WO2023228996A1 - 接着剤用洗浄剤組成物 - Google Patents

接着剤用洗浄剤組成物 Download PDF

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Publication number
WO2023228996A1
WO2023228996A1 PCT/JP2023/019445 JP2023019445W WO2023228996A1 WO 2023228996 A1 WO2023228996 A1 WO 2023228996A1 JP 2023019445 W JP2023019445 W JP 2023019445W WO 2023228996 A1 WO2023228996 A1 WO 2023228996A1
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WIPO (PCT)
Prior art keywords
component
adhesive
mass
less
wafer
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Ceased
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PCT/JP2023/019445
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English (en)
French (fr)
Japanese (ja)
Inventor
山田晃平
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Kao Corp
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Kao Corp
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Priority to CN202380022785.XA priority Critical patent/CN118742997A/zh
Priority to KR1020247027182A priority patent/KR20250019013A/ko
Publication of WO2023228996A1 publication Critical patent/WO2023228996A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/82—Compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • H10P70/20—Cleaning during device manufacture
    • 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
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • H10P70/50—Cleaning of wafers, substrates or parts of devices characterised by the part to be cleaned
    • H10P70/56—Cleaning of wafer backside
    • 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
    • H10P90/00—Preparation of wafers not covered by a single main group of this subclass, e.g. wafer reinforcement
    • H10P90/12—Preparing bulk and homogeneous wafers
    • H10P90/124—Preparing bulk and homogeneous wafers by processing the backside of the wafers
    • 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
    • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass

Definitions

  • the present disclosure relates to a cleaning agent composition for adhesives, and a method for manufacturing and cleaning a semiconductor substrate using the same.
  • the 3DIC technology is a technology in which wafers are stacked in multiple layers while being connected using through-silicon vias (TSV) or the like.
  • TSV through-silicon vias
  • processing such as polishing the back surface of the wafer on which circuits are formed (the surface on which no circuits are formed) to make it thinner, and then forming electrodes on the back surface.
  • the wafer before thinning is bonded (temporarily bonded) to a fixing member (support) with an adhesive, and after processing such as polishing and electrode formation, the wafer is separated from the fixing member. Adhesive often remains on the wafer separated from the fixing member, which may cause problems in subsequent steps. Therefore, a cleaning process is performed to remove the adhesive remaining on the wafer.
  • Patent Document 1 describes a rework solvent for cleaning an adhesive layer attached to a peeled semiconductor circuit forming substrate or a support substrate, which includes at least an amine solvent and a specific glycol ether solvent.
  • a rework solvent containing the following is disclosed.
  • Patent Document 2 describes a treatment liquid selected from hydroxylamine and hydroxylamine salt as a treatment liquid for removing dry etching residues.
  • a processing liquid for semiconductor devices contains at least one hydroxyallylamine compound, an organic basic compound, an alcoholic solvent, and a surfactant.
  • a treatment liquid containing, for example, 60% by mass of diethylene glycol monobutyl ether as an alcohol solvent and 0.1% by mass of cetyltrimethylammonium bromide as a surfactant.
  • Patent Document 3 describes, as a stripper composition for photoresist removal, a chain amine compound with a weight average molecular weight of 95 g/mol or more, a chain amine compound with a weight average molecular weight of 90 g/mol or less, A stripper composition for removing photoresist has been proposed, which contains a cyclic amine compound, an amide compound in which one or two straight or branched alkyl groups having 1 to 5 carbon atoms are substituted with nitrogen, and a polar organic solvent. There is.
  • a stripper for removal containing 55.5% by mass of diethylene glycol monomethyl ether, 20.0% by mass of diethylene glycol monomethyl ether as a polar organic solvent, and 0.01% by mass of polydimethylsiloxane transformed into polyether as a surfactant.
  • Compositions are disclosed.
  • the present disclosure provides a cleaning composition for removing adhesive remaining on a wafer, the composition containing an organic solvent (component A) and a surfactant (component B), wherein component B is a fluorine-containing composition.
  • component A an organic solvent
  • component B a surfactant
  • the present disclosure provides an adhesive remover for removing adhesive remaining on a wafer, which contains an organic solvent (component A) and a surfactant (component B), and component B is a fluorine-containing agent.
  • component A organic solvent
  • component B surfactant
  • 03% by mass or more and 5% by mass or less of an adhesive remover is
  • the present disclosure provides the following steps: (1) bonding the wafer to the fixing member with an adhesive; (2) polishing the surface of the wafer opposite to the bonding surface to the fixing member; and (3) (4) separating the processed wafer from the fixing member; (5) removing adhesive remaining on the separated wafer with a cleaning agent; A method for manufacturing a semiconductor substrate, wherein the cleaning agent contains an organic solvent (component A) and a surfactant (component B), and component B comprises a fluorine-based surfactant and a silicone-based surfactant.
