Cleaning methods for semiconductor substrates, manufacturing methods for processed semiconductor substrates, and applications of components used for stripping.
Patent Information
- Application Number
- TW110110434
- Authority / Receiving Office
- TW · TW
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2020-03-23
- Filing Date
- 2021-03-23
- Publication Date
- 2026-09-11
- Estimated Expiration
- 2041-03-22
Abstract
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. Prior Technology
[0002] For a long time, semiconductor wafers have been stacked in a two-dimensional planar direction. The goal is to further stack semiconductor wafers in a three-dimensional direction. This three-dimensional stacking is achieved by connecting the wafers using through-silicon vias (TSVs), and 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 wafers are stacked.
[0003] Before thinning, a semiconductor wafer (hereinafter simply referred to as a wafer) 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 bond. This temporary bond must be easily detachable from the support; if excessive 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 semiconductor wafer to detach or deviate due to polishing stress when polishing the back side. Therefore, the performance required for a temporary bond 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, thus further heat resistance is required.
[0004] Against this backdrop, in the semiconductor field, temporary adhesives primarily utilize polysiloxane-based adhesives that possess these properties. Furthermore, in polysiloxane 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 remover for silicone resins containing a polar aprotic solvent and quaternary ammonium hydroxide; Patent Document 2 discloses a remover for hardened resins containing fluorinated alkyl ammonium. However, in the recent semiconductor field, there remains an urgent need for new cleaning agent compositions, and there is a constant need for more effective cleaning agent compositions and cleaning methods.
[0005] On the other hand, semiconductor wafers are electrically connected to semiconductor chips, for example, via bump balls made of a conductive metallic material, and semiconductor packaging is miniaturized by using chips with such bump balls.
[0006] Regarding this point, since bump balls made of metals such as copper or tin lack corrosion resistance, they may be damaged by cleaning agent compositions used to remove adhesive residues from the substrate or wafer (Patent Document 3). Therefore, preventing corrosion of bump balls when cleaning the substrate can also be listed as one of the objectives pursued by cleaning agent compositions and cleaning methods. [Previous Technical Documents] [Patent Literature]
[0007] [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
[0008] [The technical problem that the invention aims to solve]
[0009] The present invention is made in view of the above circumstances, and its object is to: provide a method for cleaning a semiconductor substrate, for example, for removing the adhesive layer obtained by using a silicone-based adhesive from the surface of a semiconductor substrate, thereby reducing or suppressing damage to the bumps of the semiconductor substrate, while properly and easily removing the adhesive layer; provide a method for cleaning a processed semiconductor substrate, comprising such a cleaning method; and provide a stripping composition for use in such a cleaning method. [Technical means]
[0010] After repeated and in-depth research to solve the above-mentioned problems, the inventors discovered that by using a stripping composition containing a specified amount or more of a specified cyclic aliphatic hydrocarbon 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 effectively and easily peeled off, thereby completing the present invention.
[0011] 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 release agent, characterized in that... The above-mentioned stripping composition contains a solvent but does not contain salt; and The solvents mentioned above contain 80% by mass or more of an organic solvent represented by any one of formulas (L0) to (L4); [Chemistry 1] (In the formula, L101 to L112 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L101 to L112 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms; L201 to L210 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L201 to L210 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms; L301 to L308 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that L301 to L308 represent ... At least one of them represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms; L401 to L408 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, except that at least one of L401 to L408 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. 2. The cleaning method for a semiconductor substrate as described in 1, wherein the solvent contains 85% by mass or more of the organic solvent represented by any one of formulas (L0) to (L4). 3. The cleaning method for a semiconductor substrate as described in 2, wherein the solvent is an organic solvent represented by any one of the formulas (L0) to (L4). 4. A method for cleaning a semiconductor substrate as described in any one of 1 to 3, wherein the alkyl group having 1 to 5 carbon atoms is methyl, ethyl, n-propyl, or isopropyl; The aforementioned alkenyl groups having 2 to 5 carbon atoms are vinyl, 1-methylvinyl, or 2-methylvinyl; The 2-5 carbon group mentioned above is either ethynyl or 2-methylethynyl. 5. The cleaning method for the semiconductor substrate as described in 4, wherein one or two of L101 to L112 are alkyl groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, or alkynyl groups having 2 to 5 carbon atoms, and the remainder are hydrogen atoms; One or two of L201 to L210 mentioned above are alkyl groups with 1 to 5 carbon atoms, alkenyl groups with 2 to 5 carbon atoms, or alkynyl groups with 2 to 5 carbon atoms; the rest are hydrogen atoms. One or two of L301 to L308 mentioned above are alkyl groups with 1 to 5 carbon atoms, alkenyl groups with 2 to 5 carbon atoms, or alkynyl groups with 2 to 5 carbon atoms; the rest are hydrogen atoms. One or two of the above L401 to L408 are alkyl groups with 1 to 5 carbon atoms, alkenyl groups with 2 to 5 carbon atoms, or alkynyl groups with 2 to 5 carbon atoms, and the rest are hydrogen atoms. 6. A cleaning method for a semiconductor substrate as described in any one of 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 method for cleaning a semiconductor substrate as described in 6, wherein the adhesive component (S) contains a siloxane-based adhesive. 8. The method for cleaning a semiconductor substrate as described in 7, wherein the aforementioned silicate adhesive contains a polyorganosiloxane component (A) that has been cured by a hydrosilicification reaction. 9. A method for manufacturing a processed semiconductor substrate, comprising: Step 1: Fabricate a laminate comprising a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition; Step 2: Processing the resulting multilayer semiconductor substrate; Step 3: Separate the semiconductor substrate and the adhesive layer from the self-supporting substrate; and Step 4 involves using a stripping composition to peel off the adhesive layer on the semiconductor substrate; its characteristic is that... The above-mentioned stripping composition contains a solvent but does not contain salt; The solvents mentioned above contain 80% by mass or more of an organic solvent represented by any one of formulas (L0) to (L4); [Chemistry 2] (In the formula, L101 to L112 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L101 to L112 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms; L201 to L210 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L201 to L210 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms; L301 to L308 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that L301 to L308 represent ... At least one of them represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms; L401 to L408 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, except that at least one of L401 to L408 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. 10. A method for manufacturing a semiconductor substrate after processing as described in 9, wherein the solvent contains 85% by mass or more of an organic solvent represented by any one of formulas (L0) to (L4). 11. The method for manufacturing a semiconductor substrate after processing as described in 10, wherein the solvent is an organic solvent represented by any one of the formulas (L0) to (L4). 12. A method for manufacturing a semiconductor substrate after processing as described in any one of claims 9 to 11, wherein the alkyl group having 1 to 5 carbon atoms is methyl, ethyl, n-propyl, or isopropyl; The aforementioned alkenyl groups having 2 to 5 carbon atoms are vinyl, 1-methylvinyl, or 2-methylvinyl; The 2-5 carbon group mentioned above is either ethynyl or 2-methylethynyl. 