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
  • 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
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
• • 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
  • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
  • C08F290/126—Polymers of unsaturated carboxylic acids or derivatives thereof
• • 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
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • 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
  • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
  • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
• • 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
  • H10P72/7416—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
  • H10P72/7422—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer
• • 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, a temporary fixing adhesive, and a method for manufacturing a thin wafer.
• inorganic materials such as silicon are often used as substrates, and wafer-type substrates with a thickness of several hundred microns are often obtained by forming an insulating film on the surface, forming circuits, and thinning by grinding.
• the conventional method for this measure is to apply a temporary protective tape to the surface opposite the surface to be ground (also called the back surface), which can be peeled off after the processing process is completed.
• This tape uses an organic resin film as the base material, and while it is flexible, it lacks strength and heat resistance, making it unsuitable for use in high-temperature processes.
• a system has been proposed that provides sufficient durability to withstand the process conditions of back grinding and back electrode formation by bonding electronic device substrates to a support member made of silicon, glass, etc., via an adhesive. What is important here is the adhesive layer used when bonding the substrate to the support member. This must be able to bond the substrate to the support member without any gaps, and must be durable enough to withstand subsequent processes. Finally, it must be possible to easily peel the thinned wafer from the support member, i.e., it must be possible to temporarily fix it.
• the main processes for processing such wafers are spin coating, vacuum bonding and light curing, thinning by grinding and polishing, high-temperature treatment, laser peeling, and temporary fixing agent removal.
• the temporary fixative In the spin coating process, the temporary fixative must have an appropriate viscosity and be a Newtonian fluid (or have a shear viscosity that is independent of shear rate) so that a film of the temporary fixative can be formed uniformly on the wafer.
• the temporary fixative In the vacuum bonding/UV curing process, the temporary fixative must be able to cure in a short time by irradiating it with ultraviolet (UV) light on a supporting member such as glass, and must generate minimal outgassing (low outgassing).
• UV ultraviolet
• the temporary fixative In the thinning process using grinding and polishing, in order to avoid damage caused by the load of the grinding machine being applied locally to the substrate, the temporary fixative must have an appropriate hardness to distribute the load in the in-plane direction while preventing localized sinking of the substrate and maintaining its flatness. In addition, the temporary fixative must also have adhesion to the supporting member, an appropriate elastic modulus to protect the edges, and chemical resistance.
• the temporary fixative In the high-temperature treatment process, the temporary fixative must be heat-resistant enough to withstand long periods of high-temperature treatment in a vacuum (for example, at 300°C or higher for one hour or more).
• the temporary fixative is required to be able to be peeled off quickly using a laser such as a UV laser.
• the adhesive In the removal process, in addition to easy peelability so that the substrate can be easily peeled off from the support member, the adhesive must also have cohesive properties so that no adhesive residue remains on the substrate after peeling, and be easy to clean.
• Patent Document 1 discloses a temporary fixing composition that contains (A-1) a monofunctional (meth)acrylate whose side chain is an alkyl group having 18 or more carbon atoms and whose homopolymer has a Tg of -100°C to 60°C, (A-2) a polyfunctional (meth)acrylate, (B) a polyisobutene homopolymer and/or a polyisobutene copolymer, and (C) a photoradical polymerization initiator, and claims that the composition has excellent heat resistance, low outgassing properties, and peelability.
• A-1 a monofunctional (meth)acrylate whose side chain is an alkyl group having 18 or more carbon atoms and whose homopolymer has a Tg of -100°C to 60°C
• A-2 a polyfunctional (meth)acrylate
• B a polyisobutene homopolymer and/or a polyisobutene copolymer
• C a
• a laser is swept through a transparent support member such as glass, decomposing the adhesive layer at the irradiated points to form holes (recesses covered with the support member).
• the gas vaporized inside the holes expands at high temperature, pushing up the support member, making it easier to peel off.
• the present invention was completed in consideration of the above problems, and in one embodiment, it is an object of the present invention to provide a temporary fixing composition that has excellent peelability even when irradiated with a low-power laser. In another embodiment, it is an object of the present invention to provide a temporary fixing adhesive that includes such a temporary fixing composition, and a method for manufacturing a thin wafer using the temporary fixing adhesive.
• a temporary fixing composition comprising the following (A) to (C): (A) a polymerizable component including a (meth)acrylate containing an aromatic ring bonded to a heteroatom; (B) a photoradical polymerization initiator; and (C) an ultraviolet absorber having a polymerizable functional group.
