Method for cleaning semiconductor substrates, method for producing processed semiconductor substrates, and stripping composition

Abstract

A method for cleaning a semiconductor substrate that includes a step for using a peeling composition to peel off an adhesive layer on a semiconductor substrate, the method being characterised in that: the peeling composition contains a solvent but does not contain a salt; the solvent comprises one or more compounds with a molecular weight of less than 160, selected from aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, ether compounds, thioether compounds, ester compounds and amine compounds; and the contact angle of the peeling composition on the adhesive layer is less than 31.5 degrees.

Description

[Technical field]

[0001] The present invention relates to a method for cleaning a semiconductor substrate, a method for producing a processed semiconductor substrate, and a stripping composition. [Background technology]

[0002] Conventionally, semiconductor wafers have been integrated in a two-dimensional plane, but for the purpose of further integration, there is a demand for semiconductor integration technology that integrates (stacks) the plane in a three-dimensional direction. This three-dimensional stacking is a technology that integrates multiple layers while connecting them with through silicon vias (TSVs). When integrating multiple layers, each wafer to be integrated is thinned by polishing the side opposite the circuit surface (i.e., the back side), and the thinned semiconductor wafers are stacked.

[0003] A semiconductor wafer before thinning (also simply called a wafer here) is bonded to a support in order to be polished by a polishing device. The bond at that time must be easily peeled off after polishing, so it is called temporary bonding. This temporary bonding must be easily removed from the support, and if a large force is applied to remove it, the thinned semiconductor wafer may be cut or deformed, so it is easily removed to prevent such things from happening. However, it is not preferable for the semiconductor wafer to come off or shift due to the polishing stress when polishing the back surface. Therefore, the performance required for the temporary bonding is to withstand the stress during polishing and to be easily removed after polishing. For example, it is required to have a high stress (strong adhesive force) in the planar direction during polishing, and a low stress (weak adhesive force) in the direction crossing the planar direction during removal, i.e., the vertical direction. In addition, the processing process may reach high temperatures of 150°C or more, so heat resistance is also required.

[0004] Under these circumstances, in the semiconductor field, polysiloxane adhesives that can have these properties are mainly used as temporary adhesives. In polysiloxane-based adhesion using a polysiloxane adhesive, adhesive residues often remain on the substrate surface after the thinned substrate is peeled off. In order to avoid problems in the subsequent process, cleaning compositions have been developed to remove these residues and clean the semiconductor substrate surface (e.g., Patent Documents 1 and 2). Patent Document 1 discloses a siloxane resin remover containing a polar aprotic solvent and a quaternary ammonium hydroxide, and Patent Document 2 discloses a cured resin remover containing an alkyl ammonium fluoride. However, in the semiconductor field today, there is always a demand for new cleaning compositions, and there is always a demand for effective cleaning compositions and cleaning methods.

[0005] On the other hand, the semiconductor wafer is electrically connected to the semiconductor chip via bump balls made of a conductive material such as metal, and by using chips equipped with such bump balls, the size of semiconductor packaging is reduced. In this regard, bump balls made of metals such as copper and tin have poor corrosion resistance and therefore suffer from the problem of being damaged by cleaning compositions used to remove adhesive residues from supports and wafers (Patent Document 3). Therefore, one of the requirements for cleaning compositions and cleaning methods is to not corrode the bump balls when cleaning substrates. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2014 / 092022 [Patent Document 2] U.S. Patent No. 6,818,608 [Patent Document 3] Korean Patent Publication No. 2018-0066550 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and has an object to provide a method for cleaning a semiconductor substrate, for example, for easily and suitably removing an adhesive layer obtained from a semiconductor substrate having an adhesive layer on its surface, obtained by using a siloxane-based adhesive, while reducing or suppressing damage to bumps on the semiconductor substrate; a method for producing a processed semiconductor substrate that includes such a cleaning method; and a stripping composition for use in such a cleaning method. [Means for solving the problem]

[0008] As a result of intensive research into solving the above problems, the present inventors have discovered that an adhesive layer on a semiconductor substrate, particularly an adhesive layer which is a cured film obtained from a siloxane-based adhesive containing a polyorganosiloxane component (A) which cures by a hydrosilylation reaction, can be peeled off using a stripping composition which contains a solvent and does not contain a salt, and when cleaning the semiconductor substrate, one or more specific organic solvents having a molecular weight of less than 160 are used as the solvent, and the contact angle of the stripping composition on the adhesive layer is set to less than 31.5 degrees, thereby enabling efficient and easy peeling while reducing or suppressing damage to the bumps on the semiconductor substrate, and thus completing the present invention.

[0009] That is, the present invention provides 1. A method for cleaning a semiconductor substrate, comprising a step of peeling off an adhesive layer on a semiconductor substrate using a peeling composition, The stripping composition comprises a solvent and does not comprise a salt, the solvent is one or more selected from aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, ether compounds, thioether compounds, ester compounds, and amine compounds, each having a molecular weight of less than 160; a contact angle of the stripping composition on the adhesive layer being less than 31.5 degrees; 2. The method for cleaning a semiconductor substrate according to claim 1, wherein the molecular weight is 70 or more. 3. The method for cleaning a semiconductor substrate according to claim 1, wherein the solvent is one or more selected from the group consisting of di(n-butyl)ether, n-decane, di(n-pentyl)ether, 1-amino-n-pentane, p-menthane, butyl acetate, cyclohexane, di(n-propyl)sulfide, pentyl acetate, di(n-butyl)sulfide, mesitylene, limonene and p-cymene; 4. The method for cleaning a semiconductor substrate according to any one of 1 to 3, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) including at least one adhesive selected from the group consisting of a siloxane-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenol resin-based adhesive. 5. The method for cleaning a semiconductor substrate according to 4, wherein the adhesive component (S) contains a siloxane-based adhesive. 6. The method for cleaning a semiconductor substrate according to 5, wherein the siloxane-based adhesive contains a polyorganosiloxane component (A) that cures by a hydrosilylation reaction; 7. A first step of producing a laminate including 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 method for producing a processed semiconductor substrate, comprising a fourth step of peeling off an adhesive layer on the semiconductor substrate using a peeling composition, The stripping composition comprises a solvent and does not comprise a salt, the solvent is one or more selected from aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, ether compounds, thioether compounds, ester compounds, and amine compounds, each having a molecular weight of less than 160; a contact angle of the peeling composition on the adhesive layer being less than 31.5 degrees; 8. The method for producing a processed semiconductor substrate according to 7, wherein the molecular weight is 70 or more. 9. The method for producing a processed semiconductor substrate according to 7, wherein the solvent is one or more selected from di(n-butyl)ether, n-decane, di(n-pentyl)ether, 1-amino-n-pentane, p-menthane, butyl acetate, cyclohexane, di(n-propyl)sulfide, pentyl acetate, di(n-butyl)sulfide, mesitylene, limonene and p-cymene; 10. The method for producing a processed semiconductor substrate according to any one of 7 to 9, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) including at least one selected from a siloxane-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenol resin-based adhesive. 11. The method of claim 10, wherein the adhesive component (S) comprises a siloxane-based adhesive. 12. The method of producing a processed semiconductor substrate according to claim 11, wherein the siloxane-based adhesive comprises a polyorganosiloxane component (A) that cures by a hydrosilylation reaction; 13. A stripping composition used for stripping an adhesive layer on a semiconductor substrate when cleaning the semiconductor substrate, comprising: The solvent contains one or more compounds selected from aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, ether compounds, thioether compounds, ester compounds, and amine compounds, each having a molecular weight of less than 160; Contains no salt, a peeling composition having a contact angle on the adhesive layer of less than 31.5 degrees; 14. The stripping composition according to 13, wherein the molecular weight is 70 or more. 15. The stripping composition according to 13, wherein the solvent is one or more selected from di(n-butyl)ether, n-decane, di(n-pentyl)ether, 1-amino-n-pentane, p-menthane, butyl acetate, cyclohexane, di(n-propyl)sulfide, pentyl acetate, di(n-butyl)sulfide, mesitylene, limonene, and p-cymene; 16. The peeling composition according to any one of 13 to 15, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) including at least one selected from a siloxane-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenol resin-based adhesive; 17. The stripping composition of 16, wherein the adhesive component (S) comprises a siloxane-based adhesive. 18. The release composition of claim 17, wherein the siloxane-based adhesive comprises a polyorganosiloxane component (A) that cures by a hydrosilylation reaction. Effect of the Invention

[0010] By using the semiconductor substrate cleaning method of the present invention, an adhesive layer obtained, for example, using a siloxane-based adhesive can be suitably and easily removed from a semiconductor substrate having the adhesive layer on its surface, which is expected to lead to the efficient production of good semiconductor elements. In particular, when a semiconductor substrate having an adhesive layer is provided with bumps, the adhesive layer can be suitably and easily removed while avoiding or suppressing damage to the bumps, which is expected to enable the production of high-quality semiconductor elements that are highly efficient and reliable. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The method for cleaning a semiconductor substrate of the present invention includes a step of peeling off an adhesive layer on a semiconductor substrate using a peeling composition, the peeling composition containing a solvent but not containing a salt, the solvent consisting of one or more compounds selected from aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, ether compounds, thioether compounds, ester compounds and amine compounds having a molecular weight of less than 160, and the contact angle of the peeling composition on the adhesive layer is less than 31.5 degrees.