13. The method for manufacturing the processed semiconductor substrate as described in 12, wherein one or two of L101 to L112 are alkyl groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, or alkynyl groups having 2 to 5 carbon atoms, and the remainder are hydrogen atoms; One or two of L201 to L210 mentioned above are alkyl groups with 1 to 5 carbon atoms, alkenyl groups with 2 to 5 carbon atoms, or alkynyl groups with 2 to 5 carbon atoms; the rest are hydrogen atoms. One or two of L301 to L308 mentioned above are alkyl groups with 1 to 5 carbon atoms, alkenyl groups with 2 to 5 carbon atoms, or alkynyl groups with 2 to 5 carbon atoms; the rest are hydrogen atoms. One or two of the above L401 to L408 are alkyl groups with 1 to 5 carbon atoms, alkenyl groups with 2 to 5 carbon atoms, or alkynyl groups with 2 to 5 carbon atoms, and the rest are hydrogen atoms. 14. A method for manufacturing a processed semiconductor substrate as described in any one of 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 resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives. 15. A method for manufacturing a semiconductor substrate after processing as described in 14, wherein the adhesive component (S) contains a siloxane-based adhesive. 16. A method for manufacturing a semiconductor substrate after processing as described in 15, wherein the aforementioned silicate adhesive contains a polyorganosiloxane component (A) that is cured by a hydrosilicification reaction. 17. A release composition for removing an adhesive layer from a semiconductor substrate during cleaning, characterized in that, Contains solvent but does not contain salt; The solvents described above contain 80% by mass or more of an organic solvent represented by any one of formulas (L0) to (L4); [Chemistry 3] (In the formula, L101 to L112 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L101 to L112 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms; L201 to L210 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L201 to L210 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms; L301 to L308 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that L301 to L308 represent ... At least one of them represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms; L401 to L408 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, except that at least one of L401 to L408 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. 18. The stripping composition as described in 17, wherein the solvent contains 85% by mass or more of the organic solvent represented by any one of formulas (L0) to (L4) described above. 19. The stripping composition as described in 18, wherein the solvent is made from an organic solvent represented by any one of the formulas (L0) to (L4). 20. A stripping composition as described in any one of 17 to 19, wherein the alkyl group having 1 to 5 carbon atoms is methyl, ethyl, n-propyl, or isopropyl; The aforementioned alkenyl groups having 2 to 5 carbon atoms are vinyl, 1-methylvinyl, or 2-methylvinyl; The 2-5 carbon group mentioned above is either ethynyl or 2-methylethynyl. 21. The stripping composition as described in 20, wherein one or two of L101 to L112 are alkyl groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, or alkynyl groups having 2 to 5 carbon atoms, and the remainder are hydrogen atoms; One or two of L201 to L210 mentioned above are alkyl groups with 1 to 5 carbon atoms, alkenyl groups with 2 to 5 carbon atoms, or alkynyl groups with 2 to 5 carbon atoms; the rest are hydrogen atoms. One or two of L301 to L308 mentioned above are alkyl groups with 1 to 5 carbon atoms, alkenyl groups with 2 to 5 carbon atoms, or alkynyl groups with 2 to 5 carbon atoms; the rest are hydrogen atoms. One or two of the above L401 to L408 are alkyl groups with 1 to 5 carbon atoms, alkenyl groups with 2 to 5 carbon atoms, or alkynyl groups with 2 to 5 carbon atoms, and the rest are hydrogen atoms. 22. The peeling composition as described in any one of 17 to 21, 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 resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives. 23. The peeling composition as described in 22, wherein the adhesive component (S) contains a siloxane-based adhesive. 24. The peeling composition as described in 23, wherein the aforementioned silicone adhesive contains a polyorganosiloxane component (A) that has been cured by a hydrosilicification reaction. [Effects of the Invention]
[0012] By using the cleaning method of the semiconductor substrate of the present invention, for example, the adhesive layer on the surface of a semiconductor substrate having an adhesive layer obtained by using a silicone adhesive can be properly and easily removed, thus enabling the manufacture of highly efficient and good semiconductor devices. In particular, when a semiconductor substrate with an adhesive layer has bumps, damage to the bumps can be avoided or suppressed, and the adhesive layer can be removed properly and easily. Therefore, the manufacture of high-efficiency, high-reliability, and high-quality semiconductor devices can be expected. Implementation
[0013] The cleaning method for a semiconductor substrate of the present invention includes the step of peeling off the adhesive layer on the semiconductor substrate using a stripping composition, wherein the stripping composition contains a solvent and does not contain a salt; the solvent contains 80% by mass or more of an organic solvent represented by any one of formulas (L0) to (L4).
[0014] [Chemistry 4]
[0015] Semiconductor substrates, such as wafers, include silicon wafers with a diameter of 300 mm and a thickness of about 770 μm, but are not limited to these.
[0016] The adhesive layer on this semiconductor substrate is, for example, a film obtained from an adhesive composition containing adhesive component (S).
[0017] Such adhesive components (S) are not particularly limited as long as they are used for this purpose, and examples include: silicone adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, phenolic resin adhesives, etc.
[0018] Among these, from the perspective that it exhibits ideal adhesion during wafer processing, can be properly peeled off after processing, and also has excellent heat resistance, the ideal adhesive component (S) is a silicate-based adhesive.
[0019] In an ideal state, 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 selected from SiO2 (Q unit), R1 R2 R3 SiO1 / 2 (M unit), R4 R5 SiO2 / 2 (D unit), and R6 SiO3 / 2. The polysiloxane (A1) contains one or more units selected from the group of siloxane units (T units) represented by SiO2; and the polysiloxane (A1) contains one or more units selected from the group of siloxane units (Q' units) represented by SiO2, siloxane units (M' units) represented by R1' R2' R3' SiO1 / 2, siloxane units (D' units) represented by R4' R5' SiO2 / 2, and siloxane units (T' units) represented by R6' SiO3 / 2, and simultaneously contains at least one unit selected from the group of the above-mentioned M' units, D' units, and T' units; the polysiloxane (A2) contains units selected from the group of siloxane units (Q' units) represented by SiO2, siloxane units (M' units) represented by R1' R2' R3' SiO1 / 2, and siloxane units (D' units) represented by R4' R5' SiO2 / 2, and siloxane units (T' units) represented by R6' SiO3 / 2, and simultaneously contains at least one unit selected from the group of the above-mentioned M' units, D' units, and T' units; the polysiloxane (A2) contains units selected from the group of siloxane units (Q' units) represented by SiO2, siloxane units (Q' units) represented by R1' R2' R3', and siloxane units (D' units) represented by R4' R5' SiO2 / 2, and siloxane units (T ... The unit comprises one or more units from the group consisting of siloxane units represented by 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.
[0020] R1 to R6 are groups or atoms bonded to silicon atoms, each independently representing an alkyl, alkenyl, or hydrogen atom.
[0021] R1' to R6' are groups bonded to silicon atoms, each independently representing an alkyl or alkenyl group, except that at least one of R1' to R6' is an alkenyl group.
[0022] R1” ~ R6” are groups or atoms bonded to silicon atoms, each independently representing an alkyl group or a hydrogen atom, but at least one of R1” ~ R6” is a hydrogen atom.
[0023] Alkyl groups can be straight-chain, branched, or cyclic, but straight-chain or branched alkyl groups are preferred. There is no particular limitation on the number of carbon atoms, but it is usually 1 to 40, ideally less than 30, more ideally less than 20, and even more ideally less than 10.
[0024] 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, etc. 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 is used.
