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

Abstract

Provided is a cleaning method for a semiconductor substrate, which includes a step of peeling an adhesive layer on a semiconductor substrate using a peeling composition, the peeling composition containing a solvent, not containing a salt, the solvent containing 80% by mass or more of an organic solvent represented by formula (1). In formula (1), L represents a substituent substituted on a benzene ring, each independently represents an alkyl group having 1 to 4 carbon atoms, and k represents the number of L and is an integer of 0 to 5.

Description

Technical Field

[0001] This invention relates to a method for cleaning a semiconductor substrate, a method for manufacturing a processed semiconductor substrate, 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 multi-layer integration, grinding is used to thin the side (back side) of each integrated wafer opposite to the formed circuit surface, and the thinned semiconductor wafers are then layered.

[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 peeled off after polishing; therefore, it is called a temporary bond. This temporary bond must be easily detachable from the support to prevent the thinned semiconductor wafer from being cut or deformed when a large force is applied during removal. However, it is undesirable for the support to detach or shift due to polishing stress during back-side polishing of the semiconductor wafer. Therefore, the desired performance for temporary bonds is: resistance to the stress during polishing and easy removal after polishing. For example, the following performance is 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 for removing this residue and cleaning the semiconductor substrate surface have been developed (e.g., Patent Documents 1 and 2). Patent Document 1 discloses a remover for siloxane resins comprising a polar aprotic solvent and a quaternary ammonium hydroxide, while Patent Document 2 discloses a remover for cured resins comprising fluorinated alkyl / ammonium compounds. However, in the recent semiconductor field, the need for new cleaning agent compositions and effective cleaning methods persists.

[0005] On the other hand, semiconductor wafers are electrically connected to semiconductor chips, for example, through bump balls made of conductive metallic material. By using chips with such bump balls, miniaturization of semiconductor packaging can be achieved.

[0006] In this respect, bump balls made of metals such as copper and tin lack corrosion resistance, thus causing damage to the cleaning agent composition used to remove adhesive residues from the support and wafer (Patent Document 3). As one of the objectives of the cleaning agent composition and cleaning method, it is possible to avoid corroding the bump balls 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 semiconductor substrate processed by such a cleaning method, and a stripping composition for such a cleaning method, which is used, for example, to properly and easily remove an adhesive layer from a semiconductor substrate having an adhesive layer obtained using a siloxane-based adhesive on the surface of the semiconductor substrate, and to reduce or suppress 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 in-depth research and found that by using a stripping composition containing a specified amount or more of a specified aromatic hydrocarbon compound as a solvent and without salt, the adhesive layer on the semiconductor substrate can be efficiently and easily stripped, 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 hydrogenation silanization reaction, and damage to the bumps of the semiconductor substrate is reduced or suppressed, thereby completing the present invention.

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

[0017] 1. A method for cleaning a semiconductor substrate, comprising a step of using a stripping composition to strip an adhesive layer on the semiconductor substrate, characterized in that the stripping composition comprises a solvent, does not contain a salt, and the solvent comprises 80% by mass or more of an organic solvent of formula (1).

[0018]

[0019] (In the formula, L represents a substituent inserted into the benzene ring, each independently representing an alkyl group with 1 to 4 carbon atoms, and k represents the number of L groups, which is an integer from 0 to 5.)

[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 shown in formula (1) above.

[0021] 3. The method for cleaning a semiconductor substrate according to 2, wherein the solvent is composed of an organic solvent as shown in formula (1) above.

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

[0023] 5. The method for cleaning a semiconductor substrate according to 1, wherein the organic solvent shown in formula (1) above is selected from at least one of toluene, mesitylene, p-isopropyltoluene and 1,2,4-trimethylbenzene.

[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 by using an adhesive composition containing 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 includes 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 using a peeling composition to peel off the adhesive layer on the semiconductor substrate, wherein the peeling composition comprises a solvent and does not contain a salt, and the solvent comprises 80% by mass or more of an organic solvent of formula (1).

[0028]

[0029] (In the formula, L represents a substituent inserted into the benzene ring, each independently representing an alkyl group with 1 to 4 carbon atoms, and k represents the number of L groups, which is an integer from 0 to 5.)

[0030] 10. A method for manufacturing a processed semiconductor substrate according to 9, wherein the solvent comprises 85% by mass or more of the organic solvent shown in formula (1) above.

[0031] 11. A method for manufacturing a processed semiconductor substrate according to 10, wherein the solvent is composed of an organic solvent as shown in formula (1) above.

[0032] 12. A method for manufacturing a processed semiconductor substrate according to any one of 9 to 11, wherein L is methyl or isopropyl.

[0033] 13. The method for manufacturing the processed semiconductor substrate according to 12, wherein the organic solvent shown in the above formula (1) is selected from at least one of toluene, mesitylene, p-isopropyltoluene and 1,2,4-trimethylbenzene.

[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 the 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 for stripping an adhesive layer on a semiconductor substrate during cleaning, characterized in that the stripping composition comprises a solvent, does not contain a salt, and the solvent comprises 80% by mass or more of an organic solvent of formula (1).

