Classifications

• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
• • 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
  • 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
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • 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
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers 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
  • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/08—Homopolymers or copolymers of acrylic acid esters
• • 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
  • 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
  • H10P72/7402—Wafer tapes, e.g. grinding or dicing support tapes
• • 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
• • 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

Definitions

• the present invention relates to a composition used for temporary fixation.
• inorganic materials such as silicon are used as substrates, and the thickness is obtained by forming an insulating film on the surface, forming a circuit, thinning it by grinding, etc.
• a wafer-type substrate of about 100 ⁇ m is often used.
• this measure has been taken by applying a temporary fixing protective tape to the surface opposite to 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 a base material, and although it is flexible, it has insufficient strength and heat resistance, making it unsuitable for use in processes that involve high temperatures.
• a system has been proposed in which a substrate for an electronic device is bonded to a support such as silicon or glass via an adhesive to provide sufficient durability against the conditions of back grinding and back electrode formation processes.
• a support such as silicon or glass
• an adhesive to provide sufficient durability against the conditions of back grinding and back electrode formation processes.
• the adhesive layer used to bond the substrate to the support This requires that the substrate can be bonded to the support without any gaps, has sufficient durability to withstand subsequent processes, and finally that the thinned wafer can be easily peeled off from the support, in other words, it must be temporarily fixed. It is.
• Processing of such wafers mainly includes a spin coating process, a vacuum bonding and photocuring process, a thinning process by grinding and polishing, a high temperature treatment process, a laser peeling process, and a temporary fixing agent removal process.
• the temporary fixing agent In the spin coating process, in order to uniformly form a film of the temporary fixing agent on the wafer, the temporary fixing agent must have an appropriate viscosity and be a Newtonian fluid (or shear rate independent of shear viscosity). ) is required.
• the temporary fixing agent is required to be able to be cured by irradiation with light such as ultraviolet (UV) light on a support such as glass in a short time, and to generate little outgas (low outgas property).
• light such as ultraviolet (UV) light
• UV ultraviolet
• the load is distributed in the in-plane direction and the planarity is maintained by preventing local subsidence of the substrate.
• Temporary fixatives are required to have appropriate hardness.
• adhesive strength with the support, a moderately high elastic modulus to protect edges, and chemical resistance are also required.
• the temporary fixing agent is required to have heat resistance that can withstand long-term high-temperature treatment in vacuum (for example, at 300° C. or more for one hour or more).
• the temporary fixing agent is required to be capable of high-speed peeling using a laser such as a UV laser.
• Patent Document 1 a monofunctional (meth)acrylate whose side chain is an alkyl group having 18 or more carbon atoms and whose homopolymer Tg is -100°C to 60°C; -2) Discloses a temporary fixing composition containing a polyfunctional (meth)acrylate, (B) a polyisobutene homopolymer and/or a polyisobutene copolymer, and (C) a photoradical polymerization initiator, which has high heat resistance and low heat resistance. It is said to have excellent outgassing properties and peelability.
• the present invention can provide the following aspects.
• B At 23°C and shear as measured by a rotary rheometer.
• Either the viscosity at a speed of 1 s -1 is 1000 mPa ⁇ s or more under atmospheric pressure, or it is a solid at 23°C, or the molecular weight is 500 or more and the shear rate is 1 s at 23°C as measured by a rotary rheometer.
• a polyfunctional (meth)acrylate (C) photoradical polymerization initiator whose viscosity at -1 is 100 mPa ⁇ s or more and less than 1000 mPa ⁇ s under atmospheric pressure.
• Aspect 2 In the mass ratio of component (A) and component (B), the amount of component (A) is in the range of 5 to 65%, The composition for temporary fixation according to aspect 1.
• Aspect 3 The temporary fixing composition according to aspect 1 or 2, wherein the component (A) is an aliphatic monofunctional (meth)acrylate.
• Aspect 4 The temporary fixing composition according to aspect 3, wherein the aliphatic group of component (A) has 6 or more and 30 or less carbon atoms.
• Aspect 5 The temporary fixing composition according to any one of aspects 1 to 4, wherein the component (B) contains an oligomer or a polymer.
• Aspect 6 The temporary fixing composition according to any one of aspects 1 to 5, further comprising the following (D). (D) UV absorber
• Aspect 8 The cured product according to aspect 7, which has a 2% mass reduction temperature of 300° C. or higher in a nitrogen atmosphere.
• a method for manufacturing a substrate for an electronic device comprising: Mixing a monofunctional (meth)acrylate, a polyfunctional (meth)acrylate, and a photoradical polymerization initiator to prepare a composition having a viscosity in the range of 500 to 10,000 mPa ⁇ s at 23°C; Applying the prepared composition onto a silicon wafer by a spin coating method so that the surface of the applied composition has a flatness with only a difference in height of 40 ⁇ m or less; A manufacturing method comprising the step of adhering a support to the silicon wafer so as to sandwich the applied composition.
• a temporary fixing adhesive comprising the temporary fixing composition according to any one of aspects 1 to 6.
• An adhesive body comprising the temporary fixing adhesive according to aspect 10 and a base material to be bonded with the temporary fixing adhesive.
