Cleaning method for semiconductor substrates, manufacturing method for processed semiconductor substrates, and components for stripping.

Abstract

This invention provides a method for cleaning a semiconductor substrate, for example, for removing an adhesive layer obtained using a silicone-based adhesive from the surface of a semiconductor substrate, thereby appropriately and easily removing the adhesive layer; a method for manufacturing a semiconductor substrate after processing using such a cleaning method; and a stripping composition for such a cleaning method. The method for cleaning the semiconductor substrate includes the step of stripping the adhesive layer on the semiconductor substrate using a stripping composition containing a solvent and not containing a salt, wherein the solvent contains 80% by mass or more of an organic solvent represented by formula (L). (In the formula, L1 and L2 each independently represent an alkyl group having 2 to 4 carbon atoms, and L3 represents O or S.)

Description

[Technical Field]

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

[0002] Semiconductor wafers have always been stacked in a two-dimensional planar direction. To further enhance this stacking, a semiconductor stacking technology is being pursued that stacks (layers) the planar surface in a three-dimensional direction. This three-dimensional stacking utilizes through-silicon vias (TSVs) for interconnection, simultaneously stacking multiple layers. In multi-layer stacking, each wafer is thinned by grinding the side opposite to the formed circuit surface (i.e., the back side), and then the thinned semiconductor wafer is stacked.

[0003] A semiconductor wafer (hereinafter simply referred to as a wafer) before thinning is bonded to a support for polishing using a polishing apparatus. This bonding must be easily removable after polishing and is therefore called a temporary bonding. This temporary bonding must be easily detachable from the support; if a large force is applied for removal, the thinned semiconductor wafer may break or deform. To avoid this, it must be easily detachable. However, it is undesirable for the back side of the semiconductor wafer to detach or deviate due to polishing stress. Therefore, the performance required for temporary bonding is to withstand the stress during polishing and to be easily detachable after polishing. For example, it requires high stress (strong adhesion) in the planar direction during polishing and low stress (weak adhesion) in the longitudinal direction (the direction intersecting the planar direction during removal). Furthermore, the processing steps sometimes reach temperatures above 150°C; therefore, heat resistance is also required.

[0004] Against this backdrop, in the semiconductor field, temporary adhesives mainly use polysiloxane-based adhesives that possess these properties. Furthermore, in polysiloxane-based bonding using polysiloxane-based adhesives, adhesive residues often remain on the substrate surface after the thinned substrate is peeled off. To avoid adverse conditions in subsequent steps, cleaning agent compositions for removing these residues and cleaning the semiconductor substrate surface have been continuously developed (e.g., Patent Documents 1 and 2). Patent Document 1 discloses a silicone resin remover containing a polar aprotic solvent and a quaternary ammonium hydroxide; Patent Document 2 discloses a curing resin remover containing fluorinated alkyl ammonium. However, in the recent semiconductor field, there has always been an urgent need for new cleaning agent compositions, and there has always been an urgent need for effective cleaning agent compositions and cleaning methods.

[0005] On the other hand, semiconductor wafers are electrically connected to semiconductor chips via bump balls made of conductive materials such as metal, and miniaturization of semiconductor packaging is achieved by using chips with such bump balls. In this regard, bump balls made of metals such as copper or tin have poor corrosion resistance and can be damaged by the cleaning agent composition used to remove adhesive residues from the support and wafer (Patent Document 3). Therefore, one of the desired aspects of the cleaning agent composition and cleaning method is that the bump balls are not corroded during substrate cleaning. [Prior Art Documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2014 / 092022 [Patent Document 2] US Patent No. 6818608 [Patent Document 3] Korean Patent Publication No. 2018-0066550 [Summary of the Invention]

[0007] [The technical problem that the invention aims to solve]

[0008] This invention is made in view of the above-mentioned circumstances, and its object is to: provide a method for cleaning a semiconductor substrate, for example, for use on a semiconductor substrate having an adhesive layer obtained using a silicone-based adhesive on its surface, reducing or suppressing damage to the bumps of the semiconductor substrate, while appropriately and easily removing the adhesive layer; provide a method for manufacturing a processed semiconductor substrate, which includes such a cleaning method; and provide a stripping composition for use in such a cleaning method. [Technical Means]

[0009] After repeated and in-depth research in order to solve the above-mentioned problems, the inventors discovered that by using a stripping composition containing a specified amount or more of a specified ether compound and / or a specified thioether compound as a solvent and without salt, damage to the bumps of the semiconductor substrate can be reduced or suppressed. At the same time, the adhesive layer on the semiconductor substrate, especially the adhesive layer of the hardened film obtained by the silicone adhesive containing the polyorganosiloxane component (A) hardened by the hydrosilicification reaction, can be efficiently and easily stripped, thereby completing the present invention.

[0010] That is, the present invention provides: 1. A method for cleaning a semiconductor substrate, comprising the step of peeling off an adhesive layer on the semiconductor substrate using a stripping composition, characterized in that the stripping composition contains a solvent and does not contain a salt; and the solvent contains 80% by mass or more of an organic solvent represented by formula (L); [Chemical 1] (wherein, L1 and L2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L3 represents O or S.). 2. The method for cleaning a semiconductor substrate as described in claim 1, wherein the solvent contains 85% by mass or more of the organic solvent represented by formula (L). 3. The method for cleaning a semiconductor substrate as described in claim 2, wherein the solvent is composed of the organic solvent represented by formula (L). 4. The method for cleaning a semiconductor substrate as described in any one of claims 1 to 3, wherein L1 and L2 are the same functional group. 5. The cleaning method for a semiconductor substrate as described in claim 4, wherein the alkyl group having 2 to 5 carbon atoms is ethyl, n-propyl, or n-butyl. 6. The cleaning method for a semiconductor substrate as described in any one of claims 1 to 5, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S); the adhesive component (S) contains at least one selected from silicone adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives. 7. The cleaning method for a semiconductor substrate as described in claim 6, wherein the adhesive component (S) contains a silicone adhesive. 8. The cleaning method for a semiconductor substrate as described in claim 7, wherein the silicone adhesive contains a polyorganosiloxane component (A) that is cured by a hydrogenation reaction. 9. A method for manufacturing a processed semiconductor substrate, comprising: a first step of manufacturing a laminate having a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition; a second step of processing the semiconductor substrate of the obtained laminate; a third step of separating the semiconductor substrate and the adhesive layer from the support substrate; and a fourth step of peeling off the adhesive layer on the semiconductor substrate using a peeling composition; characterized in that the peeling composition contains a solvent and does not contain a salt; and the solvent contains 80% by mass or more of an organic solvent represented by formula (L); [Chemical 2] (wherein, L1 and L2 each independently represent an alkyl group having 2 to 5 carbon atoms; L3 represents O or S.). 10. The method for manufacturing a processed semiconductor substrate as described in claim 9, wherein the solvent contains 85% by mass or more of the organic solvent represented by formula (L). 11. A method for manufacturing a processed semiconductor substrate as described in item 10, wherein the solvent is formed from the organic solvent represented by formula (L).12. A method for manufacturing a processed semiconductor substrate as described in any one of claims 9 to 11, wherein L1 and L2 are the same functional group. 13. A method for manufacturing a processed semiconductor substrate as described in claim 12, wherein the alkyl group having 2 to 5 carbon atoms is ethyl, n-propyl, or n-butyl. 14. A method for manufacturing a processed semiconductor substrate as described in any one of claims 9 to 13, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S); wherein the adhesive component (S) contains at least one selected from silicone adhesives, acrylic adhesives, epoxy adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic adhesives. 15. A method for manufacturing a processed semiconductor substrate as described in claim 14, wherein the adhesive component (S) contains a silicone adhesive. 16. A method for manufacturing a processed semiconductor substrate as described in claim 15, wherein the aforementioned silicate adhesive contains a polyorganosiloxane component (A) that is cured by a hydrosilicification reaction. 17. A stripping composition for stripping an adhesive layer on a semiconductor substrate during cleaning, characterized in that it contains a solvent and does not contain a salt; and the solvent contains at least 80% by mass of an organic solvent represented by formula (L); [Chemical 3] (where L1 and L2 each independently represent an alkyl group having 2 to 5 carbon atoms; L3 represents O or S). 18. A stripping composition as described in claim 17, wherein the solvent contains at least 85% by mass of the aforementioned organic solvent represented by formula (L). 19. A stripping composition as described in claim 18, wherein the solvent is composed of the aforementioned organic solvent represented by formula (L). 20. A release composition as described in any one of claims 17 to 19, wherein L1 and L2 are the same group. 21. A release composition as described in claim 20, wherein the alkyl group having 2 to 5 carbon atoms is ethyl, n-propyl, or n-butyl. 22. A release composition as described in any one of claims 17 to 21, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S); the adhesive component (S) contains at least one selected from silicone adhesives, acrylic adhesives, epoxy adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic adhesives. 23. A release composition as described in claim 22, wherein the adhesive component (S) contains a silicone adhesive. 24. The peeling composition as described in item 23, wherein the aforementioned silicate adhesive contains a polyorganosiloxane component (A) that is cured by a hydrosilicification reaction. [Effects of the Invention]

