Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P70/00—Cleaning of wafers, substrates or parts of devices
  • H10P70/20—Cleaning during device manufacture
• • C—CHEMISTRY; METALLURGY
  • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • C—CHEMISTRY; METALLURGY
  • 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
  • C11D7/266—Esters or carbonates
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
  • C11D7/5004—Organic solvents
  • C11D7/5027—Hydrocarbons
• • 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
  • H10P50/286—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials
  • H10P50/287—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials by chemical means
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/7402—Wafer tapes, e.g. grinding or dicing support tapes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
  • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2483/00—Presence of polysiloxane
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces
  • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/7416—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/744—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 cleaning a semiconductor substrate, a method for producing a processed semiconductor substrate, and a composition for peeling. Background technology
• semiconductor wafers that have been integrated in a two-dimensional plane direction are required to have a semiconductor integration technology in which planes are further integrated (laminated) in a three-dimensional direction for the purpose of further integration.
• This three-dimensional lamination is a technology that integrates in multiple layers while connecting with through silicon vias (Ding 3 V: 1: II " ⁇ Li 9 1 * 1 3 1 II ⁇ ⁇ 11 VI 3).
• Ding 3 V: 1: II " ⁇ Li 9 1 * 1 3 1 II ⁇ ⁇ 11 VI 3 through silicon vias
• a pre-thinned semiconductor wafer (also referred to here simply as a wafer) is glued to a support for polishing with a polishing machine.
• the adhesion at that time is called temporary adhesion because it must be easily peeled off after polishing.
• This temporary bond must be easily removed from the support, and the thinned semiconductor wafer may be cut or deformed if a large force is applied to the removal, which does not occur. Like, it is easily removed.
• the semiconductor wafer comes off or shifts due to polishing stress when polishing the back surface. Therefore, the performance required for temporary bonding is to withstand the stress during polishing and to be easily removed after polishing.
• the processing process may reach a high temperature of 150 ° C or higher, and heat resistance is also required.
• ⁇ 02 821/193516 2 ⁇ (: 171? 2021/011675)
• polysiloxane-based adhesives capable of having these performances are mainly used as temporary adhesives.
• adhesive residue often remains on the surface of the substrate after the thinned substrate is peeled off, but this avoids problems in the subsequent steps. Therefore, a cleaning agent composition for removing this residue and cleaning the surface of a semiconductor substrate has been developed (for example, Patent Documents 1 and 2).
• Patent Document 1 discloses a siloxane resin remover containing a polar aprotic solvent and a quaternary ammonium hydroxide
• Patent Document 2 discloses a cured resin remover containing alkyl-ammonium fluoride. Has been done. However, in the semiconductor field these days, there is always a demand for new cleaning agent compositions, and there is always a demand for effective cleaning agent compositions and cleaning methods.
• a semiconductor wafer is electrically connected to a semiconductor chip via, for example, a bump ball made of a conductive material of metal, and by using a chip provided with such a bump ball, semiconductor / caging is performed.
• bump balls from metals such as copper and tin have poor corrosion resistance, and therefore have the problem of being damaged by the cleaning agent composition for removing adhesive residues on supports and wafers (patented).
• Document 3 it is mentioned as one of the matters required for the cleaning agent composition and the cleaning method that the bump copper is not corroded when cleaning the substrate.
• Patent Document 1 International Publication No. 2 0 1 4/0 9 2 0 2 2
• Patent Document 2 US Patent No. 6 8 1 8 6 0 8
• Patent Document 3 Korean Patent Publication 2 0 1 8 — 0 0 6 6 5 5 0
• Outline of the invention The problem that the invention is trying to solve ⁇ 02 821/193516 3 ⁇ (: 171? 2021/011675)
• the present invention has been made in view of the above circumstances. For example, damage to bumps of a semiconductor substrate is reduced or suppressed from a semiconductor substrate having an adhesive layer on its surface obtained by using a siloxane-based adhesive.
• a method for cleaning a semiconductor substrate for suitablely and easily removing the adhesive layer, a method for producing a processed semiconductor substrate including such a cleaning method, and a peeling composition used for such a cleaning method is to provide. Means to solve problems
• the present inventors have conducted a siloxane-based adhesive containing a polyorganosyloxane component (8) that cures the adhesive layer on a semiconductor substrate, particularly by a hydrosilylation reaction.
• a peeling composition containing a predetermined amount or more of a predetermined ester compound as a solvent and not containing a salt in the adhesive layer which is a cured film obtained from the above, damage to bumps of the semiconductor substrate is reduced or suppressed.
• they have found that they can be peeled off efficiently and easily, and have completed the present invention.
• a method for cleaning a semiconductor substrate which comprises a step of peeling an adhesive layer on a semiconductor substrate with a peeling composition, wherein the peeling composition contains a solvent, does not contain a salt, and is a solvent.
• a method for cleaning a semiconductor substrate which is characterized by containing 80% by mass or more of an organic solvent represented by the formula (! _).
• l 1 and 1_ 2 are each independently, the sum of carbon atoms in the alkyl group 1_ 2 and the number of carbon atoms in the alkyl group, an alkyl group of from 1 to 6 carbon atoms, with 6 or less be.
• the above solvent contains 85% by mass or more of the organic solvent represented by the above formula (1_) 1 ⁇ 02021/193516 How to clean the semiconductor substrate of ⁇ (: 171? 2021/011675,
• the above is the cleaning method for the semiconductor substrate of any of 1 to 3 which is a methyl group.
• ⁇ 2 is a petyl group or a pentyl group 4 How to clean the semiconductor substrate
• At least the above adhesive layer is selected from siloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polypeptide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenol resin-based adhesives.
• the above-mentioned adhesive component (3) is a method for cleaning 6 semiconductor substrates containing a siloxane-based adhesive.
• the first step of manufacturing a laminate having a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition the second step of processing the semiconductor substrate of the obtained laminate, from the support substrate.
• the peeling composition in the method for manufacturing a processed semiconductor substrate which includes the third step of separating the semiconductor substrate and the adhesive layer, and the fourth step of peeling the adhesive layer on the semiconductor substrate using the peeling composition.
