Cleaning method of semiconductor substrate, method for manufacturing processed semiconductor substrate, and composition for peeling

Abstract

A cleaning method of a semiconductor substrate, which includes a step of peeling an adhesive layer on a semiconductor substrate using a peeling composition, characterized in that the peeling composition contains a solvent, does not contain a salt, the solvent contains one or two or more selected from the group consisting of an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, an ether compound, a sulfide compound, an ester compound, and an amine compound having a molecular weight of less than 160, and a contact angle of the peeling composition on the adhesive layer is less than 31.5 degrees.

Description

TECHNICAL FIELD

[0001] The present application relates to a cleaning method for a semiconductor substrate, a manufacturing method for a processed semiconductor substrate, and a peeling composition. BACKGROUND

[0002] As for the semiconductor wafers integrated in two-dimensional planar directions in the past, in order to further integrate, a semiconductor integration technology is pursued in which the planar direction is further integrated (stacked) in a three-dimensional direction. This three-dimensional stacking is a technology in which, while being wired, a silicon through electrode (TSV: through silicon via) is integrated in multiple layers. When integrated in multiple layers, the side (i.e., the back surface) of each wafer integrated opposite the circuit surface formed is thinned by polishing, and the thinned semiconductor wafers are stacked.

[0003] The semiconductor wafer (hereinafter also simply referred to as a wafer) before thinning is adhered to a support body in order to be polished by a polishing device. The adhesion at this time must be easily peeled off after polishing, and is therefore called temporary adhesion. This temporary adhesion must be easily detached from the support body, and when a large force is applied to the detachment, the thinned semiconductor wafer is sometimes cut or deformed, and is easily detached in a manner to prevent such a situation from occurring. However, when the back surface of the semiconductor wafer is polished, the support body is detached or deviated due to polishing stress, which is not preferable. Therefore, the performance pursued for the temporary adhesion is to withstand the stress at the time of polishing and to be easily detached after polishing. For example, the following performance is pursued: high stress (strong adhesion) with respect to the planar direction at the time of polishing, and low stress (weak adhesion) with respect to the direction intersecting the planar direction, i.e., the longitudinal direction, at the time of detachment. Furthermore, in the processing process, a high temperature of 150°C or higher is sometimes reached, and further, heat resistance is also required.

[0004] Under such circumstances, in the semiconductor field, a polysiloxane-based adhesive that can have these performances is mainly used as a temporary adhesive. Furthermore, in the polysiloxane-based adhesion using a polysiloxane-based adhesive, after the thinned substrate is peeled off, the adhesive residue often remains on the substrate surface, but in order to avoid a bad situation in the subsequent process, a cleaning agent composition for removing the residue and cleaning the surface of the semiconductor substrate is developed (for example, Patent Documents 1 and 2). In Patent Document 1, a remover containing a polar aprotic solvent and a quaternary ammonium hydroxide is disclosed, and in Patent Document 2, a cured resin remover containing a fluorinated alkyl / ammonium is disclosed. However, in the recent semiconductor field, the demand for a new cleaning agent composition has always existed, and the demand for an effective cleaning agent composition and a cleaning method has always existed.

[0005] On the other hand, a semiconductor wafer is electrically connected to a semiconductor chip, for example, by a bump ball composed of a conductive material of metal, and a chip provided with such a bump ball is used, and thus miniaturization of a semiconductor package is sought.

[0006] At this point, the bump ball made of a metal such as copper or tin lacks corrosion resistance, and thus there is a problem that a cleaning agent composition used to remove an adhesive residue of a support or a wafer is damaged (Patent Document 3), and as one of matters sought for a cleaning agent composition and a cleaning method, it can be listed that the bump ball is not corroded when a substrate is cleaned.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: International Publication No. 2014 / 092022

[0010] Patent Document 2: U.S. Patent No. 6818608

[0011] Patent Document 3: Korean Patent Publication No. 2018-0066550 SUMMARY

[0012] PROBLEMS TO BE SOLVED BY THE INVENTION

[0013] The present invention was completed in view of the above circumstances, and aims to provide a cleaning method of a semiconductor substrate, for example, for appropriately and easily removing an adhesive layer from a semiconductor substrate having the adhesive layer obtained using a siloxane-based adhesive on a surface of the semiconductor substrate, and reducing or inhibiting damage to a bump of the semiconductor substrate, a manufacturing method of a processed semiconductor substrate including such a cleaning method, and a peeling composition for such a cleaning method.

[0014] SOLUTION TO THE PROBLEM

[0015] The present inventors and others have conducted intensive research in order to solve the above problems, and as a result, it has been found that when an adhesive layer on a semiconductor substrate, particularly a cured film, i.e., an adhesive layer, obtained from a siloxane-based adhesive containing a polyorganosiloxane component (A) cured by a hydrosilylation reaction, is peeled by using a peeling composition containing a solvent and not containing a salt, and the semiconductor substrate is cleaned, by using one or two or more specific organic solvents having a molecular weight of less than 160 as the above solvent, and making the contact angle of the above peeling composition on the above adhesive layer less than 31.5 degrees, damage to the bump of the semiconductor substrate can be reduced or inhibited, and peeling can be efficiently and easily performed, and thus the present invention has been completed.

[0016] That is, the present invention provides the following.

[0017] 1. A cleaning method for a semiconductor substrate, comprising a step of peeling an adhesive layer on a semiconductor substrate using a peeling composition, characterized in that the peeling composition contains a solvent, does not contain a salt, the solvent contains one or two or more selected from the group consisting of an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, an ether compound, a thioether compound, an ester compound, and an amine compound having a molecular weight of less than 160, and a contact angle of the peeling composition on the adhesive layer is less than 31.5 degrees.

[0018] 2. The cleaning method for a semiconductor substrate according to claim 1, wherein the molecular weight is 70 or more.

[0019] 3. The cleaning method for a semiconductor substrate according to claim 1, wherein the solvent contains one or two or more selected from the group consisting of di(n-butyl) ether, n-decane, di(n-pentyl) ether, 1-amino-n-pentane, p-menthane, butyl acetate, cyclohexane, di(n-propyl) sulfide, amyl acetate, di(n-butyl) sulfide, mesitylene, limonene, and p-cymene.

[0020] 4. The cleaning method for a semiconductor substrate according to any one of claims 1 to 3, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S), and the adhesive component (S) contains at least one selected from the group consisting of a silicone-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide-based adhesive, and a phenol resin-based adhesive.

[0021] 5. The cleaning method for a semiconductor substrate according to claim 4, wherein the adhesive component (S) contains a silicone-based adhesive.

[0022] 6. The cleaning method for a semiconductor substrate according to claim 5, wherein the silicone-based adhesive contains a polyorganosiloxane component (A) cured by a hydrosilylation reaction.

[0023] 7. A manufacturing method for a processed semiconductor substrate, characterized by comprising: a first step of manufacturing a laminate having a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition; a second step of processing the semiconductor substrate of the obtained laminate; a third step of separating the semiconductor substrate and the adhesive layer from the support substrate; and a fourth step of peeling the adhesive layer on the semiconductor substrate using a peeling composition, the peeling composition containing a solvent, not containing a salt, the solvent containing one or two or more selected from the group consisting of an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, an ether compound, a thioether compound, an ester compound, and an amine compound having a molecular weight of less than 160, and a contact angle of the peeling composition on the adhesive layer being less than 31.5 degrees.

[0024] 8. The method for producing a processed semiconductor substrate according to 7, wherein the molecular weight is 70 or more.

[0025] 9. The method for producing a processed semiconductor substrate according to 7, wherein the solvent comprises one or two or more selected from the group consisting of di(n-butyl) ether, n-decane, di(n-pentyl) ether, 1-amino-n-pentane, p-menthane, butyl acetate, cyclohexane, di(n-propyl) sulfide, amyl acetate, di(n-butyl) sulfide, mesitylene, limonene, and p-cymene.

[0026] 10. The method for producing a processed semiconductor substrate according to any one of 7 to 9, wherein the adhesive layer is a film obtained using an adhesive composition comprising an adhesive component (S), the adhesive component (S) comprising at least one selected from the group consisting of a silicone-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide-based adhesive, and a phenol resin-based adhesive.

[0027] 11. The method for producing a processed semiconductor substrate according to 10, wherein the adhesive component (S) comprises a silicone-based adhesive.

[0028] 12. The method for producing a processed semiconductor substrate according to 11, wherein the silicone-based adhesive comprises a polyorganosiloxane component (A) cured by hydrosilylation reaction.

[0029] 13. A peeling composition for peeling an adhesive layer on a semiconductor substrate when the semiconductor substrate is cleaned, characterized in that the peeling composition comprises a solvent, does not comprise a salt, the solvent comprises one or two or more selected from the group consisting of an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, an ether compound, a sulfide compound, an ester compound, and an amine compound having a molecular weight of less than 160, and a contact angle on the adhesive layer is less than 31.5 degrees.

[0030] 14. The peeling composition according to 13, wherein the molecular weight is 70 or more.

[0031] 15. The peeling composition according to 13, wherein the solvent comprises one or two or more selected from the group consisting of di(n-butyl) ether, n-decane, di(n-pentyl) ether, 1-amino-n-pentane, p-menthane, butyl acetate, cyclohexane, di(n-propyl) sulfide, amyl acetate, di(n-butyl) sulfide, mesitylene, limonene, and p-cymene.

[0032] 16. The peeling composition according to any one of 13 to 15, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S), and the adhesive component (S) contains at least one selected from the group consisting of a silicone-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenol resin-based adhesive.

[0033] 17. The peeling composition according to 16, wherein the adhesive component (S) contains a silicone-based adhesive.

[0034] 18. The peeling composition according to 17, wherein the silicone-based adhesive contains a polyorganosiloxane component (A) cured by a hydrosilylation reaction.

