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

Abstract

A method for cleaning a semiconductor substrate includes a step of peeling off an adhesive layer on the semiconductor substrate using a peeling composition, wherein the peeling composition comprises a solvent and is salt-free, and the solvent comprises at least 80% by mass of an organic solvent represented by formula (L). (Where L is the organic solvent represented by the formula). 1 and L 2 Each alkyl group having 1 to 6 carbon atoms is represented independently, L 1 The number of carbon atoms in the alkyl group and L 2 (The total number of carbon atoms in the alkyl groups is 6 or less.)

Description

Technical Field

[0001] This invention relates to a method for cleaning semiconductor substrates, a method for manufacturing processed semiconductor substrates, and a composition for stripping. Background Technology

[0002] In contrast to traditional semiconductor wafers integrated in a two-dimensional planar direction, semiconductor integration technology aims for further integration in a three-dimensional direction (layering). This three-dimensional layering is a technique that integrates multiple layers while simultaneously wiring through silicon vias (TSVs). During multilayer integration, grinding is used to thin the side (back side) of each integrated wafer opposite to the circuit surface, and then the thinned semiconductor wafers are stacked.

[0003] Before thinning, the semiconductor wafer (hereinafter simply referred to as the wafer) is bonded to a support for polishing using a polishing apparatus. This bonding must be easily detachable after polishing, hence the term "temporary bonding." This temporary bonding must be easily removed from the support. When large forces are applied during removal, the thinned semiconductor wafer may sometimes be cut or deformed. To avoid this, the temporary bonding must be easily detachable. However, detachment or displacement due to polishing stress during back-side polishing of the semiconductor wafer is undesirable. Therefore, the desired performance for temporary bonding is resistance to polishing stress and easy removal after polishing. For example, the following properties are desired: high stress (strong adhesion) relative to the planar direction during polishing and low stress (weak adhesion) relative to the longitudinal direction intersecting the planar direction during removal. Furthermore, since the processing steps sometimes involve temperatures exceeding 150°C, heat resistance is also required.

[0004] In this context, polysiloxane-based adhesives, possessing these properties, are primarily used as temporary adhesives in the semiconductor field. Furthermore, in polysiloxane-based bonding using polysiloxane adhesives, adhesive residue often remains on the substrate surface after the thinned substrate is peeled off. To avoid defects in subsequent processes, cleaning agent compositions have been developed to remove this residue and clean the semiconductor substrate surface (e.g., Patent Documents 1 and 2). Patent Document 1 discloses a remover for siloxane resins comprising a polar aprotic solvent and quaternary ammonium hydroxide, while Patent Document 2 discloses a remover for cured resins comprising fluorinated alkyl / ammonium compounds. However, in the recent semiconductor field, there has consistently been a demand for new cleaning agent compositions and effective cleaning methods.

[0005] On the other hand, semiconductor wafers are electrically connected to semiconductor chips by means of bump balls, for example, made of conductive materials of metal. By using chips with such bump balls, miniaturization of semiconductor packaging is achieved.

[0006] In this regard, bump balls formed from metals such as copper and tin lack corrosion resistance, and therefore there is a problem that the cleaning agent composition used to remove adhesive residues from the support and wafer is damaged (Patent Document 3). As one of the requirements of the cleaning agent composition and cleaning method, it can be listed that the bump balls are not corroded when cleaning the substrate.

[0007] Existing technical documents

[0008] Patent documents

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

[0010] Patent Document 2: US Patent No. 6,818,608

[0011] Patent Document 3: Korean Patent Publication No. 2018-0066550 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] The present invention was made in view of the above circumstances, and its object is to provide a method for cleaning a semiconductor substrate, a method for manufacturing a processed semiconductor substrate including such a cleaning method, and a peeling composition for such a cleaning method, the semiconductor substrate cleaning method being used to properly and easily remove an adhesive layer from a semiconductor substrate having an adhesive layer on its surface obtained using, for example, a siloxane-based adhesive, while reducing or suppressing damage to the bumps of the semiconductor substrate.

[0014] Solution for solving the problem

[0015] In order to solve the above-mentioned problems, the inventors conducted repeated and in-depth research and discovered the following facts, thereby completing the present invention: by using a stripping composition containing a specified amount or more of a specified ester compound as a solvent and free of salt, damage to the bumps of a semiconductor substrate can be reduced or suppressed, and the adhesive layer on the semiconductor substrate can be stripped efficiently and easily, especially the cured film, i.e., the adhesive layer, obtained by a siloxane-based adhesive containing a polyorganosiloxane component (A) that is cured by a hydrogenated silanization reaction.

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

[0017] 1. A method for cleaning a semiconductor substrate, characterized in that it includes a step of using a stripping composition to strip an adhesive layer on the semiconductor substrate, the stripping composition comprising a solvent and being salt-free, the solvent comprising at least 80% by mass of an organic solvent represented by formula (L).

[0018]

[0019] (where L) 1 and L 2 Each alkyl group having 1 to 6 carbon atoms is represented independently, L 1 The number of carbon atoms in the alkyl group and L 2 (The total number of carbon atoms in the alkyl groups is 6 or less.)

[0020] 2. The method for cleaning a semiconductor substrate according to 1, wherein the solvent comprises 85% by mass or more of the organic solvent represented by the formula (L).

[0021] 3. The method for cleaning a semiconductor substrate according to 2, wherein the solvent is composed of an organic solvent represented by the formula (L).

[0022] 4. A method for cleaning a semiconductor substrate according to any one of 1 to 3, wherein the L 1 It is a methyl group.

[0023] 5. The semiconductor substrate cleaning method according to 4, wherein the L 2 It is either butyl or pentyl.

[0024] 6. A method for cleaning a semiconductor substrate according to any one of 1 to 5, characterized in that the adhesive layer is a film obtained using an adhesive composition comprising an adhesive component (S), wherein the adhesive component (S) comprises at least one selected from siloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenolic resin-based adhesives.

[0025] 7. The method for cleaning a semiconductor substrate according to 6, wherein the adhesive component (S) comprises a siloxane-based adhesive.

[0026] 8. The method for cleaning a semiconductor substrate according to 7, wherein the siloxane-based adhesive comprises a polyorganosiloxane component (A) cured by a hydrogenation silanization reaction.

[0027] 9. A method for manufacturing a processed semiconductor substrate, characterized in that it comprises: 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 off the adhesive layer on the semiconductor substrate using a peeling composition, wherein the peeling composition comprises a solvent and is salt-free, and the solvent comprises at least 80% by mass of an organic solvent represented by formula (L).

[0028]

[0029] (where L) 1 and L 2 Each alkyl group having 1 to 6 carbon atoms is represented independently, L 1 The number of carbon atoms in the alkyl group and L 2 (The total number of carbon atoms in the alkyl groups is 6 or less.)

[0030] 10. The method for manufacturing the processed semiconductor substrate according to 9, wherein the solvent comprises 85% by mass or more of the organic solvent represented by the formula (L).

[0031] 11. The method for manufacturing the processed semiconductor substrate according to 10, wherein the solvent is composed of an organic solvent represented by the formula (L).

[0032] 12. A method for manufacturing a processed semiconductor substrate according to any one of claims 9 to 11, wherein the L 1 It is a methyl group.

[0033] 13. The method for manufacturing the processed semiconductor substrate according to 12, wherein the L 2 It is either butyl or pentyl.

[0034] 14. A method for manufacturing a processed semiconductor substrate according to any one of 9 to 13, characterized in that the adhesive layer is a film obtained using an adhesive composition comprising an adhesive component (S), wherein the adhesive component (S) comprises at least one selected from siloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenolic resin-based adhesives.

[0035] 15. The method for manufacturing the processed semiconductor substrate according to 14, wherein the adhesive component (S) comprises a siloxane-based adhesive.

