Classifications

• • 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
  • C11D7/22—Organic compounds
  • C11D7/24—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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/26—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
  • 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
  • C11D7/34—Organic compounds containing sulfur
• • 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
• • 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
  • H10P70/00—Cleaning of wafers, substrates or parts of devices
  • H10P70/20—Cleaning during device manufacture
• • 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
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/60—Wet etching
  • H10P50/68—Wet etching of insulating materials
  • H10P50/683—Wet etching of insulating materials of inorganic materials
• • 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 method for manufacturing a semiconductor substrate, a method for manufacturing a processed semiconductor substrate, and a composition for stripping and dissolving.
• Unthinned semiconductor wafers are attached to a support in order to be polished with a polishing device.
• the adhesive used at this time is called temporary adhesive because it must be easily peeled off after polishing.
• This temporary adhesive must be easily removed from the support, and if a large force is applied to remove it, the thinned semiconductor wafer may be cut or deformed, so it is easily removed to prevent this from happening.
• the processing process can reach high temperatures of over 150°C, so heat resistance is also required.
• Patent Documents 1 and 2 disclose a siloxane resin remover that contains a polar aprotic solvent and a quaternary ammonium hydroxide
• Patent Document 2 discloses a cured resin remover that contains an alkyl ammonium fluoride.
• Patent Document 3 discloses a stripping composition containing a specific solvent, and describes the use of the stripping composition to clean semiconductor substrates.
• Patent Documents 1 and 2 attempt to remove adhesive residues from the substrate surface by dissolving the adhesive residues on the substrate surface, but it has been found that attempting to remove adhesive residues from the substrate surface by dissolving them in this way takes a long time.
• the present inventors have studied cleaning compositions and found that a composition containing a specific component can swell the adhesive layer and peel it off from the substrate.
• the use of a composition containing this specific component is effective for removing the adhesive layer from the substrate in a short time.
• the cleaning composition (peeling composition) described in the above Patent Document 3 can also be an effective component for removing the adhesive layer from the substrate in a short time.
• the present invention has been made in consideration of the above circumstances, and aims to provide a method for manufacturing a semiconductor substrate including a semiconductor substrate cleaning step, which allows for simple operations to more quickly and cleanly remove (clean) an adhesive layer obtained on the surface of a semiconductor substrate, for example, obtained using a siloxane-based adhesive, a method for manufacturing a processed semiconductor substrate including such a semiconductor manufacturing method, and a composition for use in such a cleaning step.
• the inventors discovered that the above problems could be solved by cleaning the adhesive layer on a semiconductor substrate, particularly the cured film obtained from a siloxane-based adhesive containing a polyorganosiloxane component (A') that cures by a hydrosilylation reaction, with a composition containing specific components, thereby swelling and peeling the adhesive layer and dissolving it together in a single cleaning operation, thereby removing the adhesive layer from the semiconductor substrate, and thus completing the present invention.
• a siloxane-based adhesive containing a polyorganosiloxane component (A') that cures by a hydrosilylation reaction
• a method for producing a semiconductor substrate comprising the steps of peeling and dissolving an adhesive layer on a semiconductor substrate using a composition for peeling and dissolving, and cleaning the adhesive layer
• the stripping and dissolving composition comprises: [I] Component: a dissolving component containing a quaternary ammonium salt and an amide-based solvent; [II] Component: A stripping component comprising one or more solvents selected from ether compounds, thioether compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, ester compounds, and amine compounds, each having a molecular weight of less than 160;
• a method for manufacturing a semiconductor substrate characterized in that when the composition for peeling and dissolution is dropped onto an adhesive layer disposed on a semiconductor substrate, the contact angle of the composition for peeling and dissolution is greater than 22.6 degrees and less than 46.1 degrees.
• a method for producing a processed semiconductor substrate comprising the steps of: producing a processed semiconductor substrate using the method for producing a semiconductor substrate as defined in [1];
• the method for manufacturing the processed semiconductor substrate includes: A first step of producing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition; A second step of processing the semiconductor substrate of the obtained laminate;
• a method for producing a processed semiconductor substrate comprising: a third step of separating the semiconductor substrate and the adhesive layer from the supporting substrate; and a fourth step of performing a cleaning step as defined in [1], in which the adhesive layer on the semiconductor substrate is removed by peeling and dissolving using a composition for peeling and dissolving.
• a composition for stripping and dissolving used for stripping, dissolving and removing an adhesive layer on a semiconductor substrate when cleaning the semiconductor substrate comprising:
• the stripping and dissolving composition comprises: [I] Component: a dissolving component containing a quaternary ammonium salt and an amide-based solvent; [II] Component: A stripping component comprising one or more solvents selected from ether compounds, thioether compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, ester compounds, and amine compounds, each having a molecular weight of less than 160;
• a composition for peeling and dissolving characterized in that when the composition for peeling and dissolving is dropped onto an adhesive layer disposed on a semiconductor substrate, the contact angle of the composition for peeling and dissolving is greater than 22.6 degrees and less than 46.1 degrees.
• composition for stripping and dissolving according to [20], wherein the glycol ether solvent of the component [III] is a solvent represented by the following formula (T): (In the formula, X1 and X3 each independently represent an alkyl group or an acyl group ( X4 -C( O)-), X2 represents an alkylene group, and n represents 2 or 3. X4 represents an alkyl group.) [22] The composition for stripping and dissolving according to any one of [15] to [21], wherein the quaternary ammonium salt of the component [I] is a halogen-containing quaternary ammonium salt.
• siloxane-based adhesive contains a polyorganosiloxane component (A') that cures by a hydrosilylation reaction.
• the present invention provides a method for manufacturing a semiconductor substrate including a cleaning step for a semiconductor substrate, which allows an adhesive layer to be removed (cleaned) from a semiconductor substrate having an adhesive layer on its surface with simple operations, in a shorter time, and more cleanly, a method for manufacturing a processed semiconductor substrate including such a semiconductor manufacturing method, and a composition for use in such a cleaning step.
• the method for producing a semiconductor substrate of the present invention includes a step of peeling and dissolving an adhesive layer on a semiconductor substrate using a composition for peeling and dissolving.
• the composition for stripping and dissolving comprises [I] Component: a dissolving component containing a quaternary ammonium salt and an amide-based solvent; Component [II]: A stripping component comprising one or more solvents selected from ether compounds, thioether compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, ester compounds, and amine compounds, each having a molecular weight of less than 160.
• the peeling and dissolving composition is one that, when dropped onto an adhesive layer disposed on a semiconductor substrate and the contact angle of the peeling and dissolving composition is measured, exhibits a contact angle that is greater than 22.6 degrees and less than 46.1 degrees.
• the stripping and dissolving composition may further contain component [III]: a glycol ether solvent.
• the main material constituting the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, but examples thereof include silicon, silicon carbide, and compound semiconductors.
• the shape of the semiconductor substrate is not particularly limited, but may be, for example, a disk shape. Note that the disk-shaped semiconductor substrate does not need to have a perfectly circular surface, and for example, the outer periphery of the semiconductor substrate may have a straight line portion called an orientation flat, or may have a cut called a notch.
• the thickness of the disk-shaped semiconductor substrate may be appropriately determined depending on the intended use of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 ⁇ m.
• the diameter of the disk-shaped semiconductor substrate may be appropriately determined depending on the intended use of the semiconductor substrate, and is not particularly limited, but may be, for example, 100 to 1,000 mm.
• the semiconductor substrate is, for example, a wafer, and a specific example thereof is a silicon wafer with a diameter of about 300 mm and a thickness of about 770 ⁇ m, but is not limited to this.