[0038]

[0039] (In the formula, L represents a substituent inserted into the benzene ring, each independently representing an alkyl group with 1 to 4 carbon atoms, and k represents the number of L groups, which is an integer from 0 to 5.)

[0040] 18. The stripping composition according to 17, wherein the solvent comprises 85% by mass or more of the organic solvent shown in formula (1) above.

[0041] 19. The stripping composition according to 18, wherein the solvent is composed of an organic solvent represented by the formula (1) above.

[0042] 20. A stripping composition according to any one of 17 to 19, wherein L is methyl or isopropyl.

[0043] 21. The stripping composition according to 20, wherein the organic solvent represented by the above formula (1) is selected from at least one of toluene, mesitylene, p-isopropyltoluene and 1,2,4-trimethylbenzene.

[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 containing an adhesive component (S), wherein the adhesive component (S) comprises at least one selected from siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin 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 semiconductor substrate cleaning method of the present invention, for example, the adhesive layer on the surface of the semiconductor substrate having an adhesive layer obtained using a siloxane-based adhesive can be properly and easily removed, thus enabling the efficient and high-quality manufacture of 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, efficient, reliable and good semiconductor device manufacturing can be expected. Detailed Implementation

[0050] The cleaning method for a semiconductor substrate of the present invention includes a step of using a stripping composition to strip an adhesive layer on a semiconductor substrate, wherein the stripping composition contains a solvent but does not contain a salt, and the solvent contains 80% by mass or more of an organic solvent of formula (1).

[0051]

[0052] Semiconductor substrates include wafers, such as silicon wafers with a diameter of 300 mm and a thickness of about 770 μm, but are not limited to these.

[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 components (S) are not particularly limited as long as they are used for this purpose. Examples include: siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, phenolic resin adhesives, etc.

[0055] Among them, as the adhesive component (S), siloxane-based adhesives are preferred because they exhibit appropriate adhesion when processing wafers, can be properly peeled off after processing, and have excellent heat resistance.

[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 shown are shown. 4 R 5 SiO 2／2 The siloxane unit (D unit) and R shown are shown. 6 SiO 3／2The polysiloxane (A1) comprises one or more units from the group consisting of the shown siloxane units (T units), wherein the polysiloxane (A1) includes polyorganosiloxane (a1) and polyorganosiloxane (a2), and the polyorganosiloxane (a1) includes siloxane units (Q' units) selected from SiO2 and R... 1 'R 2 'R 3 'SiO 1／2 The siloxane unit (M' unit) and R shown are shown. 4 'R 5 'SiO 2／2 The siloxane unit (D' unit) and R shown are shown. 6 'SiO 3／2 The polyorganosiloxane (a2) comprises one or more units selected from the group consisting of the siloxane units (T' units) shown, and includes at least one unit selected from the group consisting of the M' units, D' units, and T' units. 1 R 2 "R 3 "SiO" 1／2 The siloxane unit (M” unit) and R shown 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 described above.

[0057] R 1 ~R 6 These are groups or atoms bonded to silicon atoms, and can be independently represented as alkyl, alkenyl, or hydrogen atoms.

[0058] 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.

[0059] 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.

[0060] 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.

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

[0070] Furthermore, when the polyorganosiloxane contained in two or more polyorganosiloxanes (a1) is included, the combination of (Q' unit and M' unit) and (D' unit and M' unit), the combination of (T' unit and M' unit) and (D' unit and M' unit), and the combination of (Q' unit, T' unit and M' unit) and (T' unit and M' unit) 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 can be listed as (M” unit and D” unit), (Q” unit and M” unit), (Q” unit, T” unit and M” unit), but are not limited to these.

[0073] Polyorganosiloxanes (a1) are composed of siloxane units formed by the bonding of alkyl and / or alkenyl groups to their silicon atoms, 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 alkyl and / or hydrogen atoms with their silicon atoms, R 1 "~R 6 The ratio of all substituents to hydrogen atoms in the substituted atoms 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 polyorganosiloxanes (a1) and (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 viscosities in this invention are values ​​measured using an E-type rotational viscometer at 25°C.

[0079] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via a hydrosilylation reaction to form a film. Therefore, the curing mechanism is different from that via, for example, silanol groups, and thus, neither siloxane needs to contain functional groups such as silanol groups or alkyloxy groups that are formed by hydrolysis.

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

[0081] Such platinum-based 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-based metal catalysts include: platinum black, platinum chloride, 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] As complexes of platinum and olefins, for example, complexes of divinyltetramethyldisiloxane and platinum can be listed, but are not limited to this.

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

[0085] For the purpose of inhibiting the hydrosilylation reaction, the polyorganosiloxane component (A) 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 viewpoint of achieving this effect, the amount of polymerization inhibitor is usually above 1000.0 ppm relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2), and below 10000.0 ppm from the viewpoint of preventing excessive inhibition of the hydrosilanization reaction.

