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
  • C11D7/50—Solvents
  • C11D7/5004—Organic solvents
  • C11D7/5022—Organic solvents containing oxygen
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/43—Solvents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
  • C09J183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P70/00—Cleaning of wafers, substrates or parts of devices
  • H10P70/20—Cleaning during device manufacture
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P70/00—Cleaning of wafers, substrates or parts of devices
  • H10P70/30—Cleaning after the substrates have been singulated
• • 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
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
  • H10P50/282—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials
  • H10P50/283—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials by chemical means

Definitions

• the present invention relates to a method for cleaning a semiconductor substrate, a method for manufacturing a processed semiconductor substrate, and a composition for peeling and dissolving.
• semiconductor wafers have conventionally been integrated in a two-dimensional planar direction, but for the purpose of further integration, there is a need for a semiconductor integration technology in which the planar surfaces are further integrated (stacked) in a three-dimensional direction.
• This three-dimensional stacking is a technology in which devices are integrated into multiple layers while being connected using through silicon vias (TSV).
• TSV through silicon vias
• An unthinned semiconductor wafer (herein also referred to simply as a wafer) is bonded to a support for polishing in a polishing device. Since the adhesion at that time must be easily peeled off after polishing, it is called temporary adhesion. This temporary bond must be easily removed from the support, and the thinned semiconductor wafer may be cut or deformed if large forces are applied during removal, and measures must be taken to prevent this from occurring. can be easily removed. However, it is undesirable for the polishing member to come off or shift due to polishing stress during backside polishing of the semiconductor wafer. Therefore, the performance required for temporary bonding is that it can withstand stress during polishing and be easily removed after polishing.
• performance is required to have high stress (strong adhesive force) in the planar direction during polishing and low stress (weak adhesive force) in the direction crossing the planar direction, that is, the vertical direction, during removal.
• weak adhesive force strong adhesive force
• heat resistance is also required, as temperatures may reach temperatures of 150° C. or higher during the processing process.
• Patent Documents 1 and 2 disclose a siloxane resin remover containing a polar aprotic solvent and quaternary ammonium hydroxide
• Patent Document 2 discloses a cured resin remover containing alkyl ammonium fluoride. has been done.
• Patent Document 1 discloses a siloxane resin remover containing a polar aprotic solvent and quaternary ammonium hydroxide
• Patent Document 2 discloses a cured resin remover containing alkyl ammonium fluoride. has been done.
• Patent Document 1 discloses a siloxane resin remover containing a polar aprotic solvent and quaternary ammonium hydroxide
• Patent Document 2 discloses a cured resin remover containing alkyl ammonium fluoride. has been done.
• Patent Documents 1 and 2 above attempt to remove adhesive residue from the substrate surface by dissolving the adhesive residue on the substrate surface. Attempts to remove adhesive residues from substrate surfaces have been found to take a long time to remove.
• the present inventors found that when a composition containing a specific component is used, the adhesive layer can be swollen and the adhesive layer can be peeled off from the substrate. By using a composition containing this specific component, the adhesive layer can be removed from the substrate in a short time.
• a composition containing this specific component By using a composition containing this specific component, the adhesive layer can be removed from the substrate in a short time.
• there is room for improvement from the perspective of removing adhesive residue from the substrate surface more cleanly in a shorter time with a simple operation, and in search of a more effective cleaning method, a new cleaning method The development of compositions for use in cleaning methods and cleaning methods is progressing.
• the present invention has been developed in view of the above circumstances, and can be easily removed (cleaned) from a semiconductor substrate having an adhesive layer obtained using a siloxane adhesive on its surface in a shorter time and more cleanly. ), a method for manufacturing a processed semiconductor substrate including such a cleaning method, and a composition for use in such a cleaning method.
• adhesive layers on semiconductor substrates can be made from siloxane-based adhesives containing a polyorganosiloxane component (A') that hardens through a hydrosilylation reaction.
• A' polyorganosiloxane component
• the adhesive layer is swollen and peeled and dissolved in one cleaning operation.
• the inventors have discovered that the above problems can be solved by removing the adhesive layer from the semiconductor substrate, and have completed the present invention.
• a method for cleaning a semiconductor substrate comprising a step of peeling and dissolving an adhesive layer on the semiconductor substrate using a peeling and dissolving composition
• the stripping and dissolving composition is [I] Component: quaternary ammonium salt, [II] Component: an amide solvent; and [III] Component: a solvent represented by the following formula (G).
• 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 in L 11 and in the alkyl group in L 12 is 7 or less.
• R 0 represents an ethyl group, a propyl group, or an isopropyl group
• R A and R B each independently represent an alkyl group having 1 to 4 carbon atoms.
• 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).
• 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 is a bond bonded to the carbon atom in formula (Y).
• the adhesive layer is at least one selected from siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.
• the adhesive component (S) includes a siloxane adhesive.
• a processed semiconductor comprising: a third step of separating the semiconductor substrate and the adhesive layer from the supporting substrate; and a fourth step of removing the adhesive layer on the semiconductor substrate by peeling and dissolving it using a peeling and dissolving composition.
• the stripping and dissolving composition is [I] Component: quaternary ammonium salt, [II] Component: an amide solvent; and [III] Component: a solvent represented by the following formula (G).
• 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 in L 11 and in the alkyl group in L 12 is 7 or less.
• the stripping and dissolving composition further contains component [IV]: a solvent represented by the following formula (T) or the following formula (L).
• T a solvent represented by the following formula (T) or the following formula (L).
• X 4 represents an alkyl group.
• 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 11 is a methyl group.
• L 12 is a butyl group or a pentyl group.
• the adhesive layer is at least one selected from siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.
• a peeling and dissolving composition used for peeling and dissolving and removing the adhesive layer on the semiconductor substrate when cleaning the semiconductor substrate comprising: A peeling and dissolving composition characterized in that the peeling and dissolving composition satisfies at least any of the following (i) to (iv).
• the peeling and dissolving composition is Contains the following [I] component, the following [II] component, and the following [III] component, The content of the component [II] in 100% by mass of the aprotic solvent is 20% by mass or less, and the content of the component [III] is 60% by mass or more.
• the peeling and dissolving composition is Contains the following [I] component, the following [II] component, and the following [III] component, The content of the component [III] in 100% by mass of the aprotic solvent is 70% by mass or more.
• the peeling and dissolving composition is Contains the following [I] component, the following [II] component, the following [III] component, and the following [IV] component,
• the [IV] component contains a solvent represented by the following formula (L), When the aprotic solvent is 100% by mass, the content of the component [III] is greater than 31% by mass, and the content of the component [IV] is less than 30% by mass.