[0036] 16. The method for manufacturing a processed semiconductor substrate according to 15, wherein the siloxane-based adhesive comprises a polyorganosiloxane component (A) cured by a hydrogenation silanization reaction.

[0037] 17. A stripping composition, characterized in that it is used to strip an adhesive layer on a semiconductor substrate during cleaning, the stripping composition comprising a solvent and being salt-free, the solvent comprising at least 80% by mass of an organic solvent represented by formula (L).

[0038]

[0039] (where L) 1 and L 2 Each alkyl group having 1 to 6 carbon atoms is represented independently, L 1 The number of carbon atoms in the alkyl group and L 2 (The total number of carbon atoms in the alkyl groups is 6 or less.)

[0040] 18. The stripping composition according to 17, wherein the solvent comprises more than 85% by mass of an organic solvent represented by the formula (L).

[0041] 19. The stripping composition according to 18, wherein the solvent is composed of an organic solvent represented by the formula (L).

[0042] 20. The peeling composition according to any one of 17 to 19, wherein the L 1 It is a methyl group.

[0043] 21. The peeling composition according to 20, wherein the L 2 It is either butyl or pentyl.

[0044] 22. The peeling composition according to any one of 17 to 21, characterized in that the adhesive layer is a film obtained using an adhesive composition comprising an adhesive component (S), wherein the adhesive component (S) comprises at least one selected from siloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenolic resin-based adhesives.

[0045] 23. The peeling composition according to 22, wherein the adhesive component (S) comprises a siloxane-based adhesive.

[0046] 24. The peeling composition according to 23, wherein the siloxane-based adhesive comprises a polyorganosiloxane component (A) cured by a hydrogenation silanization reaction.

[0047] Invention Effects

[0048] By using the cleaning method of the semiconductor substrate of the present invention, the adhesive layer having an adhesive layer obtained by using, for example, a siloxane-based adhesive can be properly and easily removed from the semiconductor substrate, thereby enabling the manufacture of highly efficient and good semiconductor devices.

[0049] In particular, when a semiconductor substrate with an adhesive layer has bumps, damage to the bumps can be avoided or suppressed, and the adhesive layer can be removed properly and easily. Therefore, the manufacture of high-efficiency, high-reliability, and high-quality semiconductor devices can be expected. Detailed Implementation

[0050] The semiconductor substrate cleaning method of the present invention includes a step of peeling off an adhesive layer on the semiconductor substrate using a peeling composition, wherein the peeling composition contains a solvent and is salt-free, and the solvent contains 80% by mass or more of an organic solvent represented by formula (L).

[0051]

[0052] Semiconductor substrates are, for example, wafers. Specific examples include silicon wafers with a diameter of 300 mm and a thickness of about 770 μm, but they are not limited to this.

[0053] The adhesive layer on the semiconductor substrate is, for example, a film obtained from an adhesive composition containing an adhesive component (S).

[0054] Such adhesive component (S) is not particularly limited as long as it is an adhesive component used for this purpose. Examples include siloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, phenolic resin-based adhesives, etc.

[0055] Among these considerations, considering that it exhibits appropriate adhesion during wafer processing, can be properly peeled off after processing, and has excellent heat resistance, siloxane-based adhesives are preferred as adhesive component (S).

[0056] In a preferred embodiment, the adhesive composition used in this invention comprises a polyorganosiloxane component (A) cured by a hydrosilylation reaction as an adhesive component. In a more preferred embodiment, the polyorganosiloxane component (A) cured by a hydrosilylation reaction comprises a polysiloxane (A1) and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) comprises siloxane units (Q units) selected from SiO2 and R... 1 R 2 R 3 SiO 1 / 2 The siloxane unit (M unit) and R represented are... 4 R 5 SiO2 / 2 The siloxane unit (D unit) and R are represented 6 SiO 3 / 2 The polysiloxane (A1) comprises one or more units from the group consisting of the siloxane units (T units) represented by the polysiloxane (A1), and the polysiloxane (A2) comprises polyorganosiloxane (A1) and polyorganosiloxane (A2), wherein the polyorganosiloxane (A1) comprises siloxane units (Q' units) selected from those represented by SiO2 and R. 1 'R 2 'R 3 'SiO 1 / 2 The siloxane unit (M' unit) and R are represented by 4 'R 5 'SiO 2 / 2 The siloxane unit (D' unit) and R are represented 6 'SiO 3 / 2 The polyorganosiloxane (a2) comprises one or more units selected from the group consisting of the siloxane units (T' units) represented by the term, and includes at least one unit selected from the group consisting of the M' unit, D' unit, and T' unit described above. 1 "R 2 "R 3 "SiO" 1 / 2 The siloxane unit (M” unit) and R are represented by 4 "R 5 "SiO" 2 / 2 The siloxane unit (D” unit) and R are represented 6 "SiO" 3 / 2 The siloxane unit (T” unit) represents one or more units from the group consisting of the siloxane unit (T” unit) and includes at least one unit selected from the group consisting of the M” unit, D” unit and T” unit.

[0057] R 1 ~R 6 The groups or atoms bonded to silicon atoms are represented independently as alkyl, alkenyl, or hydrogen atoms, respectively.

[0058] R 1 '~R 6 'A group bonded to a silicon atom, independently representing either alkyl or alkenyl groups, but R 1 '~R 6 At least one of them is an alkenyl group.

[0059] R 1 "~R 6 "The group or atom bonded to the silicon atom is represented independently by an alkyl group or a hydrogen atom, but R..." 1 "~R 6At least one of the elements is a hydrogen atom.

[0060] The alkyl group can be any of straight-chain, branched, or cyclic, preferably straight-chain or branched alkyl groups. The number of carbon atoms is not particularly limited, usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0061] 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.

[0062] Among them, methyl is preferred.

[0063] Specific examples of cyclic alkyl groups include: cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl Cycloalkyl groups such as 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 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, as well as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, dicyclodecyl, etc., but not limited to these.

[0064] The alkenyl group can be either linear or branched, and its number of carbon atoms is not particularly limited, usually ranging from 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0065] Specific examples of alkenyl groups include: vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 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-isopropylvinyl, 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-butylvinyl, 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-butylvinyl, 1,3-di Methyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-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 The range includes, but is not limited to, methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylenecyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylenecyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl.

[0066] Among them, vinyl and 2-propylene groups are preferred.

[0067] As described above, polysiloxane (A1) comprises polyorganosiloxane (a1) and polyorganosiloxane (a2). The alkenyl group contained in polyorganosiloxane (a1) and the hydrogen atoms (Si-H groups) contained in polyorganosiloxane (a2) are cured by forming a cross-linked structure through a hydrosilylation reaction based on a platinum group metal catalyst (A2).

[0068] The polyorganosiloxane (a1) comprises one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and comprises at least one unit selected from the group consisting of the aforementioned M' units, D' units, and T' units. Two or more polyorganosiloxanes satisfying this condition may also be used in combination as the polyorganosiloxane (a1).

[0069] Examples of preferred combinations of two or more selected from the group consisting of Q' unit, M' unit, D' unit and T' unit include: (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit and M' unit), but are not limited to these.

[0070] Furthermore, when the polyorganosiloxane contained in two or more polyorganosiloxanes (a1) is included, combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but not limited thereto.

[0071] The polyorganosiloxane (a2) comprises one or more units selected from the group consisting of Q” units, M” units, D” units and T” units, and comprises at least one unit selected from the group consisting of the aforementioned M” units, D” units and T” units. As the polyorganosiloxane (a2), two or more polyorganosiloxanes satisfying such conditions may also be used in combination.

[0072] As a preferred combination of two or more selected from the group consisting of Q” unit, M” unit, D” unit and T” unit, examples include: (M” unit and D” unit), (Q” unit and M” unit), (Q” unit, T” unit and M” unit), but it is not limited to these.