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

[0089] As such a stripping agent component (B), typical examples include polyorganosiloxanes, 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, and preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000, from the viewpoint of achieving the effects of the present invention with good reproducibility. Its dispersity is typically 1.0 to 10.0, and preferably 1.5 to 5.0, more preferably 2.0 to 3.0, from the viewpoint of achieving the effects of the present invention with good reproducibility. 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 shown (D) 10 Polyorganosiloxane (unit).

[0092] R 11 It is a group bonded to silicon atoms, representing an alkyl group, R. 12 It is a group bonded to a silicon atom, representing an epoxy group or an organic group containing an epoxy group. As specific examples of alkyl groups, the examples mentioned above can be listed.

[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 contain the aforementioned siloxane units (D 10 (unit), except D 10 In addition to the unit, it may also include the above-mentioned Q unit, M unit and / or T unit.

[0097] In a preferred embodiment, as a specific example of an epoxy-containing polyorganosiloxane, the following can be listed: consisting only of 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. 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) as shown in formula (A-1), ECMS-327 (manufactured by Gelest Corporation, weight average molecular weight 28,800) as shown in formula (A-2), KF-101 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 31,800) as shown in formula (A-3), KF-1001 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 55,600) as shown in formula (A-4), KF-1005 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 11,500) as shown in formula (A-5), X-22-343 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 2,400) as shown in formula (A-6), and BY16-839 (Dow Chemical Industry Co., Ltd., weight average molecular weight 2,400) as shown in formula (A-7). The products are not limited to these, such as Corning (weight average molecular weight 51,700) and ECMS-327 (Gelest (weight average molecular weight 28,800) as shown in formula (A-8).

[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 are the number of repeating units, respectively. R is an alkylene group with 1 to 10 carbon atoms.)

[0106]

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

[0108]

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

[0110]

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

[0112]

[0113] (m and n are the number of repeating units, respectively. R is 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, for example, those containing R... 210 R 220 SiO 2 / 2 The siloxane unit shown (D) 200 Polyorganosiloxanes (units), preferably containing R 21 R 21 SiO 2 / 2 The siloxane unit shown (D) 20 Polyorganosiloxane (unit).

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

[0118] R 21 This is a group bonded to silicon atoms, representing an alkyl group. Specific examples of alkyl groups can be listed above. Among them, 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 above-mentioned Q unit, M unit and / or T unit.

[0121] In a particular scheme, as a specific example of a methyl-containing polyorganosiloxane, one can list: consisting only of 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 a preferred embodiment, as a specific example of a methyl-containing polyorganosiloxane, the following can be listed: consisting only of 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, for methyl-containing polyorganosiloxanes, a typical example is dimethyl silicone oil composed of polydimethylsiloxane. This viscosity value is expressed as kinematic viscosity, centistokes (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 using the kinematic viscosity (mm). Specifically, it can be calculated from the viscosity and density measured at 25°C using an E-type rotational viscometer. 2 / s) = Viscosity (mPa·s) / Density (g / cm³) 3 This formula is used to calculate the result.

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

[0125] Examples of phenyl-containing polyorganosiloxanes include those containing R. 31 R 32 SiO 2／2 The siloxane unit shown (D) 30 (unit) phenyl-containing polyorganosiloxanes.

[0126] R 31 It is a group bonded to silicon atoms, representing phenyl or alkyl, R 32 It is a group bonded to a silicon atom, representing a phenyl group. Specific examples of alkyl groups can be listed above, with methyl being preferred.

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

[0128] In a preferred embodiment, as a specific example of a phenyl-containing polyorganosiloxane, the following can be listed: consisting only of 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, and preferably 100,000 or less from the viewpoint of inhibiting precipitation in adhesive compositions.

[0130] As a specific example of a phenyl-containing polyorganosiloxane, one can be listed as: PMM-1043 (manufactured by Gelest Corporation, weight-average molecular weight 67,000, viscosity 30,000 mmHg), as shown in formula (C-1). 2 / s), the trade name PMM-1025 shown in formula (C-2) (manufactured by Gelest Company, weight average molecular weight 25200, viscosity 500 mm) 2 / s), the trade name KF50-3000CS shown in 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 shown in formula (C-4) (manufactured by MOMENTIVE, weight average molecular weight 1800, viscosity 100mm) 2 / s), the trade name TSF433 shown in formula (C-5) (manufactured by MOMENTIVE, weight average molecular weight 3000, viscosity 450 mm) 2 / s), the trade name PDM-0421 shown in formula (C-6) (manufactured by Gelest Company, weight average molecular weight 6200, viscosity 100mm) 2 / s), the trade name PDM-0821 shown in formula (C-7) (manufactured by Gelest Company, weight average molecular weight 8600, viscosity 125mm) 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, but 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 is appropriately set by taking into account the desired viscosity of the composition, the coating method used, the thickness of the film produced, etc., but its content is in the range of about 10 to 90% by mass relative to the whole 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 the solvent contained in the composition.