• the stripping and dissolving composition comprises: Contains the following [I] component, the following [II] component, the following [III] component, and the following [IV] component,
• the [IV] component contains a solvent represented by the following formula (T),
• T a solvent represented by the following formula (T)
• the aprotic solvent 100% by mass
• the content of the component [III] is greater than 31% by mass
• the content of the component [IV] is less than 30% by mass
• the content of the component [II] is less than 30% by mass.
• the content is 20% by mass or less.
• component [I] is a quaternary ammonium salt
• [II] Component is an amide solvent
• [III] Component is a solvent represented by the following formula (G)
• [IV] Component represents a solvent represented by the following formula (T) or the following formula (L).
• 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 in L 11 and in the alkyl group in L 12 is 7 or less.
• X 2 represents an alkylene group
• n is 2 or 3.
• X 4 represents an alkyl group.
• 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 3 represents O or S.
• the adhesive layer is at least one selected from siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.
• the peeling and dissolving composition according to any one of [21] to [25], which is a film obtained using an adhesive composition containing an adhesive component (S).
• a method for cleaning a semiconductor substrate which can remove (clean) a semiconductor substrate having an adhesive layer on its surface with a simple operation, in a shorter time, and more cleanly, includes such a cleaning method.
• a method for manufacturing a processed semiconductor substrate and a composition for use in such a cleaning method can be provided.
• the method for cleaning a semiconductor substrate of the present invention includes a step of peeling and dissolving an adhesive layer on a semiconductor substrate using a peeling and dissolving composition.
• the stripping and dissolving composition is [I] Component: quaternary ammonium salt, [II] Component: An amide solvent, and [III] Component: A solvent represented by the following formula (G).
• 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 in L 11 and in the alkyl group in L 12 is 7 or less.
• the stripping and dissolving composition may further contain a [IV] component: a solvent represented by the following formula (T) or the following formula (L).
• L 1 and L 2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L 3 represents O or S.
• the main material constituting the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, and examples thereof include silicon, silicon carbide, and compound semiconductors.
• the shape of the semiconductor substrate is not particularly limited, it is, for example, disc-shaped.
• the surface of a disk-shaped semiconductor substrate does not need to have a completely circular shape; for example, the outer periphery of the semiconductor substrate may have a straight part called an orientation flat, or a straight part called a notch. It may have a notch.
• the thickness of the disk-shaped semiconductor substrate may be determined as appropriate depending on the intended use of the semiconductor substrate, and is, for example, 500 to 1,000 ⁇ m, although it is not particularly limited.
• the diameter of the disk-shaped semiconductor substrate may be determined as appropriate 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 includes a silicon wafer with a diameter of about 300 mm and a thickness of about 770 ⁇ m, but is not limited thereto.
• 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 include siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, and polyamide adhesives. adhesives, polystyrene adhesives, polyimide adhesives, phenolic resin adhesives, and the like.
• siloxane adhesives are preferred as the adhesive component (S) because they exhibit suitable adhesion when processing wafers, etc., can be peeled off after processing, and have excellent heat resistance. is preferred.
• the adhesive composition used in the present invention contains, as an adhesive component, a component (A) that is cured by a hydrosilylation reaction.
• the adhesive composition used in the present invention contains polyorganosiloxane.
• Component (A) may be a component that hardens through a hydrosilylation reaction, or may be a polyorganosiloxane component (A') that hardens through a hydrosilylation reaction.
• component (A) includes, for example, a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, as an example of component (A'), and Si- It contains a polyorganosiloxane (a2) having an H group and a 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 hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.
• the polyorganosiloxane component (A') that is cured by a hydrosilylation reaction has siloxane units (Q units) represented by SiO 2 , R 1 R 2 R 3 SiO 1/2
• siloxane units (M units) siloxane units represented by R 4 R 5 SiO 2/2
• siloxane units (T units) represented by R 6 SiO 3/2
• a polysiloxane (A1) containing two or more types of units and a platinum group metal catalyst (A2) wherein the polysiloxane (A1) is a siloxane unit (Q' unit) represented by SiO2 , R1 'R 2 'R 3 'SiO 1/2 siloxane unit (M' unit), R 4 'R 5 'SiO 2/2 siloxane unit (D' unit) and R 6 'SiO 3 Contains one or more units selected from the group consisting of siloxane units (T
• Polyorganosiloxane (a1') containing seeds, siloxane units represented by SiO2 (Q” units), siloxane units represented by R1 " R2 " R3 "SiO1 /2 (M” units) , one selected from the group consisting of siloxane units (D” units) represented by R 4 "R 5 "SiO 2/2 and siloxane units (T” units) represented by R 6 "SiO 3/2 , or
• the polyorganosiloxane (a2') contains two or more types of units and also contains at least one type selected from the group consisting of M" units, D" units, and T" units. Note that (a1') is an example of (a1), and (a2') is an example of (a2).
• R 1 to R 6 are groups or atoms bonded to a 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 hydroxy 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, but R 1 ′ to R 6 At least one of ' is an optionally substituted alkenyl group.
• substituents include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.
• R 1 ” to R 6 are groups or atoms bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or a hydrogen atom, but at least one of R 1 ” to R 6 ” One is a hydrogen atom.
• substituents include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.
• the alkyl group may be linear, branched, or cyclic, but a linear or branched alkyl group is preferable, and the number of carbon atoms thereof is not particularly limited, but is usually 1 to 40. It is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less.
• optionally substituted linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group.
• the optionally substituted cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, and a 2-methyl-cyclopropyl group.
• the alkenyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more Preferably it is 10 or less.
• linear or branched alkenyl groups that may be substituted include, but are not limited to, vinyl groups, allyl groups, butenyl groups, pentenyl groups, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, more preferably 1 to 6. Among these, ethenyl group and 2-propenyl group are particularly preferred.
• the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl, cyclohexenyl, etc., and the number of carbon atoms thereof is usually 4 to 14, preferably 5 to 10, More preferably 5 to 6.
• polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'), but the alkenyl group contained in polyorganosiloxane (a1') and polyorganosiloxane (a2' ) and the hydrogen atoms (Si—H group) contained in the compound form a crosslinked structure through a hydrosilylation reaction using a platinum group metal catalyst (A2) and are cured. As a result, a cured film is formed.
• the polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, as well as M' units, D' units, and It contains at least one type selected from the group consisting of T' units.
• a combination of two or more polyorganosiloxanes satisfying such conditions may be used.
