Methods for manufacturing adhesive compositions, laminates, and processed semiconductor substrates

Abstract

An adhesive composition for forming an adhesive layer for temporarily bonding a semiconductor substrate or electronic device layer to a support substrate, the adhesive composition containing a release agent component, wherein the absolute value of the difference (A-B) between the surface free energy (A) of the semiconductor substrate or the electronic device layer and the surface free energy (B) of the release agent component is less than 20 mN / m.

Description

Technical Field

[0001] This invention relates to adhesive compositions, laminates, and methods for manufacturing processed semiconductor substrates. Background Technology

[0002] In contrast to semiconductor wafers traditionally integrated in a two-dimensional planar direction, semiconductor integration technology aims for further integration by stacking the planar material in a three-dimensional direction. This three-dimensional stacking is a technique that integrates multiple layers while simultaneously connecting them via through-silicon vias (TSVs). During multi-layer integration, the back side (opposite to the circuit surface) of each wafer to be integrated is thinned through grinding, and the thinned semiconductor wafers are then stacked.

[0003] Before thinning, the semiconductor wafer (hereinafter referred to as the wafer) is bonded to a support for polishing using a polishing apparatus. This bond must be easily peeled off after polishing; therefore, it is called a temporary bond. This temporary bond must be easily detached from the support. When applying significant force for detachment, the thinned semiconductor wafer may sometimes be cut or deformed; to prevent this, it must be easily detached. However, during polishing of the back side of the semiconductor wafer, it may detach or shift due to polishing stress, which is undesirable. Therefore, the desired performance of a temporary bond is: to withstand the stress during polishing and to be easily detached after polishing.

[0004] As temporary adhesives for such temporary bonding, adhesives containing polydimethylsiloxane (Patent Document 1) and temporary adhesives containing epoxy-modified polysiloxane (Patent Document 2) have been proposed.

[0005] Existing technical documents Patent documents Patent Document 1: International Publication No. 2017 / 221772 Patent Document 2: International Publication No. 2018 / 216732 Summary of the Invention

[0006] The problem that the invention aims to solve The surface of the wafer is sometimes composed of materials other than silicon (e.g., SiN, Cu), and sometimes electrodes are disposed thereon. Even in this case, the adhesive layer formed by the temporary adhesive (adhesive composition) is required to peel well from the wafer.

[0007] The object of the present invention is to provide an adhesive composition capable of forming an adhesive layer with excellent peelability, a laminate using the adhesive composition, and a method for manufacturing a processed semiconductor substrate or electronic device layer using the laminate.

[0008] Solution for solving the problem The inventors conducted in-depth research to solve the aforementioned technical problem and found that the technical problem could be solved, thus completing the present invention with the following main points.

[0009] That is, the present invention includes the following.

[0010] [1] An adhesive composition for forming an adhesive layer for temporarily bonding a semiconductor substrate or an electronic device layer to a support substrate, the adhesive composition containing a release agent component, wherein the absolute value of the difference (A-B) between the surface free energy (A) of the semiconductor substrate or the electronic device layer and the surface free energy (B) of the release agent component is less than 20 mN / m.

[0011] [2] According to the adhesive composition of [1], wherein the absolute value of the difference (A-B) is less than 15 mN / m.

[0012] [3] The adhesive composition according to [1] or [2], wherein the release agent component comprises a polyorganosiloxane.

[0013] [4] An adhesive composition according to any one of [1] to [3], wherein the adhesive composition contains an adhesive component.

[0014] [5] The adhesive composition according to [4], wherein the adhesive component is a component that is cured by a hydrosilylation reaction.

[0015] [6] According to the adhesive composition of [5], wherein the component cured by the hydrosilylation reaction contains: an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms (A-1); a Si-H group (A-2); and a platinum group metal catalyst (A-3).

[0016] [7] The adhesive composition according to [6], wherein the component (A-1) contains: a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms.

[0017] [8] The adhesive composition according to [6] or [7], wherein the component (A-2) contains: a polyorganosiloxane having a Si-H group.

[0018] [9] A laminate comprising: a semiconductor substrate or an electronic device layer; a support substrate; and an adhesive layer disposed between the semiconductor substrate or the electronic device layer and the support substrate, the adhesive layer being an adhesive layer formed of an adhesive composition as described in any one of [1] to [8].

[0019]

[10] A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: a 5A step of processing the semiconductor substrate of a laminate as described in [9], or a 5B step of processing the electronic device layer of a laminate as described in [9]; and a 6A step of separating the semiconductor substrate processed by the 5A step from the support substrate, or a 6B step of separating the electronic device layer processed by the 5B step from the support substrate.

[0020] Invention Effects According to the present invention, an adhesive composition capable of forming an adhesive layer with excellent peelability, a laminate using the adhesive composition, and a method for manufacturing a processed semiconductor substrate or electronic device layer using the laminate are provided. Attached Figure Description

[0021] Figure 1 This is a schematic cross-sectional view of an example of a laminate in the first embodiment.

[0022] Figure 2 This is a schematic cross-sectional view of another example of the laminate in the first embodiment.

[0023] Figure 3A This is a schematic cross-sectional view (one of the views) used to illustrate a method for manufacturing a laminated body representing an example of a first embodiment.

[0024] Figure 3B This is a schematic cross-sectional view (second one) used to illustrate a method for manufacturing a laminated body representing an example of the first embodiment.

[0025] Figure 4 This is a schematic cross-sectional view of an example of a laminate in the second embodiment.

[0026] Figure 5 This is a schematic cross-sectional view of another example of the laminate in the second embodiment.

[0027] Figure 6A This is a schematic cross-sectional view (one of the views) used to illustrate a method for manufacturing a laminate, representing an example of a second embodiment.

[0028] Figure 6B This is a schematic cross-sectional view (second one) used to illustrate a method for manufacturing a laminated body representing an example of a second embodiment.

[0029] Figure 6C This is a schematic cross-sectional view (third one) used to illustrate a method for manufacturing a laminated body representing an example of the second embodiment.

[0030] Figure 7AThis is a schematic cross-sectional view (one of the views) used to illustrate the processing method of a laminated body representing an example of a first embodiment.

[0031] Figure 7B This is a schematic cross-sectional view (second one) used to illustrate the processing method of a laminated body representing an example of the first embodiment.

[0032] Figure 7C This is a schematic cross-sectional view (third one) used to illustrate the processing method of a laminated body representing an example of the first embodiment.

[0033] Figure 7D This is a schematic cross-sectional view (fourth one) used to illustrate the processing method of a laminated body representing an example of the first embodiment.

[0034] Figure 8A This is a schematic cross-sectional view (one of the views) used to illustrate the processing method of a laminated body representing an example of the second embodiment.

[0035] Figure 8B This is a schematic cross-sectional view (second one) used to illustrate the processing method of a laminated body representing an example of the second embodiment.

[0036] Figure 8C This is a schematic cross-sectional view (third one) used to illustrate the processing method of a laminated body representing an example of the second embodiment.

[0037] Figure 8D This is a schematic cross-sectional view (fourth one) used to illustrate the processing method of a laminated body representing an example of the second embodiment.

[0038] Figure 8E This is a schematic cross-sectional view (fifth) used to illustrate the processing method of a laminated body representing an example of the second embodiment.

[0039] Figure 8F This is a schematic cross-sectional view (sixth) used to illustrate the processing method of a laminated body representing an example of the second embodiment. Detailed Implementation

[0040] (Adhesive composition) The adhesive composition of the present invention is an adhesive composition for forming an adhesive layer for temporarily bonding a semiconductor substrate or electronic device layer to a support substrate.

[0041] The adhesive composition contains a release agent component.

[0042] Regarding the adhesive composition, the absolute value of the difference (A-B) between the surface free energy (A) of the semiconductor substrate or electronic device layer and the surface free energy (B) of the release agent component is less than 20 mN / m.

[0043] When the absolute value of the difference (A-B) between the surface free energy (A) of the semiconductor substrate or electronic device layer and the surface free energy (B) of the release agent component contained in the adhesive composition is less than 20 mN / m, an adhesive layer with excellent peelability to the semiconductor substrate or electronic device layer can be formed.

[0044] The absolute value of the difference (A-B) is 20 mN / m or less. From the viewpoint of obtaining the effects of the present invention more appropriately, the absolute value of the difference (A-B) is preferably 15 mN / m or less, and more preferably 13 mN / m or less. There is no particular limitation on the lower limit of the absolute value of the difference (A-B). For example, the absolute value of the difference (A-B) can be 0 mN / m or more, or 1 mN / m or more.

[0045] Surface free energy can be determined, for example, using the results of contact angle measurements performed using a contact angle meter. In contact angle measurements, water and diiodomethane are used to determine the contact angle of the surface from which the surface free energy is to be calculated. Using the results, the surface free energy is determined by a static method. The theoretical formula for surface free energy is the Owens and Wendt formula.

[0046] When determining the contact angle of a release agent component, for example, an evaluation sample is prepared by dissolving the release agent component in a solvent (e.g., hexamethyldisiloxane). This evaluation sample is then spin-coated to form a film of the release agent component. The contact angle is then determined for the resulting film. Typically, the solvent evaporates and is removed during spin-coating.

[0047] Furthermore, if the surface composition of the semiconductor substrate or electronic device layer is uniform, the contact angle can be determined for an appropriate location of the semiconductor substrate or electronic device layer (the predetermined location in contact with the adhesive layer).

[0048] On the other hand, when the surface composition of a semiconductor substrate or electronic device layer is non-uniform (e.g., when electrodes are formed on a portion of the surface), the contact angle of each component is measured, the surface free energy of each component is calculated, and the surface free energy of the semiconductor substrate or electronic device layer is calculated by combining the area ratio of each component. An example is illustrated using a silicon wafer with electrodes coated with SiN. The silicon wafer with electrodes coated with SiN has an SiN-coated surface without electrodes and an electrode surface with electrodes on the SiN-coated surface, with an area ratio of SiN-coated surface (X1)% and electrode surface (X2)% (X1 + X2 = 100%). Therefore, the surface free energy of the SiN-coated surface [(S1) mN / m] and the surface free energy of the electrode surface [(S2) mN / m] are calculated separately, and then weighted by the area ratio of the SiN-coated surface to the electrode surface, the surface free energy (S) of the silicon wafer with electrodes coated with SiN is calculated using the following formula.

[0049] (S)mN / m=[[(S2)mN / m]×X1 / 100]+[[(S2)mN / m]×X2 / 100] Examples of adhesive compositions include, but are not limited to, polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenolic resin-based adhesives.

[0050] Among them, since it exhibits appropriate adhesion during the processing of semiconductor substrates and the like, can be properly peeled off after processing, has excellent heat resistance, and can be properly removed by the cleaning agent composition, polysiloxane-based adhesives are preferred as adhesive compositions.

[0051] The adhesive composition contains, for example, an adhesive component.

[0052] <Adhesive Composition> There are no particular limitations on the adhesive component, but a curable component is preferred, and a component that cures through a hydrosilylation reaction is more preferred.

[0053] There are no particular limitations on the components that are cured by the hydrosilylation reaction, but it is preferred to contain: a component having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms (hereinafter sometimes referred to as "component (A-1)"), a component having a Si-H group (hereinafter sometimes referred to as "component (A-2)"), and a platinum group metal catalyst (A-3).

