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
  • H10P70/00—Cleaning of wafers, substrates or parts of devices
  • H10P70/20—Cleaning during device manufacture
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • C—CHEMISTRY; METALLURGY
  • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
• • 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
  • C11D3/2068—Ethers
• • 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
  • C11D3/24—Organic compounds containing halogen
  • C11D3/245—Organic compounds containing halogen containing fluorine
• • 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
• • 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
  • C11D3/30—Amines; Substituted amines ; Quaternized amines
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/28—Organic compounds containing halogen
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/32—Organic compounds containing nitrogen
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/32—Organic compounds containing nitrogen
  • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
  • C11D7/5004—Organic solvents
  • C11D7/5013—Organic solvents containing nitrogen
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
  • C11D7/5004—Organic solvents
  • C11D7/5022—Organic solvents containing oxygen
• • 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
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
  • H10P50/282—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials
  • H10P50/283—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials by chemical means
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
  • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2483/00—Presence of polysiloxane
• • 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
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces
  • C11D2111/22—Electronic devices, e.g. PCBs 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/7422—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/744—Details of chemical or physical process used for separating the auxiliary support from a device or a wafer

Definitions

• the present invention relates to a cleaning composition and a cleaning method used for removing an adhesive residue after peeling temporary adhesion by an adhesive layer obtained by using a polysiloxane adhesive formed on a semiconductor substrate, for example. ..
• each integrated wafer is thinned by polishing the side opposite to the formed circuit surface (that is, the back surface), and the thinned semiconductor wafers are stacked.
• a semiconductor wafer before thinning (also simply referred to as a wafer here) is adhered to a support for polishing with a polishing apparatus. Since the adhesion at that time must be easily peeled off after polishing, it is called temporary adhesion. This temporary adhesion must be easily removed from the support, and if a large force is applied to the removal, the thinned semiconductor wafer may be cut or deformed. Easily removed. However, it is not preferable that the back surface of the semiconductor wafer be removed or displaced by polishing stress during polishing. Therefore, the performance required for temporary adhesion is to withstand the stress during polishing and be easily removed after polishing.
• the performance is required to have high stress (strong adhesive force) in the plane direction during polishing and low stress (weak adhesive force) in the vertical direction during removal.
• the processing step may reach a high temperature of 150° C. or higher, and heat resistance is also required.
• polysiloxane adhesives that can provide these properties are mainly used as temporary adhesives. Then, in polysiloxane-based adhesion using a polysiloxane-based adhesive, adhesive residue often remains on the substrate surface after peeling the thinned substrate, but in order to avoid problems in subsequent steps.
• a cleaning agent composition for removing this residue and cleaning the surface of the semiconductor substrate has been developed (for example, Patent Documents 1 and 2), and in the recent semiconductor field, a new cleaning agent composition has been developed. There is always a desire for.
• Patent Document 1 discloses a siloxane resin remover containing a polar aprotic solvent and a quaternary ammonium hydroxide
• Patent Document 2 discloses a cured resin remover containing alkyl fluoride ammonium.
• the emergence of a more effective detergent composition is desired.
• the present invention has been made in view of the above circumstances, and when cleaning a substrate such as a semiconductor substrate, an adhesive residue after peeling temporary adhesion by an adhesive layer obtained using a polysiloxane adhesive is used. It is an object of the present invention to provide a cleaning composition and a cleaning method that can obtain a good cleaning property and that can clean a substrate with high efficiency without corroding the substrate.
• Patent Documents 1 and 2 do not include a description that teaches or suggests a specific configuration of the cleaning composition of the present invention.
• the present invention is 1.
• a cleaning composition used for removing a polysiloxane adhesive remaining on a substrate comprising tetra(hydrocarbon)ammonium fluoride and an organic solvent, wherein the organic solvent is an alkylene glycol dialkyl ether.
• a cleaning composition comprising a lactam compound represented by the formula (1), (In the formula, R 101 represents an alkyl group having 1 to 6 carbon atoms, and R 102 represents an alkylene group having 1 to 6 carbon atoms.) 2.
• the alkylene glycol dialkyl ether is at least one selected from ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ethane, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol dipropyl ether.
• 1 or 2 cleaning composition including 4. Any one of 1 to 3, wherein the tetra(hydrocarbon)ammonium fluoride includes at least one selected from tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride and tetrabutylammonium fluoride.
• Cleaning composition 5.
• the detergent composition according to any one of 1 to 4, wherein the ratio of the alkylene glycol dialkyl ether to the lactam compound is a mass ratio of the alkylene glycol dialkyl ether:the lactam compound 30:70 to 80:20, 6.