• l 1 and 1_ 2 are each independently, the sum of carbon atoms in the alkyl group 1_ 2 and the number of carbon atoms in the alkyl group, an alkyl group of from 1 to 6 carbon atoms, with 6 or less be.
• ⁇ 2 is a petit group or a pentyl group 1 2 How to manufacture a processed semiconductor substrate
• the above adhesive layer is selected from siloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polypeptide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenol resin-based adhesives.
• l 1 and 1_ 2 are each independently, the sum of carbon atoms in the alkyl group 1_ 2 and the number of carbon atoms in the alkyl group represents an alkyl group of from 1 to 6 carbon atoms, the teeth 1, 6 It is as follows.
• the above! -1 is a composition for exfoliation of any of 17 to 19 which is a methyl group.
• the above adhesive layer is selected from siloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polypeptide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenol resin-based adhesives.
• the above adhesive component (3) is a peeling composition of 2 2 containing a siloxane-based adhesive.
• siloxane-based adhesive provides a peeling composition of 23 containing a polyorganosiloxane component (8) that is cured by a hydrosilylation reaction.
• the adhesive layer can be suitably and easily removed from a semiconductor substrate having an adhesive layer on its surface obtained by using a siloxane-based adhesive.
• a siloxane-based adhesive for example, the adhesive layer can be suitably and easily removed from a semiconductor substrate having an adhesive layer on its surface obtained by using a siloxane-based adhesive.
• Highly efficient and good semiconductor device production can be expected.
• ⁇ 02 821/193516 7 ⁇ (: 171-2021 / 011675
• the adhesive layer can be suitably and easily used while avoiding or suppressing damage to the bumps. Since it can be removed, it can be expected to manufacture a good semiconductor element with high efficiency and high reliability.
• the method for cleaning a semiconductor substrate of the present invention includes a step of peeling an adhesive layer on a semiconductor substrate using a peeling composition, wherein the peeling composition contains a solvent and does not contain a salt.
• the above solvent contains 80% by mass or more of the organic solvent represented by the formula (! _).
• the semiconductor substrate is, for example, a wafer, and specific examples thereof include, but are not limited to, a silicon wafer having a diameter of about 30 and a thickness of about 770.
• the adhesive layer on such a semiconductor substrate is, for example, a film obtained from an adhesive composition containing an adhesive component (3).
• an adhesive component (3) is not particularly limited as long as it is used for this kind of application.
• a siloxane-based adhesive an acrylic resin-based adhesive, an epoxy resin-based adhesive, and a polyami.
• examples include de-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenol resin-based adhesives.
• a siloxane-based adhesive is used as the adhesive component (3) because it exhibits suitable adhesive ability during processing of wafers, etc., can be preferably peeled off after processing, and has excellent heat resistance. Is preferable.
• the adhesive composition used in the present invention contains, as an adhesive component, a polyorganosiloxane component (8) that is cured by a hydrosilylation reaction, and in a more preferred embodiment, a hydrosilylation reaction.
• the polyorganosiloxane component (8) that is cured by is a siloxane unit represented by 3 ⁇ ⁇ 2. ⁇ 02 821/193516 8 ⁇ (: 171? 2021/011675)
• Siloxane unit represented by (mouth “unit) 3 ⁇ ⁇ Including one or more units selected from the group consisting of siloxane units (chome “units” represented by 3/2, and the above 1 ⁇ / 1" unit, mouth “unit and chome” Includes polyorganosiloxane (32) containing at least one selected from the group consisting of units.
• [0016] is a group or atom bonded to a silicon atom, which is independent of each other.
• Alkyl group Alkenyl group or hydrogen atom.
• [0017] is a group attached to a silicon atom, which independently represents an alkyl group or an alkenyl group. At least one of the ⁇ [3 ⁇ 4 6 'are A alkenyl group.
• [0018] is a group or atom bonded to a silicon atom, which independently represents an alkyl group or a hydrogen atom. At least one of ⁇ [3 ⁇ 4 6 ”is a hydrogen atom.
• 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 used. It is 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
• ⁇ 02 821/193516 9 ⁇ (: 17 2021/011675)
• linear or branched alkyl group examples include methyl group, ethyl group, ⁇ _propyl group, ⁇ -propyl group, ⁇ _butyl group, ⁇ -butyl group, 3 _butyl group, _butyl.
• cyclic alkyl group examples include a cyclopropyl group, a cyclobutyl group, and the like.
• the alkenyl group may be in the form of a linear chain or a branched chain, and the number of carbon atoms thereof is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably. Is 20 or less, more preferably 10 or less.
• alkenyl group examples include ethenyl group, 1 —propenyl group, 2 — pacteneyl group, 1 — methyl-1 — ethenyl group, 1 — butenyl group, 2 — butenyl group, 3 — butenyl.
• polysiloxane (8 1) contains polyorganosiloxane (3 1) and polyorganosiloxane (3 2), but the alkenyl group contained in polyorganosiloxane (31) and polyorgano.
• Hydrogen atoms (3 _ 1 to 1 group) contained in siloxane (3 2) form a crosslinked structure and harden by a hydrosilylation reaction with a platinum group metal-based catalyst (82).
• Polyorganosiloxane (3 1) contains one or more units selected from the group consisting of ⁇ 'units, IV!'Units, mouth'units and cho'units, and the above IV!' It contains at least one selected from the group consisting of units, mouth'units and cho'units.
• polyorganosiloxane (31) two or more types of polyorganosiloxane that satisfy these conditions may be used in combination.
• Preferred combinations of two or more selected from the group consisting of 0'units, IV!' Units, mouth'units and Ding' units are (0' units and IV!' Units), (0' units and IV!'Units), (Ding' units and IV!'Units), (0' units and ⁇ r units and IV!' Units), but are not limited to these.
• polyorganoshirokisan contained in polyorganosiloxane (3 1) when two or more kinds of polyorganoshirokisan contained in polyorganosiloxane (3 1) are contained, (0'unit and IV!' Unit) and (0' unit and IV!' Unit) and Combination of, (Ding'unit and 1 ⁇ / 1'unit) and (0'unit and 1 ⁇ / 1'unit), (0'unit and Ding'unit and IV!'Unit) and (Ding' Combinations of units and IV!'Units) are preferred, but not limited to these.