[0054] <<Ingredients (A-1) and Ingredients (A-2)>> The adhesive composition preferably contains component (A-1).

[0055] The adhesive composition preferably contains component (A-2).

[0056] Hereinafter, the combination of component (A-1), component (A-2), and platinum group metal catalyst (A-3) will sometimes be referred to as "curable component (A)" or "component (A)".

[0057] From the viewpoint of properly obtaining the effects of the present invention, component (A-1) preferably contains: a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms.

[0058] From the viewpoint of properly obtaining the effects of the present invention, component (A-2) preferably contains: a polyorganosiloxane having Si-H groups (a2).

[0059] Here, alkenyl groups with 2 to 40 carbon atoms can be substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, and heteroaryl groups.

[0060] In another preferred embodiment, the adhesive composition cured by a hydrosilylation reaction comprises a polysiloxane (A1) and a platinum group metal catalyst (A-3), wherein the polysiloxane (A1) comprises siloxane units (Q units) selected from SiO2, R... 1 R 2 R 3 SiO 1 / 2 The siloxane unit (M unit) and R shown are shown. 4 R 5 SiO 2 / 2 The siloxane unit (D unit) and R shown are shown. 6 SiO 3 / 2 The polysiloxane (A1) comprises one or more units from the group consisting of the shown siloxane units (T units), and the polysiloxane (A1) includes polyorganosiloxane (a1') and polyorganosiloxane (a2'), wherein the polyorganosiloxane (a1') comprises siloxane units (Q' units) selected from SiO2, R 1 'R 2 'R 3 'SiO 1 / 2 The siloxane unit (M' unit) and R shown are shown. 4 'R 5 'SiO 2 / 2 The siloxane unit (D' unit) and R shown are shown. 6 'SiO 3 / 2 The polyorganosiloxane (a2') comprises one or more units selected from the group consisting of siloxane units (T' units) shown, and includes at least one unit selected from the group consisting of M' units, D' units, and T' units. 1 R2 R 3 "SiO" 1 / 2 The siloxane unit (M” unit) and R shown 4 R 5 "SiO" 2 / 2 The siloxane unit (D” unit) and R shown are shown. 6 "SiO" 3 / 2 The siloxane unit (T” unit) shown is one or more units from the group consisting of the siloxane unit (T” unit), and includes at least one unit selected from the group consisting of the M” unit, the D” unit and the T” unit.

[0061] It should be noted that (a1') is an example of (a1), and (a2') is an example of (a2).

[0062] R 1 ~R 6 These are groups or atoms bonded to silicon atoms, each independently representing a substituted alkyl group, a substituted alkenyl group, or a hydrogen atom. Examples of substituents include: halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0063] R 1 '~R 6 'A group bonded to a silicon atom, each independently representing a substituted alkyl or substituted alkenyl group, R 1 '~R 6 At least one of the groups is an alkenyl group that can be substituted. Examples of substituents include: halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0064] R 1 "~R 6 "R represents a group or atom bonded to a silicon atom, each independently representing a substitutable alkyl or hydrogen atom, R" 1 "~R 6 At least one of the elements is a hydrogen atom. Examples of substituents include: halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0065] The alkyl group can be any type of straight-chain, branched, or cyclic, with straight-chain or branched alkyl groups being preferred. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0066] Specific examples of linear or branched alkyl groups that can be substituted include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1- Dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these, generally have 1 to 14 carbon atoms, preferably 1 to 10, more preferably 1 to 6. Among them, methyl is particularly preferred.

[0067] Specific examples of substituted 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, 2,4-dimethyl-cyclobutyl Cycloalkyl groups such as 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.; bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, etc., but not limited thereto, wherein the number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0068] The alkenyl group can be any type of linear or branched chain, and its number of carbon atoms is not particularly limited, usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0069] Specific examples of linear or branched alkenyl groups that can be substituted include vinyl, allyl, butenyl, pentenyl, etc., but are not limited thereto. The number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among these, vinyl and 2-propenyl are particularly preferred.

[0070] Specific examples of cyclic alkenyl groups that can be replaced include cyclopentenyl, cyclohexenyl, etc., but are not limited to these. The number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0071] As described above, the polysiloxane (A1) comprises polyorganosiloxane (a1') and polyorganosiloxane (a2'). The alkenyl group contained in the polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in the polyorganosiloxane (a2') form a cross-linked structure and are cured through a hydrosilylation reaction using a platinum group metal catalyst (A-3). The result is the formation of a cured film.

[0072] The polyorganosiloxane (a1') comprises one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and includes at least one unit selected from the group consisting of M' units, D' units, and T' units. Two or more polyorganosiloxanes satisfying these conditions may also be used in combination as the polyorganosiloxane (a1').

[0073] As for preferred combinations of two or more selected from the group consisting of Q' unit, M' unit, D' unit and T' unit, examples include: (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit and M' unit), but not limited to these.

[0074] Furthermore, when the polyorganosiloxanes contained in two or more polyorganosiloxanes (a1') are included, combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but not limited thereto.

[0075] The polyorganosiloxane (a2') comprises one or more units selected from the group consisting of Q" units, M" units, D" units, and T" units, and comprises at least one unit selected from the group consisting of M" units, D" units, and T" units. As a polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying such conditions may also be used in combination.

[0076] As for two or more preferred combinations selected from the group consisting of Q” units, M” units, D” units and T” units, examples include: (M” units and D” units), (Q” units and M” units), (Q” units, T” units and M” units), but are not limited to these.

[0077] Polyorganosiloxanes (a1') are composed of siloxane units formed by the bonding of silicon atoms with alkyl and / or alkenyl groups, R 1 '~R 6 The proportion of alkenyl groups in all the substituents shown is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, with the remainder being R 1 '~R 6 'It can be set as an alkyl group.'

[0078] Polyorganosiloxanes (a2') are composed of siloxane units formed by the bonding of silicon atoms with alkyl and / or hydrogen atoms, R 1 "~R 6 The proportion of all substituents and hydrogen atoms in the substituted atoms shown is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, with the remainder being R. 1 "~R 6 "It can be set as an alkyl group."

[0079] In the case where the adhesive composition comprises (a1) and (a2), in a preferred embodiment of the invention, the molar ratio of the alkenyl group contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bond contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0080] The weight-average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, and is usually 500 to 1,000,000. From the viewpoint of achieving the effect of the present invention with good reproducibility, it is preferably 5,000 to 50,000.

[0081] It should be noted that, in this invention, the weight-average molecular weight, number-average molecular weight, and dispersity of the polyorganosiloxane can be determined, for example, using a GPC apparatus (TOSOH Corporation EcoSEC, HLC-8320GPC) and a GPC column (TOSOH Corporation TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H), with the column temperature set to 40°C, tetrahydrofuran used as the eluent (dissolution solvent), the flow rate set to 0.35 mL / min, and polystyrene (Showa Denko Corporation, Shodex) used as the standard sample.

[0082] The viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are not particularly limited, and are typically 10 to 1,000,000 mPa·s each. From the viewpoint of achieving the effects of the present invention with good reproducibility, 50 to 10,000 mPa·s is preferred. It should be noted that the viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are values ​​measured using an E-type rotational viscometer at 25°C.

[0083] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via a hydrogenation silanization reaction. Therefore, their curing mechanism is different from that via, for example, silanol groups. Consequently, any siloxane does not need to contain silanol groups, such as alkoxy groups, which are formed by hydrolysis to form silanol groups.

[0084] <<Platinum Group Metal Catalysts (A-3)>> Platinum group metal catalysts are platinum group metal catalysts.

[0085] Such platinum group metal catalysts are used to promote the hydrosilylation reaction of alkenes and Si-H groups.

[0086] As a specific example of a platinum group metal catalyst, a substance known as a platinum group compound (platinum or a compound containing platinum) can be used.

[0087] Specific examples include: platinum micro powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with dienes, platinum-olefin complexes, platinum-carbonyl complexes (such as bis(acetoacetic acid)platinum and bis(acetylacetone)platinum), chloroplatinic acid-alkenylsiloxane complexes (such as chloroplatinic acid-divinyltetramethyldisiloxane complex and chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex), platinum-alkenylsiloxane complexes (such as platinum-divinyltetramethyldisiloxane complex and platinum-tetravinyltetramethylcyclotetrasiloxane complex), and complexes of chloroplatinic acid with alkynyl alcohols. Among these, platinum-alkenylsiloxane complexes are particularly preferred due to their high promoting effect on the hydrogenation silylation reaction.

[0088] These hydrogen silanization reactions can use a single catalyst or a combination of two or more catalysts.

[0089] The alkenylsiloxane used in platinum-alkenylsiloxane complexes is not particularly limited, and examples include: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxane oligomers formed by substituting a portion of the methyl group of these alkenylsiloxanes with ethyl, phenyl, or the like, and alkenylsiloxane oligomers formed by substituting the vinyl group of these alkenylsiloxanes with allyl, hexenyl, or the like. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because of the good stability of the resulting platinum-alkenylsiloxane complexes.

[0090] The content of the platinum group metal catalyst (A-3) in the adhesive composition is not particularly limited, for example, it is in the range of 0.1 to 50.0 ppm relative to the total mass of components (A-1) and (A-2).

[0091] <<Polymer Inhibitors>> To inhibit the hydrosilylation reaction, the adhesive component may contain polymerization inhibitors.

[0092] There are no particular limitations on polymerization inhibitors as long as they can inhibit the hydrosilylation reaction. Specific examples include 1-ethynyl-1-cyclohexanol, 1,1-diphenyl-2-propynyl-1-ol, and other alkynols.

[0093] There is no particular limitation on the amount of polymerization inhibitor. For example, from the viewpoint of obtaining its effect, it is usually above 1000.0 ppm relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2), and usually below 10000.0 ppm from the viewpoint of preventing excessive inhibition of the hydrosilanization reaction.

[0094] <Stripping Agent Ingredients> There are no particular limitations on the components of the stripping agent, but from the viewpoint of obtaining the effects of the present invention more appropriately, polyorganosiloxanes are preferred.

[0095] Polysiloxanes used as release agents typically do not react with adhesive components.

[0096] For example, the polyorganosiloxane used as a stripping agent is a component that does not undergo hydrogenation silanization.

[0097] As a polyorganosiloxane, there is no particular limitation. Examples include: polydimethylsiloxane, epoxy-containing polyorganosiloxane, phenyl-containing polyorganosiloxane, methanol-modified polyorganosiloxane, etc.

[0098] <<Polydimethylsiloxane>> The "polydimethylsiloxane" in this invention is different from epoxy-containing polydimethylsiloxane, phenyl-containing polydimethylsiloxane, methanol-modified polyorganosiloxane, etc. It is an unmodified polyorganosiloxane, which has methyl as an organic group bonded to silicon atoms.

[0099] As a specific example of polydimethylsiloxane, polydimethylsiloxanes represented by formula (M1) can be listed, but are not limited thereto. (n4 represents the number of repeating units, which is a positive integer.) The weight-average molecular weight of polydimethylsiloxane is not particularly limited, but is typically 100,000 to 2,000,000. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. Furthermore, its dispersibility is not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of achieving proper exfoliation with good reproducibility, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. It should be noted that the weight-average molecular weight and dispersibility can be determined by the methods described above for polyorganosiloxanes.