[0012] The semiconductor substrate is, for example, a wafer, and a specific example thereof is a silicon wafer having a diameter of about 300 mm and a thickness of about 770 μm, but is not limited to this.

[0013] The adhesive layer on such a semiconductor substrate is, for example, a film obtained from an adhesive composition containing an adhesive component (S). Such adhesive component (S) is not particularly limited as long as it is used for this type of application, and examples thereof include siloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenolic resin-based adhesives. Among these, siloxane-based adhesives are preferred as the adhesive component (S) because they exhibit suitable adhesive properties during processing of wafers and the like, can be easily peeled off after processing, and also have excellent heat resistance.

[0014] In a preferred embodiment, the adhesive composition used in the present invention contains, as an adhesive component, a polyorganosiloxane component (A) that cures by a hydrosilylation reaction. In a more preferred embodiment, the polyorganosiloxane component (A) that cures by a hydrosilylation reaction contains a siloxane unit (Q unit) represented by SiO2, R 1 R 2 R 3 SiO 1 / 2 Siloxane unit (M unit) represented by R 4 R 5 SiO 2 / 2 Siloxane units (D units) represented by the formula 6 SiO 3 / 2 and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) contains one or more units selected from the group consisting of siloxane units (T units) represented by SiO2, siloxane units (Q' units) represented by R 1 'R 2 'R 3 'SiO 1 / 2 Siloxane unit (M' unit) represented by R 4 'R 5 'SiO 2 / 2 Siloxane units (D' units) represented by the formula 6 'SiO 3 / 2and at least one unit selected from the group consisting of M' units, D' units and T' units, and a polyorganosiloxane (a1) containing one or more units selected from the group consisting of siloxane units (T' units) represented by the following formula: 1 "R 2 "R 3 "SiO 1 / 2 Siloxane unit (M” unit) represented by R 4 "R 5 "SiO 2 / 2 Siloxane units (D" units) represented by the formula 6 "SiO 3 / 2 and a polyorganosiloxane (a2) containing one or more units selected from the group consisting of siloxane units (T″ units) represented by the following formula:

[0015] R 1 ~R 6 are groups or atoms bonded to the silicon atom, and each independently represents an alkyl group, an alkenyl group, or a hydrogen atom.

[0016] R 1 '~R 6 R ′ is a group bonded to a silicon atom, and each independently represents an alkyl group or an alkenyl group. 1 '~R 6 At least one of is an alkenyl group.

[0017] R 1 ”~R 6 " are groups or atoms bonded to the silicon atom, each independently representing an alkyl group or a hydrogen atom, R 1 ”~R 6 At least one of " is a hydrogen atom.

[0018] The alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group. 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.

[0019] Specific examples of linear or branched alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-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, and 3-methyl-n-pentyl. Examples of the aryl group include, but are not limited to, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group. Of these, a methyl group is preferred.

[0020] Specific examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a 1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a 3-ethyl-cyclobutyl group, a 1,2-dimethyl-cyclobutyl group, a 1,3-dimethyl-cyclobutyl group, a 2,2-dimethyl-cyclobutyl group, a 2,3-dimethyl-cyclobutyl group, a 2,4-dimethyl cycloalkyl groups such as cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl; and bicycloalkyl groups such as bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl.

[0021] The alkenyl group may be either linear or branched, and the number of carbon atoms therein is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0022] Specific examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2- propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-i-propylethenyl, 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 group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 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-s-butylethenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-i-butylethenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl- Examples of the cyclopentyl group include, but are not limited to, a 2-propenyl group, a 1-methyl-2-cyclopentenyl group, a 1-methyl-3-cyclopentenyl group, a 2-methyl-1-cyclopentenyl group, a 2-methyl-2-cyclopentenyl group, a 2-methyl-3-cyclopentenyl group, a 2-methyl-4-cyclopentenyl group, a 2-methyl-5-cyclopentenyl group, a 2-methylene-cyclopentyl group, a 3-methyl-1-cyclopentenyl group, a 3-methyl-2-cyclopentenyl group, a 3-methyl-3-cyclopentenyl group, a 3-methyl-4-cyclopentenyl group, a 3-methyl-5-cyclopentenyl group, a 3-methylene-cyclopentyl group, a 1-cyclohexenyl group, a 2-cyclohexenyl group, and a 3-cyclohexenyl group. Of these, ethenyl and 2-propenyl are preferred.

[0023] As described above, the polysiloxane (A1) contains the polyorganosiloxane (a1) and the polyorganosiloxane (a2), and the alkenyl group contained in the polyorganosiloxane (a1) and the hydrogen atom (Si-H group) contained in the polyorganosiloxane (a2) form a crosslinked structure through a hydrosilylation reaction in the presence of a platinum group metal catalyst (A2), thereby curing.

[0024] The polyorganosiloxane (a1) contains one or more units selected from the group consisting of Q' units, M' units, D' units and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units and T' units. As the polyorganosiloxane (a1), a combination of two or more polyorganosiloxanes satisfying such conditions may be used.

[0025] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units) and (Q' units, T' units and M' units).

[0026] In addition, when the polyorganosiloxane (a1) contains two or more types of polyorganosiloxanes, 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 are not limited to these.

[0027] The polyorganosiloxane (a2) contains one or more units selected from the group consisting of Q″ units, M″ units, D″ units, and T″ units, and also contains at least one unit selected from the group consisting of M″ units, D″ units, and T″ units. As the polyorganosiloxane (a2), a combination of two or more polyorganosiloxanes satisfying such conditions may be used.

[0028] Preferred combinations of two or more selected from the group consisting of Q″ units, M″ units, D″ units and T″ units include, but are not limited to, (M″ units and D″ units), (Q″ units and M″ units), and (Q″ units, T″ units and M″ units).

[0029] The polyorganosiloxane (a1) is composed of siloxane units having alkyl and / or alkenyl groups bonded to the silicon atoms thereof.1 '~R 6 The proportion of alkenyl groups in all the substituents represented by R 1 '~R 6 ' can be an alkyl group.

[0030] The polyorganosiloxane (a2) is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to the silicon atom. 1 ”~R 6 The proportion of hydrogen atoms in all the substituents and substituted atoms represented by R 1 ”~R 6 " can be an alkyl group.

[0031] The polysiloxane (A1) contains a polyorganosiloxane (a1) and a polyorganosiloxane (a2). In a preferred embodiment, the molar ratio of the alkenyl groups contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0032] The weight average molecular weight of each of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) is usually from 500 to 1,000,000, but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably from 5,000 to 50,000. The weight average molecular weight, number average molecular weight and dispersity in the present invention can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC, manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H, manufactured by Tosoh Corporation), setting the column temperature at 40° C., using tetrahydrofuran as an eluent (elution solvent), setting the flow rate (flow velocity) at 0.35 mL / min, and using polystyrene (manufactured by Sigma-Aldrich) as a standard sample.

[0033] The viscosity of each of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) is usually 10 to 1,000,000 (mPa·s), but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 50 to 10,000 (mPa·s). Note that the viscosity in the present invention is a value measured by an E-type rotational viscometer at 25°C.

[0034] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other to form a film by hydrosilylation, and therefore the mechanism of cure is different from that via, for example, silanol groups, and therefore neither siloxane needs to contain silanol groups or functional groups that form silanol groups upon hydrolysis, such as alkyloxy groups.

[0035] In a preferred embodiment, the adhesive component (S) contains a platinum group metal catalyst (A2) together with the above-mentioned polysiloxane (A1). Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl groups of the polyorganosiloxane (a1) and the Si-H groups of the polyorganosiloxane (a2).