• Polyorganosiloxane (3 2) contains one or more units selected from the group consisting of ⁇ "units, 1 ⁇ / 1" units, mouth “units and chome” units, and the above 1 It contains at least one selected from the group consisting of ⁇ / 1 "units, mouth” units and "ding" units.
• ⁇ 02 821/193516 13 ⁇ (: 171-2021 / 011675) You may use two or more types of polyorganosiloxane that satisfy the conditions.
• Polyorganosiloxane (31) is composed of siloxane units in which an alkyl group and / or an alkenyl group are bonded to the silicon atom.
• the proportion of alkenyl groups in the total substituents represented by 1 ' ⁇ is preferably 0.1 mol% to 500 mol%, more preferably 0.5 mol% to 300 mol%. Yes, the rest ⁇ [3 ⁇ 4 6 'can be an alkyl group.
• Polyorganosiloxane (32) is composed of siloxane units in which an alkyl group and / or a hydrogen atom are bonded to the silicon atom.
• the proportion of hydrogen atom in all substituents and substituents represented by is preferably 0.1 mol% to 500 mol%, more preferably 1.0 mol% to
• the polysiloxane (8 1) contains a polyorganosiloxane (3 1) and a polyorganosiloxane (32), but in a preferred embodiment, the alkenyl group and the polyorganosi contained in the polyorganosiloxane (31).
• the molar ratio with the hydrogen atoms constituting the 3 ⁇ _1 to 1 bond contained in loxane (32) is in the range of 1.0: 0.5 to 1.0: 0.66.
• the weight average molecular weights of polyorganosiloxane (3 1) and polyorganosiloxane (32) are usually 500 to 1,000,000, respectively, but from the viewpoint of realizing the effects of the present invention with good reproducibility. , Preferably from 5,000 to 50,000.
• the weight average molecular weight and number average molecular weight and dispersity of the present invention for example, ⁇ ⁇ apparatus (Tosoh Corporation Seimi hundred 3 snake ⁇ 1 to 11_ ⁇ one 8320_Rei? ⁇ 02 821/193516 14 ⁇ (: 171?
• the column temperature was set to 40 ° ⁇ , tetrahydrofuran was used as the eluent (eluting solvent), the flow rate (flow rate) was ⁇ .35! _ / Min, And policeylene (manufactured by Sigma Aldrich) was used as the standard sample. Can be measured.
• the viscosity of the [0034] polyorganosiloxane (3 1) and polyorganosiloxane (32), respectively, is usually 1 0-1 000000 (Rei_1 3.3), to achieve good reproducibility the effects of the present invention From the point of view, it is preferably 50 to 10000 (3).
• the viscosity in the present invention is a value measured by a snake-type rotating viscometer at 25 ° ⁇ .
• Polyorganosiloxane (81) and polyorganosiloxane (82) react with each other to form a film by a hydrosilylation reaction. Therefore, its curing mechanism is different, for example via silanol groups, and therefore any siloxane must contain a silanol group or a functional group that forms a silanol group by hydrolysis, such as an alkyloxy group. There is no.
• the adhesive component (3) comprises a platinum group metal-based catalyst (82) in addition to the polysiloxane (81) described above.
• a platinum-based metal catalyst is a catalyst for accelerating the hydrosilylation reaction between the alkenyl group of polyorganosiloxane (3 1) and the 3rd order 1 to 1 group of polyorganosiloxane (3 2). ..
• platinum-based metal catalysts include platinum black, second platinum chloride, platinum chloride acid, a reaction product of platinum chloride acid and monovalent alcohol, a complex of platinum chloride acid and olefins, and platinum bis.
• platinum-based catalysts such as acetoacetate.
• the complex of platinum and olefins include, but are not limited to, a complex of divinyltetramethyldisyloxane and platinum.
• the amount of the platinum group metal catalyst (eight 2) is usually based on the total amount of the polyorganosiloxane (3 1) and polyorganosiloxane (32), 1. ⁇ _ ⁇ 50. ⁇ 02 821/193516 15 ⁇ (: 171? 2021/011675)
• the polyorganosiloxane component (8) may contain a polymerization inhibitor (83) for the purpose of suppressing the progress of the hydrosilylation reaction.
• the polymerization inhibitor is not particularly limited as long as it can suppress the progress of the hydroxylation reaction, and specific examples thereof include 1-ethynyl-1-cyclohexanol, 1, 1 —diphenyl-2-propion-1 —. Examples include Archinyl Polymerization such as Samurai.
• the amount of the polymerization inhibitor is usually 100 ⁇ . ⁇ ⁇ 1 or more with respect to the total amount of polyorganosiloxane (3 1) and polyorganosiloxane (3 2) from the viewpoint of obtaining the effect, and hydrosilylation. From the viewpoint of preventing excessive suppression of the reaction, it is 100 0 0 ⁇ . ⁇ 111 or less.
• the adhesive composition used in the present invention may contain a release agent component (Snake).
• a release agent component Snake
• the obtained adhesive layer can be appropriately peeled off with good reproducibility.
• Typical examples of such a release agent component (min) include polyorganoshiroxane, and specific examples thereof include epoxy group-containing polyorganoshiroxane, methyl group-containing polyorganosiloxane, and phenyl group-containing. Examples include, but are not limited to, polyorganoshiroxane.
• the weight average molecular weight of polyorganosiloxane which is a release agent component ( ⁇ )
• ⁇ is usually 100 0 0 0 0 to 200 0 0 0 0 0, but the effects of the present invention are realized with good reproducibility.
• it is preferably 2 0 0 0 0 0 to 1 2 0 0 0 0, more preferably 3 0 0 0 0 0 0 to 9 0 0 0 0 0, and the degree of dispersion is usually 1.0 0 to 1.
• it is 0.0, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0, from the viewpoint of realizing the effects of the present invention with good reproducibility.
• the weight average molecular weight and the degree of dispersion can be measured by the above-mentioned method.
• Examples of the epoxy group-containing polyorganosiloxane include ⁇ Those containing a siloxane unit represented by ⁇ / 2 (mouth 1 ⁇ unit) can be mentioned.