[0100] The viscosity of polydimethylsiloxane is not particularly limited, and is typically 1,000 to 2,000,000 mm. 2 / s. It should be noted that the viscosity of polydimethylsiloxane is expressed as kinematic viscosity, denoted as centistokes (cSt) = mm. 2 / s. This can be calculated by dividing viscosity (mPa•s) by density (g / cm³). 3 The value can be determined from the viscosity and density measured at 25°C using a type E rotational viscometer, and can be derived from the kinematic viscosity (mm). 2 / s) = viscosity (mPa•s) / density (g / cm³) 3 The formula is used to calculate the result.

[0101] <<Epoxy-containing Polyorganosiloxanes>> As epoxy-containing polyorganosiloxanes, examples include those containing R 11 R 12 SiO 2 / 2 The siloxane unit shown (D) 10 Polyorganosiloxanes (units).

[0102] R 11 The group that bonds to silicon atoms represents an alkyl group, R. 12 The group that bonds to silicon atoms represents an epoxy group or an organic group containing an epoxy group. Specific examples of alkyl groups can be listed above.

[0103] The epoxy group in an organic group containing an epoxy group can be an independent epoxy group without condensing with other rings, or it can be an epoxy group that forms a fused ring with other rings, like 1,2-epoxycyclohexyl.

[0104] Specific examples of organic groups containing epoxy groups include 3-epoxypropoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl, but are not limited to these.

[0105] In this invention, as a preferred example of an epoxy-containing polyorganosiloxane, an epoxy-containing polydimethylsiloxane can be listed, but is not limited thereto.

[0106] Epoxy-containing polyorganosiloxanes contain the aforementioned siloxane units (D 10 (unit), but except for D 10 In addition to the unit, it may also include Q units, M units and / or T units.

[0107] In a preferred embodiment of the present invention, specific examples of epoxy-containing polyorganosiloxanes include those composed solely of D... 10 Polyorganosiloxanes composed of units containing D 10 Polyorganosiloxanes containing D and Q units 10 Polyorganosiloxanes containing D and M units 10 Polyorganosiloxanes containing D and T units 10 Polyorganosiloxanes containing D, Q, and M units 10 Polyorganosiloxanes containing D, M, and T units 10 Polyorganosiloxanes with units such as Q-unit, M-unit, and T-unit.

[0108] Epoxy-containing polyorganosiloxanes can have epoxy groups on their side chains, epoxy groups on one end, or epoxy groups on both ends.

[0109] The epoxy-containing polyorganosiloxane is preferably a polydimethylsiloxane with an epoxy value of 0.1 to 5. Furthermore, its weight-average molecular weight is not particularly limited, and is typically 1,500 to 500,000, but is preferably 100,000 or less from the viewpoint of suppressing precipitation in the composition.

[0110] Specific examples of epoxy-containing polyorganosiloxanes include, but are not limited to, the polyorganosiloxanes represented by formulas (E1) to (E3). (m1 and n1 represent the number of each repeating unit, which are positive integers.) (m2 and n2 represent the number of repeating units, which are positive integers. R is an alkylene group with 1 to 10 carbon atoms that can be interrupted by at least one of oxygen atoms and unsaturated bonds (e.g., carbon-carbon double bonds, carbon-carbon triple bonds, -N=N-).) (m3, n3, and o3 represent the number of repeating units, which are positive integers. R is an alkylene group with 1 to 10 carbon atoms that can be interrupted by at least one of oxygen atoms and unsaturated bonds (e.g., carbon-carbon double bonds, carbon-carbon triple bonds, -N=N-).) In the above general formula, when m1, m2, m3, and o3 are 2 or more, these repeating units can be arranged adjacently to form blocks, or they can be arranged randomly.

[0111] It should be noted that the polyorganosiloxane shown in formula (E3) is an epoxy-containing polyorganosiloxane because it contains both epoxy groups and phenyl groups, and it is also a phenyl-containing polyorganosiloxane. It should also be noted that epoxy-containing polyorganosiloxanes may or may not contain phenyl groups.

[0112] The weight-average molecular weight of the epoxy-containing polyorganosiloxane is not particularly limited, but is typically 100,000 to 2,000,000. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. Furthermore, its dispersity is not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of achieving appropriate exfoliation with good reproducibility, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. It should be noted that the weight-average molecular weight and dispersity can be determined using the methods described above for polyorganosiloxanes.

[0113] The viscosity of epoxy-containing polyorganosiloxanes is not particularly limited, and is typically 1,000 to 2,000,000 mm. 2 / s. It should be noted that the viscosity of epoxy-containing polyorganosiloxanes is expressed as kinematic viscosity, denoted as centistokes (cSt) = mm. 2 / s. This can be calculated by dividing viscosity (mPa•s) by density (g / cm³). 3 The value can be determined from the viscosity and density measured at 25°C using a type E rotational viscometer, and can be derived from the kinematic viscosity (mm). 2 / s) = viscosity (mPa•s) / density (g / cm³) 3 The formula is used to calculate the result.

[0114] <<Phenyl-containing polyorganosiloxanes>> As phenyl-containing polyorganosiloxanes, examples include those containing R 31 R32 SiO 2 / 2 The siloxane unit shown (D) 30 Polyorganosiloxanes (units).

[0115] R 31 The group that bonds to silicon atoms represents a phenyl or alkyl group, R. 32 The group that bonds to silicon atoms is represented by phenyl. Specific examples of alkyl groups include those mentioned above, with methyl being the most preferred.

[0116] Phenyl-containing polyorganosiloxanes contain the aforementioned siloxane units (D 30 (unit), but except for D 30 In addition to the unit, it may also include Q units, M units and / or T units.

[0117] In a preferred embodiment, a specific example of a phenyl-containing polyorganosiloxane can be listed as one composed only of D 30 Polyorganosiloxanes composed of units containing D 30 Polyorganosiloxanes containing D and Q units 30 Polyorganosiloxanes containing D and M units 30 Polyorganosiloxanes containing D and T units 30 Polyorganosiloxanes containing D, Q, and M units 30 Polyorganosiloxanes containing D, M, and T units 30 Polyorganosiloxanes with units of Q, M, and T.

[0118] Specific examples of phenyl-containing polyorganosiloxanes include, but are not limited to, polyorganosiloxanes represented by formula (P1) or (P2). (m5 and n5 represent the number of each repeating unit, which are positive integers.) (m6 and n6 represent the number of each repeating unit, which are positive integers.) In the above general formula, when m5 and m6 are 2 or more, these repeating units can be arranged adjacently to form a block, or they can be arranged randomly.

[0119] <<Methanol-Modified Polyorganosiloxane>> There are no particular restrictions as it is a methanol-modified polyorganosiloxane.

[0120] Methanol-modified polyorganosiloxanes are polyorganosiloxanes with hydroxyl groups that are directly bonded to carbon atoms. Therefore, the methanol (carbinol) in "methanol-modified polyorganosiloxanes" is not limited to methanol in the narrow sense, but also includes methanol derivatives.

[0121] Methanol-modified polyorganosiloxanes, for example, methanol-modified polydimethylsiloxane.

[0122] The number of hydroxyl groups that are directly bonded to carbon atoms in methanol-modified polyorganosiloxanes is not particularly limited; it can be one or more.

[0123] Methanol-modified polyorganosiloxanes can have hydroxyl groups directly bonded to carbon atoms in their side chains, or hydroxyl groups directly bonded to carbon atoms in one end, or hydroxyl groups directly bonded to carbon atoms in both ends.

[0124] Methanol-modified polyorganosiloxanes preferably have hydroxyl groups directly bonded to carbon atoms in their side chains. In this case, even a small amount of methanol-modified polyorganosiloxane can impart good peelability to the adhesive layer formed from the adhesive composition.

[0125] Methanol-modified polyorganosiloxanes, for example, have groups represented by the following formula (Cg) as groups that are directly bonded to silicon atoms. (In formula (Cg), R 1 This indicates a group with one or more carbon atoms. * indicates a bond bonded to a silicon atom. In formula (Cg), the hydroxyl group is directly bonded to a carbon atom. The number of hydroxyl groups directly bonded to carbon atoms in the group represented by formula (Cg) can be one or more. For example, two, three, four, etc., can be listed.

[0126] As R 1 The number of carbon atoms is not particularly limited; for example, it can be 1 to 30, 1 to 20, or 1 to 10.

[0127] As the group represented by formula (Cg), for example, the groups represented by formulas (Cg-1) to (Cg-4) can be listed below. (In formula (Cg-1), R 11 It refers to an alkylene group with 1 to 6 carbon atoms that can be replaced by an alkoxy group with 1 to 3 carbon atoms.

[0128] In formula (Cg-2), R 12 R represents an alkylene group having 1 to 6 carbon atoms.13 It refers to an alkylene group with 1 to 6 carbon atoms that can be replaced by an alkoxy or hydroxyl group with 1 to 3 carbon atoms.

[0129] In formula (Cg-3), R 14 R represents an alkylene group having 1 to 6 carbon atoms. 15 This indicates an alkylene group with 1 to 3 carbon atoms. m represents an integer from 1 to 10.

[0130] In formula (Cg-4), R 16 ~R 18 Each can be used independently to represent an alkylene group having 1 to 6 carbon atoms.

[0131] In formulas (Cg-1) to (Cg-4), * represents a bond bonded to a silicon atom. R 11 ~R 18 The alkylene groups can be linear, branched, or cyclic.

[0132] As a group represented by formula (Cg), the following groups can be listed as examples. (In the formula, m1 represents an integer from 2 to 10. * represents a bond bonded to a silicon atom.) Methanol-modified polyorganosiloxanes are represented, for example, by the following formula (CPS-1) or formula (CPS-2). (In formula (CPS-1), R) 51 Each group independently represents a hydrocarbon group. X 1 The group represented by the above formula (Cg) is indicated. n1 represents an integer greater than or equal to 0. n2 represents an integer greater than or equal to 1.

[0133] In formula (CPS-2), R 52 Each group independently represents a hydrocarbon group. X 2 X represents the group shown in the above formula (Cg). 3 This represents a hydrocarbon group or a group represented by the above formula (Cg). n3 represents an integer greater than or equal to 0. As R 51 R 52 and X 3 The hydrocarbon group in the form of the alkyl group can be exemplified by alkyl groups having 1 to 8 carbon atoms. Methyl groups are preferred as alkyl groups having 1 to 8 carbon atoms. That is, methanol-modified polyorganosiloxanes are preferably polydimethylsiloxanes represented by the formula (CPS-1a) or (CPS-2a). (In formula (CPS-1a), X) 1The group represented by the above formula (Cg) is indicated. n1 represents an integer greater than or equal to 0. n2 represents an integer greater than or equal to 1.

[0134] In formula (CPS-2a), X 2 X represents the group shown in the above formula (Cg). 3 This represents a methyl group or a group represented by the above formula (Cg). n3 represents an integer greater than or equal to 0. It should be noted that the methanol-modified polyorganosiloxane shown in formula (CPS-1) and the methanol-modified polydimethylsiloxane shown in formula (CPS-1a) have hydroxyl groups in their side chains that are directly bonded to carbon atoms.