• the adhesive layer on the semiconductor substrate is, for example, a film obtained from an adhesive composition containing an adhesive component (S).
• an adhesive component (S) is not particularly limited as long as it is used for this type of application, and examples thereof include siloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenol resin-based adhesives.
• siloxane-based adhesives are preferred as the adhesive component (S) because they exhibit suitable adhesive properties during processing of wafers and the like, can be easily peeled off after processing, and also have excellent heat resistance.
• the adhesive composition used in the present invention contains, as an adhesive component, component (A) that cures via a hydrosilylation reaction.
• the adhesive composition used in the present invention contains a polyorganosiloxane.
• Component (A) may be a component that cures by a hydrosilylation reaction, or it may be a polyorganosiloxane component (A') that cures by a hydrosilylation reaction.
• component (A) contains, for example, polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom as an example of component (A'), polyorganosiloxane (a2) having a Si-H group, and platinum group metal catalyst (A2).
• the alkenyl group having 2 to 40 carbon atoms may be substituted.
• the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.
• the polyorganosiloxane component (A' ) that cures by a hydrosilylation reaction comprises a polysiloxane ( A1 ) containing one or more units selected from the group consisting of siloxane units represented by SiO2 (Q units), siloxane units represented by R1R2R3SiO1/2 ( M units ), siloxane units represented by R4R5SiO2 / 2 (D units ) , and siloxane units represented by R6SiO3/2 ( T units ), and a platinum group metal catalyst ( A2 ).
• R 1 to R 6 are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom.
• substituents include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.
• R 1 ' to R 6 ' are groups bonded to a silicon atom and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, with at least one of R 1 ' to R 6 ' being an optionally substituted alkenyl group.
• substituents include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.
• R 1 ′′ to R 6 ′′ are groups or atoms bonded to the silicon atom and each independently represents an optionally substituted alkyl group or a hydrogen atom, with at least one of R 1 ′′ to R 6 ′′ being a hydrogen atom.
• substituents include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.
• the alkyl group may be linear, branched, or cyclic, but linear or branched alkyl groups are preferred, and the number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
• optionally substituted straight-chain or branched-chain alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, tertiary butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, and 5-methyl-n-pentyl.
• alkyl group examples include, but are not limited to, ethyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl groups.
• the number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6.
• the methyl group is particularly preferred.
• optionally substituted cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethyl ...propyl
• the alkenyl group may be either linear or branched, and the number of carbon atoms is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
• the optionally substituted linear or branched alkenyl group include, but are not limited to, a vinyl group, an allyl group, a butenyl group, a pentenyl group, and the like, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among these, an ethenyl group and a 2-propenyl group are particularly preferred.
• Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl, cyclohexenyl, and the like, and the number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.
• polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'), and the alkenyl groups contained in polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in polyorganosiloxane (a2') form a crosslinked structure through a hydrosilylation reaction caused by a platinum group metal catalyst (A2), which then hardens. As a result, a hardened film is formed.
• Polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units, and T' units.
• polyorganosiloxane (a1') a combination of two or more polyorganosiloxanes satisfying such conditions may be used.
• Q' units, M' units, D' units and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units and M' units).
• the polyorganosiloxane (a1') contains two or more types of polyorganosiloxane, combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but are not limited to these.
• Polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units, and T" units, and also contains at least one unit selected from the group consisting of M" units, D" units, and T" units.
• polyorganosiloxane (a2') a combination of two or more polyorganosiloxanes satisfying these conditions may be used.
• Preferred combinations of two or more selected from the group consisting of Q" units, M" units, D" units and T" units include, but are not limited to, (M" units and D" units), (Q" units and M” units), and (Q" units, T" units and M” units).
• the polyorganosiloxane (a1') is composed of siloxane units having alkyl and/or alkenyl groups bonded to the silicon atoms thereof, and the proportion of alkenyl groups in all of the substituents represented by R 1 ' to R 6 ' is preferably 0.1 to 50.0 mol %, more preferably 0.5 to 30.0 mol %, and the remaining R 1 ' to R 6 ' can be alkyl groups.
• the polyorganosiloxane (a2') is composed of siloxane units in which alkyl groups and/or hydrogen atoms are bonded to the silicon atoms, and the proportion of hydrogen atoms in all the substituents and substituted atoms represented by R 1 "to R 6 " is preferably 0.1 to 50.0 mol %, more preferably 10.0 to 40.0 mol %, and the remaining R 1 "to R 6 " can be alkyl groups.
• component (A) contains (a1) and (a2)
• the molar ratio of the alkenyl groups contained in polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bonds contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.
• the weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000.
• the weight average molecular weight and number average molecular weight and dispersity of the polyorganosiloxane can be measured using, for example, a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex, manufactured by Showa Denko K.K.) as a standard sample.
• a GPC apparatus EuSEC, HLC-8320GPC manufactured by Tosoh Corporation
• GPC column TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation
• a column temperature 40 ° C.
• the viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are not particularly limited, but are usually 10 to 1,000,000 (mPa ⁇ s), and from the viewpoint of realizing the effects of the present invention with good reproducibility, are preferably 50 to 20,000 (mPa ⁇ s).
• the viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are values measured with an E-type rotational viscometer at 25°C.
• Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other to form a film by a hydrosilylation reaction.
• the mechanism of curing is therefore different from that via, for example, silanol groups, and therefore neither siloxane needs to contain a silanol group or a functional group that forms a silanol group by hydrolysis, such as an alkyloxy group.
• the adhesive composition contains a platinum group metal catalyst (A2) together with the polyorganosiloxane component (A').
• a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl groups of the polyorganosiloxane (a1) and the Si-H groups of the polyorganosiloxane (a2).
• platinum-based metal catalysts include platinum black, platinic chloride, chloroplatinic acid, a reaction product of chloroplatinic acid with a monohydric alcohol, a complex of chloroplatinic acid with an olefin, platinum bisacetoacetate, and other platinum-based catalysts, but are not limited to these.
• An example of a complex of platinum with an olefin is, but is not limited to, a complex of divinyltetramethyldisiloxane with platinum.
• the amount of the platinum group metal catalyst (A2) is not particularly limited, but is usually in the range of 1.0 to 50.0 ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).
• the polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of inhibiting the progress of the hydrosilylation reaction.
• the polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction. Specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol.
• the amount of the polymerization inhibitor is not particularly limited, but is usually 1000.0 ppm or more based on the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.
• the adhesive composition used in the present invention may contain a release agent component (B).
• a release agent component (B) By including such a release agent component (B) in the adhesive composition used in the present invention, the resulting adhesive layer can be preferably peeled off with good reproducibility.
• a typical example of such a release agent component (B) is polyorganosiloxane.
• specific examples thereof include, but are not limited to, epoxy group-containing polyorganosiloxane, methyl group-containing polyorganosiloxane, and phenyl group-containing polyorganosiloxane.
• the release agent component (B) includes polydimethylsiloxane, which may be modified.
• polydimethylsiloxane examples include, but are not limited to, epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, and phenyl group-containing polydimethylsiloxane.
• the weight average molecular weight of the polyorganosiloxane, which is the release agent component (B), is not particularly limited, but is usually 100,000 to 2,000,000, and from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000.
• the dispersity is not particularly limited, but is usually 1.0 to 10.0, and from the viewpoint of realizing suitable release with good reproducibility, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0.
• the weight average molecular weight and dispersity can be measured by the above-mentioned method for polysiloxane.