[0035] Effects of the Invention

[0036] By using the cleaning method of a semiconductor substrate according to the present application, for example, the adhesive layer obtained using a silicone-based adhesive can be appropriately and easily removed from a semiconductor substrate having the adhesive layer on the surface thereof, and thus efficient and good production of semiconductor elements can be expected.

[0037] In particular, in the case where the semiconductor substrate having the adhesive layer has a bump, damage to the bump can be avoided or suppressed, and the adhesive layer can be appropriately and easily removed, and thus efficient, high-reliability, and good production of semiconductor elements can be expected. DETAILED DESCRIPTION

[0038] The cleaning method of a semiconductor substrate according to the present application includes a step of peeling an adhesive layer on a semiconductor substrate using a peeling composition, the peeling composition containing a solvent and not containing a salt, the solvent containing one or two or more selected from the group consisting of an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, an ether compound, a thioether compound, an ester compound, and an amine compound having a molecular weight of less than 160, and a contact angle of the peeling composition on the adhesive layer being less than 31.5 degrees.

[0039] The semiconductor substrate is, for example, a wafer, and as specific examples thereof, a silicon wafer having a diameter of 300 mm and a thickness of about 770 μm, and the like can be given, but is not limited thereto.

[0040] The adhesive layer on the semiconductor substrate is, for example, a film obtained from an adhesive composition containing an adhesive component (S).

[0041] Such an adhesive component (S) is not particularly limited as long as it is used for such a use, and for example, a silicone-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, a phenolic resin-based adhesive, or the like can be exemplified.

[0042] Among them, as the adhesive component (S), a silicone-based adhesive is preferable because it exhibits an appropriate adhesive ability when processing a wafer or the like, is appropriately peeled after processing, and further has excellent heat resistance.

[0043] In a preferable embodiment, the adhesive composition used in the present application contains a polyorganosiloxane component (A) cured by a hydrosilylation reaction as an adhesive component, and in a more preferable embodiment, the polyorganosiloxane component (A) cured by a hydrosilylation reaction contains a polysiloxane (Al) and a platinum group metal-based catalyst (A2), the polysiloxane (Al) contains one or two or more units selected from the group consisting of a siloxane unit represented by SiO2 (Q unit), a siloxane unit represented by R 1 R 2 R 3 SiO 1 / 2 a siloxane unit represented by R 4 R 5 SiO 2 / 2 a siloxane unit represented by R 6 SiO 3 / 2 a siloxane unit represented by R 1 ’R 2 ’R 3 ’SiO 1 / 2 a siloxane unit represented by R 4 ’R 5 ’SiO 2 / 2 a siloxane unit represented by R 6 ’SiO 3 / 2 a siloxane unit represented by R 1 ”R 2 ”R 3 ”SiO 1 / 2 a siloxane unit represented by R 4"R 5 "SiO" 2 / 2 The siloxane unit (D” unit) and R shown are shown. 6 "SiO" 3 / 2 The siloxane unit (T” unit) shown is one or more units from the group consisting of the siloxane unit (T” unit) shown, and includes at least one unit selected from the group consisting of the M” unit, D” unit and T” unit.

[0044] R 1 ~R 6 These are groups or atoms bonded to silicon atoms, and can be independently represented as alkyl, alkenyl, or hydrogen atoms.

[0045] R 1 '~R 6 ' is a group bonded to a silicon atom, which can independently represent alkyl or alkenyl groups, but R 1 '~R 6 At least one of them is an alkenyl group.

[0046] R 1 "~R 6 "" represents a group or atom bonded to a silicon atom, and can be independently represented by an alkyl group or a hydrogen atom, but R 1 "~R 6 At least one of the elements is a hydrogen atom.

[0047] Alkyl groups can be any of straight-chain, branched, or cyclic, with straight-chain or branched alkyl groups being preferred. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0048] Specific examples of straight-chain or branched alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl n-butyl, 2-methyl n-butyl, 3-methyl n-butyl, 1,1-dimethyl n-propyl, 1,2-dimethyl n-propyl, 2,2-dimethyl n-propyl, 1-ethyl n-propyl, n-hexyl, 1-methyl n-pentyl, 2-methyl n-pentyl, 3-methyl n-pentyl. 4-Methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these.

[0049] Among them, methyl is preferred.

[0050] As specific examples of the cyclic alkyl group, there can be mentioned cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-iso-propylcyclopropyl, 2-iso-propylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl, and the like, cyclic alkyl groups, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, and the like, bicyclic alkyl groups, and the like, but are not limited thereto.

[0051] The alkenyl group can be either linear or branched, and the number of carbon atoms is not particularly limited, and is usually from 2 to 40, preferably 30 or less, more preferably 20 or less, and still more preferably 10 or less.

[0052] As specific examples of the alkenyl group, the following can be given: ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylethenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylethenyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylethenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-iso-butylethenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-iso-propyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, and the like, but are not limited thereto.

[0053] Among them, vinyl, 2-propenyl are preferred.

[0054] As described above, the polysiloxane (Al) contains the polyorganosiloxane (al) and the polyorganosiloxane (a2), and the alkenyl group contained in the polyorganosiloxane (al) and the hydrogen atom (Si-H group) contained in the polyorganosiloxane (a2) are cured by forming a crosslinked structure through hydrosilylation reaction based on the platinum group metal-based catalyst (A2).

[0055] The polyorganosiloxane (al) contains one or two or more units selected from the group consisting of a Q' unit, an M' unit, a D' unit, and a T' unit, and contains at least one selected from the group consisting of the above-mentioned M' unit, D' unit, and T' unit. As the polyorganosiloxane (al), two or more polyorganosiloxanes satisfying such conditions can also be used in combination.

[0056] As the preferred combination of two or more selected from the group consisting of a Q' unit, an M' unit, a D' unit, and a T' unit, (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit, and M' unit) can be cited, but are not limited thereto.

[0057] Further, in the case of containing two or more polyorganosiloxanes (al), combinations of (Q' unit and M' unit) and (D' unit and M' unit), (T' unit and M' unit) and (D' unit and M' unit), (Q' unit, T' unit, and M' unit) and (T' unit and M' unit) are preferred, but are not limited thereto.

[0058] The polyorganosiloxane (a2) contains one or two or more units selected from the group consisting of a Q" unit, a M" unit, a D" unit, and a T" unit, and contains at least one selected from the group consisting of the above-mentioned M" unit, D" unit, and T" unit. Two or more polyorganosiloxanes satisfying such conditions can also be used in combination as the polyorganosiloxane (a2).

[0059] As the preferred combination of two or more selected from the group consisting of a Q" unit, a M" unit, a D" unit, and a T" unit, (a M" unit and a D" unit), (a Q" unit and a M" unit), and (a Q" unit, a T" unit, and a M" unit) can be cited, but are not limited thereto.

[0060] The polyorganosiloxane (al) is composed of siloxane units in which an alkyl group and / or an alkenyl group is bonded to a silicon atom, R 1 '~R 6 The proportion of the alkenyl group in all the substituents represented by R 1 '~R 6 ' can be an alkyl group.

[0061] The polyorganosiloxane (a2) is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to a silicon atom, R 1 "~R 6 The proportion of the hydrogen atom in all the substituents represented by R 1 "~R 6 " can be an alkyl group.

[0062] The polysiloxane (Al) contains the polyorganosiloxane (al) and the polyorganosiloxane (a2), and in one preferred embodiment, the molar ratio of the alkenyl group contained in the polyorganosiloxane (al) to the hydrogen atom constituting the Si-H bond contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0063] The weight average molecular weight of the polyorganosiloxane (al) and the polyorganosiloxane (a2) is usually 500 to 1,000,000, and preferably 5,000 to 50,000 from the viewpoint of achieving the effects of the present application with good reproducibility.

[0064] Note that the weight average molecular weight, the number average molecular weight, and the dispersity in the present application can be measured, for example, using a GPC device (EcoSEC, HLC-8320 GPC, manufactured by Tosoh Corporation) and GPC columns (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H, manufactured by Tosoh Corporation), setting the column temperature to 40°C, using tetrahydrofuran as an eluent (dissolution solvent), setting the flow rate (flow velocity) to 0.35 mL / min, and using polystyrene (manufactured by Sigma-Aldrich Corporation) as a standard sample.

[0065] The viscosity of the polyorganosiloxane (al) and the polyorganosiloxane (a2) is generally 10 to 1,000,000 (mPa-s), and preferably 50 to 10,000 (mPa-s) from the viewpoint of achieving the effects of the present application with good reproducibility. Note that the viscosity in the present application is a value measured at 25°C using an E-type rotational viscometer.

[0066] The polyorganosiloxane (al) and the polyorganosiloxane (a2) are reacted with each other by hydrosilylation reaction, thereby becoming a film. Therefore, the mechanism of the curing is different from, for example, a mechanism via a silanol group, and thus neither of the siloxanes needs to include a functional group such as a silanol group or an alkyloxy group that forms a silanol group by hydrolysis.

[0067] In a preferred embodiment, the adhesive component (S) includes the polysiloxane (Al) and the platinum group metal-based catalyst (A2) described above.

[0068] Such a platinum-based metal catalyst is a catalyst for promoting hydrosilylation reaction of the alkenyl group of the polyorganosiloxane (al) and the Si-H group of the polyorganosiloxane (a2).

[0069] As specific examples of the platinum-based metal catalyst, platinum black, platinum chloride, chloroplatinic acid, a reactant of chloroplatinic acid with a monohydric alcohol, a complex of chloroplatinic acid with an olefin, platinum bisacetylacetate, and the like can be given, but the present application is not limited thereto.

[0070] As the complex of platinum with an olefin, for example, a complex of divinyltetramethyldisiloxane with platinum can be given, but the present application is not limited thereto.