[0135] The methanol-modified polyorganosiloxane shown in formula (CPS-2) and the methanol-modified polydimethylsiloxane shown in formula (CPS-2a) have hydroxyl groups that are directly bonded to carbon atoms at one or both ends.

[0136] It should be noted that in the methanol-modified polyorganosiloxane shown in formula (CPS-1), when n2 is 2 or more, -Si(R 51 (X) 1 The siloxane units shown in )-O- can be arranged adjacently to form blocks, or they can be arranged randomly.

[0137] Furthermore, in the methanol-modified polydimethylsiloxane shown in formula (CPS-1a), when n2 is 2 or more, -Si(CH3)(X 1 The siloxane units shown in )-O- can be arranged adjacently to form blocks, or they can be arranged randomly.

[0138] The weight-average molecular weight of the methanol-modified polyorganosiloxane is not particularly limited, but is typically 500 to 1,000,000. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000. Furthermore, its dispersibility is not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of achieving proper exfoliation with good reproducibility, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0.

[0139] The viscosity of methanol-modified polyorganosiloxanes is not particularly limited, and is typically 100–200,000 mm. 2 / s. It should be noted that the viscosity of polydimethylsiloxane is expressed as kinematic viscosity, denoted as centistokes (cSt) = mm. 2 / s. This can be calculated by dividing viscosity (mPa•s) by density (g / cm³). 3 The value can be determined from the viscosity and density measured at 25°C using a type E rotational viscometer, and can be derived from the kinematic viscosity (mm). 2 / s) = viscosity (mPa•s) / density (g / cm³) 3 The formula is used to calculate the result.

[0140] Polyorganosiloxanes used as stripping agents can be used alone or in combination of two or more. Here, "two or more polyorganosiloxanes" refers to, for example, a combination of polydimethylsiloxane and an epoxy-containing polyorganosiloxane, or a combination of polydimethylsiloxane and a phenyl-containing polyorganosiloxane, etc., and does not refer to a combination of two epoxy-containing polyorganosiloxanes with different molecular weights, viscosities, or types of epoxy groups.

[0141] The polyorganosiloxane used as a stripping agent component (B) can be a commercially available product or a synthetic product.

[0142] Commercially available polyorganosiloxanes include, for example, the WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST manufactured by Wacker Chemie. GUM; 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.; epoxy-containing polysiloxanes (trade names CMS-227, ECMS-327, EMS-622) manufactured by Gelest Co., Ltd.; epoxy-containing polysiloxanes (KF-101, KF-1001, KF-1005, X-22-343) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy-containing polysiloxanes (DOWSIL) manufactured by DOW TORAY Co., Ltd. BY16-839, DOWSIL8413, DOWSIL8411; phenyl-containing polyorganosiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest Corporation; phenyl-containing polyorganosiloxanes (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd.; phenyl-containing polyorganosiloxanes (TSF431, TSF433) manufactured by Momentive Corporation, etc., but not limited to these.

[0143] In addition, commercially available methanol-modified polyorganosiloxanes include, for example: KF6000, KF6001, KF6002, KF6003, X-22-4039, and X-22-4015 manufactured by Shin-Etsu Silicones Co., Ltd.; DMS-C15, DMS-C16, DMS-C21, DMS-C23, DBE-C25, DBE-C22, DMS-CA21, DMS-CS26, CMS-221, CMS-222, CMS-832, CMS-626, MCR-C12, MCR-C18, MCR-C22, MCS-C11, MCS-C13, MCR-C61, MCR-C62, and MCR-C63 manufactured by Dow Toray Co., Ltd.; and DOWSIL BY 16-201 and DOWSIL BY 16-201 manufactured by Dow Toray Co., Ltd. SF 8427 Fluid, DOWSIL SF 8428 Fluid, etc.

[0144] The content of the release agent component in the adhesive composition is not particularly limited. From the viewpoint of properly obtaining the effects of the present invention, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more, relative to the non-volatile components of the adhesive composition. As for the upper limit, there is no particular limitation, but for example, it is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

[0145] The non-volatile components of an adhesive composition refer to components other than solvents in the adhesive composition.

[0146] <Solvent> For purposes such as viscosity adjustment, adhesive compositions may contain solvents, such as aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but are not limited to these.

[0147] More specifically, examples include: hexane, heptane, octane, nonane, isononane, decane, undecane, dodecane, isododecane, menthol, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc., but are not limited to these. Such solvents can be used alone or in combination of two or more.

[0148] When the adhesive composition contains a solvent, its content is appropriately set taking into account the desired viscosity of the composition, the coating method used, the thickness of the film produced, etc., and is in the range of about 10 to 90% by mass relative to the whole composition.

[0149] The viscosity of the adhesive composition used in this invention is not particularly limited, but is typically 500 to 20000 mPa•s at 25°C, preferably 1000 to 10000 mPa•s.

[0150] An example of the adhesive composition used in this invention can be manufactured by mixing component (A), release agent component (B), and solvent.

[0151] The mixing order is not particularly limited. As an example of a method for easily and reproducibly producing an adhesive composition, examples include: dissolving component (A) and release agent component (B) in a solvent; dissolving a portion of component (A) and release agent component (B) in a solvent, dissolving the remainder in a solvent, and mixing the resulting solutions, but this is not a limitation. It should be noted that, during the preparation of the adhesive composition, appropriate heating may be applied within a range that will not cause the components to decompose or deteriorate.

[0152] In this invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the manufacturing of the adhesive composition or after all the components have been mixed.

[0153] (Layered structure) The laminate of the present invention comprises: a semiconductor substrate or electronic device layer, a support substrate, and an adhesive layer.

[0154] The laminate of the present invention may further have a release agent layer, in which case it is configured to have: a semiconductor substrate or electronic device layer, a support substrate, a release agent layer and an adhesive layer.

[0155] The adhesive layer is disposed between the semiconductor substrate or electronic device layer and the support substrate.

[0156] Regarding the laminates of the present invention, for example, the adhesive layer is formed from an adhesive composition containing a release agent component.

[0157] In the case of the laminate of the present invention, for example, the absolute value of the difference (A-B) between the surface free energy (A) of the semiconductor substrate or electronic device layer and the surface free energy (B) of the stripping agent component is 20 mN / m or less.

[0158] The absolute value of the difference (A-B) is, for example, 20 mN / m or less. From the viewpoint of more appropriately obtaining the effects of the present invention, the absolute value of the difference (A-B) is preferably 15 mN / m or less, more preferably 13 mN / m or less. There is no particular limitation on the lower limit of the absolute value of the difference (A-B), and the absolute value of the difference (A-B) can be, for example, 0 mN / m or more, or 1 mN / m or more.

[0159] The method for determining surface free energy is as described above.

[0160] The laminate of the present invention is used for temporary bonding during the processing of semiconductor substrates or electronic device layers, and can be appropriately used for processes such as thinning of semiconductor substrates or electronic device layers.

[0161] During the thinning and other processing of the semiconductor substrate, the semiconductor substrate is supported by a support substrate. On the other hand, after the semiconductor substrate is processed, the support substrate is separated from the semiconductor substrate.

[0162] Furthermore, during the thinning and other processing of the electronic device layer, the electronic device layer is supported by a support substrate. On the other hand, after the processing of the electronic device layer, the support substrate is subsequently separated from the electronic device layer.

[0163] After the semiconductor substrate or electronic device layer is separated from the support substrate, the residues of the release agent layer and adhesive layer remaining on the semiconductor substrate, electronic device layer or support substrate can be removed, for example, by a cleaning agent composition used for cleaning the semiconductor substrate.

[0164] The cases are divided into those with a semiconductor substrate and those with an electronic device layer, which will be explained in detail below.

[0165] The first embodiment described below describes the case where the laminate has a semiconductor substrate, and the second embodiment described below describes the case where the laminate has an electronic device layer.

[0166] <First Implementation> A laminate containing a semiconductor substrate is used for the processing of the semiconductor substrate. During the processing of the semiconductor substrate, the semiconductor substrate is bonded to a support substrate. After the processing of the semiconductor substrate, the semiconductor substrate is separated from the support substrate.

[0167] <<Semiconductor Substrates>> As the main material constituting the entire semiconductor substrate, there are no particular limitations as long as it is used for this purpose. Examples include: silicon, silicon carbide, compound semiconductors, and glass substrates with organic resins.

[0168] The shape of the semiconductor substrate is not particularly limited; for example, it can be disc-shaped. It should be noted that a disc-shaped semiconductor substrate does not need to have a completely circular surface. For example, the outer periphery of the semiconductor substrate can have a straight section called an orientation flat, or it can have a notch.

[0169] The thickness of the disc-shaped semiconductor substrate can be appropriately determined according to the intended use of the semiconductor substrate, and there is no particular limitation. For example, it can be 500 to 1000 μm.

[0170] The diameter of the disc-shaped semiconductor substrate can be appropriately determined according to the intended use of the semiconductor substrate, and there is no particular limitation. For example, it can be 100 to 1000 mm.

[0171] Semiconductor substrates can also have bumps. Bumps refer to protruding terminals. For example, bumps can be electrodes.

[0172] In a laminate, where the semiconductor substrate has bumps, the semiconductor substrate has bumps on the support substrate side.

[0173] In semiconductor substrates, bumps are typically formed on the surface where circuitry is formed. The circuitry can be single-layered or multi-layered. There are no particular restrictions on the shape of the circuitry.

[0174] In a semiconductor substrate, the side opposite to the side with bumps (the back side) is the side to be processed.

[0175] There are no particular limitations on the material, size, shape, structure, or density of bumps on a semiconductor substrate.

[0176] Examples of bumps include: spherical bumps, printed bumps, stud bumps, plated bumps, etc.

[0177] Typically, the height, radius, and spacing of the bumps are determined appropriately based on the conditions that the bump height is approximately 1–200 μm, the bump radius is approximately 1–200 μm, and the bump spacing is approximately 1–500 μm.

[0178] Materials used for bumps include, for example, low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. Bumps can be composed of a single component or multiple components. More specifically, examples include SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other alloy plating layers with Sn as the main component.

[0179] In addition, the bump can also have a stacked structure, which includes a metal layer composed of at least one of these components.

[0180] An example of a semiconductor substrate is a silicon wafer with a diameter of 300 mm and a thickness of about 770 μm.

[0181] <<Support substrate>> As a support substrate, there are no particular limitations as long as it is a component that can support the semiconductor substrate during processing. Examples include glass support substrates and silicon support substrates.

[0182] The shape of the support substrate is not particularly limited; for example, a disc shape can be cited. It should be noted that the disc-shaped support substrate does not need to have a completely circular surface. For example, the outer periphery of the support substrate may have a straight section called an orientation plane, or it may have a cutout called a groove.

[0183] The thickness of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and there is no particular limitation. For example, it can be 500 to 1000 μm.

[0184] The diameter of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and there is no particular limitation. For example, it can be 100 to 1000 mm.

[0185] An example of a support substrate is a glass wafer with a diameter of 300 mm and a thickness of about 700 μm.

[0186] It should be noted that when the peeling in the laminate is performed by light irradiation, a substrate that is transparent to the light used can be used as the support substrate.

[0187] <<Adhesive Layer>> An adhesive layer is disposed between the support substrate and the semiconductor substrate.

[0188] The adhesive layer may be bonded to a semiconductor substrate, for example. The adhesive layer may also be bonded to a support substrate, for example.