[0025] 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-cyclobutyl Cycloalkyl groups such as 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.; and bicycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, dicyclodecyl, etc., but not limited to these.
[0026] Alkenyl groups can be either linear or branched, and their carbon number is not particularly limited, usually ranging from 2 to 40, ideally below 30, even more ideally below 20, and even more ideally below 10.
[0027] 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 1,3-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, the compounds are vinyl and 2-propenyl.
[0028] As described above, polysiloxane (A1) contains polyorganosiloxane (a1) and polyorganosiloxane (a2). The alkenyl group contained in polyorganosiloxane (a1) and the hydrogen atoms (Si-H group) contained in polyorganosiloxane (a2) are cross-linked and hardened by hydrosilicification reaction through a platinum group metal catalyst (A2).
[0029] Polyorganosiloxane (a1) contains one or more units selected from the group consisting of Q', M', D' and T' units, and simultaneously contains at least one unit selected from the group consisting of M', D' and T' units. Polyorganosiloxane (a1) can also be used in combination of two or more polyorganosiloxanes that satisfy such conditions.
[0030] Ideal combinations selected from two or more groups of Q', M', D' and T' units can be listed as: (Q' and M' units), (D' and M' units), (T' and M' units), (Q', T' and M' units), but are not limited to these.
[0031] Furthermore, in cases where the polyorganosiloxanes contained in two or more polyorganosiloxanes (a1) are present, ideally it is a combination of (Q' units and M' units) and (D' units and M' units), a combination of (T' units and M' units) and (D' units and M' units), or a combination of (Q' units, T' units and M' units) and (T' units and M' units), but is not limited to these.
[0032] 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. Polyorganosiloxane (a2) can also be used in combination of two or more polyorganosiloxanes that satisfy such conditions.
[0033] Ideal combinations selected from two or more of the groups of Q” units, M” units, D” units and T” units can be listed as: (M” units and D” units), (Q” units and M” units), (Q” units, T” units and M” units), but are not limited to these.
[0034] Polyorganosiloxanes (a1) are 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 remainder R1' to R6' can be alkyl groups.
[0035] Polyorganosiloxanes (a2) are 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” to R6” is ideally 0.1 mol% to 50.0 mol%, more ideally 10.0 mol% to 40.0 mol%, and the remainder R1” to R6” can be alkyl groups.
[0036] Polysiloxane (A1) contains polyorganosiloxane (a1) and polyorganosiloxane (a2). However, in an ideal state, the molar ratio of the alkenyl group in polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bond in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.
[0037] The weight average molecular weights of the polyorganosiloxane (a1) and polyorganosiloxane (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 in this 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.
[0038] The viscosities of the polyorganosiloxanes (a1) and (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 are ideal. Furthermore, the viscosity values of the present invention are measured at 25°C using an E-type rotational viscometer.
[0039] Polyorganosiloxanes (a1) and (a2) are formed into films by reacting with each other through a hydrosilicification reaction. Therefore, their curing mechanism is different from that of silanol groups, for example. 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.
[0040] In the ideal sample, the adhesive component (S) contains both the aforementioned polysiloxane (A1) and platinum group metal catalyst (A2). Such a platinum group metal catalyst is used to promote the hydrosilicification reaction between the alkenyl group of polyorganosiloxane (a1) and the Si-H group of polyorganosiloxane (a2).
[0041] 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. Complexes of platinum with alkenes include, for example, complexes of divinyltetramethyldisiloxane with 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.
[0042] The polyorganosiloxane component (A) may also contain a polymerization inhibitor (A3) for the purpose of inhibiting the hydrosiliconization reaction. Polymerization inhibitors are not particularly limited as long as they can inhibit the hydrosiliconization reaction. Specific examples include alkynols 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 polyorganosiloxane (a1) and polyorganosiloxane (a2), is generally above 1000.0 ppm from the viewpoint of achieving its effect; and generally below 10000.0 ppm from the viewpoint of preventing excessive inhibition of the hydrosiliconization reaction.
[0043] The adhesive composition used in this invention may also contain a release agent component (B). By including such a release agent component (B) in the adhesive composition used in this invention, the obtained adhesive layer can be reproducibly and appropriately peeled off. Such a stripping agent component (B) typically includes polyorganosiloxanes, and specific examples include: polyorganosiloxanes containing epoxy groups, polyorganosiloxanes containing methyl groups, polyorganosiloxanes containing phenyl groups, etc., but are not limited to these.
[0044] 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.
[0045] Examples of epoxy-containing polyorganosiloxanes include those containing siloxane units (D10 units) represented by R11 R12 SiO2 / 2.
[0046] 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.
[0047] Furthermore, 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 like 1,2-epoxycyclohexyl, an epoxy group that forms a condensed ring with other rings.
[0048] Specific examples of organic groups containing epoxy groups include 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl, but are not limited to these. In this invention, an ideal example of an epoxy-containing polyorganosiloxane may be an epoxy-containing polydimethylsiloxane, but it is not limited thereto.
[0049] The epoxy-containing polyorganosiloxane contains the aforementioned siloxane unit (D10 unit), but may also contain the aforementioned Q unit, M unit and / or T unit in addition to the D10 unit.
[0050] In an ideal state, specific examples of epoxy-containing polyorganosiloxanes 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.
[0051] Ideally, epoxy-containing polyorganosiloxanes, specifically epoxy-containing polydimethylsiloxanes with an epoxy value of 0.1 to 5, should have a weight-average molecular weight of 1,500 to 500,000. However, from the viewpoint of inhibiting precipitation in adhesive compositions, a weight-average molecular weight of less than 100,000 is preferable.
[0052] 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 55), represented by formula (A-4). Trade names including 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), are not limited to these.
[0053] [Chemistry 5] (m and n are the number of repeating units.)
[0054] [Chemistry 6] (m and n are the number of repeating units.)
[0055] [Chemistry 7] (m and n represent the number of repeating units; R represents an alkyl group with 1 to 10 carbon atoms.)
[0056] [Chemistry 8] (m and n represent the number of repeating units; R represents an alkyl group with 1 to 10 carbon atoms.)
[0057] [Chemistry 9] (m, n, and o represent the number of repeating units; R represents an alkyl group with 1 to 10 carbon atoms.)
[0058] [Chemistry 10] (m and n represent the number of repeating units; R represents an alkyl group with 1 to 10 carbon atoms.)
[0059] [Chemistry 11] (m and n represent the number of repeating units; R represents an alkyl group with 1 to 10 carbon atoms.)
[0060] [Chemistry 12] (m and n are the number of repeating units.)
[0061] Methyl-containing polyorganosiloxanes include, for example, those containing siloxane units (D200 units) represented by R210 R220 SiO2 / 2, and ideally those containing siloxane units (D20 units) represented by R21 R21 SiO2 / 2.
[0062] R210 and R220 are groups bonded to silicon atoms, each representing an alkyl group, but at least one of them is methyl; specific examples of alkyl groups can be listed as above.
[0063] R21 is a group bonded to a silicon atom, representing an alkyl group; specific examples of alkyl groups can be listed as above. Among them, methyl is the ideal alkyl group.
[0064] An ideal example of a methyl-containing polyorganosiloxane is polydimethylsiloxane, but it is not limited thereto.