[0073] Polyorganosiloxanes (a1) are composed of siloxane units formed by the bonding of silicon atoms with alkyl and / or alkenyl groups, but R 1 '~R 6 The proportion of alkenyl groups in all the substituents shown is preferably 0.1 mol% to 50.0 mol%, more preferably 0.5 mol% to 30.0 mol%, with the remainder being R. 1 '~R 6 'It can be set as an alkyl group.'

[0074] Polyorganosiloxanes (a2) are composed of siloxane units formed by the bonding of silicon atoms with alkyl and / or hydrogen atoms, but R 1 "~R 6 The proportion of hydrogen atoms in all substituents and substituted atoms shown is preferably 0.1 mol% to 50.0 mol%, more preferably 10.0 mol% to 40.0 mol%, with the remainder being R. 1 "~R 6 "It can be set as an alkyl group."

[0075] Polysiloxane (A1) comprises polyorganosiloxane (a1) and polyorganosiloxane (a2). In a preferred embodiment, the molar ratio of the alkenyl group contained in polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bond contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0076] The weight-average molecular weights of polyorganosiloxane (a1) and polyorganosiloxane (a2) are typically 500 to 1,000,000, and preferably 5,000 to 50,000 from the viewpoint of achieving the effects of the present invention with good reproducibility.

[0077] It should be noted that the weight-average molecular weight, number-average molecular weight, and dispersity in this invention can be determined using, for example, a GPC apparatus (Tosoh EcoSEC, HLC-8320GPC) and a GPC column (Tosoh TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H), with the column temperature set to 40°C, tetrahydrofuran used as the eluent (dissolution solvent), the flow rate set to 0.35 mL / min, and polystyrene (Sigma-Aldrich) used as the standard sample.

[0078] The viscosities of the polyorganosiloxane (a1) and polyorganosiloxane (a2) are typically 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 invention with good reproducibility. It should be noted that the viscosity values ​​in this invention are measured using an E-type rotational viscometer at 25°C.

[0079] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other to form a film via a hydrosilylation reaction. Therefore, its curing mechanism is different from that of, for example, via silanol groups. Thus, any siloxane does not need to contain silanol groups or functional groups such as alkyloxy groups that form silanol groups through hydrolysis.

[0080] In a preferred embodiment, the adhesive component (S) comprises the aforementioned polysiloxane (A1) and platinum group metal catalyst (A2).

[0081] Such platinum group metal catalysts are used to promote the hydrosilylation reaction of the alkenyl group of polyorganosiloxane (a1) with the Si-H group of polyorganosiloxane (a2).

[0082] Specific examples of platinum group metal catalysts include: platinum black, platinum tetrachloride, chloroplatinic acid, the reaction product of chloroplatinic acid and a monohydric alcohol, the complex of chloroplatinic acid and an olefin, and platinum diacetate, but are not limited to these.

[0083] Examples of platinum complexes with alkenes include, but are not limited to, complexes of divinyltetramethyldisiloxane with platinum.

[0084] Typically, the amount of platinum group metal catalyst (A2) is in the range of 1.0 ppm to 50.0 ppm relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2).

[0085] The polyorganosiloxane component (A) is intended to inhibit the hydrosilylation reaction and may also contain a polymerization inhibitor (A3).

[0086] There are no particular limitations on polymerization inhibitors as long as they can inhibit the hydrosilylation reaction. Specific examples include 1-ethynyl-1-cyclohexanol, 1,1-diphenyl-2-propynyl-1-ol, and other alkynyl alcohols.

[0087] From the perspective of achieving the desired effect, the amount of polymerization inhibitor is usually above 1000.0 ppm relative to the combined amount of polyorganosiloxane (a1) and polyorganosiloxane (a2), while from the perspective of preventing excessive inhibition of the hydrosilanization reaction, the amount of polymerization inhibitor is below 10000.0 ppm.

[0088] The adhesive composition used in this invention may also contain a release agent component (B). By including such a release agent component (B) in the adhesive composition used in this invention, the obtained adhesive layer can be reproducibly and appropriately peeled off.

[0089] As such a stripping agent component (B), typically, polyorganosiloxanes can be listed, and specific examples include: epoxy-containing polyorganosiloxanes, methyl-containing polyorganosiloxanes, phenyl-containing polyorganosiloxanes, etc., but are not limited to these.

[0090] The weight-average molecular weight of the polyorganosiloxane used as the stripping agent component (B) is typically 100,000 to 2,000,000, but from the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000. Its dispersity is typically 1.0 to 10.0, but from the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. It should be noted that the weight-average molecular weight and dispersity can be determined by the methods described above.

[0091] As epoxy-containing polyorganosiloxanes, examples include those containing R 11 R 12 SiO 2 / 2 The siloxane unit (D) represents 10 Polyorganosiloxane (unit).

[0092] R 11 The group that bonds to silicon atoms represents an alkyl group, R. 12 The group that bonds to silicon atoms represents an epoxy group or an organic group containing an epoxy group. Specific examples of alkyl groups can be listed above.

[0093] In addition, the epoxy group in an organic group containing an epoxy group can be an independent epoxy group that does not condense with other rings, or it can be an epoxy group that forms a condensed ring with other rings, such as 1,2-epoxycyclohexyl.

[0094] Specific examples of organic groups containing epoxy groups include 3-epoxypropoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl, but are not limited to these.

[0095] In this invention, as a preferred example of an epoxy-containing polyorganosiloxane, an epoxy-containing polydimethylsiloxane can be listed, but it is not limited thereto.

[0096] Epoxy-containing polyorganosiloxanes comprise the aforementioned siloxane units (D 10 (unit), but except for D 10 In addition to the unit, it may also include the above-mentioned Q unit, M unit and / or T unit.

[0097] In preferred embodiments, specific examples of epoxy-containing polyorganosiloxanes include: those derived from D 10 Polyorganosiloxanes composed of units containing D 10 Polyorganosiloxanes containing D and Q units 10 Polyorganosiloxanes containing D and M units 10 Polyorganosiloxanes containing D and T units 10 Polyorganosiloxanes containing D, Q, and M units 10 Polyorganosiloxanes containing D, M, and T units 10 Polyorganosiloxanes with units such as Q-unit, M-unit, and T-unit.

[0098] The epoxy-containing polyorganosiloxane is preferably an epoxy-containing polydimethylsiloxane with an epoxy value of 0.1 to 5, and its weight-average molecular weight is usually 1,500 to 500,000, but from the viewpoint of inhibiting precipitation in the adhesive composition, its weight-average molecular weight is preferably 100,000 or less.

[0099] Specific examples of epoxy-containing polyorganosiloxanes include: CMS-227 (manufactured by Gelest Corporation, weight average molecular weight 27,000), represented by formula (A-1); ECMS-327 (manufactured by Gelest Corporation, weight average molecular weight 28,800), represented by formula (A-2); and KF-101 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 31,800), represented by formula (A-3). Trade names represented by (A-4) include KF-1001 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 55600), KF-1005 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 11500), X-22-343 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 2400), BY16-839 (manufactured by Dow Corning Co., Ltd., weight average molecular weight 51700), and ECMS-327 (manufactured by Gelest Co., Ltd., weight average molecular weight 28800), but are not limited to these.

[0100]

[0101] (m and n are the number of repeating units, respectively.)

[0102]

[0103] (m and n are the number of repeating units, respectively.)

[0104]

[0105] (m and n represent the number of repeating units, respectively. R represents an alkylene group with 1 to 10 carbon atoms.)

[0106]

[0107] (m and n represent the number of repeating units, respectively. R represents an alkylene group with 1 to 10 carbon atoms.)

[0108]

[0109] (m, n, and o represent the number of repeating units, respectively. R represents an alkylene group with 1 to 10 carbon atoms.)

[0110]

[0111] (m and n represent the number of repeating units, respectively. R represents an alkylene group with 1 to 10 carbon atoms.)