• the lactam compound contains at least one selected from N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, and the alkylene glycol dialkyl ether is ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl.
• One cleaning composition comprising at least one selected from tetraethylammonium, tetrapropylammonium fluoride and tetrabutylammonium fluoride, 7. 6.
• the detergent composition according to 6, wherein the ratio of the alkylene glycol dialkyl ether to the lactam compound is a mass ratio of the alkylene glycol dialkyl ether:the lactam compound 30:70 to 80:20, 8.
• Agent composition 9.
• a cleaning method which comprises removing the adhesive residue remaining on a substrate by using the cleaning composition according to any one of 1 to 8. 10.
• the cleaning composition comprises: a third step of performing cleaning, and a fourth step of cleaning and removing the adhesive residue remaining on the peeled semiconductor substrate with a cleaning composition.
• a method for manufacturing a processed semiconductor substrate which comprises using the cleaning composition according to any one of 1 to 8.
• the cleaning composition of the present invention it is possible to clean a substrate such as a semiconductor substrate to which an adhesive residue is adhered after peeling temporary adhesion by an adhesive layer obtained by using a polysiloxane adhesive in a short time. Therefore, it is possible to perform the process with high efficiency without corroding the substrate.
• the cleaning composition of the present invention is a cleaning composition used for removing a polysiloxane adhesive remaining on a substrate such as a semiconductor substrate, and comprises tetra(hydrocarbon)ammonium fluoride and an organic solvent.
• the organic solvent contains an alkylene glycol dialkyl ether and a lactam compound represented by the formula (1).
• R 101 represents an alkyl group having 1 to 6 carbon atoms
• R 102 represents an alkylene group having 1 to 6 carbon atoms.
• hydrocarbon group in tetra(hydrocarbon)ammonium fluoride examples include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and 6 to 20 carbon atoms.
• alkyl groups having 1 to 20 carbon atoms alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and 6 to 20 carbon atoms.
• Aryl groups and the like are examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride.
• the tetra(hydrocarbon)ammonium fluoride comprises tetraalkylammonium fluoride.
• Specific examples of the tetraalkylammonium fluoride include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride and the like. Of these, tetrabutylammonium fluoride is preferable.
• a hydrate may be used. Further, tetra(hydrocarbon)ammonium fluoride may be used alone or in combination of two or more kinds.
• the amount of tetra(hydrocarbon)ammonium fluoride is not particularly limited as long as it dissolves in the solvent contained in the detergent composition, but is usually 0.1 to 30% by mass with respect to the detergent composition. is there.
• alkylene glycol dialkyl ether examples include ethylene glycol dimethyl ether (also referred to as dimethoxyethane; the same applies below), ethylene glycol diethyl ether (diethoxyethane), ethylene glycol dipropylethane (dipropoxyethane), ethylene glycol dibutyl ether (diene glycol Butoxyethane), propylene glycol dimethyl ether (dimethoxypropane), propylene glycol diethyl ether (diethoxypropane), propylene glycol dipropyl ether (dipropoxypropane) and the like, but are not limited thereto.
• the alkylene glycol dialkyl ethers may be used alone or in combination of two or more.
• the amount of alkylene glycol dialkyl ether is 1 to 98.9% by mass based on the detergent composition.
• alkyl group having 1 to 6 carbon atoms examples include methyl group, ethyl group, n-propyl group, n-butyl group and the like. Specific examples include, but are not limited to, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and the like.
• lactam compound represented by the above formula (1) examples include an ⁇ -lactam compound, a ⁇ -lactam compound, a ⁇ -lactam compound, and a ⁇ -lactam compound. These may be used alone or Two or more kinds can be used in combination.
• the lactam compound represented by the above formula (1) contains 1-alkyl-2-pyrrolidone (N-alkyl- ⁇ -butyrolactam), and in a more preferred embodiment, N- It contains methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it contains N-methylpyrrolidone (NMP).
• the amount of the lactam compound represented by the above formula (1) is usually 1 to 98.9 mass% with respect to the detergent composition.
• the cleaning composition of the present invention usually contains only an organic solvent as a solvent.
• only organic solvent means that only the organic solvent is intentionally used as a solvent, and the existence of water contained in the organic solvent and other components is not denied.
• the detergent composition of the present invention contains only the above alkylene glycol dialkyl ether and the lactam compound represented by the above formula (1) as the organic solvent.
• the above-mentioned tetra(hydrocarbon)ammonium fluoride is dissolved in the solvent contained in the detergent composition.