  • the cleaning agent contains an organic solvent (component A) and a surfactant (component B)
  • component B comprises a fluorine-based surfactant and a silicone-based surfactant.
  • At least one selected surfactant the content of component A is 90% by mass or more and 99.97% by mass or less, and the content of component B is 0.03% by mass or more and 5% by mass or less,
  • the present invention relates to a cleaning composition and a method for manufacturing a semiconductor substrate.
  • the present disclosure provides the following steps: (1) bonding the wafer to the fixing member with an adhesive; (2) polishing the surface of the wafer opposite to the bonding surface to the fixing member; and (3) Processing the polished surface of the wafer, (4) Separating the processed wafer from the fixing member, and (5) Using an adhesive remover to remove adhesive remaining on the separated wafer.
  • a method for manufacturing a semiconductor substrate comprising: the adhesive removing agent containing an organic solvent (component A) and a surfactant (component B), and component B containing a fluorine-based surfactant and a silicone-based surfactant; At least one type of surfactant selected from surfactants, the content of component A is 90% by mass or more and 99.97% by mass or less, and the content of component B is 0.03% by mass or more and 5% by mass.
  • the present invention relates to a method for manufacturing a semiconductor substrate, which is an adhesive remover, as follows.
  • the present disclosure includes a step of removing the adhesive remaining on the wafer with a cleaning agent after separating the wafer bonded to the fixing member with an adhesive from the fixing member, and the cleaning agent includes an organic solvent ( Contains component A) and a surfactant (component B), component B is at least one surfactant selected from fluorosurfactants and silicone surfactants, and the content of component A is 90%.
  • the present invention relates to a cleaning method, which is a cleaning composition, in which the content of component B is 0.03 to 5% by mass.
  • the present disclosure includes a step of removing adhesive remaining on the wafer with an adhesive remover after separating the wafer bonded to the fixing member from the fixing member, and wherein the adhesive remover removes the adhesive remaining on the wafer.
  • the present invention relates to an adhesive removing method, which is an adhesive removing agent having a content of 90% by mass or more and 99.97% by mass or less, and a content of component B of 0.03% by mass or more and 5% by mass or less.
  • FIG. 1 is a flowchart showing each step of the method for manufacturing a semiconductor substrate according to the present disclosure.
  • FIG. 2 is a schematic diagram for explaining each step in an embodiment of the method for manufacturing a semiconductor substrate of the present disclosure.
  • processing such as electrode formation after polishing a wafer that has been bonded (temporarily bonded) to a fixing member (supporting body) with adhesive is performed at a high temperature of 150°C or higher. If the adhesive deteriorates due to heating, it tends to be difficult to remove.
  • the cleaning composition is required to have excellent removability (cleanability) for such adhesives.
  • the compositions proposed in Patent Documents 1 to 3 do not have sufficient removability for adhesives.
  • the present disclosure provides an adhesive cleaning composition with excellent adhesive removability, and a method for manufacturing and cleaning a semiconductor substrate using the same.
  • an adhesive cleaning composition with excellent adhesive removability, and a method for manufacturing and cleaning a semiconductor substrate using the same.
  • the present disclosure is based on the finding that adhesives can be efficiently removed by using a cleaning composition containing predetermined amounts of an organic solvent and a specific surfactant.
  • the present disclosure provides a cleaning composition for removing adhesive remaining on a wafer, the composition containing an organic solvent (component A) and a surfactant (component B), wherein component B is a fluorine-containing composition.
  • component A an organic solvent
  • component B a surfactant
  • At least one type of surfactant selected from surfactants and silicone surfactants the content of component A is 90% by mass or more and 99.97% by mass or less, and the content of component B is 0.9% by mass or more.
  • the present invention relates to a cleaning composition for adhesives (hereinafter also referred to as "cleaning composition of the present disclosure") having a cleaning composition of 03% by mass or more and 5% by mass or less.
  • a cleaning composition with excellent adhesive removability can be provided.
  • high-quality semiconductor substrates can be obtained with high yield.
  • the organic solvent (component A) penetrates into the adhesive remaining on the wafer and swells, thereby generating stress on the adhesive surface of the adhesive and promoting peeling of the adhesive. It is thought that then. Furthermore, by using a specific surfactant (component B) in combination with an appropriate amount of organic solvent (component A) to adsorb an appropriate amount of organic solvent (component A) to the adhesive surface, the cleaning composition can more easily penetrate into the adhesive and release the adhesive.
  • the organic solvent (hereinafter also referred to as "component A") contained in the cleaning composition of the present disclosure is, for example, selected from glycol ether (component A1), hydrocarbon (component A2), and pyrrolidone compound (component A3). Examples include organic solvents containing at least one kind. Component A may be used alone or in combination of two or more.