• the temporary fixing composition in which the equivalent of the aromatic ring bonded to a heteroatom contained in 1 g of the temporary fixing composition is 0.50 mmol or more and 3 mmol or less.
• the component (A) contains one or more selected from the group consisting of 9,9-bis[4-(2-hydroxy C1 - C20 alkoxy)phenyl]fluorene di(meth)acrylate, C1 - C20 alkoxylated bisphenol A di(meth)acrylate, 1,3-bis(2-(meth)acryloyloxy C1 - C20 alkyl)benzene, 2,2-bis(4-
• [5] The temporary fixing composition according to any one of items [1] to [4], wherein the component (C) has one or more selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton, and has a polymerizable functional group.
• a temporary fixing adhesive comprising the temporary fixing composition according to any one of [1] to [6].
• the method includes a step of irradiating the support member with light having a wavelength of 350 nm to 385 nm to decompose the adhesive layer, thereby peeling the thin wafer from the support member.
• a composition comprising the following (A) to (C): (A) a polymerizable component comprising a (meth)acrylate containing an aromatic ring bonded to a heteroatom; (B) a polymerization initiator; and (C) an ultraviolet absorber having a polymerizable functional group.
• the composition has an equivalent of an aromatic ring bonded to a heteroatom in 1 g of the composition of 0.50 mmol or more and 3 mmol or less.
• the present invention it is possible to provide a temporary fixing composition that has excellent peelability even when irradiated with a low-power laser.
• the present invention can provide a temporary fixing adhesive that includes such a temporary fixing composition, and a method for manufacturing a thin wafer using the temporary fixing adhesive.
• (meth)acrylate refers to a compound having one or more (meth)acryloyl groups in one molecule.
• Monofunctional (meth)acrylate refers to a compound having one (meth)acryloyl group in one molecule.
• Multifunctional (meth)acrylate refers to a compound having two or more (meth)acryloyl groups in one molecule.
• n-functional (meth)acrylate refers to a compound having n (meth)acryloyl groups in one molecule.
• the polymerizable functional group in the multifunctional (meth)acrylate may have only acryloyl groups, may have only methacryloyl groups, or may have both acryloyl groups and methacryloyl groups.
• the notations such as "C 1 to C 20 " and "C 10 to C 20 " mean a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 10 to 20 carbon atoms.
• the present invention provides a temporary fixing composition containing the following (A) to (C): (A) a polymerizable component including a (meth)acrylate containing an aromatic ring bonded to a heteroatom; (B) a photoradical polymerization initiator; and (C) an ultraviolet absorber having a polymerizable functional group.
• a polymerizable component including a (meth)acrylate containing an aromatic ring bonded to a heteroatom
• B a photoradical polymerization initiator
• an ultraviolet absorber having a polymerizable functional group.
• the equivalent of the aromatic ring bonded to the heteroatom contained in 1 g of the temporary fixing composition is 0.5 mmol or more and 3.0 mmol or less.
• the polymerizable component (A) contained in the temporary fixing composition of this embodiment plays a role in forming a (meth)acrylic polymer skeleton.
• the temporary fixing composition of this embodiment may also contain a non-polymerizable component, but the amount of the non-polymerizable component is preferably less than 15 parts by mass relative to 100 parts by mass of the total of the non-polymerizable component and the (A) component.
• the term "non-polymerizable component” is defined as anything other than the (B) component, i.e., anything not used in the technical field as a photoradical polymerization initiator.
• the polymerizable component (A) contained in the temporary fixing composition of this embodiment contains a (meth)acryloyl group and plays a role in forming a (meth)acrylic polymerization backbone.
• the polymerizable component is preferably a polymerizable organic compound component.
• the (A) component may preferably contain a compound having two or more (meth)acryloyl groups.
• the (A) component may be a monofunctional (meth)acrylate, a bifunctional (meth)acrylate, or a trifunctional or higher polyfunctional (meth)acrylate, or a mixture thereof.
• the (A) component may preferably contain a combination of a polyfunctional (meth)acrylate and a monofunctional (meth)acrylate (more preferably a combination of a bifunctional (meth)acrylate and a monofunctional (meth)acrylate).