• a novel composition can be obtained that can reduce the inclusion of air bubbles in the spin coating process in the manufacture of electronic devices.
• monofunctional (meth)acrylate refers to a compound having one (meth)acryloyl group in one molecule.
• Polyfunctional (meth)acrylate refers to a compound having two or more (meth)acryloyl groups in one molecule.
• the n-functional (meth)acrylate refers to a compound having n (meth)acryloyl groups in one molecule.
• the polymerizable functional group in the polyfunctional (meth)acrylate may have only an acryloyl group, only a methacryloyl group, or both an acryloyl group and a methacryloyl group.
• An embodiment of the present invention includes (A) monofunctional (meth)acrylate having predetermined physical properties, (B) polyfunctional (meth)acrylate having predetermined physical properties, and (C) a radical photopolymerization initiator.
• a temporary fixing composition also referred to as a "temporary fixing agent" having a predetermined viscosity as a whole can be provided.
• the present inventor discovered that during the process of applying a temporary fixing agent by spin coating in the process of manufacturing substrates for electronic devices, as the target substrate rotates, the temporary fixing agent on it is slightly deformed by centrifugal force, and the slight deformation occurs. It was discovered that the amount of air bubbles affects the presence or absence of air bubbles, and the present invention was conceived based on this finding.
• edge bead a bulge
• the edge bead In the field of temporary fixatives, it was unknown what caused edge beads to occur. In other words, if multiple conditions are not met, including the combination of the surface tension of the monofunctional (meth)acrylate and the viscosity of the polyfunctional (meth)acrylate, and the viscosity of the mixture, the edge bead will become high.
• the problem was solved by the present invention based on the discovery that if the thickness is 40 ⁇ m or less, air bubbles are difficult to enter when the wafer and support are bonded together.
• the viscosity of the entire composition is in the range of 500 to 10,000 mPa ⁇ s at a shear rate of 1 s ⁇ 1 as measured by a rotary rheometer at 23° C. (under atmospheric pressure).
• the viscosity is preferably 500 to 8000 mPa ⁇ s, more preferably 500 to 5000 mPa ⁇ s. If the viscosity of the entire composition is less than 500 mPa ⁇ s, the coating properties will be low and it cannot be put to practical use. Moreover, if the viscosity of the entire composition exceeds 10,000 mPa ⁇ s, the viscosity is too high and is not suitable for spin coating. Further, in this specification, the viscosity of component (B), which will be described later, is also measured in the same manner as above.
• the monofunctional (meth)acrylate which is the component (A) contained in the present composition is characterized in that the surface tension measured by the ds/de method using the pendant drop method at 23°C is in the range of 20 to 30 mN/m. do.
• the ds/de method refers to the maximum diameter (equatorial plane diameter) de of a hanging drop formed by the pendant drop method, and the suspension at a position elevated by de from the lowest end of the hanging drop.
• This method measures the droplet diameter ds and calculates the surface tension ⁇ using the following formula.
• ⁇ ⁇ g(de) 2 (1/H)
• ⁇ density
• g gravitational acceleration
• 1/H a correction term obtained from ds/de.
• the ds/de method is known, for example, from the following documents. https://www.scas.co.jp/technical-informations/technical-news/pdf/tn142.pdf
• component (A) The type of component can be selected based on the ds/de method.
• component (A) contains two or more types of monofunctional (meth)acrylates, it can be determined by measuring the surface tension of the mixture.
• the surface tension of the entire composition can be measured in the same manner as for component (A) alone, and may preferably be in the range of 28 to 33 mN/m at 23°C.
• Component (A) is preferably an aliphatic monofunctional (meth)acrylate.
• the number of carbon atoms in the aliphatic group may be 6 or more and 30 or less, and more preferably 8 or more and 20 or less.
• highly polar monofunctional (meth)acrylates such as acryloylmorpholine generally have too high a surface tension and are considered unsuitable.
• the amount of component (A) is preferably in the range of 5 to 65%, more preferably 5 to 60%, and even more preferably 10 to 50%.
• the polyfunctional (meth)acrylate which is component (B) contained in the present composition has a viscosity of 1000 mPa ⁇ s or more at a shear rate of 1 s ⁇ 1 at 23° C. under atmospheric pressure as measured by a rotary rheometer, or is solid at 23°C, or has a molecular weight of 500 or more, and has a viscosity of 100 mPa ⁇ s or more and less than 1000 mPa ⁇ s (preferably is 120 mPa ⁇ s or more and less than 1000 mPa ⁇ s).
• the viscosity at 23°C is 1000 mPa ⁇ s or more under atmospheric pressure, or it is a solid at 23°C
• the latter actually explains the upper limit of the viscosity.
• the fact that it is a solid can also be interpreted as having a very high viscosity.
• component (B) having such a viscosity or molecular weight or being solid at room temperature with component (A) above, component (A) It is presumed that the alkyl group of the molecule comes to the surface facing the outside of the molecule, resulting in the effect of reducing edge beads.