  • the total content of glycol ether (component A1), hydrocarbon (component A2), and pyrrolidone compound (component A3) in component A is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass. %.
  • the glycol ether (hereinafter also referred to as "component A1”) may include a compound represented by the following formula (I) from the viewpoint of improving the removability of the adhesive.
  • the content of the compound represented by the following formula (I) in component A1 is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass.
  • R represents a hydrocarbon group having 1 to 6 carbon atoms
  • AO represents an ethyleneoxy group (EO) or a propyleneoxy group (PO)
  • n is the number of moles of AO added. The number is 1 or more and 3 or less.
  • R is preferably a phenyl group or an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, from the viewpoint of improving the removability of the adhesive. An alkyl group of 1 or more and 4 or less is more preferable.
  • AO is preferably an ethyleneoxy group (EO).
  • n is preferably 1 or more and 3 or less, and more preferably 1 or 2.
  • Examples of the compound represented by the above formula (I) include monophenyl ethers such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, and triethylene glycol monophenyl ether; having an alkyl group having 1 to 6 carbon atoms; Examples include monoalkyl ethers such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, and tripropylene glycol monoalkyl ether.
  • monophenyl ethers such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, and triethylene glycol monophenyl ether; having an alkyl group having 1 to 6 carbon atoms;
  • Examples include monoalkyl ethers such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, and tripropylene glycol monoalkyl ether.
  • the compounds represented by the above formula (I) include ethylene glycol monoalkyl ether and diethylene glycol monoalkyl ether, which have an alkyl group having 1 to 6 carbon atoms, from the viewpoint of improving the removability of the adhesive.
  • Monoalkyl ethers such as , triethylene glycol monoalkyl ether, and tripropylene glycol monoalkyl ether are preferred.
  • Examples of the compound represented by the above formula (I) include ethylene glycol monobutyl ether (butyl glycol), diethylene glycol monoethyl ether (ethyl diglycol), diethylene glycol monohexyl ether (hexyl diglycol), and diethylene glycol monobutyl ether (BDG). ).
  • the hydrocarbon (hereinafter also referred to as "component A2”) may include, for example, an organic solvent such as an alicyclic hydrocarbon or an aromatic hydrocarbon, from the viewpoint of improving the removability of the adhesive.
  • an organic solvent such as an alicyclic hydrocarbon or an aromatic hydrocarbon
  • alicyclic hydrocarbons include cycloalkanes such as cyclohexane.
  • aromatic hydrocarbons include toluene, ethylbenzene, xylene, and mesitylene (1,3,5-trimethylbenzene).
  • the number of carbon atoms in component A2 is preferably 5 or more, more preferably 6 or more, from the viewpoint of improving the removability of the adhesive, and from the same viewpoint, 14 or less, more preferably 12 or less, and still more 10 or less. It is preferably 9 or less, and more preferably 9 or less.
  • component A2 is an alicyclic hydrocarbon, from the same viewpoint, the number of carbon atoms in component A2 is preferably 5 or more, preferably 14 or less, more preferably 10 or less, and even more preferably 8 or less.
  • component A2 is an aromatic hydrocarbon
  • the number of carbon atoms in component A2 is preferably 5 or more, more preferably 6 or more, even more preferably 7 or more, and preferably 14 or less, and 12 or less. More preferably, it is 10 or less.
  • examples of the pyrrolidone compound include a compound represented by the following formula (II) from the viewpoint of improving adhesive removability.
  • R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, and a hydrocarbon group having 1 to 8 carbon atoms. It is preferably a hydroxyalkyl group or a hydroxyl group having 3 or less carbon atoms, and more preferably any one of R 1 , R 2 , R 3 , or R 4 is a hydrocarbon group having 1 or more carbon atoms and 8 carbon atoms or less. It is more preferably a hydrocarbon group of 1 or more and 6 or less, and even more preferably a methyl group, an ethyl group, or a vinyl group.
  • Examples of the compound represented by the above formula (II) include 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-vinyl-2-pyrrolidone, 1-phenyl-2-pyrrolidone , 1-cyclohexyl-2-pyrrolidone, 1-octyl-2-pyrrolidone, 3-hydroxypropyl-2-pyrrolidone, 4-hydroxy-2-pyrrolidone, 4-phenyl-2-pyrrolidone and 5-methyl-2-pyrrolidone, etc. can be mentioned.
  • examples of the compound represented by the above formula (II) include 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, and 1-vinyl-2-pyrrolidone.
  • 2-pyrrolidone 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, and 1-vinyl-2-pyrrolidone.
  • 1-phenyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-octyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone are preferred; At least one selected from -ethyl-2-pyrrolidone and 1-vinyl-2-pyrrolidone is more preferred, and N-methyl-2-pyrrolidone (NMP) is even more preferred.