• the complex viscosity of the polyorganosiloxane which is the release agent component (B) can be measured at 25° C. using a rheometer (for example, Rheometer MCR-302 manufactured by Anton Paar KK).
• An example of the epoxy group-containing polyorganosiloxane is one containing a siloxane unit ( D10 unit) represented by R 11 R 12 SiO 2/2 .
• 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
• specific examples of the alkyl group include those mentioned above.
• the epoxy group in the organic group containing an epoxy group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group.
• Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.
• a preferred example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but is not limited thereto.
• the epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane units ( D10 units), and may contain Q units, M units and/or T units in addition to the D10 units.
• specific examples of the epoxy group-containing polyorganosiloxane include a polyorganosiloxane consisting of only D10 units, a polyorganosiloxane containing D10 units and Q units, a polyorganosiloxane containing D10 units and M units, a polyorganosiloxane containing D10 units and T units, a polyorganosiloxane containing D10 units, Q units and M units, a polyorganosiloxane containing D10 units, M units and T units, a polyorganosiloxane containing D10 units, Q units, M units and T units, a polyorganosiloxane containing D10 units, Q units, M units and T units, a polyorganosiloxane containing D10
• the epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5.
• the weight average molecular weight is not particularly limited, but is usually 1,500 to 500,000, and from the viewpoint of suppressing precipitation in the adhesive, is preferably 100,000 or less.
• epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).
• Examples of the methyl group-containing polyorganosiloxane include those containing siloxane units (D 200 units) represented by R 210 R 220 SiO 2/2 , preferably those containing siloxane units (D 20 units) represented by R 21 R 21 SiO 2/2 .
• R 210 and R 220 are groups bonded to a silicon atom, and each independently represents an alkyl group, with at least one being a methyl group. Specific examples of the alkyl group include those mentioned above.
• R21 is a group bonded to a silicon atom and represents an alkyl group, specific examples of which include those mentioned above, with a methyl group being preferred as R21 .
• a preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.
• the methyl group-containing polyorganosiloxane contains the above-mentioned siloxane units (D 200 units or D 20 units), but may contain Q units, M units and/or T units in addition to the D 200 units and D 20 units.
• methyl group-containing polyorganosiloxane examples include a polyorganosiloxane consisting of only D 200 units, a polyorganosiloxane containing D 200 units and Q units, a polyorganosiloxane containing D 200 units and M units, a polyorganosiloxane containing D 200 units and T units, a polyorganosiloxane containing D 200 units, Q units and M units, a polyorganosiloxane containing D 200 units, M units and T units, and a polyorganosiloxane containing D 200 units, Q units, M units and T units.
• methyl group-containing polyorganosiloxane examples include a polyorganosiloxane consisting only of D20 units, a polyorganosiloxane containing D20 units and Q units, a polyorganosiloxane containing D20 units and M units, a polyorganosiloxane containing D20 units and T units, a polyorganosiloxane containing D20 units, Q units and M units, a polyorganosiloxane containing D20 units, M units and T units, and a polyorganosiloxane containing D20 units, Q units, M units and T units.
• methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1).
• n4 indicates the number of repeating units and is a positive integer.
• phenyl group-containing polyorganosiloxane is one containing a siloxane unit ( D30 unit) represented by R 31 R 32 SiO 2/2 .
• R 31 is a group bonded to a silicon atom and represents a phenyl group or an alkyl group.
• R 32 is a group bonded to a silicon atom and represents a phenyl group. Specific examples of the alkyl group include those mentioned above, but a methyl group is preferred.
• the phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane units ( D30 units), and may contain Q units, M units and/or T units in addition to the D30 units.
• phenyl group-containing polyorganosiloxane examples include a polyorganosiloxane consisting of only D30 units, a polyorganosiloxane containing D30 units and Q units, a polyorganosiloxane containing D30 units and M units, a polyorganosiloxane containing D30 units and T units, a polyorganosiloxane containing D30 units, Q units and M units, a polyorganosiloxane containing D30 units, M units and T units, and a polyorganosiloxane containing D30 units, Q units, M units and T units.
• phenyl-containing polyorganosiloxanes include, but are not limited to, those represented by formula (P1) or (P2).
• the polyorganosiloxane which is the release agent component (B) may be a commercially available product or may be synthesized.
• Commercially available polyorganosiloxanes include, for example, WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST GUM, which are products of Wacker Chemical Co., Ltd., dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), and cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy group-containing polyorganosiloxane (product name CMS-227, ECMS-327) manufactured by Gelest Co., Ltd., and cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.
• Epoxy group-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343), epoxy group-containing polyorganosiloxane (BY16-839) manufactured by Dow Corning; phenyl group-containing polyorganosiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest, phenyl group-containing polyorganosiloxane (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd., phenyl group-containing polyorganosiloxanes (TSF431, TSF433) manufactured by MOMENTIVE, and the like can be mentioned, but are not limited thereto.
• the adhesive composition used in the present invention contains a release agent component (B) in addition to the curable component (A), and in a more preferred embodiment, the release agent component (B) contains a polyorganosiloxane.
• the adhesive composition used in the present invention can contain the curable component (A) and the release agent component (B) in any ratio.
• the ratio of the curable component (A) to the release agent component (B) in terms of mass ratio [(A):(B)] is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25.
• the ratio of component (A') to release agent component (B) is, in mass ratio [(A'):(B)], preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.
• the adhesive composition used in the present invention may contain a solvent for the purpose of adjusting the viscosity, etc.
• a solvent for the purpose of adjusting the viscosity, etc.
• specific examples of the solvent include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc.
• examples of the solvent include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc.
• solvents can be used alone or in combination of two or more.
• the content of the solvent is appropriately set taking into consideration the viscosity of the desired composition, the coating method to be used, the thickness of the thin film to be produced, etc., but is in the range of about 10 to 90 mass % of the entire composition.
• the viscosity of the adhesive composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa ⁇ s, and preferably 1,000 to 5,000 mPa ⁇ s at 25° C.
• the viscosity of the adhesive composition used in the present invention can be adjusted by changing the types of solvents used, their ratios, the concentrations of the film constituent components, etc., taking into consideration various factors such as the coating method used and the desired film thickness.
• the film constituent components refer to components other than the solvent contained in the composition.
• An example of an adhesive composition for use in the present invention can be prepared by mixing component (A), release agent component (B), and, if used, solvent.
• the mixing order is not particularly limited, but examples of a method for easily and reproducibly producing a peeling adhesive composition include, but are not limited to, a method of dissolving component (A) and release agent component (B) in a solvent, or a method of dissolving a part of component (A) and release agent component (B) in a solvent and the rest in a solvent, and mixing the obtained solutions.
• heating may be performed appropriately within a range that does not cause the components to decompose or change in quality.
• the solvent, solution, etc. used may be filtered using a filter during the production of the adhesive composition or after all of the components have been mixed.
• the thickness of the adhesive layer is not particularly limited, but from the viewpoint of obtaining a good peeling effect with good reproducibility, it is preferably 10 to 100 ⁇ m, and more preferably 20 to 50 ⁇ m.
• Stripping and dissolving compositions are compositions used in semiconductor substrate manufacturing methods to remove adhesive layers from semiconductor substrates.
• the peeling and dissolving composition contains a peeling component that swells in the adhesive layer to peel the adhesive layer from the semiconductor substrate, and a dissolving component that dissolves the adhesive layer.