• the detergent composition of the present invention can be obtained by mixing the above-mentioned tetra(hydrocarbon)ammonium fluoride, the above-mentioned alkylene glycol dialkyl ether, the lactam compound represented by the above formula (1) and, if necessary, other components.
• the components can be mixed in any order as long as there is no problem such as a problem such as precipitation or separation of a liquid that does not achieve the object of the present invention. .. That is, a part of all the components of the cleaning composition may be mixed in advance and then the remaining components may be mixed, or all the components may be mixed at once. If necessary, the detergent composition may be filtered. Further, when the components used have hygroscopicity or deliquescent, for example, all or part of the work of preparing the detergent composition may be performed under an inert gas.
• the above-described cleaning composition of the present invention has good cleaning properties for polysiloxane adhesives, and has excellent cleaning speed and cleaning durability. Specifically, regarding the cleaning rate, at room temperature (23° C.), when the adhesive layer obtained from the adhesive composition was brought into contact with the cleaning composition of the present invention for 5 minutes, the film thickness decreased before and after the contact.
• the etching rate [ ⁇ m/min] calculated by dividing the measured amount by the cleaning time is usually 5.0 [ ⁇ m/min] or more, and in a preferred embodiment, 7.0 [ ⁇ m/min] or more, It is 7.5 [ ⁇ m/min] or more in a more preferred embodiment, 8.0 [ ⁇ m/min] or more in an even more preferred embodiment, and 9.0 [ ⁇ m/min] or more in an even more preferred embodiment.
• the cleaning durability when the adhesive solid 1 g obtained from the adhesive composition is brought into contact with the cleaning composition 2 g of the present invention at room temperature (23° C.), the cleaning composition of the present invention is obtained. Usually dissolves most of the adhesive solid in 12 to 24 hours, dissolves and removes the adhesive solid in 2 to 12 hours in a preferred embodiment, and dissolves the adhesive solid in 1 to 2 hours in a more preferred embodiment. Cut off.
• the present invention it is possible to wash the substrate in a short time by washing and removing the polysiloxane-based adhesive remaining on the substrate such as a semiconductor substrate by using the above-mentioned detergent composition, and it is possible to achieve high efficiency.
• excellent cleaning of substrates such as semiconductor substrates can be performed.
• the cleaning composition of the present invention is used for cleaning the surface of various substrates such as semiconductor substrates, and the object of the cleaning is not limited to silicon semiconductor substrates, for example, germanium substrates.
• Suitable use of the cleaning composition of the present invention in a semiconductor process includes use in a method of manufacturing a thinned substrate used in a semiconductor packaging technology such as TSV. Specifically, a first step of manufacturing a laminated body including a semiconductor substrate, a supporting substrate, and an adhesive layer obtained from an adhesive composition, a second step of processing the semiconductor substrate of the obtained laminated body, and a processing In the manufacturing method including a third step of peeling the semiconductor substrate later and a fourth step of cleaning and removing the adhesive residue remaining on the peeled semiconductor substrate with a cleaning composition, the cleaning of the present invention as a cleaning composition An agent composition is used.
• the adhesive composition used for forming the adhesive layer in the first step is typically at least silicone, acrylic resin, epoxy resin, polyamide, polystyrene, polyimide or phenol resin. Although an adhesive selected from one kind may be used, it is effective to employ the cleaning composition of the present invention particularly for cleaning a polysiloxane-based adhesive, and among them, a component which is cured by a hydrosilylation reaction.
• the cleaning composition of the present invention is effective for cleaning and removing the adhesive residue of the polysiloxane adhesive containing (A).
• the component (A) which is cured by the hydrosilylation reaction contained in the adhesive composition is, for example, a siloxane unit (Q unit) represented by SiO 2 or a siloxane unit (R 1 R 2 R 3 SiO 1/2 ) represented by M unit), one or two kinds selected from the group consisting of a siloxane unit (D unit) represented by R 4 R 5 SiO 2/2 and a siloxane unit (T unit) represented by R 6 SiO 3/2.
• polysiloxane (A1) containing the above units and a platinum group metal-based catalyst (A2)
• the polysiloxane (A1) is a siloxane unit (Q′ unit) represented by SiO 2 , R 1 ′R 2 'R 3' siloxane units (M 'units), R 4' represented by SiO 1/2 R 5 'siloxane units (D represented by SiO 2/2' units) and R 6 'SiO 3/2
• M'units, D'units and T'units which contains one or more units selected from the group consisting of siloxane units (T' units) represented by Containing a polyorganosiloxane (a1), a siloxane unit represented by SiO 2 (Q′′ unit), a siloxane unit represented by R 1 ′′R 2 ′′R 3 ′′SiO 1/2 (M′′ unit), R 4 "R 5" siloxane units (D represented by
• R 1 to R 6 are groups or atoms bonded to a silicon atom, and each independently represent an alkyl group, an alkenyl group or a hydrogen atom.