  • NMP N-methyl-2-pyrrolidone
  • component A includes ethylene glycol monobutyl ether (butyl glycol), diethylene glycol monoethyl ether (ethyl diglycol), diethylene glycol monohexyl ether (hexyl diglycol), and diethylene glycol monobutyl ether (BDG). , cyclohexane, and N-methyl-2-pyrrolidone (NMP). From the viewpoint of improving the removability of the adhesive, component A is preferably used alone or in combination with component A1 and component A2.
  • the content of component A in the cleaning composition of the present disclosure is 90% by mass or more, preferably 94% by mass or more, from the viewpoint of improving adhesive removability and stability as a cleaning composition, It is more preferably 95% by mass or more, and from the viewpoint of improving adhesive removability and stability as a cleaning composition, it is preferably 99.97% by mass or less and 99.5% by mass or less, and 99.9% by mass or less. It is more preferably 3% by mass or less, and even more preferably 99.1% by mass or less.
  • the content of component A in the cleaning composition of the present disclosure is 90% by mass or more and 99.97% by mass or less, preferably 90% by mass or more and 99.5% by mass or less, and 90% by mass or more and 99.5% by mass or less. It is more preferably 99.3% by mass or less, and even more preferably 95% by mass or more and 99.1% by mass or less.
  • the content of component A refers to their total content.
  • the content of each component in the cleaning composition can be the content of each component at the time of cleaning, that is, at the time when the cleaning composition starts to be used for cleaning.
  • the content of each component in the cleaning composition of the present disclosure can be considered as the blending amount of each component in the cleaning composition of the present disclosure in one or more embodiments.
  • the surfactant (hereinafter also referred to as “component B") contained in the cleaning composition of the present disclosure includes a fluorine-based surfactant (component B1) and a silicone-based surfactant (component B1). At least one type selected from B2). Component B may be used alone or in combination of two or more.
  • component B1 fluorine-based surfactant
  • component B1 examples include surfactants having a perfluoroalkyl group from the viewpoint of improving adhesive removability.
  • the fluorosurfactant commercially available products can be used. Examples of commercially available fluorosurfactants include Surflon (registered trademark) S661, S647, and S651 manufactured by AGC Seimi Chemical Co., Ltd.
  • silicone surfactant examples include polyether-modified silicone from the viewpoint of improving adhesive removability.
  • examples of polyether-modified silicones include linear polyether-modified silicones, linear alkyl-co-modified polyether-modified silicones, branched polyether-modified silicones, and branched alkyl-co-modified polyether-modified silicones.
  • linear polyether-modified silicones are preferred, such as polyoxyethylene/methylpolysiloxane copolymers such as PEG-12 dimethicone.
  • the HLB of component B2 is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and preferably 8 or less, more preferably 7 or less, and still more preferably 6 or less.
  • the HLB of component B is preferably 2 or more and 8 or less, more preferably 3 or more and 7 or less, and even more preferably 4 or more and 6 or less.
  • the HLB of a surfactant is a value determined by the Griffin method.
  • the content of component B in the cleaning composition of the present disclosure is 0.03% by mass or more, preferably 0.075% by mass or more, and 0.25% by mass from the viewpoint of improving adhesive removability.
  • the above is more preferable, 0.5% by mass or more is even more preferable, 0.75% by weight or more is even more preferable, and from the viewpoint of improving adhesive removability and stability as a cleaning composition, 5% by weight or less
  • the content is preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less.
  • the content of component B in the cleaning composition of the present disclosure is 0.03% by mass or more and 5% by mass or less, preferably 0.075% by mass or more and 4% by mass or less, and 0.075% by mass or more and 4% by mass or less. It is more preferably .25% by mass or more and 3% by mass or less, even more preferably 0.5% by mass or more and 2% by mass or less, and even more preferably 0.75% by mass or more and 2% by mass or less.
  • the content of component B refers to their total content.
  • the cleaning composition of the present disclosure does not contain water or has a water content of 10% by mass or less.
  • water hereinafter also referred to as "component C"
  • component C includes ion exchange water, RO water, distilled water, pure water, ultrapure water, and the like.
  • the content of component C in the cleaning composition of the present disclosure is the remainder after excluding component A, component B, and optional components described below. be able to.
  • the content of component C in the cleaning composition of the present disclosure is preferably 10% by mass or less, more preferably 5% by mass or less, and 3% by mass or less. is more preferable, 1% by weight or less is even more preferable, and 0% by weight (ie, not included) is even more preferable.
  • the cleaning composition of the present disclosure may further contain water (component C) or other components as necessary.