[0036] Specific examples of platinum-based metal catalysts include platinum black, platinic chloride, chloroplatinic acid, a reaction product of chloroplatinic acid with a monohydric alcohol, a complex of chloroplatinic acid with an olefin, platinum bisacetoacetate, and other platinum-based catalysts, but are not limited to these. An example of a complex of platinum with an olefin is, but is not limited to, a complex of divinyltetramethyldisiloxane with platinum. The amount of the platinum group metal catalyst (A2) is usually in the range of 1.0 to 50.0 ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0037] The polyorganosiloxane component (A) may contain a polymerization inhibitor (A3) for the purpose of inhibiting the progress of the hydrosilylation reaction. The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction. Specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol. The amount of the polymerization inhibitor is usually 1000.0 ppm or more, based on the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2), from the viewpoint of obtaining the effect, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0038] The adhesive composition used in the present invention may contain a release agent component (B). By including such a release agent component (B) in the adhesive composition used in the present invention, the resulting adhesive layer can be preferably peeled off with good reproducibility. A typical example of such a release agent component (B) is a polyorganosiloxane, and specific examples thereof include, but are not limited to, epoxy group-containing polyorganosiloxane, methyl group-containing polyorganosiloxane, and phenyl group-containing polyorganosiloxane.

[0039] The weight average molecular weight of the polyorganosiloxane which is the release agent component (B) is usually 100000 to 2000000, but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 200000 to 1200000, more preferably 300000 to 900000, and its dispersity is usually 1.0 to 10.0, but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight average molecular weight and dispersity can be measured by the above-mentioned method.

[0040] Examples of epoxy group-containing polyorganosiloxanes include R 11 R 12 SiO 2 / 2 The siloxane unit (D 10 Examples include those containing the unit.

[0041] R 11 is a group bonded to a silicon atom and represents an alkyl group; R 12 is a group bonded to a silicon atom, and represents an epoxy group or an organic group containing an epoxy group. Specific examples of the alkyl group include those listed above.

[0042] Furthermore, the epoxy group in the organic group containing an epoxy group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group.

[0043] Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl. In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but is not limited thereto.

[0044] The epoxy group-containing polyorganosiloxane is a polyorganosiloxane having the above-mentioned siloxane unit (D 10 D 10In addition to the units, the above Q units, M units and / or T units may be included.

[0045] In a preferred embodiment, specific examples of the epoxy group-containing polyorganosiloxane include D 10 Polyorganosiloxane consisting of only units, D 10 Polyorganosiloxanes containing D units and Q units; 10 Polyorganosiloxanes containing D units and M units; 10 Polyorganosiloxanes containing D units and T units; 10 Polyorganosiloxanes containing units, Q units and M units, D 10 Polyorganosiloxanes containing units, M units and T units, D 10 and polyorganosiloxanes containing Q units, M units and T units.

[0046] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. The weight average molecular weight is usually 1,500 to 500,000, but from the viewpoint of suppressing precipitation in the adhesive composition, it is preferably 100,000 or less.

[0047] Specific examples of epoxy group-containing polyorganosiloxanes include CMS-227 (manufactured by Gelest Co., Ltd., weight average molecular weight 27,000) represented by formula (A-1), ECMS-327 (manufactured by Gelest Co., Ltd., weight average molecular weight 28,800) represented by formula (A-2), KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 31,800) represented by formula (A-3), and KF-1001 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 55,600) represented by formula (A-4). ), trade name KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 11,500) represented by formula (A-5), trade name X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 2,400) represented by formula (A-6), trade name BY16-839 (manufactured by Dow Corning Corporation, weight average molecular weight 51,700) represented by formula (A-7), trade name ECMS-327 (manufactured by Gelest Corporation, weight average molecular weight 28,800) represented by formula (A-8), and the like, but are not limited to these.

[0048] [ka] (m and n are the numbers of repeating units.)

[0049] [ka] (m and n are the numbers of repeating units.)

[0050] [ka] (m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0051] [ka] (m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0052] [ka] (m, n, and o are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0053] [ka] (m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0054] [ka] (m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0055] [ka] (m and n are the numbers of repeating units.)

[0056] Examples of the methyl group-containing polyorganosiloxane include R 210 R 220 SiO 2 / 2 The siloxane unit (D 200 units), preferably R 21 R 21 SiO 2 / 2 The siloxane unit (D 20 Examples include those containing the unit.

[0057] R 210 and R 220 are groups bonded to a silicon atom, and each independently represents an alkyl group, with at least one being a methyl group. Specific examples of the alkyl group include those listed above. R 21 is a group bonded to a silicon atom, and represents an alkyl group. Specific examples of the alkyl group include those listed above. 21 As the alkyl group, a methyl group is preferable. A preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.

[0058] The methyl group-containing polyorganosiloxane is a polyorganosiloxane having the above-mentioned siloxane unit (D 200 Unit or D 20 D 200 Units and D 20 In addition to the units, the above Q units, M units and / or T units may be included.

[0059] In one embodiment, specific examples of the methyl group-containing polyorganosiloxane include D 200 Polyorganosiloxane consisting of only units, D 200 Polyorganosiloxanes containing D units and Q units; 200 Polyorganosiloxanes containing D units and M units; 200 Polyorganosiloxanes containing D units and T units; 200 Polyorganosiloxanes containing units, Q units and M units, D 200 Polyorganosiloxanes containing units, M units and T units, D 200 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0060] In a preferred embodiment, specific examples of the methyl group-containing polyorganosiloxane include D 20 Polyorganosiloxane consisting of only units, D 20 Polyorganosiloxanes containing D units and Q units; 20 Polyorganosiloxanes containing D units and M units; 20 Polyorganosiloxanes containing D units and T units; 20 Polyorganosiloxanes containing units, Q units and M units, D 20 Polyorganosiloxanes containing units, M units and T units, D 20 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0061] The viscosity of methyl group-containing polyorganosiloxane is usually 1,000 to 2,000,000 mm 2 / s, but preferably 10,000 to 1,000,000 mm 2 / s. The methyl group-containing polyorganosiloxane is typically a dimethyl silicone oil made of polydimethylsiloxane. This viscosity value is indicated as a kinematic viscosity, and is expressed as centistokes (cSt) = mm 2 / s. Kinematic viscosity can be measured with a kinematic viscometer. Viscosity (mPa s) can also be converted to density (g / cm 3 It can also be calculated by dividing by the viscosity (mm 2 / s)=viscosity (mPa s) / density (g / cm 3 ) can be calculated from the formula:

[0062] Specific examples of methyl group-containing polyorganosiloxanes include the WACKERSILICONE FLUID AK series manufactured by Wacker Chemical Co., Ltd., dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) and cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd., but are not limited to these.

[0063] Examples of the phenyl group-containing polyorganosiloxane include R 31 R 32 SiO 2 / 2 The siloxane unit (D 30 Examples include those containing the unit.

[0064] R 31 is a group bonded to a silicon atom and represents a phenyl group or an alkyl group; R 32 is a group bonded to a silicon atom and represents a phenyl group. Specific examples of the alkyl group include those listed above, with a methyl group being preferred.

[0065] The phenyl group-containing polyorganosiloxane is a polyorganosiloxane having the above-mentioned siloxane unit (D30 D 30 In addition to the units, the above Q units, M units and / or T units may be included.

[0066] In a preferred embodiment, specific examples of the phenyl group-containing polyorganosiloxane include D 30 Polyorganosiloxane consisting of only units, D 30 Polyorganosiloxanes containing D units and Q units; 30 Polyorganosiloxanes containing D units and M units; 30 Polyorganosiloxanes containing D units and T units; 30 Polyorganosiloxanes containing units, Q units and M units, D 30 Polyorganosiloxanes containing units, M units and T units, D 30 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0067] The weight average molecular weight of the phenyl group-containing polyorganosiloxane is usually 1,500 to 500,000, but from the viewpoint of inhibiting precipitation in the adhesive composition, it is preferably 100,000 or less.