[0189] The adhesive layer is an adhesive layer formed from an adhesive composition.

[0190] The thickness of the adhesive layer in the laminate of the present invention is not particularly limited, and is generally 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity of the thick film, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 100 μm or less.

[0191] The method for forming an adhesive layer from an adhesive composition is described in detail in the explanatory section of "A Method for Manufacturing an Example of a Laminate in the First Embodiment" described below.

[0192] <<Release Agent Layer>> Laminated bodies may have a release agent layer.

[0193] In a laminate containing a release agent layer, the semiconductor substrate and the support substrate are separated, for example, by irradiating the release agent layer with light.

[0194] The release agent layer is formed, for example, from a release agent composition.

[0195] <<<Removing Agent Composition>>> The stripping agent composition contains, for example, at least an organic resin or a polyphenol derivative, and further, as needed, other ingredients.

[0196] The organic resin is preferably a substance that can exert appropriate peeling ability. When the semiconductor substrate and the support substrate are separated by irradiating the release agent layer with light, the organic resin absorbs light and undergoes appropriate deterioration (e.g., decomposition) to improve the peeling ability.

[0197] In the case of a laminate having a release agent layer formed from a release agent composition, peeling can be achieved, for example, by irradiating the release agent layer with a laser, without applying an excessive load for peeling.

[0198] The adhesive strength of the release agent layer in a laminate may decrease due to laser irradiation compared to before irradiation. That is, in a laminate, for example during a process such as thinning a semiconductor substrate, the semiconductor substrate is properly supported by a support substrate that transmits laser light through the adhesive layer and the release agent layer. After the process is completed, by irradiating the support substrate side with laser light, the laser light transmitted through the support substrate is absorbed by the release agent layer, and the release agent layer deteriorates (e.g., separates) at the interface between the release agent layer and the adhesive layer, at the interface between the release agent layer and the support substrate, or inside the release agent layer. As a result, proper peeling (separation) can be achieved without applying excessive load for peeling.

[0199] Examples of organic resins include phenolic varnish resins. Details about them will be described later.

[0200] As a preferred embodiment, the stripping agent composition contains at least phenolic varnish resin, and further contains other components such as crosslinking agents, acid-generating agents, acids, surfactants, and solvents as needed.

[0201] As another preferred embodiment, the stripping agent composition contains at least a polyphenol derivative and a crosslinking agent, and may further contain other components such as an acid-producing agent, an acid, a surfactant, and a solvent, as needed.

[0202] As another preferred embodiment, the stripping agent composition contains at least an organic resin and a branched polysilane, and further contains, as needed, other components such as a crosslinking agent, an acid-generating agent, an acid, a surfactant, and a solvent.

[0203] <<<<Phenolic Varnish Resin>>>> Phenolic varnish resins, for example, are resins obtained by condensing at least one of phenolic compounds, carbazole compounds, and aromatic amine compounds with at least one of aldehyde compounds, ketone compounds, and divinyl compounds under an acid catalyst.

[0204] Examples of phenolic compounds include: phenols, naphthols, anthraquinones, and hydroxypyrenes. Examples of phenols include: phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis(4-hydroxyphenyl)fluorene, and 1,1,2,2-tetra(4-hydroxyphenyl)ethane. Examples of naphthols include: 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthol, 2,7-dihydroxynaphthol, and 9,9-bis(6-hydroxynaphthyl)fluorene. Examples of anthraquinones include: 9-anthraquinone. Examples of hydroxypyrenes include: 1-hydroxypyrene and 2-hydroxypyrene.

[0205] Examples of carbazole compounds include: carbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'-bis(9H-carbazole-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, 9-(1 H-benzotriazole-1-ylmethyl)-9H-carbazole, 9-acetyl-3,6-diiodocarbazole, 9-benzoylcarbazole, 9-benzoylcarbazole-6-dicarbaldehyde, 9-benzylcarbazole-3-carbaldehyde, 9-methylcarbazole, 9-phenylcarbazole, 9-vinylcarbazole, carbazole potassium, carbazole-N-formyl chloride, N-ethylcarbazole-3-carbaldehyde, N-((9-ethylcarbazole-3-yl)methylene)-2-methyl-1-dihydroindoleamine, etc.

[0206] Examples of aromatic amine compounds include diphenylamine and N-phenyl-1-naphthylamine.

[0207] They can be used individually or in combination of two or more.

[0208] They can also have substituents. For example, they can also have substituents on the aromatic ring.

[0209] Examples of aldehyde compounds include: formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentanal, caproaldehyde, 2-methylbutyraldehyde, hexanal, undecanoaldehyde, 7-methoxy-3,7-dimethyloctaldehyde, cyclohexaneformaldehyde, 3-methyl-2-butyraldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, and adipicaldehyde; unsaturated aliphatic aldehydes such as acrolein and methacrolein; heterocyclic aldehydes such as furfural and pyridineformaldehyde; and aromatic aldehydes such as benzaldehyde, naphthaldehyde, anthracene formaldehyde, phenanthrene formaldehyde, salicylaldehyde, phenylacetaldehyde, 3-phenylpropanaldehyde, tolualdehyde, (N,N-dimethylamino)benzaldehyde, and acetoxybenzaldehyde. Aromatic aldehydes are preferred.

[0210] Examples of ketone compounds include diphenyl ketones, phenylnaphthyl ketones, dinaphthyl ketones, phenyltolyl ketones, xylyl ketones, and other diaryl ketone compounds.

[0211] Examples of divinyl compounds include: divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinyl-2-norbornene, divinylpyrene, limonene, and 5-vinylnorbornene.

[0212] They can be used individually or in combination of two or more.

[0213] Phenolic varnish resins, for example, are phenolic varnish resins that deteriorate due to the absorption of light irradiated from the support substrate side. This deterioration can be, for example, photodecomposition.

[0214] Phenolic varnish resins may include, for example, at least one of the structural units shown in formula (C1-1), formula (C1-2), and formula (C1-3). In the formula, C 1 The group C represents a group derived from an aromatic compound containing a nitrogen atom. 2 C represents a group containing a tertiary carbon atom whose side chain has at least one selected from the group consisting of secondary carbon atoms, quaternary carbon atoms, and aromatic rings. 3 The C group represents a group derived from aliphatic polycyclic compounds. 4 This indicates a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenyl.

[0215] That is, phenolic varnish resins contain, for example, one or more of the following structural units.

[0216] • A structural unit having a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom in the side chain having at least one of the groups selected from the group consisting of secondary carbon atoms, quaternary carbon atoms and aromatic rings (Formula (C1-1)).

[0217] • It has a structural unit that is bonded to a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound (formula (C1-2)).

[0218] • A structural unit having a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenyl and a group containing a tertiary carbon atom in the side chain having at least one of the groups selected from the group consisting of quaternary carbon atoms and aromatic rings (Formula (C1-3)).

[0219] In a preferred embodiment, the phenolic varnish resin comprises: a structural unit having a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in the side chain (Formula (C1-1)); and a structural unit having a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound (Formula (C1-2)) or both.

[0220] C 1 That is, groups derived from aromatic compounds containing nitrogen atoms, such as groups derived from carbazole, groups derived from N-phenyl-1-naphthylamine, groups derived from N-phenyl-2-naphthylamine, etc., but not limited to these.

[0221] C 2 That is, the side chain has at least one group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring, and includes a tertiary carbon atom. For example, groups derived from 1-naphthaldehyde, groups derived from 1-pyrene formaldehyde, groups derived from 4-(trifluoromethyl)benzaldehyde, groups derived from acetaldehyde, etc., but are not limited to these.

[0222] C 3 That is, the groups derived from aliphatic polycyclic compounds can be derived from dicyclopentadiene, but are not limited to this.

[0223] C 4 It is a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenyl.

[0224] In a preferred embodiment, the phenolic varnish resin includes, for example, the structural unit shown in the following formula (C1-1-1) as the structural unit shown in formula (C1-1). In formula (C1-1-1), R 901 and R 902 The substituents that replace the ring can be represented independently as halogen atoms, nitro, cyano, amino, hydroxyl, carboxyl, substituted alkyl, substituted alkenyl, or substituted aryl groups.

[0225] R 903 It represents a hydrogen atom, a substituted alkyl group, a substituted alkenyl group, or a substituted aryl group.

[0226] R 904 It represents a hydrogen atom, a substituted aryl group, or a substituted heteroaryl group.

[0227] R 905 This indicates a substituted alkyl group, a substituted aryl group, or a substituted heteroaryl group.

[0228] R 904 Group and R 905 Groups can bond with each other to form divalent groups.

[0229] Substituents for alkyl and alkenyl groups include: halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0230] Substituents for aryl and heteroaryl groups include: halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, alkyl groups, alkenyl groups, etc.

[0231] h 1 and h 2 Each can independently represent an integer from 0 to 3.

[0232] The number of carbon atoms in the substituted alkyl and substituted alkenyl groups is generally 40 or less, preferably 30 or less, and more preferably 20 or less, from the viewpoint of solubility.

[0233] The number of carbon atoms of the aryl and heteroaryl groups that can be substituted is generally 40 or less, preferably 30 or less, and more preferably 20 or less, from the viewpoint of solubility.

[0234] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0235] Specific examples of alkyl groups that can be substituted include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4- Methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these.

[0236] Specific examples of alkenyl groups that can be substituted 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-propenyl -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 alkenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3 -Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl, 2- 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.

[0237] Specific examples of aryl groups that can be substituted include: phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-nitrophenyl, 4-cyanophenyl, 1-naphthyl, 2-naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, etc., but are not limited to these.

[0238] Specific examples of heteroaryl groups that can be substituted include: 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isooxazolyl, 4-isooxazolyl, 5-isooxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, etc., but are not limited to these.

[0239] The following are specific examples of the structural units shown in equation (C1-1-1), but are not limited to these examples. In a preferred embodiment, the phenolic varnish resin includes, for example, the structural unit shown in the following formula (C1-1-2) as the structural unit shown in formula (C1-1). In formula (C1-1-2), Ar 901 and Ar 902 Each independently represents an aromatic ring such as a benzene ring or a naphthalene ring, R 901 ~R 905 and h 1 and h 2 It means the same as above.

[0240] The following are specific examples of the structural units shown in equation (C1-1-2), but are not limited to these examples. In a preferred embodiment, the phenolic varnish resin contains, for example, the structural unit shown in formula (C1-2-1) or (C1-2-2) as the structural unit shown in formula (C1-2). In the above formula, R 906 ~R 909 Substituents that are bonded to the ring can be independently represented by halogen atoms, nitro, cyano, amino, hydroxyl, carboxyl, substituted alkyl, substituted alkenyl, or substituted aryl groups. Specific examples and preferred carbon numbers for halogen atoms, substituted alkyl, substituted alkenyl, and substituted aryl groups are listed above. 3 ~h 6 Each element independently represents an integer from 0 to 3, R 901 ~R 903 and h 1 and h 2 It means the same as above.

[0241] The following are specific examples of the structural units shown in equations (C1-2-1) and (C1-2-2), but are not limited to these examples. The following are specific examples of the structural units shown in equation (C1-3), but are not limited to these examples. As described above, phenolic varnish resin is, for example, a resin obtained by condensing at least one of phenolic compounds, carbazole compounds, and aromatic amine compounds with at least one of aldehyde compounds, ketone compounds, and divinyl compounds under an acid catalyst.