• Q' units, M' units, D' units and T' units include (Q' units and M' units), (D' units and M' units), (T' unit and M' unit), (Q' unit, T' unit and M' unit), but are not limited to these.
• the polyorganosiloxane (a1') contains two or more types of polyorganosiloxanes
• a combination of (Q' unit and M' unit) and (D' unit and M' unit), (T' Combinations of (unit and M' unit) and (D' unit and M' unit) are preferred, Not limited to these.
• the 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 M" units, D" units, and It contains at least one type selected from the group consisting of T'' units.As the polyorganosiloxane (a2'), two or more types of polyorganosiloxanes satisfying such conditions may be used in combination.
• Preferred combinations of two or more selected from the group consisting of Q" units, M" units, D" units, and T" units include (M" units and D” units), (Q" units and M” units), (Q" units, T" units, and M” units), but are not limited to these.
• the polyorganosiloxane (a1') is composed of siloxane units in which an alkyl group and/or an alkenyl group are bonded to the silicon atom, and in all the substituents represented by R 1 ' to R 6 ',
• the proportion of alkenyl groups 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 an alkyl group. .
• Polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and/or a hydrogen atom are bonded to a silicon atom, and all substituents represented by R 1 '' to R 6 '' and The proportion of hydrogen atoms in the substituent atoms is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remaining R 1 '' to R 6 '' are alkyl groups. can do.
• component (A) contains (a1) and (a2)
• the alkenyl group contained in the polyorganosiloxane (a1) and the Si-H bond contained in the polyorganosiloxane (a2) The molar ratio of hydrogen atoms to hydrogen atoms 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 viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but each is usually 10 to 1,000,000 (mPa ⁇ s), and is preferably from the viewpoint of achieving the effects of the present invention with good reproducibility. is 50 to 20000 (mPa ⁇ s).
• the viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is a value measured with an E-type rotational viscometer at 25°C.
• the polyorganosiloxane (a1) and the polyorganosiloxane (a2) react with each other to form a film through a hydrosilylation reaction. Therefore, the mechanism of curing is different from that via, for example, silanol groups, and therefore it is not necessary for any siloxane to contain silanol groups or functional groups that form silanol groups by hydrolysis, such as alkyloxy groups. None.
• 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 group of the polyorganosiloxane (a1) and the Si--H group of the polyorganosiloxane (a2).
• platinum-based metal catalysts include platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. Examples include, but are not limited to, platinum-based catalysts. Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum.
• the amount of 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 polyorganosiloxane (a1) and polyorganosiloxane (a2). .
• the polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing 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, and specific examples thereof include 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol. and other alkynyl alcohols.
• the amount of the polymerization inhibitor is not particularly limited, but it 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 it is necessary to prevent the hydrosilylation reaction.
• the content is 10,000.0 ppm or less from the viewpoint of preventing excessive suppression of
• the adhesive composition used in the present invention may contain a release agent component (B).
• a release agent component (B) typically includes polyorganosiloxane.
• specific examples thereof include, but are not limited to, epoxy group-containing polyorganosiloxane, methyl group-containing polyorganosiloxane, phenyl group-containing polyorganosiloxane, and the like.
• the release agent component (B) includes polydimethylsiloxane, and the polydimethylsiloxane 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 that is the release agent component (B) is not particularly limited, but is usually 100,000 to 2,000,000, and from the viewpoint of achieving 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. Further, the degree of dispersion is not particularly limited, but is usually 1.0 to 10.0, preferably 1.5 to 5.0, more preferably 2 .0 to 3.0. Note that the weight average molecular weight and the degree of dispersion can be measured by the method described above regarding 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).
• epoxy group-containing polyorganosiloxane examples include those containing a siloxane unit (D 10 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 are , the above-mentioned examples can be cited.
• the epoxy group in an organic group containing an epoxy group may be an independent epoxy group without being fused with other rings, or may form a fused ring with other rings, such as a 1,2-epoxycyclohexyl group. It may also be an epoxy group.
• Specific examples of organic groups containing epoxy groups include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.
• a preferable example of the epoxy group-containing polyorganosiloxane includes, but is not limited to, epoxy group-containing polydimethylsiloxane.
• the epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit ( D10 unit), but may also contain Q unit, M unit and/or T unit in addition to D10 unit.
• specific examples of the epoxy group-containing polyorganosiloxane include a polyorganosiloxane containing only D 10 units, a polyorganosiloxane containing D 10 units and Q unit, and a polyorganosiloxane containing D 10 units and M unit.
• polyorganosiloxane containing D 10 units and T units polyorganosiloxanes containing D 10 units, Q units and M units, polyorganosiloxanes containing D 10 units, M units and T units.
• the epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. Further, the weight average molecular weight thereof is not particularly limited, but is usually 1,500 to 500,000, and preferably 100,000 or less from the viewpoint of suppressing precipitation in the adhesive.
• epoxy group-containing polyorganosiloxane examples 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 siloxane units represented by R 21 R 21 SiO 2/2 . ( D20 units).
• R 210 and R 220 are groups bonded to a silicon atom, and each independently represents an alkyl group, and at least one of them is a methyl group, and specific examples of the alkyl group include the above-mentioned examples.
• R 21 is a group bonded to a silicon atom and represents an alkyl group, and specific examples of the alkyl group include those mentioned above. Among these, R 21 is preferably a methyl group.
• a preferable example of the methyl group-containing polyorganosiloxane includes polydimethylsiloxane, but is not limited thereto.
• the methyl group-containing polyorganosiloxane contains the aforementioned siloxane units (D 200 units or D 20 units), but in addition to the D 200 units and D 20 units, it may also contain Q units, M units, and/or T units. .
• methyl group-containing polyorganosiloxane examples include a polyorganosiloxane containing only D 200 units, a polyorganosiloxane containing D 200 units and Q units, and a polyorganosiloxane containing D 200 units and M units.
• polyorganosiloxane containing D 200 units and T units polyorganosiloxanes containing D 200 units, Q units and M units
• polyorganosiloxanes containing D 200 units, M units and T units examples of the methyl group-containing polyorganosiloxane.
• methyl group-containing polyorganosiloxane examples include polyorganosiloxanes containing only D20 units, polyorganosiloxanes containing D20 units and Q units, and polyorganosiloxanes containing D20 units and M units.
• methyl group-containing polyorganosiloxane examples include, but are not limited to, those represented by formula (M1).
• n4 indicates the number of repeating units and is a positive integer.