[0011] By using the cleaning method of the semiconductor substrate of the present invention, for example, from a semiconductor substrate having an adhesive layer obtained by using a silicone-based adhesive on its surface, the adhesive layer can be appropriately and easily removed. Therefore, high-efficiency and good manufacturing of semiconductor elements can be expected. In particular, when the semiconductor substrate having an adhesive layer is provided with bumps, since damage to the bumps can be avoided or suppressed, and at the same time the adhesive layer can be appropriately and easily removed, high-efficiency, high-reliability, and good manufacturing of semiconductor elements can be expected.

Embodiment

[0012] The cleaning method of the semiconductor substrate of the present invention includes a step of peeling an adhesive layer on the semiconductor substrate using a peeling composition, and the above-mentioned peeling composition contains a solvent and does not contain salt, and the above-mentioned solvent contains 80% by mass or more of an organic solvent represented by the formula (L).

[0013] [Chemical formula 4]

[0014] The semiconductor substrate is, for example, a wafer, and specific examples thereof include a silicon wafer having a diameter of 300 mm and a thickness of about 770 μm, but are not limited thereto.

[0015] The adhesive layer on such a semiconductor substrate is, for example, a film obtained from an adhesive composition containing an adhesive component (S). Such an adhesive component (S) is not particularly limited as long as it is used for such a purpose, and examples thereof include: silicone-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, phenolic resin-based adhesives, etc. Among these, from the viewpoint of exhibiting ideal adhesive ability during processing of wafers, etc., being appropriately peeled after processing, and further having excellent heat resistance, the adhesive component (S) is preferably a silicone-based adhesive.

[0016] Ideally, the adhesive composition used in this invention contains a polyorganosiloxane component (A) that is cured by hydrosilicification; more ideally, the polyorganosiloxane component (A) that is cured by hydrosilicification contains a polysiloxane (A1) and a platinum group metal catalyst (A2), and the polysiloxane (A1) contains a silicon oxane unit (Q unit) selected from SiO2 and a silicon oxane unit (R1R). The polysiloxane (A1) comprises one or more units from the group consisting of siloxane units represented by 2R3SiO1 / 2 (M unit), siloxane units represented by R4R5SiO2 / 2 (D unit), and siloxane units represented by R6SiO3 / 2 (T unit); the polysiloxane (A1) contains a polyorganosiloxane (a1) and a polyorganosiloxane (a2), and the polyorganosiloxane (a1) contains siloxane units selected from those represented by SiO2 ( The polyorganosiloxane (a2) contains one or more units selected from the group consisting of Q' unit, siloxane units represented by R1'R2'R3'SiO1 / 2 (M' unit), siloxane units represented by R4'R5'SiO2 / 2 (D' unit), and siloxane units represented by R6'SiO3 / 2 (T' unit), and simultaneously contains at least one unit selected from the group consisting of the aforementioned M' unit, D' unit, and T' unit. It comprises one or more units from the group consisting of siloxane units represented by SiO2 (Q" unit), siloxane units represented by R1"R2"R3"SiO1 / 2 (M" unit), siloxane units represented by R4"R5"SiO2 / 2 (D" unit), and siloxane units represented by R6"SiO3 / 2 (T" unit), and simultaneously contains at least one unit selected from the group consisting of the above-mentioned M" unit, D" unit, and T" unit.

[0017] R1~R6 are groups or atoms bonded to silicon atoms, each independently representing an alkyl, alkenyl or hydrogen atom.

[0018] R1'~R6' are groups bonded to silicon atoms, each independently representing an alkyl or alkenyl group, except that at least one of R1'~R6' is an alkenyl group.

[0019] R1''~R6'' are groups or atoms bonded to silicon atoms, each independently representing an alkyl group or a hydrogen atom, except that at least one of R1''~R6'' is a hydrogen atom.

[0020] Alkyl groups can be straight-chain, branched, or cyclic, but ideally they are straight-chain or branched alkyl groups. The number of carbon atoms is not particularly limited, usually 1 to 40, ideally 30 or less, more ideally 20 or less, and even more ideally 10 or less.

[0021] Specific examples of straight-chain or branched alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-Methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these. Ideally, the methyl group should be used.

[0022] Specific examples of cyclic alkyl groups include: cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl- Cycloalkyl groups such as cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-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, 2-ethyl-3-methyl-cyclopropyl, etc.; bicycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, dicyclodecyl, etc., but not limited to these.

[0023] Alkenyl group can be either linear or branched, and its number of carbon atoms is not particularly limited. It is usually 2 to 40, ideally less than 30, more ideally less than 20, and even more ideally less than 10.

[0024] Specific examples of alkenyl groups include: vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl 2-Methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-secondary butylvinyl, 1,3- Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-Tributylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl, 2- Methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, etc., but not limited to these. Ideally, these should be vinyl or 2-propenyl.

[0025] As described above, the polysiloxane (A1) contains polyorganosiloxane (a1) and polyorganosiloxane (a2), and the alkenyl group contained in the polyorganosiloxane (a1) and the hydrogen atoms (Si-H group) contained in the polyorganosiloxane (a2) are cross-linked and hardened by a platinum group metal catalyst (A2) through a hydrosilicification reaction.

[0026] The polyorganosiloxane (a1) contains one or more units selected from the group consisting of Q' units, M' units, D' units and T' units, and simultaneously contains at least one unit selected from the group consisting of the aforementioned M' units, D' units and T' units. Two or more polyorganosiloxanes satisfying such conditions may also be used in combination.

[0027] Two or more ideal combinations selected from the group of Q' unit, M' unit, D' unit and T' unit can be listed as: (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit and M' unit), but are not limited to these.

[0028] Furthermore, the polyorganosiloxane (a1) may contain two or more types of polyorganosiloxanes, ideally a combination of (Q' unit and M' unit) and (D' unit and M' unit), a combination of (T' unit and M' unit) and (D' unit and M' unit), or a combination of (Q' unit, T' unit and M' unit) and (T' unit and M' unit), but is not limited to these.

[0029] The polyorganosiloxane (a2) contains one or more units selected from the group consisting of Q” units, M” units, D” units and T” units, and simultaneously contains at least one unit selected from the group consisting of the aforementioned M” units, D” units and T” units. The polyorganosiloxane (a2) may also be used in combination with two or more polyorganosiloxanes that satisfy such conditions.

[0030] Two or more ideal combinations selected from the group of Q” unit, M” unit, D” unit and T” unit can be listed as: (M” unit and D” unit), (Q” unit and M” unit), (Q” unit, T” unit and M” unit), but are not limited to these.