[0242] In this condensation reaction, an aldehyde or ketone compound is typically used in a ratio of 0.1 to 10 equivalents relative to 1 equivalent of the benzene ring constituting the carbazole compound.

[0243] In the above condensation reaction, an acid catalyst is usually used.

[0244] Examples of acid catalysts include: inorganic acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid, but are not limited to these.

[0245] The amount of acid catalyst is determined appropriately based on the type of acid used, etc., and therefore cannot be specified in general terms. It is usually appropriately determined in the range of 0.001 to 10,000 parts by mass relative to 100 parts by mass of carbazole compound.

[0246] When the above condensation reaction is carried out in the presence of liquids in either the raw material compound or the acid catalyst, a solvent may sometimes be omitted, but a solvent is usually used.

[0247] There are no particular limitations on such solvents as long as they do not hinder the reaction; typical examples include ether compounds such as tetrahydrofuran and dioxane.

[0248] The reaction temperature is usually appropriately determined within the range of 40℃ to 200℃. The reaction time varies depending on the reaction temperature, so it cannot be generally specified. It is usually appropriately determined within the range of 30 minutes to 50 hours.

[0249] After the reaction is complete, if necessary, the resin is purified and isolated using conventional methods, and the resulting phenolic varnish resin is used in the preparation of the stripping agent composition.

[0250] Based on the above description and common technical knowledge, those skilled in the art can determine the manufacturing conditions of phenolic varnish resin without excessive burden, and therefore can manufacture phenolic varnish resin.

[0251] The weight-average molecular weight of organic resins such as phenolic varnish resin is typically 500 to 200,000. From the viewpoint of ensuring solubility in solvents and good mixing with branched polysilanes to obtain a uniform film during film formation, it is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, even more preferably 5,000 or less, and even more preferably 3,000 or less. From the viewpoint of improving film strength, it is preferably 600 or more, more preferably 700 or more, even more preferably 800 or more, even more preferably 900 or more, and even more preferably 1,000 or more.

[0252] It should be noted that, in this invention, the weight-average molecular weight, number-average molecular weight, and dispersity of the organic resins such as phenolic varnish resins used as polymers can be determined, for example, using a GPC apparatus (TOSOH Corporation EcoSEC, HLC-8320GPC) and a GPC column (TOSOH Corporation TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H), with the column temperature set to 40°C, tetrahydrofuran used as the eluent (dissolution solvent), the flow rate set to 0.35 mL / min, and polystyrene (Sigma Aldrich) used as the standard sample.

[0253] The organic resin contained in the above-mentioned release agent composition is preferably phenolic varnish resin. Therefore, the above-mentioned release agent composition preferably contains phenolic varnish resin alone as an organic resin. For purposes such as adjusting the film properties, it may also contain phenolic varnish resin and other polymers.

[0254] Other examples of such polymers include: polyacrylate compounds, polymethacrylate compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydride, polyacrylonitrile compounds, etc.

[0255] The content of phenolic varnish resin in the stripping agent composition is not particularly limited, but it is preferably 70% by mass or more relative to the total amount of polymer contained in the stripping agent composition.

[0256] The content of phenolic varnish resin in the stripping agent composition is not particularly limited, but is preferably 50 to 100% by mass relative to the film-forming components. It should be noted that, in this invention, the film-forming components refer to components other than the solvent contained in the composition.

[0257] <<<<Polyphenolic Derivatives>>>> Polyphenolic derivatives are represented, for example, by the following formula (P). In formula (P), Ar represents arylene, and the number of carbon atoms is not particularly limited, usually 6 to 60. From the viewpoint of preparing a release agent composition with excellent uniformity and obtaining a release agent layer with better reproducibility and flatness, it is preferably 30 or less, more preferably 20 or less, even more preferably 18 or less, and even more preferably 12 or less.

[0258] Specific examples of such arylene groups include: 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthodiyl, 1,8-naphthodiyl, 2,6-naphthodiyl, 2,7-naphthodiyl, 1,2-anthratriyl, 1,3-anthratriyl, 1,4-anthratriyl, 1,5-anthratriyl, 1,6-anthratriyl, 1,7-anthratriyl, 1,8-anthratriyl, 2,3-anthratriyl, 2,6-anthratriyl, 2,7-anthratriyl, 2,9-anthratriyl, 2,10-anthratriyl, 9,10-anthratriyl, etc., derived from fused-ring aromatic hydrocarbon compounds by removing two hydrogen atoms from the aromatic ring; biphenyl-4,4'-diyl, p-terphenyl-4,4”-diyl, etc., derived from ring-linked aromatic hydrocarbon compounds by removing two hydrogen atoms from the aromatic ring, etc., but are not limited to these.

[0259] From the viewpoint of producing a release agent layer exhibiting good peelability and obtaining a laminate in which the support substrate can be well separated with good reproducibility, the polyphenol derivative shown in formula (P) is preferably the polyphenol derivative shown in formula (P-1), more preferably the polyphenol derivative shown in formula (P-1-1), and even more preferably the polyphenol derivative shown in formula (P1). The content of the polyphenol derivative in the stripping agent composition is not particularly limited, but is preferably 50 to 100% by mass relative to the film composition.

[0260] <<<<Branched Polysilane>>>> The above-mentioned stripping agent composition may also contain branched polysilanes.

[0261] Branched polysilanes have Si-Si bonds and a branched structure. By including branched polysilanes in the above-mentioned release agent composition, the release agent layer formed by the resulting film cannot be properly removed by any of organic solvents, acids, or chemical solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.), but can be properly removed by the cleaning agent composition. As a result, by cleaning each substrate with the cleaning agent composition after separating the semiconductor substrate of the laminate from the support substrate, the residue of the release agent layer on the substrate can be properly removed. The reason is not yet clear, but it is speculated as follows: depending on the type of terminal groups (terminal substituents (atoms)) of polysilane, polysilane can react with organic resins to crosslink. In addition, branched polysilane has more terminal groups (terminal substituents (atoms)) than linear polysilane. Therefore, it can be considered that branched polysilane has more crosslinking points than linear polysilane. Through moderate and appropriate curing via such more crosslinking points in branched polysilane, it is possible to achieve both the property that it will not be properly removed by organic solvents, acids and chemicals used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.) and the property that it can be properly removed by cleaning agent compositions.

[0262] Branched polysilanes preferably include the structural unit shown in formula (B). In equation (B), R B This refers to a hydrogen atom, hydroxyl group, silyl group, or organic group. Specific examples of such organic groups include: hydrocarbon groups (substituted alkyl, substituted alkenyl, substituted aryl, substituted aralkyl), and corresponding ether groups (substituted alkoxy, substituted aryloxy, substituted arylalkoxy, etc.). These organic groups are typically hydrocarbon groups such as alkyl, alkenyl, aryl, and aralkyl. Furthermore, hydrogen atoms, hydroxyl groups, alkoxy groups, and silyl groups are often substituted at the terminal.

[0263] The alkyl groups that can be substituted can be any type of straight-chain, branched, or cyclic.

[0264] Specific examples of linear or branched alkyl groups that can be substituted include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1- Dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these, and the number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6.

[0265] Specific examples of substituted 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, 2,4-dimethyl-cyclobutyl Cycloalkyl groups such as 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.; bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, etc., but not limited thereto, wherein the number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0266] Alkenes can be any type of linear, branched, or cyclic.

[0267] Specific examples of linear or branched alkenyl groups that can be substituted include vinyl, allyl, butenyl, pentenyl, etc., but are not limited thereto. The number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6.

[0268] Specific examples of cyclic alkenyl groups that can be replaced include cyclopentenyl, cyclohexenyl, etc., but are not limited to these. The number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0269] Specific examples of aryl groups that can be substituted include: phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 3,5-dimethylphenyl, 1-naphthyl, 2-naphthyl, etc., but are not limited to these. The number of carbon atoms is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 12.

[0270] Specific examples of substituted aralkyl groups include benzyl, phenethyl, and phenylpropyl, but are not limited to these. Preferably, the substituted aralkyl group is a group in which one hydrogen atom of an alkyl group having 1 to 4 carbon atoms is replaced by an aryl group having 6 to 20 carbon atoms.

[0271] The alkyl portion of the substituted alkoxy group can be any of the following: straight-chain, branched, or cyclic.

[0272] Specific examples of linear or branched alkoxy groups that can be substituted include methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, etc., but are not limited thereto. The number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6.

[0273] Specific examples of substituted cyclic alkoxy groups include cyclopentoxy, cyclohexyloxy, etc., but are not limited thereto. The number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0274] Specific examples of aryloxy groups that can be substituted include phenoxy, 1-naphthoxy, 2-naphthoxy, etc., but are not limited thereto. The number of carbon atoms is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 10.

[0275] Specific examples of substituted arylalkoxy groups include benzyloxy, phenylethoxy, and phenylpropoxy, but are not limited to these. Preferably, the substituted arylalkoxy group is a group formed by replacing one hydrogen atom of an alkoxy group having 1 to 4 carbon atoms with an aryl group having 6 to 20 carbon atoms.

[0276] Specific examples of silanes include methylsilane, diethylsilane, propanesilane, etc., but are not limited to these. The number of silicon atoms is usually 1 to 10, preferably 1 to 6.

[0277] In R B In the case of the aforementioned organic group or silyl group, at least one hydrogen atom may be substituted by a substituent. Specific examples of such substituents include hydroxyl, alkyl, aryl, alkoxy, etc.

[0278] From the perspective of suppressing accidental peeling when the laminate comes into contact with any of the organic solvents, acids, or chemical solutions used in the manufacture of semiconductor devices (alkaline developing solutions, hydrogen peroxide, etc.); and from the perspective of properly removing residues of the release agent layer from the substrates after the semiconductor substrate of the laminate has been separated from the support substrate and each substrate has been cleaned with a cleaning agent composition, R B Preferably alkyl or aryl, more preferably aryl, even more preferably phenyl, 1-naphthyl or 2-naphthyl, and even more preferably phenyl.

[0279] The branched polysilane may also include the structural unit shown in formula (B), the structural unit shown in formula (S) below, and the structural unit shown in formula (N) below. From the viewpoint of suppressing accidental peeling when the laminate comes into contact with any of the organic solvents, acids, or chemical solutions (alkaline developer, hydrogen peroxide, etc.) used in the manufacture of semiconductor devices, and from the viewpoint of properly removing residues of the release agent layer on the substrate after the semiconductor substrate of the laminate has been separated from the support substrate and each substrate has been cleaned with a cleaning agent composition, the content of the structural unit shown in formula (B) in the branched polysilane is generally 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more. (R) S1 and R S2 Indicates with R B (Same meaning.) The terminal groups (terminal substituents (atoms)) of branched polysilanes can typically be hydrogen atoms, hydroxyl groups, halogen atoms (chlorine atoms, etc.), alkyl groups, aryl groups, alkoxy groups, silyl groups, etc. Among these, hydroxyl, methyl, and phenyl groups are most common, with methyl being preferred. The terminal group can also be trimethylsilyl.

[0280] In one embodiment, the average degree of polymerization of the branched polysilane, expressed in terms of silicon atoms (i.e., the average number of silicon atoms per molecule), is typically 2 to 100, preferably 3 to 80, more preferably 5 to 50, and even more preferably 10 to 30.