[0071] Generally, the amount of the platinum group metal-based catalyst (A2) is in the range of 1.0 to 50.0 ppm relative to the total amount of the polyorganosiloxane (al) and the polyorganosiloxane (a2).

[0072] The polyorganosiloxane component (A) can also include a polymerization inhibitor (A3) for the purpose of inhibiting the progress of hydrosilylation reaction.

[0073] The polymerization inhibitor is not particularly limited as long as it inhibits the progress of the hydrosilylation reaction, and as specific examples thereof, acetylenic alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propynyl-1-ol can be given.

[0074] The amount of the polymerization inhibitor is generally 1000.0 ppm or more, from the viewpoint of obtaining the effect, and is 10000.0 ppm or less, from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction, with respect to the total amount of the polyorganosiloxane (al) and the polyorganosiloxane (a2).

[0075] The adhesive composition used in the present application can contain a release agent component (B). By including such a release agent component (B) in the adhesive composition used in the present application, the obtained adhesive layer can be appropriately released with good reproducibility.

[0076] As such a release agent component (B), typically, polyorganosiloxanes can be given, and as specific examples thereof, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, phenyl group-containing polyorganosiloxanes, and the like can be given, but are not limited thereto.

[0077] The weight average molecular weight of the polyorganosiloxane as the release agent component (B) is generally 100000 to 2000000, and from the viewpoint of achieving the effect of the present application with good reproducibility, it is preferably 200000 to 1200000, more preferably 300000 to 900000, and the dispersity thereof is generally 1.0 to 10.0, and from the viewpoint of achieving the effect of the present application with good reproducibility, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. Note that the weight average molecular weight and the dispersity can be measured by the above-described methods.

[0078] As the epoxy group-containing polyorganosiloxane, for example, a polyorganosiloxane containing a siloxane unit (D 11 R 12 SiO 2 / 2 indicated by the formula (D 10 unit) can be given.

[0079] R 11 is a group bonded to a silicon atom, and represents an alkyl group, R 12 is a group bonded to a silicon atom, and represents an epoxy group or an organic group containing an epoxy group, and as specific examples of the alkyl group, the above-described examples can be given.

[0080] Further, the epoxy group in the organic group containing an epoxy group can be an epoxy group that is not condensed with other rings independently, or can be an epoxy group that forms a condensed ring with other rings, like a 1,2-epoxycyclohexyl group.

[0081] Specific examples of the organic group containing an epoxy group include 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, but are not limited thereto.

[0082] In the present application, as a preferable example of the polyorganosiloxane containing an epoxy group, a polydimethylsiloxane containing an epoxy group can be given, but is not limited thereto.

[0083] The polyorganosiloxane containing an epoxy group contains the above-described siloxane unit (D 10 unit, and can contain the above-described Q unit, M unit and / or T unit in addition to the D 10 unit.

[0084] In a preferable aspect, as specific examples of the polyorganosiloxane containing an epoxy group, a polyorganosiloxane composed of only the D 10 unit, a polyorganosiloxane containing the D 10 unit and the Q unit, a polyorganosiloxane containing the D 10 unit and the M unit, a polyorganosiloxane containing the D 10 unit and the T unit, a polyorganosiloxane containing the D 10 unit, the Q unit and the M unit, a polyorganosiloxane containing the D 10 unit, the M unit and the T unit, a polyorganosiloxane containing the D 10 unit, the Q unit, the M unit and the T unit, and the like can be given.

[0085] The polyorganosiloxane containing an epoxy group is preferably a polydimethylsiloxane containing an epoxy group having an epoxy value of 0.1 to 5, and the weight average molecular weight thereof is usually 1500 to 500000, and from the viewpoint of suppressing precipitation in the adhesive composition, the weight average molecular weight thereof is preferably 100000 or less.

[0086] As specific examples of the polyorganosiloxane containing an epoxy group, there can be mentioned, for example, CMS-227 (manufactured by Gelest, Inc., weight average molecular weight: 27,000) represented by the formula (A-1), ECMS-327 (manufactured by Gelest, Inc., weight average molecular weight: 28,800) represented by the formula (A-2), KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: 31,800) represented by the formula (A-3), KF-1001 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: 55,600) represented by the formula (A-4), KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: 11,500) represented by the formula (A-5), X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: 2,400) represented by the formula (A-6), BY16-839 (manufactured by Dow Corning Toray Co., Ltd., weight average molecular weight: 51,700) represented by the formula (A-7), ECMS-327 (manufactured by Gelest, Inc., weight average molecular weight: 28,800) represented by the formula (A-8), and the like, but are not limited thereto.

[0087]

[0088] (m and n are the number of repeating units, respectively.)

[0089]

[0090] (m and n are the number of repeating units, respectively.)

[0091]

[0092] (m and n are the number of repeating units, respectively. R is an alkylene group having 1 to 10 carbon atoms.)

[0093]

[0094] (m and n are the number of repeating units, respectively. R is an alkylene group having 1 to 10 carbon atoms.)

[0095]

[0096] (m, n and o are the number of repeating units, respectively. R is an alkylene group having 1 to 10 carbon atoms.)

[0097]

[0098] (m and n are the number of repeating units, respectively. R is an alkylene group having 1 to 10 carbon atoms.)

[0099]

[0100] (m and n are the number of repeating units, respectively. R is an alkylene group having 1 to 10 carbon atoms.)

[0101]

[0102] (m and n are the number of repeating units, respectively.)

[0103] As the polyorganosiloxane containing a methyl group, for example, a polyorganosiloxane containing a siloxane unit (D 210 R 220 SiO 2 / 2 siloxane unit (D 200 unit) represented by the formula: 21 R 21 SiO 2 / 2 siloxane unit (D 20 unit) represented by the formula:

[0104] R 210 and R 220 are groups bonded to a silicon atom, and each independently represent an alkyl group, but at least one is a methyl group, and as specific examples of the alkyl group, the above examples can be cited.

[0105] R 21 is a group bonded to a silicon atom, and represents an alkyl group, and as specific examples of the alkyl group, the above examples can be cited. Among them, as R 21 , a methyl group is preferred.

[0106] As a preferred example of the polyorganosiloxane containing a methyl group, a polydimethylsiloxane can be cited, but is not limited thereto.

[0107] The polyorganosiloxane containing a methyl group contains the above-described siloxane unit (D 200 unit or D 20 unit), but in addition to the D 200 unit and the D 20 unit, the above-described Q unit, M unit and / or T unit can be contained.

[0108] In a certain aspect, as specific examples of the polyorganosiloxane containing a methyl group, a polyorganosiloxane consisting only of a D 200 unit, a polyorganosiloxane containing a D 200 unit and a Q unit, a polyorganosiloxane containing a D 200 unit and an M unit, a polyorganosiloxane containing a D 200 unit and a T unit, a polyorganosiloxane containing a D 200 unit, a Q unit and an M unit, a polyorganosiloxane containing a D 200 unit, an M unit and a T unit, a polyorganosiloxane containing a D 200Polyorganosiloxane of the unit, the Q unit, the M unit, and the T unit.

[0109] In a preferred embodiment, as specific examples of the polyorganosiloxane containing a methyl group, there can be mentioned a polyorganosiloxane consisting only of the D 20 unit, a polyorganosiloxane containing the D 20 unit and the Q unit, a polyorganosiloxane containing the D 20 unit and the M unit, a polyorganosiloxane containing the D 20 unit and the T unit, a polyorganosiloxane containing the D 20 unit, the Q unit, and the M unit, a polyorganosiloxane containing the D 20 unit, the M unit, and the T unit, and a polyorganosiloxane containing the D 20 unit, the Q unit, the M unit, and the T unit.

[0110] The viscosity of the polyorganosiloxane containing a methyl group is usually 1000 to 2000000 mm 2 / s, preferably 10000 to 1000000 mm 2 / s. Note that, as the polyorganosiloxane containing a methyl group, typically there is a dimethyl silicone oil (Silicone Oil) consisting of polydimethylsiloxane. The value of the viscosity is expressed in kinematic viscosity, cSt = mm 2 / s. The kinematic viscosity can be measured using a kinematic viscometer. In addition, it can also be calculated from the viscosity (mPa-s) divided by the density (g / cm 3 ). That is, it can be calculated from the viscosity and the density measured at 25°C using an E-type rotational viscometer. It can be calculated from the formula, kinematic viscosity (mm 2 / s) = viscosity (mPa-s) / density (g / cm 3 ).

[0111] As specific examples of the polyorganosiloxane containing a methyl group, there can be mentioned WACKER SILICONE FLUID AK series manufactured by Wacker Chemie, dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), cyclic dimethyl silicone oil (KF-995), and the like manufactured by Shin-Etsu Chemical Co., Ltd., but not limited thereto.

[0112] As the polyorganosiloxane containing a phenyl group, there can be mentioned a polyorganosiloxane containing a siloxane unit (D 31 R 32 SiO 2 / 2 indicated by the formula. 30 unit).

[0113] R 31 is a group bonded to a silicon atom, represents a phenyl group or an alkyl group, R 32 is a group bonded to a silicon atom, represents a phenyl group, and as specific examples of the alkyl group, the above examples can be listed, with methyl group being preferred.

[0114] The phenyl group-containing polyorganosiloxane contains the above-described siloxane unit (D 30 unit), but in addition to the D 30 unit, the above-described Q unit, M unit and / or T unit can also be contained.

[0115] In a preferred embodiment, as specific examples of the phenyl group-containing polyorganosiloxane, the following can be listed: a polyorganosiloxane composed only of the D 30 unit, a polyorganosiloxane containing the D 30 unit and the Q unit, a polyorganosiloxane containing the D 30 unit and the M unit, a polyorganosiloxane containing the D 30 unit and the T unit, a polyorganosiloxane containing the D 30 unit, the Q unit and the M unit, a polyorganosiloxane containing the D 30 unit, the M unit and the T unit, and a polyorganosiloxane containing the D 30 unit, the Q unit, the M unit and the T unit.