[0031] The polyorganosiloxane (a1) is composed of siloxane units with alkyl and / or alkenyl groups bonded to their silicon atoms. However, the proportion of alkenyl groups in all substituents represented by R1' to R6' is ideally 0.1 mol% to 50.0 mol%, more ideally 0.5 mol% to 30.0 mol%, and the remaining R1' to R6' can be alkyl groups.

[0032] The polyorganosiloxane (a2) is composed of siloxane units with alkyl and / or hydrogen atoms bonded to their silicon atoms. However, the proportion of hydrogen atoms in all substituents and substituent atoms represented by R1”~R6” is ideally 0.1 mol%~50.0 mol%, more ideally 10.0 mol%~40.0 mol%, and the remaining R1”~R6” can be alkyl.

[0033] Polysiloxane (A1) contains polyorganosiloxane (a1) and polyorganosiloxane (a2), but in an ideal state, the molar ratio of the alkenyl group contained in polyorganosiloxane (a1) to the hydrogen atoms that constitute the Si-H bond contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0034] The weight-average molecular weights of the polyorganosiloxanes (a1) and (a2) are typically 500 to 1,000,000, but from the viewpoint of achieving the effects of the present invention with good reproducibility, 5,000 to 50,000 are ideal, respectively. Furthermore, the weight-average molecular weight, number-average molecular weight, and dispersity of the present invention can be determined, for example, using a gel permeation chromatography (GPC) apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), with the column temperature set to 40°C, tetrahydrofuran used as the dissolution solution, the flow rate set to 0.35 mL / min, and polystyrene (manufactured by Sigma-Aldrich) used as the standard sample.

[0035] The viscosities of the polyorganosiloxane (a1) and polyorganosiloxane (a2) are typically 10 to 1,000,000 mPa·s, but from the viewpoint of achieving the effects of the present invention with good reproducibility, 50 to 10,000 mPa·s is ideal. Furthermore, the viscosity of the present invention is measured at 25°C using an E-type rotational viscometer.

[0036] Polyorganosiloxane (a1) and polyorganosiloxane (a2) are formed into a film by reacting with each other through a hydrosilicification reaction. Therefore, their curing mechanism is different from that of, for example, via silanol groups. Thus, neither of the siloxanes needs to contain silanol groups or functional groups such as alkoxy groups that are formed by hydrolysis of silanol groups.

[0037] In the ideal sample, the adhesive component (S) simultaneously contains the aforementioned polysiloxane (A1) and platinum group metal catalyst (A2). This platinum group metal catalyst is used to promote the hydrosilylation reaction between the alkenyl group of the polyorganosiloxane (a1) and the Si-H group of the polyorganosiloxane (a2).

[0038] Specific examples of platinum group metal catalysts include: platinum black, platinum tetrachloride, chloroplatinic acid, reactants of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and alkenes, platinum diacetate, etc., but are not limited to these. Examples of platinum-alkene complexes include, for instance, complexes of divinyltetramethyldisiloxane and platinum, but are not limited to these. The amount of platinum group metal catalyst (A2), relative to the combined amount of polyorganosiloxane (a1) and polyorganosiloxane (a2), is typically in the range of 1.0 to 50.0 ppm.

[0039] The polyorganosiloxane component (A) may also contain a polymerization inhibitor (A3) for the purpose of inhibiting the hydrosiliconization reaction. The polymerization inhibitor is not particularly limited as long as it can inhibit the hydrosiliconization reaction; specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propynyl-1-ol. The amount of polymerization inhibitor, relative to the combined amount of the polyorganosiloxane (a1) and polyorganosiloxane (a2), is generally 1000.0 ppm or more from the viewpoint of achieving its effect; and generally 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosiliconization reaction.

[0040] The adhesive composition used in this invention may also contain a release agent component (B). Because the adhesive composition used in this invention contains such a release agent component (B), the obtained adhesive layer can be reproducibly and appropriately released. Such a release agent component (B) typically includes polyorganosiloxanes, and specific examples include epoxy-containing polyorganosiloxanes, methyl-containing polyorganosiloxanes, phenyl-containing polyorganosiloxanes, etc., but is not limited to these.

[0041] The weight-average molecular weight of the polyorganosiloxane in the stripping agent component (B) is typically 100,000 to 2,000,000, but from the viewpoint of achieving the effects of the present invention with good reproducibility, it is ideally 200,000 to 1,200,000, and more ideally 300,000 to 900,000; its dispersibility is typically 1.0 to 10.0, but from the viewpoint of achieving the effects of the present invention with good reproducibility, it is ideally 1.5 to 5.0, and more ideally 2.0 to 3.0. Furthermore, the weight-average molecular weight and dispersibility can be determined using the methods described above.

[0042] Polyorganosiloxanes containing epoxy groups may include, for example, siloxane units (D10 units) represented by R11R12SiO2 / 2.

[0043] R11 is a group bonded to a silicon atom, representing an alkyl group; R12 is a group bonded to a silicon atom, representing an epoxy group or an organic group containing an epoxy group; specific examples of alkyl groups can be listed as above.

[0044] In addition, the epoxy group in an organic group containing an epoxy group may be an independent epoxy group without condensing with other rings, or it may be an epoxy group that forms a condensed ring with other rings, like 1,2-epoxycyclohexyl.

[0045] Specific examples of an organic group containing an epoxy group include 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl, but are not limited thereto. An ideal example of an epoxy-containing polyorganosiloxane in this invention is epoxy-containing polydimethylsiloxane, but is not limited thereto.

[0046] An epoxy-containing polyorganosiloxane contains the above-mentioned siloxane unit (D10 unit), but may also contain the above-mentioned Q unit, M unit and / or T unit in addition to the D10 unit.

[0047] In an ideal state, specific examples of polyorganosiloxanes containing epoxy groups can be listed as follows: polyorganosiloxanes composed only of D10 units; polyorganosiloxanes containing D10 units and Q units; polyorganosiloxanes containing D10 units and M units; polyorganosiloxanes containing D10 units and T units; polyorganosiloxanes containing D10 units, Q units and M units; polyorganosiloxanes containing D10 units, M units and T units; and polyorganosiloxanes containing D10 units, Q units, M units and T units, etc.

[0048] An epoxy-containing polyorganosiloxane, preferably an epoxy-containing polydimethylsiloxane with an epoxy value of 0.1 to 5, typically with a weight average molecular weight of 1,500 to 500,000, but ideally below 100,000 from the viewpoint of inhibiting precipitation in the adhesive composition.

[0049] Specific examples of epoxy-containing polyorganosiloxanes include: CMS-227 (manufactured by Gelest Corporation, weight average molecular weight 27,000), represented by formula (A-1); ECMS-327 (manufactured by Gelest Corporation, weight average molecular weight 28,800), represented by formula (A-2); KF-101 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 31,800), represented by formula (A-3); and KF-1001 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 31,800), represented by formula (A-4). The products listed are, but are not limited to, the following: KF-1005 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 11,500), X-22-343 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 2,400), BY16-839 (manufactured by Dow Corning, Ltd., weight average molecular weight 51,700), and ECMS-327 (manufactured by Gelest, Ltd., weight average molecular weight 28,800), denoted by formula (A-5); X-22-343 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 2,400), denoted by formula (A-7); BY16-839 (manufactured by Dow Corning, Ltd., weight average molecular weight 51,700), denoted by formula (A-8); and ECMS-327 (manufactured by Gelest, Ltd., weight average molecular weight 28,800).

[0050] [Chemical Formula 5] (m and n are the numbers of repeating units respectively.)

[0051] [Chemical Formula 6] (m and n are the numbers of repeating units respectively.)

[0052] [Chemical Formula 7] (m and n are the numbers of repeating units respectively. R is an alkylene group having 1 to 10 carbon atoms.)

[0053] [Chemical Formula 8] (m and n are the numbers of repeating units respectively. R is an alkylene group having 1 to 10 carbon atoms.)