[0068] A specific example of the phenyl group-containing polyorganosiloxane is PMM-1043 (trade name, manufactured by Gelest, Inc., weight average molecular weight 67,000, viscosity 30,000 mm), represented by formula (C-1). 2 / s), and PMM-1025 (trade name, manufactured by Gelest, Inc., weight average molecular weight 25,200, viscosity 500 mm 2 / s), the trade name KF50-3000CS (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 39,400, viscosity 3000 mm 2 / s), and the product name TSF431 (manufactured by MOMENTIVE Co., Ltd., weight average molecular weight 1,800, viscosity 100 mm 2 / s), and the product name TSF433 (manufactured by MOMENTIVE, weight average molecular weight 3,000, viscosity 450 mm 2 / s), and PDM-0421 (trade name, manufactured by Gelest, Inc., weight average molecular weight 6,200, viscosity 100 mm 2 / s), and PDM-0821 (manufactured by Gelest, Inc., weight average molecular weight 8,600, viscosity 125 mm 2 / s), but are not limited to these.

[0069] [ka] (m and n represent the number of repeating units.)

[0070] [ka] (m and n represent the number of repeating units.)

[0071] [ka] (m and n represent the number of repeating units.)

[0072] [ka] (m and n represent the number of repeating units.)

[0073] [ka] (m and n represent the number of repeating units.)

[0074] [ka] (m and n represent the number of repeating units.)

[0075] [ka] (m and n represent the number of repeating units.)

[0076] In a preferred embodiment, the adhesive composition used in the present invention contains a release agent component (B) together with a polyorganosiloxane component (A) that cures via a hydrosilylation reaction, and in a more preferred embodiment, the release agent component (B) contains a polyorganosiloxane.

[0077] The adhesive composition used in the present invention can contain the adhesive component (S) and the release agent component (B) in any ratio. In consideration of the balance between adhesion and releasability, the ratio of component (S) to component (B) by mass is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25. That is, when the polyorganosiloxane component (A) that cures by a hydrosilylation reaction is contained, the mass ratio of component (A) to component (B) is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25.

[0078] The adhesive composition used in the present invention may contain a solvent for the purpose of adjusting the viscosity, etc., and specific examples of the solvent include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc.

[0079] More specifically, examples of the solvent include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc. Such solvents may be used alone or in combination of two or more.

[0080] When the adhesive composition used in the present invention contains a solvent, the content of the solvent is appropriately set taking into consideration the desired viscosity of the composition, the coating method to be used, the thickness of the thin film to be produced, etc., but is in the range of about 10 to 90 mass % of the entire composition.

[0081] The viscosity of the adhesive composition used in the present invention is usually 500 to 20,000 mPa·s, and preferably 1,000 to 5,000 mPa·s at 25° C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the types and ratios of organic solvents used, the concentrations of film constituent components, etc., taking into consideration various factors such as the coating method used and the desired film thickness. In the present invention, the film constituent components refer to components other than the solvent contained in the composition.

[0082] The adhesive composition used in the present invention can be prepared by mixing the adhesive component (S) with the release agent component (B), if used, and a solvent. The mixing order is not particularly limited, but examples of methods for easily and reproducibly producing an adhesive composition include, but are not limited to, a method of dissolving the adhesive component (S) and the release agent component (B) in a solvent, or a method of dissolving a part of the adhesive component (S) and the release agent component (B) in a solvent and the remaining part in a solvent, and mixing the obtained solutions. Note that when preparing the adhesive composition, heating may be performed appropriately within a range that does not cause the components to decompose or change in quality. In the present invention, for the purpose of removing foreign matter, the adhesive composition may be filtered using a sub-micrometer filter or the like during the production of the adhesive composition or after all of the components have been mixed.

[0083] As described above, the method for cleaning a semiconductor substrate of the present invention includes a step of peeling off an adhesive layer on a semiconductor substrate using a peeling composition, the peeling composition containing a solvent but not containing a salt, and the solvent is one or more compounds selected from aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, ether compounds, thioether compounds, ester compounds, and amine compounds, all of which have a molecular weight of less than 160. Although it is not clear why the use of such a specific organic solvent enables the peeling to be completed in a shorter time, it is presumed that this is due to the high compatibility between the specific organic solvent and the adhesive layer. In addition, the reason why the use of such a molecular weight allows for shorter peeling times is unclear, but it is presumed that this is because a solvent with a lower molecular weight has a higher penetrability into the adhesive layer.

[0084] The aliphatic hydrocarbon compound having a molecular weight of less than 160 may be an aliphatic saturated hydrocarbon compound or an aliphatic unsaturated hydrocarbon compound, and may be linear, branched, or cyclic, or a combination thereof. Specific examples include, but are not limited to, decane, p-menthane, cyclohexane, limonene, and the like.

[0085] An aromatic hydrocarbon compound having a molecular weight of less than 160 is typically, but not limited to, a compound containing an uncondensed benzene ring having a substituent such as an alkyl group, e.g., a methyl group, an ethyl group, or an isopropyl group, and the substituent is selected so as to satisfy the molecular weight requirement. Specific examples include, but are not limited to, toluene, mesitylene, p-cymene, and the like.

[0086] Although not limited thereto, ether compounds having a molecular weight of less than 160 typically have a structure in which two alkyl groups, such as ethyl groups, n-propyl, isopropyl, n-butyl groups, and n-pentyl groups, are linked via an ether bond, and the two alkyl groups are selected so as to satisfy the molecular weight requirement. Specific examples thereof include, but are not limited to, di(n-butyl) ether, di(n-pentyl) ether, and the like.

[0087] Although not limited thereto, thioether compounds having a molecular weight of less than 160 typically have a structure in which two alkyl groups, such as ethyl groups, isopropyl groups, n-butyl groups, n-pentyl groups, etc., are linked via a thioether bond, and the two alkyl groups are selected so as to satisfy the molecular weight requirement. Specific examples thereof include, but are not limited to, di(n-propyl)sulfide, di(n-butyl)sulfide, and the like.

[0088] Although not limited thereto, the ester compound having a molecular weight of less than 160 typically has an acetoxy group bonded to an alkyl group such as an ethyl group, an n-butyl group, or an n-pentyl group, and the alkyl group is selected so as to satisfy the molecular weight requirement. Specific examples include, but are not limited to, butyl acetate, pentyl acetate, and the like.

[0089] Although not limited thereto, the amine compound having a molecular weight of less than 160 typically has an amino group bonded to the end of a linear or branched, preferably linear, alkyl group, and the alkyl group is selected so as to satisfy the molecular weight requirement. Specific examples thereof include, but are not limited to, 1-amino-n-butane, 1-amino-n-pentane, and the like.

[0090] The solvent contained in the stripping composition used in the present invention is the specific organic solvent described above, and is composed of one or more kinds of organic solvents having a molecular weight of less than 160. Most preferably, the solvent contained in the stripping composition is entirely composed of one or more of the specific organic solvents listed above, and ideally does not contain other solvents as impurities; however, there is a limit to how much the purity can be improved by purification, and this is technically impossible. Therefore, in the present invention, the solvent contained in the above-mentioned stripping composition is intended to be the above-mentioned specific organic solvent alone, and does not deny that impurities such as water and organic solvents which are not easily separated due to their similar structure or properties are contained in the above-mentioned specific organic solvent in bulk. For these reasons, the content of the specific organic solvent in the solvent contained in the stripping composition may not be exactly 100% as a purity value by gas chromatography, and 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.

[0091] In the present invention, the molecular weight of the specific organic solvent contained in the stripping composition is less than 160, but from the viewpoint of achieving stripping in a shorter time with good reproducibility, it is preferably less than 150, more preferably less than 130, even more preferably less than 110, and even more preferably less than 90. On the other hand, the lower limit of the molecular weight of the specific organic solvent contained in the stripping composition is usually 70, in one embodiment 75, and in another embodiment 80, from the viewpoint of achieving stripping in a shorter time with good reproducibility.

[0092] Among the specific organic solvents mentioned above, aliphatic saturated hydrocarbon compounds and ether compounds are particularly preferred from the viewpoint of achieving stripping in a shorter time with good reproducibility.

[0093] The stripping composition used in the present invention does not contain any salt. Specific examples of such salts include those used for this type of application, typically ammonium salts such as tetrabutylammonium hydroxide and tetrabutylammonium fluoride (also called tetrabutylammonium fluoride), which are added for the purpose of facilitating removal of the adhesive layer or adhesive layer residue. The stripping composition used in the present invention contains a specific organic solvent that satisfies the above conditions, and therefore does not need to contain such a salt. Since such salts can cause damage such as corrosion to a substrate, particularly a substrate with bumps, a stripping composition that does not contain salt is used in the present invention. However, in cases where a trace amount of salt is originally contained as an impurity in the bulk solvent that constitutes the stripping composition, the presence of the salt is not denied.