• [0042] is a group attached to a silicon atom and represents an alkyl group
• [3 ⁇ 4 1 2 is a ke. ⁇ 02021/193516 16 ⁇ (: 171-2021/011675
• Specific examples of the alkyl group include the above-mentioned examples. be able to.
• the epoxy group in the organic group containing an epoxy group may be an independent epoxy group without condensation with other rings, and other rings such as 1,2-epoxide cyclohexyl group. It may be an epoxy group forming a fused ring with.
• organic group containing an epoxy group examples include, but are not limited to, 3-glycidoxypropyl, 2- (3,4-epoxycyclohexyl) ethyl.
• a preferable example of the epoxy group-containing polyorganosiloxane includes, but is not limited to, an epoxy group-containing polydimethylsiloxane.
• the epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit ( 10 units in the mouth), It may include the above 0 units, IV! Units and / or Ding units.
• the epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5, and the weight average molecular weight thereof is usually 1,500 to 500,00. Although it is 0, it is preferably 100, 0 0 or less from the viewpoint of suppressing precipitation in the adhesive composition.
• the trade name represented by the formula (8_1) is ⁇ ! ⁇ / 1 3 _ 2 2 7 (manufactured by Gerest, weight average molecular weight 2 7, 0). ⁇ 02 821/193516 17 ⁇ (: 171? 2021/011675)
• n are the number of repeating units, respectively. Is an alkylene group having 1 to 10 carbon atoms. )
• n and ⁇ are the number of repeating units, respectively. Is an alkylene group having 1 to 10 carbon atoms.
• methyl group-containing polyorganosiloxane for example, [3 ⁇ 4 21 ⁇ [3 ⁇ 4 220 3 1]
• Siloxane unit represented by 2/2 ⁇ 2 ⁇ ⁇ unit
• Those containing siloxane units represented by 2/2 mouth 2 ⁇ units
• [3 ⁇ 4 21 . And [3 ⁇ 4 22 . Is a group bonded to a silicon atom and independently represents an alkyl group, but at least one of them is a methyl group, and specific examples of the alkyl group include the above-mentioned examples.
• [3 ⁇ 4 21 is a group bonded to a silicon atom, represents an alkyl group, and specific examples of the alkyl group include the above-mentioned examples. Above all A methyl group is preferable.
• a preferred example of the methyl group-containing polyorganosiloxane is, but is not limited to, polydimethylsiloxane.
• the methyl group-containing polyorganosiloxane is the above-mentioned siloxane unit (0 2 ⁇ ⁇ unit or Unit), but in addition to the mouth 2 ⁇ ⁇ unit and 2 ⁇ unit, above Note: Q units, M units and / or T units may be included.
• a methyl group-containing polyorganosiloxane the polyorganosiloxane containing polyorganosiloxane, D 2 ⁇ Q and Q units comprising only D 2 ⁇ Q units, D 2 polyorgano siloxane containing a QQ units and M units, a polyorganosiloxane comprising a polyorganosiloxane, D 2 ⁇ Q units of the Q units and M units and a D 2 ⁇ Q units and T units, and D 2 QQ units polyorganosiloxanes comprising an M unit and T unit, poly organosiloxanes containing a D 2 hundred units and Q units and M units and T units.
• methyl group-containing polyorganosiloxane examples include polyorganosiloxane consisting of only D 20 units, polyorganosiloxane containing D 20 units and Q unit, D 2 Q units and M.
• Porioruga Roh siloxane containing a unit, a polyorganosiloxane containing a D 20 units and T units, a polyorganosiloxane containing a D 20 units of the Q units and M units, and a D 2 ⁇ units and M units and T units polyorganosiloxanes comprising, poly organosiloxanes containing a D 2 ⁇ units and Q units and M units and T units.
• Methyl group-containing polyorganosiloxanes typically have a viscosity of 1,000 to 2,000.
• the methyl group-containing polyorganosiloxane is typically a dimethylsilicone oil composed of polydimethylsiloxane.
• the kinematic viscosity can be measured with a kinematic viscometer. It can also be calculated by dividing the viscosity (m P a-s) by the density (g / cm 3).
• kinematic viscosity (mm 2 / s) viscosity (m P as) / density (g / cm 3).
• methyl group-containing polyorganosiloxane examples include the WACKE RSILI CON EFLUIDAK series manufactured by Wacker Chemi and the dimethyl silicone oil (K F-96 L, K F-96) manufactured by Shin-Etsu Chemical Co., Ltd. ⁇ 02 821/193516 21 ⁇ (: 171? 2021/011675 8), [ ⁇ -96, ⁇ -961 ⁇ 1, [ ⁇ -69, [ ⁇ -9 65, [ ⁇ -968)), Cyclic dimethyl silicone oil ( ⁇ -995), etc., but are not limited to these.
• Examples of the phenyl group-containing polyorganosiloxane include, for example.
• [0065] is a group bonded to a silicon atom and represents a phenyl group or an alkyl group
• [3 ⁇ 4 32 is a group bonded to a silicon atom and represents a phenyl group.
• Specific examples of the alkyl group include Although the above examples can be given, the methyl group is preferred.
• the phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit ( 30 units in the mouth), but may contain the above 0 units, IV! Units and / or Ding units in addition to the 3 ⁇ units in the mouth. good.
• phenyl group-containing polyorganosiloxane comprising only the mouth 30 units
• a polyorganosiloxane comprising a ⁇ 30 units and ⁇ units, 0 3 ⁇ units and IV! polyol Ganoderma siloxane including a unit
• the polyorganosiloxane including a mouth 30 units and the Ding unit
• polyorganosiloxanes containing a ⁇ 30 units and ⁇ units and IV! unit and 0 30 units and IV! units and Ding unit
• polyorganosiloxanes including, polyorganosiloxane, and the like, including a 0 3 ⁇ units and ⁇ units and IV! units and Ding unit.
• the weight average molecular weight of the phenyl group-containing polyorganosiloxane is usually 1,500 to 5,000,000, but from the viewpoint of suppressing precipitation in the adhesive composition, it is preferably 100,000. It is as follows.