• the type of component (B) can be selected based on the method of measuring viscosity. When component (B) contains two or more types of polyfunctional (meth)acrylates, it can be determined by measuring the viscosity of the mixture.
• Component (B) may be a monomer or may contain an oligomer or polymer.
• the photoradical polymerization initiator which is component (C) contained in this composition, is a substance that can initiate radical polymerization of components (A) and (B) when irradiated with light, such as ultraviolet rays or visible light ( For example, it refers to a compound whose molecules are cleaved and split into two or more radicals by irradiation with a wavelength of 350 nm to 700 nm, preferably 365 nm to 500 nm, more preferably 385 nm to 450 nm.
• photoradical polymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis( ⁇ 5 -2,4-cyclopentadiene).
• Component (C) may include one or more types or a combination of two or more types of these.
• component (C) may include an acylphosphine oxide compound.
• Preferred acylphosphine oxide compounds include one or more of the group consisting of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• As a photo-radical polymerization initiator it is highly sensitive, has photofading properties, and has excellent deep curing properties, and the absorption wavelength range for generating radicals extends to a relatively long wavelength range. It is preferable. In the preferred compound described above, the absorption wavelength range is 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 below.
• the degree of inhibition of UV curing by the UV absorber is small, and radical polymerization can be initiated with light of a longer wavelength. Therefore, even in the coexistence of a UV absorber, radical polymerization can be initiated and cured efficiently at a relatively high rate.
• the photoradical polymerization initiator can be selected based on absorbance. Specifically, when dissolved at a concentration of 0.1% by mass in a solvent that does not have maximum absorption in the wavelength range of 300nm to 500nm (for example, acetonitrile or toluene), the absorbance at a wavelength of 365nm is 0.1%. 5 or more, the absorbance is 0.5 or more at a wavelength of 385 nm, and the absorbance is 0.5 or more at a wavelength of 405 nm. , a photoradical polymerization initiator can be selected.
• 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 at a concentration of 0.1% by mass in acetonitrile as a solvent.
• bis( ⁇ 5 -2,4-cyclopentadien-1-yl)-bis having an absorption wavelength range of 400 to 500 nm is recommended.
• (2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium can also be used as a photoradical polymerization initiator.
• temporary fixing is not a layer compatible with the UV laser peeling process, and is used for temporary fixation to prevent damage from bonding the substrate to the support substrate to the heating process.
• oxime ester compounds can also be selected as photoradical polymerization initiators for resin compositions.
• acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like. 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 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 and the like.
• oxime ester compounds examples 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.
• the amount of photoradical polymerization initiator used is 0.01 parts by mass per 100 parts by mass of components (A) and (B) in terms of reaction rate, heat resistance after curing, and low outgas properties. ⁇ 5 parts by mass is preferred, and 0.1 to 1 part by mass is more preferred. When the amount of component (C) is 0.01 parts by mass or more, sufficient curability is obtained, and when it is 5 parts by mass or less, low outgassing properties and heat resistance are less likely to be impaired.
• the present composition may contain a UV absorber as component (D).
• a UV absorber means, for example, that its molecules are cut and decomposed and vaporized by irradiation with ultraviolet or visible laser, and this decomposition and vaporization occurs at the interface between the support base material (or substrate) and the temporary fixing agent. refers to a compound that causes the loss of the adhesive force between the temporary fixing agent and the support substrate (or support) that was maintained until just before the peeling process.
• UV absorbers benzotriazole compounds, benzophenone compounds, and hydroxyphenyltriazine 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 , 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole has good compatibility with resin components, UV absorption properties, low outgas properties, and heat resistance. Particularly preferred from this point of view.
• 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 One or more selected from the group consisting of 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine is component (A) and component (B). This is particularly preferred from the viewpoints of compatibility with the polymer, UV absorption properties, low outgassing properties, and heat resistance.
• benzophenone compounds include 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-diacryloyloxy.
• benzophenone and hydroxybenzophenone compounds are particularly preferred from the viewpoint of compatibility with components (A) and (B), UV absorption characteristics, 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].
• component (A) have excellent compatibility with component (A), have a high melting point, and have a relatively low vapor pressure at temperatures below 300°C, so they can be used in a wide range of amounts, and after curing This can contribute to reducing outgassing from the temporary fixing composition under this temperature condition.
• component (D) As the UV absorber, the following absorbers selected based on UV transmittance can be most preferably used. When component (D) has such a UV transmittance, it is possible to appropriately control curing and peeling of the composition.
• the transmittance at a wavelength of 355 nm at an optical path length of 1 cm is 50% or less.
• the transmittance is preferably higher than 50% at a wavelength of 385 to 420 nm. More preferably, the transmittance is 40% or less at a wavelength of 355 nm, and the transmittance is 60% or more at a wavelength of 385 to 420 nm.