[0065] Methyl-containing polyorganosiloxanes contain the aforementioned siloxane units (D200 units or D20 units), but may also contain the aforementioned Q units, M units and / or T units in addition to D200 units and D20 units.
[0066] Specific examples of methyl-containing polyorganosiloxanes in a given state can be listed as follows: polyorganosiloxanes composed solely 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.
[0067] In an ideal state, specific examples of methyl-containing polyorganosiloxanes can be listed as follows: polyorganosiloxanes composed solely 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.
[0068] The viscosity of methyl-containing polyorganosiloxanes is typically 1,000–2,000,000 mm² / s, but ideally 10,000–1,000,000 mm² / s. 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 by an E-type rotational viscometer at 25°C. It can be calculated using the formula: Kinematic viscosity (mm² / s) = Viscosity (mPa·s) / Density (g / cm³).
[0069] Specific examples of methyl-containing polyorganosiloxanes include: WACKERSILICONE FLUID AK series manufactured by Wacker Chemie, 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.
[0070] Examples of phenyl-containing polyorganosiloxanes include those containing siloxane units (D30 units) represented by R31 R32 SiO2 / 2.
[0071] R31 is a group bonded to a silicon atom, representing phenyl or alkyl; R32 is a group bonded to a silicon atom, representing phenyl; specific examples of alkyl groups can be listed as above, but methyl is ideal.
[0072] The phenyl-containing polyorganosiloxane contains the aforementioned siloxane unit (D30 unit), but may also contain the aforementioned Q unit, M unit and / or T unit in addition to the D30 unit.
[0073] In an ideal state, specific examples of phenyl-containing polyorganosiloxanes can be listed as follows: polyorganosiloxanes composed solely of D30 units; polyorganosiloxanes containing D30 units and Q units; polyorganosiloxanes containing D30 units and M units; polyorganosiloxanes containing D30 units and T units; polyorganosiloxanes containing D30 units, Q units, and M units; polyorganosiloxanes containing D30 units, M units, and T units; and polyorganosiloxanes containing D30 units, Q units, M units, and T units.
[0074] The weight average molecular weight of phenyl-containing polyorganosiloxanes is typically 1,500 to 500,000, but from the viewpoint of inhibiting precipitation in adhesive compositions, it is ideally below 100,000.
[0075] Specific examples of phenyl-containing polyorganosiloxanes include: PMM-1043 (manufactured by Gelest Corporation, weight average molecular weight 67,000, viscosity 30,000 mm² / s), represented by formula (C-1); PMM-1025 (manufactured by Gelest Corporation, weight average molecular weight 25,200, viscosity 500 mm² / s), represented by formula (C-2); KF50-3000CS (manufactured by Shin-Etsu Chemical Industry Co., Ltd., weight average molecular weight 39,400, viscosity 3000 mm² / s), represented by formula (C-3); TSF431 (manufactured by Momentive Corporation, weight average molecular weight 1,800, viscosity 100 mm² / s), represented by formula (C-4); and TSF433 (manufactured by Momentive Corporation, weight average molecular weight 3,000, viscosity 450 mm² / s), represented by formula (C-5). Trade names such as PDM-0421 (manufactured by Gelest Co., Ltd., weight average molecular weight 6,200, viscosity 100 mm² / s) and PDM-0821 (manufactured by Gelest Co., Ltd., weight average molecular weight 8,600, viscosity 125 mm² / s), denoted by formula (C-6), are not limited to these.
[0076] [Chemistry 13] (m and n represent the number of repeating units.)
[0077] [Chemistry 14] (m and n represent the number of repeating units.)
[0078] [Chemistry 15] (m and n represent the number of repeating units.)
[0079] [Chemistry 16] (m and n represent the number of repeating units.)
[0080] [Chemistry 17] (m and n represent the number of repeating units.)
[0081] [Chemistry 18] (m and n represent the number of repeating units.)
[0082] [Chemistry 19] (m and n represent the number of repeating units.)
[0083] In an ideal state, the adhesive composition used in this invention contains both a polyorganosiloxane component (A) that has been cured by hydrosilicification and a release agent component (B); in a more ideal state, the release agent component (B) contains a polyorganosiloxane.
[0084] The adhesive composition used in this invention can contain adhesive component (S) and release agent component (B) in any ratio. However, considering the balance between adhesion and release properties, the ratio of component (S) to component (B) by mass is ideally 99.995:0.005 to 30:70, and more ideally 99.9:0.1 to 75:25. That is, in the case of a polyorganosiloxane component (A) that has been hardened by the hydrosilicification reaction, the ratio of component (A) to component (B) by mass is ideally 99.995:0.005~30:70, and more ideally 99.9:0.1~75:25.
[0085] The adhesive composition used in this invention may also contain solvents for purposes such as viscosity adjustment, and specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but are not limited to these.
[0086] More specifically, examples include: hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthol, limonene, toluene, xylene, symmetrical trimethylbenzene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc., but not limited to these. Such solvents can be used alone or in combination of two or more.
[0087] When the adhesive composition used in this invention contains solvent, its content is appropriately set considering factors such as the desired viscosity of the composition, the coating method used, and the thickness of the film to be produced, but relative to the total composition, it is in the range of about 10 to 90% by mass.
[0088] 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 of organic solvent used or its ratio, the concentration of film components, etc., taking into account various factors such as the coating method used and the desired film thickness. In this invention, the membrane constituents refer to components other than the solvent contained in the composition.
[0089] The adhesive composition used in this invention can be manufactured by mixing adhesive components (S), and then mixing release agent components (B) and solvents when in use.
[0090] There is no particular limitation on the mixing order. However, examples of methods that can easily and reproducibly produce adhesive compositions include: dissolving the adhesive component (S) and the release agent component (B) in a solvent; or dissolving a portion of the adhesive component (S) and the release agent component (B) in a solvent, dissolving the remaining portion in the solvent, and then mixing the resulting solutions. However, these methods are not limited to these. Furthermore, when preparing adhesive compositions, heating can be appropriately carried out within a range that will not cause the components to decompose or deteriorate.
[0091] In this invention, for the purpose of removing foreign matter, filtration can also be performed using a submicron-sized filter or the like during the manufacturing process of the adhesive composition or after mixing all the components.
[0092] 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 any one of formulas (L0) to (L4). Therefore, the organic solvent, as long as it is included in any formula, can be a single type or two or more types. Furthermore, from the viewpoint of achieving faster peeling of the adhesive layer and the ease of obtaining the compound, the aforementioned solvent is ideally an organic solvent containing at least one of the formulas (L0) to (L2).
[0093] In the above formulas (L1) to (L4), L101 to L112 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L101 to L112 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms; L201 to L210 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L201 to L210 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms; L301 to L308 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that L301 to L308 At least one of them represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms; L401 to L408 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, except that at least one of L401 to L408 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms.
[0094] Alkyl groups can be straight-chain, branched, or cyclic, with straight-chain or branched alkyl groups being the most ideal.
[0095] Specific examples of straight-chain or branched alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, etc., but are not limited to these.
[0096] From the perspective of achieving faster peeling of the adhesive layer, the ideal is methyl, ethyl, n-propyl or isopropyl, with methyl and isopropyl being more ideal.
[0097] Specific examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, etc., but are not limited to these.