• R 1 ′ to R 6 ′ are groups bonded to a silicon atom, and each independently represent an alkyl group or an alkenyl group, and at least one of R 1 ′ to R 6 ′ is an alkenyl group.
• R 1 ′′ to R 6 ′′ are groups or atoms bonded to a silicon atom, and each independently represent an alkyl group or a hydrogen atom, but at least one of R 1 ′′ to R 6 ′′ is a hydrogen atom. ..
• the alkyl group may be linear, branched or cyclic, but is preferably a linear or branched alkyl group, and the carbon number thereof is not particularly limited, but is usually 1 to 40. It is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less.
• linear or branched alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group.
• N-pentyl group 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl- n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl -N-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2, 2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1-e
• cyclic alkyl group examples include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3 -Methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group Group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3- Dimethyl-cyclobutyl group, 2,2-dimethyl-methyl-
• the alkenyl group may be linear or branched, and the carbon number thereof is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and still more It is preferably 10 or less.
• alkenyl group examples include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and 2-methyl-1.
• the polysiloxane (A1) includes the polyorganosiloxane (a1) and the polyorganosiloxane (a2), but is included in the alkenyl group contained in the polyorganosiloxane (a1) and the polyorganosiloxane (a2).
• a hydrogen atom (Si—H group) forms a crosslinked structure by a hydrosilylation reaction with the platinum group metal-based catalyst (A2) and is cured.
• the polyorganosiloxane (a1) contains one or more units selected from the group consisting of Q'units, M'units, D'units and T'units, as well as the M'units, D'units and It contains at least one selected from the group consisting of T′ units.
• the polyorganosiloxane (a1) two or more kinds of polyorganosiloxane satisfying such conditions may be used in combination.
• Preferred combinations of two or more selected from the group consisting of Q'units, M'units, D'units and T'units include (Q' units and M'units), (D' units and M'units), (T′ unit and M′ unit), (Q′ unit, T′ unit and M′ unit), but not limited thereto.
• the polyorganosiloxane (a2) contains one or more units selected from the group consisting of Q′′ units, M′′ units, D′′ units and T′′ units, and the above M′′ units, D′′ units and It contains at least one selected from the group consisting of T′′ units.
• the polyorganosiloxane (a2) two or more polyorganosiloxanes satisfying such a condition may be used in combination.
• Preferred combinations of two or more selected from the group consisting of Q′′ unit, M′′ unit, D′′ unit and T′′ unit include (M′′ unit and D′′ unit), (Q′′ unit and M′′ unit), (Q′′ unit, T′′ unit, M′′ unit), but not limited thereto.
• the polyorganosiloxane (a1) is composed of a siloxane unit in which an alkyl group and/or an alkenyl group is bonded to its silicon atom, and the alkenyl in all the substituents represented by R 1 ′ to R 6 ′.
• the ratio of the groups is preferably 0.1 mol% to 50.0 mol%, more preferably 0.5 mol% to 30.0 mol%, and the remaining R 1 ′ to R 6 ′ are alkyl groups. be able to.
• the polyorganosiloxane (a2) is composed of a siloxane unit in which an alkyl group and/or a hydrogen atom is bonded to its silicon atom, and all the substituents and the substituents represented by R 1 ′′ to R 6 ′′.
• the proportion of hydrogen atoms in the atoms is preferably 0.1 mol% to 50.0 mol%, more preferably 10.0 mol% to 40.0 mol%, and the remaining R 1 ′′ to R 6 ′′ are It can be an alkyl group.
• the polysiloxane (A1) contains the polyorganosiloxane (a1) and the polyorganosiloxane (a2), but in a preferred embodiment of the present invention, the alkenyl group contained in the polyorganosiloxane (a1) and the polyorganosiloxane
• the molar ratio with respect to the hydrogen atom constituting the Si—H bond contained in (a2) may be in the range of 1.0:0.5 to 1.0:0.66.
• the weight average molecular weight of each of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) is usually 500 to 1,000,000, but preferably 5,000 to 50,000.
• the weight average molecular weight is, for example, GPC device (EcoSEC, HLC-8320GPC manufactured by Tosoh Corp.) and GPC column (Shodex (registered trademark), KF-803L, KF-802 and KF-801 manufactured by Showa Denko KK. ) Is used, the column temperature is 40° C., tetrahydrofuran is used as an eluent (elution solvent), the flow rate (flow rate) is 1.0 mL/min, and polystyrene (manufactured by Sigma-Aldrich) is used as a standard sample for measurement. be able to.