• UV absorbers examples include the following. 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole (RUVA-93 manufactured by Otsuka Chemical Co., Ltd., molecular weight 323.0), 2-(2H-benzotriazol-2-yl)-4,6 -Bis(1-methyl-1-phenylethyl)phenol (Tinuvin 900 manufactured by BASF, Adekastab LA-24 manufactured by Adeka, EVERSORB 76/EVERSORB 234 manufactured by Everlight Chemical, molecular weight 447), 2-(2H-benzotriazole- 2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (Tinuvin 928 manufactured by BASF, EVERSORB 89/89FD manufactured by Everlight Chemical, molecular weight 442),
• the UV transmittance of the cured product in this specification is a value obtained by reflectance measurement spectroscopy. Specifically, the transmittance was measured using a reflectance spectrometer (V-650 manufactured by JASCO Corporation) using a cured film with a thickness of approximately 50 ⁇ m sandwiched between PET resin sheets under the following conditions. ) is obtained using
• the amount of the UV absorber as component (D) is preferably 0.01 to 5 parts by mass, and 0.5 to 2.5 parts by mass based on 100 parts by mass of components (A) and (B). More preferred. When it is 0.01 parts by mass or more, a sufficient UV laser peeling rate can be obtained, and when it is 5 parts by mass or less, effects such as low outgassing properties and heat resistance are not easily impaired can be obtained.
• the weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene. Specifically, the weight average molecular weight is determined by creating a calibration curve with commercially available standard polystyrene using a GPC system (SC-8010 manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent under the following conditions. .
• GPC gel permeation chromatography
• a cured product of the composition described above can also be provided.
• Such curing may be performed using a light source described below.
• the cured product is in the form of a cured film with a thickness of 50 ⁇ m, it is preferable that one or more of the following conditions be satisfied, and more preferably that all of the following conditions are satisfied.
• the following conditions can be met, for example, by using a UV absorber.
• the light transmittance in a wavelength region of 395 nm or more among the wavelengths of the light source used for curing is 70% or more.
• the light transmittance in the wavelength range of 385 nm or more and less than 395 nm among 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 is 1% or less.
• the present composition can be used as a temporary fixing resin composition, a temporary fixing adhesive, a pressure-sensitive 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 visible light or ultraviolet light region (the wavelength or center wavelength is preferably 350 to 405 nm, 365 to 405 nm) is more preferable, and 385 to 405 nm is most preferable), and the energy amount is preferably 1 to 20,000 mJ/cm 2 .
• the energy amount is 1 mJ/cm 2 or more, sufficient adhesion is obtained, and when it is 20,000 mJ/cm 2 or less, productivity is excellent, and decomposition products from the photoradical polymerization initiator are difficult to generate, suppressing outgas generation. be done.
• productivity adhesion, low outgas properties, and easy peelability, it is preferably 1000 to 10000 mJ/cm 2 .
• the substrates to be bonded with the present composition it is preferable that at least one of the substrates be a transparent substrate that transmits light.
• the transparent substrate include inorganic substrates such as crystal, glass, quartz, calcium fluoride, and magnesium fluoride, and organic substrates such as plastic.
• inorganic base materials are preferred because they are versatile and can provide great effects.
• one or more selected from glass and quartz is preferred.
• the present composition may be 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, sealing, and coating various optical components, optical devices, and electronic components.
• the composition of the present invention is suitable for applications that require a wide variety of durability such as solvent resistance, heat resistance, adhesiveness, etc., particularly for semiconductor manufacturing process applications.
• the cured product of this composition can be used in processes in a wide temperature range from room temperature to high temperatures.
• the heating temperature during the process is preferably 350°C or lower, more preferably 300°C or lower, and most preferably 250°C or lower. In a preferred embodiment, the temperature at which the heating mass reduction rate of the cured product is 2% may be 250° C. or higher.
• the bonded body bonded with the present composition has high shear adhesive strength and can withstand thinning processes, etc., and can be easily peeled off after passing through a heating process such as forming an insulating film. When used at high temperatures, the cured product of the present composition can be used in a high temperature process, for example, preferably at 200°C or higher, more preferably at 250°C or higher.
• an adhesive body is also provided in which substrates are adhered by using the present composition as an adhesive.
• the adhesive body can be peeled off by applying external force. For example, it can be peeled off by inserting a knife, sheet, or wire into the joint. Alternatively, it is also possible to peel off the adhesive by irradiating the optically transparent base material side of the adhesive body with a UV laser or an IR laser so as to scan the entire surface.
• a method of manufacturing thin wafers can also be provided.
• the manufacturing method uses the above-mentioned temporary fixing composition or temporary fixing adhesive (hereinafter also simply referred to as adhesive or temporary fixing agent) as an adhesive layer between a wafer having a semiconductor circuit, etc. and a support. It is characterized by the use of
• the method for manufacturing the thin wafer includes the following steps (a) to (e).
• Step (a) includes bonding the circuit-forming surface of a wafer having a circuit-forming surface on the front surface and a non-circuit-forming surface on the back surface to a support body through an adhesive. This is a process in which an adhesive is applied onto the wafer with circuits using a spin coating method, and the adhesive is bonded to the other support or the wafer with circuits under vacuum.
• a wafer having a circuit formation surface and a circuit non-formation surface is a wafer in which one surface is a circuit formation surface and the other surface is a circuit non-formation surface.
• the wafer to which the present invention is applicable is usually a semiconductor wafer.