[0098] Alkenes with 2 to 5 carbon atoms can be linear, branched, or cyclic. Specific examples include: vinyl, n-1-propenyl, n-2-propenyl, 1-methylvinyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, but are not limited to these.
[0099] From the perspective of achieving reproducibility and faster peeling of the adhesive layer, vinyl, 1-methyl vinyl, 2-methyl vinyl, and more preferably 1-methyl vinyl are ideal.
[0100] Alkynyl groups with 2 to 5 carbon atoms can be linear, branched, or cyclic. Specific examples include: ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl, 1-methyl-2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n-butynyl, 1,1-dimethyl-n-propynyl, etc., but are not limited to these.
[0101] From the perspective of achieving reproducibility and faster peeling of the adhesive layer, acetylenic or 2-methylacetylenic groups are ideal.
[0102] From the viewpoint of achieving reproducibility and faster peeling of the adhesive layer, ideally, one or two of L101 to L112 should be independently alkyl, alkenyl, or alkynyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; more ideally, L101 should be alkyl, alkenyl, or alkynyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; or, L101 and L107 should be independently alkyl, alkenyl, or alkynyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; even more ideally, L101 should be alkyl or alkenyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; or, L101 and L107 should be independently alkyl or alkenyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms.
[0103] From the viewpoint of achieving reproducibility and faster peeling of the adhesive layer, ideally, one or two of L201 to L210 should be independently alkyl, alkenyl, or alkynyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; more ideally, L201 should be alkyl, alkenyl, or alkynyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; or, L201 and L205 should be independently alkyl, alkenyl, or alkynyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; even more ideally, L201 and L205 should be independently alkyl or alkenyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; even further ideally, L201 should be alkyl with 1 to 5 carbon atoms, L205 should be alkenyl with 2 to 5 carbon atoms, and the remainder should be hydrogen atoms.
[0104] From the viewpoint of achieving reproducibility and faster peeling of the adhesive layer, ideally, one or two of L301 to L308 should be alkyl, alkenyl, or alkynyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; more ideally, L301 should be alkyl, alkenyl, or alkynyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; or, L301 and L304 should each be independently alkyl, alkenyl, or alkynyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; even more ideally, L301 should be alkyl or alkenyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; or, L301 and L304 should each be independently alkyl or alkenyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; even further ideally, L301 should be... It consists of alkyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms. Alternatively, L301 and L304 are alkyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms.
[0105] From the perspective of achieving reproducibility and faster peeling of the adhesive layer, ideally, one or two of L401 to L408 should be alkyl, alkenyl, or alkynyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; more ideally, L401 should be alkyl, alkenyl, or alkynyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; or L401 and L405 should each be independently alkyl, alkenyl, or alkynyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; even more ideally, L401 should be alkyl or alkenyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; or L401 and L405 should each be independently alkyl or alkenyl with 1 to 5 carbon atoms, and the remainder should be hydrogen atoms; even further ideally, L401 should be... It consists of alkyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms; or L401 and L405 are alkyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms.
[0106] From the perspective of achieving reproducibility and peeling of the adhesive layer in a shorter time, and from the perspective of the ease of obtaining the compound, ideal examples of organic solvents represented by any of formulas (L0) to (L4) can be listed as: cyclohexane, p-menthane, isopropylcyclohexane, limonene, etc.
[0107] The stripping composition used in this invention does not contain salt. Specific examples of such salts can be listed, typically ammonium salts such as tetrabutylammonium hydroxide and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride) added for the purpose of promoting the removal of adhesive layers or adhesive layer residues.
[0108] The stripping composition used in this invention does not need to contain such salts because it contains an organic solvent represented by any one of formulas (L0) to (L4).
[0109] Since such salts may cause corrosion or other damage to the substrate, especially to substrates with bumps, a salt-free stripping composition is used in this invention. However, in cases where trace amounts of salt are present as impurities in the overall solvent constituting the stripping composition from the beginning, the presence of salt is not necessarily negated.
[0110] In the peeling composition used in this invention, the content of the organic solvent represented by any one of formulas (L0) to (L4) is 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 ensuring that the content of the organic solvent represented by any one of formulas (L0) to (L4) is 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 will be significantly longer and therefore undesirable.
[0111] Ideally, the solvent contained in the above-mentioned stripping composition is an organic solvent represented by any one of the formulas (L0) to (L4). In this case, it is ideal that the solvent contained in the above-mentioned stripping composition is made entirely of organic solvents represented by any one of the above formulas (L0) to (L4), without containing other solvents as impurities. However, there are limits to improving the purity through refining, which is technically impossible. Therefore, in this invention, the solvent contained in the above-mentioned stripping composition is intentionally made only of organic solvents represented by any one of the above formulas (L0) to (L4), and does not exclude the possibility of impurities such as water contained in the organic solvents represented by any one of the above formulas (L0) to (L4) as a whole, or organic solvents that are not easy to separate due to similar structure or properties. As such, when the solvent contained in the above-mentioned stripping composition is an organic solvent represented by any of the above formulas (L0) to (L4), the content of the organic solvent represented by any of the above formulas (L0) to (L4) in the solvent contained in the above-mentioned stripping composition may not be exactly 100% according to the purity value obtained by gas chromatography. It is 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.
[0112] In this invention, the adhesive layer on the semiconductor substrate is swollen by continuously contacting the release component, thereby allowing it to be peeled off from the semiconductor substrate.
[0113] The method for continuously contacting the adhesive layer on the semiconductor substrate with the release component is not particularly limited as long as the adhesive layer on the semiconductor substrate is in continuous contact with the release component in time. This continuous contact in time is not limited to the case where the adhesive layer is always in contact with the release component. For example, it also includes the case where the adhesive layer is in contact with the organic solvent for a certain period of time, the contact is temporarily stopped once, and then the contact 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 component, but also includes the case where a part of the adhesive layer is in contact with the release component. 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 component. In addition, it is ideal for the entire adhesive layer on the semiconductor substrate to be in contact with the release component.
[0114] 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.
[0115] To immerse the adhesive layer on a semiconductor substrate in a release composition, for example, the semiconductor substrate with the adhesive layer attached can be immersed in the release composition. The immersion time is not particularly limited as long as the adhesion layer swells and can be peeled off from the semiconductor substrate. However, from the point of view of achieving more effective cleaning with good reproducibility, it should be more than 5 seconds; from the point of view of production volume in the process, it should be less than 5 minutes.
[0116] When the adhesive layer on the semiconductor substrate is immersed in the release molecule, the semiconductor substrate with the adhesive layer can be moved in the release molecule to cause convection in the release molecule, and the release molecule can be vibrated by ultrasound, thereby promoting the release of the adhesive layer.
[0117] To move a semiconductor substrate with an adhesive layer attached in a peeling composition, for example, a vibrating washer or a paddle washer can be used. When such an washer is used, by moving or rotating the platform on which the semiconductor substrate with the adhesive layer is placed, 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 its movement or rotation, thereby promoting not only the swelling of the adhesive layer on the semiconductor substrate, but also the peeling of the adhesive layer from the semiconductor substrate.
[0118] In order to facilitate the convection of the stripping components, in addition to the aforementioned shaking or paddle washing machines, a convection washing machine can typically be used, which enables the stripping components around a semiconductor substrate with an adhesive layer fixed on a platform to be convected by an agitator.
