting bonded body was ground and polished to a thickness of 50 ⁇ m, and then heat-treated for 1 hour under a high temperature and reduced pressure environment of 300° C. and 20 Pa.
• Viscosity (“Spin Coating Process Suitability”, “Viscosity” in Tables 1a, 1b, 2): In the above “compatibility of materials”, the viscosity of the liquid resin composition that maintains a uniform state at 23° C. was measured, and the suitability for spin coating on the upper surface of the substrate assumed in the actual process was evaluated. Using a rheometer MCR302 manufactured by Anton-Paar, the viscosity was measured at a temperature of 23° C. using a cone plate CP50-2.
• the shear viscosity at a shear rate of 1 s -1 is preferably 1000 mPa s or more and less than 4000 mPa s, or 4000 mPa s or more and 10000 mPa s or less, or 100 mPa s or more and less than 1000 mPa s. Those exceeding 10000 mPa ⁇ s or less than 100 mPa ⁇ s were rated as failing.
• the viscosity is preferably 100 to 10000 mPa ⁇ s from the point of suitability for the spin coating process. In addition, subsequent evaluation was omitted about the example which became "impossible.” The same applies to the following.
• Heating resistance 1 in Tables 1a, 1b, and 2, “2% heating mass reduction temperature of cured body under nitrogen atmosphere”: 2 to 10 mg of the resulting cured product was heated from 30° C. to 600° C. at a temperature elevation rate of 10° C./min under a nitrogen stream using a differential thermal/thermomass simultaneous measurement device “TG-DTA STA-2500” manufactured by Netch Japan Co., Ltd. The temperature was raised to °C, and the heating mass loss rate of the obtained cured product was measured. The 2% heating mass loss temperature of the cured body was shown.
• a value of 300°C or higher is excellent, a value of 250°C or higher and lower than 300°C is good, a value of 200°C or higher and lower than 250°C is acceptable, and a value of lower than 200°C is indicated. made things impossible.
• a value of 250°C or higher is excellent, a value of 200°C or higher and lower than 250°C is good, a value of 150°C or higher and lower than 200°C is acceptable, and a value of lower than 150°C is indicated. made things impossible.
• the temperature at which the heating mass reduction rate becomes 2% is preferably 150° C. or higher, more preferably 250° C. or higher, from the viewpoint of suitability for semiconductor manufacturing high-temperature processes.
• Pressure change under reduced pressure conditions (“outgassing” in Table 4, “pressure when reaching 300°C”): A ⁇ 4-inch sheet with 50 ⁇ m thick PTFE cut into ⁇ 3 inches is placed on a 4-inch silicon wafer, a liquid resin composition is applied to the cut-out portion, the PET sheet and the 4-inch wafer are laminated, and the LED integrated light amount is 5000 mJ/cm 2 . It was cured under the conditions (center wavelength: 405 nm, illuminance: 100 mW/cm 2 ). The LEDs were illuminated from the 4 inch glass wafer surface. After curing, the PET film was peeled off, and the laminated body of the wafer and the resin composition was cut into a diameter of 1 cm to obtain a test piece.
• the temperature was raised from 50°C to 600°C at a rate of 10°C/min under reduced pressure conditions of 1 to 2 x 10 -6 Pa using the TE-360S vacuum heated gas extraction/mass spectrometer, and the pressure increased due to outgassing. was measured.
• a pressure maintained at less than 5 ⁇ 10 -6 Pa until reaching 300°C was excellent, a pressure maintained at 5 ⁇ 10 -6 or more and less than 1 ⁇ 10 -5 Pa was good, 1 ⁇ 10 -5 or more and 5 ⁇ 10 Those that maintained less than ⁇ 4 Pa were accepted, and those that reached 5 ⁇ 10 ⁇ 4 Pa or more were rejected. From the viewpoint of suitability for semiconductor manufacturing high-temperature processes, it is preferably less than 5 ⁇ 10 ⁇ 4 Pa, more preferably less than 5 ⁇ 10 ⁇ 6 Pa.
• Adhesiveness at high temperature (Tables 1a, 1b, 2 "adhesiveness under high temperature conditions (300 ° C. / 1 h / reduced pressure 20 Pa)", “width of discoloration at outer edge”, “peeling by heating”): Prepared Using the liquid resin composition, a 4-inch silicon wafer (diameter 10 cm ⁇ thickness 0.47 mm) and a 4-inch glass wafer (diameter 10 cm ⁇ thickness 0.7 mm) were bonded together. At the time of lamination, the thickness of the resin composition was adjusted by adding 0.1% by mass of silica particles (trade name: Hipresica TS N3N, average particle size: 50 ⁇ m) manufactured by Ube Exsimo Co., Ltd.