• Examples of the phenyl group-containing polyorganosiloxane include those containing a siloxane unit (D 30 unit) represented by R 31 R 32 SiO 2/2 .
• R 31 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 the above-mentioned examples. can be mentioned, but methyl group is preferred.
• the phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit ( D30 unit), but may also contain Q unit, M unit and/or T unit in addition to D30 unit.
• phenyl group-containing polyorganosiloxane examples include polyorganosiloxanes containing only D 30 units, polyorganosiloxanes containing D 30 units and Q units, and polyorganosiloxanes containing D 30 units and M units.
• polyorganosiloxane containing D 30 units and T units polyorganosiloxanes containing D 30 units, Q units and M units, polyorganosiloxanes containing D 30 units, M units and T units.
• phenyl group-containing polyorganosiloxane examples include, but are not limited to, those represented by formula (P1) or (P2).
• the polyorganosiloxane that is the release agent component (B) may be a commercially available product or a synthesized product.
• Commercially available polyorganosiloxane products include, for example, WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) manufactured by Wacker Chemi, GENIOPLAST GUM, and dimethyl silicone manufactured by Shin-Etsu Chemical Co., Ltd.
• Epoxy group-containing polyorganosiloxane (KF-101, KF-1001, KF-1005, X-22-343), Dow Corning epoxy Group-containing polyorganosiloxane (BY16-839); phenyl group-containing polyorganosiloxane (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest, phenyl group-containing polyorganosiloxane manufactured by Shin-Etsu Chemical Co., Ltd. Examples include, but are not limited to, siloxane (KF50-3000CS) and phenyl group-containing polyorganosiloxane (TSF431, TSF433) manufactured by MOMENTIVE.
• the adhesive composition used in the present invention contains a release agent component (B) together with the curing component (A), and in a more preferred embodiment, a polyorganosiloxane is included as the release agent component (B).
• An example of the adhesive composition used in the present invention can contain a curing component (A) and a release agent component (B) in any ratio.
• the ratio of component (A) and release agent component (B) is a mass ratio [(A):(B)], preferably 99.995:0.005 to 30:70, more preferably 99.9. :0.1 to 75:25. That is, when a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction is included, the ratio of the component (A') to the release agent component (B) is the mass ratio [(A'):(B)] The ratio is 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 viscosity, etc.
• a solvent for the purpose of adjusting viscosity etc.
• Specific examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc. but not limited to.
• the solvent includes hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl Examples include, but are not limited to, ketone, 2-octanone, 2-nonanone, 5-nonanone, and the like. Such solvents can be used alone or in combination of two or more.
• the content thereof is determined as appropriate by taking into consideration the viscosity of the desired composition, the coating method employed, the thickness of the thin film to be produced, etc.
• the amount ranges from about 10 to 90% by mass based on 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, 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 film constituents, etc., taking into account various factors such as the application method used and desired film thickness. It is.
• the membrane constituent component means a component other than the solvent contained in the composition.
• An example of the adhesive composition used in the present invention can be produced by mixing component (A), release agent component (B), and, if used, a solvent.
• the mixing order is not particularly limited, but as an example of a method that can easily and reproducibly produce a release adhesive composition, for example, component (A) and release agent component (B) are mixed in a solvent. Examples include, but are not limited to, a method of dissolving component (A) and a part of component (B) of the release agent in a solvent, dissolving the remainder in a solvent, and mixing the resulting solutions.
• heating may be carried out as appropriate within a range where the components do not decompose or change in quality.
• the solvent, solution, etc. used may be filtered using a filter or the like during the production of the adhesive composition or after all the components are 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, more preferably 20 to 50 ⁇ m.
• a stripping and dissolving composition is a composition used in a method of cleaning a semiconductor substrate to remove an adhesive layer from the semiconductor substrate.
• the peeling and dissolving composition contains a component for causing the adhesive layer to swell and peeling the adhesive layer from the semiconductor substrate, and a component for dissolving the adhesive layer.
• the stripping and dissolving composition includes: [I] Component: quaternary ammonium salt, [II] Component: An amide solvent, and [III] Component: A solvent represented by the following formula (G).
• 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 in L 11 and in the alkyl group in L 12 is 7 or less.
• the stripping and dissolving composition may further contain a [IV] component: a solvent represented by the following formula (T) or the following formula (L).
• L 1 and L 2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L 3 represents O or S.
• the quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it can be used for this type of use. Quaternary ammonium salts are effective as components for dissolving adhesive layers. Such quaternary ammonium cations typically include tetra(hydrocarbon) ammonium cations.
• anions that form a pair with it include hydroxide ion (OH - ); halogen ions such as fluorine ion (F - ), chloride ion (Cl - ), bromine ion (Br - ), and iodine ion (I - ). ; tetrafluoroborate ion (BF 4 ⁇ ); hexafluorophosphate ion (PF 6 ⁇ ), and the like, but are not limited to these.
• the quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.
• the halogen atom may be contained in the cation or the anion, but is preferably contained in the anion.
• the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon) ammonium fluoride.
• hydrocarbon groups in tetra(hydrocarbon) ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and 6 to 20 carbon atoms. Examples include aryl groups such as
• the tetra(hydrocarbon) ammonium fluoride comprises tetraalkylammonium fluoride.
• tetraalkylammonium fluoride examples include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also referred to as tetrabutylammonium fluoride). Not limited. Among these, tetrabutylammonium fluoride is preferred.
• a hydrate of the quaternary ammonium salt such as tetra(hydrocarbon) ammonium fluoride may be used. Further, 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 stripping and dissolving composition, but it is better to include it in a small amount to avoid damage to the dicing tape during the cleaning process described below. This is preferable because it can be effectively prevented. Specifically, for example, the amount is usually 0.1 to 5% by mass based on the composition for peeling and dissolving.
• the amide solvent is effective as a component for dissolving the quaternary ammonium salt well and obtaining a stripping and dissolving composition with excellent uniformity.
• the amide solvent is preferably an N-substituted amide compound having 4 or more carbon atoms and having 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 specifically includes a methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, n-butyl group, and isobutyl group. , s-butyl group, t-butyl group, cyclobutyl group, etc.
• R A and R B are preferably a methyl group or an ethyl group, both are more preferably a methyl group or an ethyl group, and both are even more preferably 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, Examples include 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, and the like. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyramide 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 a corresponding carboxylic acid ester and an amine, or a commercially available product may be used.
• preferable amide solvents include, for example, compounds represented by formula (Y) including lactam compounds.
• 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 methyl group, ethyl group, n-propyl group, n-butyl group, etc.