• the polyfunctional (meth)acrylate that the (A) component may contain may be an aromatic bifunctional (meth)acrylate, an alicyclic bifunctional (meth)acrylate, or a mixture thereof, from the viewpoint of providing a rigid structure.
• the (A) component may contain an acyclic polyfunctional (meth)acrylate.
• the polyfunctional (meth)acrylate may be a monomer or a polymer, or a mixture thereof. That is, the above-mentioned polymerizable polymer may be a polymer of a polyfunctional (meth)acrylate.
• the molecular weight of the polyfunctional (meth)acrylate monomer is preferably 900 or less, more preferably 700 or less, even more preferably 500 or less, and even more preferably 400 or less.
• the weight average molecular weight of the multifunctional (meth)acrylate polymer is preferably 5000 to 200000.
• a suitable viscosity can be obtained when blended with other polymerizable components.
• a suitable thickening effect can be obtained. From this viewpoint, it is more preferable that the weight average molecular weight of the multifunctional (meth)acrylate polymer be 6000 or more, and even more preferable that it be 7000 or more.
• the weight average molecular weight of the multifunctional (meth)acrylate polymer be 200000 or less, good spin coatability with low shear rate dependency can be obtained. From this viewpoint, it is more preferable that the weight average molecular weight of the multifunctional (meth)acrylate polymer be 190000 or less, even more preferable that it be 180000 or less, even more preferable that it be 150000 or less, and particularly preferable that it be 100000 or less.
• the functional group equivalent weight of the polyfunctional (meth)acrylate polymer is preferably 500 to 20,000, more preferably 700 to 10,000, and most preferably 1,000 to 7,000.
• aromatic difunctional (meth)acrylates include 9,9-bis[4-(2-hydroxy C 1 -C 20 alkoxy)phenyl]fluorene di(meth)acrylate, C 1 -C 20 alkoxylated bisphenol A di(meth)acrylate, benzyl di(meth)acrylate, 1,3-bis(2-(meth)acryloyloxy C 1 -C 20 alkyl)benzene, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, or structural isomers thereof.
• di(meth)acrylates having a condensed ring skeleton such as a fluorene, indene, indecene, anthracene, azulene, or triphenylene skeleton may be included.
• alicyclic bifunctional (meth)acrylates include C1 - C20 alkoxylated hydrogenated bisphenol A di(meth)acrylate, 1,3-di(meth)acryloyloxyadamantane, tricyclo C10 - C20 alkane dimethanol di(meth)acrylate, dicyclo C5 - C20 di(meth)acrylate, or structural isomers thereof.
• Examples of acyclic bifunctional (meth)acrylates include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and caprolactone modified hydroxypivalic acid neopentyl glycol di(meth)acrylate.
• component (A) may contain a polyfunctional (meth)acrylate having three or more functional groups.
• trifunctional (meth)acrylates include ethylene oxide-modified isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and tris[(meth)acryloyloxyethyl]isocyanurate.
• tetrafunctional or higher (meth)acrylates examples include ditrimethylolpropane tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.
• the monofunctional (meth)acrylate that may be contained in component (A) is preferably a monofunctional (meth)acrylate having a molecular weight of 550 or less, and more preferably a monofunctional alkyl (meth)acrylate having an alkyl group.
• the alkyl group is preferably one or more selected from linear alkyl groups, branched alkyl groups, and alicyclic alkyl groups, and more preferably one or more selected from linear alkyl groups and branched alkyl groups.
• component (A) has a long chain and branched or cyclic alkyl group, for example, a branched alkyl group having 18 to 40 carbon atoms, more preferably 18 to 32 carbon atoms, such as an isostearyl group, an isotetracosanyl group (e.g., 2-decyl-1-tetradecanyl group), an isotriacontanyl group (e.g., 2-tetradecyl-1-octadecanyl group), or a cycloalkyl group.
• a branched alkyl group having 18 to 40 carbon atoms, more preferably 18 to 32 carbon atoms, such as an isostearyl group, an isotetracosany
• component (A) one or more selected from the group consisting of stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, 2-decyl-1-tetradecanyl (meth)acrylate, 2-dodecyl-1-hexadecanyl (meth)acrylate, and 2-tetradecyl-1-octadecanyl (meth)acrylate are preferred.
• the (meth)acrylate of the following formula 1 is preferred.
• R 1 is a hydrogen atom or a methyl group, and a hydrogen atom is more preferable, and R 2 is an alkyl group having preferably 18 to 32 carbon atoms.