[0112]

[0113] (m and n represent the number of repeating units, respectively. R represents an alkylene group with 1 to 10 carbon atoms.)

[0114]

[0115] (m and n are the number of repeating units, respectively.)

[0116] As methyl-containing polyorganosiloxanes, examples include those containing R 210 R 220 SiO 2 / 2 The siloxane unit (D) represents 200 (unit), preferably containing R 21 R 21 SiO 2 / 2 The siloxane unit (D) represents 20 Polyorganosiloxane (unit).

[0117] R 210 and R 220 The groups bonded to silicon atoms are each independently represented as alkyl groups, but at least one of them is methyl. The examples above can be listed as specific examples of alkyl groups.

[0118] R 21 The group that bonds to a silicon atom is represented by an alkyl group, and the examples above can be cited as specific examples of alkyl groups. Wherein, as R 21 Methyl group is preferred.

[0119] As a preferred example of a methyl-containing polyorganosiloxane, polydimethylsiloxane can be listed, but is not limited thereto.

[0120] Methyl-containing polyorganosiloxanes contain the aforementioned siloxane units (D... 200 Unit or D 20 (unit), but except for D 200 Unit and D 20 In addition to the unit, it may also include the aforementioned Q unit, M unit and / or T unit.

[0121] In a particular scheme, as a specific example of a methyl-containing polyorganosiloxane, the following can be listed: [The following is a list of examples of polyorganosiloxanes containing D...] 200 Polyorganosiloxanes composed of units containing D 200 Polyorganosiloxanes containing D and Q units 200 Polyorganosiloxanes containing D and M units 200 Polyorganosiloxanes containing D and T units 200 Polyorganosiloxanes containing D, Q, and M units 200 Polyorganosiloxanes containing D, M, and T units 200Polyorganosiloxanes with units of Q, M, and T.

[0122] In preferred embodiments, specific examples of methyl-containing polyorganosiloxanes include: those derived from D 20 Polyorganosiloxanes composed of units containing D 20 Polyorganosiloxanes containing D and Q units 20 Polyorganosiloxanes containing D and M units 20 Polyorganosiloxanes containing D and T units 20 Polyorganosiloxanes containing D, Q, and M units 20 Polyorganosiloxanes containing D, M, and T units 20 Polyorganosiloxanes with units of Q, M, and T.

[0123] The viscosity of methyl-containing polyorganosiloxanes is typically 1,000–2,000,000 mm. 2 / s, preferably 10000~1000000mm 2 / s. It should be noted that, typically, methyl-containing polyorganosiloxanes are dimethyl silicone oils composed of polydimethylsiloxane. Their viscosity is expressed as kinematic viscosity, cSt = mm. 2 kinematic viscosity can be measured using a kinematic viscometer. Alternatively, viscosity (mPa·s) can be divided by density (g / cm³). 3 The viscosity can be determined from the viscosity and density measured at 25°C using a type E rotational viscometer. The kinematic viscosity (mm) can be calculated from this. 2 / s) = viscosity (mPa·s) / density (g / cm³) 3 The formula is used to calculate the result.

[0124] Specific examples of methyl-containing polyorganosiloxanes include the WACKERSILICONE FLUID AK series manufactured by Wacker Chemie, dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) and cyclic dimethyl silicone oils (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd., but are not limited to these.

[0125] As phenyl-containing polyorganosiloxanes, examples include those containing R 31 R 32 SiO 2 / 2 The siloxane unit (D) represents 30 Polyorganosiloxane (unit).

[0126] R 31The group that bonds to silicon atoms represents a phenyl or alkyl group, R. 32 The group that bonds to silicon atoms is represented by phenyl. Specific examples of alkyl groups can be listed above, with methyl being preferred.

[0127] Phenyl-containing polyorganosiloxanes include the aforementioned siloxane units (D... 30 (unit), but except for D 30 In addition to the unit, it may also include the aforementioned Q unit, M unit and / or T unit.

[0128] In preferred embodiments, specific examples of phenyl-containing polyorganosiloxanes include: those derived from D 30 Polyorganosiloxanes composed of units containing D 30 Polyorganosiloxanes containing D and Q units 30 Polyorganosiloxanes containing D and M units 30 Polyorganosiloxanes containing D and T units 30 Polyorganosiloxanes containing D, Q, and M units 30 Polyorganosiloxanes containing D, M, and T units 30 Polyorganosiloxanes with units of Q, M, and T.

[0129] The weight-average molecular weight of phenyl-containing polyorganosiloxanes is typically 1,500 to 500,000, but from the viewpoint of inhibiting precipitation in adhesive compositions, it is preferably 100,000 or less.

[0130] Specific examples of phenyl-containing polyorganosiloxanes include: PMM-1043 (manufactured by Gelest, Inc., represented by formula (C-1), with a weight-average molecular weight of 67,000 and a viscosity of 30,000 mmHg), which has a weight-average molecular weight of 67,000 and a viscosity of 30,000 mmHg. 2 / s), the trade name PMM-1025 represented by formula (C-2) (manufactured by Gelest, Inc., with a weight-average molecular weight of 25200 and a viscosity of 500 mm). 2 / s), the trade name KF50-3000CS represented by formula (C-3) (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 39400, viscosity 3000 mm). 2 / s), the trade name TSF431 represented by formula (C-4) (manufactured by MOMENTIVE, weight average molecular weight 1800, viscosity 100mm), 2 / s), the trade name TSF433 represented by formula (C-5) (manufactured by MOMENTIVE, weight average molecular weight 3000, viscosity 450 mm). 2 / s), the trade name PDM-0421 (manufactured by Gelest, Inc., weight average molecular weight 6200, viscosity 100 mm) represented by formula (C-6), is used. 2 / s), the trade name PDM-0821 (manufactured by Gelest, Inc., weight average molecular weight 8600, viscosity 125 mm) represented by formula (C-7). 2 (s), etc., but not limited to this.

[0131]

[0132] (m and n represent the number of repeating units.)

[0133]

[0134] (m and n represent the number of repeating units.)

[0135]

[0136] (m and n represent the number of repeating units.)

[0137]

[0138] (m and n represent the number of repeating units.)

[0139]

[0140] (m and n represent the number of repeating units.)

[0141]

[0142] (m and n represent the number of repeating units.)

[0143]

[0144] (m and n represent the number of repeating units.)

[0145] In a preferred embodiment, the adhesive composition used in this invention comprises a polyorganosiloxane component (A) cured by a hydrosilanization reaction and a release agent component (B). In a more preferred embodiment, the release agent component (B) comprises a polyorganosiloxane.

[0146] The adhesive composition used in this invention may contain adhesive component (S) and release agent component (B) in any ratio. Considering the balance between adhesion and release properties, the ratio of component (S) to component (B) by mass is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0147] That is, when the polyorganosiloxane component (A) is included and cured by the hydrosilanization reaction, the ratio of component (A) to component (B) by mass is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0148] The adhesive composition used in this invention may contain solvents for purposes such as viscosity adjustment. Specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but it is not limited to these.

[0149] More specifically, examples include: hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthol, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc., but are not limited to these. Such solvents can be used alone or in combination of two or more.

[0150] When the adhesive composition used in this invention contains a solvent, its content can be appropriately set taking into account the desired viscosity of the composition, the coating method used, the thickness of the film produced, etc., and is in the range of about 10 to 90% by mass relative to the total composition.

[0151] The viscosity of the adhesive composition used in this invention is typically 500–20000 mPa·s at 25°C, preferably 1000–5000 mPa·s. The viscosity of the adhesive composition used in this invention can be adjusted by considering various factors such as the coating method used, the desired film thickness, and by changing the type of organic solvent used, their ratio, and the concentration of film components.

[0152] In this invention, the membrane constituents refer to components other than solvents contained in the composition.