• alkylene group having 1 to 6 carbon atoms include , methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, etc., but are not limited thereto.
• 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 is bonded to a carbon atom in formula (Y).
• *2 represents a bond bonded to the nitrogen atom in formula (Y).
• lactam compound represented by formula (Y) examples include ⁇ -lactam compounds, ⁇ -lactam compounds, ⁇ -lactam compounds, ⁇ -lactam compounds, etc., which may be used singly or in combination. More than one species can be used in combination.
• the lactam compound represented by formula (Y) contains 1-alkyl-2-pyrrolidone (N-alkyl- ⁇ -butyrolactam), and 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-methylpyrrolidone
• NMP N-methylpyrrolidone
• NMP N-methylpyrrolidone
• NMP N-methylpyrrolidone
• component [II] it is more preferable to use an acid amide derivative represented by formula (Z) in consideration of operational constraints based on regulations regarding the use of chemical substances.
• the content of the amide solvent in the stripping and dissolving composition can be 50% by mass or less when the aprotic solvent is 100% by mass in the stripping and dissolving composition. Further, the content of the amide solvent is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 50% by mass or less, and 40% by mass or less when the aprotic solvent is 100% by mass. It is more preferably 30% by mass or less, even more preferably 20% by mass or less. In the present invention, the content of the solvents to be mixed is defined as a ratio based on 100% by mass of the aprotic solvent, which is a solvent that does not have a hydroxyl group (-OH).
• the aprotic solvent refers to, for example, N,N-dimethylpropionamide, butyl acetate, dipropylene glycol dimethyl ether, dibutyl ether, etc., and the mixing ratio can be determined based on the total amount of these solvents. .
• Solvent represented by formula (G) >> The solvent represented by the following formula (G) is effective as a 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 number of carbon atoms in the alkyl group of L 12 is: 7 or less.
• L 11 and L 12 each independently represent an alkyl group having 1 to 6 carbon atoms, but the total number of carbon atoms in the alkyl group of L 11 and the number of carbon atoms in the alkyl group of L 12 is 7 or less. With such a carbon number, the adhesive layer can be peeled off in a short time 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 group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group.
• n-pentyl group 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl- n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl -n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2, 2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 2-
• cyclic alkyl group examples include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3 -Methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3- Dimethyl-cyclobutyl group, 2,2-dimethyl-methyl-
• the above L 11 is preferably a methyl group
• the above L 12 is preferably a butyl group or a pentyl group.
• Preferred examples of the organic solvent represented by formula (G) include butyl acetate, pentyl acetate, etc. from the viewpoint of realizing peeling of the adhesive layer in a short time with good reproducibility and from the viewpoint of easy availability of the compound. Can be mentioned.
• the content of the solvent represented by formula (G) in the stripping and dissolving composition is greater than 31% by mass when the aprotic solvent is 100% by mass in the stripping and dissolving composition. be able to.
• the content of the solvent represented by formula (G) in the stripping and dissolving composition is more than 31% by mass when the aprotic solvent is 100% by mass in the stripping and dissolving composition. Preferably, it is more than 35% by mass, 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. . Any combination of these upper and lower limits may be used.
• a solvent for component [IV] represented by the following formula (T) or the following formula (L) is contained in the composition for peeling and dissolving, and a solvent for component [III] represented by formula (G) is added. It can be mixed with a solvent, but in that case, the combined content of component [III] and component [IV] is 30 to 90% by mass when the aprotic solvent is 100% by mass. It is preferable.
• Solvent represented by formula (T) or formula (L) is an amide-based solvent that is the above-mentioned [II] component in a stripping and dissolving composition containing a quaternary ammonium salt that is the above-mentioned [I] component. It is effective as an adjusting component for improving the compatibility and releasability of the solvent and the solvent represented by the above formula (G), which is the above component [III].
• the [IV] component is a solvent represented by the formula (L)
• it has good compatibility with the solvent represented by the above formula (G), which is the above [III] component, and the effects of the present invention are improved.
• a stripping and dissolving composition shown can be formed.
• Examples of the alkylene group represented by X 2 include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, and a 1,2-propylene group.
• Examples of the alkyl group represented by X 4 include alkyl groups having 1 to 4 carbon atoms, including the same alkyl groups as X 1 and X 3 .
• Preferred examples of the solvent represented by formula (T) include dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and the like.
• 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 realizing peeling of the adhesive layer in a short time with good reproducibility, it is preferably linear or branched. It is a branched alkyl group, more preferably a straight chain.
• linear or branched alkyl groups include ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n- Examples include, but are not limited to, pentyl groups.
• cyclic alkyl group examples include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, and the like.
• the alkyl group having 2 to 5 carbon atoms is preferably an ethyl group, n-propyl group, n-butyl group, or n-pentyl group, and more preferably is an ethyl group, n-propyl group or n-butyl group.
• L 1 and L 2 are the same group.
• di(n-butyl) ether is a preferable example of the organic solvent represented by formula (L). , diethyl ether, di(n-pentyl) ether, di(n-propyl) sulfide and the like.
• the content of the solvent represented by formula (T) or formula (L) in the stripping and dissolving composition is 30% by mass when the aprotic solvent is 100% by mass in the stripping and dissolving composition. Preferably, it is less than % by mass.
• the content of the solvent represented by formula (T) or formula (L) in the stripping and dissolving composition is 30% by mass when the aprotic solvent is 100% by mass in the stripping and dissolving composition. It is preferably less than 25% by mass, more preferably 25% by mass or less, even more preferably 20% by mass or less.
• the content of the solvent represented by formula (L) in the composition for peeling and dissolution is as follows:
• the aprotic solvent is 100% by mass, less than 30% by mass is more preferable.
• a peeling and dissolving composition is continuously brought into contact with the adhesive layer on the semiconductor substrate.
• the adhesive layer is swollen and peeled off, and the adhesive layer is dissolved.
• Swelling, peeling, and dissolution of the adhesive layer are performed together in a cleaning operation using a single cleaning composition, so that the adhesive layer can be removed from a semiconductor substrate in a shorter time and more cleanly with a simple cleaning operation. Can be removed (washed).
• removal refers to the removal of the adhesive layer from the semiconductor substrate, and even when the adhesive layer swells and is peeled off from the semiconductor substrate, the adhesive layer dissolves in a solution and the semiconductor Even when it disappears from the substrate, it is included in “removal (cleaning)".
• the method of continuously contacting the adhesive layer on the semiconductor substrate with the stripping and dissolving composition is particularly limited as long as the adhesive layer on the semiconductor substrate is brought into continuous contact with the stripping and dissolving composition over time.