• GPC device EcoSEC, HLC-8320GPC manufactured by Tosoh Corp.
• GPC column Shodex (registered trademark), KF-803L, KF-802 and KF-801 manufactured by Showa Denko KK. ) Is used, the column temperature is 40° C., tetrahydrofuran is used as
• the polyorganosilosan (a1) and the polyorganosilosan (a2) contained in the adhesive composition react with each other by a hydrosilylation reaction to form a cured film. Therefore, the mechanism of its curing is different from that through, for example, a silanol group, and therefore any siloxane has a silanol group or a functional group capable of forming a silanol group by hydrolysis such as an alkyloxy group. It need not be included.
• the component (A) contains a platinum group metal-based catalyst (A2).
• a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl group of the polyorganosiloxane (a1) and the Si—H group of the polyorganosiloxane (a2).
• platinum-based metal catalysts include platinum black, secondary platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate and the like. Platinum-based catalysts, but are not limited thereto. Examples of the complex of platinum and olefins include, but are not limited to, a complex of divinyltetramethyldisiloxane and platinum.
• the amount of the platinum group metal catalyst (A2) is usually in the range of 1.0 to 50.0 ppm with respect to the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).
• the component (A) may include a polymerization inhibitor (A3). That is, by including a polymerization inhibitor in the adhesive composition, it is possible to suitably control the curing by heating during bonding, and to obtain an adhesive composition that gives an adhesive layer excellent in adhesiveness and releasability with good reproducibility. You can
• the polymerization inhibitor is not particularly limited as long as it can suppress the progress of the hydrosilylation reaction, and specific examples thereof include 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyne-1-. Examples thereof include, but are not limited to, an alkynylalkyl alcohol which may be substituted with an aryl group such as all.
• the amount of the polymerization inhibitor is usually 1000.0 ppm or more with respect to the polyorganosiloxane (a1) and the polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and from the viewpoint of preventing excessive suppression of the hydrosilylation reaction. To 10000.0 ppm or less.
• the adhesive composition contains at least one component (B) selected from the group consisting of a component containing an epoxy-modified polyorganosiloxane, a component containing a methyl group-containing polyorganosiloxane and a component containing a phenyl group-containing polyorganosiloxane (B ) May be included.
• a component (B) selected from the group consisting of a component containing an epoxy-modified polyorganosiloxane, a component containing a methyl group-containing polyorganosiloxane and a component containing a phenyl group-containing polyorganosiloxane (B ) May be included.
• Examples of the epoxy-modified polyorganosiloxane include a siloxane unit represented by R 210 R 220 SiO 2/2 (D 200 unit), preferably a siloxane unit represented by R 11 R 12 SiO 2/2 (D 10 unit). ) Is included.
• R 11 is a group bonded to a silicon atom and represents an alkyl group
• R 12 is a group bonded to a silicon atom, and represents an epoxy group or an organic group containing an epoxy group, and specific examples of the alkyl group include The above-mentioned examples can be given.
• the epoxy group in the organic group containing an epoxy group may be an independent epoxy group without being condensed with other rings, and may be condensed with other rings such as a 1,2-epoxycyclohexyl group. It may be an epoxy group formed.
• organic group containing an epoxy group examples include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.
• a preferable example of the epoxy-modified polyorganosiloxane may include, but is not limited to, an epoxy-modified polydimethylsiloxane.
• the epoxy-modified polyorganosiloxane contains the above-mentioned siloxane unit (D 10 unit), but may contain the above Q unit, M unit and/or T unit in addition to D 10 unit.
• epoxy-modified polyorganosiloxane examples include a polyorganosiloxane consisting of D 10 units only, a polyorganosiloxane containing D 10 units and Q units, and a polyorganosiloxane containing D 10 units and M units.
• the epoxy-modified polyorganosiloxane is preferably an epoxy-modified polydimethylsiloxane having an epoxy value of 0.1 to 5, and the weight average molecular weight thereof is usually 1,500 to 500,000. From the viewpoint of suppressing precipitation, it is preferably 100,000 or less.
• epoxy-modified polyorganosiloxane examples include a trade name CMS-227 represented by the formula (A-1) (manufactured by Gerest Co., weight average molecular weight 27,000) and a product represented by the formula (A-2).
• R is an alkylene group having 1 to 10 carbon atoms.
• R is an alkylene group having 1 to 10 carbon atoms.
• R is an alkylene group having 1 to 10 carbon atoms.