• composition for stripping and dissolving comprises: [I] Component: a dissolving component containing a quaternary ammonium salt and an amide-based solvent; Component [II]: A stripping component comprising one or more solvents selected from ether compounds, thioether compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, ester compounds, and amine compounds, each having a molecular weight of less than 160.
• the stripping and dissolving composition may further contain component [III]: a glycol ether solvent.
• the contact angle is greater than 22.6 degrees and less than 46.1 degrees.
• Component [I] refers to a dissolving component containing a quaternary ammonium salt and an amide solvent.
• Such quaternary ammonium cations typically include tetra(hydrocarbon)ammonium cations, while their counter anions include, but are not limited to, hydroxide ion (OH ⁇ ), halogen ions such as fluoride ion (F ⁇ ), chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), and iodide ion (I ⁇ ), tetrafluoroborate ion (BF 4 ⁇ ), and hexafluorophosphate ion (PF 6 ⁇ ).
• hydroxide ion OH ⁇
• halogen ions such as fluoride ion (F ⁇ ), chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), and iodide ion (I ⁇ ), tetrafluoroborate ion (BF 4 ⁇ ), and hexafluorophosphate i
• the quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, and more preferably a fluorine-containing quaternary ammonium salt.
• the halogen atom may be contained in either the cation or the anion, but is preferably contained in the anion.
• the fluorine-containing quaternary ammonium salt is a tetra(hydrocarbon)ammonium fluoride.
• the hydrocarbon group in the tetra(hydrocarbon)ammonium fluoride include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
• the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride.
• tetraalkylammonium fluoride examples include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also called tetrabutylammonium fluoride), etc. Among these, tetrabutylammonium fluoride is preferred.
• the quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of a hydrate.
• the quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used alone or in combination of two or more.
• the amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the composition for peeling and dissolving, but it is preferable to include a small amount of the quaternary ammonium salt since this can effectively prevent the problem of damage to the dicing tape in the cleaning step described below. Specifically, the amount is usually 0.1 to 5 mass % relative to the composition for peeling and dissolving, for example.
• the amide-based solvent is effective as a component for dissolving the quaternary ammonium salt well and obtaining a stripping and dissolving composition having excellent uniformity.
• the amide solvent is preferably an N-substituted amide compound having 4 or more carbon atoms and no active hydrogen on the nitrogen atom.
• a suitable example of the amide solvent is an acid amide derivative represented by the following formula (Z).
• R 0 represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group.
• R A and R B each independently represent an alkyl group having 1 to 4 carbon atoms.
• the alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group.
• R A and R B are preferably a methyl group or an ethyl group, more preferably both are a methyl group or an ethyl group, and even more preferably both are a methyl group.
• the acid amide derivatives represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N,N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, N-ethyl-N-methylisobutyric acid amide, etc.
• N,N-dimethylpropionamide and N,N-dimethylisobutyric acid amide are particularly preferred, and N,N-dimethylpropionamide is more preferred.
• the acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between the corresponding carboxylic acid ester and an amine, or a commercially available product may be used.
• Another example of a preferred amide solvent is a compound represented by formula (Y), which includes a lactam compound, etc.
• R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• R 102 represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).
• alkyl group having 1 to 6 carbon atoms for R 102 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc.
• alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc., but are not limited to these.
• R 103 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• R 104 represents an alkylene group having 1 to 5 carbon atoms
• *1 represents a bond bonded to a carbon atom in formula (Y)
• *2 represents a bond bonded to a nitrogen atom in formula (Y).
• lactam compounds represented by formula (Y) include ⁇ -lactam compounds, ⁇ -lactam compounds, ⁇ -lactam compounds, ⁇ -lactam compounds, etc., which can be used alone or in combination of two or more.
• the lactam compound represented by formula (Y) comprises 1-alkyl-2-pyrrolidone (N-alkyl- ⁇ -butyrolactam), in a more preferred embodiment, N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, N-methylpyrrolidone (NMP).
• NMP N-methylpyrrolidone
• NMP N-ethylpyrrolidone
• NMP N-methylpyrrolidone
• NMP N-methylpyrrolidone
• NMP N-methylpyrrolidone
• the content of the amide-based solvent in the composition for stripping and dissolving can be 70% by mass or less when the aprotic solvent in the composition for stripping and dissolving is taken as 100% by mass.
• the content of the amide solvent is preferably 10 to 55 mass%, more preferably 20 to 50 mass%, further preferably 20 to 45 mass%, and particularly preferably 20 to 40 mass%, based on 100 mass% of the aprotic solvent.
• the content of the mixed solvent is defined as a ratio when the aprotic solvent, which is a solvent having no hydroxyl group (—OH), is taken as 100 mass %. Therefore, protic solvents such as water, methanol, and 1-methoxy-2-propanol are not included in the content ratio criteria.
• the aprotic solvent refers to, for example, N,N-dimethylpropionamide, dibutyl ether, dipropylene glycol dimethyl ether, butyl acetate, etc., and the mixing ratio can be determined based on the total amount of these.
• the component [II] is a stripping component consisting of one or more solvents selected from ether compounds, thioether compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, ester compounds, and amine compounds, all of which have a molecular weight of less than 160.
• the solvent for the ether compound or thioether compound is preferably a solvent represented by the following formula (L-1).
• the solvent represented by the following formula (L-1) is effective as a peeling component for swelling the adhesive layer and peeling the adhesive layer from the semiconductor substrate.
• L 1 and L 2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L 3 represents O or S.
• L 1 and L 2 may be the same group or different groups, but from the viewpoint of availability, it is preferable that they are the same group.
• the alkyl group having 2 to 5 carbon atoms may be linear, branched, or cyclic, but from the viewpoint of achieving reproducible peeling of the adhesive layer in a short time, it is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
• linear or branched alkyl groups include, but are not limited to, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, and n-pentyl groups.
• cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, and cyclopentyl groups.
• the alkyl group having 2 to 5 carbon atoms is preferably an ethyl group, an n-propyl group, an n-butyl group, or an n-pentyl group, and more preferably an ethyl group, an n-propyl group, or an n-butyl group.
• L 1 and L 2 are the same group.
• organic solvent represented by formula (L-1) examples include di(n-butyl) ether, diethyl ether, di(n-pentyl) ether, di(n-propyl) sulfide, dibutyl sulfide, etc.
• the content of the solvent represented by formula (L-1) in the composition for stripping and dissolving can be 30% by mass or more when the aprotic solvent in the composition for stripping and dissolving is 100% by mass.
• the content of the solvent represented by formula (L-1) in the composition for stripping and dissolving is preferably 30% by mass or more, more preferably 31% by mass or more, even more preferably 40% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less, when the aprotic solvent in the composition for stripping and dissolving is taken as 100% by mass. Any combination of these upper and lower limits is acceptable. Therefore, the content of the solvent represented by formula (L-1) is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, when the aprotic solvent in the composition for stripping and dissolving is taken as 100% by mass.
• the aromatic hydrocarbon compound solvent is preferably a solvent represented by the following formula (L-2).
• the solvent represented by the following formula (L-2) is effective as a peeling component for swelling the adhesive layer and peeling the adhesive layer from the semiconductor substrate.
• L 5 represents a substituent substituted on a benzene ring, each independently representing an alkyl group having 1 to 4 carbon atoms; k represents the number of L 5 and is an integer of 0 to 5.
• the alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group.
• linear or branched alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, and t-butyl groups.
• cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, and 2-methyl-cyclopropyl groups.
• L5 is preferably a methyl group or an isopropyl group.
• k is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less.
• organic solvent represented by formula (L-2) examples include toluene, mesitylene, p-cymene, 1,2,4-trimethylbenzene, etc.