[0116] The weight average molecular weight of the phenyl group-containing polyorganosiloxane is usually 1500 to 500,000, and from the viewpoint of suppressing precipitation in the adhesive composition, etc., it is preferably 100,000 or less.

[0117] As specific examples of the phenyl group-containing polyorganosiloxane, the following can be listed: PMM-1043 (Gelest Co., Ltd. product, weight average molecular weight 67,000, viscosity 30,000 mm 2 / s) represented by formula (C-1), PMM-1025 (Gelest Co., Ltd. product, weight average molecular weight 25,200, viscosity 500 mm 2 / s) represented by formula (C-2), KF50-3000CS (Shin-Etsu Chemical Co., Ltd. product, weight average molecular weight 39,400, viscosity 3,000 mm 2 / s) represented by formula (C-3), TSF431 (Momentive Co., Ltd. product, weight average molecular weight 1,800, viscosity 100 mm 2 / s) represented by formula (C-4), and TSF433 (Momentive Co., Ltd. product, weight average molecular weight 3,000, viscosity 450 mm 2(C-6) PDM-0421 (manufactured by Gelest, weight average molecular weight: 6200, viscosity: 100 mm2 / s), and the like, but is not limited thereto. 2 (C-7) PDM-0821 (manufactured by Gelest, weight average molecular weight: 8600, viscosity: 125 mm2 / s), and the like, but is not limited thereto. 2 (C-7) PDM-0821 (manufactured by Gelest, weight average molecular weight: 8600, viscosity: 125 mm2 / s), and the like, but is not limited thereto.

[0118]

[0119] (m and n represent the number of repeating units.)

[0120]

[0121] (m and n represent the number of repeating units.)

[0122]

[0123] (m and n represent the number of repeating units.)

[0124]

[0125] (m and n represent the number of repeating units.)

[0126]

[0127] (m and n represent the number of repeating units.)

[0128]

[0129] (m and n represent the number of repeating units.)

[0130]

[0131] (m and n represent the number of repeating units.)

[0132] In a preferred embodiment, the adhesive composition used in the present application includes a polyorganosiloxane component (A) cured by a hydrosilylation reaction and a release agent component (B), and in a more preferred embodiment, as the release agent component (B), a polyorganosiloxane is included.

[0133] The adhesive composition used in the present application can include the adhesive component (S) and the release agent component (B) in any ratio, but in consideration of the balance between adhesiveness and releasability, the ratio of the component (S) to the component (B) is preferably 99.995:0.005 to 30:70 in terms of mass ratio, and more preferably 99.9:0.1 to 75:25.

[0134] That is, in the case where the polyorganosiloxane component (A) cured by a hydrosilylation reaction is contained, the ratio of the component (A) to the component (B) is preferably 99.995:0.005 to 30:70 in terms of mass ratio, and more preferably 99.9:0.1 to 75:25.

[0135] The adhesive composition used in the present application can also contain a solvent for the purpose of adjusting the viscosity, etc., and as specific examples thereof, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc. can be given, but are not limited thereto.

[0136] More specifically, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc. can be given, but are not limited thereto. Such a solvent can be used singly or in combination of two or more.

[0137] In the case where the adhesive composition used in the present application contains a solvent, the content thereof is appropriately set in consideration of the viscosity of the desired composition, the coating method to be employed, the thickness of the film to be produced, etc., but is in the range of about 10 to 90 mass% with respect to the entire composition.

[0138] The viscosity of the adhesive composition used in the present application is generally 500 to 20,000 mPa-s at 25°C, and is preferably 1,000 to 5,000 mPa-s. The viscosity of the adhesive composition used in the present application can be adjusted by changing the kind of the organic solvent to be used, the ratio thereof, the concentration of the film-constituting component, etc. in consideration of various factors such as the coating method to be used and the desired film thickness.

[0139] In the present application, the film-constituting component refers to a component other than the solvent contained in the composition.

[0140] The adhesive composition used in the present application can be produced by mixing the adhesive component (S) used, the release agent component (B) and a solvent.

[0141] The mixing order is not particularly limited, and as one example of a method capable of easily and reproducibly producing the adhesive composition, a method in which the adhesive component (S) and the release agent component (B) are dissolved in a solvent, a method in which a part of the adhesive component (S) and the release agent component (B) are dissolved in a solvent, the remaining parts are dissolved in a solvent, and the resulting solutions are mixed, etc. can be given, but are not limited thereto. Note that, in producing the adhesive composition, appropriate heating can be performed within a range in which the components are not decomposed or deteriorated.

[0142] In the present application, in order to remove foreign matter, a filter or the like of a submicron level can be used for filtration at a middle of the production of the adhesive composition or after mixing all the components.

[0143] As described above, the cleaning method of a semiconductor substrate of the present application includes a step of peeling an adhesive layer on a semiconductor substrate using a peeling composition, the peeling composition containing a solvent and not containing a salt, the solvent containing one or two or more selected from the group consisting of an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, an ether compound, a thioether compound, an ester compound, and an amine compound having a molecular weight of less than 160.

[0144] The reason why peeling can be achieved in a shorter time by using such a specific organic solvent is not certain, but it is presumed because the above specific organic solvent has high compatibility with the above adhesive layer.

[0145] Further, the reason why peeling can be achieved in a shorter time by using such a molecular weight is not certain, but it is presumed because a solvent having a low molecular weight has high penetrability into the above adhesive layer.

[0146] The aliphatic hydrocarbon compound having a molecular weight of less than 160 can be an aliphatic saturated hydrocarbon compound, an aliphatic unsaturated hydrocarbon compound, a straight chain, a branched chain, or a cyclic or a combination thereof.

[0147] As specific examples, decane, p-menthane, cyclohexane, limonene, and the like can be listed, but are not limited thereto.

[0148] The aromatic hydrocarbon compound having a molecular weight of less than 160 is not limited thereto, and is typically a compound having an alkyl group or the like as a substituent, containing an uncondensed benzene ring, the alkyl group being, for example, a methyl group, an ethyl group, an isopropyl group, or the like, the substituent being selected in a manner to satisfy the molecular weight.

[0149] As specific examples, toluene, mesitylene, p-cymene, and the like can be listed, but are not limited thereto.

[0150] As the ether compound having a molecular weight of less than 160, it is not limited thereto, and is typically an ether compound having a structure in which two alkyl groups, for example, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, or the like, are connected via an ether bond, the two alkyl groups being selected in a manner to satisfy the molecular weight.

[0151] As specific examples thereof, di(n-butyl) ether, di(n-pentyl) ether, and the like can be listed, but are not limited thereto.

[0152] As the thioether compound having a molecular weight of less than 160, not particularly limited thereto, typically a thioether compound having a structure in which two alkyl groups such as ethyl group, isopropyl group, n-butyl group, n-pentyl group, and the like are connected via a thioether bond is exemplified, and the two alkyl groups are selected in a manner to satisfy the molecular weight.

[0153] As specific examples thereof, di(n-propyl) sulfide, di(n-butyl) sulfide, and the like can be exemplified, but not particularly limited thereto.

[0154] As the ester compound having a molecular weight of less than 160, not particularly limited thereto, typically an ester compound in which an alkyl group such as ethyl group, n-butyl group, n-pentyl group, and the like is bonded to an acetoxy group is exemplified, and the alkyl group is selected in a manner to satisfy the molecular weight.

[0155] As specific examples thereof, butyl acetate, pentyl acetate, and the like can be exemplified, but not particularly limited thereto.

[0156] As the amine compound having a molecular weight of less than 160, not particularly limited thereto, typically an amine compound in which an amino group is bonded to a terminal of a straight-chain or branched-chain, preferably straight-chain alkyl group is exemplified, and the alkyl group is selected in a manner to satisfy the molecular weight.

[0157] As specific examples thereof, 1-amino-n-butane, 1-amino-n-pentane, and the like can be exemplified, but not particularly limited thereto.

[0158] The solvent contained in the peeling composition used in the present application is a solvent containing one or two or more of the above-described specific organic solvents, i.e., organic solvents having a molecular weight of less than 160.

[0159] Most preferably, desirably, the solvent contained in the peeling composition consists of only one or two or more of the above-described specific organic solvents, and does not contain other solvents as impurities, but there is a limit to the improvement in purity by purification, and it is technically impossible.

[0160] Therefore, in the present application, as the solvent contained in the above-described peeling composition, intentionally used is a solvent consisting of only the above-described specific organic solvents, and it is not denied that the following cases are included: water and impurities such as organic solvents which are similar in structure or properties and are not easily separated are contained in the bulk of the above-described specific organic solvents.

[0161] From such a situation, in the solvent contained in the above-described peeling composition, the content of the above-described specific organic solvents can sometimes not be exactly 100% in terms of the value of the purity obtained by gas chromatography, and is usually 94% or more, preferably 95% or more, more preferably 96% or more, further preferably 97% or more, still further preferably 98% or more, and yet further preferably 99% or more.

[0162] In the present application, the molecular weight of the above-mentioned specific organic solvent contained in the above-mentioned peeling composition is less than 160, and from the viewpoint of achieving peeling in a shorter time with good reproducibility, it is preferably less than 150, more preferably less than 130, further preferably less than 110, and still further preferably less than 90.

[0163] On the other hand, from the viewpoint of achieving peeling in a shorter time with good reproducibility, the lower limit value of the molecular weight of the above-mentioned specific organic solvent contained in the above-mentioned peeling composition is generally 70, in one aspect 75, and in another aspect 80.