• R 1 is a hydrogen atom or a methyl group, and a hydrogen atom is more preferable
• R 2 is an alkyl group having preferably 18 to 32 carbon atoms.
• One or more of these (meth)acrylates can be used.
• (meth)acrylates having a linear or branched alkyl group such as stearyl(meth)acrylate, isostearyl(meth)acrylate, nonadecyl(meth)acrylate, eicodecyl(meth)acrylate, behenyl(meth)acrylate, 2-decyl-1-tetradecanyl(meth)acrylate, and 2-tetradecyl-1-octadecanyl(meth)acrylate.
• component (A) contains a (meth)acrylate that contains an aromatic ring bonded to a heteroatom.
• the (meth)acrylate containing an aromatic ring bonded to a heteroatom may be a monofunctional (meth)acrylate, a difunctional (meth)acrylate, or a trifunctional or higher polyfunctional (meth)acrylate, or a mixture thereof.
• component (A) may include a combination of a polyfunctional (meth)acrylate and a monofunctional (meth)acrylate, a combination of a polyfunctional (meth)acrylate and a polymerizable polymer, or a combination of a polyfunctional (meth)acrylate, a monofunctional (meth)acrylate, and a polymerizable polymer.
• the number of aromatic rings per molecule is not particularly limited, and may be one, two, three, four or more, or a mixture of (meth)acrylates having these numbers of aromatic rings.
• aromatic rings that are not bonded to a heteroatom may also be present.
• the (meth)acrylate containing an aromatic ring bonded to a heteroatom constitutes a part or all of the equivalent amount of aromatic rings bonded to a heteroatom contained in 1 g of the temporary fixing composition of the present invention, as described below.
• bifunctional (meth)acrylates containing an aromatic ring bonded to a heteroatom include, in component (A), 9,9-bis[4-(2-hydroxy C 1 -C 20 alkoxy)phenyl]fluorene di(meth)acrylate, C 1 -C 20 alkoxylated bisphenol A di(meth)acrylate, 1,3-bis(2-(meth)acryloyloxy C 1 -C 20 alkyl)benzene, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane (including ethoxylated bisphenol A di(meth)acrylate), or one or more selected from the group consisting of structural isomers thereof.
• di(meth)acrylates having a condensed ring skeleton such as a fluorene, indene, indecene, anthracene, azulene, or triphenylene skeleton may be included.
• Examples of monofunctional (meth)acrylates containing an aromatic ring bonded to a heteroatom include nonylphenoxy polyethylene glycol (meth)acrylate (including nonylphenol EO-modified (meth)acrylate), phenoxyethyl (meth)acrylate, or one or more selected from the group consisting of structural isomers thereof.
• (meth)acrylates having a condensed ring skeleton such as a fluorene, indene, indecene, anthracene, azulene, or triphenylene skeleton may be included.
• the total amount of (meth)acrylates containing an aromatic ring bonded to a heteroatom in component (A) may be in the range of 5 to 100% by mass, based on the total mass of component (A).
• the total amount of (meth)acrylates containing an aromatic ring bonded to a heteroatom in component (A) may be preferably 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, or 60% by mass or more, based on the total mass of component (A).
• the total amount of (meth)acrylates containing an aromatic ring bonded to a heteroatom in component (A) may be preferably 100% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, or 70% by mass or less.
• the content of component (A) is preferably 60 to 100 mass%, 70 to 98 mass%, 80 to 96 mass%, or 85 to 94 mass% relative to the total amount of the temporary fixing composition.
• the amount of non-polymerizable components contained in the temporary fixing composition of this embodiment may be 0% by mass or more and less than 10% by mass, or 0% by mass or more and less than 5% by mass.
• the amount of non-polymerizable components may be 10% by mass or less, or 5% by mass or less. More preferably, the temporary fixing composition of this embodiment may not contain any non-polymerizable components except for component (B).
• the polymerization initiator which is the component (B) contained in the temporary fixing composition of the present embodiment, and preferably a photoradical polymerization initiator, is a substance that can initiate polymerization of the component (A) upon irradiation with light.
• the photoradical polymerization initiator is, for example, a compound whose molecules are cleaved and split into two or more radicals upon irradiation with ultraviolet light or visible light (for example, wavelengths of 350 to 700 nm, preferably 365 to 500 nm, and more preferably 385 to 450 nm).