[0054] [Chemical Formula 9] (m, n and o are the numbers of repeating units respectively. R is an alkylene group having 1 to 10 carbon atoms.)

[0055] [Chemical Formula 10] (m and n are the numbers of repeating units respectively. R is an alkylene group having 1 to 10 carbon atoms.) [(0056] [Chemical Formula 11] (m and n are the numbers of repeating units respectively. R is an alkylene group having 1 to 10 carbon atoms.)

[0057] [Chemical Formula 12] (m and n are the numbers of repeating units respectively.)

[0058] Examples of the methyl-containing polyorganosiloxane include, for example, a siloxane unit represented by R210R220SiO2 / 2 (D200 unit), and preferably a siloxane unit represented by R21R21SiO2 / 2 (D20 unit).

[0059] R210 and R220 are groups bonded to a silicon atom, each independently representing an alkyl group, provided that at least one of them is a methyl group; specific examples of the alkyl group can be exemplified as above. R21 is a group bonded to a silicon atom, representing an alkyl group; specific examples of the alkyl group can be exemplified as above. Among them, R21 is preferably a methyl group. A preferred example of the methyl-containing polyorganosiloxane includes polydimethylsiloxane, but is not limited thereto.

[0060] The methyl-containing polyorganosiloxane contains the above siloxane unit (D200 unit or D20 unit), but in addition to the D200 unit and the D20 unit, it may also contain the above Q unit, M unit and / or T unit.

[0061] Specific examples of methyl-containing polyorganosiloxanes in a certain state sample include: polyorganosiloxanes composed only of D200 units; polyorganosiloxanes containing D200 units and Q units; polyorganosiloxanes containing D200 units and M units; polyorganosiloxanes containing D200 units and T units; polyorganosiloxanes containing D200 units, Q units and M units; polyorganosiloxanes containing D200 units, M units and T units; and polyorganosiloxanes containing D200 units, Q units, M units and T units.

[0062] In an ideal state, specific examples of methyl-containing polyorganosiloxanes can be listed as follows: polyorganosiloxanes composed only of D20 units; polyorganosiloxanes containing D20 units and Q units; polyorganosiloxanes containing D20 units and M units; polyorganosiloxanes containing D20 units and T units; polyorganosiloxanes containing D20 units, Q units and M units; polyorganosiloxanes containing D20 units, M units and T units; and polyorganosiloxanes containing D20 units, Q units, M units and T units.

[0063] The viscosity of methyl-containing polyorganosiloxanes is typically 1,000 to 2,000,000 mm² / s, but ideally 10,000 to 1,000,000 mm² / s. Furthermore, methyl-containing polyorganosiloxanes are typically dimethyl silicone oils made from polydimethylsiloxane. This viscosity value is expressed as kinematic viscosity, centistokes (cSt) = mm² / s. Kinematic viscosity can be measured using a kinematic viscometer. Alternatively, it can be obtained by dividing viscosity (mPa·s) by density (g / cm³). That is, it can be obtained from the viscosity and density measured at 25°C using an E-type rotational viscometer. It can be calculated using the formula: Kinematic viscosity (mm² / s) = Viscosity (mPa·s) / Density (g / cm³).

[0064] Specific examples of methyl-containing polyorganosiloxanes include: WACKERSILICONE FLUID AK series manufactured by Wacker Chemie Corporation, or dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) and cyclic dimethyl silicone oils (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd., but are not limited to these.

[0065] Phenyl-containing polyorganosiloxanes, for example, those containing siloxane units (D30 units) represented by R31R32SiO2 / 2.

[0066] R31 is a group bonded to a silicon atom, representing a phenyl group or an alkyl group; R32 is a group bonded to a silicon atom, representing a phenyl group; specific examples of the alkyl group can be listed as the above examples, but methyl is preferred.

[0067] The phenyl-containing polyorganosiloxane contains the above-mentioned siloxane unit (D30 unit), but in addition to the D30 unit, it may also contain the above-mentioned Q unit, M unit and / or T unit.

[0068] In a preferred embodiment, specific examples of the phenyl-containing polyorganosiloxane include: a polyorganosiloxane composed only of D30 units; a polyorganosiloxane containing D30 units and Q units; a polyorganosiloxane containing D30 units and M units; a polyorganosiloxane containing D30 units and T units; a polyorganosiloxane containing D30 units, Q units and M units; a polyorganosiloxane containing D30 units, M units and T units; a polyorganosiloxane containing D30 units, Q units, M units and T units.

[0069] The weight-average molecular weight of the phenyl-containing polyorganosiloxane is usually 1,500 to 500,000, but from the viewpoint of suppressing precipitation in the adhesive composition, etc., it is preferably 100,000 or less.

[0070] Specific examples of the phenyl-containing polyorganosiloxane include: the product name PMM-1043 (manufactured by Gelest, weight-average molecular weight 67,000, viscosity 30,000 mm2 / s) represented by formula (C-1); the product name PMM-1025 (manufactured by Gelest, weight-average molecular weight 25,200, viscosity 500 mm2 / s) represented by formula (C-2); the product name KF50-3000CS (manufactured by Shin-Etsu Chemical Co., Ltd., weight-average molecular weight 39,400, viscosity 3000 mm2 / s) represented by formula (C-3); the product name TSF431 (manufactured by Momentive, weight-average molecular weight 1,800, viscosity 100 mm2 / s) represented by formula (C-4); the product name TSF433 (manufactured by Momentive, weight-average molecular weight ३,०००, viscosity 450 mm2 / s) represented by formula (C-5); the product name PDM-0421 (manufactured by Gelest, weight-average molecular weight 6,200, viscosity 100 mm2 / s) represented by formula (C-6); the product name PDM-0821 (manufactured by Gelest, weight-average molecular weight 8,600, viscosity 125 mm2 / s) represented by formula (C-7), etc., but are not limited to these.

[0071] [Chemical formula 13] (m and n represent the number of repeating units.)

[0072] [Chemical Formula 14] (m and n represent the number of repeating units.)

[0073] [Chemical Formula 15] (m and n represent the number of repeating units.)

[0074] [Chemical Formula 16] (m and n represent the number of repeating units.)

[0075] [Chemical Formula 17] (m and n represent the number of repeating units.)

[0076] [Chemical Formula 18] (m and n represent the number of repeating units.)

[0077] [Chemical Formula 19] (m and n represent the number of repeating units.)

[0078] In an ideal aspect, the adhesive composition used in the present invention simultaneously contains a polyorganosiloxane component (A) and a release agent component (B) that are hardened by a hydrosilylation reaction; in a more ideal aspect, the release agent component (B) contains a polyorganosiloxane.

[0079] The adhesive composition used in the present invention can contain an adhesive component (S) and a release agent component (B) in any ratio. However, considering the balance between adhesiveness and peelability, the ratio of component (S) to component (B), in terms of mass ratio, is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25. That is, in the case of containing a polyorganosiloxane component (A) that is hardened by a hydrosilylation reaction, the ratio of component (A) to component (B), in terms of mass ratio, is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0080] The adhesive composition used in the present invention can also contain a solvent for the purpose of adjusting viscosity, etc. Specific examples thereof include: aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but are not limited to these.

[0081] More specifically, examples include: hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, sym-trimethylbenzene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc., but are not limited to these. Such solvents can be used alone or in combination of two or more.

[0082] When the adhesive composition used in this invention contains a solvent, the content of the solvent is appropriately set by taking into account the desired viscosity of the composition, the coating method used, the thickness of the film produced, etc., but relative to the composition as a whole, it is in the range of about 10 to 90% by mass.

[0083] The viscosity of the adhesive composition used in this invention is typically 500~20,000 mPa·s at 25°C, ideally 1,000~5,000 mPa·s. The viscosity of the adhesive composition used in this invention can be adjusted by changing the type or ratio of the organic solvent used, the concentration of the film constituent components, etc., taking into account various factors such as the coating method used and the desired film thickness. In this invention, the film constituent components refer to components other than the solvent contained in the composition.