[0119] To vibrate the components to be stripped using ultrasound, an ultrasonic cleaner or ultrasonic probe can be used, typically at 20 kHz to 5 MHz.
[0120] To continuously supply the release agent to the adhesive layer on the semiconductor substrate, the release agent can be continuously contacted towards the adhesive layer on the semiconductor substrate. For example, if the adhesive layer on the semiconductor substrate is facing upwards, the release agent, either in rod form or in a mist form, is supplied from above (including obliquely above) the adhesive layer on the semiconductor substrate via a nozzle of a cleaning device. Ideally, the rod-shaped release agent should be supplied to the adhesive layer on the semiconductor substrate continuously over time. This continuous supply over time is not limited to the case where the release agent is continuously supplied to the adhesive layer on the semiconductor substrate; it also includes cases where the supply of the release agent is temporarily stopped after a certain period of time and then resumed, and cases where this operation is repeated. However, from the viewpoint of achieving more effective cleaning with good reproducibility, it is ideal that the release agent is continuously supplied to the adhesive layer on the semiconductor substrate.
[0121] When the stripping component is supplied in rod form to the adhesive layer on a semiconductor substrate, the flow rate is typically 200~500 mL / min.
[0122] In one 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.
[0123] The cleaning method for the semiconductor substrate of the present invention may also include the step of removing the adhesive layer after peeling.
[0124] The method for removing the adhesive layer after peeling is not particularly limited as long as the adhesive layer can be removed from the semiconductor substrate. When immersing the semiconductor substrate with the adhesive layer attached in the peeling composition, it is not necessary to remove the semiconductor substrate from the peeling composition to remove the adhesive layer; alternatively, the semiconductor substrate can be removed from the peeling composition to remove the adhesive layer. In this case, there are also situations where simply removing the semiconductor substrate from the peeling composition will leave most of the adhesive layer naturally remaining in the composition, thus removing most of it.
[0125] Specific examples of methods for removing the adhesive layer after peeling include: removing it by adsorption or suction using a device, removing it by blowing it away with gas through an air gun, removing it by moving or rotating the semiconductor substrate up and down or left and right using centrifugal force, etc., but are not limited to these methods.
[0126] After removing the adhesive layer, if necessary, the semiconductor substrate can be dried using conventional methods.
[0127] 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 from the semiconductor substrate, and the ideal state and conditions are as described above. The stripping composition of the present invention can be manufactured by mixing solvents constituting the composition in any order, if necessary. In this case, filtration may also be performed if necessary.
[0128] By using the cleaning method for semiconductor substrates 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 can be removed efficiently, especially the adhesive layer of the hardened film obtained by a silicone adhesive containing a polyorganosiloxane component (A) that has been hardened by a hydrosilicification reaction. High-efficiency and good semiconductor device manufacturing can be expected.
[0129] 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 mentioned above, various substrates such as germanium substrates, gallium-arsenic substrates, gallium-phosphorus substrates, gallium-arsenic-aluminum substrates, aluminum-plated silicon substrates, copper-plated silicon substrates, silver-plated silicon substrates, gold-plated silicon substrates, titanium-plated silicon substrates, silicon substrates with silicon nitride films, silicon substrates with silicon oxide films, silicon substrates with polyimide films, glass substrates, quartz substrates, liquid crystal substrates, organic EL substrates, etc.
[0130] Examples of the use of the cleaning method for semiconductor substrates of the present invention in semiconductor manufacturing processes include: its use in manufacturing methods for semiconductor substrates after thinning and other processing in semiconductor packaging technologies such as TSV.
[0131] Specifically, the method for manufacturing 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 semiconductor substrate of the obtained laminate; a third step of separating the processed semiconductor substrate and the adhesive layer from the support substrate; and a fourth step of removing the adhesive layer from the processed semiconductor substrate and cleaning the processed semiconductor substrate; and in this fourth step, the cleaning method of the semiconductor substrate of the present invention is used.
[0132] Although various adhesives described above can be used as 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 by polysiloxane-based adhesives, and is even more effective for removing adhesive layers obtained by polysiloxane-based adhesives containing polyorganosiloxane component (A) that has hardened due to the hydrosilicification reaction.
[0133] Therefore, the following describes an example of removing the adhesive layer obtained by using a polysiloxane-based adhesive (adhesive composition) to manufacture a processed semiconductor substrate, using the cleaning method of the present invention, but the present invention is not limited thereto.
[0134] First, the first step of manufacturing a laminate comprising a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition will be described.
[0135] In one embodiment, the first step comprises: coating an adhesive composition onto the surface of a semiconductor substrate or a support substrate to form an adhesive coating layer; bonding the semiconductor substrate and the support substrate via the adhesive coating layer, and applying a load in the thickness direction of the semiconductor substrate and the support substrate to make them adhered while performing at least one of a heat treatment and a decompression treatment, and then performing a post-heat treatment to form a laminate.
[0136] In other embodiments, this first step includes, for example: coating an adhesive composition onto the circuit surface of a semiconductor substrate wafer and heating it to form an adhesive coating layer; coating a release agent composition onto the surface of a support substrate and heating it to form a release agent coating layer; and simultaneously applying a load in the thickness direction of the semiconductor substrate and the support substrate to make them adhere tightly while performing at least one of heat treatment and decompression 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 laminate. Furthermore, although the adhesive composition is coated and heated on the semiconductor substrate and the release agent composition is coated and heated on the support substrate respectively, the coating and heating of the adhesive composition and the release agent composition can also be performed sequentially on either substrate. The choice of which treatment conditions to use among the above-mentioned samples—heat treatment, depressurization treatment, or a combination of both—is determined by 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 components, the film thickness, and the desired adhesion strength.
[0137] 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.
[0138] Wafers can be exemplified by, for example, silicon wafers or glass wafers with a diameter of 300 mm and a thickness of approximately 770 μm, but are not limited to these.
[0139] In particular, the semiconductor substrate cleaning method of the present invention can effectively clean the substrate while suppressing damage to the bumps of the semiconductor substrate with bumps attached.
[0140] Specific examples of such bumped semiconductor substrates include silicon wafers with bumps such as ball bumps, printed bumps, stud bumps, and plated bumps; typically, the bump height can be appropriately selected from approximately 1 to 200 μm, the bump diameter from 1 to 200 μm, and the bump pitch from 1 to 500 μm.
[0141] Specific examples of plated bumps include: SnAg (tin-silver) bumps, SnBi (tin-bismuth) bumps, Sn (tin) bumps, AuSn (gold-tin) bumps, and other alloy plating with Sn (tin) as the main component, but are not limited to these.
[0142] The support (carrier) is not particularly limited, but examples include silicon wafers with a diameter of about 300 mm and a thickness of about 700 mm, but it is not limited to these.
[0143] The composition of a stripper may include compositions containing stripper ingredients used for this purpose.
[0144] There are no particular limitations on the coating method, but spin coating is usually used. 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 on top. This is also called coating or coated film.
[0145] 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, and the desired thickness of the adhesive layer, so it cannot be specified in general. However, it is usually 80~150℃, and the heating time is usually 30 seconds to 5 minutes.