• this temporal continuity includes not only the case in which the adhesive layer is constantly in contact with the peeling and dissolving composition, but also the case in which, for example, after the adhesive layer has been in contact with the organic solvent for a certain period of time, the contact It also includes cases where the contact is stopped once and then the contact is made again, or cases where this is repeated.In addition, it includes cases where the entire adhesive layer on the semiconductor substrate is in contact with the peeling and dissolving composition, as well as cases where only a portion of the adhesive layer is in contact with the peeling and dissolving composition.
• the adhesive layer on the semiconductor substrate is swollen and dissolved by immersing the adhesive layer in a peeling and dissolving composition to remove or bond the adhesive layer on the semiconductor substrate.
• the layer is swollen and dissolved by continuously applying a stripping and dissolving composition onto the adhesive layer and removed from the semiconductor substrate.
• the semiconductor substrate with the adhesive layer attached may be immersed in the composition for peeling and dissolving.
• the immersion time is the time required for swelling and dissolution of the adhesive layer to occur and for the adhesive layer to peel off from the semiconductor substrate, and is not particularly limited, but from the viewpoint of achieving more effective cleaning with good reproducibility, It is more than seconds, and from the viewpoint of process throughput, it is less than 5 minutes.
• the adhesive layer on the semiconductor substrate is immersed in the peeling and dissolving composition
• the semiconductor substrate with the adhesive layer is moved in the peeling and dissolving composition, the peeling and dissolving composition is caused to circulate, and the peeling is performed using ultrasonic waves.
• the removal (cleaning) of the adhesive layer may be promoted by vibrating the dissolving composition.
• a swing cleaning machine for example, a paddle type cleaning machine, etc. may be used. If such a cleaning machine is used, the adhesive layer will be removed.
• the adhesive layer on the semiconductor substrate receives relative convection, or the convection generated by the movement or rotation is transferred to the adhesive layer on the semiconductor substrate. This promotes not only the swelling and dissolution of the adhesive layer on the semiconductor substrate, but also the peeling and dissolution of the adhesive layer from the semiconductor substrate.
• a semiconductor substrate with an adhesive layer is fixed on a stage etc.
• a convection cleaning machine that can create a state in which the stripping and dissolving composition around the stripping and dissolving composition is convected by a stirrer may be used.
• an ultrasonic cleaner or an ultrasonic probe may be used, and the conditions are usually 20 kHz to 5 MHz.
• the peeling and dissolving composition In order to continuously supply the peeling and dissolving composition onto the adhesive layer on the semiconductor substrate, it is sufficient to continuously apply the peeling and dissolving composition toward the adhesive layer on the semiconductor substrate.
• a rod-shaped or mist-like A stripping and dissolving composition preferably in the form of a rod, is applied onto the adhesive layer on the semiconductor substrate with temporal continuity.
• the temporal continuity in this case is not limited to the case where the stripping and dissolving composition is constantly supplied onto the adhesive layer on the semiconductor substrate, but also, for example, after the stripping and dissolving composition is supplied for a certain period of time.
• the stripping and dissolving composition is applied to the surface of the semiconductor substrate. Preferably it is always applied above the adhesive layer.
• the flow rate is usually 200 to 500 mL/min.
• the adhesive layer on the semiconductor substrate is exposed to the vapor of the stripping and dissolving composition using, for example, a steam cleaning machine. May be brought into contact.
• the semiconductor cleaning method of the present invention When the semiconductor cleaning method of the present invention is used, as described above, the swelling, peeling, and dissolution of the adhesive layer are performed at the same time, so that the semiconductor substrate can be cleaned in a shorter time and more cleanly with a simple cleaning operation.
• the adhesive layer can be removed (cleaned).
• damage to the dicing tape during the cleaning process can be prevented. 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 side is removed from the semiconductor wafer by cleaning with a cleaning composition.
• a cleaning composition of the type that attempts to dissolve and remove adhesive residue such as the cleaning compositions of Patent Documents 1 and 2 above
• the surface of the dicing tape will change.
• the dicing tape is damaged.
• a semiconductor substrate with an adhesive layer is cleaned using the peeling and dissolving composition of the present invention, most of the adhesive layer can be peeled off in a short time, and even a small amount of the adhesive layer remaining after peeling can be used for peeling and dissolving. Since it is dissolved by the dissolved components in the composition, the entire removal (cleaning) time for removing the adhesive layer is short, and damage to the dicing tape during 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.
• the proportion of the dissolved component that is, the component [I] (quaternary ammonium salt) is small, which also effectively contributes to preventing damage to the dicing tape.
• the adhesive layer removal step is performed using the peeling and dissolving composition of the present invention, damage to the dicing tape can be effectively prevented.
• the semiconductor substrate cleaning method 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 top of the semiconductor substrate.
• the peeled adhesive layer present in the stripping and dissolving composition may be removed without taking out the semiconductor substrate from the stripping and dissolving composition.
• the peeled adhesive layer may be removed by taking out the semiconductor substrate from the peeling and dissolving composition and separating the semiconductor substrate from the peeled adhesive layer. At this time, by simply taking out the semiconductor substrate from the peeling and dissolving composition, the peeled adhesive layer may naturally remain in the peeling and dissolving composition, and most of it may be removed.
• methods for removing the peeled adhesive layer include, for example, removing the peeled adhesive layer by suction or suction using a device, removing the peeled adhesive layer by blowing it away with a gas such as an air gun, and removing the peeled adhesive layer from above or below the semiconductor substrate. Examples include, but are not limited to, methods such as removing the peeled adhesive layer by centrifugal force caused by moving it left and right or rotating it.
• the peeling and dissolving composition used in the semiconductor substrate cleaning method of the present invention is also an object of the present invention.
• the peeling and dissolving composition of the present invention is used to remove (clean) an adhesive layer on a semiconductor substrate from the semiconductor substrate, and preferred embodiments and conditions are as described above.
• the stripping and dissolving composition 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.
• Preferred embodiments of the stripping and dissolving composition of the present invention include stripping and dissolving compositions that meet at least any of the following (i) to (iv).
• the peeling and dissolving composition contains a [I] component, a [II] component, and a [III] component, The content of the component [II] in 100% by mass of the aprotic solvent is 20% by mass or less, and the content of the component [III] is 60% by mass or more.
• the peeling and dissolving composition contains a [I] component, a [II] component, and a [III] component, The content of the component [III] in 100% by mass of the aprotic solvent is 70% by mass or more.