• the trade name represented by the formula ( ⁇ _ 1) is 1 ⁇ / 11 ⁇ / 1 — 1 043 (06 1 63 1, ⁇ n c. average molecular weight 67, 00 0, viscosity 30, 000 0101 2/3), trade name 1 ⁇ / 11 ⁇ / 11 025 (06 1 63 1 you express by the formula ( ⁇ one 2)
• n c made the weight average molecular weight of 5, 20 0, viscosity 500 Rei_1_rei_1 2/3), (trade name represented by ⁇ one 3) ⁇ 5 0-3 00003 (Shin-Etsu Chemical Co., formulas, Ltd., weight average Molecular weight 39, 400, ⁇ 02 821/193516 22 ⁇ (: 171? 2021/011675 Viscosity 3000 Product name represented by the formula (01 4) 3 43 1 (IV! ⁇ IV! Min 1 ⁇ 1 manufactured by IV Misha, weight average molecular weight 1,800,
• the adhesive composition used in the present invention contains a release agent component (Snake) together with a polyorganosiloxane component (8) that is cured by a hydrosilylation reaction, and in a more preferred embodiment, a release agent.
• a release agent component Snake
• the adhesive composition used in the present invention may contain an adhesive component (3) and a release agent component (Snake) in an arbitrary ratio, but considers the balance between adhesiveness and peelability.
• the ratio of the component (3) to the component (Snake) is the mass ratio, preferably 99. 9 9 5: 0.005 to 30: 70, more preferably 99.9: ⁇ . 1 to 75: 2. It is 5. That is, when a polyorganosiloxane component () that is cured by a hydrosilylation reaction is contained, the ratio of the component () to the component (Snake) is a mass ratio, preferably 99. 99 5: ⁇ . 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, and specific examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and ketones. However, it is not limited to these.
• Examples include, but are not limited to, petityl acetate, diisoptylketone, 2-octane, 2-nonane, 5-nonanone, etc.
• Such a solvent can be used alone or in combination of two or more.
• the adhesive composition used in the present invention contains a solvent
• the content thereof is appropriately set in consideration of the viscosity of the desired composition, the coating method to be adopted, the thickness of the thin film to be produced, and the like. However, it is in the range of about 10 to 90% by mass with respect to the entire composition.
• the viscosity of the adhesive composition used in the present invention is 25 ° ⁇ , usually 500 to 20, 0 00 3, preferably 1,000 to 5,000 to 3.
• the viscosity of the adhesive composition used in the present invention is adjusted by changing the types of organic solvents used, their ratios, the concentration of film constituents, etc., in consideration of various factors such as the coating method used and the desired film thickness. It is possible.
• the film constituent component means a component other than the solvent contained in the composition.
• the adhesive composition used in the present invention can be produced by mixing an adhesive component (3), and when used, a release agent component (Snake) and a solvent.
• the mixing order is not particularly limited, but as an example of a method for producing an adhesive composition easily and with good reproducibility, for example, an adhesive component) and a release agent component (mi) are dissolved in a solvent.
• an adhesive component for example, an adhesive component
• a release agent component mi
• filtration may be performed using a submicrometer-order fill, etc. during the production of the adhesive composition or after mixing all the components.
• the method for cleaning a semiconductor substrate of the present invention includes a step of peeling the adhesive layer on the semiconductor substrate with a peeling composition, wherein the peeling composition contains a solvent and a salt.
• the above solvent contains 80% by mass or more of the organic solvent represented by the formula (1-).
• the organic solvent represented by the formula (1_) may be one kind alone or two or more kinds.
• 1_ 1 and 1_ 2 are each independently of carbon atoms in the alkyl group of 1_ 2 and the number of carbon atoms of to alkyl groups represents an alkyl Le group of from 1 to 6 carbon The total number is less than or equal to 6. By using such a carbon number, it is possible to realize peeling of the adhesive layer 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, more preferably a linear alkyl group.
• linear or branched alkyl group examples include a methyl group, an ethyl group, and the like.
• ⁇ ⁇ 02021/193516 26 ⁇ (17 2021/011675 ⁇ _ propyl, ⁇ -propyl group, ⁇ _ butyl group, ⁇ -butyl group, _ butyl group, _ butyl group, ⁇ Penchiru group, 1 - methyl _ ⁇ _ Butyl group, 2 — methyl _ ⁇ _ butyl group, 3 — methyl _ ⁇ _ butyl group, 1, 1 — dimethyl _ ⁇ _ propyl group, 1, 2 — dimethyl _ propyl group, 2, 2 — dimethyl Group, 1 — Ethyl-Propyl Group, Propyl-Hexyl, 1 — Methyl-Propyl , 4 — Methyl-Pentyl Group, 1, 1 — Dimethyl-Butyl Group, 1, 2
• cyclic alkyl group examples include a cyclopropyl group, a cyclobutyl group, and the like.
• the 1-1 is preferably a methyl group
• the! - 2 is preferably a heptyl group or downy pentyl group.
• a preferable example of the organic solvent represented by the formula () is petityl vinegar. , Pentyl acetate and the like.
• the peeling composition used in the present invention does not contain a salt.
• a salt include those used for this type of application, typically tetrabutylammonium hydroxy, which is added for the purpose of promoting the removal of the adhesive layer and the adhesive layer residue. Do, tetrabutylammonium fluoride (also called tetrabutylammonium fluoride) and other ammonium salts. Since the peeling composition used in the present invention contains an organic solvent represented by the formula (), it is not necessary to contain such a salt. Since such a salt can cause damage such as corrosion to a substrate, particularly a bumped substrate, etc., in the present invention, a salt-free peeling composition is used. However, if the bulk solvent constituting the peeling composition contains a trace amount of salt as an impurity from the beginning, the existence of the salt is not denied.
• the content of the organic solvent represented by the above formula (1_) is 80% by mass or more, preferably 85% by mass or more. It is preferably 87% by mass or more, and even more preferably 89% by mass or more.
• the solvent contained in the peeling composition comprises an organic solvent represented by the above formula (1_).