• 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-phosphorous wafers, gallium-arsenide-aluminum wafers, etc. Can be mentioned.
• the thickness of the wafer is not particularly limited, but is preferably 600 to 800 ⁇ m, more preferably 625 to 775 ⁇ m.
• As the support for example, a transparent base material that transmits light is used.
• Step (b) is a step of photocuring the adhesive.
• the amount of energy in the visible light or ultraviolet region (the wavelength or center wavelength is preferably 350 to 405 nm, more preferably 365 to 405 nm, most preferably 385 to 405 nm) is It is preferable to irradiate at 1 to 20,000 mJ/cm 2 .
• the energy amount is 1 mJ/cm 2 or more, sufficient adhesion is obtained, and when it is 20,000 mJ/cm 2 or less, productivity is excellent, decomposition products from the photoradical polymerization initiator are difficult to generate, and outgas generation is also suppressed. be done.
• the range is more preferably 1000 to 10000 mJ/cm 2 .
• a black light, UV-LED, or visible light-LED can be used as a light source, and for example, the following light sources can be used.
• the black light a light containing a component having a wavelength of 385 nm or more is preferably used, regardless of its center wavelength. Note that when a wavelength range is described in this specification, whether the center wavelength is included in the range is determined based on whether the center wavelength is included in the range.
• ⁇ Black light (center wavelength 365 nm, illuminance 10 mW/cm 2 , TUV-8271 manufactured by Toyo Adtech Co., Ltd.)
• ⁇ UV-LED (wavelength 385 ⁇ 5nm, illuminance 350mW/cm 2 (conditions: work distance 20mm from the tip of the mirror unit), HOYA H-4MLH200-V2-1S19+ specially designed mirror unit)
• ⁇ UV-LED wavelength 395 ⁇ 5nm, illuminance 375mW/cm 2 (conditions: work distance 20mm from the tip of the mirror unit), HOYA H-4MLH200-V3-1S19+ specially designed mirror unit)
• ⁇ UV-LED (wavelength 405 ⁇ 5nm, illuminance 400mW/cm 2 (conditions: work distance 20mm from the tip of the mirror unit), HOYA H-4MLH200-V4-1S19+ specially designed mirror unit)
• ⁇ UV-LED (center wavelength 405 nm, il
• UV-LEDs or UV-LEDs which require a smaller integrated light amount (shorter irradiation time) than black lights, which generally have a broad irradiation wavelength and therefore have a large integrated light amount and tend to require a long irradiation time, are used.
• Visible light - LED may be used as the light source. That is, by using an LED light source with a narrow irradiation wavelength band, temporary fixing can be performed in a short time, resulting in the effect that the time required for the manufacturing process can be shortened.
• Step (c) is a step of grinding and/or polishing the non-circuit-forming surface of the wafer bonded to the support, that is, grinding the back side of the wafer of the wafer processed body obtained by bonding in step (a). This is the process of reducing the thickness of the wafer.
• the thickness of the thinned wafer is preferably 10 to 300 ⁇ m, more preferably 30 to 100 ⁇ m.
• There is no particular restriction on the method of grinding/polishing the back surface of the wafer and a known grinding/polishing method may be employed. Grinding is preferably performed while cooling the wafer and a grindstone (such as a diamond-edged grindstone) by pouring water over them.
• Step (d) is a step of processing the circuit-free surface of the wafer workpiece whose circuit-free surface has been ground/polished, that is, the circuit-free surface of the wafer workpiece which has been thinned by back 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, etc. wet etching for etching a metal sputtered layer, resist coating, exposure, and development to form a pattern as a mask for metal wiring formation
• resist Conventionally known processes include peeling off, dry etching, formation of metal plating, silicon etching for TSV formation, and formation of an oxide film on the silicon surface.
• Step (e) is a peeling step.
• This step is a step of peeling the wafer processed in step (d) from the wafer processing body.
• this is a process of performing various processing on a thinned wafer and then peeling the wafer from the wafer processing body before dicing.
• a dicing tape can be attached to the thinned and processed surface in advance.
• This peeling step is generally carried out at a relatively low temperature from room temperature to about 60°C.
• any of the known UV laser peeling process, IR laser peeling process, or mechanical peeling process can be adopted.
• the UV laser peeling process is, for example, irradiating the entire surface of the wafer workpiece with a UV laser in a tangential direction from the end of the wafer workpiece on the side of the optically transparent support, scanning back and forth in a straight line. This is a process in which the adhesive layer is decomposed and peeled off using laser energy. Such a peeling process is described in, for example, Japanese Translated Patent Application Publication No. 2019-501790 and Japanese Translated Patent Application Publication No. 2016-500918.
• the IR laser peeling process is, for example, irradiating the entire surface of the wafer workpiece with an IR laser in a tangential direction from the end of the wafer workpiece on the side of the optically transparent support, scanning back and forth in a straight line.
• This is a process in which the adhesive layer is heated and decomposed using laser energy and then peeled off.
• a peeling process is described in, for example, Japanese Patent No. 4,565,804.