[0094] In the present invention, the contact angle of the peeling composition on the adhesive layer must be less than 31.5 degrees. By adopting such a value, peeling can be achieved in a shorter time. Although the reason is unclear, it is presumed that the higher the wettability when the peeling composition is dropped onto the adhesive layer, the higher the penetration of the peeling composition into the adhesive layer.

[0095] In the present invention, from the viewpoint of achieving peeling in a short time with good feasibility, the contact angle of the peeling composition on the adhesive layer is less than 30.0 degrees in one embodiment, less than 28.0 degrees in another embodiment, and less than 27.0 degrees in still another embodiment, and the lower limit is not particularly limited, but is 15.0 degrees in one embodiment, 20.0 degrees in another embodiment, and 24.0 degrees in still another embodiment.

[0096] In the present invention, the adhesive layer used when measuring the contact angle of the peeling composition is produced using an adhesive composition that contains the adhesive component (S) but does not contain the release agent component (H), while the adhesive layer removed by the semiconductor substrate cleaning method of the present invention may be produced using either an adhesive composition that contains the release agent component (H) or an adhesive composition that does not contain the release agent component (H), but from the viewpoint of achieving peeling in a shorter period of time with good reproducibility, the adhesive layer removed by the semiconductor substrate cleaning method of the present invention is produced from an adhesive composition that contains the release agent component (H). The contact angle can be measured, for example, using a fully automatic contact angle measuring instrument DM-701 manufactured by Kyowa Interface Science Co., Ltd.

[0097] In the present invention, the adhesive layer on the semiconductor substrate is continuously brought into contact with the stripping composition to cause the adhesive layer to swell and be stripped from the semiconductor substrate. The method of continuously contacting the adhesive layer on the semiconductor substrate with the peeling composition is not particularly limited as long as the adhesive layer on the semiconductor substrate is in contact with the peeling composition with temporal continuity. This temporal continuity includes not only the case where the adhesive layer is in constant contact with the peeling composition, but also, for example, the case where the adhesive layer is in contact with the organic solvent for a certain period of time, the contact is stopped once, and the contact is resumed or repeated. Also, it includes not only the case where the entire adhesive layer on the semiconductor substrate is in contact with the peeling composition, but also the case where only a part of the adhesive layer is in contact with the peeling composition. From the viewpoint of realizing more effective cleaning with good reproducibility, an embodiment in which the adhesive layer on the semiconductor substrate is in constant contact with the peeling composition is preferred, and an embodiment in which the entire adhesive layer on the semiconductor substrate is in contact with the peeling composition is preferred.

[0098] Therefore, in a preferred embodiment of the present invention, the adhesive layer on the semiconductor substrate is swelled by immersing the adhesive layer in a peeling composition and then peeled off from the semiconductor substrate, or the adhesive layer on the semiconductor substrate is swelled by continuously supplying a peeling composition onto the adhesive layer and then peeled off from the semiconductor substrate.

[0099] In order to immerse the adhesive layer on the semiconductor substrate in the stripping composition, for example, the semiconductor substrate with the adhesive layer attached thereto may be immersed in the stripping composition. The immersion time is not particularly limited as long as swelling of the adhesive layer occurs and the adhesive layer is peeled off from the semiconductor substrate, but is 5 seconds or more from the viewpoint of achieving more effective cleaning with good reproducibility, and 5 minutes or less from the viewpoint of process throughput.

[0100] When the adhesive layer on the semiconductor substrate is immersed in the peeling composition, peeling of the adhesive layer may be promoted by moving the semiconductor substrate with the adhesive layer in the peeling composition, by causing convection in the peeling composition, by vibrating the peeling composition with ultrasonic waves, or the like.

[0101] In order to move the semiconductor substrate with the adhesive layer in the stripping composition, for example, a rocking cleaner, a paddle-type cleaner, or the like may be used. When such a cleaner is used, the platform on which the semiconductor substrate with the adhesive layer is placed moves or rotates up and down or left and right, so that the adhesive layer on the semiconductor substrate is subjected to relative convection, or the adhesive layer on the semiconductor substrate is subjected to convection generated by that movement or rotation, which not only causes the adhesive layer on the semiconductor substrate to swell, but also promotes peeling of the adhesive layer from the semiconductor substrate.

[0102] In order to convect the stripping composition, in addition to the above-mentioned oscillating cleaner or paddle type cleaner, for example, typically, a convection cleaner may be used in which the semiconductor substrate with the adhesive layer is fixed on a stage or the like, and the stripping composition around the substrate is caused to convect by an agitator.

[0103] In order to vibrate the stripping composition with ultrasonic waves, an ultrasonic cleaner or an ultrasonic probe may be used, and the conditions are usually 20 kHz to 5 MHz.

[0104] In order to continuously supply the peeling composition onto the adhesive layer on the semiconductor substrate, the peeling composition should be continuously applied to the adhesive layer on the semiconductor substrate. For example, if the adhesive layer on the semiconductor substrate faces upward, for example, from above (including diagonally above) the adhesive layer on the semiconductor substrate, a rod-shaped or misty, preferably rod-shaped, peeling composition is supplied continuously over time onto the adhesive layer on the semiconductor substrate by a nozzle of a cleaning device. In this case, the time continuity includes not only the case where the peeling composition is constantly supplied onto the adhesive layer on the semiconductor substrate, but also the case where, for example, the supply of the peeling composition is stopped once after a certain period of time, and then the supply is resumed or repeated, but from the viewpoint of realizing more effective cleaning with good reproducibility, it is preferable that the peeling composition is constantly supplied onto the adhesive layer on the semiconductor substrate.

[0105] When the stripping composition is supplied in a rod shape onto the adhesive layer on the semiconductor substrate, the flow rate is usually 200 to 500 mL / min.

[0106] In one embodiment of the present invention, in order to ensure that the adhesive layer on the semiconductor substrate is constantly in contact with the stripping composition, the adhesive layer may be brought into contact with the vapor of the stripping composition, for example, using a steam cleaner.

[0107] The method for cleaning a semiconductor substrate of the present invention may include a step of removing the peeled adhesive layer. The method for removing the peeled adhesive layer is not particularly limited as long as the peeled adhesive layer is removed from the semiconductor substrate, and when the semiconductor substrate with the adhesive layer is immersed in the peeling composition, the peeled adhesive layer may be removed without removing the semiconductor substrate from the peeling composition, or the peeled adhesive layer may be removed after removing the semiconductor substrate from the peeling composition. In this case, the peeled adhesive layer may naturally remain in the peeling composition by simply removing the semiconductor substrate from the peeling composition, and most of it may be removed.

[0108] Specific examples of methods for removing the peeled adhesive layer include, but are not limited to, removal by adsorption or suction using a device, removal by blowing off with gas such as an air gun, removal by centrifugal force caused by moving or rotating the semiconductor substrate up and down or left and right, and the like.

[0109] After removing the peeled adhesive layer, the semiconductor substrate is dried, etc., if necessary, in accordance with a standard method.

[0110] The present invention also covers the peeling composition used in the semiconductor substrate cleaning method of the present invention. The peeling composition of the present invention is used to peel off an adhesive layer on a semiconductor substrate from the semiconductor substrate, and the preferred embodiments and conditions are as described above. The peeling composition of the present invention can be produced by mixing the solvents constituting the composition in any order if necessary. At that time, filtration or the like may be performed if necessary.

[0111] By using the semiconductor substrate cleaning method of the present invention described above, it is possible to efficiently remove the adhesive layer on the semiconductor substrate, particularly the adhesive layer which is a cured film obtained from a siloxane-based adhesive containing a polyorganosiloxane component (A) that cures by a hydrosilylation reaction, while suppressing damage to the semiconductor substrate, particularly the bumps on the semiconductor substrate, and it is expected that high-efficiency and good semiconductor element production can be achieved.

[0112] The semiconductor substrates to be cleaned by the cleaning method of the present invention include, in addition to silicon semiconductor substrates such as the silicon wafers described above, various substrates such as germanium substrates, gallium arsenide substrates, gallium phosphide substrates, gallium arsenide-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 a silicon nitride film formed thereon, silicon substrates with a silicon oxide film formed thereon, silicon substrates with a polyimide film formed thereon, glass substrates, quartz substrates, liquid crystal substrates, and organic EL substrates.

[0113] An example of the use of the semiconductor substrate cleaning method of the present invention in a semiconductor process is a method for manufacturing processed semiconductor substrates, such as thinned ones, used in semiconductor packaging techniques such as TSV. Specifically, the method for producing a semiconductor substrate that has been processed, such as thinned, includes a first step of producing 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 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, and in this fourth step, the method for cleaning a semiconductor substrate of the present invention is used.