[0153] The adhesive composition used in this invention can be manufactured by mixing an adhesive component (S), a release agent component (B) used in the case of use, and a solvent.

[0154] The mixing order is not particularly limited. As an example of a method for easily and reproducibly producing an adhesive composition, examples include: dissolving the adhesive component (S) and the release agent component (B) in a solvent; dissolving a portion of the adhesive component (S) and the release agent component (B) in a solvent, dissolving the remainder in a solvent, and mixing the resulting solutions. However, this method is not limited to these methods. It should be noted that, during the preparation of the adhesive composition, appropriate heating may be applied within a range that does not cause the components to decompose or deteriorate.

[0155] In this invention, for the purpose of removing foreign matter, filtration may be performed using a submicron-sized filter or the like during the manufacturing of the adhesive composition or after all the components have been mixed.

[0156] As described above, the cleaning method for the semiconductor substrate of the present invention includes a step of using a stripping composition to strip the adhesive layer on the semiconductor substrate, wherein the stripping composition contains a solvent and is salt-free, and the solvent contains 80% by mass or more of an organic solvent represented by formula (L).

[0157] Here, the organic solvent represented by formula (L) can be a single type or two or more types.

[0158] In the above formula (L), L 1 and L 2 Each alkyl group having 1 to 6 carbon atoms is represented independently, L 1 The number of carbon atoms in the alkyl group and L 2 The total number of carbon atoms in the alkyl groups is 6 or less. By setting this number of carbon atoms, the adhesive layer can be peeled off with good reproducibility in a short time.

[0159] The alkyl group can be any of the following: straight-chain, branched, or cyclic, preferably straight-chain or branched, and more preferably straight-chain alkyl.

[0160] 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.

[0161] Specific examples of cyclic alkyl groups include: cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2 Cycloalkyl groups, including 2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 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, etc., but not limited to these.

[0162] From the perspective of achieving reproducibility and faster peeling of the adhesive layer, the above-mentioned L 1 Preferably methyl, in addition, the above-mentioned L 2 Butyl or pentyl are preferred.

[0163] From the viewpoints of achieving reproducibility and faster peeling of the adhesive layer, and from the viewpoints of the ease of obtaining the compound, butyl acetate, amyl acetate, etc., can be listed as preferred examples of the organic solvent represented by formula (L).

[0164] The stripping composition used in this invention does not contain salt.

[0165] As specific examples of such salts, those used for this purpose can be listed, typically ammonium salts such as tetrabutylammonium hydroxide and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride) added for the purpose of promoting the removal of adhesive layers and adhesive layer residues.

[0166] The stripping composition used in this invention contains an organic solvent represented by formula (L), and therefore does not need to contain such a salt.

[0167] Such salts can cause corrosion and other damage to the substrate, especially the substrate with bumps. Therefore, in this invention, a salt-free stripping composition is used. However, the presence of trace amounts of salt as an impurity in the solvent constituting the bulk of the stripping composition is not negated.

[0168] In the peeling composition used in this invention, the content of the organic solvent represented by the above formula (L) in the solvent is 80% by mass or more, preferably 85% by mass or more, more preferably 87% by mass or more, and even more preferably 89% by mass or more. By setting the content of the organic solvent represented by the above formula (L) within such a range, the peeling of the adhesive layer can be achieved in a short time. On the other hand, if the content is outside this range, the peeling time becomes significantly longer, which is therefore not preferred.

[0169] Most preferably, the solvent contained in the above-mentioned stripping composition is composed of an organic solvent represented by the above formula (L).

[0170] In this case, ideally, the solvent contained in the above-mentioned stripping composition is composed entirely of the organic solvent represented by the above formula (L), without containing other solvents as impurities. However, there are limits to the improvement of the purity of the purified product, which is technically impossible.

[0171] Therefore, in this invention, the solvent contained in the above-mentioned stripping composition is intentionally used as an organic solvent represented by the above formula (L), without denying that impurities such as water and organic solvents that are not easily separated due to similar structure or properties are included in the organic solvent represented by the above formula (L) of the main body.

[0172] Considering this situation, when the solvent contained in the above-mentioned stripping composition is composed of an organic solvent represented by the above formula (L), the content of the organic solvent represented by the above formula (L) in the solvent contained in the above-mentioned stripping composition, as a purity value obtained by gas chromatography, may not be completely 100%, usually 94% or more, preferably 95% or more, more preferably 96% or more, even more preferably 97% or more, even more preferably 98% or more, and even more preferably 99% or more.

[0173] In this invention, the adhesive layer on the semiconductor substrate is swelled by continuously contacting the adhesive layer with the release composition, and then peeled off from the semiconductor substrate.

[0174] The method of continuously contacting the adhesive layer on the semiconductor substrate with the release composition is not particularly limited as long as the adhesive layer on the semiconductor substrate and the release composition are in continuous contact for a period of time. This continuous contact includes not only the case where the adhesive layer is always in contact with the release composition, but also, for example, the case where the adhesive layer is in contact with an organic solvent for a certain period of time, the contact is temporarily stopped, and then the contact is resumed, or the contact is repeated. Furthermore, it includes not only the case where the entire adhesive layer on the semiconductor substrate is in contact with the release composition, but also the case where a portion of the adhesive layer is in contact with the release composition. However, from the viewpoint of achieving more effective cleaning with good reproducibility, it is preferable that the adhesive layer on the semiconductor substrate is always in contact with the release composition. Moreover, it is preferable that the entire adhesive layer on the semiconductor substrate is in contact with the release composition.

[0175] Therefore, in a preferred embodiment of the present invention, the adhesive layer on the semiconductor substrate is swelled and peeled off from the semiconductor substrate by immersing the adhesive layer in the release composition; or the adhesive layer on the semiconductor substrate is swelled and peeled off from the semiconductor substrate by continuously supplying the release composition to the adhesive layer.

[0176] To immerse the adhesive layer on a semiconductor substrate in a release composition, for example, the semiconductor substrate with the adhesive layer can be immersed in the release composition.

[0177] There is no particular limitation on the immersion time as long as the adhesive layer swells and peels off from the semiconductor substrate. From the viewpoint of achieving more effective cleaning with good reproducibility, it should be more than 5 seconds, and from the viewpoint of process throughput, it should be less than 5 minutes.

[0178] When the adhesive layer on a semiconductor substrate is immersed in the release composition, the semiconductor substrate with the adhesive layer can be moved in the release composition, the release composition can be convected, and the release composition can be vibrated by ultrasound, thereby promoting the release of the adhesive layer.

[0179] To move the semiconductor substrate with the adhesive layer in the peeling composition, a shaking cleaner or a paddle cleaner can be used. If such a cleaner is used, the adhesive layer on the semiconductor substrate is moved up and down or left and right or rotated by moving or rotating the table on which the semiconductor substrate with the adhesive layer is placed. This causes convection on the adhesive layer on the semiconductor substrate, or convection caused by the movement or rotation, which not only promotes the swelling of the adhesive layer on the semiconductor substrate, but also promotes the peeling of the adhesive layer from the semiconductor substrate.

[0180] In order to make the stripping composition convection, in addition to the shaking cleaner and paddle cleaner mentioned above, for example, a convection cleaner can be used, which can make the stripping composition around the semiconductor substrate with the adhesive layer convection by a stirrer when the substrate is fixed to a worktable or the like.

[0181] To vibrate the peeling composition using ultrasound, an ultrasonic cleaner and an ultrasonic probe can be used, typically at 20 kHz to 5 MHz.