• the solvent contained in the peeling composition is completely composed of only the organic solvent represented by the above formula (1_) and does not contain other solvents as impurities, but by purification. There is a limit to the improvement of purity, which is technically impossible. Therefore, in the present invention, the solvent contained in the peeling composition is only the organic solvent represented by the above formula (), which is intentionally used as the solvent, and has water and structure. It does not deny that impurities such as organic solvents, which are similar in nature or similar in nature and are not easy to separate, are contained in the organic solvent represented by the above formula (1_) in bulk.
• the solvent contained in the peeling composition is composed of the organic solvent represented by the above formula (1_), it is represented by the above formula (1_) among the solvents contained in the peeling composition.
• the content of the organic solvent may not be completely 100% as a pure value by gas chromatography, and is usually 94% or more, preferably 95% or more, more preferably 96%. As described above, it is even more preferably 97% or more, further preferably 98% or more, and even more preferably 99% or more.
• the adhesive layer on the semiconductor substrate is continuously brought into contact with the peeling composition to swell the adhesive layer and peel it from the semiconductor substrate.
• the method of continuously contacting the adhesive layer on the semiconductor substrate with the release composition is not particularly limited as long as the adhesive layer on the semiconductor substrate is in contact with the release composition with temporal continuity.
• This temporal continuity is not limited to the case where the adhesive layer is always in contact with the delamination composition, for example, once the adhesive layer has been in contact with the organic solvent for a certain period of time. This includes the case where the contact is paused and the contact is repeated, and not only when the entire adhesive layer on the semiconductor substrate is in contact with the peeling composition, but also a part of the adhesive layer is for peeling.
• the adhesive layer on the conductor substrate is always in contact with the peeling composition, and the entire adhesive layer on the semiconductor substrate is the peeling composition.
• the aspect of being in contact with an object is preferable.
• the adhesive layer on the semiconductor substrate is swollen by immersing the above-mentioned adhesive layer in the peeling composition to peel off from the semiconductor substrate or on the semiconductor substrate.
• the adhesive layer is swelled by continuously supplying the peeling composition onto the adhesive layer, and is peeled from the semiconductor substrate.
• the semiconductor substrate with the adhesive layer may be immersed in the release composition.
• the immersion time is not particularly limited as long as the adhesive layer swells and the adhesive layer is peeled off from the semiconductor substrate, but it should be 5 seconds or more from the viewpoint of achieving more effective cleaning with good reproducibility. Yes, less than 5 minutes from the point of view of process sloops.
• the adhesive layer on the semiconductor substrate is immersed in the peeling composition
• the semiconductor substrate with the adhesive layer is moved in the peeling composition, the peeling composition is convoluted, and the peeling composition is used for peeling by ultrasonic waves.
• the peeling of the adhesive layer may be promoted by vibrating the composition or the like.
• a rocking washer, a paddle-type washer, or the like may be used. If such a washer is used, the adhesive layer may be used.
• the adhesive layer on the semiconductor substrate receives relative convection, or the convection generated by the movement or rotation is transferred on the semiconductor substrate.
• the adhesive layer receives it, and not only the swelling of the adhesive layer on the semiconductor substrate but also the peeling of the adhesive layer from the semiconductor substrate is promoted.
• a convection washer that can realize a state in which the peeling composition around it is convected by a stirrer may be used.
• an ultrasonic cleaner or super sound ⁇ 02 821/193516 30 ⁇ (: 17 2021/011675 A wave probe may be used, and the condition is usually 20 k H z to 5 MH z.
• the peeling composition may be continuously applied toward the adhesive layer on the semiconductor substrate.
• the adhesive layer on the semiconductor substrate is facing upward, for example, from above the adhesive layer on the semiconductor substrate (including diagonally above), a rod-shaped or rod-shaped or by a nozzle of a cleaning device, etc.
• a mist-like, preferably rod-like release composition is supplied over the adhesive layer on the semiconductor substrate with temporal continuity.
• the temporal continuity is not only when the peeling composition is always supplied on the adhesive layer on the semiconductor substrate, but also, for example, after the peeling composition is supplied for a certain period of time, the supply is applied.
• the peeling composition is placed on the adhesive layer on the semiconductor substrate from the viewpoint of achieving more effective cleaning with good reproducibility, although it may be the case that the supply is paused and then re-supplied or repeated. It is preferable that it is always supplied.
• the flow rate is usually 200 to 500! _ / Min.
• a steam washer is used to remove the adhesive layer on the semiconductor substrate with the steam of the peeling composition. May be in contact with.
• the method for cleaning 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 top of the semiconductor substrate, and when the semiconductor substrate with the adhesive layer is immersed in the peeling composition, the method is not particularly limited.
• the peeled adhesive layer may be removed without removing the semiconductor substrate from the peeling composition, or the semi-conductor substrate may be taken out from the peeling composition to remove the peeled adhesive layer. At this time, by simply taking out the semiconductor substrate from the peeling composition, the peeled adhesive layer may naturally remain in the peeling composition and most of it may be removed.
• the semiconductor substrate is dried according to a conventional method.
• the peeling composition used in the method for cleaning a semiconductor substrate of the present invention is also an object of the present invention.
• the peeling composition of the present invention is used for peeling an adhesive layer on a semiconductor substrate from the semiconductor substrate, and preferred embodiments and conditions are as described above.
• the peeling composition of the present invention can be produced by mixing the solutions constituting the composition in any order, if necessary. At that time, filtration may be performed if necessary.
• the adhesive layer which is a cured film obtained from a siloxane-based adhesive containing the polyorganosiloxane component (8), can be effectively removed, and high-efficiency and good semiconductor devices can be expected to be manufactured.
• the semiconductor substrate to be cleaned by the cleaning method of the present invention includes, for example, a germanium substrate, a gallium-arsenic substrate, a gallium-phosphorus substrate, and a gallium-arsenic-aluminium substrate.
• a germanium substrate such as the silicon wafer described above
• a gallium-arsenic substrate such as the silicon wafer described above
• a gallium-phosphorus substrate such as the silicon wafer described above
• a gallium-arsenic-aluminium substrate includes aluminum-plated 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, It also includes various substrates such as quartz substrates, liquid crystal substrates, and organic semiconductor substrates!
• the first step of manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition obtained.