[0114] The adhesive composition used to form the adhesive layer in the first step may be any of the various adhesives described above. However, the method for cleaning a semiconductor substrate of the present invention is effective for removing an adhesive layer obtained from a polysiloxane-based adhesive, and is more effective for removing an adhesive layer obtained from a polysiloxane-based adhesive containing component (A) that cures by a hydrosilylation reaction. Therefore, the following describes an example in which an adhesive layer obtained using a polysiloxane-based adhesive (adhesive composition) is removed by the cleaning method of the present invention when a semiconductor substrate is manufactured using the adhesive layer, but the present invention is not limited thereto.

[0115] First, a first step for producing a laminate including a semiconductor substrate, a supporting substrate, and an adhesive layer obtained from an adhesive composition will be described.

[0116] In one embodiment, the first step includes a step of applying an adhesive composition to a surface of a semiconductor substrate or a supporting substrate to form an adhesive coating layer, and a step of bonding the semiconductor substrate and the supporting substrate together via the adhesive coating layer, applying a load in the thickness direction of the semiconductor substrate and the supporting substrate while performing at least one of a heat treatment and a decompression treatment, thereby bonding the substrates together, and then performing a post-heat treatment to form a laminate. In another embodiment, the first step includes, for example, a step of applying an adhesive composition to the circuit surface of a semiconductor substrate wafer and heating it to form an adhesive coating layer, a step of applying a release agent composition to 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 bond the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate while performing at least one of a heat treatment and a decompression treatment, and then performing a post-heat treatment to form a laminate. Note that the adhesive composition is applied to the semiconductor substrate and the release agent composition is applied to the support substrate, respectively, and heated, but the adhesive composition and the release agent composition may be applied and heated sequentially to either one of the substrates, respectively. In each of the above embodiments, the treatment conditions to be adopted, that is, the heat treatment, the reduced pressure treatment, or a combination of the two, are determined in consideration of 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 desired adhesive strength.

[0117] Here, for example, the semiconductor substrate is a wafer and the support substrate is a support body, and the adhesive composition may be applied to either or both of the semiconductor substrate and the support substrate.

[0118] Examples of the wafer include, but are not limited to, silicon wafers and glass wafers having a diameter of about 300 mm and a thickness of about 770 μm. In particular, the method for cleaning a semiconductor substrate of the present invention can effectively clean a semiconductor substrate having bumps while suppressing damage to the bumps. Specific examples of such semiconductor substrates with bumps include silicon wafers having bumps such as ball bumps, printed bumps, stud bumps, and plated bumps. The bump height is usually appropriately selected from about 1 to 200 μm, the bump diameter from 1 to 200 μm, and the bump pitch from 1 to 500 μm. Specific examples of plated bumps include alloy plating mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps, but are not limited to these.

[0119] The support (carrier) is not particularly limited, but may be, for example, a silicon wafer having a diameter of about 300 mm and a thickness of about 700 μm, but is not limited thereto.

[0120] Stripper compositions include compositions that contain stripper components used for this type of application.

[0121] The coating method is not particularly limited, but is usually a spin coating method. Note that a method of forming a coating film by a separate spin coating method or the like and attaching a sheet-like coating film may also be adopted, and this method is also referred to as coating or coating film.

[0122] The heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the desired thickness of the adhesive layer, etc., but is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes.

[0123] The heating temperature of the applied release agent composition cannot be generally specified because it varies depending on the types and amounts of crosslinking agent, acid generator, acid, etc., whether a solvent is contained, the desired thickness of the release layer, etc., but is preferably 120°C or higher from the viewpoint of achieving suitable curing, and is preferably 260°C or lower from the viewpoint of preventing excessive curing, and the heating time is usually 1 to 10 minutes. Heating can be carried out using a hot plate, an oven, or the like.

[0124] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it is usually 5 to 500 μm.

[0125] The thickness of the release agent coating layer obtained by coating the release agent composition and heating it is usually 5 to 500 μm.

[0126] The heat treatment temperature is appropriately determined usually within the range of 20 to 150° C., taking into consideration the viewpoint of softening the adhesive coating layer to realize suitable bonding with the release agent coating layer, the viewpoint of achieving suitable hardening of the release agent coating layer, etc. In particular, from the viewpoint of suppressing or avoiding excessive hardening or unnecessary deterioration of the adhesive component or release agent component, the heat treatment temperature is preferably 130° C. or less, more preferably 90° C. or less, and the heating time is usually 30 seconds or more, preferably 1 minute or more, from the viewpoint of reliably expressing adhesive ability and peeling ability, but is usually 10 minutes or less, preferably 5 minutes or less, from the viewpoint of suppressing deterioration of the adhesive layer and other members.

[0127] The reduced pressure treatment may be performed by exposing the semiconductor substrate, the adhesive coated layer and the support substrate, or the semiconductor substrate, the adhesive coated layer, the release agent coated layer and the support substrate, to an atmospheric pressure of 10 to 10,000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

[0128] In a preferred embodiment of the present invention, the substrate and the coating layer or the coating layers are bonded together, preferably by a reduced pressure treatment, more preferably by a combination of a heat treatment and a reduced pressure treatment.

[0129] The load in the thickness direction of the semiconductor substrate and the supporting substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the supporting substrate, and the layers therebetween and can firmly adhere to them, but is usually within the range of 10 to 1000 N.

[0130] The post-heating temperature is preferably 120° C. or higher from the viewpoint of obtaining a sufficient curing speed, and is preferably 260° C. or lower from the viewpoint of preventing deterioration of the substrate, adhesive component, release agent component, etc. The heating time is usually 1 minute or more from the viewpoint of realizing suitable bonding of the wafer by curing, and preferably 5 minutes or more from the viewpoint of stabilizing the physical properties of the adhesive, and is usually 180 minutes or less, preferably 120 minutes or less from the viewpoint of avoiding adverse effects on the adhesive layer due to excessive heating. Heating can be performed using a hot plate, an oven, etc. One purpose of the post-heat treatment is to more suitably cure the adhesive component (S).

[0131] Next, a second step of processing the semiconductor substrate of the stack obtained by the method described above will be described. An example of the processing applied to the laminate used in the present invention is processing of the back surface opposite to the circuit surface of the semiconductor substrate, typically thinning the wafer by polishing the back surface of the wafer. Using such a thinned wafer, through-silicon vias (TSVs) and the like are formed, and then the thinned wafer is peeled off from the support to form a wafer stack, which is then three-dimensionally mounted. In addition, before and after that, wafer back electrodes and the like are also formed. In the thinning of the wafer and the TSV process, heat of 250 to 350° C. is applied while the wafer is attached to the support, and the adhesive layer contained in the laminate used in the present invention has heat resistance to that heat. 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 polishing the back surface opposite the circuit surface on the front surface.

[0132] The third step of separating the processed semiconductor substrate and adhesive layer from the support substrate will now be described. In the third step, the processed semiconductor substrate and adhesive layer are separated from the support substrate, and in this case, if a release layer is included in the laminate, the release layer is usually removed together with the support substrate. The method for separating the processed semiconductor substrate and adhesive layer from the semiconductor substrate can be simply to peel between the adhesive layer and the release layer or support substrate in contact therewith. Examples of such peeling methods include, but are not limited to, laser peeling, mechanical peeling using equipment with sharp edges, and manual peeling.

[0133] Next, a fourth step of removing the adhesive layer on the processed semiconductor substrate and cleaning the processed semiconductor substrate will be described. The fourth step is a step of removing the adhesive layer on the semiconductor substrate by the cleaning method of the present invention, specifically, for example, the adhesive layer on the thinned substrate is efficiently removed by the cleaning method of the present invention. The conditions for this step are as described above.

[0134] After the fourth step, if necessary, the adhesive layer residue remaining on the semiconductor substrate may be removed using a cleaning composition containing a salt, but care should be taken not to damage the semiconductor substrate, particularly the bumps of a semiconductor substrate having bumps.