• photoradical polymerization initiator examples include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis( ⁇ 5-2,4-cyclopentadiene-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-acetyloxime).
• the component (B) contained in the temporary fixing composition may contain an acylphosphine oxide compound.
• Preferred acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• the photoradical polymerization initiator is preferably highly sensitive and has excellent deep curing properties due to its photofading resistance, and also has an absorption wavelength range for generating radicals that extends to a relatively long wavelength range.
• the above-mentioned preferred compounds have an absorption wavelength range up to a wavelength of about 440 nm, which is significantly different from the absorption wavelength range of the UV absorbent used in the UV laser peeling process described below.
• the degree of UV curing inhibition by the UV absorbent is small, and radical polymerization can be initiated with light of a longer wavelength. Therefore, even in the presence of a UV absorbent, the effect of initiating radical polymerization and curing efficiently at a relatively high speed can be obtained.
• the photoradical polymerization initiator can be selected based on absorbance.
• the photoradical polymerization initiator can be selected from one or more compounds that, when dissolved at a concentration of 0.1% by mass in a solvent (e.g., acetonitrile or toluene) that does not have a maximum absorption in the wavelength region of 300 to 500 nm, satisfy one or more of the following conditions: absorbance at a wavelength of 365 nm is 0.5 or more, absorbance at a wavelength of 385 nm is 0.5 or more, and absorbance at a wavelength of 405 nm is 0.5 or more.
• a solvent e.g., acetonitrile or toluene
• Examples of compounds that satisfy such conditions include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), which has an absorbance of 0.5 or more at a wavelength of 365 nm when dissolved at a concentration of 0.1% by mass in acetonitrile as a solvent; 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, which has an absorbance of 0.5 or more at wavelengths of 365 nm and 385 nm; and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, which have an absorbance of 0.5 or more at wavelengths of 365 nm, 385 nm, and 405 nm.
• bis( ⁇ 5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium which has an absorption wavelength range of 400 to 500 nm, can also be used as a photoradical polymerization initiator.
• acylphosphine oxide compounds titanocene compounds, and ⁇ -aminoalkylphenone compounds are preferred in terms of reaction speed, heat resistance after curing, low outgassing, and absorption characteristics in a region different from the wavelength of the UV laser used in the UV laser peeling described below and the absorption wavelength region of the UV absorber used in the UV laser peeling.
• oxime ester compounds can also be selected as photoradical polymerization initiators for resin compositions for temporary fixing applications to prevent damage from bonding to the support member of the substrate to be processed until the heating process, which is not a layer for the UV laser peeling process, among the temporary fixing compositions having the structure described below.
• Acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Among these, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is particularly preferred.
• Titanocene compounds include bis( ⁇ 5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.
• ⁇ -aminoalkylphenone compounds examples include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, etc.
• Oxime ester compounds include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), etc. Among these, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) is preferred.
• component (B) in the temporary fixing composition is one or more selected from bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime).
• the amount of (B) photoradical polymerization initiator used is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, even more preferably 0.1 to 2 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of the total of (A) components, in terms of reaction speed, heat resistance after curing, and low outgassing. If the (B) component is 0.01 part by mass or more, sufficient curing properties are obtained, and if it is 5 parts by mass or less, the effect of low outgassing properties and heat resistance being less likely to be impaired is obtained.
• the ultraviolet absorber (UV absorber) having a polymerizable functional group which is the component (C) contained in the temporary fixing composition of this embodiment, refers to a compound whose molecules are cut and decomposed/vaporized by irradiation with an ultraviolet or visible light laser, and the decomposition/vaporization occurs at the interface between the support member and the cured product of the temporary fixing composition (hereinafter also referred to as the temporary fixing agent), causing the loss of adhesion between the cured product of the temporary fixing composition and the support member that was maintained until just before the UV laser peeling process.
• the component (C) is a compound having one or more selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton (preferably a hindered phenol skeleton).
• the reason for having these skeletons is to obtain the degree of overlap with the UV laser light wavelength in the UV absorption wavelength region, UV absorption characteristics at the same wavelength, low outgassing properties, and heat resistance.
• the polymerizable functional group of the component (C) is preferably a (meth)acryloyl group.
• the component (C) preferably has an absorption peak for light having a wavelength of 350 nm to 385 nm.