[0182] To continuously supply the release composition to the adhesive layer on the semiconductor substrate, it is sufficient to continuously supply the release composition towards the adhesive layer on the semiconductor substrate. For example, if the adhesive layer on the semiconductor substrate faces upwards, a rod-shaped or mist-like, preferably rod-shaped, release composition is supplied to the adhesive layer on the semiconductor substrate from above (including obliquely above) using a nozzle or similar device of a cleaning apparatus in a time-continuous manner. This time-continuous supply includes not only continuously supplying the release composition to the adhesive layer on the semiconductor substrate, but also, for example, temporarily stopping the supply after a certain period of supplying the release composition, resuming the supply, or repeating the supply process. However, from the viewpoint of achieving more effective cleaning with good reproducibility, it is preferable to continuously supply the release composition to the adhesive layer on the semiconductor substrate.

[0183] When the release composition is supplied in a rod-like manner to the adhesive layer on a semiconductor substrate, the flow rate is typically 200–500 mL / min.

[0184] In one aspect of the present invention, in order to achieve a state of constant contact with the release composition, for example, a steam cleaner can be used to bring the adhesive layer on the semiconductor substrate into contact with the vapor of the release composition.

[0185] The cleaning method for the semiconductor substrate of the present invention may include a process of removing the adhesive layer after peeling.

[0186] There are no particular limitations on the method for removing the peeled adhesive layer, as long as the adhesive layer peeled from the semiconductor substrate is removed. When the semiconductor substrate with the adhesive layer is immersed in the release composition, the peeled adhesive layer can be removed without removing the semiconductor substrate from the release composition, or the peeled adhesive layer can be removed by removing the semiconductor substrate from the release composition. In this case, by simply removing the semiconductor substrate from the release composition, the peeled adhesive layer will naturally remain in the release composition, and sometimes most of it can be removed.

[0187] Specific examples of methods for removing the peeled adhesive layer include: removing it by adsorption or attraction using a device; removing it by blowing it away with gas from an air gun or the like; removing it by centrifugal force generated by moving or rotating the semiconductor substrate up and down or left and right, but these methods are not limited to.

[0188] After removing the peeled adhesive layer, the semiconductor substrate should be dried using conventional methods if necessary.

[0189] The stripping composition used in the semiconductor substrate cleaning method of the present invention is also the subject of the present invention. The stripping composition of the present invention is used to peel the adhesive layer on a semiconductor substrate from the semiconductor substrate, and the preferred embodiments and conditions are as described above. The stripping composition of the present invention can be manufactured by mixing the solvents constituting the composition in any order, if desired. In this case, filtration or the like may also be performed if necessary.

[0190] By using the semiconductor substrate cleaning method of the present invention described above, damage to the semiconductor substrate, especially the bumps of the semiconductor substrate, can be suppressed, and the adhesive layer on the semiconductor substrate, especially the cured film obtained by the adhesive layer of the substrate, particularly the adhesive layer obtained by the siloxane adhesive containing the polyorganosiloxane component (A) cured by the hydrogenation silanization reaction, can be efficiently removed, and the high-efficiency and good semiconductor device manufacturing can be expected.

[0191] In addition to silicon semiconductor substrates such as silicon wafers, the semiconductor substrates targeted by the cleaning method of the present invention also include various substrates such as germanium substrates, gallium-arsenic substrates, gallium-phosphorus substrates, gallium-arsenic-aluminum substrates, aluminum-plated silicon substrates, copper-plated silicon substrates, silver-plated silicon substrates, gold-plated silicon substrates, titanium-plated silicon substrates, silicon substrates with silicon nitride films, silicon substrates with silicon oxide films, silicon substrates with polyimide films, glass substrates, quartz substrates, liquid crystal substrates, organic EL substrates, etc.

[0192] Examples of the use of the cleaning method for the semiconductor substrate of the present invention in semiconductor processes include its use in manufacturing methods for semiconductor substrates that have undergone thinning or other processes, which are used in semiconductor packaging technologies such as TSV.

[0193] Specifically, a method for manufacturing a semiconductor substrate that has undergone thinning or other processing includes: a first step of manufacturing a laminate comprising 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, wherein the semiconductor substrate cleaning method of the present invention is used in the fourth step.

[0194] As an adhesive composition used to form an adhesive layer in the first process, various adhesives described above can be used, but the cleaning method for semiconductor substrates of the present invention is effective for removing adhesive layers obtained from polysiloxane-based adhesives, and even more effective for removing adhesive layers obtained from polysiloxane-based adhesives containing component (A) cured by a hydrogenation silanization reaction.

[0195] Therefore, the following describes an example of removing the adhesive layer using the cleaning method of the present invention when manufacturing a processed semiconductor substrate using an adhesive layer obtained using a polysiloxane-based adhesive (adhesive composition), but the present invention is not limited thereto.

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

[0197] In one embodiment, the first step includes the following steps: applying an adhesive composition to the surface of a semiconductor substrate or a support substrate to form an adhesive coating layer; and laminating the semiconductor substrate and the support substrate by means of the adhesive coating layer, applying a load in the thickness direction of the semiconductor substrate and the support substrate to make them adhere while performing at least one of a heat treatment and a decompression treatment, and then performing a post-heat treatment, thereby forming a laminate.

[0198] In other embodiments, the first step includes the following steps: for example, coating an adhesive composition onto the circuit surface of a semiconductor substrate wafer and heating it to form an adhesive coating layer; coating a release agent composition onto the surface of a support substrate and heating it to form a release agent coating layer; and applying a load in the thickness direction of the semiconductor substrate and the support substrate to bond them together while subjecting at least one of heat treatment and decompression treatment to the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate, followed by a post-heat treatment, thereby forming a laminate. It should be noted that while the adhesive composition is coated onto the semiconductor substrate and the release agent composition is coated onto the support substrate and heated, the coating and heating of the adhesive composition and release agent composition can also be performed sequentially on either substrate.

[0199] In the above schemes, the choice of which treatment condition to use—heat treatment, depressurization treatment, or a combination of both—is determined based on various factors such as the type of adhesive composition, the specific composition of the release agent composition, the compatibility of the films obtained from the two compositions, the film thickness, and the required adhesive strength.

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

[0201] As for wafers, examples include silicon wafers with a diameter of 300 mm and a thickness of about 770 μm, and glass wafers, but they are not limited to these.

[0202] In particular, the semiconductor substrate cleaning method of the present invention can suppress damage to the bumps of the bumped semiconductor substrate and can effectively clean the substrate.

[0203] As a specific example of such a bumped semiconductor substrate, silicon wafers with bumps such as ball bumps, printed bumps, stud bumps, and plated bumps can be listed. Typically, the bump height is selected from approximately 1 to 200 μm, the bump diameter is 1 to 200 μm, and the bump spacing is 1 to 500 μm.

[0204] Specific examples of plated bumps include SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other Sn-based alloy platings, but are not limited to these.

[0205] The support (carrier) is not particularly limited. For example, a silicon wafer with a diameter of about 300 mm and a thickness of about 700 mm can be listed, but it is not limited to this.

[0206] Examples of stripping agent compositions include compositions containing stripping agent components for this purpose.

[0207] There are no particular limitations on the coating method; spin coating is the most common. It should be noted that a separate method, such as spin coating, can also be used to form a coating film and then attach a sheet-like coating film; this is also referred to as coating or coating film.

[0208] The heating temperature of the coated adhesive composition varies depending on the type and amount of adhesive components contained in the adhesive composition, whether it contains solvent, the desired thickness of the adhesive layer, etc., so it cannot be specified in general. It is usually 80℃ to 150℃, and the heating time is usually 30 seconds to 5 minutes.

[0209] The heating temperature of the coating release agent composition varies depending on the type and amount of crosslinking agent, acid-generating agent, acid, etc., whether it contains solvent, the desired thickness of the release layer, etc., and therefore cannot be specified in general. From the viewpoint of achieving proper curing, it is 120°C or higher, and from the viewpoint of preventing over-curing, it is preferably 260°C or lower. The heating time is usually 1 minute to 10 minutes.

[0210] Heating can be done using heating plates, ovens, etc.