[0084] The adhesive composition used in this invention can be manufactured by mixing adhesive components (S), and then mixing release agent components (B) and solvent when needed. The mixing order is not particularly limited, but examples of methods that can easily and reproducibly manufacture the adhesive composition include: dissolving adhesive components (S) and release agent components (B) in a solvent; or dissolving a portion of adhesive components (S) and release agent components (B) in a solvent, dissolving the remaining portion in the solvent, and then mixing the resulting solutions. However, this method is not limited to these. Furthermore, when preparing the adhesive composition, heating can be appropriately applied within a range that will not decompose or deteriorate the components. In this invention, for the purpose of removing foreign matter, filtration can be performed during the manufacturing process of the adhesive composition or after mixing all components using a submicron-sized filter or the like.

[0085] The cleaning method for the semiconductor substrate of the present invention, as described above, includes the step of peeling off the adhesive layer on the semiconductor substrate using a stripping composition; the stripping composition contains a solvent and does not contain salt; the solvent contains 80% by mass or more of an organic solvent represented by formula (L). Here, the organic solvent represented by formula (L) may be a single type or two or more types.

[0086] In the above formula (L), L1 and L2 each independently represent alkyl groups with 2 to 5 carbon atoms, and L3 represents O or S.

[0087] The alkyl group having 2 to 5 carbon atoms can be any of straight-chain, branched, or cyclic. However, from the viewpoint of achieving good reproducibility and quick peeling of the adhesive layer, straight-chain or branched alkyl groups are ideal, and straight-chain alkyl groups are even more ideal.

[0088] Specific examples of straight-chain or branched alkyl groups include: ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, etc., but are not limited to these.

[0089] Specific examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, etc., but are not limited to these.

[0090] From the viewpoint of achieving reproducibility and rapid peeling of the adhesive layer, the alkyl group having 2 to 5 carbon atoms is ideally ethyl, n-propyl, n-butyl, or n-pentyl, and more ideally ethyl, n-propyl, or n-butyl.

[0091] From the viewpoint of achieving reproducibility and peeling of the adhesive layer in a shorter time, and from the viewpoint of the easy availability of the compound, L1 and L2 are ideally the same group.

[0092] From the viewpoint of achieving reproducibility and peeling of the adhesive layer in a shorter time, and from the viewpoint of the easy availability of the compound, ideal examples of organic solvents represented by formula (L) can be listed as: di(n-butyl) ether, diethyl ether, di(n-pentyl) ether, di(n-propyl) sulfide, etc.

[0093] The stripping composition used in this invention does not contain salt. Specific examples of such salts include those used for this purpose, typically ammonium salts such as tetrabutylammonium hydroxide and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride), which are added to facilitate the removal of the adhesive layer and adhesive layer residue. The stripping composition used in this invention does not need to contain such salts because it contains an organic solvent represented by formula (L). Since such salts may cause corrosion or other damage to the substrate, especially to substrates with attached bumps, a salt-free stripping composition is used in this invention. However, the presence of trace amounts of salt as impurities in the overall solvent constituting the stripping composition from the outset does not negate the existence of the salts.

[0094] The solvent contained in the peeling composition used in this invention contains an organic solvent expressed by formula (L) of 80% by mass or more, ideally 85% by mass or more, more ideally 87% by mass or more, and even more ideally 89% by mass or more. By making the content of the organic solvent expressed by formula (L) within such a range, the peeling of the adhesive layer can be achieved in a short time. On the other hand, if the content is outside this range, the peeling time becomes significantly longer and is therefore undesirable.

[0095] Ideally, the solvent contained in the above-mentioned stripping composition is composed of an organic solvent represented by formula (L). In this case, the solvent contained in the above-mentioned stripping composition is ideally composed entirely of an organic solvent represented by formula (L) without containing other solvents as impurities. However, there are limits to improving the purity through purification, which is technically impossible. Therefore, in this invention, the solvent contained in the above-mentioned stripping composition is intentionally composed solely of an organic solvent represented by formula (L), and does not exclude the possibility that the organic solvent represented by formula (L) contains impurities such as water or organic solvents that are difficult to separate due to similar structure or properties. As such, the solvent contained in the above-mentioned stripping composition is composed of the organic solvent represented by the above formula (L). The purity value of the organic solvent represented by the above formula (L) in the solvent contained in the above-mentioned stripping composition may not be completely 100%, usually 94% or more, ideally 95% or more, even more ideally 96% or more, even more ideally 97% or more, even more ideally 98% or more, and even more ideally 99% or more.

[0096] In this invention, the adhesive layer on the semiconductor substrate is continuously contacted with the release molecule, causing the adhesive layer to swell and thus peel off from the semiconductor substrate. The method of continuously contacting the adhesive layer on the semiconductor substrate with the release molecule is not particularly limited as long as the adhesive layer on the semiconductor substrate is in continuous contact with the release molecule over time. This continuous contact over time is not limited to the case where the adhesive layer is always in contact with the release molecule; for example, it also includes the case where the adhesive layer is in contact with an organic solvent for a certain period of time, then the contact is temporarily stopped once, and then the contact is repeated, and the operation is repeated. Furthermore, it is not limited to the case where the entire adhesive layer on the semiconductor substrate is in contact with the release molecule, but it also includes the case where a portion of the adhesive layer is in contact with the release molecule. However, from the viewpoint of achieving more effective cleaning with good reproducibility, it is ideal for the adhesive layer on the semiconductor substrate to be in continuous contact with the release molecule; furthermore, it is ideal for the entire adhesive layer on the semiconductor substrate to be in contact with the release molecule.

[0097] Therefore, in the ideal form of the present invention, the adhesive layer on the semiconductor substrate is swelled by immersing the adhesive layer in the release composition, thereby being peeled off from the semiconductor substrate, or the adhesive layer on the semiconductor substrate is swelled by continuously supplying the release composition to the adhesive layer, thereby being peeled off from the semiconductor substrate.

[0098] In order to immerse the adhesive layer on the semiconductor substrate in the release composition, for example, the semiconductor substrate with the adhesive layer attached may be immersed in the release composition. The immersion time is not particularly limited as long as the adhesive layer swells and can be peeled off from the semiconductor substrate, but from the viewpoint of achieving more effective cleaning with good reproducibility, it is 5 seconds or more; from the viewpoint of production volume in the manufacturing process, it is 5 minutes or less.

[0099] When the adhesive layer on the semiconductor substrate is immersed in the stripping composition, the semiconductor substrate with the adhesive layer can be moved in the stripping composition, the stripping composition can be convectioned, and the stripping composition can be vibrated by ultrasonic waves, thereby promoting the stripping of the adhesive layer.

[0100] In order to move a semiconductor substrate with an adhesive layer attached in a peeling composition, for example, a shaking cleaner or a paddle cleaner can be used. If such a cleaner is used, by moving or rotating the platform on which the semiconductor substrate with the adhesive layer is placed up and down or left and right, 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 the movement or rotation, thereby not only promoting the swelling of the adhesive layer on the semiconductor substrate, but also promoting the peeling of the adhesive layer from the semiconductor substrate.

[0101] In order to facilitate the convection of the stripping components, in addition to the shaking washers and paddle washers mentioned above, for example, a convection washer can typically be used, which enables the stripping components around a semiconductor substrate with an adhesive layer fixed on a platform to be convectioned by an agitator.

[0102] In order to vibrate the stripping components by means of ultrasound, an ultrasonic cleaner or an ultrasonic probe can be used, the conditions of which are usually 20kHz to 5MHz.