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

[0154] The mixing order is not particularly limited. As an example of a method that can easily and reproducibly produce 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 remaining portion in a solvent, and mixing the resulting solutions, but the method is not limited to these. It should be noted that, when preparing the adhesive composition, appropriate heating can 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 can 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 but does not contain a salt, and the solvent contains 80% by mass or more of the organic solvent shown in formula (1).

[0157] Here, the organic solvent shown in formula (1) can be a single type or two or more types.

[0158] In the above formula (1), L represents a substituent inserted into the benzene ring, each of which independently represents an alkyl group with 1 to 4 carbon atoms, and k represents the number of L, which is an integer from 0 to 5.

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

[0160] Specific examples of straight-chain or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc., but are not limited to these.

[0161] Specific examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, etc., but are not limited to these.

[0162] From the perspectives of achieving reproducibility and peeling of the adhesive layer in a shorter time, and the ease of obtaining the compound, L is preferably methyl or isopropyl.

[0163] From the viewpoints of achieving reproducibility and peeling of the adhesive layer in a shorter time, and from the viewpoints of the ease of obtaining the compound, k is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less.

[0164] From the viewpoints of achieving reproducibility and peeling of the adhesive layer in a shorter time, and from the viewpoints of the ease of obtaining the compound, examples of preferred organic solvents as shown in formula (1) include toluene, mesitylene, p-isopropyltoluene, 1,2,4-trimethylbenzene, etc.

[0165] The stripping composition used in this invention does not contain salt.

[0166] 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.

[0167] The stripping composition used in this invention contains the organic solvent shown in formula (1), but does not need to contain such a salt.

[0168] Such salts can cause damage such as corrosion to substrates, especially substrates with bumps. Therefore, the present invention uses a stripping composition that does not contain salt. However, the presence of salt is not denied even if the bulk solvent constituting the stripping composition contains trace amounts of salt as an impurity from the beginning.

[0169] In the peeling composition used in this invention, the content of the organic solvent shown in formula (1) above 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 shown in formula (1) above 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 increases significantly, which is therefore not preferred.

[0170] Most preferably, the solvent contained in the above-mentioned stripping composition is composed of an organic solvent as shown in formula (1) above.

[0171] In this case, ideally, the solvent contained in the above-mentioned stripping composition is entirely composed of the organic solvent shown in the above formula (1), without containing other solvents as impurities. However, there are limits to improving the purity through refining, which is technically impossible.

[0172] Therefore, in this invention, regarding the solvent contained in the above-mentioned stripping composition, the solvent used is intentionally composed only of the organic solvent shown in the above formula (1), and does not exclude the following cases: the organic solvent shown in the above formula (1) of this body includes water and other impurities such as organic solvents that are similar in structure or properties and are not easily separated.

[0173] Considering this situation, when the solvent contained in the above-mentioned stripping composition is composed of the organic solvent shown in the above formula (1), the content of the organic solvent shown in the above formula (1) in the solvent contained in the above-mentioned stripping composition, based on the purity value obtained by gas chromatography, may not be completely 100%, but is 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.

[0174] In this invention, the adhesive layer on the semiconductor substrate is continuously contacted with the release composition, causing the adhesive layer to swell and peel off from the semiconductor substrate.

[0175] Regarding the method of continuously contacting the adhesive layer on the semiconductor substrate with the release composition, there is no particular limitation as long as the adhesive layer on the semiconductor substrate and the release composition are in contact in a manner that is continuous over time. This continuous over time includes not only the case where the adhesive layer is always in contact with the release composition, but also, for example, the case where, after the adhesive layer has been in contact with the organic solvent for a certain period of time, the contact is temporarily stopped and then the contact is resumed, or the above situation 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. From the viewpoint of achieving more effective cleaning with good reproducibility, the scheme in which the adhesive layer on the semiconductor substrate is always in contact with the release composition is preferred. Moreover, the scheme in which the entire adhesive layer on the semiconductor substrate is in contact with the release composition is preferred.

[0176] 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 peeling composition, or by continuously supplying the peeling composition to the adhesive layer to swell and peel off from the semiconductor substrate.

[0177] 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.

[0178] There is no particular limitation on the immersion time as long as it can cause the adhesive layer to swell and peel off from the semiconductor substrate. From the point of view of achieving more effective cleaning with good reproducibility, it should be more than 5 seconds, and from the point of view of process throughput, it should be less than 5 minutes.

[0179] When immersing the adhesive layer on a semiconductor substrate in a release composition, the release of the adhesive layer can be promoted by moving the semiconductor substrate with the adhesive layer in the release composition, causing the release composition to convect, or using ultrasound to vibrate the release composition.

[0180] In order to move the semiconductor substrate with the adhesive layer in the peeling composition, for example, a oscillating cleaner or a paddle cleaner can be used. If such a cleaner is used, by moving or rotating the platform carrying the semiconductor substrate with the adhesive layer up and down or left and right, the adhesive layer on the semiconductor substrate is subjected to convection relative to each other, or the adhesive layer on the semiconductor substrate is subjected to convection generated by its movement or rotation. This 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.