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

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

[0213] From the perspectives of softening the adhesive coating layer to achieve proper adhesion with the release agent coating layer and achieving proper curing of the release agent coating layer, the heat treatment is generally appropriately determined within the range of 20 to 150°C. In particular, from the viewpoint of suppressing / avoiding over-curing and unnecessary deterioration of the adhesive and release agent components, it is preferable to be below 130°C, more preferably below 90°C. From the viewpoint of reliably exhibiting adhesion and peeling ability, the heating time is generally 30 seconds or more, preferably 1 minute or more. From the viewpoint of suppressing deterioration of the adhesive layer and other components, it is generally 10 minutes or less, preferably 5 minutes or less.

[0214] The depressurization process involves exposing the semiconductor substrate, adhesive coating layer, and support substrate, or the semiconductor substrate, adhesive coating layer, release agent coating layer, and support substrate, to an atmospheric pressure of 10 Pa to 10,000 Pa. The depressurization process typically lasts from 1 to 30 minutes.

[0215] In a preferred embodiment of the present invention, the substrate and the coating layer or the coating layer are preferably bonded together by a decompression treatment, more preferably by a combination of a heat treatment and a decompression 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 and the support substrate or the layers between them, and can firmly seal them together. It is usually in the range of 10 to 1000 N.

[0217] From the viewpoint of achieving sufficient curing speed, the post-heating temperature is preferably 120°C or higher. From the viewpoint of preventing deterioration of the substrate, adhesive components, release agent components, etc., the post-heating temperature is preferably 260°C or lower. From the viewpoint of achieving proper bonding of the cured wafer, the heating time is typically 1 minute or more. Furthermore, from the viewpoint of stabilizing the physical properties of the adhesive, the heating time is preferably 5 minutes or more. From the viewpoint of avoiding adverse effects on the adhesive layer caused by excessive heating, the heating time is typically 180 minutes or less, preferably 120 minutes or less. Heating can be performed using a heating plate, oven, etc.

[0218] It should be noted that one of the purposes of post-heat treatment is to allow the adhesive component (S) to cure more properly.

[0219] Next, the second step of processing the semiconductor substrate of the laminate obtained by the method described above will be explained.

[0220] As an example of the processing performed on the laminate used in this invention, the processing of the back side of the semiconductor substrate opposite to the circuit surface can be cited. Typically, wafer thinning achieved by grinding the back side of the wafer can be cited. Using such a thinned wafer, through-silicon electrodes (TSVs) are formed, and then the thinned wafer is peeled from the support to form a wafer laminate for three-dimensional mounting. In addition, wafer back electrodes are formed before and after three-dimensional mounting. Heat of 250 to 350°C is applied to the wafer in a bonded state to the support during the wafer thinning and TSV processes, but the adhesive layer included in the laminate used in this invention is heat-resistant to this heat.

[0221] For example, a wafer with a diameter of 300 mm and a thickness of about 770 μm can be thinned to a thickness of about 80 μm to 4 μm by grinding the back side opposite to the circuit surface.

[0222] The third step, which separates the processed semiconductor substrate and adhesive layer from the support substrate, will be described.

[0223] In the third step, the processed semiconductor substrate and adhesive layer are separated from the support substrate. At this time, if the laminate includes a release layer, the release layer is usually removed along with the support substrate.

[0224] The method for separating the processed semiconductor substrate and the adhesive layer from the semiconductor substrate is simply to peel the adhesive layer from the release layer or the support substrate that is in contact with it. Such peeling methods include the following: laser peeling, mechanical peeling using a device with a sharp point, and peeling by manual tearing, but are not limited to these.

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

[0226] The fourth step is the process of removing the adhesive layer on the semiconductor substrate using the cleaning method of the present invention. Specifically, for example, the adhesive layer on the thinned substrate is efficiently removed using the cleaning method of the present invention. The conditions at this time are as described above.

[0227] After the fourth step, if necessary, a cleaning agent composition containing salt can be used to remove the adhesive layer residue remaining on the semiconductor substrate, but care should be taken to avoid damaging the semiconductor substrate, especially the bumps of the semiconductor substrate with bumps.

[0228] The method for manufacturing the processed semiconductor substrate of the present invention includes the first to fourth steps described above, and may also include steps other than these steps. Furthermore, various modifications can be made to the above-described constituent elements and method elements related to the first to fourth steps, as long as they do not depart from the spirit of the present invention.

[0229] Example

[0230] The present invention will now be described with reference to examples and comparative examples, but the present invention is not limited to the examples described below. It should be noted that the purity of the apparatus used in the present invention and the solvent used for the stripping composition, obtained by gas chromatography, is as described below.

[0231] [Device]

[0232] (1) Rotation-revolution mixer: ARE-500 rotation-revolution mixer manufactured by THINKY Corporation.

[0233] (2) Viscometer: TVE-22H rotational viscometer manufactured by Toki Sangyo Co., Ltd.

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

[0235] (4) Optical microscope: OLYMPUS Corporation Semiconductor / FPD Inspection Microscope MX61L.

[0236] [solvent]

[0237] N-Methylpyrrolidone: Produced by Kanto Chemical Co., Ltd., purity > 99.0%.

[0238] Butyl acetate: manufactured by Kanto Chemical Co., Ltd., purity > 98.0%.

[0239] Amyl acetate: Produced by Tokyo Chemical Industry Co., Ltd., purity > 99.0%.

[0240] Heptyl acetate: Produced by Tokyo Chemical Industry Co., Ltd., purity > 99.0%.

[0241] Octyl acetate: Produced by Tokyo Chemical Industry Co., Ltd., purity > 98.0%.

[0242] [1] Preparation of adhesive composition

[0243] [Preparation Example 1]

[0244] Add 95g of vinyl-containing MQ resin (manufactured by Wacker Chemie Co., Ltd.) as (a1), 93.4g of p-menthane (manufactured by NIPPON TERPENE CHEMICALS Co., Ltd.) as solvent, and 0.41g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as (A2) to a 600mL mixing container for a rotary mixer, and mix for 5 minutes.

[0245] To the obtained mixture, add 19.0 g of a SiH-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 100 mPa·s (a2), 29.5 g of a vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 200 mPa·s (a1), and (B) a polydimethylsiloxane with a viscosity of 1,000,000 mm. 2 65.9 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK1000000) and 0.41 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) as (A3) were further stirred for 5 minutes using a rotary mixer.

[0246] Next, 0.20 g of platinum catalyst (manufactured by Wacker Chemie) as (A2) and 17.7 g of vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1000 mPa·s as (a1) were added to the obtained mixture. The mixture was stirred for 5 minutes using a rotary mixer. 14.9 g of the separately obtained mixture was further stirred for 5 minutes using a rotary mixer. The obtained mixture was then filtered through a 300-mesh nylon filter to obtain the adhesive composition.

[0247] [2] Fabrication of the substrate for evaluation

[0248] [Manufacturing Example 1]

[0249] The composition obtained in Preparation Example 1 was coated on a 4cm×4cm Si wafer (775μm thick) serving as the device side using a spin coater. The wafer was heated at 120°C for 1.5 minutes and then at 200°C for 10 minutes using a heating plate to form a 60μm thick film on the wafer, resulting in a wafer with an adhesive layer.

[0250] [Manufacturing Example 2]

[0251] Cut the bumped substrate to prepare a 4cm × 4cm sample substrate. It should be noted that each sample substrate has 5044 bumps. In terms of the bump structure, the pillars are made of copper, the caps are made of tin-silver (1.8% by mass of silver), and the space between the pillars and the caps is made of nickel.

[0252] [3] Measurement of peeling time

[0253] [Example 1-1]

[0254] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of butyl acetate, which is the peeling composition of Example 1-1, and the time from when the adhesive layer began to peel off from the wafer was measured, which was 16 seconds.