[0103] In order to continuously supply the stripping composition to the adhesive layer on the semiconductor substrate, the stripping composition can be continuously added towards the adhesive layer on the semiconductor substrate. For example, if the adhesive layer on the semiconductor substrate is facing upwards, the stripping composition in rod or mist form can be supplied from above (including obliquely above) the adhesive layer on the semiconductor substrate via a nozzle of a cleaning device. Ideally, the rod-shaped stripping composition should be continuously supplied to the adhesive layer on the semiconductor substrate in time. This continuity in time is not limited to the case where the stripping composition is always supplied to the adhesive layer on the semiconductor substrate. For example, it also includes the case where the supply of the stripping composition is temporarily stopped once after a certain period of time, and then the supply is resumed, or the operation is repeated. However, from the viewpoint of achieving more effective cleaning with good reproducibility, it is ideal for the stripping composition to be continuously supplied to the adhesive layer on the semiconductor substrate.

[0104] When the stripping composition is supplied to the adhesive layer on the semiconductor substrate in the form of a rod, the flow rate is usually 200~500 mL / min.

[0105] In a certain embodiment of the present invention, in order to achieve a state in which the substrate is always in contact with the stripping component, a steam cleaner may be used to bring the adhesive layer on the semiconductor substrate into contact with the vapor of the stripping component.

[0106] The cleaning method for the semiconductor substrate of the present invention may also include a step of removing the peeled adhesive layer. The method for removing the peeled adhesive layer is not particularly limited as long as it can be removed from the semiconductor substrate. In the case where the semiconductor substrate with the adhesive layer attached is immersed in the stripping composition, the peeled adhesive layer may be removed without removing the semiconductor substrate from the stripping composition, or the peeled adhesive layer may be removed by removing the semiconductor substrate from the stripping composition. In this case, there are also cases where simply removing the semiconductor substrate from the stripping composition leaves the peeled adhesive layer naturally remaining in the stripping composition, and most of it can be removed.

[0107] Specific examples of methods for removing the adhesive layer after peeling include the following methods: using a device to adsorb or suction to remove it, using a gas gun or the like to blow it away to remove it, using centrifugal force generated by moving or rotating the semiconductor substrate up and down or left and right, etc., but not limited to these methods.

[0108] After removing the adhesive layer after peeling, if necessary, the semiconductor substrate may be dried using conventional methods.

[0109] The stripping composition used in the semiconductor substrate cleaning method of the present invention is also the subject of the present invention. The stripping composition of the present invention is used to peel the adhesive layer on the semiconductor substrate from the semiconductor substrate, and its ideal state and conditions are as described above. If necessary, the stripping composition of the present invention can be manufactured by mixing the solvents constituting the composition in any order. At this time, filtration may also be performed if necessary.

[0110] By using the cleaning method of the semiconductor substrate of the present invention described above, damage to the semiconductor substrate, especially to the bumps of the semiconductor substrate, can be suppressed, and the adhesive layer on the semiconductor substrate, especially the adhesive layer of the hardened film obtained from the silicone adhesive containing the polyorganosiloxane component (A) hardened by the hydrosilicification reaction, can be effectively removed, and the manufacture of semiconductor devices with high efficiency and good performance can be expected.

[0111] The semiconductor substrate to be cleaned by the cleaning method of the present invention includes, in addition to silicon semiconductor substrates such as silicon wafers, such as germanium substrates, gallium-arsenic substrates, gallium-phosphorus substrates, gallium-arsenic-aluminum substrates, aluminum-plated silicon substrates, copper-plated silicon substrates, silver-plated silicon substrates, gold-plated silicon substrates, titanium-plated silicon substrates, silicon substrates with silicon nitride films, silicon substrates with silicon oxide films, silicon substrates with polyimide films, glass substrates, quartz substrates, liquid crystal substrates, organic EL substrates, and other various substrates.

[0112] Examples of the use of the semiconductor substrate cleaning method of the present invention in semiconductor manufacturing processes include its use in manufacturing methods of semiconductor substrates after thinning and other processing in semiconductor packaging technologies such as TSV. Specifically, the manufacturing method of a semiconductor substrate after thinning and other processing includes: a first step of manufacturing a laminate comprising a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition; a second step of processing the obtained laminate into a semiconductor substrate; a third step of separating the processed semiconductor substrate and the adhesive layer from the support substrate; and a fourth step of removing the adhesive layer from the processed semiconductor substrate and cleaning the processed semiconductor substrate, wherein the fourth step uses the semiconductor substrate cleaning method of the present invention.

[0113] Although various adhesives described above can be used for the adhesive composition used to form the adhesive layer in step 1, the cleaning method for the semiconductor substrate of the present invention is effective for removing adhesive layers obtained from polysiloxane-based adhesives, and is even more effective for removing adhesive layers obtained from polysiloxane-based adhesives containing component (A) that is cured by a hydrosilicification reaction. Therefore, the following description focuses on an example of removing the adhesive layer obtained using a polysiloxane-based adhesive (adhesive composition) when manufacturing a processed semiconductor substrate, using the cleaning method of the present invention; however, the present invention is not limited thereto.

[0114] First, the first step of manufacturing a laminate having a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition will be described.

[0115] In one embodiment, the first step includes: forming an adhesive coating layer by coating an adhesive composition onto the surface of a semiconductor substrate or a support substrate; bonding the semiconductor substrate and the support substrate via the adhesive coating layer, and simultaneously applying a load in the thickness direction of the semiconductor substrate and the support substrate to make them adhere closely while performing at least one of a heat treatment and a depressurization treatment, and then performing a post-heat treatment to form a multilayer. In other embodiments, the first step may, for example, include: coating an adhesive composition onto the circuit surface of a wafer of the semiconductor substrate and heating it to form an adhesive coating layer; coating a release agent composition onto the surface of the support substrate and heating it to form a release agent coating layer; and simultaneously applying a load in the thickness direction of the semiconductor substrate and the support substrate to make them adhere closely while performing at least one of a heat treatment and a depressurization treatment on the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate, and then performing a post-heat treatment to form a multilayer. Furthermore, although the adhesive composition is separately coated onto the semiconductor substrate and heated, and the release agent composition is separately coated onto the support substrate and heated, the adhesive composition and release agent composition can also be coated and heated sequentially on either substrate. The choice between heat treatment, reduced pressure treatment, or a combination of both in the above-mentioned cases is determined after considering 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 adhesion strength.

[0116] Here, for example, the semiconductor substrate is a wafer, and the support substrate is a support. The object to which the adhesive composition is coated can be either the semiconductor substrate or the support substrate, or both.

[0117] The wafer can be, for example, a silicon wafer or a glass wafer with a diameter of about 300 mm and a thickness of about 770 μm, but is not limited to these. In particular, the cleaning method for the semiconductor substrate of the present invention can suppress damage to the bumps of the bumped semiconductor substrate, while effectively cleaning the substrate. Specific examples of such bumped semiconductor substrates include silicon wafers with bumps such as ball bumps, printed bumps, stud bumps, and plated bumps, which are usually appropriately selected from conditions of bump height of about 1 to 200 μm, bump diameter of 1 to 200 μm, and bump pitch of 1 to 500 μm. Specific examples of plated bumps include SnAg (tin-silver) bumps, SnBi (tin-bismuth) bumps, Sn (tin) bumps, AuSn (gold-tin) bumps, and alloys with Sn as the main component, but are not limited to these.

[0118] The support (carrier) is not particularly limited. Examples include silicon wafers with a diameter of 300 mm and a thickness of about 700 μm, but it is not limited to these.

[0119] The stripping agent composition may include compositions containing stripping agent components used for this purpose.

[0120] There is no particular limitation on the coating method, usually spin coating. Alternatively, another method can be used, such as spin coating, to form a coated film, and then a sheet-like coated film can be laminated. This is also called coating or coated film.

[0121] The heating temperature of the coated adhesive composition varies depending on the type and amount of adhesive components contained in the adhesive composition, whether it contains solvent, the desired thickness of the adhesive layer, etc., and therefore cannot be determined in general. However, it is usually 80°C to 150°C, and the heating time is usually 30 seconds to 5 minutes.