[0181] In order to make the stripping composition convection, in addition to the oscillating cleaner and paddle cleaner mentioned above, for example, the following convection cleaner is typically used: a convection cleaner that can make the stripping composition around it convection by a stirrer when the semiconductor substrate with the adhesive layer is fixed on a table, etc.

[0182] To utilize ultrasound to peel the composition, an ultrasonic cleaner and an ultrasonic probe are used, typically at 20 kHz to 5 MHz.

[0183] To continuously supply the release composition to the adhesive layer on the semiconductor substrate, it is sufficient to continuously touch the adhesive layer on the semiconductor substrate with the release composition. For example, if the adhesive layer on the semiconductor substrate is facing upwards, for instance, from above (including obliquely above) the adhesive layer on the semiconductor substrate, a rod-shaped or mist-like, preferably rod-shaped, release composition is supplied to the adhesive layer on the semiconductor substrate in a manner that is continuous over time through a nozzle or the like of a cleaning device. This continuous over time 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 and then resuming the supply, or repeating the above process. From the viewpoint of achieving more efficient cleaning with good reproducibility, it is preferable to continuously supply the release composition to the adhesive layer on the semiconductor substrate.

[0184] 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.

[0185] In one aspect of the present invention, in order to achieve a state of constant contact with the release composition, a steam cleaner can be used, for example, to bring the adhesive layer on the semiconductor substrate into contact with the vapor of the release composition.

[0186] The cleaning method for the semiconductor substrate of the present invention may also include a step of removing the peeled adhesive layer.

[0187] The method for removing the peeled adhesive layer is not particularly limited as long as it can be removed from the semiconductor substrate. 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, sometimes by simply removing the semiconductor substrate from the release composition, the peeled adhesive layer can be left naturally in the release composition, and most of it can be removed.

[0188] 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, and removing it by centrifugal force generated by moving or rotating the semiconductor substrate up and down or left and right, but are not limited to these methods.

[0189] After removing the peeled adhesive layer, the semiconductor substrate is dried using conventional methods as needed.

[0190] 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 various conditions are as described above. Regarding the stripping composition of the present invention, if necessary, it can be manufactured by mixing the solvents constituting the composition in any order. In this case, filtration or the like can also be performed if necessary.

[0191] 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 siloxane-based adhesive containing the polyorganosiloxane component (A) cured by the hydrogenation silanization reaction, can be efficiently removed, and efficient and good semiconductor device manufacturing can be expected.

[0192] In addition to silicon semiconductor substrates such as silicon wafers, the semiconductor substrates targeted by the cleaning method of the present invention also include, for example, 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 nitride film-forming silicon substrates, silicon oxide film-forming silicon substrates, polyimide film-forming silicon substrates, glass substrates, quartz substrates, liquid crystal substrates, organic EL substrates, and other various substrates.

[0193] As an example of the use of the cleaning method for the semiconductor substrate of the present invention in semiconductor processes, its use can be cited in the manufacturing method of semiconductor substrates that have undergone thinning and other processes for semiconductor packaging technologies such as TSV.

[0194] 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 cleaning method of the semiconductor substrate of the present invention is used in the fourth step.

[0195] As an adhesive composition for forming an adhesive layer in the first process, various adhesives described above can be used, but for the cleaning method of the semiconductor substrate of the present invention, it is effective for removing adhesive layers obtained by polysiloxane-based adhesives, and even more effective for removing adhesive layers obtained by polysiloxane-based adhesives containing component (A) cured by a hydrogenation silanization reaction.

[0196] 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 by using a polysiloxane-based adhesive (adhesive composition), but the present invention is not limited thereto.

[0197] 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.

[0198] In one embodiment, the first step includes: a step of coating an adhesive composition onto the surface of a semiconductor substrate or a support substrate to form an adhesive coating layer; and a step of bonding the semiconductor substrate and the support substrate together via the adhesive coating layer, applying a load in the thickness direction of the semiconductor substrate and the support substrate to make them bonded while performing at least one of a heat treatment and a decompression treatment, followed by a post-heat treatment, thereby forming a laminate.

[0199] In other embodiments, the first step may include, for example, a step of coating an adhesive composition onto the circuit surface of a wafer on a semiconductor substrate and heating it to form an adhesive coating layer; a step of coating a release agent composition onto the surface of a support substrate and heating it to form a release agent coating layer; and a step of applying a load in the thickness direction of the semiconductor substrate and the support substrate to adhere 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.

[0200] In the above schemes, the choice of heat treatment, decompression treatment, or a combination of both can be determined based on various factors such as the type of adhesive composition, the specific composition of the release agent composition, the phase properties of the film obtained from the two compositions, the film thickness, and the desired adhesive strength.

[0201] 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.

[0202] Examples of wafers 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.

[0203] In particular, the cleaning method for semiconductor substrates of the present invention can suppress damage to the bumps of the bumped semiconductor substrate and effectively clean the substrate.