• the content of the solvent represented by formula (L-2) in the composition for stripping and dissolving is preferably 30 to 90% by mass, and more preferably 40 to 80% by mass, when the aprotic solvent in the composition for stripping and dissolving is taken as 100% by mass.
• the aliphatic hydrocarbon compound solvent is preferably a solvent represented by the following formulas (L-3-0) to (L-3-5).
• the solvent represented by any one of the following formulas (L-3-0) to (L-3-5) is effective as a peeling component for swelling the adhesive layer and peeling the adhesive layer from the semiconductor substrate.
• L 101 to L 112 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, with at least one of L 101 to L 112 representing an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms
• L 201 to L 210 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, with at least one of L 201 to L 210 representing an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms
• the alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group.
• linear or branched alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, and t-butyl groups.
• methyl groups, ethyl groups, n-propyl groups, and isopropyl groups are preferred, with methyl groups and isopropyl groups being more preferred.
• cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, and cyclopentyl groups.
• the alkenyl group having 2 to 5 carbon atoms may be linear, branched, or cyclic, and specific examples include, but are not limited to, ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, and n-1-pentenyl.
• the ethenyl group, the 1-methylethenyl group, and the 2-methylethenyl group are preferred, with the 1-methylethenyl group being more preferred.
• the alkynyl group having 2 to 5 carbon atoms may be linear, branched, or cyclic, and specific examples include, but are not limited to, ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl, 1-methyl-2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n-butynyl, and 1,1-dimethyl-n-propynyl.
• ethynyl and 2-methylethynyl groups are preferred from the viewpoint of achieving reproducible peeling of the adhesive layer in a shorter time.
• one or two of L 101 to L 112 are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms; more preferably, L 101 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms; or, L 101 and L 107 are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms; even more preferably, L 101 is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms; even more preferably, L 101 is an alkyl
• one or two of L 201 to L 210 are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms; more preferably, L 201 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms; or, L 201 and L 205 are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms; even more preferably, L 201 and L 205 are each independently an alkyl group having 1 to 5 carbon atoms or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms; even
• one or two of L 301 to L 308 are an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms
• L 301 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms
• L 301 and L 304 are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms
• L 301 is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
• one or two of L 401 to L 408 are an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms
• L 401 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms
• L 401 and L 405 are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and the remainder are hydrogen atoms
• L 401 is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
• organic solvent represented by any of formulas (L-3-0) to (L-3-5) include cyclohexane, p-menthane, isopropylcyclohexane, limonene, n-decane, etc.
• the content of the solvent represented by any one of formulas (L-3-0) to (L-3-5) (hereinafter, formulas (L-3-0) to (L-3-5) are also collectively referred to as formula (L-3), etc.) in the composition for stripping and dissolution can be 20% by mass or more when the aprotic solvent in the composition for stripping and dissolution is taken as 100% by mass.
• the content of the solvent represented by formula (L-3) or the like in the composition for stripping and dissolution is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, preferably 80% by mass or less, and more preferably 60% by mass or less, when the aprotic solvent in the composition for stripping and dissolution is taken as 100% by mass.
• These upper and lower limits may be in any combination.
• the solvent for the ester compound is preferably a solvent represented by the following formula (L-4).
• the solvent represented by the following formula (L-4) is effective as a peeling component for swelling the adhesive layer and peeling the adhesive layer from the semiconductor substrate.
• L 11 and L 12 each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms in the alkyl group of L 11 and the alkyl group of L 12 is 7 or less.
• L11 and L12 each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms in the alkyl group of L11 and the alkyl group of L12 is 7 or less. By setting the number of carbon atoms in this range, peeling of the adhesive layer in a short time can be realized with good reproducibility.
• the alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
• linear or branched alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, and 3-methyl-n-pentyl.
• dimethyl-n-butyl group examples include, but are not limited to, 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, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group.
• cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,
• Examples of cycloalkyl groups include, but are not limited to, 2-dimethyl-cyclobutyl group, 2,3-
• L 11 is preferably a methyl group
• L 12 is preferably a butyl group or a pentyl group.
• organic solvent represented by formula (L-4) examples include butyl acetate, pentyl acetate, etc.
• the content of the solvent represented by formula (L-4) in the composition for stripping and dissolving can be more than 31% by mass when the aprotic solvent in the composition for stripping and dissolving is taken as 100% by mass.
• the content of the solvent represented by formula (L-4) in the composition for stripping and dissolution is preferably more than 31% by mass, more preferably more than 35% by mass, even more preferably 40% by mass or more, even more preferably 60% by mass or more, particularly preferably 70% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less, when the aprotic solvent in the composition for stripping and dissolution is taken as 100% by mass. Any combination of these upper and lower limits is acceptable.
• Component [III] refers to a solvent for glycol ethers.
• the glycol ether solvent is preferably a solvent represented by the following formula (T).
• the solvent represented by the following formula (T) is effective as an adjusting component for enhancing the compatibility between the amide solvent, which is the component [I-2], and the solvent, which is the component [II], in the stripping and dissolving composition containing the quaternary ammonium salt, which is the component [I-1].
• Examples of the alkyl group represented by X1 and X3 include alkyl groups having 1 to 4 carbon atoms, more specifically, methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, t-butyl groups, and the like.
• Examples of the alkylene group represented by X2 include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, and a 1,2-propylene group.
• the alkyl group represented by X4 may be, for example, an alkyl group having 1 to 4 carbon atoms, and may be the same as the alkyl groups represented by X1 and X3 .
• Preferred examples of the solvent represented by formula (T) include dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc.
• the contact angle is greater than 22.6 degrees and less than 46.1 degrees.
• the contact angle of the peeling and dissolving composition when dropped onto an adhesive layer must be greater than 22.6 degrees and less than 46.1 degrees.
• the contact angle is preferably 24 degrees or more and 40 degrees or less, and more preferably 26 degrees or more and 38 degrees or less.
• the adhesive layer removed by the method for cleaning a semiconductor substrate may be produced using either an adhesive composition containing the release agent component (B) or an adhesive composition not containing the release agent component (B).
• an adhesive composition containing the release agent component (B) it is desirable that the adhesive layer removed by the method for cleaning a semiconductor substrate of the present invention be produced from an adhesive composition containing the release agent component (B).
• an adhesive layer produced from an adhesive composition excluding the release agent component (B) is used.
• the contact angle of the stripping and dissolving composition when the contact angle of the stripping and dissolving composition is measured, components that do not significantly affect the value of the contact angle may be removed in order to increase the accuracy of the measurement.
• the measurement is performed using a peeling and dissolving composition that does not contain the quaternary ammonium salt of the above-mentioned component [I-1].
• the contact angle can be measured, for example, using a fully automatic contact angle meter DM-701 manufactured by Kyowa Interface Science Co., Ltd.
• the adhesive layer on the semiconductor substrate is continuously contacted with the peeling and dissolving composition.
• the adhesive layer is swelled to peel off and the adhesive layer is dissolved at the same time.
• the adhesive layer can be removed (cleaned) from the semiconductor substrate in a shorter time and more cleanly with a simple cleaning operation.
• removal refers to removing the adhesive layer from the semiconductor substrate, and includes both the case where the adhesive layer swells and peels off from the semiconductor substrate, and the case where the adhesive layer dissolves in a solution and is removed from the semiconductor substrate.