• the adhesive composition used for forming the adhesive layer in the first step the above-mentioned various adhesives can be used, but the method for cleaning the semiconductor substrate of the present invention is from a polysiloxane-based adhesive. It is effective for removing the obtained adhesive layer, and is more effective for removing the adhesive layer obtained from the polysiloxane-based adhesive containing the component (8) that is cured by the hydrosilylation reaction. Therefore, the following is an example of removing the adhesive layer by the cleaning method of the present invention when manufacturing a semiconductor substrate processed by using the adhesive layer obtained by using a polysiloxane-based adhesive (adhesive composition). However, the present invention is not limited to this.
• the first step is to apply an adhesive composition to the surface of the semiconductor substrate or support substrate to form an adhesive coating layer, and to bond the semiconductor substrate to the supporting substrate.
• an adhesive composition to the surface of the semiconductor substrate or support substrate to form an adhesive coating layer, and to bond the semiconductor substrate to the supporting substrate.
• the process of applying the release agent composition to the surface and heating it to form the release agent coating layer, and the release of the adhesive coating layer of the semiconductor substrate and the support substrate ⁇ 02 821/193516 33 ⁇ (: 171-2021 / 011675) While performing at least one of heat treatment and decompression treatment, a load in the thickness direction of the semi-conductor substrate and the support substrate is applied to bring them into close contact with each other. After that, a step of forming a laminate by carrying out a post-heating treatment is included.
• the adhesive composition is applied to a semiconductor substrate, and the release agent composition is applied to a support substrate and heated.
• the adhesive composition and the release agent composition may be sequentially applied to and heated on one of the substrates.
• any of the treatment conditions of heat treatment, decompression treatment, or a combination of both is adopted. Whether or not it is determined in consideration of various circumstances such as the type of adhesive composition, the specific composition of the release agent composition, the compatibility of the film obtained from both compositions, the film thickness, and the required adhesive strength.
• the semiconductor substrate is a wafer and the support substrate is a support.
• the target to which the adhesive composition is applied may be one or both of the semiconductor substrate and the support substrate.
• the diameter Examples include, but are not limited to, silicon wafers and glass wafers having a thickness of about 770.
• the semiconductor substrate cleaning method of the present invention can effectively clean the substrate while suppressing damage to the bumps of the bumped semiconductor substrate.
• Specific examples of such a semiconductor substrate with bumps include a silicon wafer having bumps such as ball bumps, printed bumps, stud bumps, and plated bumps.
• the bump height is about 1 to 200
• the bump diameter is about 1.
• Specific examples of plating bumps that are appropriately selected from the conditions of 1 to 2 0 0 ⁇ 1, bump pitch 1 ⁇ ! to 500 0 are S n A g bump, S n B i bump, and so on. Examples include, but are not limited to, alloy plating mainly composed of 3 such as bumps and 8 ri 3 bumps.
• the support (carrier) is not particularly limited, and examples thereof include silicon wafers having a diameter of 300 0 01 01 and a thickness of about 700 0 01 01, but are not limited thereto.
• ⁇ 02 821/193516 34 ⁇ (: 171? 2021/011675)
• release agent composition examples include compositions containing a release agent component used in this type of application.
• the coating method is not particularly limited, but is usually a spin coating method.
• a method of separately forming a coating film by a spin coating method or the like and attaching a sheet-shaped coating film may be adopted, which is also referred to as coating or coating film.
• the heating temperature of the applied adhesive composition varies depending on the type and amount of the adhesive component contained in the adhesive composition, whether or not a solvent is contained, the desired thickness of the adhesive layer, and the like. Although it cannot be specified unconditionally, it is usually 80 ° ⁇ to 150 ° ⁇ , and the heating time is usually 30 seconds to 5 minutes.
• the heating temperature of the applied release agent composition is the type and amount of cross-linking agent, acid generator, acid, etc.
• a solvent Whether or not a solvent is contained, depends on the desired thickness of the release layer, etc., so it cannot be unconditionally specified, but from the viewpoint of achieving suitable curing, it is 120 ° ⁇ or more and excessive curing. From the viewpoint of preventing the problem , the temperature is preferably 260 ° or less, and the heating time is usually 1 minute to 100 minutes. Heating can be performed using a hot plate, a talented bun, or the like.
• the film thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it is usually 5 to 500 ⁇ !.
• the film thickness of the release agent coating layer obtained by applying the release agent composition and heating the release agent composition is usually 5 to 500 ⁇ !.
• the heat treatment is usually performed in consideration of the viewpoint of softening the adhesive coating layer to achieve suitable bonding with the release agent coating layer, the viewpoint of achieving suitable curing of the release agent coating layer, and the like. It is appropriately determined from the range of 0 to 150 ° ⁇ .
• the adhesive component and the release agent component it is preferably 130 ° ⁇ or less, more preferably 90 ° ⁇ or less, and its heating time is From the viewpoint of reliably developing the adhesive ability and peeling ability, it 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, it is usually 10 minutes or less, preferably 10 minutes or less. Is less than 5 minutes.
• the decompression treatment is performed on the semiconductor substrate, the adhesive coating layer and the support substrate, or the semiconductor substrate.
• ⁇ 02 821/193516 35 ⁇ (: 171? 2021/011675)
• the adhesive coating layer, the release agent coating layer and the support substrate may be placed under an atmospheric pressure of 103 to 10 and ⁇ 3.
• the decompression treatment time is usually 1 to 30 minutes.
• the substrate and the coating layer or the coating layers are bonded to each other, preferably by a reduced pressure treatment, more preferably by a combined heat treatment and a reduced pressure treatment.
• the load in the thickness direction of the semiconductor substrate and the support substrate is particularly limited as long as the load does not adversely affect the semiconductor substrate and the support substrate and the layer between them and can firmly adhere them. Not, but usually within the range of 10 to 100 0 0 1 ⁇ !.
• the post-heating temperature is preferably 120 ° ⁇ or higher from the viewpoint of obtaining a sufficient curing rate, and preferably 260 ° from the viewpoint of preventing deterioration of the substrate, the adhesive component, the release agent component, and the like. ° ⁇ or less.