[0135] The method for manufacturing a processed semiconductor substrate of the present invention includes the above-mentioned steps 1 to 4, but may include steps other than these. Furthermore, the above-mentioned components and method elements related to steps 1 to 4 may be modified in various ways without departing from the gist of the present invention. EXAMPLES

[0136] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The purity of the solvent used for the device and the stripping composition used in the present invention, as determined by gas chromatography, is as follows. [Device] (1) Rotating / revolving mixer: manufactured by Thinky Corporation Rotation and revolution mixer ARE-500 (2) Viscometer: Rotational viscometer TVE-22H manufactured by Toki Sangyo Co., Ltd. (3) Agitator: AS ONE Mix Rotor Variable 1-1186-12 (4) Contact angle meter: Fully automatic contact angle meter DM-701 manufactured by Kyowa Interface Science Co., Ltd. (5) Optical microscope: Olympus Corporation Semiconductor / FPD inspection microscope MX61L

[0137] [solvent] Di(n-butyl) ether: Tokyo Chemical Industry Co., Ltd. Purity: >99.0% n-Decane: Sankyo Chemical Co., Ltd. Purity >97.0% Di(n-pentyl) ether: Tokyo Chemical Industry Co., Ltd. Purity: >98.0% 1-Amino-n-pentane: Tokyo Chemical Industry Co., Ltd. Purity: >98.0% p-Menthane: Nippon Terpene Chemical Co., Ltd. Purity: >96.0% Butyl acetate: Kanto Chemical Co., Ltd. Purity: >98.0% Cyclohexane: Kanto Chemical Co., Ltd. Purity >99.5% Di(n-propyl)sulfide: Tokyo Chemical Industry Co., Ltd. Purity >98.0% Pentyl acetate: Tokyo Chemical Industry Co., Ltd. Purity >99.0% Di(n-butyl) sulfide: Tokyo Chemical Industry Co., Ltd. Purity: >98.0% Mesitylene: Fujifilm Wako Pure Chemical Industries, Ltd. Purity >97.0% Limonene: Tokyo Chemical Industry Co., Ltd. Purity >95.0% p-Cymene: Tokyo Chemical Industry Co., Ltd. Purity >95.0% n-Octyl-1-amine: Tokyo Chemical Industry Co., Ltd. Purity >98.0% Cyclooctane: Tokyo Chemical Industry Co., Ltd. Purity >98.0% Heptyl acetate: Tokyo Chemical Industry Co., Ltd. Purity >99.0% 5-Nonanone: Tokyo Chemical Industry Co., Ltd. Purity >98.0% 1,4-Diisopropylbenzene: Tokyo Chemical Industry Co., Ltd. Purity >98.0% Octyl acetate: Tokyo Chemical Industry Co., Ltd. Purity >98.0% n-Dodecane: Tokyo Chemical Industry Co., Ltd. Purity >99.5% 1-Pentanol: Tokyo Chemical Industry Co., Ltd. Purity >99.0% Acetone: Junsei Chemical Co., Ltd. Purity >99.0% Tetramethylurea: Tokyo Chemical Industry Co., Ltd. Purity >98.0% N-Methylpyrrolidone: Kanto Chemical Co., Ltd. Purity: >99.0%

[0138] [1] Preparation of adhesive composition [Preparation Example 1] In a 600 mL stirring vessel dedicated to the planetary centrifugal mixer, 95 g of vinyl group-containing MQ resin (manufactured by Wacker Chemie) as (a1), 93.4 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) as a solvent, and 0.41 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as (A2) were added, and the mixture was stirred for 5 minutes with the planetary centrifugal mixer. The mixture thus obtained was mixed with 19.0 g of a linear polydimethylsiloxane containing a SiH group (manufactured by Wacker Chemical Co.) having a viscosity of 100 mPa·s as (a2), 29.5 g of a linear polydimethylsiloxane containing a vinyl group (manufactured by Wacker Chemical Co.) having a viscosity of 200 mPa·s as (a1), and 100 g of a polydimethylsiloxane having a viscosity of 1,000,000 mm 2 To the mixture were added 65.9 g of polyorganosiloxane (manufactured by Wacker Chemical Industries, product name AK1000000) having a molecular weight of 100 / s and 0.41 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemical Industries) as (A3), and the mixture was stirred for an additional 5 minutes using a planetary centrifugal mixer. Thereafter, 0.20 g of a platinum catalyst (A2) (manufactured by Wacker Chem. Co.) and 17.7 g of a vinyl-containing linear polydimethylsiloxane (a1) with a viscosity of 1000 mPa s (manufactured by Wacker Chem. Co.) were stirred for 5 minutes in a planetary centrifugal mixer to obtain a mixture, and 14.9 g of the mixture was added to the mixture and stirred for an additional 5 minutes in the planetary centrifugal mixer. The mixture was then filtered through a 300 mesh nylon filter to obtain an adhesive composition.

[0139] [Preparation Example 2] In a 600 mL stirring vessel dedicated to the planetary centrifugal mixer, 80 g of MQ resin (manufactured by Wacker Chemical Industries, Ltd.) containing polysiloxane and vinyl groups as (a1), 2.52 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemical Industries, Ltd.) having a viscosity of 100 mPa s as (a2), 5.89 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemical Industries, Ltd.) having a viscosity of 70 mPa s as (a2), and 0.22 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemical Industries, Ltd.) as (A3) were placed and stirred for 5 minutes with a stirrer. To the resulting mixture, 3.96 g of a mixture obtained by stirring 0.147 g of a platinum catalyst (manufactured by Wacker Chemical Industries, Ltd.) as (A2) and 5.81 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemical Industries, Ltd.) with a viscosity of 1000 mPa s as (a1) for 5 minutes with a stirrer was added, and the mixture was stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain an adhesive composition.

[0140] [2] Preparation of evaluation board [Production Example 1] The composition obtained in Preparation Example 1 was applied using a spin coater to a 4 cm x 4 cm Si wafer (thickness 775 μm) as the device side wafer, and heated using a hot plate at 120°C for 1.5 minutes and then at 200°C for 10 minutes to form a thin film with a thickness of 60 μm on the wafer, thereby obtaining a wafer with an adhesive layer.

[0141] [Production Example 2] The composition obtained in Preparation Example 2 was applied to a 4 cm x 4 cm Si wafer (thickness 775 μm) as the device side wafer using a spin coater, and heated at 200°C for 10 minutes using a hot plate to form a thin film with a thickness of 60 μm on the wafer, thereby obtaining a wafer with an adhesive layer.

[0142] [Production Example 3] The substrate with bumps was cut to prepare sample substrates measuring 4 cm x 4 cm. Each sample substrate had 5,044 bumps, and the bump structure consisted of copper pillars, tin-silver (1.8% silver by mass) caps, and nickel between the pillars and the caps.

[0143] [3] Measurement of peeling time [Example 1] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of di(n-butyl) ether as the peeling composition of Example 1, and the time until the adhesive layer began to peel off from the wafer was measured, which was 11 seconds.

[0144] [Example 2] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of n-decane as the peeling composition of Example 2, and the time until the adhesive layer began to peel off from the wafer was measured, which was 18 seconds.

[0145] [Example 3] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of di(n-pentyl) ether as the peeling composition of Example 3, and the time until the adhesive layer began to peel off from the wafer was measured, which was 23 seconds.

[0146] [Example 4] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of 1-amino-n-pentane as the peeling composition of Example 4, and the time until the adhesive layer began to peel off from the wafer was measured, which was 12 seconds.

[0147] [Example 5] The wafer with the adhesive layer produced in Production Example 1 was immersed in 9 mL of p-menthane as the peeling composition of Example 5, and the time until the adhesive layer started to peel off from the wafer was measured, which was 22 seconds.

[0148] [Example 6] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of butyl acetate as the peeling composition of Example 6, and the time until the adhesive layer began to peel off from the wafer was measured, which was 16 seconds.

[0149] [Example 7] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of cyclohexane as the peeling composition of Example 7, and the time until the adhesive layer began to peel off from the wafer was measured, which was 11 seconds.

[0150] [Example 8] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of di(n-propyl)sulfide as the peeling composition of Example 8, and the time until the adhesive layer began to peel off from the wafer was measured, which was 12 seconds.

[0151] [Example 9] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of pentyl acetate as the stripping composition of Example 9, and the time until the adhesive layer began to peel off from the wafer was measured, which was 21 seconds.

[0152] [Example 10] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of di(n-butyl) sulfide as the peeling composition of Example 10, and the time until the adhesive layer began to peel off from the wafer was measured, which was 22 seconds.

[0153] [Example 11] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of mesitylene as the peeling composition of Example 11, and the time until the adhesive layer began to peel off from the wafer was measured, which was 18 seconds.

[0154] [Example 12] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of limonene as the stripping composition of Example 12, and the time until the adhesive layer began to peel off from the wafer was measured, which was 18 seconds.