• a light-to-heat conversion layer for example, 3M's LTHC; Light-To-Heat-Conversion release coating
• 3M's LTHC Light-To-Heat-Conversion release coating
• the LTHC When using 3M's LTHC, for example, the LTHC is spin-coated onto a glass support and cured. Then, the temporary fixing agent layer can be spin-coated onto the wafer, bonded to the glass support on which the LTHC layer is formed, and cured by UV.
• a method of carrying out an IR laser stripping process using 3M's LTHC is described, for example, in the same patent number 4,565,804.
• the wafer In the mechanical peeling process, for example, the wafer is fixed horizontally with the wafer facing down in order to insert a blade into the interface edge of the wafer to generate a cleavage between the wafer and the support.
• This is a peeling process, which includes a step of applying upward stress to the upper support and/or the blade after inserting the blade to advance the cleavage and peel the wafer/support.
• Such a peeling process is described in, for example, Japanese Patent No. 6377956 and Japanese Patent Application Laid-open No. 2016-106404.
• any of these methods can be used to remove the composition.
• one of the wafers or the support of the wafer processing body is fixed horizontally, and a blade is inserted or a solvent (e.g., pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene, etc.)
• a solvent e.g., pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene, etc.
• These peeling methods are usually carried out at room temperature, but it is also preferable to heat the film at an
• the process of peeling the processed wafer from the support in step (e) above further includes: (f) a step of adhering a dicing tape to the wafer surface of the processed wafer; (g) vacuum suctioning the dicing tape surface to the suction surface; (h) peeling off the support from the processed wafer at a temperature of the suction surface in a temperature range of 10 to 100°C; It is preferable to include. In this way, the support can be easily peeled off from the processed wafer, and the subsequent dicing process can be easily performed.
• the manufacturing method may further include (i) placing the processed wafer, with the optically transparent support side up, in a horizontal place, preferably using a dicing tape; installation/fixing process; (j) irradiating the entire surface of the wafer in a scanning manner with a laser from the support side of the processed wafer; It is preferable to include. In this way, the support can be easily peeled off from the processed wafer, and the subsequent dicing process can be easily performed.
• step (k) a step of removing the temporary fixing agent remaining on the surface of the wafer; It is necessary to implement To remove the temporary fixing agent, while the thinned side is vacuum-adsorbed to the adsorption surface, apply adhesive tape such as dicing tape to the entire surface of the other side where the temporary fixing agent remains.
• a method of peeling off the temporary fixing agent along with the tape and a method of removing the wafer with a solvent (for example, an aliphatic or aromatic hydrocarbon-based solvent such as pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene, etc.).
• a solvent for example, an aliphatic or aromatic hydrocarbon-based solvent such as pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene, etc.
• a solvent for example, an aliphatic or aromatic hydrocarbon-based solvent such as pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene,
• the wafer from which the temporary fixing agent has been removed may be allowed to proceed to the next step without cleaning the surface.
• cleaning (l) Hold the wafer from which the support and temporary fixing agent have been removed, with the circuit forming side facing up, and place it in a solvent (e.g., a fat such as pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene, etc.). It is preferable to perform a cleaning step using a hydrocarbon-based or aromatic hydrocarbon-based solvent.
• a portion 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). Further, although it is preferable to wash and reuse the peeled support, adhesive residue may adhere to the surface of the support.
• Methods for removing these adhesive residues include solvents (for example, aliphatic or aromatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene, etc.). Examples include a method of immersing the material in water, swelling it, and peeling it off.
• various methods such as those described below can be employed in curing the composition to obtain a cured product.
• a first layer consisting of a temporary fixing composition containing at least components (A) to (C) and not containing a UV absorber as component (D), and at least (A) -
• the concentration distribution of the components is different in the thickness direction, or that the concentration distribution of the components is different on the upper surface and the lower surface in the thickness direction of the cured product.
• a black light or UV-LED can be used as a light source (the method described below is similar).
• An example of a black light is TUV-8271 manufactured by Toyo Adtech Co., Ltd. (center wavelength 365 nm, illuminance 10 mW/cm 2 ).
• a specially designed mirror unit for H-4MLH200-V2-1S19+ manufactured by HOYA Corporation (wavelength 385 ⁇ 5 nm, illuminance 350 mW/cm 2 , conditions: scan pitch from the tip of the mirror unit 20 mm), manufactured by HOYA Corporation H-4MLH200-V3-1S19+ specially designed mirror unit (wavelength 395 ⁇ 5nm, illuminance 375mW/cm 2 , conditions: working distance from the tip of the mirror unit 20mm), H-4MLH200-V4-1S19+ specially designed mirror unit manufactured by HOYA Corporation (Wavelength: 405 ⁇ 5 nm, illuminance: 400 mW/cm 2 , conditions: work distance from the tip of the mirror unit: 20 mm).
• a layer of a commercially available LTHC agent (light-to-heat converting agent) is placed on a layer of a temporary fixing composition containing at least components (A) to (C) and cured, resulting in a multilayer A cured product may also be obtained. This provides the effect of easily obtaining a cured product.
• the cured product obtained by the method described above can be combined with an adherend to provide a structure.