• the heating time is usually 1 minute or more from the viewpoint of realizing suitable bonding of the wafer by curing, and more preferably 5 minutes or more from the viewpoint of stabilizing the physical properties of the adhesive, and adhesion by excessive heating is performed. From the viewpoint of avoiding adverse effects on the layer, it is usually 180 minutes or less, preferably 120 minutes or less. Heating can be performed using a hot plate, a talented oven, or the like.
• One purpose of the post-heat treatment is to more preferably cure the adhesive component (3).
• An example of processing applied to the laminate used in the present invention is processing of the back surface opposite to the circuit surface of the front surface of the semiconductor substrate, and typically, thinning of the wafer by polishing the back surface of the wafer is performed. Can be mentioned. Using such a thinned wafer, through silicon vias (Cho 3), etc. are formed, and then the thinned wafer is peeled off from the support to form a wafer laminate, which is then three-dimensionally mounted. .. Around that time, the back electrode of the wafer and the like are also formed.
• Heat of 250 to 350 ° ⁇ is applied to the thinning of the wafer and the 3V process while it is adhered to the support, but the adhesive layer contained in the laminate used in the present invention has that heat.
• Heat resistance to ⁇ 02 821/193516 36 ⁇ (: 171? 2021/011675 I have, for example.
• Wafers with a thickness of about 770 can be thinned to a thickness of about 80
• the third step of separating the processed semiconductor substrate and the adhesive layer from the support substrate will 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 the adhesive layer from the semiconductor substrate may be the peeling between the bonding layer and the peeling layer or the supporting substrate in contact with the bonded layer.
• Such a peeling method includes laser peeling. Mechanical peeling by equipment having a ridge, peeling by manual peeling, etc. can be mentioned, but the peeling is not limited to these.
• the fourth step is a step of removing the adhesive layer on the semiconductor substrate by the cleaning method of the present invention. Specifically, for example, the adhesive layer on the thinned substrate is efficiently removed by the cleaning method of the present invention.
• the conditions at this time are as described above.
• a cleaning agent composition containing a salt may be used to remove the adhesive layer residue remaining on the semiconductor base plate, but the semiconductor substrate, especially the semiconductor having bumps, may be removed. Be careful not to damage the bumps on the board.
• the method for manufacturing a processed semiconductor substrate of the present invention includes the above-mentioned first steps to fourth steps, but may include steps other than these steps.
• the above-mentioned components and method elements related to the first to fourth steps may be changed in various ways as long as they do not deviate from the gist of the present invention.
• Rotational revolution mixer Shinky Co., Ltd. Rotating revolution mixer 1 5 0 0
• the resulting mixture contains 3 ⁇ 1 ⁇ 1 groups with a viscosity of 100 3 3 as (32) Linear polydimethylsiloxane (manufactured by Wacker Chemi) 1 9. 09, Viscosity as (3 1) 200 ⁇ 1 3 Vinyl Group-containing linear polydimethylsiloxane
• Preparation Example 1 The composition obtained in Preparation Example 1 is applied to a 3 wafer (thickness 775) of 4001X4001 as a wafer on the device side with a spin coater, and 1 20 ° using a hot plate. The wafer was heated at ⁇ for 1.5 minutes and then at 200 ° ⁇ for 10 minutes to form a thin film with a thickness of 60 on the wafer to obtain a wafer with an adhesive layer.
• Example 1 _ 1 The wafer with an adhesive layer produced in Production Example 1 is immersed in petit acetate 9! _ As the peeling composition of Example 1 _ 1, and the adhesive layer starts peeling from the wafer. When the time required to complete the process was measured, it was 16 seconds.
• Example 1-2 ⁇ 02 821/193516 39 Wafer (: 171-2021 / 011675)
• the wafer with adhesive layer prepared in Production Example 1 is mixed with petit acetate as the peeling composition of Example 1 _ 2 and 1 ⁇ 1-methylpyrrolidone.
• the time from immersion in the solvent (9: 1 (/)) 9! _ To the start of peeling of the adhesive layer from the wafer was measured and found to be 21 seconds.
• Example 2-1 The wafer with an adhesive layer produced in Production Example 1 is immersed in pentyl acetate 9! _ As the peeling composition of Example 2 _ 1, and the adhesive layer is peeled off from the wafer. When the time until the start of was measured, it was 21 seconds.
• Example 2 _ 2 The wafer with an adhesive layer produced in Production Example 1 is used as a mixed solvent of pentyl acetate and 1 ⁇ ! — Methylpyrrolidone as a peeling composition of Example 2 _ 2. 1 (/)) It was 27 seconds when the time from the wafer top to the start of peeling of the adhesive layer was measured after immersing in 9! _.
• Comparative Example 4 -3 The wafer with an adhesive layer produced in Production Example 1 is used as a mixed solvent of octyl acetate and 1 ⁇ 1-methylpyrrolidone as a peeling composition of Comparative Example 4_3 (7: 3 (7: 3). /)) It was 153 seconds when the time from the wafer top to the start of peeling was measured by immersing in 9! _.
• Table 1 shows the results of Examples and Comparative Examples. As shown in Table 1, when a peeling composition containing 80% by mass or more of the organic solvent represented by the formula (! _), Ptyl acetate or Pentyl acetate, was used in the solvent of the peeling composition (Example). 1 _ 1 to 2 _ 2), a peeling composition in which the content of the organic solvent represented by the formula (! _) Is less than 80% by mass (Comparative Examples 1 _ 1 and 2 _ 1) and the formula (! _) A place that does not contain an organic solvent represented by ⁇ 02 821/193516 41 ⁇ (: 171? 2021/011675 (Comparative example 3 _ 1 to 3 _ 3 and 4 _ 1 to 4 _ 3) Compared to the case where the peeling composition is used, it is on the semiconductor substrate. The peeling time of the adhesive layer was extremely short.
• Example 3-1 The sample substrate prepared in Production Example 2 was immersed in the exfoliating composition of Example 1 _ 1 of butyl acetate 9! _, Allowed to stand for 1 hour, and then washed with isopropanol and acetone. Then, the presence or absence of bump damage was observed with an optical microscope. As a result, no bump damage was observed.

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