• the peeling and dissolving composition contains a [I] component, a [II] component, a [III] component, and a [IV] component,
• the [IV] component contains a solvent represented by the above formula (L),
• the aprotic solvent is 100% by mass, the content of the component [III] is more than 31% by mass, and the content of the component [IV] is less than 30% by mass.
• the peeling and dissolving composition includes component [I], component [II], component [III], and component [IV], and the component [IV] contains a solvent represented by the above formula (L), and when the aprotic solvent is 100% by mass, the content of the component [III] is more than 35% by mass, and the content of the component [IV] is Compositions that have less than 30% by weight are included.
• the peeling and dissolving composition contains a [I] component, a [II] component, a [III] component, and a [IV] component
• the [IV] component contains a solvent represented by the above formula (T)
• T solvent represented by the above formula (T)
• the aprotic solvent is 100% by mass
• the content of the component [III] is more than 31% by mass
• the content of the component [IV] is less than 30% by mass
• the content of the component [II] is less than 30% by mass.
• the content is 20% by mass or less.
• the stripping and dissolving composition contains component [I], component [II], component [III], and component [IV]
• the component [IV] is represented by the above formula (L).
• the aprotic solvent is 100% by mass
• the [II] component is 30% by mass or more and 50% by mass or less
• the [III] component is more than 31% by mass and 50% by mass.
• the following compositions in which the component [IV] is 10% by mass or more and less than 30% by mass also show good results.
• the adhesive layer on the substrate of the semiconductor substrate in particular, the hardening obtained from the siloxane adhesive containing the polyorganosiloxane component (A') that hardens by a hydrosilylation reaction. It becomes possible to efficiently remove the adhesive layer, which is a film, and it is expected that highly efficient and good semiconductor devices can be manufactured.
• a processed semiconductor substrate with a clean surface without any remaining adhesive layer can be manufactured.
• an example of the use of the semiconductor substrate cleaning method of the present invention in a semiconductor process includes use in a method for manufacturing a processed semiconductor substrate such as thinning used in semiconductor packaging technology such as TSV.
• Semiconductor substrates to be cleaned in the cleaning method of the present invention include silicon semiconductor substrates such as the silicon wafers described above, as well as germanium substrates, gallium-arsenide substrates, gallium-phosphorus substrates, gallium-arsenide-aluminum substrates, and aluminum plated substrates. Silicon substrate, copper-plated silicon substrate, silver-plated silicon substrate, gold-plated silicon substrate, titanium-plated silicon substrate, silicon nitride film-formed silicon substrate, silicon oxide film-formed silicon substrate, polyimide film-formed silicon substrate, glass substrate, quartz substrate, liquid crystal substrate , and various substrates such as organic EL substrates.
• 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 cleaning 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 the various adhesives mentioned above can be used, but the semiconductor substrate cleaning method of the present invention uses an adhesive composition obtained from a polysiloxane adhesive. It is effective for removing adhesive layers obtained from polysiloxane adhesives containing component (A) that is cured by a hydrosilylation reaction. Therefore, an example will be described below in which when manufacturing a semiconductor substrate processed using an adhesive layer obtained using a polysiloxane adhesive (adhesive composition), the adhesive layer is removed by the cleaning method of the present invention.
• the present invention is not limited thereto.
• the first step of manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition will be described below.
• the first step includes a step of applying an adhesive composition to the surface of the semiconductor substrate or the supporting substrate to form an adhesive coating layer, and a step of connecting the semiconductor substrate and the supporting substrate via the adhesive coating layer.
• a step of forming a laminate by applying a load in the thickness direction of the semiconductor substrate and the support substrate to bring them into close contact with each other while performing at least one of heat treatment and depressurization treatment, and then performing post-heat treatment. including.
• the first step may include, for example, applying an adhesive composition to the circuit surface of the semiconductor substrate wafer and heating it to form an adhesive coating layer; A step of applying a release agent composition and heating it to form a release agent coating layer, and at least one of heat treatment and reduced pressure treatment of the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate. while applying a load in the thickness direction of the semiconductor substrate and the support substrate to bring them into close contact with each other, and then performing post-heat treatment to form a laminate. Note that although the adhesive composition was applied to the semiconductor substrate and the release agent composition was applied to the supporting substrate and heated, the adhesive composition and release agent composition were applied and heated to either one of the substrates in sequence. You may go.
• the type of adhesive composition, the specific composition of the release agent composition, and the compatibility of the film obtained from both compositions determine whether heat treatment, reduced pressure treatment, or a combination of the two is used. It is determined after taking into consideration various circumstances such as , film thickness, and desired adhesive strength.
• the semiconductor substrate is a wafer
• the support substrate is a support body.
• the object to which the adhesive composition is applied may be either the semiconductor substrate or the support substrate, or both.
• the wafer examples include, but are not limited to, silicon wafers and glass wafers with a diameter of about 300 mm and a thickness of about 770 ⁇ m.
• the semiconductor substrate cleaning method of the present invention can effectively clean a semiconductor substrate with bumps.
• Specific examples of such bumped semiconductor substrates include silicon wafers having bumps such as ball bumps, printed bumps, stud bumps, and plated bumps, and usually have a bump height of about 1 to 200 ⁇ m and a bump diameter of 1 to 200 ⁇ m. , a bump pitch of 1 to 500 ⁇ m.
• Specific examples of plated bumps include, but are not limited to, Sn-based alloy plating such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps.
• the support is not particularly limited, and examples include, but are not limited to, silicon wafers with a diameter of 300 mm and a thickness of about 700 ⁇ m.
• release agent composition examples include compositions containing a release agent component used for this type of use.
• the coating method is not particularly limited, but is usually a spin coating method. Note that a method may also be adopted in which a coating film is separately formed by a spin coating method or the like and a sheet-like coating film is attached, and this is also referred to as coating or coating film.
• the heating temperature of the applied adhesive composition cannot be unconditionally defined because it varies depending 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.
• the heating time 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 unconditionally defined because it varies depending on the type and amount of the crosslinking agent, acid generator, acid, etc., whether a solvent is included, the desired thickness of the release layer, etc.
• the temperature is preferably 120°C or higher, and from the viewpoint of preventing excessive curing, the temperature is preferably 260°C or lower, and the heating time is usually 1 to 10 minutes. Heating can be performed using a hot plate, 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 carried out at a temperature of 20 to 150°C, taking into account the viewpoints of softening the adhesive coating layer to achieve suitable bonding with the release agent coating layer, and achieving suitable curing of the release agent coating layer. It is determined as appropriate from the range of .