  • Other components include components that can be used in ordinary cleaning agents, such as solvents other than component A, alkaline agents, amines, surfactants other than component B, chelating agents, thickeners, and dispersants. agents, rust preventives, polymer compounds, solubilizers, antioxidants, preservatives, antifoaming agents, antibacterial agents, and the like.
  • the cleaning composition of the present disclosure can be substantially free of at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts.
  • the content of the hydroxylamine compound in the cleaning composition of the present disclosure is preferably less than 1% by mass, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0. Mass%.
  • the cleaning composition of the present disclosure preferably does not substantially contain a basic compound.
  • the content of the basic compound in the cleaning composition of the present disclosure is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0.
  • the cleaning composition of the present disclosure may be substantially free of chain amine compounds having a weight average molecular weight of 95 g/mol or more.
  • the content of the chain amine compound having a weight average molecular weight of 95 g/mol or more in the cleaning composition of the present disclosure is preferably less than 0.1% by mass, more preferably 0.05% by mass or less, and even more preferably It is 0% by mass.
  • the cleaning composition of the present disclosure may be substantially free of chain amine compounds having a weight average molecular weight of 90 g/mol or less.
  • the content of the chain amine compound having a weight average molecular weight of 90 g/mol or less in the cleaning composition of the present disclosure is preferably less than 0.5% by mass, more preferably 0.1% by mass or less, and even more preferably It is 0% by mass.
  • the cleaning composition of the present disclosure can be substantially free of cyclic amine compounds.
  • the content of the cyclic amine compound in the cleaning composition of the present disclosure is preferably less than 0.1% by mass, more preferably 0.05% by mass or less, and even more preferably 0% by mass.
  • the cleaning composition of the present disclosure can be substantially free of 1,1,1,3,3-pentafluorobutane.
  • the content of 1,1,1,3,3-pentafluorobutane in the cleaning composition of the present disclosure is preferably less than 70% by mass, more preferably 50% by mass or less, and even more preferably 10% by mass.
  • the content is preferably 1% by mass or less, and even more preferably 0% by mass.
  • the cleaning composition of the present disclosure can be substantially free of at least one solvent selected from isopropanolamine, monoethanolamine, and N-substituted ethanolamine.
  • the content of the solvent in the cleaning composition of the present disclosure is preferably less than 3% by mass, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and even more preferably 0% by mass. be.
  • the cleaning composition of the present disclosure can be substantially free of etchant.
  • the content of the etchant in the cleaning composition of the present disclosure is preferably less than 0.1% by weight, more preferably 0.05% by weight or less, and even more preferably 0% by weight.
  • the cleaning composition of the present disclosure can be produced by blending the components A to B and, if necessary, the optional components (component C and other components) described above by a known method.
  • the cleaning composition of the present disclosure can contain at least the components A to B described above. Therefore, the present disclosure relates to a method for producing a cleaning composition, which includes at least the step of blending the components AB.
  • "blending" includes mixing components A to B and optionally the above-mentioned optional components (component C and other components) simultaneously or in any order.
  • the preferred blending amount of each component can be the same as the preferred content of each component of the cleaning composition of the present disclosure described above.
  • the cleaning composition of the present disclosure can be used to remove adhesive remaining on a wafer after the wafer is separated from the fixing member.
  • the cleaning composition of the present disclosure is an adhesive remover (hereinafter also referred to as "the adhesive remover of the present disclosure").
  • the cleaning composition of the present disclosure or the adhesive remover of the present disclosure is used to remove adhesive from a substrate (wafer) to which the adhesive is attached. That is, the present disclosure, in one aspect, relates to the use of a cleaning composition of the present disclosure or an adhesive remover of the present disclosure to remove adhesive from a substrate to which adhesive has been deposited.
  • An example of the object to be cleaned is a substrate (wafer) to which an adhesive is attached.
  • the substrate may be a semiconductor substrate.
  • the semiconductor substrate examples include wafers such as silicon wafers, germanium wafers, gallium-arsenide wafers, gallium-phosphorus wafers, and gallium-arsenide-aluminum wafers.
  • the substrate includes a substrate having pads and/or lands that are parts for bonding and mounting. Examples of pad and land members include metals such as gold and copper.
  • the substrate (wafer) to which the adhesive is attached may be a wafer that has been adhered to a fixing member with an adhesive and has been separated from the fixing member.
  • the wafer after being separated from the fixing member is a substrate having a metal pad and an adhesive attached to the metal pad.
  • the present disclosure provides a method of using the cleaning composition of the present disclosure as a cleaning agent for removing adhesive remaining on a wafer after the wafer adhesively adhered to a fixing member is separated from the fixing member.
  • the present disclosure provides a method of using the adhesive remover of the present disclosure as a remover for removing adhesive remaining on a wafer after the wafer adhesively adhered to a fixing member is separated from the fixing member.