• R is an alkylene group having 1 to 10 carbon atoms.
• R is an alkylene group having 1 to 10 carbon atoms.
• methyl group-containing polyorganosiloxane for example, a siloxane unit represented by R 210 R 220 SiO 2/2 (D 200 unit), preferably a siloxane unit represented by R 21 R 21 SiO 2/2 (D 20 Units) are included.
• R 210 and R 220 are groups bonded to a silicon atom, and each independently represent an alkyl group, but at least one is a methyl group, and specific examples of the alkyl group include the above-mentioned examples. it can.
• R 21 is a group bonded to a silicon atom and represents an alkyl group. Specific examples of the alkyl group include the above-mentioned examples. Of these, a methyl group is preferable as R 21 .
• a preferable example of the methyl group-containing polyorganosiloxane may include, but is not limited to, polydimethylsiloxane.
• the methyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 200 unit or D 20 unit), but contains the above Q unit, M unit and/or T unit in addition to D 200 unit and D 20 unit. You may stay.
• methyl group-containing polyorganosiloxane examples include polyorganosiloxane consisting of D 200 units only, polyorganosiloxane containing D 200 units and Q units, and D 200 units and M units.
• methyl group-containing polyorganosiloxane comprises a polyorganosiloxane comprising only D 20 units, a polyorganosiloxane containing a D 20 and Q units, and a D 20 units and M units Polyorganosiloxane, polyorganosiloxane containing D 20 units and T units, polyorganosiloxane containing D 20 units, Q units and M units, polyorganosiloxane containing D 20 units, M units and T units, D Mention may be made of polyorganosiloxanes containing 20 units, Q units, M units and T units.
• the viscosity of the methyl group-containing polyorganosiloxane is usually 1,000 to 2,000,000 mm 2 /s, preferably 10,000 to 1,000,000 mm 2 /s.
• the methyl group-containing polyorganosiloxane is typically dimethyl silicone oil made of polydimethylsiloxane.
• the kinematic viscosity can be measured with a kinematic viscometer. It can also be obtained by dividing the viscosity (mPa ⁇ s) by the density (g/cm 3 ).
• methyl group-containing polyorganosiloxane examples include WACKER (registered trademark SILICONE FLUID AK series) manufactured by Wacker and dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF manufactured by Shin-Etsu Chemical Co., Ltd.). -96H, KF-69, KF-965, KF-968), cyclic dimethyl silicone oil (KF-995) and the like, but are not limited thereto.
• Examples of the phenyl group-containing polyorganosiloxane include those containing a siloxane unit (D 30 unit) represented by R 31 R 32 SiO 2/2 .
• R 31 represents a group bonded to a silicon atom and represents a phenyl group or an alkyl group
• R 32 represents a group bonded to a silicon atom and represents a phenyl group
• specific examples of the alkyl group include the above-mentioned examples.
• a methyl group is preferable.
• the phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 30 unit), but may contain the above Q unit, M unit and/or T unit in addition to the D 30 unit.
• phenyl group-containing polyorganosiloxane examples include a polyorganosiloxane consisting of D 30 units only, a polyorganosiloxane containing D 30 units and Q units, and a D 30 unit and M units.
• the weight average molecular weight of the phenyl group-containing polyorganosiloxane is usually 1,500 to 500,000, but is preferably 100,000 or less from the viewpoint of suppressing precipitation in the adhesive composition.
• phenyl group-containing polyorganosiloxane examples include trade name PMM-1043 represented by formula (C-1) (manufactured by Gelest, Inc., weight average molecular weight 67,000, viscosity 30,000 mm 2 /s), Product name PMM-1025 represented by formula (C-2) (manufactured by Gelest, Inc., weight average molecular weight 25,200, viscosity 500 mm 2 /s), product name KF50- represented by formula (C-3) 3000CS (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 39,400, viscosity 3000 mm 2 /s), trade name TSF431 represented by formula (C-4) (manufactured by MOMENTIVE, weight average molecular weight 1,800, viscosity) 100 mm 2 /s), trade name represented by formula (C-5) TSF433 (manufactured by MOMENTIVE, weight average molecular weight 3,000, viscosity
• the polysiloxane-based adhesive composition may contain the component (A) and the component (B) in an arbitrary ratio, but in consideration of the balance between adhesiveness and releasability, the component (A) and the component (B) are combined.
• the ratio is a mass ratio, preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25.
• Such an adhesive composition may contain a solvent for the purpose of adjusting viscosity, and specific examples thereof include, but are not limited to, aliphatic hydrocarbon water, aromatic hydrocarbon, and ketone. ..