[0164] In particular, among the above-mentioned specific organic solvents, aliphatic saturated hydrocarbon compounds and ether compounds are preferred from the viewpoint of achieving peeling in a shorter time with good reproducibility.

[0165] The peeling composition used in the present application does not contain a salt.

[0166] As specific examples of such a salt, there can be mentioned ammonium salts such as tetrabutylammonium hydroxide, tetrabutylammonium fluoride (also referred to as fluorinated tetrabutylammonium) and the like, which are added for the purpose of facilitating removal of the adhesive layer, adhesive layer residue and the like.

[0167] The peeling composition used in the present application contains a specific organic solvent satisfying the above-mentioned condition, and therefore does not need to contain such a salt.

[0168] Such a salt can cause damage such as corrosion to the substrate, particularly a bump-equipped substrate and the like, and therefore a peeling composition not containing a salt is used in the present application. However, in the case where a trace amount of a salt is contained as an impurity in the bulk solvent constituting the peeling composition from the beginning, the presence of the salt is not denied.

[0169] In the present application, it is necessary to set the contact angle of the peeling composition on the adhesive layer to less than 31.5 degrees. By adopting such a value, peeling in a shorter time can be achieved. The reason is not certain, but it is presumed that the higher the wettability when the peeling composition is dropped on the adhesive layer, the higher the penetration of the peeling composition into the adhesive layer.

[0170] In the present application, from the viewpoint of achieving peeling in a shorter time with good reproducibility, in one aspect, the contact angle of the peeling composition on the adhesive layer is less than 30.0 degrees, in another aspect, the contact angle of the peeling composition on the adhesive layer is less than 28.0 degrees, and in still another aspect, the contact angle of the peeling composition on the adhesive layer is less than 27.0 degrees, and the lower limit value thereof is not particularly limited, in one aspect 15.0 degrees, in another aspect 20.0 degrees, and in still another aspect 24.0 degrees.

[0171] In the present application, the adhesive layer used when measuring the contact angle of the peeling composition is produced using an adhesive composition containing the adhesive component (S) and not containing the releasing agent component (H), whereas the adhesive layer removed by the cleaning method for a semiconductor substrate of the present application can be produced using either an adhesive composition containing the releasing agent component (H) or an adhesive composition not containing the releasing agent component (H), but from the viewpoint of achieving peeling in a shorter time with good reproducibility and the like, the adhesive layer removed by the cleaning method for a semiconductor substrate of the present application is produced from an adhesive composition containing the releasing agent component (H).

[0172] Note that the contact angle can be measured, for example, using a fully automatic contact angle measuring instrument DM-701 manufactured by Kyowa Interface Science Co., Ltd.

[0173] In the present application, the adhesive layer on the semiconductor substrate is swelled by continuously contacting the adhesive layer on the semiconductor substrate with the peeling composition, and peeled from the semiconductor substrate.

[0174] As for the method of continuously contacting the adhesive layer on the semiconductor substrate with the peeling composition, there is no particular limitation as long as the adhesive layer on the semiconductor substrate is contacted with the peeling composition in a manner having continuity in time, and the continuity in time includes not only the case where the adhesive layer is always in contact with the peeling composition, but also, for example, the case where the contact is temporarily stopped after the contact of the adhesive layer with the organic solvent is performed for a certain period of time, and the contact is performed again, or the case where the above-mentioned cases are repeated, and in addition, the case where the entire adhesive layer on the semiconductor substrate is in contact with the peeling composition, and the case where a part of the adhesive layer is in contact with the peeling composition, and from the viewpoint of achieving more efficient cleaning with good reproducibility, the case where the adhesive layer on the semiconductor substrate is always in contact with the peeling composition is preferred, and in addition, the case where the entire adhesive layer on the semiconductor substrate is in contact with the peeling composition is preferred.

[0175] Therefore, in one preferred embodiment of the present application, the adhesive layer on the semiconductor substrate is swelled by immersing the above-mentioned adhesive layer in the peeling composition, and peeled from the semiconductor substrate, or the adhesive layer on the semiconductor substrate is swelled by continuously supplying the peeling composition onto the above-mentioned adhesive layer, and peeled from the semiconductor substrate.

[0176] In order to immerse the adhesive layer on the semiconductor substrate in the peeling composition, for example, the semiconductor substrate with the adhesive layer can be immersed in the peeling composition.

[0177] The immersion time is not particularly limited as long as the swelling of the adhesive layer and the peeling of the adhesive layer from the semiconductor substrate are induced, and from the viewpoint of achieving more efficient cleaning with good reproducibility, it is 5 seconds or more, and from the viewpoint of the throughput in the process, it is 5 minutes or less.

[0178] When the adhesive layer on the semiconductor substrate is immersed in the peeling composition, the peeling of the adhesive layer can be promoted by moving the semiconductor substrate with the adhesive layer in the peeling composition, causing the peeling composition to flow, vibrating the peeling composition with ultrasonic waves, or the like.

[0179] To move the semiconductor substrate with the adhesive layer in the peeling composition, for example, a swing cleaning machine, a paddle cleaning machine, or the like can be used. If such a cleaning machine is used, the semiconductor substrate with the adhesive layer is moved up and down or left and right on the stage, or is rotated, so that the adhesive layer on the semiconductor substrate is relatively subjected to the flow or is subjected to the flow generated by the movement or rotation, thereby promoting the swelling of the adhesive layer on the semiconductor substrate and the peeling of the adhesive layer from the semiconductor substrate.

[0180] To cause the peeling composition to flow, in addition to the swing cleaning machine or the paddle cleaning machine described above, for example, a convection cleaning machine that can achieve a state in which the peeling composition around the semiconductor substrate with the adhesive layer is caused to flow by a stirrer can be typically used in a state in which the semiconductor substrate with the adhesive layer is fixed to the stage or the like.

[0181] To vibrate the peeling composition with ultrasonic waves, an ultrasonic cleaning machine or an ultrasonic probe can be used, and the conditions are generally 20 kHz to 5 MHz.

[0182] To continuously supply the peeling composition to the adhesive layer on the semiconductor substrate, the peeling composition is only required to be continuously brought into contact with the adhesive layer on the semiconductor substrate. As an example, if the adhesive layer on the semiconductor substrate faces upward, the peeling composition in a rod shape or a mist shape, preferably a rod shape, is supplied to the adhesive layer on the semiconductor substrate from above (including diagonally above) the adhesive layer on the semiconductor substrate, for example, by a nozzle or the like of a cleaning device, in a manner having continuity in time. The continuity in time in this case also includes not only a case in which the peeling composition is supplied to the adhesive layer on the semiconductor substrate all the time, but also a case in which the supply of the peeling composition is temporarily stopped after the supply is performed for a certain period of time and the supply is performed again or a case in which the above cases are repeated, and it is preferable that the peeling composition be supplied to the adhesive layer on the semiconductor substrate all the time from the viewpoint of achieving more efficient cleaning with good reproducibility.

[0183] When the peeling composition is supplied to the adhesive layer on the semiconductor substrate in a rod shape, the flow rate is generally 200 to 500 mL / min.

[0184] In a certain aspect of the present application, to achieve a state in which the adhesive layer on the semiconductor substrate is always in contact with the peeling composition, for example, a vapor cleaning machine can be used to bring the adhesive layer on the semiconductor substrate into contact with the vapor of the peeling composition.

[0185] The cleaning method of the semiconductor substrate of the present application can also include a step of removing the peeled adhesive layer.

[0186] The method of removing the peeled adhesive layer is not particularly limited as long as it can remove the peeled adhesive layer from the semiconductor substrate, and in the case where the semiconductor substrate with the adhesive layer is immersed in the peeling composition, the peeled adhesive layer can be removed without taking out the semiconductor substrate from the peeling composition or by taking out the semiconductor substrate from the peeling composition. At this time, the peeled adhesive layer can be naturally left in the peeling composition and removed by taking out the semiconductor substrate from the peeling composition only.

[0187] As specific examples of the method of removing the peeled adhesive layer, there can be mentioned a method of removing by using a device to adsorb or attract, a method of removing by using a gas gun or the like to blow away with a gas, a method of removing by using centrifugal force or the like generated by moving the semiconductor substrate up and down or left and right or rotating, and the like, but the present application is not limited thereto.

[0188] After the peeled adhesive layer is removed, drying or the like of the semiconductor substrate is performed as necessary according to a conventional method.

[0189] The peeling composition used in the cleaning method of the semiconductor substrate of the present application is also an object of the present application. The peeling composition of the present application is used to peel the adhesive layer on the semiconductor substrate from the semiconductor substrate, and the preferred aspects and various conditions are as described above. The peeling composition of the present application can be manufactured by mixing the solvents constituting the composition in an arbitrary order, if necessary. At this time, filtration or the like can also be performed, if necessary.

[0190] By using the cleaning method of the semiconductor substrate of the present application described above, damage to the semiconductor substrate, particularly the bump of the semiconductor substrate, can be suppressed, and the adhesive layer on the semiconductor substrate, particularly the cured film, i.e., the adhesive layer, obtained from a siloxane-based adhesive containing the polyorganosiloxane component (A) cured by hydrosilylation reaction, can be efficiently removed, and efficient and good production of semiconductor elements can be expected.

[0191] The semiconductor substrate which is the cleaning target of the cleaning method of the present application includes, in addition to the silicon wafer and the like, various substrates such as a germanium substrate, a gallium-arsenic substrate, a gallium-phosphorus substrate, a gallium-arsenic-aluminum substrate, an aluminum-plated silicon substrate, a copper-plated silicon substrate, a silver-plated silicon substrate, a gold-plated silicon substrate, a titanium-plated silicon substrate, a silicon nitride film-formed silicon substrate, a silicon oxide film-formed silicon substrate, a polyimide film-formed silicon substrate, a glass substrate, a quartz substrate, a liquid crystal substrate, an organic EL substrate, and the like.