  • the wafer fixed to the fixing member with an adhesive has been subjected to a heat treatment at a temperature of 230° C. or higher.
  • the heat treatment includes heat treatment in a processing step described below.
  • the substrate (wafer) to which an adhesive has been adhered may be a substrate to which an adhesive has been adhered, which is used in a manufacturing process of a three-dimensional integrated circuit (3DIC).
  • the present disclosure relates, in one aspect, to the use of the cleaning compositions of the present disclosure as a cleaning agent for removing adhesives used in three-dimensional integrated circuit manufacturing processes.
  • the present disclosure in other aspects, relates to the use of the adhesive remover of the present disclosure as a remover for removing adhesives used in three-dimensional integrated circuit manufacturing processes.
  • the substrate (wafer) to which the adhesive is attached has been subjected to a heat treatment at a temperature of 230° C. or higher.
  • the heat treatment includes heat treatment in a processing step described below.
  • the present disclosure provides the following steps: (1) bonding the wafer to the fixing member with an adhesive; (2) polishing the surface of the wafer opposite to the bonding surface to the fixing member; and (3) (4) separating the processed wafer from the fixing member; (5) removing adhesive remaining on the separated wafer with a cleaning agent; A method for manufacturing a semiconductor substrate, wherein the cleaning agent contains an organic solvent (component A) and a surfactant (component B), and component B comprises a fluorine-based surfactant and a silicone-based surfactant.
  • the cleaning agent contains an organic solvent (component A) and a surfactant (component B)
  • component B comprises a fluorine-based surfactant and a silicone-based surfactant.
  • the present invention relates to a method for manufacturing a semiconductor substrate (hereinafter also referred to as "the method for manufacturing a semiconductor substrate of the present disclosure"), which is a cleaning composition.
  • the cleaning agent used in step (5) is the cleaning agent composition of the present disclosure described above.
  • FIG. 1 is a flowchart showing each step of the method for manufacturing a semiconductor substrate according to the present disclosure.
  • FIG. 2 is a schematic diagram for explaining each step in an embodiment of the method for manufacturing a semiconductor substrate of the present disclosure.
  • Step (1) is a step (adhesion step) of bonding the wafer 3 to the fixing member 1 with the adhesive 2 (step S1).
  • step (1) includes a step (1-1) of applying an adhesive to the surface of the wafer or the fixing member to form an adhesive layer, and a step (1-1) of coating the wafer and the fixing member with the adhesive layer. It includes a step (1-2) of bonding through a heat treatment and bonding.
  • the wafer used in step (1) examples include silicon wafers and glass wafers with a diameter of 100 to 500 mm and a thickness of 50 to 2,000 ⁇ m.
  • the wafer used in step (1) is a substrate having metal pads.
  • the fixing member used in step (1) is not particularly limited, but includes, for example, a substrate such as a silicon wafer or a glass plate with a diameter of 100 to 500 mm and a thickness of 50 to 20,000 ⁇ m.
  • the adhesive used in step (1) should be able to bond the substrate to the fixing member, have durability that can withstand polishing and processing steps, and allow the substrate to be easily separated from the fixing member in the separation step.
  • an adhesive for example, an adhesive used in the manufacturing process of 3DIC can be mentioned.
  • the adhesive used in the 3DIC manufacturing process include polysiloxane-based, acrylic-based, or methacrylic-based adhesives (adhesive compositions).
  • the adhesive composition described in JP-A-2021-161196 can be mentioned.
  • the adhesive composition used in step (1) contains a polysiloxane, an acrylic ester, or a methacrylic ester as an adhesive component, and further contains a platinum group metal catalyst and a release agent. It may also contain components, solvents, etc.
  • the viscosity of the adhesive composition used in step (1) can be adjusted by appropriately changing the concentration of the contained components, etc., depending on the coating method, film thickness, etc.
  • step (1-1) the method for applying the adhesive (adhesive composition) is not particularly limited, but examples include spin coating.
  • the thickness of the coating layer (adhesive layer) of the adhesive (adhesive composition) is, for example, 5 to 500 ⁇ m.
  • step (1-1) includes bonding the surface of the wafer having the metal pad and the fixing member with an adhesive.
  • the temperature of the heat treatment is, for example, 80° C. or higher, and preferably 150° C. or lower from the viewpoint of suppressing excessive curing of the adhesive.
  • the heat treatment time is, for example, 30 seconds or more, and is preferably 10 minutes or less from the viewpoint of suppressing deterioration of the adhesive layer and other members. Heating can be performed using a hot plate, oven, or the like.
  • the thickness of the adhesive layer after heat treatment is, for example, 5 ⁇ m or more and 100 ⁇ m or less.
  • Step (2) is a step (polishing step) of polishing the surface (back surface) 3a of the wafer 3 opposite to the surface bonded to the fixing member 1 (step S2).