• the first manufacturing method includes a step of applying and partially curing a first temporary fixing composition containing at least components (A) to (C) and not containing component (D) on the wafer; A step of applying a second temporary fixing composition containing at least components (A) to (D) on the partially cured temporary fixing composition; The method may further include the step of further placing a transparent substrate thereon and photocuring it.
• a first temporary fixing composition containing at least components (A) to (C) and no component (D) is applied onto the wafer, and if necessary, a step of partially curing, a step of applying a second temporary fixing composition containing at least components (A) to (D) on the transparent substrate and partially curing the wafer and the transparent substrate as necessary;
• the same composition used in the temporary fixing composition of the present invention is a photothermal conversion method that absorbs IR laser light and converts it into heat, which is described in Japanese Patent No. 4,565,804. It can also be used as a raw material for LTHC) layer. By adding this composition as a component of the light-to-thermal conversion (LTHC) layer, it becomes possible to improve its heat resistance.
• a method for manufacturing a semiconductor wafer which includes the step of peeling off the semiconductor wafer base material by irradiating the semiconductor wafer base material with laser light (less than or equal to 100 nm). In this manufacturing method, both the curing and peeling steps are performed at room temperature, there is no need to heat or cool the component, there is generally no need to use solvents, etc., and it is simple and quick. It has the advantage of short cycle time.
• the cured temporary fixing adhesive may constitute a single layer in the adhesive body. By doing so, it becomes possible to simplify the process and shorten takt time.
• the composition contains both the photoradical polymerization initiator as component (C) and the UV absorber as component (D), so that even if it is a single layer temporary fixing adhesive, It is possible to achieve both a fast curing speed and a fast peeling speed. Furthermore, when the temporary fixing adhesive is UV-cured, it is possible to significantly reduce the amount of uncured UV-curable monomer components remaining in the cured product, improving the heat resistance of the cured product, and improving the heat resistance of the cured product. It becomes possible to reduce the volatile content at the bottom. That is, for example, it is possible to increase the 2% heating mass reduction temperature in Tg/DTA measurement of the cured product.
• Temporary fixing adhesives that have a cured product with high heat resistance and a reduced volatile content under a nitrogen atmosphere are extremely useful in recent semiconductor manufacturing processes.
• the main cured product preferably has a 2% mass loss temperature of 300°C or higher, preferably 320°C or higher, and more preferably 326°C or higher under a nitrogen atmosphere.
• a method of manufacturing a substrate for an electronic device involves mixing a monofunctional (meth)acrylate, a polyfunctional (meth)acrylate, and a photoradical polymerization initiator to prepare a composition having a viscosity in the range of 500 to 10,000 mPa ⁇ s at 23°C. a step of applying the prepared composition onto a silicon wafer by a spin coating method so that the surface of the applied composition is flat with a height difference of 40 ⁇ m or less; The method may include a step of adhering a support to the silicon wafer so as to sandwich the composition therebetween. In this specification, the flatness of the surface of the composition is measured after it has been applied with a spin coater and cured under the conditions described in the Examples below.
• Curable resin compositions (hereinafter also referred to as liquid resin compositions) having the compositions shown in the table below (unit: parts by mass) were prepared and evaluated. The following compounds were selected as each component.
• composition The following was used as component (A).
• component (A) The value of surface tension was measured at 23°C by the ds/de method using "OCA20" manufactured by Hideko Seiki Co., Ltd. Note that the surface tension of the entire composition was also measured in the same manner.
• LA Lauryl acrylate (“LA” manufactured by Osaka Organic Chemical Industry Co., Ltd., surface tension 29.3 mN/m)
• NOAA n-octyl acrylate
• NOAA n-octyl acrylate
• INAA Isononyl acrylate
• INAA Isononyl acrylate
• ISTA Isostearyl acrylate
• Isostearyl acrylate (“ISTA” manufactured by Osaka Organic Chemical Industry Co., Ltd., surface tension 26.3 mN/m)
• ACMO Acryloylmorpholine (“ACMO” manufactured by KJ Chemicals, surface tension 44.6mN/m)
• HX-620 Caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate (Nippon Kayaku Co., Ltd. "Kayarad HX-620", m+n ⁇ 4, (average) molecular weight 768, viscosity 290 mPa ⁇ s)
• HX-220 Caprolactone-modified hydroxypivalate neopentyl glycol diacrylate (Nippon Kayaku Co., Ltd.