• the method of continuously contacting the adhesive layer on the semiconductor substrate with the composition for peeling and dissolving is not particularly limited as long as the adhesive layer on the semiconductor substrate is in contact with the composition for peeling and dissolving with time continuity. This time continuity includes not only the case where the adhesive layer is always in contact with the composition for peeling and dissolving, but also, for example, the case where the adhesive layer is in contact with the organic solvent for a certain period of time, the contact is stopped once, and the contact is resumed or repeated.
• the adhesive layer on the semiconductor substrate is in contact with the composition for peeling and dissolving, but also the case where a part of the adhesive layer is in contact with the composition for peeling and dissolving. From the viewpoint of realizing more effective cleaning with good reproducibility, an embodiment in which the adhesive layer on the semiconductor substrate is always in contact with the composition for peeling and dissolving, and an embodiment in which the entire adhesive layer on the semiconductor substrate is in contact with the composition for peeling and dissolving are preferred.
• the adhesive layer on the semiconductor substrate is removed from the semiconductor substrate by swelling and dissolving the adhesive layer by immersing the adhesive layer in a peeling and dissolving composition, or by continuously supplying the peeling and dissolving composition onto the adhesive layer, by swelling and dissolving the adhesive layer on the semiconductor substrate.
• the semiconductor substrate with the adhesive layer attached thereto may be immersed in the composition for peeling and dissolving.
• the immersion time is the time until the adhesive layer swells and dissolves and peels off from the semiconductor substrate, and is not particularly limited, but is 5 seconds or more from the viewpoint of achieving more effective cleaning with good reproducibility, and is 5 minutes or less from the viewpoint of process throughput.
• removal (cleaning) of the adhesive layer may be promoted by moving the semiconductor substrate with the adhesive layer in the peeling and dissolving composition, by creating a convection current in the peeling and dissolving composition, by vibrating the peeling and dissolving composition with ultrasonic waves, etc.
• a swinging cleaner, a paddle type cleaner, or the like may be used.
• the platform on which the semiconductor substrate with the adhesive layer is placed moves or rotates up and down or left and right, causing the adhesive layer on the semiconductor substrate to be subjected to relative convection, or the adhesive layer on the semiconductor substrate to be subjected to convection generated by that movement or rotation, which not only promotes swelling and dissolution of the adhesive layer on the semiconductor substrate, but also promotes peeling and dissolution of the adhesive layer from the semiconductor substrate.
• a convection cleaner In order to convect the stripping and dissolving composition, in addition to the above-mentioned oscillating cleaner and paddle type cleaner, for example, a convection cleaner can be used, which typically uses an agitator to create a state in which the semiconductor substrate with the adhesive layer is fixed to a stage or the like and the stripping and dissolving composition around the substrate is convected.
• an ultrasonic cleaner or ultrasonic probe may be used, and the conditions are usually 20 kHz to 5 MHz.
• the peeling and dissolving composition may be continuously applied toward the adhesive layer on the semiconductor substrate.
• a rod-shaped or mist-shaped, preferably rod-shaped, peeling and dissolving composition is continuously supplied onto the adhesive layer on the semiconductor substrate from above (including diagonally above) the adhesive layer on the semiconductor substrate using a nozzle or the like of a cleaning device.
• the continuity in time does not only include the case where the peeling and dissolving composition is constantly supplied onto the adhesive layer on the semiconductor substrate, but also includes, for example, the case where the peeling and dissolving composition is supplied for a certain period of time, then the supply is stopped once, and then the supply is resumed or repeated.
• the peeling and dissolving composition is constantly supplied onto the adhesive layer on the semiconductor substrate.
• the flow rate is typically 200 to 500 mL/min.
• the adhesive layer on the semiconductor substrate in order to ensure that the adhesive layer on the semiconductor substrate is in constant contact with the stripping and dissolving composition, the adhesive layer may be brought into contact with the vapor of the stripping and dissolving composition, for example, using a steam cleaner.
• the adhesive layer is swelled, peeled off, and dissolved at the same time, so that the adhesive layer can be removed (cleaned) from the semiconductor substrate more quickly and more cleanly by a simple cleaning operation.
• the semiconductor manufacturing method of the present invention can also prevent damage to the dicing tape during the cleaning process. For example, after a semiconductor wafer is polished and thinned, the thinned semiconductor wafer is mounted on a dicing tape, and then the semiconductor wafer and the support are separated (peeled off). After the support is separated (peeled off), the adhesive layer remaining on the semiconductor wafer is removed from the semiconductor wafer and cleaned with a cleaning composition.
• a cleaning composition that dissolves and removes adhesive residues such as the cleaning compositions of Patent Documents 1 and 2
• the surface of the dicing tape will change and the dicing tape will be damaged.
• a semiconductor substrate with an adhesive layer is cleaned using the composition for peeling and dissolving of the present invention, most of the adhesive layer can be peeled off in a short time, and the small amount of adhesive layer remaining after peeling is dissolved by the soluble component in the composition for peeling and dissolving, so the total removal (cleaning) time for removing the adhesive layer can be short, and damage to the dicing tape in the cleaning process can be effectively prevented.
• the composition for peeling and dissolving of the present invention contains not only a component for dissolving the adhesive layer, but also a component for swelling and peeling the adhesive layer, and as a result, the proportion of the soluble component in the composition, that is, the component [I-1] (quaternary ammonium salt), can be reduced, which also effectively contributes to preventing damage to the dicing tape.
• the adhesive layer removal step is carried out using the peeling and dissolving composition of the present invention, damage to the dicing tape can be effectively prevented.
• the method for producing a semiconductor substrate of the present invention may include a step of removing the peeled adhesive layer.
• the method for removing the peeled adhesive layer is not particularly limited as long as the peeled adhesive layer is removed from the semiconductor substrate.
• the peeled adhesive layer present in the peeling and dissolving composition may be removed without removing the semiconductor substrate from the peeling and dissolving composition.
• the semiconductor substrate may be removed from the peeling and dissolving composition, and the peeled adhesive layer may be removed by pulling the semiconductor substrate away from the peeled adhesive layer.
• the peeled adhesive layer may naturally remain in the peeling and dissolving composition by simply removing the semiconductor substrate from the peeling and dissolving composition, and most of it may be removed.
• methods for removing the peeled adhesive layer include, but are not limited to, removing the peeled adhesive layer by adsorption or suction using a device, removing the peeled adhesive layer by blowing it away with gas from an air gun or the like, and removing the peeled adhesive layer by centrifugal force caused by moving or rotating the semiconductor substrate up and down or left and right.
• composition for stripping and dissolving The present invention also relates to a composition for stripping and dissolving used in the method for producing a semiconductor substrate of the present invention.
• the composition for stripping and dissolving of the present invention is used to remove (clean) an adhesive layer on a semiconductor substrate from the semiconductor substrate, and the preferred embodiments and conditions are as described above.
• the composition for stripping and dissolving of the present invention can be produced by mixing the solvents constituting the composition in any order if necessary. At that time, filtration, etc. may be performed if necessary.
• the content of the component [II], which contributes to swelling and peeling the adhesive layer, is relatively high, so that when the composition for peeling and dissolving of the present invention is brought into contact with the adhesive layer, the adhesive layer is swelled to peel it and the adhesive layer is dissolved at the same time.
• Publication A describes a method for cleaning an adhesive on a semiconductor substrate and a cleaning composition used in the manufacturing method thereof.
• the adhesive described in Publication A is not a type of adhesive that can be swelled and peeled off by a cleaning composition as the subject of the present invention. Therefore, Publication A does not have the idea of swelling and peeling off the adhesive layer as a means for removing the adhesive, and the cleaning composition described in Publication A is only intended to dissolve the adhesive layer and remove the adhesive layer.