  • the polishing method include mechanical polishing using abrasive grains, chemical mechanical polishing, and the like.
  • the thickness of the polished wafer (thinned wafer) is preferably 200 ⁇ m or less, for example, 50 ⁇ m to 200 ⁇ m.
  • Step (3) is a step (processing step) of processing the polished surface (back surface of the thinned wafer) 3a of the wafer 3 (step S3).
  • step (3) includes an electrode forming step, a metal wiring forming step, a protective film forming step, and the like.
  • metal sputtering to form electrodes wet etching, resist coating, pattern formation, resist peeling, dry etching, metal plating formation, silicon etching to form through-silicon vias (TSV), and oxide film formation on silicon surfaces.
  • TSV through-silicon vias
  • oxide film formation on silicon surfaces examples include the following.
  • the processing is performed at a high temperature of 150° C. or higher in one or more embodiments.
  • heat treatment at a temperature of 250° C. or more and 350° C. or less may be performed, for example.
  • Step (4) is a step (separation step) of separating the processed wafer 3 and the fixing member 1 (step S4).
  • the separation method include solvent peeling, laser peeling, mechanical peeling, and the like.
  • Step (5) is a step (cleaning step) of removing the adhesive (adhesive residue) 2a remaining on the separated wafer 3 with a cleaning agent (step S5).
  • the separated wafer is a substrate to which an adhesive is attached (the above-mentioned object to be cleaned), such as a substrate to which an adhesive is attached to a metal pad.
  • the cleaning agent used in step (5) include the cleaning agent composition of the present disclosure described above.
  • An example of a method for removing the adhesive is immersion cleaning.
  • the temperature of the cleaning agent is preferably 40° C. or more and 70° C.
  • the immersion time is preferably 1 minute or more and 60 minutes or less. It is preferable that the cleaning agent is subjected to ultrasonic vibration, for example, 25 to 50 kHz is preferable, and 35 to 45 kHz is more preferable from the viewpoint of suppressing damage to the substrate.
  • the substrate after cleaning may be rinsed with water or alcohol, and then dried.
  • step (5) is a step of removing adhesive remaining on the separated wafers using an adhesive remover.
  • the adhesive removing agent used in step (5) include the adhesive removing agent of the present disclosure described above. That is, in one or more embodiments, the method for manufacturing a semiconductor substrate of the present disclosure includes (1) bonding the wafer to a fixing member with an adhesive; and (2) opposite bonding surface of the wafer to the fixing member. (3) Processing the polished surface of the wafer; (4) Separating the processed wafer from the fixing member; and (5) Remaining on the separated wafer.
  • a method of manufacturing a semiconductor substrate includes the step of removing an adhesive using an adhesive remover of the present disclosure.
  • the present disclosure includes a step (cleaning step) of removing the adhesive remaining on the wafer with a cleaning agent after separating the wafer bonded to the fixing member with an adhesive from the fixing member, and the cleaning agent is , contains an organic solvent (component A) and a surfactant (component B), where component B is at least one surfactant selected from fluorine-based surfactants and silicone-based surfactants;
  • a cleaning method hereinafter referred to as “this disclosure (also referred to as “cleaning method”).
  • the cleaning agent is the cleaning agent composition of the present disclosure described above.
  • the method for removing the adhesive includes the same method as the removal method in step (5) in the semiconductor substrate manufacturing method of the present disclosure described above.
  • the wafer bonded to the fixing member with an adhesive is preferably subjected to heat treatment at a temperature of 230° C. or higher, more preferably 270° C. or higher, in one or more embodiments. .
  • heat treatment at a temperature of 230°C or higher is for joining a circuit-formed substrate with a device such as a semiconductor chip and another circuit-formed substrate using solder or metal fine particles. Examples include heat treatment.
  • the heat treatment step may be performed after the processing step (3) and before step (4).
  • the object to be cleaned in the cleaning method of the present disclosure includes a wafer that has undergone steps (1) to (4) in the semiconductor substrate manufacturing method of the present disclosure.
  • the cleaning step in the cleaning method of the present disclosure includes separating the wafer bonded to the fixing member with an adhesive from the fixing member, and then removing the adhesive remaining on the wafer with an adhesive remover. process (removal process).
  • the adhesive removing agent in the removing step include the adhesive removing agent of the present disclosure described above. That is, in one or more embodiments, the cleaning method of the present disclosure removes the adhesive remaining on the wafer with the adhesive remover of the present disclosure after separating the wafer bonded to the fixing member with an adhesive from the fixing member. This is an adhesive removal method including a step of removing adhesive.
  • the present disclosure relates to a kit for use in either the cleaning method of the present disclosure or the semiconductor substrate manufacturing method of the present disclosure (hereinafter also referred to as "the kit of the present disclosure").