• the adhesive was cured under the conditions of an LED integrated light quantity of 5000 mJ/cm 2 (center wavelength of 405 nm, illuminance of 100 mW/cm 2 ) to prepare a test piece for evaluating adhesiveness under high temperature and reduced pressure conditions.
• the adhesive was applied to the entire surface of the bonding surfaces.
• the LEDs were illuminated from the 4 inch glass wafer surface.
• the completed test piece was placed on a hot plate in a vacuum hot plate chamber manufactured by MSA Factory with the 4-inch silicon wafer side down and heated, and the width of the discolored area at the outer edge toward the center of the wafer and from the glass side The presence or absence of peeling that can be visually confirmed was observed.
• UV laser peeling process suitability (“UV laser peelability” in Tables 1a, 1b, 2, “Minimum time required to achieve complete peeling”, and “UV laser irradiation conditions” in Table 3): 8 obtained A 210 mm square area fixed at the center of the inch test piece was irradiated with a UV laser so as to scan the entire surface of the test piece from the glass support side of the inch test piece. The conditions shown in Table 3 as the UV laser irradiation conditions were sequentially applied to each of the examples in Tables 1a and 1b for evaluation.
• UV laser QLA-355 manufactured by Quark Technology Co., Ltd., output 9.3 W, pulse energy 235 ⁇ J, energy density 11968 mJ/cm 2 , frequency 40 kHz, beam diameter (spot diameter) 50 ⁇ m, scan pitch 500 ⁇ m, scan speed 20 m/s. It was used under the conditions shown in condition number 9 in Table 3 (Table 3 describes trials for examining this optimum condition).
• the suitability of the UV laser peeling process was evaluated by the minimum value of the time required for the UV laser irradiation process to obtain this state of complete peeling. Those with the minimum required time of less than 15 seconds were evaluated as excellent, those with 15 seconds or more and less than 30 seconds as good, those with 30 seconds or more and less than 60 seconds as acceptable, and those with 60 seconds or more as unacceptable.
• the resin composition of the present invention is a composition excellent in compatibility, suitability for spin coating processes, and heat resistance. That is, when the component (B) is not used as in Comparative Example 1, compatibility with the spin coating process cannot be obtained. Moreover, when the component (A) was not used as in Comparative Examples 2 and 3, the composition became solid, which was also unsuitable for the spin coating process.
• the resin composition of the present invention ensures the compatibility of materials and the minimum viscosity necessary for spin coating, and is excellent in adhesiveness, heat resistance and peelability at room temperature and high temperature conditions.
• the resin composition according to this example has suitability for a UV laser stripping process and suitability for a mechanical stripping process.
• a thin and sharp metal blade for generating cleavage was inserted into the substrate interface at the edge of the silicon wafer/glass support laminate prepared by the method described in the above example, and then the glass support was placed horizontally with the glass support facing upward. After inserting the blade, an upward stress is applied to the upper support to promote the cleavage, thereby separating the wafer from the support.
• the Maszara test As a method for evaluating the energy required for peeling, a method called the Maszara test was used in which a thin and sharp blade was inserted for a given distance and the distance over which the cleavage progressed at that time was measured. Also in the same test, the sample bonded with the liquid resin having the composition of Example 1 shows a sufficiently low value.
• the resin composition according to this example is compatible with a UV laser stripping process.
• the silicon wafer/glass support laminate prepared by the method described in the above example is fixed to a fixing device with the silicon wafer facing downward, and a UV laser QLA-355 manufactured by Quark Technology Co., Ltd. is emitted from the glass support side.
• a frequency of 40 kHz, a scan pitch of 200 ⁇ m, and a beam diameter of 50 ⁇ m the peel force was measured in the same procedure as in (3) Evaluation of suitability for the mechanical peeling process. It had dropped to 0N.
• composition that can be provided by the present invention is excellent in heat resistance, low outgassing properties, and releasability.
• the composition of the present invention is excellent in workability and productivity in the production of various electronic parts, optical parts and optical devices, because it easily develops strong adhesiveness only by irradiation with ultraviolet rays or visible light.
• the cured product of the composition of the present invention has an extremely small amount of outgassing even at a high temperature of 250°C.
• the compositions of the present invention are easy to peel off after processing. Therefore, various electronic components, optical components, and optical devices bonded using the composition of the present invention can be applied even when vapor deposition treatment at high temperatures exceeding 200 ° C. or baking coating at high temperatures is applied. It is possible.
• optical components such as image sensors are also being surface-mounted on circuit boards. In that case, it is passed through a high temperature solder reflow. In recent years, especially with lead-free solder, the temperature conditions for solder reflow have become severe. In such a production process, in order to improve the quality of optical parts and optical devices, or to improve productivity and production yield, the composition of the present invention is used at a location where it is sufficiently resistant to high-temperature heat treatment. requested. Optical parts and optical devices manufactured using the composition of the present invention are industrially very useful because they can withstand the high-temperature heat treatment.

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