[0146] 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 release layer thickness, so it cannot be specified in general. However, from the point of view of achieving suitable curing, it is above 120°C; from the point of view of preventing over-curing, it is below 260°C; and the heating time is usually 1 to 10 minutes. Heating can be done using heating plates, ovens, etc.
[0147] The thickness of the adhesive coating layer obtained by coating the adhesive composition and then heating it is typically 5~500μm.
[0148] The thickness of the release agent coating layer obtained by coating the release agent composition and then heating it is typically 5~500μm.
[0149] The heat treatment, considering both the need to soften the adhesive coating to achieve suitable adhesion with the release agent coating and the need for appropriate hardening of the release agent coating, is generally appropriately determined within the range of 20 to 150°C. In particular, from the viewpoint of suppressing or avoiding excessive hardening or unnecessary deterioration of the adhesive or release agent components, 130°C or lower is ideal, and 90°C or lower is even more ideal. The heating time, from the viewpoint of reliably demonstrating adhesion or release ability, is generally 30 seconds or more, ideally 1 minute or more; however, from the viewpoint of suppressing deterioration of the adhesive layer or other components, it is generally 10 minutes or less, ideally 5 minutes or less.
[0150] Pressure reduction 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 pressure reduction treatment time is typically 1 to 30 minutes.
[0151] In the ideal embodiment 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.
[0152] 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 can ensure that they are securely attached, but it is usually in the range of 10 to 1000 N.
[0153] From the viewpoint of achieving sufficient curing speed, the post-heating temperature is ideally above 120°C; from the viewpoint of preventing deterioration of the substrate, adhesive components, and release agent components, it is ideally below 260°C. The heating time, from the viewpoint of achieving suitable wafer bonding resulting from curing, is typically above 1 minute; further from the viewpoint of stabilizing the physical properties of the adhesive, it is ideally above 5 minutes; from the viewpoint of avoiding adverse effects on the adhesive layer due to overheating, it is typically below 180 minutes, ideally below 120 minutes. Heating can be performed using a heating plate, oven, etc.
[0154] Furthermore, one of the purposes of post-heat treatment is to allow the adhesive component (S) to harden more appropriately.
[0155] Next, the second step of processing the semiconductor substrate of the multilayer obtained by the method described above will be explained.
[0156] One example of the processing of the multilayer used in this invention is the processing of 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 vias (TSVs) are formed, and then the thinned wafer is peeled off from the support to form a multilayer wafer, thereby achieving three-dimensional mounting. Furthermore, back-side electrodes are formed before and after this process. Although the wafer is subjected to heat of 250-350°C while attached to the support during the wafer thinning and TSV processes, the adhesive layer contained in the multilayer used in this invention has heat resistance to this heat.
[0157] For example, a wafer with a diameter of 300 mm and a thickness of about 770 μm can be ground to the back side, which is opposite to the circuit surface, so that it can be thinned to a thickness of about 80~4 μm.
[0158] The third step, which involves separating the semiconductor substrate, the adhesive layer, and the support substrate after processing, will be explained.
[0159] In step 3, the processed semiconductor substrate, adhesive layer, and support substrate are separated. At this time, if the laminate contains a release layer, the release layer and support substrate are usually removed simultaneously.
[0160] The method for separating the processed semiconductor substrate and the adhesive layer and the support substrate can be to peel between the adhesive layer and the release layer or support substrate in contact with it; such peeling methods include: laser peeling, mechanical peeling by means of a material with sharp edges, peeling by manual tearing, etc., but are not limited to these.
[0161] Next, the fourth step of removing the adhesive layer from the processed semiconductor substrate and cleaning the processed semiconductor substrate will be described. Step 4 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 effectively remove the adhesive layer on the thinned substrate. The conditions at this time are as described above.
[0162] After step 4, if necessary, the adhesive residue remaining on the semiconductor substrate can also be removed by a cleaning agent containing salt. However, care must be taken not to damage the semiconductor substrate, especially the bumps on the semiconductor substrate with bumps.
[0163] The method for manufacturing the processed semiconductor substrate of the present invention includes steps 1 to 4 as described above, but may also include steps other than these. Furthermore, the aforementioned constituent elements and method elements related to steps 1 to 4 may be modified in various ways as long as they do not depart from the spirit of the present invention. [Example]
[0164] The following examples and comparative examples illustrate the present invention, 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: [device] (1) Rotation-revolution mixer: ARE-500 rotation-revolution mixer manufactured by THINKY CORPORATION. (2) Viscometer: TVE-22H rotational viscometer manufactured by Toki Industrial Co., Ltd. (3) Mixer: AS ONE Mix Rotor Variable 1-1186-12 (4) Optical microscope: MX61L semiconductor / FPD (flat panel display) inspection microscope manufactured by Olympus Corporation.
[0165] [solvent] N-Methylpyrrolidone: Manufactured by Kanto Chemical Co., Ltd., purity >99.0%. Limonene: Manufactured by Tokyo Chemical Industry Co., Ltd., purity >95.0% p-Menthane: Produced by Nippon Terpene Chemicals, purity >96.0%. Isopropylcyclohexane: Manufactured by Tokyo Chemical Industry Co., Ltd., purity >99.0%. Cyclohexane: Produced by Kanto Chemical Co., Ltd., purity >99.5% 1,4-Diisopropylbenzene: Manufactured by Tokyo Chemical Industry Co., Ltd., purity >98.0% Cyclooctane: Manufactured by Tokyo Chemical Industry Co., Ltd., purity >98.0%
[0166] [1] Preparation of adhesive composition [Modulation 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 Terpenoid Chemical 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.
[0167] To the obtained mixture, add: 19.0 g of SiH-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 100 mPa·s as (a2), 29.5 g of vinyl-containing 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), and further stir for 5 minutes using a rotary mixer.
[0168] Subsequently, 14.9 g of the following mixture was added to the obtained mixture: a mixture obtained by mixing 0.20 g of platinum catalyst (manufactured by Wacker Chemie) as (A2) and 17.7 g of vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1000 mPa·s as (a1) with a rotary mixer for 5 minutes; the mixture was further mixed with a rotary mixer for 5 minutes, and then filtered through a 300-mesh nylon filter to obtain the adhesive composition.
[0169] [2] Evaluation of substrate fabrication [Manufacturing Example 1] The composition obtained in Preparation Example 1 was coated on a 4cm×4cm silicon wafer (775μm thick) that served as the device side using a spin coater. The wafer was then heated at 120°C for 1.5 minutes and then at 200°C for 10 minutes to form a 60μm thick film on the wafer, thereby obtaining a wafer with an adhesive layer.
[0170] [Manufacturing Example 2] The substrate with bumps is cut to prepare a 4cm×4cm sample substrate. Each sample substrate has 5044 bumps, and the bump structure 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.
[0171] [3] Measurement of peeling time [Example 1-1] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of limonene, 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 18 seconds.
[0172] [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 limonene and N-methylpyrrolidone, which are the peeling components of Examples 1-2, and the time until the adhesive layer began to peel off from the wafer was measured to be 21 seconds.
[0173] [Comparative Example 1] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of a mixed solvent (7:3 (w / w)) of limonene and N-methylpyrrolidone, 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 30 seconds.
[0174] [Example 2] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of p-menthane, 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 22 seconds.
[0175] [Example 3] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of isopropylcyclohexane, 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 20 seconds.