[0255] [Examples 1-2]

[0256] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent (9:1 (w / w)) of butyl acetate and N-methylpyrrolidone, which is the peeling composition of Examples 1-2. The time from when the adhesive layer began to peel off from the wafer was measured, and the result was 21 seconds.

[0257] [Example 2-1]

[0258] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of amyl acetate, which is the peeling composition of Example 2-1, and the time from when the adhesive layer began to peel off from the wafer was measured, which was 21 seconds.

[0259] [Example 2-2]

[0260] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent (9:1 (w / w)) of amyl acetate and N-methylpyrrolidone, which is the peeling composition of Example 2-2. The time from when the adhesive layer began to peel off from the wafer was measured, and the result was 27 seconds.

[0261] [Comparative Example 1-1]

[0262] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent (7:3 (w / w)) of butyl acetate and N-methylpyrrolidone, which is the peeling composition of Comparative Example 1-1. The time from when the adhesive layer began to peel off from the wafer was measured, and the result was 56 seconds.

[0263] [Comparative Example 2-1]

[0264] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent (7:3 (w / w)) of amyl acetate and N-methylpyrrolidone, which is the peeling composition of Comparative Example 2-1. The time from when the adhesive layer began to peel off from the wafer was measured, and the result was 65 seconds.

[0265] [Comparative Example 3-1]

[0266] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of heptyl acetate, which is a peeling composition used in Comparative Example 3-1, and the time from when the adhesive layer began to peel off from the wafer was measured. The result was 38 seconds.

[0267] [Comparative Example 3-2]

[0268] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent (9:1 (w / w)) of heptyl acetate and N-methylpyrrolidone, which is the peeling composition of Comparative Example 3-2. The time from when the adhesive layer began to peel off from the wafer was measured, and the result was 47 seconds.

[0269] [Comparative Example 3-3]

[0270] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent (7:3 (w / w)) of heptyl acetate and N-methylpyrrolidone, which is the peeling composition of Comparative Examples 3-3. The time from when the adhesive layer began to peel off from the wafer was measured, and the result was 114 seconds.

[0271] [Comparative Example 4-1]

[0272] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of octyl acetate, which is a peeling composition used in Comparative Example 4-1. The time from when the adhesive layer began to peel off from the wafer was measured, and the result was 51 seconds.

[0273] [Comparative Example 4-2]

[0274] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent (9:1 (w / w)) of octyl acetate and N-methylpyrrolidone, which is the peeling composition of Comparative Example 4-2. The time from when the adhesive layer began to peel off from the wafer was measured, and the result was 59 seconds.

[0275] [Comparative Example 4-3]

[0276] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent (7:3 (w / w)) of octyl acetate and N-methylpyrrolidone, which is the peeling composition of Comparative Examples 4-3. The time from when the adhesive layer began to peel off from the wafer was measured, and the result was 153 seconds.

[0277] The results of the examples and comparative examples are shown in Table 1. As shown in Table 1, when using a stripping composition containing butyl acetate or amyl acetate as an organic solvent represented by formula (L) at more than 80% by mass in the solvent of the stripping composition (Examples 1-1 to Examples 2-2), the peeling time of the adhesive layer on the semiconductor substrate is extremely short compared to the cases where the content of the organic solvent represented by formula (L) is less than 80% by mass (Comparative Examples 1-1 and 2-1) or the cases where the organic solvent represented by formula (L) is not used (Comparative Examples 3-1 to 3-3 and 4-1 to 4-3).

[0278] [Table 1]

[0279]

[0280] [4] Observation of damage to substrates with bumps

[0281] [Example 3-1]

[0282] The sample substrate prepared in Manufacturing Example 2 was immersed in 9 mL of butyl acetate, which is the release composition of Example 1-1. After standing for 1 hour, it was washed with isopropanol and acetone, and observed for bump damage using an optical microscope. As a result, no bump damage was observed.

[0283] [Comparative Example 5-1]

[0284] 2 g of tetrabutylammonium fluoride / trihydrate (manufactured by Kanto Chemical Co., Ltd.) and 18 g of butyl acetate were thoroughly stirred using a mixing rotor at room temperature, but residual tetrabutylammonium fluoride dissolved. Therefore, the supernatant of the solution was recovered.

[0285] Then, the sample substrate prepared in Manufacturing Example 2 was immersed in 9 mL of the supernatant of the recovered solution, allowed to stand for 1 hour, and then cleaned with isopropanol and acetone. The substrate was then observed with an optical microscope for any bump damage. As a result, damaged bumps were identified throughout the entire sample substrate (estimated number of damaged bumps: 1000-2000).

Claims

1. A cleaning method for a semiconductor substrate, characterized by comprising a step of peeling an adhesive layer on a semiconductor substrate using a peeling composition, the peeling composition contains a solvent and is free of salt, the solvent contains 80% by mass or more of an organic solvent represented by formula (L), the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) that contains a polyorganosiloxane component (A) cured by a hydrosilation reaction. wherein L 1 and L 2 each independently represents an alkyl group having 1 to 6 carbon atoms, L 1 the total number of carbon atoms of the alkyl group of L 2 is 6 or less, 2. The cleaning method for a semiconductor substrate according to claim 1, wherein the solvent contains 85% by mass or more of the organic solvent represented by formula (L).

3. The cleaning method for a semiconductor substrate according to claim 2, wherein the solvent consists of the organic solvent represented by formula (L).

4. The cleaning method for a semiconductor substrate according to claim 1, wherein 5. The cleaning method for a semiconductor substrate according to claim 4, wherein The L 1 is methyl.

6. The cleaning method for a semiconductor substrate according to any one of claims 1 to 5, characterized in that The L 2 is butyl or pentyl. the adhesive component (S) further contains at least one selected from the group consisting of 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. comprising:

7. A method for manufacturing a processed semiconductor substrate, characterized by, a first step of producing 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, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) that contains a polyorganosiloxane component (A) cured by a hydrosilation reaction, the peeling composition contains a solvent and is free of salt, the solvent contains 80% by mass or more of an organic solvent represented by formula (L), 8. The method for producing a processed semiconductor substrate according to claim 7, wherein the solvent contains 85% by mass or more of the organic solvent represented by formula (L). wherein L 1 and L 2 each independently represents an alkyl group having 1 to 6 carbon atoms, L 1 the total number of carbon atoms of the alkyl group of L 2 the total number of carbon atoms of the alkyl group of L 9. The method for producing a processed semiconductor substrate according to claim 8, wherein the solvent consists of the organic solvent represented by formula (L).

10. The method for producing a processed semiconductor substrate according to claim 7, wherein 11. The method for producing a processed semiconductor substrate according to claim 10, wherein 12. The method for producing a processed semiconductor substrate according to any one of claims 7 to 11, characterized in that The L 1 is methyl. the adhesive component (S) further contains at least one selected from the group consisting of 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. The L 2 is butyl or pentyl.

13. A peeling composition, characterized by for peeling an adhesive layer on a semiconductor substrate when the semiconductor substrate is cleaned, ​ ​ The adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) containing a polyorganosiloxane component (A) cured by a hydrosilylation reaction, The peeling composition contains a solvent and is free of salt, The solvent contains 80% by mass or more of an organic solvent represented by formula (L), wherein L 1 and L 2 each independently represents an alkyl group having 1 to 6 carbon atoms, L 1 the total number of carbon atoms of the alkyl group of L 2 the total number of carbon atoms of the alkyl group of L 14. The peeling composition according to claim 13, wherein The solvent contains 85% by mass or more of the organic solvent represented by formula (L).

15. The peeling composition according to claim 14, wherein The solvent consists of the organic solvent represented by formula (L).

16. The peeling composition according to claim 13, wherein The L 1 is methyl.

17. The peeling composition according to claim 16, wherein The L 2 is butyl or pentyl.

18. The peeling composition according to any one of claims 13 to 17, characterized in that The adhesive component (S) further contains at least one selected from the group consisting of 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.

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