[0281] In one embodiment, the upper limit of the weight-average molecular weight of the branched polysilane is typically 30,000, preferably 20,000, more preferably 10,000, even more preferably 5,000, further preferably 2,000, and even more preferably 1,500. The lower limit is typically 50, preferably 100, more preferably 150, even more preferably 200, even more preferably 300, and even more preferably 500.

[0282] The average degree of polymerization and weight-average molecular weight of branched polysilanes can be determined, for example, using a GPC apparatus (EcoSEC, HLC-8220GPC, TOSOH Corporation) and GPC columns (Shodex KF-803L, KF-802, and KF-801, successively, manufactured by Showa Denko Corporation), with the column temperature set to 40°C, tetrahydrofuran used as the eluent (dissolution solvent), the flow rate set to 1.00 mL / min, and polystyrene (manufactured by Sigma Aldrich) used as the standard sample.

[0283] If the degree of polymerization and weight-average molecular weight of the branched polysilane used are too small, the branched polysilane may vaporize due to heating during the formation of the film as a release agent layer or during the processing of the laminate containing the obtained release agent layer, or adverse conditions may occur due to poor film strength. If the degree of polymerization and molecular weight of the branched polysilane used are too large, depending on the type of solvent used to prepare the release agent composition, sufficient solubility may not be ensured, resulting in precipitation in the composition, or insufficient mixing with the resin, making it impossible to obtain a highly uniform film with good reproducibility.

[0284] Therefore, from the viewpoint of obtaining a laminate with a release agent layer that facilitates the proper manufacture of semiconductor devices with better reproducibility, it is ideal that the degree of polymerization and weight-average molecular weight of the branched polysilane meet the above-mentioned ranges.

[0285] From the viewpoint of obtaining a release agent layer with good reproducibility and excellent heat resistance, the 5% weight reduction temperature of the branched polysilane is generally 300°C or higher, preferably 350°C or higher, more preferably 365°C or higher, even more preferably 380°C or higher, even more preferably 395°C or higher, and even more preferably 400°C or higher.

[0286] The 5% weight reduction temperature of branched polysilanes can be determined, for example, by using NETZSCH 2010SR, to heat from room temperature (25°C) to 400°C in air at a rate of 10°C / min.

[0287] From the viewpoint of properly removing residues of the release agent layer on the substrate after cleaning each substrate with a cleaning agent composition following separation of the semiconductor substrate and the support substrate of the laminate, and from the viewpoint of preparing a release agent composition with good reproducibility and excellent uniformity, branched polysilanes are preferably dissolved in any of the following: ether compounds such as tetrahydrofuran; aromatic compounds such as toluene; glycol ether ester compounds such as propylene glycol monomethyl ether acetate; ketone compounds such as cyclohexanone and methyl ethyl ketone; and glycol ether compounds such as propylene glycol monomethyl ether. It should be noted that dissolution in this case refers to a situation where, when a 10% by mass solution is attempted to be dissolved at room temperature (25°C) using a shaker, dissolution can be visually confirmed within 1 hour.

[0288] Branched polysilanes can be in any form, either solid or liquid, at room temperature.

[0289] Branched polysilanes can be manufactured using known methods as described in Japanese Patent Application Publication Nos. 2011-208054, 2007-106894, 2007-145879, and WO2005 / 113648. They are also available as commercially available products. Specific examples of commercially available products include, but are not limited to, OGSOL SI-20-10 and SI-20-14, polysilanes for silicon materials manufactured by OSAKA GAS CHEMICALS Co., Ltd.

[0290] As a preferred example of a branched polysilane, the following substances can be listed, but are not limited thereto. (Ph represents phenyl, R) E Each independently represents a terminal substituent, representing an atom or group, n b (Indicates the number of repeating units.) The content of branched polysilane in the above-mentioned stripping agent composition is generally 10 to 90% by mass relative to the film composition. From the viewpoint of achieving good reproducibility of a film that cannot be properly removed by organic solvents, acids or chemical solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.), but can be properly removed by the cleaning agent composition, it is preferably 15 to 80% by mass, more preferably 20 to 70% by mass, even more preferably 25 to 60% by mass, and even more preferably 30 to 50% by mass.

[0291] <<<<Cross-linking agent>>>> The stripper composition may also contain a crosslinking agent.

[0292] Crosslinking agents can sometimes undergo crosslinking reactions due to self-condensation. In the presence of crosslinking substituents in phenolic varnish resins, they can undergo crosslinking reactions with these crosslinking substituents.

[0293] Specific examples of crosslinking agents are not particularly limited, but typically include: phenolic crosslinking agents, melamine-based crosslinking agents, urea-based crosslinking agents, thiourea-based crosslinking agents, etc., which have crosslinking-forming groups such as hydroxymethyl, methoxymethyl, butoxymethyl, etc. in the molecule. They can be low molecular weight compounds or high molecular weight compounds.

[0294] The crosslinking agent contained in the stripping agent composition usually has two or more crosslinking forming groups. From the viewpoint of achieving more appropriate curing with good reproducibility, the number of crosslinking forming groups contained in the compound as the crosslinking agent is preferably 2 to 10, more preferably 2 to 6.

[0295] From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the stripping agent composition preferably has an aromatic ring (e.g., benzene ring, naphthalene ring) in the molecule. Phenolic crosslinking agents are typical examples of such crosslinking agents, but are not limited thereto.

[0296] A phenolic crosslinking agent having a crosslinking forming group refers to a compound having a crosslinking forming group bonded to an aromatic ring and having at least one of a phenolic hydroxyl group and an alkoxy group derived from the phenolic hydroxyl group. Examples of such alkoxy groups derived from the phenolic hydroxyl group include methoxy and butoxy, but are not limited to these.

[0297] The aromatic rings bonded by the cross-linking groups, as well as the aromatic rings bonded by phenolic hydroxyl groups and / or alkoxy groups derived from phenolic hydroxyl groups, are not limited to non-fused-ring aromatic rings such as benzene rings, but can also be fused-ring aromatic rings such as naphthalene rings and anthracene rings.

[0298] In the case of multiple aromatic rings within the molecule of a phenolic crosslinking agent, the crosslinking forming group, as well as the phenolic hydroxyl group and the alkoxy group derived from the phenolic hydroxyl group, can bond to the same aromatic ring within the molecule or to different aromatic rings.

[0299] The aromatic rings bonded by the cross-linking groups, phenolic hydroxyl groups, and alkoxy groups derived from phenolic hydroxyl groups can be further replaced by alkyl groups such as methyl, ethyl, and butyl, hydrocarbon groups such as aryl groups such as phenyl, and halogen atoms such as fluorine atoms.

[0300] For example, as a specific example of a phenolic crosslinking agent having a crosslinking-forming group, compounds represented by any of the formulas (L1) to (L4) can be listed. In each formula, each R' independently represents a fluorine atom, aryl group, or alkyl group, and each R'' independently represents a hydrogen atom or alkyl group. 1 and L 2 Each independently represents a single bond, methylene, or propane-2,2-diyl, L 3 Determined by q1, representing a single bond, methylene, propane-2,2-diyl, methane-triyl, or ethane-1,1,1-triyl, t11, t12, and t13 are integers satisfying 2≤t11≤5, 1≤t12≤4, 0≤t13≤3, and t11+t12+t13≤6; t21, t22, and t23 are integers satisfying 2≤t21≤4, 1≤t22≤3, 0≤t23≤2, and t21+t22+t23≤5; t24, t25, and t26 are integers satisfying 2≤t24≤4, 1≤t25≤3, 0≤t26≤2, and t24+t25+t26≤5; t27, t28, and t29 are integers satisfying 0≤ The integers t27≤4, 0≤t28≤4, 0≤t29≤4, and t27+t28+t29≤4 are given. t31, t32, and t33 are integers satisfying 2≤t31≤4, 1≤t32≤3, 0≤t33≤2, and t31+t32+t33≤5. t41, t42, and t43 are integers satisfying 2≤t41≤3, 1≤t42≤2, 0≤t43≤1, and t41+t42+t43≤4. q1 is 2 or 3, and q2 represents the number of repetitions, which is an integer greater than or equal to 0. Specific examples of aryl and alkyl groups can be listed, with the same groups as the specific examples below. For aryl groups, phenyl is preferred; for alkyl groups, methyl and tert-butyl are preferred.

[0301] The following are specific examples of compounds represented by formulas (L1) to (L4), but are not limited to these examples. It should be noted that these compounds can be synthesized by known methods, or obtained in the form of products from companies such as Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. A melamine-based crosslinking agent with a crosslinking-forming group refers to a melamine derivative, a 2,4-diamino-1,3,5-triazine derivative, or a 2-amino-1,3,5-triazine derivative formed by replacing at least one hydrogen atom of the amino group bonded to its triazine ring with a crosslinking-forming group. The triazine ring may further have substituents such as phenyl or aryl groups.

[0302] Specific examples of melamine-based crosslinking agents with crosslinking-forming groups include: monoalkoxymethyl melamines such as N,N,N',N',N",N"-hexa(methoxymethyl)melamine and N,N,N',N',N",N"-hexa(butoxymethyl)melamine, as well as diekoxymethyl melamine, trimekoxymethyl melamine, tetraalkoxymethyl melamine, pentaalkoxymethyl melamine, or hexaalkoxymethyl melamine; monoalkoxymethyl benzoguanamines such as N,N,N',N'-tetra(methoxymethyl)benzoguanamine and N,N,N',N'-tetra(butoxymethyl)benzoguanamine, as well as diekoxymethyl benzoguanamine, trimekoxymethyl benzoguanamine, or tetraalkoxymethyl benzoguanamine, but are not limited to these.

[0303] A urea-based crosslinking agent with a crosslinking-forming group refers to a derivative of a compound containing a urea bond, wherein at least one hydrogen atom of the NH group constituting the urea bond is replaced by a crosslinking-forming group.

[0304] Specific examples of urea-based crosslinking agents with crosslinking-forming groups include: monoalkoxymethyl urea, dialkoxymethyl urea, trimoxomethyl urea, or tetraalkoxymethyl urea, such as 1,3,4,6-tetra(methoxymethyl) urea and 1,3,4,6-tetra(butoxymethyl) urea; monoalkoxymethyl urea, dialkoxymethyl urea, trimoxomethyl urea, or tetraalkoxymethyl urea, such as 1,3-bis(methoxymethyl)urea and 1,1,3,3-tetramethoxymethyl urea; but not limited to these.

[0305] Thiourea-based crosslinking agents with crosslinking-forming groups refer to derivatives of compounds containing thiourea bonds, and have a structure in which at least one hydrogen atom of the NH group constituting the thiourea bond is replaced by a crosslinking-forming group.

[0306] Specific examples of thiourea-based crosslinking agents with crosslinking-forming groups include: 1,3-bis(methoxymethyl)thiourea, 1,1,3,3-tetramethoxymethylthiourea, etc. (monoalkoxymethylthiourea, dialkoxymethylthiourea, trialkoxymethylthiourea, or tetraalkoxymethylthiourea), but are not limited to these.