• the heating temperature is preferably 130°C or lower, more preferably 90°C or lower, and the heating time is determined by the adhesive ability and peelability. From the viewpoint of reliably developing, the time is usually 30 seconds or more, preferably 1 minute or more, but from the viewpoint of suppressing deterioration of the adhesive layer and other members, the time is usually 10 minutes or less, preferably 5 minutes or less.
• the reduced pressure treatment may be performed by exposing the semiconductor substrate, the adhesive coating layer, and the supporting substrate, or the semiconductor substrate, the adhesive coating layer, the release agent coating layer, and the supporting substrate to an atmospheric pressure of 10 to 10,000 Pa.
• the time for the reduced pressure treatment is usually 1 to 30 minutes.
• the substrate and the coating layer or the coating layers are bonded together, preferably by reduced pressure treatment, more preferably by a combination of heat treatment and reduced pressure treatment.
• the load in the thickness direction of the semiconductor substrate and the supporting substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the supporting substrate and the layer between them and can firmly adhere them, but usually It is within the range of 10 to 1000N.
• the post-heating temperature is preferably 120° C. or higher from the viewpoint of obtaining a sufficient curing rate, and 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 achieving suitable bonding of the wafers by curing, and preferably 5 minutes or more from the viewpoint of stabilizing the physical properties of the adhesive. From the viewpoint of avoiding adverse effects on the environment, the duration is usually 180 minutes or less, preferably 120 minutes or less. Heating can be performed using a hot plate, oven, or the like. Note that one purpose of the post-heat treatment is to more suitably cure the adhesive component (S).
• ⁇ Second process> a second step of processing the semiconductor substrate of the laminate obtained by the method described above will be described.
• An example of processing performed on the laminate used in the present invention includes processing the back surface of the semiconductor substrate, which is opposite to the circuit surface on the front surface, and typically involves thinning the wafer by polishing the back surface of the wafer. It will be done. Using such a thinned wafer, through-silicon vias (TSV) and the like are formed, and then the thinned wafer is peeled off from the support to form a stack of wafers, which is three-dimensionally packaged. Also, before and after this, the formation of wafer backside electrodes and the like is also performed.
• TSV through-silicon vias
• a wafer having a diameter of 300 mm and a thickness of about 770 ⁇ m can be reduced to a thickness of about 80 to 4 ⁇ m by polishing the back surface opposite to the circuit surface on the front surface.
• the third step of separating the processed semiconductor substrate, adhesive layer, and supporting substrate will be explained.
• the processed semiconductor substrate and adhesive layer are separated from the support substrate.
• the release layer is usually removed along with the supporting substrate.
• the processed semiconductor substrate and adhesive layer can be separated from the semiconductor substrate by peeling between the adhesive layer and the peeling layer or supporting substrate that is in contact with it.
• peeling methods include laser peeling, sharpening, etc. Examples include, but are not limited to, mechanical peeling using a piece of equipment, manual peeling, and the like.
• the fourth step is a step of removing the adhesive layer on the semiconductor substrate using the semiconductor substrate cleaning method of the present invention. Specifically, for example, the adhesive layer on the thinned substrate is removed by the cleaning method of the present invention for a short time. Remove it cleanly. The conditions at this time are as described above.
• the adhesive layer is simultaneously swollen and dissolved, so that in the fourth step, the semiconductor substrate can be removed more cleanly in a short time.
• the top adhesive layer can be removed.
• the method for manufacturing a processed semiconductor substrate of the present invention includes the first to fourth steps described above, but may include steps other than these steps. Moreover, the above-mentioned structural elements and methodological elements related to the first to fourth steps may be changed in various ways without departing from the gist of the present invention.
• Example 2-2 ⁇ [Example 2-5] ⁇ [Comparative Example 1-1] ⁇ [Comparative Example 1-8] Cleaning compositions were obtained in the same manner as in Example 2-1, except that the compositions were adjusted to have the compositions shown in Tables 1 to 3 (Tables 1 to 3 are also collectively referred to as Table 1, etc.).
• Example 2-6 to [Example 2-8] Example 2-1 except that N-ethyl-2-pyrrolidone was used instead of N-methyl-2-pyrrolidone as the N-substituted amide compound of component II, and the composition was adjusted to have the composition shown in Table 1.
• a cleaning composition was obtained in the same manner as above.
• Example 2-9 to [Example 2-11] Example 2-1 except that N,N-dimethylpropionamide was used instead of N-methyl-2-pyrrolidone as the N-substituted amide compound of component II, and the composition was adjusted to have the composition shown in Table 1.
• a cleaning composition was obtained in the same manner as above.
• Example 2-12 to [Example 2-14]
• N-substituted amide compound of component II 1,3-dimethyl-2-imidazolidinone was used instead of N-methyl-2-pyrrolidone, and the composition was adjusted to be as shown in Table 1.
• a cleaning composition was obtained in the same manner as in Example 2-1.
• Example 2-15 to [Example 2-16] A cleaning composition was obtained in the same manner as in Example 2-1, except that dibutyl ether was used instead of dipropylene glycol dimethyl ether as component IV, and the composition was adjusted to have the composition shown in Table 1.
• Example 1 The adhesive composition obtained in Example 1 was applied by spin coating to a 4 cm x 4 cm silicon wafer (thickness 775 ⁇ m) as a device side wafer, and heated at 110° C. for 1.5 minutes (preheating treatment). After that, the remaining solvent on the wafer was removed by heating at 200° C. for 10 minutes, and a thin film having a thickness of about 40 ⁇ m was formed on the wafer, thereby obtaining a wafer with an adhesive layer.
• the adhesive layer is removed (cleaned) from the semiconductor substrate in a short time as shown in Examples 2-1 to 2-16. I found out that it can be done. In the present invention, most of the adhesive layer can be peeled off in a short time, so even if a small amount of the adhesive layer remains after peeling, the adhesive residue can be dissolved by the dissolved components in the peeling and dissolving composition. and then cleanly removed. This is also shown by the results of Examples 2-1 to 2-16, and as shown in Examples 2-1 to 2-16, the peeling and dissolving composition of the present invention was The adhesive layer on the semiconductor substrate could be removed cleanly by simply immersing the semiconductor substrate in the liquid. That is, by using the semiconductor substrate cleaning method of the present invention, it is possible to remove (clean) the adhesive layer from the semiconductor substrate having the adhesive layer on the surface with a simple operation, in a shorter time, and more cleanly.

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• 2023
  • 2023-09-06 JP JP2024546893A patent/JPWO2024058025A1/ja active Pending
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