[0122] The heating temperature of the coated release agent composition varies depending on the type and amount of crosslinking agent, acid generating agent, acid, etc., whether it contains solvent, and the desired thickness of the release layer, etc., and therefore cannot be generalized. However, from the viewpoint of achieving suitable curing, it is 120°C or higher; from the viewpoint of preventing over-curing, it is ideally below 260°C, and the heating time is usually 1 to 10 minutes. Heating can be performed using a heating plate, oven, etc.

[0123] The thickness of the adhesive coating layer obtained by coating an adhesive composition and then heating it is typically 5 to 500 μm.

[0124] The thickness of the release agent coating layer obtained by coating the release agent composition and then heating it is typically 5 to 500 μm.

[0125] The heat treatment, taking into account the viewpoints of softening the adhesive coating layer to achieve proper adhesion with the release agent coating layer and achieving proper hardening of the release agent coating layer, is generally appropriately determined within the range of 20 to 150°C. In particular, from the viewpoint of suppressing and avoiding excessive hardening or unnecessary deterioration of the adhesive and release agent components, it is ideal to be below 130°C, and more ideally below 90°C; the heating time, from the viewpoint of reliably demonstrating adhesion and release capabilities, is generally 30 seconds or more, and ideally 1 minute or more, but from the viewpoint of suppressing deterioration of the adhesive layer and other components, it is generally 10 minutes or less, and ideally 5 minutes or less.

[0126] The depressurization treatment exposes the semiconductor substrate, adhesive coating layer, and support substrate, or the semiconductor substrate, adhesive coating layer, release agent coating layer, and support substrate, to an atmospheric pressure of 10 to 10,000 Pa. The depressurization treatment time is usually 1 to 30 minutes.

[0127] In the ideal form of the present invention, the substrate and the coating layer, or the coating layers to each other, are ideally bonded by a decompression process, and more ideally by a combination of a heat treatment and a decompression process.

[0128] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the layers between the semiconductor substrate and the support substrate and the layers therebetween, and can ensure that the layers are securely attached. It is usually in the range of 10 to 1000 N.

[0129] The post-heating temperature is ideally 120°C or higher from the viewpoint of achieving sufficient curing speed; and ideally 260°C or lower from the viewpoint of preventing deterioration of the substrate, adhesive components, release agent components, etc. The heating time is typically 1 minute or higher from the viewpoint of achieving proper wafer bonding resulting from curing; and ideally 5 minutes or higher from the viewpoint of stabilizing the physical properties of the adhesive; and typically 180 minutes or lower, ideally 120 minutes or lower, from the viewpoint of avoiding adverse effects on the adhesive layer due to overheating. Heating can be performed using a heating plate, oven, etc. Furthermore, one purpose of the post-heating treatment is to ensure more appropriate curing of the adhesive component (S).

[0130] Next, the second step of processing the semiconductor substrate of the multilayer obtained using the method described above will be explained. One example of processing the multilayer used in this invention is processing the back side, which is opposite to the circuit surface of the semiconductor substrate. Typically, this can be achieved by thinning the wafer by grinding the back side. Using this thinned wafer, through-silicon via (TSV) electrodes are formed, and then the thinned wafer is peeled off from the support to form a multilayer wafer, which is then three-dimensionally mounted. Furthermore, back-side electrodes are formed around this point. Although the wafer is subjected to heat of 250-350°C while attached to the support during the thinning and TSV processes, the adhesive layer contained in the multilayer used in this invention has heat resistance to this heat. For example, a wafer with a diameter of 300 mm and a thickness of approximately 770 μm can be thinned to a thickness of approximately 80-4 μm by grinding the back side, which is opposite to the circuit surface of the surface.

[0131] The third step, which separates the processed semiconductor substrate and the adhesive layer from the support substrate, will be described. In the third step, the processed semiconductor substrate and the adhesive layer are separated from the support substrate. At this time, if the laminate contains a release layer, the release layer and the support substrate are usually removed simultaneously. The method for separating the processed semiconductor substrate and the adhesive layer from the semiconductor substrate can be to peel the adhesive layer from the release layer or the support substrate that is in contact with it. Such peeling methods include laser peeling, mechanical peeling using a material with sharp edges, and peeling by manual tearing, but are not limited to these.

[0132] Next, the 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 the step of removing the adhesive layer on the semiconductor substrate by the cleaning method of the present invention. Specifically, for example, the cleaning method of the present invention is used to efficiently remove the adhesive layer on the thinned substrate. The various conditions at this time are as described above.

[0133] After step 4, if necessary, the adhesive residue remaining on the semiconductor substrate can be removed by a cleaning agent containing salt. However, care should be taken not to damage the semiconductor substrate, especially the bumps of a semiconductor substrate with bumps.

[0134] Although the method for manufacturing the processed semiconductor substrate of the present invention includes the first to fourth steps described above, it may also include steps other than these. Furthermore, various modifications can be made to the aforementioned constituent elements and method elements related to the first to fourth steps, as long as they do not depart from the spirit of the present invention. [Example]

[0135] The present invention is illustrated below with examples and comparative examples, but the present invention is not limited to the following examples. Furthermore, the purity of the apparatus used in the present invention and the solvent used for stripping the composition obtained by gas chromatography is as follows. [Apparatus] (1) Rotational mixer: ARE-500 rotational mixer manufactured by THINKY Corporation (2) Viscometer: TVE-22H rotational viscometer manufactured by Toki Industries, Ltd. (3) Mixer: 1-1186-12 variable stirring rotor manufactured by AS ONE Corporation (4) Optical microscope: MX61L semiconductor / FPD inspection microscope manufactured by Olympus Corporation

[0136] [Solvents] N-Methylpyrrolidone: Manufactured by Kanto Chemical Co., Ltd., purity > 99.0%; Di(n-butyl) ether: Manufactured by Tokyo Chemical Industry Co., Ltd., purity > 99.0%; Diethyl ether: Manufactured by Kanto Chemical Co., Ltd., purity > 99.5%; Di(n-propyl) ether: Manufactured by Tokyo Chemical Industry Co., Ltd., purity > 98.0%; Di(n-propyl) sulfide: Manufactured by Tokyo Chemical Industry Co., Ltd., purity > 98.0%; Di(n-pentyl) ether: Manufactured by Tokyo Chemical Industry Co., Ltd., purity > 98.0%; Di(n-butyl) sulfide: Manufactured by Tokyo Chemical Industry Co., Ltd., purity > 98.0%; 5-Nonone: Manufactured by Tokyo Chemical Industry Co., Ltd., purity > 98.0%.

[0137] 〔1〕Preparation of adhesive composition〔Preparation Example 1〕Add the following to a 600mL mixing container for a rotary mixer: 95g of vinyl-containing MQ resin (manufactured by Wacker Chemie Co., Ltd.) as (a1), 93.4g of p-menthane (manufactured by Nippon Terpene Chemicals Co., Ltd.) as a solvent, and 0.41g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as (A2), and mix with a rotary mixer for 5 minutes. Add the following to the obtained mixture: 19.0 g of SiH-based linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 100 mPa·s as (a2); 29.5 g of vinyl-based linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 200 mPa·s as (a1); 65.9 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK1000000) with a viscosity of 1,000,000 mm2 / s as (B); and 0.41 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) as (A3). Then, further stir with a rotary mixer for 5 minutes. Then, 14.9g of a mixture obtained by mixing the obtained mixture with 0.20g of platinum catalyst (manufactured by Wacker Chemie) as (A2) and 17.7g of vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1000mPa·s as (a1) for 5 minutes using a rotary mixer is added, and the mixture is further stirred for 5 minutes using a rotary mixer. The mixture is then filtered through a 300-mesh nylon filter to obtain the adhesive composition.