[0155] [Example 13] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of p-cymene as the peeling composition of Example 13, and the time until the adhesive layer started to peel off from the wafer was measured, which was 18 seconds.

[0156] [Comparative Example 1] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of n-octyl-1-amine as the peeling composition of Comparative Example 1, and the time until the adhesive layer began to peel off from the wafer was measured, which was 34 seconds.

[0157] [Comparative Example 2] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of cyclooctane as the peeling composition of Comparative Example 2, and the time until the adhesive layer began to peel off from the wafer was measured, which was 40 seconds.

[0158] [Comparative Example 3] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of heptyl acetate as the stripping composition of Comparative Example 3, and the time until the adhesive layer began to peel off from the wafer was measured, which was 38 seconds.

[0159] [Comparative Example 4] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of 5-nonanone as the peeling composition of Comparative Example 4, and the time until the adhesive layer began to peel off from the wafer was measured, which was 36 seconds.

[0160] [Comparative Example 5] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of 1,4-diisopropylbenzene as the peeling composition of Comparative Example 5, and the time until the adhesive layer began to peel off from the wafer was measured, which was 44 seconds.

[0161] [Comparative Example 6] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of octyl acetate as the stripping composition of Comparative Example 6, and the time until the adhesive layer began to peel off from the wafer was measured, which was 51 seconds.

[0162] [Comparative Example 7] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of n-dodecane as the peeling composition of Comparative Example 7, and the time until the adhesive layer began to peel off from the wafer was measured, which was 44 seconds.

[0163] [Comparative Example 8] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of 1-pentanol as the peeling composition of Comparative Example 8, and the time until the adhesive layer began to peel off from the wafer was measured. No peeling was observed even after 5 minutes had passed.

[0164] [Comparative Example 9] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of acetone as the peeling composition of Comparative Example 9, and the time until the adhesive layer began to peel off from the wafer was measured. No peeling was observed even after 5 minutes had passed.

[0165] [Comparative Example 10] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of propylene glycol monomethyl ether as the peeling composition of Comparative Example 10, and the time until the adhesive layer began to peel off from the wafer was measured. No peeling was observed even after 5 minutes had passed.

[0166] [Comparative Example 11] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of propylene glycol monomethyl ether acetate as the peeling composition of Comparative Example 11, and the time until the adhesive layer began to peel off from the wafer was measured. No peeling was observed even after 5 minutes had passed.

[0167] [Comparative Example 12] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of tetramethylurea as the peeling composition of Comparative Example 12, and the time until the adhesive layer began to peel off from the wafer was measured. No peeling was observed even after 5 minutes had passed.

[0168] [Comparative Example 13] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of N-methylpyrrolidone as the peeling composition of Comparative Example 13, and the time until the adhesive layer began to peel off from the wafer was measured. No peeling was observed even after 5 minutes had passed.

[0169] [Comparative Example 14] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of water as the peeling composition of Comparative Example 14, and the time until the adhesive layer began to peel off from the wafer was measured. No peeling was observed even after 5 minutes had passed.

[0170] [4] Contact angle measurement Each of the solvents used in the Examples and Comparative Examples was dropped onto the adhesive layer of the wafer with the adhesive layer produced in Production Example 2, and the contact angle of each was measured. The results are shown in Table 1 together with the molecular weight of the solvent.

[0171] [Table 1]

[0172] The results of the Examples and Comparative Examples, the contact angle of the stripping composition on the adhesive layer, and the molecular weight of the specific organic solvent contained in the stripping composition are shown in Tables 2 and 3. As shown in Table 2, when a specific organic solvent was used, even if the organic solvent satisfied the molecular weight conditions, the peeling time was significantly shorter in the examples in which the contact angle of the peeling composition on the adhesive layer was less than 31.5 degrees than in the comparative examples in which the contact angle was 31.5 degrees or more. Furthermore, as shown in Table 3, when a specific organic solvent was used, even if the stripping composition satisfied the contact angle condition, the peeling time was significantly shorter in the examples in which the organic solvent satisfied the molecular weight condition than in the comparative examples in which the molecular weight condition was not satisfied. Furthermore, when no specific solvent was used, even when the conditions of the contact angle and molecular weight were satisfied, peeling in a short time as in the examples was not observed (Comparative Examples 8 to 14).

[0173] [Table 2]

[0174] When the relationship between the results of the Examples and Comparative Examples and the molecular weight of the specific solvent contained in the stripping composition is examined, as shown in Table 3, the stripping time when the cleaning method of the Examples in which the molecular weight of the specific solvent contained in the stripping composition is less than 160 was used was significantly shorter than the stripping time when the cleaning method of the Comparative Examples in which the molecular weight is 160 or more was used.

[0175] [Table 3]

[0176] [5] Check for damage to the bump The sample substrates prepared in Production Example 3 were immersed in 9 mL of the stripping compositions of Examples 1 to 13, left to stand for 1 hour, washed with isopropanol and acetone, and observed for the presence or absence of bump damage under an optical microscope. As a result, no bump damage was observed in any of the substrates.

Claims

1. A method for cleaning a semiconductor substrate, comprising a step of removing an adhesive layer on a semiconductor substrate using a stripping composition, The adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S), The adhesive component (S) includes a siloxane-based adhesive containing a polyorganosiloxane component (A) that cures by a hydrosilylation reaction, The stripping composition comprises a solvent and does not comprise a salt, the solvent is one or more selected from aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, ether compounds, thioether compounds, ester compounds, and amine compounds, each having a molecular weight of less than 160; A method for cleaning a semiconductor substrate, wherein the contact angle of the stripping composition on the adhesive layer is less than 31.5 degrees.

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

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

4. The method for cleaning a semiconductor substrate according to any one of claims 1 to 3, wherein the adhesive component (S) further comprises at least one adhesive selected from the group consisting of an acrylic resin adhesive, an epoxy resin adhesive, a polyamide adhesive, a polystyrene adhesive, a polyimide adhesive, and a phenol resin adhesive.

5. A first step of producing a laminate including 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 method for producing a processed semiconductor substrate, comprising a fourth step of peeling off an 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) includes a siloxane-based adhesive containing a polyorganosiloxane component (A) that cures by a hydrosilylation reaction, The stripping composition comprises a solvent and does not comprise a salt, the solvent is one or more selected from aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, ether compounds, thioether compounds, ester compounds, and amine compounds, each having a molecular weight of less than 160; A method for producing a processed semiconductor substrate, wherein the contact angle of the stripping composition on the adhesive layer is less than 31.5 degrees.

6. 6. The method for producing a processed semiconductor substrate according to claim 5, wherein said molecular weight is 70 or more.

7. The method for producing a processed semiconductor substrate according to claim 5, wherein the solvent is one or more selected from the group consisting of di(n-butyl)ether, n-decane, di(n-pentyl)ether, 1-amino-n-pentane, p-menthane, butyl acetate, cyclohexane, di(n-propyl)sulfide, pentyl acetate, di(n-butyl)sulfide, mesitylene, limonene and p-cymene.

8. The method for producing a processed semiconductor substrate according to any one of claims 5 to 7, wherein the adhesive component (S) further comprises 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.

9. A stripping composition used for stripping an adhesive layer on a semiconductor substrate when cleaning the semiconductor substrate, comprising: The solvent contains one or more compounds selected from aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, ether compounds, thioether compounds, ester compounds, and amine compounds, each having a molecular weight of less than 160; Contains no salt, The contact angle on the adhesive layer is less than 31.5 degrees; The adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S), A peeling composition characterized in that the adhesive component (S) comprises a siloxane-based adhesive containing a polyorganosiloxane component (A) that cures by a hydrosilylation reaction.

10. 10. The stripping composition according to claim 9, wherein said molecular weight is 70 or more.

11. The stripping composition according to claim 9, wherein the solvent is one or more selected from the group consisting of di(n-butyl)ether, n-decane, di(n-pentyl)ether, 1-amino-n-pentane, p-menthane, butyl acetate, cyclohexane, di(n-propyl)sulfide, pentyl acetate, di(n-butyl)sulfide, mesitylene, limonene and p-cymene.

12. The peeling composition according to any one of claims 9 to 11, wherein the adhesive component (S) further comprises 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.

13. 13. The stripping composition of claim 12, wherein said adhesive component (S) comprises a siloxane-based adhesive.

14. 14. The stripping composition of claim 13, wherein the siloxane-based adhesive comprises a polyorganosiloxane component (A) that cures by a hydrosilylation reaction.

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