• the method for producing a processed semiconductor substrate of the present invention is a method for producing a processed semiconductor substrate by using the above-mentioned method for producing a semiconductor substrate of the present invention.
• a semiconductor wafer is polished and thinned, and then the support is separated (peeled) from the processed and thinned semiconductor wafer, and then the adhesive layer remaining on the semiconductor wafer is removed (cleaned) using the method for producing a semiconductor substrate of the present invention, thereby making it possible to produce a processed semiconductor substrate with a clean surface free of any remaining adhesive layer.
• An example of the use of the method for manufacturing a semiconductor substrate of the present invention in a semiconductor process is a method for manufacturing a processed semiconductor substrate, such as a thinned one, used in semiconductor packaging technology such as TSV.
• the semiconductor substrates to be cleaned by the manufacturing method of the present invention include, in addition to silicon semiconductor substrates such as the silicon wafers described above, various substrates such as germanium substrates, gallium arsenide substrates, gallium phosphide substrates, gallium arsenide aluminum substrates, aluminum-plated silicon substrates, copper-plated silicon substrates, silver-plated silicon substrates, gold-plated silicon substrates, titanium-plated silicon substrates, silicon substrates with a silicon nitride film formed thereon, silicon substrates with a silicon oxide film formed thereon, silicon substrates with a polyimide film formed thereon, glass substrates, quartz substrates, liquid crystal substrates, and organic EL substrates.
• various substrates such as germanium substrates, gallium arsenide substrates, gallium phosphide substrates, gallium arsenide aluminum substrates, aluminum-plated silicon substrates, copper-plated silicon substrates, silver-plated silicon substrates, gold-plated silicon substrates, titanium-plated silicon substrates, silicon substrates with a
• First step producing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition
• Second step processing the semiconductor substrate of the obtained laminate
• a third step a step of separating the semiconductor substrate and the adhesive layer from the supporting substrate
• a fourth step a step of removing the adhesive layer on the semiconductor substrate by peeling and dissolving using a composition for peeling and dissolving.
• the composition for stripping and dissolving is as explained in the section ⁇ Composition for stripping and dissolving> above.
• the method for producing a semiconductor substrate of the present invention is used. Each step will be described in detail below.
• the adhesive composition used to form the adhesive layer in the first step may be any of the various adhesives described above.
• the method for producing a semiconductor substrate of the present invention is effective for removing an adhesive layer obtained from a polysiloxane-based adhesive, and is more effective for removing an adhesive layer obtained from a polysiloxane-based adhesive containing component (A) that hardens by a hydrosilylation reaction. Therefore, the following describes an example in which, when manufacturing a semiconductor substrate processed using an adhesive layer obtained using a polysiloxane-based adhesive (adhesive composition), the adhesive layer is removed by the manufacturing method of the present invention, but the present invention is not limited thereto.
• the first step of manufacturing a laminate comprising a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition is described below.
• the first step includes a step of applying an adhesive composition to a surface of a semiconductor substrate or a supporting substrate to form an adhesive coating layer, and a step of bonding the semiconductor substrate and the supporting substrate via the adhesive coating layer, applying a load in the thickness direction of the semiconductor substrate and the supporting substrate while performing at least one of a heat treatment and a decompression treatment to bond them together, and then performing a post-heat treatment to form a laminate.
• the first step includes, for example, a step of applying an adhesive composition to the circuit surface of a semiconductor substrate wafer and heating it to form an adhesive coating layer, a step of applying a release agent composition to the surface of a support substrate and heating it to form a release agent coating layer, and a step of bonding the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing at least one of a heat treatment and a decompression treatment, and then performing a post-heat treatment to form a laminate.
• the adhesive composition is applied to the semiconductor substrate and the release agent composition is applied to the support substrate, respectively, and heated, but the adhesive composition and the release agent composition may be applied and heated sequentially to either one of the substrates, respectively.
• the treatment conditions to be adopted that is, the heat treatment, the reduced pressure treatment, or a combination of the two, are determined in consideration of various factors such as the type of adhesive composition, the specific composition of the release agent composition, the compatibility of the films obtained from the two compositions, the film thickness, and the desired adhesive strength.
• the semiconductor substrate is a wafer and the support substrate is a support body.
• the adhesive composition may be applied to either the semiconductor substrate or the support substrate, or both.
• the wafer examples include, but are not limited to, silicon wafers and glass wafers having a diameter of about 300 mm and a thickness of about 770 ⁇ m.
• the method for manufacturing a semiconductor substrate of the present invention can effectively clean a semiconductor substrate even if the substrate has bumps.
• Specific examples of such semiconductor substrates with bumps include silicon wafers having bumps such as ball bumps, printed bumps, stud bumps, and plated bumps.
• the bump height is appropriately selected from about 1 to 200 ⁇ m
• the bump diameter is 1 to 200 ⁇ m
• the bump pitch is 1 to 500 ⁇ m.
• Specific examples of plated bumps include alloy plating mainly composed of Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps, but are not limited to these.
• the support (carrier) is not particularly limited, but may be, for example, a silicon wafer with a diameter of about 300 mm and a thickness of about 700 ⁇ m, but is not limited to this.
• the stripping agent composition may be a composition containing a stripping agent component used for this type of application.
• the coating method is not particularly limited, but is usually a spin coating method. Note that a method of forming a coating film by a separate method such as spin coating and attaching a sheet-like coating film may also be used, and this method is also referred to as coating or coating film.
• the heating temperature of the applied adhesive composition cannot be generally determined because it depends on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is included, the desired thickness of the adhesive layer, etc., but it is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes.
• the heating temperature of the applied release agent composition cannot be generally specified because it varies depending on the types and amounts of the crosslinking agent, acid generator, acid, etc., whether or not a solvent is contained, the desired thickness of the release layer, etc., but is preferably 120° C. or higher from the viewpoint of achieving suitable curing, and is preferably 260° C. or lower from the viewpoint of preventing excessive curing, and the heating time is usually 1 to 10 minutes. Heating can be carried out using a hot plate, an oven, or the like.
• the thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it is usually 5 to 500 ⁇ m.
• the thickness of the release agent coating layer obtained by applying the release agent composition and heating it is usually 5 to 500 ⁇ m.
• the heat treatment is usually determined appropriately from the range of 20 to 150°C, taking into consideration the viewpoints of softening the adhesive coating layer to realize suitable bonding with the release agent coating layer, and the viewpoints of achieving suitable hardening of the release agent coating layer.
• the temperature is preferably 130°C or less, more preferably 90°C or less
• the heating time is usually 30 seconds or more, preferably 1 minute or more, from the viewpoint of reliably expressing adhesive and release capabilities, but is usually 10 minutes or less, preferably 5 minutes or less, from the viewpoint of suppressing deterioration of the adhesive layer and other members.
• the reduced pressure treatment can be performed by exposing the semiconductor substrate, adhesive coating layer, and support substrate, or the semiconductor substrate, adhesive coating layer, release agent coating layer, and support substrate, to an air pressure of 10 to 10,000 Pa.
• the reduced pressure treatment time is usually 1 to 30 minutes.
• the substrate and the coating layer, or the coating layers themselves are bonded together, preferably by a reduced pressure treatment, more preferably by a combination of a heat treatment and a reduced pressure treatment.
• the load applied in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate, and the layers between them and can firmly adhere them to each other, but is usually within the range of 10 to 1000 N.