[0204] 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 can be appropriately selected from conditions such as approximately 1 to 200 μm, bump diameter 1 to 200 μm, and bump spacing 1 to 500 μm.

[0205] Specific examples of plated bumps include SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other Sn-based alloy-plated bumps, but are not limited to these.

[0206] The support (carrier) is not particularly limited. For example, a silicon wafer with a diameter of 300 mm and a thickness of about μm can be listed, but it is not limited to this.

[0207] As a stripping agent composition, examples include compositions containing stripping agent components for this purpose.

[0208] There are no particular limitations on the coating method; spin coating is the most common. It should be noted that it is also possible to form a coating film separately using spin coating or other methods and then attach a sheet-like coating film; this is also called coating or coating film.

[0209] The heating temperature of the coated adhesive composition varies depending on the type or quantity of adhesive components included in the adhesive composition, whether it contains solvent, the desired thickness of the adhesive layer, etc., and therefore cannot be specified in general terms. It is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes.

[0210] The heating temperature of the coated release agent composition varies depending on the type or 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 terms. From the viewpoint of achieving proper curing, the heating temperature is 120°C or higher, and from the viewpoint of preventing over-curing, it is preferably 260°C or lower, and the heating time is usually 1 to 10 minutes.

[0211] Heating can be done using heating plates, ovens, etc.

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

[0213] The thickness of the release agent coating layer obtained by coating the release agent composition and heating it is typically 5 to 500 μm.

[0214] Regarding heat treatment, considering the viewpoints 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 temperature can generally be appropriately determined within the range of 20 to 150°C. In particular, from the viewpoint of suppressing or avoiding over-curing or unnecessary deterioration of the adhesive and release agent components, a temperature of 130°C or lower is preferred, more preferably 90°C or lower. From the viewpoint of reliably exhibiting adhesion and release capabilities, 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, the heating time is generally 10 minutes or less, preferably 5 minutes or less.

[0215] 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 10–10000 Pa. The depressurization process typically lasts 1–30 minutes.

[0216] In a preferred embodiment of the present invention, the substrate and the coating layer or the coating layers are preferably bonded by a decompression treatment, and more preferably by a combination of heat treatment and decompression treatment.

[0217] There are no particular limitations on the thickness direction load of the semiconductor substrate and the support substrate, as long as it does not adversely affect the semiconductor substrate, the support substrate and the layers between them, and can firmly seal them together. It is usually in the range of 10 to 1000 N.

[0218] 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., it is preferably 260°C or lower. From the viewpoint of achieving proper bonding of the cured wafers, the heating time is typically 1 minute or more; furthermore, from the viewpoint of stabilizing the physical properties of the adhesive, it is preferably 5 minutes or more; from the viewpoint of avoiding adverse effects on the adhesive layer caused by excessive heating, it is typically 180 minutes, preferably 120 minutes or lower. Heating can be performed using a heating plate, oven, etc.

[0219] It should be noted that one of the purposes of post-heat treatment is to allow the adhesive component (S) to cure more properly.

[0220] Next, the second step of processing the semiconductor substrate of the obtained laminate using the method described above will be explained.

[0221] As an example of the processing performed on the laminate used in this invention, processing on the back side opposite to the circuit surface of the semiconductor substrate 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. Furthermore, back-side electrodes are formed before and after three-dimensional mounting. During the wafer thinning and TSV processes, heat of 250 to 350°C is applied while the wafer is bonded to the support, but the adhesive layer included in the laminate used in this invention is heat-resistant to this heat.

[0222] 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 to 4 μm by grinding the back side opposite to the circuit surface.

[0223] The third process, which separates the processed semiconductor substrate and adhesive layer from the support substrate, is described.

[0224] In the third process, the processed semiconductor substrate and adhesive layer are separated from the support substrate. At this time, if the release layer is included in the laminate, the release layer is usually removed together with the support substrate.

[0225] 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 adjacent to the adhesive layer. Examples of such peeling methods include laser peeling, mechanical peeling using a device with a sharp point, and manual peeling, but it is not limited to these.

[0226] Next, the fourth step, which involves removing the adhesive layer from the processed semiconductor substrate and cleaning the processed semiconductor substrate, will be described.

[0227] The fourth step is to remove 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 various conditions at this time are as described above.

[0228] After the fourth process, if necessary, a cleaning agent composition containing salt can be used to remove adhesive layer residues remaining on the semiconductor substrate, but care should be taken not to damage the semiconductor substrate, especially the bumps of the semiconductor substrate with bumps.

[0229] The method for manufacturing the processed semiconductor substrate of the present invention includes the first to fourth steps described above, but may also include steps other than these. Furthermore, various modifications may 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.

[0230] Example

[0231] 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, based on gas chromatography, is as follows.

[0232] [Apparatus] (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 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] Mesitylene: Produced by Fujifilm and Kohden Chemical Co., Ltd., purity > 97.0%.

[0239] p-Isopropyltoluene: Produced by Tokyo Chemical Industry Co., Ltd., purity >95.0%.