• A-BPEF-2 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate (“NK Ester A-BPEF-2” manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 546, exceeding the measurement limit High viscosity, judged to be over 1000mPa ⁇ s)
• RA-341 Multifunctional methacrylate polymer ("ART CURE RA-341" manufactured by Negami Kogyo Co., Ltd., the weight average molecular weight of the main polymer is approximately 70,000, the viscosity is high beyond the measurement limit, and the viscosity is judged to be over 1000 mPa ⁇ s)
• A-BPE-2 Ethoxylated bisphenol A diacrylate (“NK ester A-BPE-2” manufactured by Shin-Nakamura Chemical Co., Ltd., in the following structural formula
• RC100C Acrylate polymer with acryloyl groups at both ends (Kaneka XMAP RC100C, manufactured by Kaneka Corporation, has the following structural formula, has a (weight average) molecular weight of 24,000, has a high viscosity exceeding the measurement limit, and has a viscosity of over 1,000 mPa ⁇ s. judgment)
• Tetrax 6T Polyisobutylene (“Tetrax Grade 6T” manufactured by ENEOS, viscosity average molecular weight 60,000)
• A-DCP Tricyclodecane dimethanol diacrylate (“NK Ester A-DCP” manufactured by Shin Nakamura Chemical Co., Ltd., molecular weight 304, viscosity 160 mPa ⁇ s)
• DCP Tricyclodecane dimethanol dimethacrylate (“NK Ester DCP” manufactured by Shin Nakamura Chemical Co., Ltd., molecular weight 332, viscosity 130 mPa ⁇ s)
• component (C) Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (“Irgacure 819” manufactured by BASF)
• component (D) 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine (“Tinuvin 460” manufactured by BASF) Hydroxyphenyltriazine UV absorber (“Tinuvin 479” manufactured by BASF) 2-(2'-Hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole (Otsuka Chemical Co., Ltd. "RUVA-93”)
• Liquid sample preparation A homogeneous mixture was obtained by heating and mixing the materials at 80°C. The viscosity of each component and the entire composition was measured as a value at a temperature of 23° C. and a shear rate of 1 s ⁇ 1 using a rotary rheometer MCR302 manufactured by Anton-Paar and a cone plate CP50-2.
• the liquid resin composition homogenized by the heating and mixing described above was sandwiched between PET films, spread to a thickness of 70 ⁇ m, and cured at a cumulative light intensity of 5000 mJ/cm 2 to produce a cured sample.
• a UV-LED center wavelength 405 nm, illuminance 100 mW/cm 2 , wafer UV irradiator MUVBA-0.4 ⁇ 0.6 ⁇ 0.2-0010 manufactured by ITEC Systems
• a 4-inch sample was obtained by bonding a 4-inch silicon wafer (diameter 10 cm x thickness 525 ⁇ m) and a 4-inch glass wafer (diameter 10 cm x thickness 0.7 mm) using the prepared liquid resin composition.
• the thickness of the resin composition was adjusted by adding and mixing 0.1% by mass of glass beads manufactured by Unitika Co., Ltd. (trade name SPL-70, average particle size 70 ⁇ m) to the temporary fixing agent. After bonding, it was cured under conditions of an integrated LED light amount of 5000 mJ/cm 2 (center wavelength 405 nm, illuminance 100 mW/cm 2 ) to produce a bonded sample.
• a UV-LED center wavelength 405 nm, illuminance 100 mW/cm 2 , wafer UV irradiator MUVBA-0.4 ⁇ 0.6 ⁇ 0.2-0010 manufactured by ITEC Systems
• the vacuum heat resistance of the obtained bonded sample was evaluated. Further, the vacuum heat resistance described below was evaluated for the obtained bonded sample.
• Each bonded sample was placed in a vacuum hot plate chamber and heated for 1 hour at 300° C. and 20 Pa. Thereafter, the circumferential edge of the silicon wafer was visually observed and evaluated according to the following criteria. Excellent: The edges were not peeled off at all. Good: The length of the peeled part at the end was less than 5 mm from the edge. Fair: The length of the peeled area at the edge was 5 mm or more and less than 10 mm from the edge. Not acceptable: The length of the peeled part at the edge was 10 mm or more from the edge.
• the bonded 4-inch sample prepared as described above was irradiated with a UV laser over a 210 mm square area fixed around the test piece in a manner that scanned the entire surface of the test piece from the glass support side.
• the UV laser irradiation conditions are shown below.
• the UV laser used was "MD-U1020C” manufactured by Keyence Corporation. Irradiation was carried out under the conditions of an output of 2.5 W, a frequency of 40 kHz, a beam diameter of 72 ⁇ m, a scan pitch of 150 ⁇ m, and a scan speed of 6 m/sec.
• the peelability after irradiation was evaluated according to the following definition.
• Excellent means that the glass support is not sticky and can be easily peeled off by hand from the temporary fixing agent. If the glass support remains sticky but can be peeled off by hand from the temporary fixing agent, it is rated “Good.” ⁇ Not possible'' means that the glass support cannot be removed by hand from the temporary fixing agent.
• edge bead height 6.5 to 7.5 g of the prepared resin composition was applied onto an 8-inch Si wafer using a spin coater (MS-A300 manufactured by Mikasa), rotated at low speed (50 rpm x 15 sec), and then rotated at high speed under the following conditions. to distribute the liquid evenly.
• the upper surface was moved into a glass chamber, the inside of the chamber was replaced with a nitrogen atmosphere, and curing was carried out under conditions of an integrated LED light amount of 8100 mJ/cm 2 (center wavelength 405 nm, illuminance 45 mW/cm 2 ). The thickest part of the edge part and the part 2 cm or more inside the edge part were measured, and the difference was taken as the height of the edge bead.

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• 2023
  • 2023-01-19 WO PCT/JP2023/001548 patent/WO2023181609A1/ja not_active Ceased
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