• the content thereof is appropriately set in consideration of the viscosity of the desired adhesive composition, the coating method to be used, the thickness of the thin film to be produced, etc. It is in the range of about 10 to 90% by mass with respect to the entire agent composition.
• the viscosity of the adhesive composition at 25° C. is usually 500 to 20,000 mPa ⁇ s, preferably 1,000 to 5,000 mPa ⁇ s. Considering various factors such as the coating method used and the desired film thickness. Then, it can be adjusted by changing the type of the organic solvent to be used, the ratio thereof, the concentration of the film constituent components, and the like.
• the film constituent component means a component other than the solvent.
• the adhesive composition used in the present invention can be produced by mixing a film constituent component and a solvent. However, when the solvent is not contained, the adhesive composition used in the present invention can be manufactured by mixing the film constituent components.
• the first step is, specifically, a step of applying the adhesive composition to the surface of the semiconductor substrate or the supporting substrate to form an adhesive coating layer, and the semiconductor substrate and the supporting substrate using the adhesive.
• the semiconductor substrate, the adhesive coating layer, and the support are applied by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing at least one of heat treatment and depressurization treatment by putting together via the coating layer.
• a post-process of bringing the substrate into close contact and then performing a post-heat treatment By the post-heat treatment in the post-process, the adhesive coating layer is finally suitably cured to form an adhesive layer, and the laminate is manufactured.
• the semiconductor substrate is a wafer and the support substrate is a support.
• the target to which the adhesive composition is applied may be either or both of the semiconductor substrate and the supporting substrate.
• the wafer include, but are not limited to, a silicon wafer and a glass wafer having a diameter of 300 mm and a thickness of about 770 ⁇ m.
• the support (carrier) is not particularly limited, and may be, for example, a silicon wafer having a diameter of 300 mm and a thickness of 700 ⁇ m, but is not limited thereto.
• the thickness of the adhesive coating layer is usually 5 to 500 ⁇ m, but from the viewpoint of maintaining the film strength, it is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, still more preferably 30 ⁇ m or more, which is caused by a thick film. From the viewpoint of avoiding nonuniformity, it is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, still more preferably 120 ⁇ m or less, and further preferably 70 ⁇ m or less.
• the coating method is not particularly limited, but is usually spin coating.
• a method in which a coating film is separately formed by a spin coating method and a sheet-shaped coating film is attached may be adopted, which is also referred to as coating or coating film.
• the temperature of the heat treatment is usually 80° C. or higher, and preferably 150° C. or lower from the viewpoint of preventing excessive curing.
• the time of the heat treatment is usually 30 seconds or more, preferably 1 minute or more from the viewpoint of surely expressing the temporary adhesion ability, but usually 10 minutes or less from the viewpoint of suppressing deterioration of the adhesive layer and other members, It is preferably 5 minutes or less.
• the reduced pressure treatment may be performed by placing the two substrates and the adhesive coating layer between them under an atmospheric pressure of 10 to 10,000 Pa.
• the time for the reduced pressure treatment is usually 1 to 30 minutes.
• the two substrates and the layers between them are bonded, preferably by heat treatment, more preferably by a combination of heat treatment and reduced pressure treatment.
• the load in the thickness direction of the semiconductor substrate and the supporting substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the supporting substrate and layers between them, and can firmly adhere them. However, it is usually in the range of 10 to 1,000 N.
• the post-heating temperature is preferably 120° C. or higher from the viewpoint of obtaining a sufficient curing rate, and is preferably 260° C. or lower from the viewpoint of preventing deterioration of the substrate or the adhesive.
• the heating time is usually 1 minute or more from the viewpoint of realizing a preferable bonding of the wafers by curing, and preferably 5 minutes or more from the viewpoint of stabilizing the physical properties of the adhesive. From the viewpoint of avoiding adverse effects on the composition, it is usually 180 minutes or less, preferably 120 minutes or less.
• the heating can be performed using a hot plate, an oven or the like.
• one purpose of the post-heat treatment is to cure the component (A) more preferably.
• An example of processing applied to the laminate used in the present invention is processing of the back surface of the surface of the semiconductor substrate opposite to the circuit surface, and typically, thinning of the wafer by polishing the back surface of the wafer is mentioned.
• a through silicon via (TSV) or the like is formed, and then the thinned wafer is peeled from the support to form a laminated body of wafers for three-dimensional mounting. Further, before and after that, the wafer back surface electrode and the like are formed. Heat of 250 to 350° C.
• a wafer having a diameter of 300 mm and a thickness of about 770 ⁇ m can be thinned to a thickness of about 80 ⁇ m to 4 ⁇ m by polishing the back surface opposite to the circuit surface.