• component (C) examples include at least one of the group consisting of 2-[2-hydroxy-5-[2-((meth)acryloyloxy)ethyl]phenyl]-2H-benzotriazole, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl(meth)acrylate, 2-(2-(2-(meth)acryloyloxy,5-methyl)phenyl-2H-benzotriazole, 1,1-bis-[2-(meth)acryloyloxy,3-(2H-benzotriazol-2-yl),5-tert-octyl]methane, and 2,2'-dihydroxy-4,4'-di(meth)acryloyloxybenzophenone, which are particularly preferred in terms of compatibility with the resin component, UV absorption properties, low outgassing, and heat resistance.
• the amount of component (C) is preferably 0.005 to 15 parts by mass, more preferably 0.01 to 12 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 7 parts by mass, per 100 parts by mass of component (A). If it is 0.01 part by mass or more, a sufficient UV laser peeling speed can be obtained, and if it is 15 parts by mass or less, the effect of low outgassing properties and heat resistance not being easily impaired can be obtained.
• the temporary fixing composition of the present invention has an equivalent of aromatic rings bonded to heteroatoms of 0.50 mmol or more and 3 mmol or less, contained per 1 g.
• Aromatic rings generally have an absorption peak at around 200 nm, but when the element adjacent to the aromatic ring is a hetero element such as P, S, or O, the conjugation length increases and the absorption edge extends to 355 nm. This is presumably why the element is more likely to absorb the energy of laser light and to decompose.
• the present invention is not bound by any theory.
• the equivalent of the aromatic ring bonded to the heteroatom contained in 1g of the temporary fixing composition is set to 0.50 mmol or more.
• the equivalent of the aromatic ring bonded to the heteroatom contained in 1g of the temporary fixing composition is preferably 0.55 mmol or more, more preferably 0.6 mmol or more, more preferably 0.60 mmol or more, even more preferably 0.65 mmol or more, even more preferably 0.7 mmol or more, and even more preferably 0.70 mmol or more.
• the equivalent of the aromatic ring bonded to the heteroatom is set to 3 mmol or less.
• the equivalent of the aromatic ring bonded to the heteroatom contained in 1 g of the temporary fixing composition is preferably 3.0 mmol or less, preferably 2.8 mmol or less, more preferably 2.5 mmol or less, even more preferably 2 mmol or less, even more preferably 2.0 mmol or less, even more preferably 1.9 mmol or less, even more preferably 1.8 mmol or less, even more preferably 1.7 mmol or less, and even more preferably 1.6 mmol or less.
• the equivalent of the aromatic ring bonded to the heteroatom does not necessarily have to be derived from component (A) and can also be derived from component (B) or (C).
• the adhesive layer can be decomposed even with a low laser output, making it possible to peel the adhesive layer with reduced heat generation.
• the decomposition of the adhesive layer is promoted, it is expected to have the advantage of being easier to clean when cleaning the remaining adhesive layer after peeling.
• the temporary fixing composition of the present invention can be used as a temporary fixing adhesive, particularly as a temporary fixing adhesive for the production of electronic devices such as thin wafers, etc.
• the temporary fixing adhesive preferably consists solely of the temporary fixing composition of the present invention.
• the present invention also provides a method for manufacturing a thin wafer using the temporary fixing adhesive of the present invention.
• the method includes a step of bonding a substrate of a thin wafer and an optically transparent support member via the temporary fixing adhesive, a step of photocuring the temporary fixing adhesive from the support member side to form an adhesive layer and bonding the substrate and the support member, a step of processing the substrate to form a thin wafer, and a step of irradiating light having a wavelength of 350 nm to 385 nm from the support member side to decompose the adhesive layer and peel off the thin wafer from the support member.
• the temporary fixing adhesive can be applied by known application methods such as spin coating, screen printing, and various coaters.
• the viscosity of the temporary fixing composition of this embodiment is preferably 500 mPa ⁇ s or more, and more preferably 1000 mPa ⁇ s or more, in terms of application and workability at 23°C (atmospheric pressure).
• the viscosity of the temporary fixing composition of this embodiment is preferably 15000 mPa ⁇ s or less, more preferably 10000 mPa ⁇ s or less, and even more preferably 5000 mPa ⁇ s or less, in terms of application and workability at 23°C (atmospheric pressure).
• a viscosity of 500 mPa ⁇ s or more provides excellent application properties, particularly application properties by spin coating.
• a viscosity of 15000 mPa ⁇ s or less provides excellent workability.