[0192] As an example of use of the cleaning method for a semiconductor substrate of the present application in a semiconductor process, a manufacturing method for a thinned semiconductor substrate or the like for a semiconductor packaging technology such as TSV can be cited.

[0193] Specifically, a manufacturing method for a thinned semiconductor substrate or the like, which includes: a first step of manufacturing a laminate provided with a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition; a second step of processing the semiconductor substrate of the obtained laminate; a third step of separating the processed semiconductor substrate and the adhesive layer from the support substrate; and a fourth step of removing the adhesive layer from the processed semiconductor substrate and cleaning the processed semiconductor substrate, in which the cleaning method for a semiconductor substrate of the present application is used.

[0194] As the adhesive composition used to form the adhesive layer in the first step, various adhesives described above can be used, but in terms of the cleaning method for a semiconductor substrate of the present application, it is effective to remove the adhesive layer obtained from a polysiloxane-based adhesive, and it is more effective to remove the adhesive layer obtained from a polysiloxane-based adhesive containing a component (A) cured by hydrosilylation reaction.

[0195] Therefore, hereinafter, an example in which the adhesive layer obtained using a polysiloxane-based adhesive (adhesive composition) is removed by the cleaning method of the present application when a processed semiconductor substrate is manufactured using the adhesive layer will be described, but the present application is not limited thereto.

[0196] First, the first step of manufacturing a laminate provided with a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition will be described.

[0197] In one aspect, the first step includes: a step of applying an adhesive composition to a surface of the semiconductor substrate or the support substrate to form an adhesive coating layer; and a step of bringing the semiconductor substrate and the support substrate together via the adhesive coating layer, making them adhere to each other while at least one of a heat treatment and a reduced pressure treatment is performed, and a load in the thickness direction of the semiconductor substrate and the support substrate is applied, and then performing a post-heat treatment, thereby manufacturing the laminate.

[0198] In other aspects, the first process may, for example, include a process of applying an adhesive composition to the circuit surface of the wafer of the semiconductor substrate and heating it to form an adhesive coating layer; a process of applying a release agent composition to the surface of the support substrate and heating it to form a release agent coating layer; and a process of making the semiconductor substrate and the support substrate adhere to each other by applying a load in the thickness direction of the semiconductor substrate and the support substrate while at least one of a heating treatment and a reduced pressure treatment is applied to the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate, and then applying a post-heating treatment, thereby producing a laminate. Note that the adhesive composition and the release agent composition may be applied to the semiconductor substrate and the support substrate, respectively, and heated, or the adhesive composition and the release agent composition may be sequentially applied to either of the substrates and heated.

[0199] In each of the above aspects, the heating treatment, the reduced pressure treatment, and which of the two is used can be determined based on various conditions such as the type of the adhesive composition, the specific composition of the release agent composition, the phase of the film obtained from the two compositions, the film thickness, and the adhesive strength to be achieved.

[0200] Here, for example, the semiconductor substrate is a wafer, and the support substrate is a support. The object to which the adhesive composition is applied can be either or both of the semiconductor substrate and the support substrate.

[0201] As the wafer, for example, a silicon wafer having a diameter of 300 mm and a thickness of about 770 μm, a glass wafer, or the like can be mentioned, but is not limited thereto.

[0202] In particular, the cleaning method for a semiconductor substrate according to the present application can suppress damage to bumps of a semiconductor substrate having bumps, and effectively clean the substrate.

[0203] As a specific example of such a semiconductor substrate having bumps, a silicon wafer having bumps such as ball bumps, print bumps, stud bumps, plated bumps, or the like can be mentioned, and generally can be appropriately selected from conditions such as a bump height of 1 to 200 μm, a bump diameter of 1 to 200 μm, and a bump pitch of 1 to 500 μm.

[0204] As a specific example of a plated bump, a plated alloy bump mainly composed of Sn such as a SnAg bump, a SnBi bump, a Sn bump, an AuSn bump, or the like can be mentioned, but is not limited thereto.

[0205] The support (carrier) is not particularly limited, and for example, a silicon wafer having a diameter of 300 mm and a thickness of about 700 μm can be mentioned, but is not limited thereto.

[0206] As the release agent composition, a composition containing a release agent component for such a use can be mentioned.

[0207] The coating method is not particularly limited, and is typically a spin coating method. Note that a method in which a coating film is formed by a spin coating method or the like and a sheet-like coating film is attached can also be employed, and this is also referred to as coating or coating film.

[0208] The heating temperature of the coated adhesive composition varies depending on the kind or amount of the adhesive component included in the adhesive composition, the presence or absence of a solvent, the desired thickness of the adhesive layer, and the like, and thus cannot be generally specified, and is typically 80 to 150 °C, and the heating time thereof is typically 30 seconds to 5 minutes.

[0209] The heating temperature of the coated release agent composition varies depending on the kind or amount of the crosslinking agent, the acid generator, the acid, and the like, the presence or absence of a solvent, the desired thickness of the release layer, and the like, and thus cannot be generally specified, and from the viewpoint of achieving appropriate curing, the heating temperature thereof is higher than or equal to 120 °C, and from the viewpoint of preventing excessive curing, is lower than or equal to 260 °C, and the heating time thereof is typically 1 to 10 minutes.

[0210] The heating can be performed using a hot plate, an oven, or the like.

[0211] The film thickness of the adhesive coating layer obtained by coating the adhesive composition and heating the same is typically 5 to 500 μm.

[0212] The film thickness of the release agent coating layer obtained by coating the release agent composition and heating the same is typically 5 to 500 μm.

[0213] From the viewpoint of softening the adhesive coating layer to achieve appropriate adhesion to the release agent coating layer, the viewpoint of achieving appropriate curing of the release agent coating layer, and the like, the heating treatment can typically be appropriately determined from a range of 20 to 150 °C. In particular, from the viewpoint of inhibiting or avoiding excessive curing or unnecessary deterioration of the adhesive component and the release agent component, it is preferably lower than or equal to 130 °C, and more preferably lower than or equal to 90 °C, and from the viewpoint of reliably exhibiting the adhesive ability and the release ability, the heating time thereof is typically longer than or equal to 30 seconds, and preferably longer than or equal to 1 minute, and from the viewpoint of inhibiting deterioration of the adhesive layer and other members, the heating time thereof is typically shorter than or equal to 10 minutes, and preferably shorter than or equal to 5 minutes.

[0214] The reduced-pressure treatment can be performed by exposing the semiconductor substrate, the adhesive coating layer, and the support substrate, or the semiconductor substrate, the adhesive coating layer, the release agent coating layer, and the support substrate to an air pressure of 10 to 10,000 Pa. The time of the reduced-pressure treatment is typically 1 to 30 minutes.

[0215] In one embodiment of the present application, the substrates and the coating layers are preferably adhered to each other by a reduced-pressure treatment, and more preferably by a combination of a heating treatment and a reduced-pressure treatment.

[0216] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate, and the layer therebetween, and can firmly bond them, and is typically in the range of 10 to 1000 N.

[0217] The post-heating temperature is preferably 120°C or higher from the viewpoint of obtaining a sufficient curing rate, and is preferably 260°C or lower from the viewpoint of preventing deterioration of the substrate, the adhesive component, the release agent component, and the like. The heating time is typically 1 minute or more from the viewpoint of achieving appropriate bonding of the wafer based on curing, and is preferably 5 minutes or more from the viewpoint of stabilizing the properties of the adhesive, and the like, and is typically 180 minutes, and is preferably 120 minutes or less from the viewpoint of avoiding adverse effects on the adhesive layer caused by excessive heating, and the like. The heating can be performed using a hot plate, an oven, or the like.

[0218] Note that one of the purposes of the post-heating treatment is to more appropriately cure the adhesive component (S).

[0219] Next, a second step of processing the semiconductor substrate of the obtained laminate by the method described above is described.

[0220] As one example of the processing performed on the laminate used in the present application, the processing of the back surface opposite the circuit surface of the semiconductor substrate can be cited, and typically, the thinning of the wafer by polishing of the wafer back surface can be cited. Using such a thinned wafer, formation of a silicon through electrode (TSV) or the like is performed, and then the thinned wafer is peeled from the support, and a laminate of wafers is formed, and three-dimensional mounting is performed. Furthermore, formation of a wafer back surface electrode or the like is performed before and after three-dimensional mounting. In the thinning of the wafer and the TSV process, heat of 250 to 350°C is applied in a state in which the wafer is adhered to the support, but the laminate used in the present application contains an adhesive layer that has heat resistance to this heat.

[0221] For example, in the case of a wafer having a diameter of 300 mm and a thickness of about 770 μm, it is possible to thin the wafer to a thickness of about 80 to 4 μm by polishing the back surface opposite the circuit surface of the surface.

[0222] A third step of separating the processed semiconductor substrate and the adhesive layer from the support substrate is described.

[0223] In the third step, the processed semiconductor substrate and the adhesive layer are separated from the support substrate. At this time, in the case where the release layer is contained in the laminate, the release layer is typically removed together with the support substrate.

[0224] The method for separating the processed semiconductor substrate and the adhesive layer from the semiconductor substrate can be any method for peeling between the adhesive layer and the peeling layer or the support substrate that is in contact with the adhesive layer, and examples of such a peeling method include laser peeling, mechanical peeling using a device having a sharp portion, and manual peeling, but the present application is not limited thereto.

[0225] Next, the fourth process of removing the adhesive layer on the processed semiconductor substrate and cleaning the processed semiconductor substrate will be described.