  • the kit of the present disclosure is a kit for producing the cleaning composition of the present disclosure. According to the kit of the present disclosure, a cleaning composition with excellent adhesive removability can be obtained.
  • the kit of the present disclosure includes a solution containing component A (first solution) and a solution containing component B (second solution) in a state where they are not mixed with each other, A kit (two-component cleaning composition) in which the first liquid and the second liquid are mixed at the time of use is included. After the first liquid and the second liquid are mixed, they may be diluted with component C (water) as necessary. Each of the first liquid and the second liquid may contain the above-mentioned optional components as necessary.
  • Cleaning rate (Number of pads where adhesive was present before cleaning - Number of pads where adhesive was present after cleaning) / (Number of pads where adhesive was present before cleaning) x 100 ⁇ Evaluation criteria> A: Cleaning rate of 90% or more B: Cleaning rate of 80% or more and less than 90% C: Cleaning rate of 70% or more and less than 80% D: Cleaning rate of less than 70% A test piece with adhesive present was used. The test piece has a size of 15 mm x 15 mm, and an adhesive (adhesive layer) is present on the entire surface of metal pads with a diameter of 450 ⁇ m arranged at a pitch of 900 ⁇ m.
  • metal pads made of gold and having a diameter of 450 ⁇ m are arranged in a grid pattern at intervals of 450 ⁇ m.
  • Acrylic adhesive was used as the adhesive.
  • the adhesive layer was formed by applying an adhesive to the entire surface of the metal pad and then heating it at 260° C. for 20 minutes. The thickness of the adhesive layer after heat treatment is 50 ⁇ m.
  • the test piece has a size of 15 mm x 15 mm, and has Al electrodes of 3 mm x 2.5 mm on a silicon wafer without any gaps.
  • the cleaning compositions of Examples 1 to 12 include Comparative Example 1 which does not contain component B, Comparative Example 2 which uses polyoxyethylene lauryl ether (non-component B) as a surfactant, and Comparative Example 2 which uses polyoxyethylene lauryl ether (non-component B) as a surfactant. It was found that the removability of the adhesive was excellent compared to Comparative Example 3, in which the content of component A was less than 0.03% by mass, and Comparative Examples 4 and 5, in which the content of component A was less than 90% by mass. It was also found that the cleaning compositions of Examples 1 to 12 were able to suppress damage to Al electrodes.
  • a cleaning composition with excellent adhesive removability can be provided. And by using the cleaning composition of the present disclosure, productivity of semiconductor substrates can be improved.
  • Fixing member 2 Adhesive 2a Adhesive residue 3 Wafer 3a Wafer polishing/processing surface

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  • Cleaning Or Drying Semiconductors (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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JP2004189943A (ja) * 2002-12-12 2004-07-08 Showa Denko Kk 洗浄剤組成物、半導体ウェーハの洗浄方法、製造方法および半導体ウェーハ
WO2014057860A1 (ja) * 2012-10-11 2014-04-17 セントラル硝子株式会社 基板の洗浄方法および洗浄液組成物
JP2016011361A (ja) * 2014-06-27 2016-01-21 東京応化工業株式会社 剥離用組成物及び剥離方法
WO2016194917A1 (ja) * 2015-06-01 2016-12-08 富士フイルム株式会社 仮止め接着剤、接着フィルム、接着性支持体、積層体およびキット
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WO2020179819A1 (ja) * 2019-03-05 2020-09-10 日産化学株式会社 洗浄剤組成物及び洗浄方法
JP2020189927A (ja) * 2019-05-22 2020-11-26 信越化学工業株式会社 基板用仮接着剤の洗浄液、基板の洗浄方法および支持体または基板の洗浄方法

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Publication number Priority date Publication date Assignee Title
JPH04111314A (ja) * 1990-08-31 1992-04-13 Nippon Steel Chem Co Ltd ウエハ研磨用接着剤
JP2001316691A (ja) * 2000-02-29 2001-11-16 Showa Denko Kk 洗浄剤組成物、洗浄方法及びその用途
JP2004189943A (ja) * 2002-12-12 2004-07-08 Showa Denko Kk 洗浄剤組成物、半導体ウェーハの洗浄方法、製造方法および半導体ウェーハ
WO2014057860A1 (ja) * 2012-10-11 2014-04-17 セントラル硝子株式会社 基板の洗浄方法および洗浄液組成物
JP2016011361A (ja) * 2014-06-27 2016-01-21 東京応化工業株式会社 剥離用組成物及び剥離方法
WO2016194917A1 (ja) * 2015-06-01 2016-12-08 富士フイルム株式会社 仮止め接着剤、接着フィルム、接着性支持体、積層体およびキット
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