• the viscosity can be measured by a known viscometer.
• Spin coating is a method of applying a liquid composition to the surface of a support member, for example, by dropping the liquid composition onto the support member and rotating the support member at a specified rotation speed. Spin coating can efficiently produce high-quality coating films.
• the substrate is cured by irradiation with light.
• the wavelength of the light can be appropriately selected according to the type of the photoradical polymerization initiator (B), typically 350 nm to 700 nm. In particular, it is preferable to irradiate with visible light or ultraviolet light (wavelength or central wavelength 365 to 405 nm) so that the energy amount is 1 to 20,000 mJ/cm 2.
• the energy amount is 1 mJ/cm 2 or more, sufficient adhesion is obtained, and if it is 20,000 mJ/cm 2 or less, the productivity is excellent, decomposition products from the photoradical polymerization initiator are unlikely to be generated, and the generation of outgassing is suppressed.
• the wavelength of the light is selected to be in a range different from the laser light wavelength when decomposing the adhesive layer described below.
• the substrate to be processed and the support member it is preferable that at least one of the substrates is 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 preferable because of their versatility and the fact that they can provide great effects.
• inorganic substrates one or more selected from glass and quartz are preferable.
• the substrate After bonding the substrate to be processed and the support member, the substrate is processed to form a thin wafer.
• the processing typically involves thinning by grinding and polishing, and high-temperature treatment.
• the adhesive layer is decomposed by irradiating it with light having a wavelength of 350 nm to 385 nm from the support member side.
• the adhesive layer is decomposed by irradiating it with a UV laser having a wavelength of 350 nm to 385 nm in a scanning manner over the entire surface.
• aromatic rings bonded to heteroatoms tend to absorb the energy of laser light with a wavelength of around 355 nm, so by setting the wavelength of the laser light within the range of 350 nm to 385 nm, the effect of improving energy absorption becomes more pronounced.
• component (A) The following was used as component (A).
• APB-001 multifunctional acrylate polymer, "APB-001” manufactured by Negami Chemical Industries, Ltd., weight average molecular weight 72,000, functional group equivalent weight 1400
• A-BPEF-2 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate ("NK Ester A-BPEF-2" manufactured by Shin-Nakamura Chemical Co., Ltd.)
• A-BPE-2 ethoxylated bisphenol A diacrylate
• HBPE-4 EO-mod
• Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BASF's "Irgacure 819") was used as component (B).
• RUVA-93 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., "RUVA-93")
• P-66 2,2'-dihydroxy-4,4'-diacryloyloxybenzophenone (manufactured by Daiwa Kasei Co., Ltd., "DAINSORB P-66")
• a razor blade was applied to the circumference of the test piece after laser irradiation to remove any protruding parts from the circumference.
• This test piece was placed and fixed on a porous chuck-type suction table with the silicon wafer facing down, and three suction cups with a diameter of 30 mm were attached from above to the glass support member of the test piece.
• a load measurement module was attached to the suction cups, and the glass support member was pulled vertically upwards to measure the load applied to peel the glass support member.
• the laser output (W) required to enable glass peeling up to a load of 10 N was measured and shown in Tables 1-1 and 1-2. The smaller the value, the easier it is to peel.
• the unit of usage is parts by mass.
• the unit of usage is parts by mass. ⁇ indicates that the temporary fixative was cracked.
• Comparative Example 1 in which the equivalent weight of the aromatic ring bonded to the heteroatom falls below the lower limit of the range of the present invention, the laser output required for peeling is high, and peelability is poor.
• Comparative Example 2 the temporary fixing agent cracked when the test piece was heat-treated, and evaluation was not possible.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Mechanical Treatment Of Semiconductor (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=92146637

Family Applications (1)

Country Status (6)

Citations (6)

• 2024
  • 2024-01-22 CN CN202480009780.8A patent/CN120641516A/zh active Pending
  • 2024-01-22 WO PCT/JP2024/001583 patent/WO2024162058A1/ja not_active Ceased
  • 2024-01-22 KR KR1020257027654A patent/KR20250136392A/ko active Pending
  • 2024-01-22 JP JP2024541004A patent/JP7628657B2/ja active Active
  • 2024-01-22 EP EP24750011.9A patent/EP4660266A1/en active Pending
  • 2024-01-25 TW TW113102927A patent/TW202436573A/zh unknown

Patent Citations (6)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events