[0138] 〔2〕Evaluation substrate fabrication〔Manufacturing Example 1〕 On a 4cm×4cm silicon wafer (775μm thick) serving as the device side, the composition obtained in Preparation Example 1 was coated using a spin coater, and heated at 120°C for 1.5 minutes using a heating plate, followed by heating at 200°C for 10 minutes, to form a thin film with a thickness of 60μm on the wafer, thereby obtaining a wafer with an attachment layer.

[0139] 〔Manufacturing Example 2〕 A substrate with bumps is cut to prepare a 4cm×4cm sample substrate. Furthermore, the number of bumps on each sample substrate is 5044, and the structure of the bumps is as follows: the pillars are made of copper; the caps are made of tin-silver (silver 1.8% by mass); and the space between the pillars and the caps is made of nickel.

[0140] 〔3〕Measurement of peeling time〔Example 1-1〕The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of di(n-butyl) ether, which is the peeling composition of Example 1-1, and the time until the adhesive layer began to peel off from the wafer was measured to be 11 seconds.

[0141] [Examples 1-2] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent (9:1 (w / w)) of di(n-butyl) ether and N-methylpyrrolidone, which is the peeling composition of Examples 1-2, and the time until the adhesive layer began to peel off from the wafer was measured to be 12 seconds.

[0142] [Example 2] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of diethyl ether, which is the peeling composition of Example 2, and the time until the adhesive layer began to peel off from the wafer was measured to be 3 seconds.

[0143] [Example 3] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of di(n-propyl) ether, which is the peeling composition of Example 3, and the time until the adhesive layer began to peel off from the wafer was measured to be 5 seconds.

[0144] [Example 4] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of the second (n-propyl) sulfide, which is the peeling composition of Example 4, and the time until the adhesive layer began to peel off from the wafer was measured to be 12 seconds.

[0145] [Example 5] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of di(n-pentyl) ether, which is the peeling composition of Example 5, and the time until the adhesive layer began to peel off from the wafer was measured to be 23 seconds.

[0146] [Example 6] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of the second (n-butyl) sulfide, which is the peeling composition of Example 6, and the time until the adhesive layer began to peel off from the wafer was measured to be 22 seconds.

[0147] [Comparative Example 1] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of 5-nonanone, which is the peeling composition of Comparative Example 1, and the time until the adhesive layer began to peel off from the wafer was measured to be 36 seconds.

[0148] The results of the examples and comparative examples are shown in Table 1. As shown in Table 1, in the case where the stripping composition contains more than 80% by mass of di(n-butyl) ether or diethyl ether, which is an organic solvent represented by formula (L), the stripping time of the adhesive layer on the semiconductor substrate is very short compared with the case where the stripping composition does not contain an organic solvent represented by formula (L) but contains a ketone containing a heteroatom compound with the same number of carbon atoms as the organic solvent and a similar structure (Comparative Example 1).

[0149] 〔Table 1〕

[0150] 〔4〕Observation of damage to the substrate with bumps 〔Example 7〕 The sample substrate prepared in Manufacturing Example 2 was immersed in 9 mL of di(n-butyl) ether, left to stand for 1 hour, washed with isopropanol and acetone, and then observed with an optical microscope for bump damage. The result was that no bump damage was observed.

[0151] [Comparative Example 2] Although 2g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) and 18g of di(n-butyl) ether were thoroughly stirred at room temperature using a stirring rotor, some tetrabutylammonium fluoride remained undissolved. Therefore, the supernatant of the solution was recovered. Then, the sample substrate prepared in Manufacturing Example 2 was immersed in 9mL of the recovered supernatant of the solution, allowed to stand for 1 hour, washed with isopropanol and acetone, and then observed under an optical microscope for bump damage. The results confirmed that there were damaged bumps throughout the entire sample substrate (the estimated number of damaged bumps was 1000~2000).

Claims

1. A method for cleaning a semiconductor substrate, comprising the step of peeling off an adhesive layer on a semiconductor substrate having a connection portion made of a conductive material using a stripping composition, characterized in that the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) of a silicate-based adhesive; the stripping composition contains a solvent and does not contain a salt; and the solvent contains 80% by mass or more of an organic solvent represented by formula (L); (wherein, L1 and L2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L3 represents O or S).

2. The cleaning method for a semiconductor substrate as described in claim 1, wherein, The solvent contains more than 85% by mass of the organic solvent represented by formula (L).

3. The cleaning method for the semiconductor substrate as described in claim 2, wherein, The solvent is made from the organic solvent represented by formula (L).

4. The cleaning method for a semiconductor substrate as described in claim 1, wherein, L1 and L2 are the same group.

5. The cleaning method for the semiconductor substrate as described in claim 4, wherein, The alkyl group having 2 to 5 carbon atoms is ethyl, n-propyl, or n-butyl.

6. A cleaning method for a semiconductor substrate as described in any one of claims 1 to 5, wherein, The adhesive component (S) further comprises at least one selected from acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives and phenolic resin adhesives.

7. The cleaning method for a semiconductor substrate as described in claim 1, wherein, The silicate adhesive contains a polyorganosiloxane component (A) that is cured by a hydrosilicification reaction.

8. A method for manufacturing a processed semiconductor substrate, comprising: a first step of manufacturing a laminate having a semiconductor substrate having a connection portion made of a conductive material, a support substrate, and an adhesive layer obtained from an adhesive composition; a second step of processing the semiconductor substrate of the obtained laminate; a third step of separating the semiconductor substrate and the adhesive layer from the support substrate; and a fourth step of peeling off the adhesive layer on the semiconductor substrate using a peeling composition; characterized in that the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) of a siloxane-based adhesive; the peeling composition contains a solvent and does not contain a salt; and the solvent contains 80% by mass or more of an organic solvent represented by formula (L); (wherein, L1 and L2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L3 represents O or S).

9. A method for manufacturing a processed semiconductor substrate as described in claim 8, wherein, The solvent contains more than 85% by mass of the organic solvent represented by formula (L).

10. A method for manufacturing the processed semiconductor substrate as described in claim 9, wherein, The solvent is made from the organic solvent represented by formula (L).

11. A method for manufacturing a processed semiconductor substrate as described in claim 8, wherein, L1 and L2 are the same group.

12. A method for manufacturing a processed semiconductor substrate as described in claim 11, wherein, The alkyl group having 2 to 5 carbon atoms is ethyl, n-propyl, or n-butyl.

13. A method for manufacturing a processed semiconductor substrate as described in any one of claims 8 to 12, wherein, The adhesive component (S) further comprises at least one selected from acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives and phenolic resin adhesives.

14. A method for manufacturing a processed semiconductor substrate as described in claim 8, wherein, The silicate adhesive contains a polyorganosiloxane component (A) that is cured by a hydrosilicification reaction.

15. A stripping composition for stripping an adhesive layer on a semiconductor substrate when cleaning a semiconductor substrate having a connector made of a conductive material, characterized in that the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) of a siloxane-based adhesive; the stripping composition contains a solvent and does not contain a salt; and the solvent contains 80% by mass or more of an organic solvent represented by formula (L); (wherein, L1 and L2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L3 represents O or S).

16. The stripping composition as described in claim 15, wherein, The solvent contains more than 85% by mass of the organic solvent represented by formula (L).

17. The stripping composition as described in claim 16, wherein, The solvent is made from the organic solvent represented by formula (L).

18. The stripping composition as described in claim 15, wherein, L1 and L2 are the same group.

19. The stripping composition as described in claim 18, wherein, The alkyl group having 2 to 5 carbon atoms is ethyl, n-propyl, or n-butyl.

20. A stripping composition as described in any one of claims 15 to 19, wherein, The adhesive component (S) further comprises at least one selected from acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives and phenolic resin adhesives.

21. The stripping composition as described in claim 15, wherein, The silicate adhesive contains a polyorganosiloxane component (A) that is cured by a hydrosilicification reaction.