[0226] The fourth process is a process for removing the adhesive layer on the semiconductor substrate by the cleaning method of the present application, and specifically, for example, the adhesive layer on the thinned substrate is efficiently removed by the cleaning method of the present application. The various conditions at this time are as described above.

[0227] After the fourth process, if necessary, the adhesive layer residue remaining on the semiconductor substrate can be removed using a cleaning agent composition containing a salt, but care should be taken not to damage the semiconductor substrate, particularly the bumps of the semiconductor substrate having bumps.

[0228] The manufacturing method of the processed semiconductor substrate of the present application includes the first to fourth processes described above, but can also include processes other than these processes. In addition, regarding the above-described elements and elements of the method related to the first to fourth processes, various modifications can be made as long as the modifications do not depart from the spirit of the present application.

[0229] Examples

[0230] Hereinafter, the present application will be described using examples and comparative examples, but the present application is not limited to the following examples. Note that the purity of the solvent for the peeling composition based on gas chromatography used in the present application is as described below.

[0231] [Apparatus]

[0232] (1) Self-rotating and revolving stirrer: self-rotating and revolving stirrer ARE-500 manufactured by THINKY Co., Ltd.

[0233] (2) Viscosity meter: rotational viscometer TVE-22H manufactured by Toyo Seiki Co., Ltd.

[0234] (3) Stirrer: Mix Rotor Variable 1-1186-12 manufactured by AS ONE Corporation.

[0235] (4) Contact angle meter: fully automatic contact angle measuring instrument DM-701 manufactured by Kyowa Interface Science Co., Ltd.

[0236] (5) Optical microscope: semiconductor / FPD inspection microscope MX61L manufactured by OLYMPUS Corporation.

[0237] [Solvent]

[0238] Di(n-butyl) ether: purity > 99.0% by Tokyo Chemical Industry Co., Ltd.

[0239] n-Decane: purity > 97.0% by San-Ai Chemical Industries, Ltd.

[0240] Di(n-pentyl) ether: purity > 98.0% by Tokyo Chemical Industry Co., Ltd.

[0241] 1-Amino-n-pentane: purity > 98.0% by Tokyo Chemical Industry Co., Ltd.

[0242] P-Menthae: purity > 96.0% by Japan Terpene Chemicals, Ltd.

[0243] Butyl acetate: purity > 98.0% by Kanto Chemical Co., Inc.

[0244] Cyclohexane: purity > 99.5% by Kanto Chemical Co., Inc.

[0245] Di(n-propyl) sulfide: purity > 98.0% by Tokyo Chemical Industry Co., Ltd.

[0246] Pentyl acetate: purity > 99.0% by Tokyo Chemical Industry Co., Ltd.

[0247] Di(n-butyl) sulfide: purity > 98.0% by Tokyo Chemical Industry Co., Ltd.

[0248] Mesitylene: purity > 97.0% by Fuji Photo Film Co., Ltd. and Wako Pure Chemical Industries, Ltd.

[0249] Limonene: purity > 95.0% by Tokyo Chemical Industry Co., Ltd.

[0250] P-Cymene: purity > 95.0% by Tokyo Chemical Industry Co., Ltd.

[0251] n-Octyl-1-amine: purity > 98.0% by Tokyo Chemical Industry Co., Ltd.

[0252] Cyclooctane: purity > 98.0% by Tokyo Chemical Industry Co., Ltd.

[0253] Heptyl acetate: purity > 99.0% by Tokyo Chemical Industry Co., Ltd.

[0254] 5-Nonanone: purity > 98.0% by Tokyo Chemical Industry Co., Ltd.

[0255] 1,4-Diisopropylbenzene: purity > 98.0% by Tokyo Chemical Industry Co., Ltd.

[0256] Octyl acetate: manufactured by Tokyo Chemical Industry Co., Ltd., purity > 98.0%.

[0257] n-Dodecane: manufactured by Tokyo Chemical Industry Co., Ltd., purity > 99.5%.

[0258] 1-Pentanol: manufactured by Tokyo Chemical Industry Co., Ltd., purity > 99.0%.

[0259] Acetone: manufactured by Sunjin Chemical Co., Ltd., purity > 99.0%.

[0260] Tetramethyl urea: manufactured by Tokyo Chemical Industry Co., Ltd., purity > 98.0%.

[0261] N-Methyl pyrrolidone: manufactured by Showa Denko K.K., purity > 99.0%.

[0262] [1] Preparation of Adhesive Composition

[0263] [Preparation Example 1]

[0264] Into a 600 mL stirring container for a self-rotating and revolving stirrer, 95 g of a vinyl group-containing MQ resin (manufactured by Wacker Chemie AG) as (al), 93.4 g of p-menthane as a solvent (manufactured by Japan Terpene Chemicals, Ltd.), and 0.41 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as (A2) were added, and stirred in a self-rotating and revolving stirrer for 5 minutes.

[0265] To the obtained mixture, 19.0 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie AG, viscosity 100 mPa-s) as (a2), 29.5 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie AG, viscosity 200 mPa-s) as (al), 65.9 g of a polyorganosiloxane (manufactured by Wacker Chemie AG, trade name AK1000000, viscosity 1000000 mm 2 / s) as (B), and 0.41 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie AG) as (A3) were added, and further stirred in a self-rotating and revolving stirrer for 5 minutes.

[0266] Subsequently, to the obtained mixture, a mixture 14.9 g obtained by stirring a platinum catalyst (Wacker Chemie Co., Ltd.) 0.20 g as (A2) and a linear vinyl group-containing dimethylsiloxane (Wacker Chemie Co., Ltd.) 17.7 g having a viscosity of 1000 mPa-s as (al) in a homomixer for 5 minutes was added, and the mixture was further stirred in the homomixer for 5 minutes. The obtained mixture was filtered with a nylon filter 300 mesh to obtain an adhesive composition.

[0267] [Preparation Example 2]

[0268] To a 600 mL stirring container for a homomixer, an MQ resin (Wacker Chemie Co., Ltd.) 80 g containing polysiloxane and a vinyl group as (al), a linear SiH group-containing dimethylsiloxane (Wacker Chemie Co., Ltd.) 2.52 g having a viscosity of 100 mPa-s as (a2), a linear SiH group-containing dimethylsiloxane (Wacker Chemie Co., Ltd.) 5.89 g having a viscosity of 70 mPa-s as (a2), and 1-ethynyl-1-cyclohexanol (Wacker Chemie Co., Ltd.) 0.22 g as (A3) were added, and the mixture was stirred in the homomixer for 5 minutes.

[0269] To the obtained mixture, a mixture 3.96 g obtained by stirring a platinum catalyst (Wacker Chemie Co., Ltd.) 0.147 g as (A2) and a linear vinyl group-containing dimethylsiloxane (Wacker Chemie Co., Ltd.) 5.81 g having a viscosity of 1000 mPa-s as (al) in the homomixer for 5 minutes was added, and the mixture was stirred in the homomixer for 5 minutes.

[0270] Finally, the obtained mixture was filtered with a nylon filter 300 mesh to obtain an adhesive composition.

[0271] [2] Production of a substrate for evaluation

[0272] [Manufacture Example 1]

[0273] On a 4 cm x 4 cm Si wafer (thickness 775 μm) as a device side wafer, the composition obtained in Preparation Example 1 was coated by a spin coater, a heated plate was used, and the wafer was heated at 120°C for 1.5 minutes and then at 200°C for 10 minutes, to form a thin film having a thickness of 60 μm on the wafer, to obtain a wafer with an adhesive layer.

[0274] [Manufacture Example 2]

[0275] On a 4 cm x 4 cm Si wafer (thickness 775 μm) as a device side wafer, the composition obtained in Preparation Example 2 was coated by a spin coater, and a thin film having a thickness of 60 μm was formed on the wafer by heating at 2000C for 10 minutes using a hot plate, to obtain a wafer with an adhesive layer.

[0276] [Production Example 3]

[0277] The substrate with bumps was cut to prepare a 4 cm x 4 cm sample substrate. Note that the number of bumps of each sample substrate was 5044, and the columnar portion was copper, the cap portion was tin-silver (silver 1.8 mass%), and the portion between the columnar portion and the cap portion was nickel, in terms of the structure of the bumps.

[0278] [3] Measurement of Peeling Time

[0279] [Example 1]

[0280] The wafer with an adhesive layer produced in Production Example 1 was immersed in 9 mL of di(n-butyl) ether of Example 1 as a peeling composition, and the time until the adhesive layer started to peel from the wafer was measured to be 11 seconds.

[0281] [Example 2]

[0282] The wafer with an adhesive layer produced in Production Example 1 was immersed in 9 mL of n-decane of Example 2 as a peeling composition, and the time until the adhesive layer started to peel from the wafer was measured to be 18 seconds.

[0283] [Example 3]

[0284] The wafer with an adhesive layer produced in Production Example 1 was immersed in 9 mL of di(n-pentyl) ether of Example 3 as a peeling composition, and the time until the adhesive layer started to peel from the wafer was measured to be 23 seconds.

[0285] [Example 4]

[0286] The wafer with an adhesive layer produced in Production Example 1 was immersed in 9 mL of 1-amino-n-pentane of Example 4 as a peeling composition, and the time until the adhesive layer started to peel from the wafer was measured to be 12 seconds.

[0287] [Example 5]

[0288] The wafer with an adhesive layer produced in Production Example 1 was immersed in 9 mL of p-menthane of Example 5 as a peeling composition, and the time until the adhesive layer started to peel from the wafer was measured to be 22 seconds.

[0289] [Example 6]

[0290] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of cyclohexane of Example 7 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 11 seconds.

[0291] [Example 7]

[0292] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of cyclohexane of Example 7 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 11 seconds.

[0293] [Example 8]

[0294] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of di(n-propyl)sulfide of Example 8 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 12 seconds.