[0240] 1,2,4-Trimethylbenzene: Produced by Tokyo Chemical Industry Co., Ltd., purity >98.0%.

[0241] 1,4-Diisopropylbenzene: Produced by Tokyo Chemical Industry Co., Ltd., purity >98.0%.

[0242] Toluene: Produced by Tokyo Chemical Industry Co., Ltd., purity >99.5%.

[0243] [1] Preparation of adhesive composition

[0244] [Preparation Example 1]

[0245] Add 95g of vinyl-containing MQ resin (manufactured by Wacker Chemie Co., Ltd.) as (a1), 93.4g of p-menthane (manufactured by Terpene Chemical Co., Ltd., Japan) 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 stir for 5 minutes.

[0246] 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 a polydimethylsiloxane (B) 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 in a rotary mixer for 5 minutes.

[0247] Subsequently, 14.9 g of a mixture obtained by mixing 0.20 g of a platinum catalyst (manufactured by Wacker Chemie) as (A2) and 17.7 g of a vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1000 mPa·s as (a1) in a rotary mixer for 5 minutes was added to the obtained mixture. The mixture was further stirred in a rotary mixer for 5 minutes, and the resulting mixture was filtered through a 300-mesh nylon filter to obtain an adhesive composition.

[0248] [2] Fabrication of the substrate for evaluation

[0249] [Manufacturing Example 1]

[0250] On a 4cm×4cm Si wafer (775μm thick) serving as the device side, the composition obtained in Preparation Example 1 was coated by spin coating. The wafer was heated at 120°C for 1.5 minutes using a heating plate, followed by heating at 200°C for 10 minutes to form a 60μm thick film on the wafer, resulting in a wafer with an adhesive layer.

[0251] [Manufacturing Example 2]

[0252] The bumped substrate is cut to prepare 4cm×4cm sample substrates. It should be noted that each sample substrate has 5044 bumps. In terms of the bump structure, the upright part is copper, the cap part is tin-silver (silver 1.8% by mass), and the part between the upright and the cap is nickel.

[0253] [3] Measurement of stripping time

[0254] [Example 1-1]

[0255] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of trimethylbenzene, the peeling composition of Example 1-1, and the time until the adhesive layer began to peel off from the wafer was measured to be 18 seconds.

[0256] [Examples 1-2]

[0257] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent of trimethylbenzene and N-methylpyrrolidone (9:1 (w / w)) used as a peeling composition in Examples 1-2, and the time until the adhesive layer began to peel off from the wafer was measured to be 24 seconds.

[0258] [Comparative Example 1]

[0259] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent of trimethylbenzene and N-methylpyrrolidone (7:3 (w / w)) used as a peeling composition in Comparative Example 1, and the time until the adhesive layer began to peel off from the wafer was measured to be 49 seconds.

[0260] [Example 2-1]

[0261] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of p-isopropyltoluene, which was used as a peeling composition in Example 2-1, and the time until the adhesive layer began to peel off from the wafer was measured to be 18 seconds.

[0262] [Example 2-2]

[0263] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent of p-isopropyltoluene and N-methylpyrrolidone (9:1 (w / w)) used as a peeling composition in Examples 2-2, and the time until the adhesive layer began to peel off from the wafer was measured to be 24 seconds.

[0264] [Comparative Example 2]

[0265] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent of p-isopropyltoluene and N-methylpyrrolidone (7:3 (w / w)) used as a peeling composition in Comparative Example 2, and the time until the adhesive layer began to peel off from the wafer was measured to be 52 seconds.

[0266] [Example 3]

[0267] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of 1,2,4-trimethylbenzene, the peeling composition of Example 3, and the time until the adhesive layer began to peel off from the wafer was measured to be 18 seconds.

[0268] [Comparative Example 3]

[0269] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of 1,4-diisopropylbenzene, which was used as a peeling composition in Comparative Example 3. The time until the adhesive layer began to peel off from the wafer was measured to be 44 seconds.

[0270] [Example 4]

[0271] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of toluene, the peeling composition of Example 4, and the time until the adhesive layer began to peel off from the wafer was measured to be 9 seconds.

[0272] The results of the examples and comparative examples are shown in Table 1. As shown in Table 1, in the case where the solvent of the stripping composition is a stripping composition containing more than 80% by mass of the organic solvent shown in Formula (1), such as mesitylene or p-isopropyltoluene (Examples 1-1 to Examples 4), compared with the case where the content of the organic solvent shown in Formula (1) is less than 80% by mass of the stripping composition (Comparative Examples 1 and 2), and the case where the organic solvent shown in Formula (1) is not contained but a stripping composition containing 1,4-diisopropylbenzene is used (Comparative Example 3), the peeling time of the adhesive layer on the semiconductor substrate is extremely short. The 1,4-diisopropylbenzene mentioned above is a compound having the same number of carbon atoms as the organic solvent shown in Formula (1) and being structurally similar.