• the method for peeling the laminate used in the present invention includes, but is not limited to, solvent peeling, laser peeling, mechanical peeling using a machine having a sharp portion, peeling peeling between a support and a wafer, and the like. Usually, peeling is performed after processing such as thinning.
• the adhesive is not necessarily completely adhered to the supporting substrate side and peeled off, but may be partially left on the processed substrate. Therefore, in the fourth step, the surface of the substrate to which the residual adhesive is attached is washed with the above-described cleaning composition of the present invention, whereby the adhesive on the substrate can be sufficiently washed and removed.
• the fourth step is a step of cleaning and removing the adhesive residue remaining on the substrate after peeling with the cleaning composition of the present invention.
• a thinned substrate on which the adhesive remains is The adhesive residue is immersed in the cleaning composition of the present invention, and if necessary, ultrasonic cleaning or the like is also used to clean and remove the adhesive residue.
• ultrasonic cleaning the conditions are appropriately determined in consideration of the surface condition of the substrate, but normally, the cleaning treatment is performed under the conditions of 20 kHz to 5 MHz and 10 seconds to 30 minutes. Adhesive residue remaining on the top can be sufficiently removed.
• the method for manufacturing a thinned substrate of the present invention includes the above-described first to fourth steps, but may include steps other than these steps.
• the substrate is immersed in various solvents or tape peeling is performed as necessary to remove the adhesive residue. May be.
• the apparatus used in the present invention is as follows.
• Viscometer Toki Sangyo Co., Ltd. rotational viscometer TVE-22H
• Stirrer Mix rotor variable 1-1118-12 made by AS ONE
• Stirrer H Aswan heating type rocking mixer HRM-1
• Contact-type film thickness meter Tokyo Seimitsu Co., Ltd. wafer thickness measuring device WT-425
• the resulting mixture contains (a2) SiH group-containing linear polydimethylsiloxane having a viscosity of 100 mPa ⁇ s (manufactured by Wacker Chemie) and (a1) vinyl group-containing linear polydimethylsiloxane having a viscosity of 200 mPa ⁇ s (Wacker Chemi). 29.5 g, (B) polyorganosiloxane having a viscosity of 1,000,000 mm 2 /s (Wacker Chemie, trade name AK1000000), (A3) 1-ethynyl-1-cyclohexanol (Wacker Chemie) 0.41 g was added, and the mixture was further stirred for 5 minutes with a rotation and revolution mixer.
• Example 2 A detergent composition was obtained in the same manner as in Example 1 except that the amount of N-methyl-2-pyrrolidone dehydration used was 33 g and the amount of 1,2-diethoxyethane used was 62 g.
• Example 3 A detergent composition was obtained in the same manner as in Example 1 except that the amount of N-methyl-2-pyrrolidone dehydration used was 38 g and the amount of 1,2-diethoxyethane used was 57 g.
• Example 4 A detergent composition was obtained in the same manner as in Example 1 except that the amount of N-methyl-2-pyrrolidone dehydration used was 43 g and the amount of 1,2-diethoxyethane used was 52 g.
• Example 2 A detergent composition was obtained in the same manner as in Example 1 except that diethylene glycol diethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,2-diethoxyethane.
• Example 3 A detergent composition was obtained in the same manner as in Example 1 except that diethylene glycol dibutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,2-diethoxyethane.
• the wafer after film formation was cut into chips of 4 cm square and the film thickness was measured using a contact type film thickness meter. Then, the chip was put in a stainless petri dish having a diameter of 9 cm, 7 mL of the obtained cleaning composition was added and the lid was covered, and then the chip was placed on a stirrer H and stirred and washed at 23° C. for 5 minutes. After washing, take out the chip, wash with isopropanol and pure water, dry bake at 150°C for 1 minute, then measure the film thickness again with a contact-type film thickness meter, and measure the decrease in film thickness before and after cleaning. Then, the reduced rate was divided by the cleaning time to calculate the etching rate [ ⁇ m/min], which was used as an index of the cleaning power. The results are shown in Table 1.
• the detergent composition of the present invention containing an alkylene glycol dialkyl ether (1,2-diethoxyethane) and a predetermined lactam compound (N-methyl-2-pyrrolidone) has a lactam compound ( Higher etching rate compared to a cleaning composition containing only N-methyl-2-pyrrolidone) (Comparative Example 1) and a cleaning composition containing a glycol compound structurally similar as a solvent (Comparative Examples 2 to 3) And showed excellent detergency persistence (good solubility).

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