[0295] [Example 9]

[0296] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of amyl acetate of Example 9 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 21 seconds.

[0297] [Example 10]

[0298] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of di(n-butyl)sulfide of Example 10 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 22 seconds.

[0299] [Example 11]

[0300] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of mesitylene of Example 11 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 18 seconds.

[0301] [Example 12]

[0302] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of limonene of Example 12 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 18 seconds.

[0303] [Example 13]

[0304] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of p-cymene of Example 13 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 18 seconds.

[0305] [Comparative Example 1]

[0306] The wafer with the adhesive layer produced in Production Example 1 was immersed in n-octyl-l-amine 9 mL of Comparative Example 1 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 34 seconds.

[0307] [Comparative Example 2]

[0308] The wafer with the adhesive layer produced in Production Example 1 was immersed in cyclooctane 9 mL of Comparative Example 2 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 40 seconds.

[0309] [Comparative Example 3]

[0310] The wafer with the adhesive layer produced in Production Example 1 was immersed in heptyl acetate 9 mL of Comparative Example 3 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 38 seconds.

[0311] [Comparative Example 4]

[0312] The wafer with the adhesive layer produced in Production Example 1 was immersed in 5-nonanone 9 mL of Comparative Example 4 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 36 seconds.

[0313] [Comparative Example 5]

[0314] The wafer with the adhesive layer produced in Production Example 1 was immersed in 1,4-diisopropylbenzene 9 mL of Comparative Example 5 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 44 seconds.

[0315] [Comparative Example 6]

[0316] The wafer with the adhesive layer produced in Production Example 1 was immersed in octyl acetate 9 mL of Comparative Example 6 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 51 seconds.

[0317] [Comparative Example 7]

[0318] The wafer with the adhesive layer produced in Production Example 1 was immersed in n-dodecane 9 mL of Comparative Example 7 as the peeling composition, and the time until the adhesive layer started to peel from the wafer was measured, which was 44 seconds.

[0319] [Comparative Example 8]

[0320] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of 1-pentanol of Comparative Example 8 as a peeling composition, and the time until the adhesive layer started to peel from the wafer was measured. The peeling was not confirmed even after 5 minutes had elapsed.

[0321] [Comparative Example 9]

[0322] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of acetone of Comparative Example 9 as a peeling composition, and the time until the adhesive layer started to peel from the wafer was measured. The peeling was not confirmed even after 5 minutes had elapsed.

[0323] [Comparative Example 10]

[0324] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of propylene glycol monomethyl ether of Comparative Example 10 as a peeling composition, and the time until the adhesive layer started to peel from the wafer was measured. The peeling was not confirmed even after 5 minutes had elapsed.

[0325] [Comparative Example 11]

[0326] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of propylene glycol monomethyl ether acetate of Comparative Example 11 as a peeling composition, and the time until the adhesive layer started to peel from the wafer was measured. The peeling was not confirmed even after 5 minutes had elapsed.

[0327] [Comparative Example 12]

[0328] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of tetramethyl urea of Comparative Example 12 as a peeling composition, and the time until the adhesive layer started to peel from the wafer was measured. The peeling was not confirmed even after 5 minutes had elapsed.

[0329] [Comparative Example 13]

[0330] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of N-methyl pyrrolidone of Comparative Example 13 as a peeling composition, and the time until the adhesive layer started to peel from the wafer was measured. The peeling was not confirmed even after 5 minutes had elapsed.

[0331] [Comparative Example 14]

[0332] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of water of Comparative Example 14 as a peeling composition, and the time until the adhesive layer started to peel from the wafer was measured. The peeling was not confirmed even after 5 minutes had elapsed.

[0333] [4] Measurement of contact angle

[0334] The contact angle of each solvent used in the examples and comparative examples was measured by dropping each solvent on the adhesive layer of the wafer with adhesive layer produced in Production Example 2. The results are shown in Table 1 together with the molecular weight of the solvent.

[0335] [Table 1]

[0336]

[0337] The results of the examples and comparative examples, the contact angle of the peeling composition on the adhesive layer, and the molecular weight of the specific organic solvent contained in the peeling composition are shown in Tables 2 and 3.

[0338] As shown in Table 2, in the case of using a specific organic solvent, even if the organic solvent satisfies the condition of the molecular weight, the peeling time is greatly shortened in the examples in which the contact angle of the peeling composition on the adhesive layer is less than 31.5 degrees, as compared with the comparative examples in which the contact angle is 31.5 degrees or more.

[0339] Further, as shown in Table 3, in the case of using a specific organic solvent, even if the peeling composition satisfies the condition of the contact angle, the peeling time is greatly shortened in the examples in which the organic solvent satisfies the condition of the molecular weight, as compared with the comparative examples in which the condition of the molecular weight is not satisfied.

[0340] Moreover, in the case of not using a specific solvent, even if the conditions of the contact angle and the molecular weight are satisfied, a short-time peeling as in the examples is not confirmed (Comparative Examples 8 to 14).

[0341] [Table 2]

[0342]

[0343] When the relationship between the results of the examples and comparative examples and the molecular weight of the specific solvent contained in the peeling composition was investigated, as shown in Table 3, the peeling time in the case of the cleaning method of the examples using a specific solvent contained in the peeling composition having a molecular weight of less than 160 was greatly shortened as compared with the peeling time in the case of the cleaning method of the comparative examples using a specific solvent having a molecular weight of 160 or more.

[0344] [Table 3]

[0345]

[0346] [5] Confirmation of Damage to Bump

[0347] Each of the sample substrates produced in Production Example 3 was immersed in 9 mL of the peeling composition of Examples 1 to 13, and after standing for 1 hour, cleaning was performed with isopropyl alcohol and acetone, and observation was performed under an optical microscope for the presence or absence of damage to the bump. As a result, no damage to the bump was observed on any of the substrates.

Claims

1. A method for cleaning a semiconductor substrate, characterized in that, This includes the process of using a release composition to peel off the adhesive layer on a semiconductor substrate. The adhesive layer is a film obtained using an adhesive composition containing adhesive component S. The adhesive component S comprises a siloxane-based adhesive containing a polyorganosiloxane component A that is cured by a hydrogenation silanization reaction. The stripping composition contains a solvent but not a salt. The solvent comprises one or more compounds selected from aliphatic hydrocarbons, aromatic hydrocarbons, ethers, thioethers, esters, and amines with a molecular weight less than 160. The contact angle of the release composition on the adhesive layer is less than 31.5 degrees.

2. The method for cleaning a semiconductor substrate according to claim 1, wherein, The molecular weight is 70 or higher.

3. The method for cleaning a semiconductor substrate according to claim 1, wherein, The solvent comprises one or more selected from di(n-butyl) ether, n-decane, di(n-pentyl) ether, 1-amino-n-pentane, p-menthane, butyl acetate, cyclohexane, di(n-propyl) sulfide, amyl acetate, di(n-butyl) sulfide, mesitylene, limonene, and p-isopropyltoluene.

4. The method for cleaning a semiconductor substrate according to any one of claims 1 to 3, wherein, The adhesive layer further comprises at least one selected from acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.

5. A method for manufacturing a processed semiconductor substrate, characterized in that, include: The first step is to manufacture a laminate comprising a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition. The second step is to process the semiconductor substrate of the obtained laminate; The third step involves separating the semiconductor substrate and the adhesive layer from the support substrate. as well as The fourth step involves using a release composition to peel off the adhesive layer on the semiconductor substrate. The adhesive layer is a film obtained using an adhesive composition containing adhesive component S. The adhesive component S comprises a siloxane-based adhesive containing a polyorganosiloxane component A that is cured by a hydrogenation silanization reaction. The stripping composition contains a solvent but not a salt. The solvent comprises one or more compounds selected from aliphatic hydrocarbons, aromatic hydrocarbons, ethers, thioethers, esters, and amines with a molecular weight less than 160. The contact angle of the release composition on the adhesive layer is less than 31.5 degrees.

6. The method for manufacturing the processed semiconductor substrate according to claim 5, wherein, The molecular weight is 70 or higher.

7. The method for manufacturing the processed semiconductor substrate according to claim 5, wherein, The solvent comprises one or more selected from di(n-butyl) ether, n-decane, di(n-pentyl) ether, 1-amino-n-pentane, p-menthane, butyl acetate, cyclohexane, di(n-propyl) sulfide, amyl acetate, di(n-butyl) sulfide, mesitylene, limonene, and p-isopropyltoluene.

8. The method for manufacturing the processed semiconductor substrate according to any one of claims 5 to 7, wherein, The adhesive layer further comprises an adhesive component S containing at least one selected from acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.

9. A peeling composition, characterized in that, Used to peel off the adhesive layer on a semiconductor substrate during cleaning. The stripping composition contains a solvent but not a salt. The solvent comprises one or more compounds selected from aliphatic hydrocarbons, aromatic hydrocarbons, ethers, thioethers, esters, and amines with a molecular weight less than 160. The contact angle on the adhesive layer is less than 31.5 degrees. The adhesive layer is a film obtained using an adhesive composition containing adhesive component S. The adhesive component S comprises a siloxane-based adhesive containing a polyorganosiloxane component A that is cured by a hydrogenation silanization reaction.

10. The peeling composition according to claim 9, wherein, The molecular weight is 70 or higher.

11. The peeling composition according to claim 9, wherein, The solvent comprises one or more selected from di(n-butyl) ether, n-decane, di(n-pentyl) ether, 1-amino-n-pentane, p-menthane, butyl acetate, cyclohexane, di(n-propyl) sulfide, amyl acetate, di(n-butyl) sulfide, mesitylene, limonene, and p-isopropyltoluene.

12. The peeling composition according to any one of claims 9 to 11, wherein, The adhesive layer further comprises an adhesive component S containing at least one selected from acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.

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