• the post-heating temperature is preferably 120° C. or higher from the viewpoint of obtaining a sufficient curing speed, and is preferably 260° C. or lower from the viewpoint of preventing deterioration of the substrate, adhesive component, release agent component, etc.
• the heating time is usually 1 minute or more from the viewpoint of realizing suitable bonding of the wafer by curing, and preferably 5 minutes or more from the viewpoint of stabilizing the physical properties of the adhesive, and is usually 180 minutes or less, preferably 120 minutes or less from the viewpoint of avoiding adverse effects on the adhesive layer due to excessive heating. Heating can be performed using a hot plate, an oven, etc.
• One purpose of the post-heat treatment is to more suitably cure the adhesive component (S).
• ⁇ Second step> a second step of processing the semiconductor substrate of the laminate obtained by the method described above will be described.
• An example of the processing applied to the laminate used in the present invention is processing of the back surface opposite to the circuit surface of the semiconductor substrate, typically thinning the wafer by polishing the back surface of the wafer. Using such a thinned wafer, through-silicon vias (TSVs) and the like are formed, and then the thinned wafer is peeled off from the support to form a wafer stack, which is then three-dimensionally mounted. In addition, before and after that, wafer back electrodes and the like are also formed. In the wafer thinning and TSV process, heat of 250 to 350° C.
• a wafer with a diameter of 300 mm and a thickness of about 770 ⁇ m can be thinned to a thickness of about 80 to 4 ⁇ m by polishing the back surface opposite the circuit surface on the front surface.
• ⁇ Third step> The third step of separating the processed semiconductor substrate and adhesive layer from the support substrate will now be described.
• the processed semiconductor substrate and adhesive layer are separated from the support substrate.
• the release layer is usually removed together with the support substrate.
• the method for separating the processed semiconductor substrate and adhesive layer from the semiconductor substrate can be simply to peel between the adhesive layer and the release layer or support substrate in contact therewith. Examples of such peeling methods include, but are not limited to, laser peeling, mechanical peeling using equipment with sharp edges, and manual peeling.
• the fourth step is a step of removing the adhesive layer on the semiconductor substrate by the method for producing a semiconductor substrate of the present invention (corresponding to the cleaning step in the method for producing a semiconductor substrate of the present invention described above), specifically, for example, the adhesive layer on the thinned substrate is cleanly removed in a short time by the method for producing a semiconductor substrate of the present invention.
• the conditions for this step are as described above.
• the adhesive layer is simultaneously swelled and dissolved, so in the fourth step, the adhesive layer on the semiconductor substrate can be removed more cleanly and in a shorter time.
• the method for manufacturing a processed semiconductor substrate of the present invention comprises the above-mentioned first to fourth steps, but may also include steps other than these. Furthermore, the above-mentioned components and methodological elements related to steps 1 to 4 may be modified in various ways without departing from the spirit of the present invention.
• Adhesive Composition 1 [Example 1-1] In a 600 mL stirring vessel dedicated to the stirrer A, 62.10 g of a vinyl group-containing linear polydimethylsiloxane having a viscosity of 200 mPa ⁇ s and represented by the following formula (V) as the aforementioned component (a1), 82.25 g of a base polymer consisting of a vinyl group-containing MQ resin (manufactured by Wacker Chem.), 15.23 g of a SiH group-containing linear polydimethylsiloxane having a viscosity of 100 mPa ⁇ s (manufactured by Wacker Chem.) as the aforementioned component (a2), and 0.42 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem.) as the aforementioned component (A3) were placed and stirred for 5 minutes with the stirrer A to obtain a mixture
• Example 1-2 In a 600 mL stirring vessel dedicated to the stirrer A, 99.12 g of p-menthane solution (concentration 80.6% by mass) of MQ resin (manufactured by Wacker Chem) having a polysiloxane skeleton and a vinyl group as the aforementioned component (a1), 22.12 g of polyorganosiloxane represented by the above-mentioned formula (M1) as the aforementioned component (B) (complex viscosity 6000 Pa s, weight average molecular weight 642,000 (dispersity 2.6), manufactured by Wacker Chem, trade name GENIOPLAST GUM), 48.89 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) and 5.43 g of n-decane (manufactured by Sankyo Chemical Co., Ltd.) were added, and stirring for 5 minutes with the stirrer A was repeated a total of 8 times with short
• Example 2-2 to [Example 2-5]
• Example 1-1 to [Comparative Example 1-3]
• a cleaning composition was obtained in the same manner as in Example 2-1, except that the composition was adjusted to the composition shown in Table 1.
• Examples 2-6 and 2-7 A cleaning composition was obtained in the same manner as in Example 2-1, except that N-ethyl-2-pyrrolidone was used instead of N-methyl-2-pyrrolidone as the N-substituted amide compound and the composition was adjusted to have the composition shown in Table 1.
• Example 2-8 To 0.36 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical), 4.8 g of N-methyl-2-pyrrolidone, 4.8 g of dibutyl ether, and 2.4 g of butyl acetate were added and stirred to obtain a cleaning composition.
• Example 2-9 To 0.36 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical), 1.2 g of N-methyl-2-pyrrolidone, 8.4 g of butyl acetate, and 2.4 g of dipropylene glycol dimethyl ether were added and stirred to obtain a cleaning composition.
• Example 2-10 To 0.36 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical), 1.2 g of N-methyl-2-pyrrolidone and 10.8 g of butyl acetate were added and stirred to obtain a cleaning composition.
• Example 2-11 0.36 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) was mixed with 3.6 g of N-methyl-2-pyrrolidone and 8.4 g of mesitylene and stirred to obtain a cleaning composition.
• Example 2-12 To 0.36 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical), 3.6 g of N-methyl-2-pyrrolidone, 3.6 g of p-menthane, and 4.8 g of dipropylene glycol dimethyl ether were added and stirred to obtain a cleaning composition.
• Example 2-13 To 0.36 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical), 4.8 g of N-methyl-2-pyrrolidone, 4.8 g of p-menthane, and 2.4 g of dipropylene glycol dimethyl ether were added and stirred to obtain a cleaning composition.
• a cleaning composition was obtained by adding 12.0 g of N-methyl-2-pyrrolidone to 0.36 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical) and stirring the mixture.
• a cleaning composition was obtained by adding 12.0 g of dibutyl ether to 0.36 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) and stirring the mixture.
• Example 1 The adhesive composition obtained in Example 1-1 was applied by spin coating to a 4 cm ⁇ 4 cm silicon wafer (thickness 775 ⁇ m) as the device side wafer, and heated at 200°C for 10 minutes to form a thin film with a thickness of approximately 65 ⁇ m on the wafer, thereby obtaining a wafer with an adhesive layer.
• Example 2 The adhesive composition obtained in Example 1-2 was applied by spin coating to a 4 cm ⁇ 4 cm silicon wafer (thickness 775 ⁇ m) as the device side wafer, and heated at 110°C for 1.5 minutes and then at 200°C for 10 minutes to form a thin film with a thickness of approximately 40 ⁇ m on the wafer, thereby obtaining a wafer with an adhesive layer.
• the adhesive layer on the semiconductor substrate could be cleanly removed by simply immersing the semiconductor substrate in the composition for peeling and dissolving of the present invention for a short time of 1 minute.
• peeling and dissolving of the adhesive on the substrate can be achieved simultaneously if the contact angle of the composition for peeling and dissolving on the adhesive layer is greater than 22.6° and less than 46.1°.
• an adhesive layer can be removed (cleaned) from a semiconductor substrate having an adhesive layer on its surface by a simple operation, in a shorter time, and more cleanly.

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