[0273] [Table 1]

[0274]

[0275] [4] Observation of damage to substrates with bumps

[0276] [Example 5]

[0277] The sample substrate prepared in Manufacturing Example 2 was immersed in 9 mL of trimethylbenzene and allowed to stand for 1 hour. It was then cleaned with isopropanol and acetone, and the substrate was observed under an optical microscope for any bump damage. No bump damage was observed.

[0278] [Comparative Example 4]

[0279] 2 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) and 18 g of mesitylene were thoroughly stirred using a mixing rotor at room temperature, and the tetrabutylammonium fluoride residue dissolved. Therefore, the supernatant of the solution was recovered.

[0280] 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 under an optical microscope for any bump damage. As a result, damaged bumps were identified throughout the entire sample substrate (the estimated number of damaged bumps was 1000 to 2000).

Claims

1. A cleaning method of a semiconductor substrate, characterized by, a process of peeling the adhesive layer on the semiconductor substrate using a peeling composition, the adhesive layer is a film obtained using an adhesive composition containing an adhesive component S, the adhesive component S contains a siloxane-based adhesive containing a polyorganosiloxane component A cured by a hydrosilylation reaction, the peeling composition contains a solvent and does not contain a salt, the solvent contains 80% by mass or more of an organic solvent represented by formula (1), In the formula, L represents a substituent group substituted on the benzene ring, and each independently represents an alkyl group having 1 to 4 carbon atoms, and k represents the number of L and is an integer of 0 to 5.

2. The cleaning method of a semiconductor substrate according to claim 1, wherein the solvent contains 85% by mass or more of the organic solvent represented by formula (1).

3. The cleaning method of a semiconductor substrate according to claim 2, wherein the solvent consists of the organic solvent represented by formula (1).

4. The cleaning method of a semiconductor substrate according to any one of claims 1 to 3, wherein the L is a methyl group or an isopropyl group.

5. The cleaning method of a semiconductor substrate according to claim 1, wherein the organic solvent represented by formula (1) is at least one selected from toluene, mesitylene, p-cymene, and 1,2,4-trimethylbenzene.

6. The cleaning method of a semiconductor substrate according to any one of claims 1 to 3, characterized in that the adhesive component S further contains at least one selected from 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.

7. A method for manufacturing a processed semiconductor substrate, characterized by, including: a first process of manufacturing a laminate provided with a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition; a second process of processing the semiconductor substrate of the obtained laminate; a third process of separating the semiconductor substrate and the adhesive layer from the support substrate; and a fourth process of peeling the adhesive layer on the semiconductor substrate using a peeling composition, the adhesive layer is a film obtained using an adhesive composition containing an adhesive component S, the adhesive component S contains a siloxane-based adhesive containing a polyorganosiloxane component A cured by a hydrosilylation reaction, the peeling composition contains a solvent and does not contain a salt, the solvent contains 80% by mass or more of an organic solvent represented by formula (1), 8. The manufacturing method of a processed semiconductor substrate according to claim 7, wherein In the formula, L represents a substituent group substituted on the benzene ring, and each independently represents an alkyl group having 1 to 4 carbon atoms, and k represents the number of L and is an integer of 0 to 5. the solvent contains 85% by mass or more of the organic solvent represented by formula (1).

9. The manufacturing method of a processed semiconductor substrate according to claim 8, wherein the solvent consists of the organic solvent represented by formula (1).

10. The manufacturing method of a processed semiconductor substrate according to any one of claims 7 to 9, wherein the L is a methyl group or an isopropyl group.

11. The manufacturing method of a processed semiconductor substrate according to claim 10, wherein the organic solvent represented by formula (1) is at least one selected from toluene, mesitylene, p-cymene, and 1,2,4-trimethylbenzene.

12. The manufacturing method of a processed semiconductor substrate according to any one of claims 7 to 9, 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.

13. A composition for peeling characterized by comprising: for peeling an adhesive layer on a semiconductor substrate when the semiconductor substrate is cleaned, The peeling composition contains a solvent and does not contain a salt, The solvent contains 80 mass% or more of an organic solvent represented by formula (1), The adhesive layer is a film obtained using an adhesive composition containing an adhesive component S, The adhesive component S contains a siloxane-based adhesive containing a polyorganosiloxane component A cured by a hydrosilylation reaction, In the formula, L represents a substituent group substituted on the benzene ring, and each independently represents an alkyl group having 1 to 4 carbon atoms, and k represents the number of L and is an integer of 0 to 5.

14. The peeling composition according to claim 13, wherein The solvent contains 85 mass% or more of the organic solvent represented by formula (1).

15. The peeling composition according to claim 14, wherein The solvent consists of the organic solvent represented by formula (1).

16. The peeling composition according to any one of claims 13 to 15, wherein The L is a methyl group or an isopropyl group.

17. The peeling composition according to claim 16, wherein The organic solvent represented by formula (1) is at least one selected from the group consisting of toluene, mesitylene, p-cymene, and 1,2,4-trimethylbenzene.

18. The peeling composition according to any one of claims 13 to 15, wherein 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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