[0176] [Example 4] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of cyclohexane, 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 11 seconds.
[0177] [Comparative Example 2] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 9 mL of 1,4-diisopropylbenzene, which is the peeling composition of Comparative Example 2, and the time until the adhesive layer began to peel off from the wafer was measured to be 44 seconds.
[0178] [Comparative Example 3] The wafer with the adhesive layer produced in Manufacturing Example 1 was immersed in 9 mL of cyclooctane, which is the peeling composition of Comparative Example 3, and the time until the adhesive layer began to peel off from the wafer was measured to be 40 seconds.
[0179] The results of the examples and comparative examples are shown in Table 1. As shown in Table 1, when using a stripping composition containing 80% by mass or more of the organic solvent represented by formula (L), such as limonene or p-menthane (Examples 1-1 to 4), compared with the use of a stripping composition containing less than 80% by mass of the organic solvent represented by formula (L) (Comparative Example 1), or the use of a stripping composition that does not contain the organic solvent represented by formula (L), but contains 1,4-diisopropylbenzene or cyclooctane, which have the same number of carbons and the same cyclic structure as the organic solvent (Comparative Examples 2 and 3), the stripping time of the adhesive layer on the semiconductor substrate is extremely short.
[0180] [Table 1]
[0181] [4] Observation of damage to substrates with bumps [Example 5] The sample substrate prepared in Example 2 was immersed in 9 mL of menthol, allowed to stand for one hour, and then washed with isopropanol and acetone. The substrate was then observed under an optical microscope for any bump damage. No bump damage was observed.
[0182] [Comparative Example 4] Although 2g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) and 18g of p-menthane were thoroughly stirred at room temperature using a stirring rotor, some tetrabutylammonium fluoride remained undissolved. Therefore, the supernatant of the solution was recovered. Furthermore, the sample substrate prepared in Manufacturing Example 2 was immersed in 9 mL of the supernatant of the recovered solution, allowed to stand for one hour, washed with isopropanol and acetone, and then observed with an optical microscope for any bump damage. The results confirmed that the entire sample substrate had damaged bumps (the estimated number of damaged bumps was 1000 to 2000).
Claims
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 adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S), the adhesive component (S) comprising a polyorganosiloxane component (A) cured by a hydrosilicification reaction; the stripping composition contains a solvent but does not contain a salt; and the solvent contains at least 80% by mass of an organic solvent represented by any one of formulas (L0) to (L4); [Chemical 1] (In the formula, L101~L112 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L101~L112 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms; L201~L210 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L201~L210 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms.) L301 to L308 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, except that at least one of L301 to L308 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms; L401 to L408 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, except that at least one of L401 to L408 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms).
2. The cleaning method for a semiconductor substrate as described in claim 1, wherein, The solvent contains 85% by mass or more of the organic solvent represented by any one of formulas (L0) to (L4).
3. The cleaning method for the semiconductor substrate as described in claim 2, wherein, The solvent is made from an organic solvent represented by any one of the formulas (L0) to (L4).
4. The cleaning method for a semiconductor substrate as described in claim 1, wherein, The alkyl group having 1 to 5 carbon atoms is methyl, ethyl, n-propyl, or isopropyl; the alkenyl group having 2 to 5 carbon atoms is vinyl, 1-methylvinyl, or 2-methylvinyl; the alkynyl group having 2 to 5 carbon atoms is ethynyl or 2-methylethynyl.
5. The cleaning method for the semiconductor substrate as described in claim 4, wherein, One or two of L101 to L112 are alkyl, alkenyl, or alkynyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms; One or two of L201 to L210 are alkyl, alkenyl, or alkynyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms; One or two of L301 to L308 are alkyl, alkenyl, or alkynyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms; One or two of L401 to L408 are alkyl, alkenyl, or alkynyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms.
6. 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 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 release composition; characterized in that the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S), the adhesive component (S) comprising a polyorganosiloxane component (A) that is cured by a hydrosilicification reaction; the release composition contains a solvent and does not contain a salt; the solvent contains 80% by mass or more of an organic solvent represented by any one of formulas (L0) to (L4); [Chemical 2] (In the formula, L101~L112 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L101~L112 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms; L201~L210 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L201~L210 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms.) L301 to L308 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, except that at least one of L301 to L308 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms; L401 to L408 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, except that at least one of L401 to L408 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms).
7. A method for manufacturing the processed semiconductor substrate as described in claim 6, wherein, The solvent contains 85% by mass or more of the organic solvent represented by any one of formulas (L0) to (L4).
8. A method for manufacturing the processed semiconductor substrate as described in claim 7, wherein, The solvent is made from any of the organic solvents represented by formulas (L0) to (L4).
9. A method for manufacturing the processed semiconductor substrate as described in claim 6, wherein, The alkyl group having 1 to 5 carbon atoms is methyl, ethyl, n-propyl, or isopropyl; the alkenyl group having 2 to 5 carbon atoms is vinyl, 1-methylvinyl, or 2-methylvinyl; the alkynyl group having 2 to 5 carbon atoms is ethynyl or 2-methylethynyl.
10. A method for manufacturing the processed semiconductor substrate as described in claim 9, wherein, One or two of L101 to L112 are alkyl, alkenyl, or alkynyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms; One or two of L201 to L210 are alkyl, alkenyl, or alkynyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms; One or two of L301 to L308 are alkyl, alkenyl, or alkynyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms; One or two of L401 to L408 are alkyl, alkenyl, or alkynyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms.
11. Use of a release composition for removing an adhesive layer from a semiconductor substrate during cleaning, characterized in that the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S), the adhesive component (S) comprising a polyorganosiloxane component (A) cured by a hydrosilicification reaction; the release composition contains a solvent but does not contain a salt; the solvent contains 80% by mass or more of an organic solvent represented by any one of formulas (L0) to (L4); [Chemical 3] (In the formula, L101~L112 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L101~L112 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms; L201~L210 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms, except that at least one of L201~L210 represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms.) L301 to L308 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, except that at least one of L301 to L308 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms; L401 to L408 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, except that at least one of L401 to L408 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms).
12. Use of the stripping composition as described in claim 11, wherein, The solvent contains 85% by mass or more of the organic solvent represented by any one of formulas (L0) to (L4).
13. Use of the stripping composition as described in claim 12, wherein, The solvent is made from any of the organic solvents represented by formulas (L0) to (L4).
14. Use of the stripping composition as described in claim 11, wherein, The alkyl group having 1 to 5 carbon atoms is methyl, ethyl, n-propyl, or isopropyl; the alkenyl group having 2 to 5 carbon atoms is vinyl, 1-methylvinyl, or 2-methylvinyl; the alkynyl group having 2 to 5 carbon atoms is ethynyl or 2-methylethynyl.
15. Use of the stripping composition as described in claim 14, wherein, One or two of L101 to L112 are alkyl, alkenyl, or alkynyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms; One or two of L201 to L210 are alkyl, alkenyl, or alkynyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms; One or two of L301 to L308 are alkyl, alkenyl, or alkynyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms; One or two of L401 to L408 are alkyl, alkenyl, or alkynyl groups with 1 to 5 carbon atoms, and the rest are hydrogen atoms.
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