[0307] The amount of crosslinking agent contained in the release agent composition varies depending on the coating method used, the desired film thickness, etc., and therefore cannot be specified in general terms. It is usually 0.01 to 50% by mass relative to the organic resin or polyphenol derivative. From the viewpoint of achieving proper curing and obtaining a laminate in which the semiconductor substrate and the support substrate can be well separated, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 5% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0308] <<<<Acid-producing agents and acids>>>> For purposes such as promoting cross-linking reactions, the stripping agent composition may also contain an acid-producing agent or an acid.

[0309] Examples of acid-producing agents include thermal acid-producing agents and photoacid-producing agents.

[0310] There are no particular limitations on thermally generated acid-producing agents, as long as they produce acid through heat. Specific examples include: 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG2689, K-PURE TAG2700 (manufactured by King Industries), as well as SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic alkyl sulfonic acid esters, but not limited to these.

[0311] Examples of photoacid-generating agents include: onium salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds.

[0312] Specific examples of onionium salt compounds include: diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethane sulfonate, diphenyliodonium nonafluoron-butane sulfonate, diphenyliodonium perfluoron-octane sulfonate, diphenyliodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethane sulfonate, etc.; sulfonium salt compounds such as triphenylsulfonium nitrate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butane sulfonate, triphenylsulfonium camphor sulfonate, triphenylsulfonium trifluoromethane sulfonate, etc., but are not limited to these.

[0313] Specific examples of sulfonylimide compounds include: N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalenediformimide, etc., but are not limited to these.

[0314] Specific examples of disulfonyl diazonium methane compounds include: bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyl diazonium methane, etc., but are not limited to these.

[0315] Specific examples of acids include: p-toluenesulfonic acid, pyridinium p-toluenesulfonate, pyridinium trifluoromethanesulfonate, pyridinium phenolsulfonate, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, and other aryl sulfonic acids, pyridinium salts, and their salts; salicylic acid, benzoic acid, hydroxybenzoic acid, naphthoic acid, and other aryl carboxylic acids, and their salts; trifluoromethanesulfonic acid, camphorsulfonic acid, and other chain or cyclic alkyl sulfonic acids, and their salts; citric acid and other chain or cyclic alkyl carboxylic acids, and their salts, but are not limited to these.

[0316] The amount of acid-generating agent and acid contained in the stripping agent composition varies depending on the type of crosslinking agent used, the heating temperature during film formation, etc., and therefore cannot be specified in general terms. It is usually 0.01 to 5% by mass relative to the film composition.

[0317] <<<<Surfactants>>>> For purposes such as adjusting the liquid properties of the composition itself, the membrane properties of the obtained membrane, and preparing a release agent composition with high uniformity and good reproducibility, the release agent composition may also contain a surfactant.

[0318] Examples of surfactants include: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. EFTOP Fluorinated surfactants such as EF301, EF303, EF352 (manufactured by Tohkem Products Co., Ltd., trade name), MEGAFACE F171, F173, R-30, R-30N (manufactured by DIC Co., Ltd., trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0319] Surfactants can be used alone or in combination of two or more.

[0320] The amount of surfactant is typically less than 2% by mass relative to the film composition of the stripper composition.

[0321] <<<< Solvent>>>> The stripping agent composition preferably contains a solvent.

[0322] As such solvents, for example, highly polar solvents that can readily dissolve the aforementioned organic resins, polyphenol derivatives, branched polysilanes, crosslinking agents, and other film-forming components can be used. Alternatively, low-polarity solvents can be used as needed for purposes such as adjusting viscosity and surface tension. It should be noted that in this invention, a low-polarity solvent is defined as a solvent with a relative permittivity of less than 7 at a frequency of 100 kHz, and a highly polarity solvent is defined as a solvent with a relative permittivity of 7 or higher at a frequency of 100 kHz. One solvent can be used alone, or two or more solvents can be used in combination.

[0323] In addition, examples of highly polar solvents include: amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolinone; ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; cyano solvents such as acetonitrile and 3-methoxypropionitrile; polyol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and sulfoxide solvents such as dimethyl sulfoxide.

[0324] Examples of low-polarity solvents include: chloroform, chlorobenzene, and other chlorine-based solvents; alkylbenzene solvents such as toluene, xylene, tetrahydronaphthalene, cyclohexylbenzene, and decylbenzene, and other aromatic hydrocarbon solvents; aliphatic alcohol solvents such as 1-octanol, 1-nonanol, and 1-decanol; ether solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; and ester solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0325] The solvent content is appropriately determined taking into account the desired viscosity of the composition, the coating method used, the thickness of the film produced, etc., and is less than 99% by mass of the total composition, preferably 70 to 99% by mass relative to the total composition, that is, the amount of film-forming components in this case is 1 to 30% by mass relative to the total composition.

[0326] The viscosity and surface tension of the stripping agent composition can be appropriately adjusted by taking into account various factors such as the coating method used, the desired film thickness, and by changing the type of solvent used, their ratio, and the concentration of film components.

[0327] In one aspect of the present invention, from the viewpoints of obtaining a composition with good reproducibility and high homogeneity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high homogeneity, the stripping agent composition comprises a glycol-based solvent. It should be noted that the term "glycol-based solvent" as used herein refers to a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0328] An example of a preferred diol solvent is represented by formula (G). In equation (G), R G1 Each independently represents a straight-chain or branched alkylene group having 2 to 4 carbon atoms, R G2 and R G3 Each independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 8 carbon atoms, or an alkyl group whose alkyl portion is a straight-chain or branched alkyl group having 1 to 8 carbon atoms, n g It is an integer from 1 to 6.

[0329] Specific examples of straight-chain or branched alkylene groups with 2 to 4 carbon atoms include: ethylene, trimethylene, 1-methylethylene, tetramethylene, 2-methylpropane-1,3-diyl, pentamethylene, hexamethylene, etc., but are not limited to these.

[0330] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, straight-chain or branched alkylene groups with 2 to 3 carbon atoms are preferred, and straight-chain or branched alkylene groups with 3 carbon atoms are more preferred.

[0331] Specific examples of alkyl groups having 1 to 8 carbon atoms, whether linear or branched, include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-... Amyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these.

[0332] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, methyl and ethyl are preferred, and methyl is more preferred.

[0333] Specific examples of alkyl acyl groups having 1 to 8 carbon atoms in a straight-chain or branched alkyl group having 1 to 8 carbon atoms can be listed as the same groups as the specific examples described above.

[0334] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, methyl carbonyl and ethyl carbonyl are preferred, and methyl carbonyl is more preferred.

[0335] From the perspectives of obtaining compositions with good reproducibility and high homogeneity, obtaining compositions with good reproducibility and high storage stability, and obtaining compositions with good reproducibility that provide highly uniform films, n g Preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and most preferably 1.

[0336] From the viewpoints of obtaining a composition with good reproducibility and high homogeneity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high homogeneity, R is preferred in formula (G). G2 and R G3 At least one of them is a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably R G2 and R G3 One of them is a straight-chain or branched alkyl group having 1 to 8 carbon atoms, and the other is an alkyl acyl group with hydrogen atoms or an alkyl part having 1 to 8 carbon atoms in a straight-chain or branched alkyl group.

[0337] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, the content of the glycol solvent is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to the solvent contained in the stripper composition.

[0338] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, the film components in the stripper composition are uniformly dispersed or dissolved in the solvent, preferably uniformly dissolved in the solvent.

[0339] The stripping agent composition can be manufactured, for example, by mixing an organic resin or polyphenol derivative, a solvent, and a crosslinking agent added as needed.

[0340] The mixing order is not particularly limited. As an example of a method for easily and reproducibly manufacturing a release agent composition, examples include: dissolving the organic resin or polyphenol derivative and the crosslinking agent in a solvent in one step; dissolving a portion of the organic resin or polyphenol derivative and the crosslinking agent in a solvent, dissolving the remainder separately in a solvent, and then mixing the resulting solutions. However, this method is not limited to these methods. Furthermore, when preparing the release agent composition, appropriate heating may be applied within a range that does not cause the components to decompose or deteriorate.

[0341] In this invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the manufacturing of the stripping agent composition or after all the components have been mixed.

[0342] The thickness of the release agent layer is not particularly limited, but is usually 5nm to 100μm. In one scheme, it is 10nm to 10μm, in another scheme it is 50nm to 1μm, and in yet another scheme it is 100nm to 700nm.

[0343] There are no particular limitations on the method of forming a release agent layer from the release agent composition. For example, the following method can be listed: forming a release agent layer by coating the release agent composition.

[0344] There are no particular limitations on the application method of the release agent composition; spin coating is the most common method.

[0345] The heating temperature of the coated release agent composition varies depending on the type and amount of release agent components contained in the release agent composition, the desired thickness of the release agent layer, etc., and therefore cannot be specified in general. From the viewpoint of achieving a suitable release agent layer with good reproducibility, it is preferably 80°C or higher and 300°C or lower. The heating time is usually appropriately determined within the range of 10 seconds to 10 minutes, depending on the heating temperature. The heating temperature is preferably 100°C or higher and 280°C or lower, more preferably 150°C or higher and 250°C or lower. The heating time is preferably 30 seconds or higher and 8 minutes or lower, more preferably 1 minute or higher and 5 minutes or lower.

[0346] Heating can be done using heating plates, ovens, etc.

[0347] The following description uses the accompanying drawings to illustrate an example of the structure of the laminate of the first embodiment.

[0348] Figure 1 A schematic cross-sectional view showing an example of a laminated body according to the first embodiment.

[0349] Figure 1The laminate sequentially comprises: a semiconductor substrate 1, an adhesive layer 2, and a support substrate 4. That is, the adhesive layer 2 is disposed between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with both the semiconductor substrate 1 and the support substrate 4.

[0350] The following description uses the accompanying drawings to illustrate another example of the structure of the laminate of the first embodiment.

[0351] Figure 2 A schematic cross-sectional view showing another example of the laminated body of the first embodiment.

[0352] Figure 2 The laminate sequentially comprises: a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4.

[0353] Adhesive layer 2 and release agent layer 3 are disposed between semiconductor substrate 1 and support substrate 4. Adhesive layer 2 is in contact with semiconductor substrate 1. Release agent layer 3 is in contact with adhesive layer 2 and support substrate 4.

[0354] <<Manufacturing Method of an Example of a Laminated Body in the First Embodiment>> In the laminated body of the first embodiment Figure 1 The laminate shown is an example. The manufacturing method of the laminate is described below.

[0355] An example of the laminate of the present invention can be manufactured by a method including the following first step to second step.

[0356] The first step is to apply an adhesive composition onto a semiconductor substrate to form an adhesive coating layer.

[0357] The second step is to heat the adhesive coating layer to form the adhesive layer.

[0358] There are no particular limitations on the coating method of the adhesive composition; spin coating is usually used. It should be noted that the following method can be used: a coating film can be separately formed by spin coating or similar methods to form a sheet-like coating film, and then the sheet-like coating film can be pasted as an adhesive coating layer.

[0359] The heating temperature of the coated adhesive composition varies depending on the type and amount of adhesive components contained in the adhesive composition, whether it contains solvent, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc., so it cannot be specified in general terms. It is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes.

[0360] When the adhesive composition contains a solvent, the coated adhesive composition is typically heated.

[0361] The thickness of the adhesive coating layer obtained by heating the coating composition, if necessary, is typically around 5 to 500 μm, appropriately determined in a manner that ultimately results in the aforementioned range of adhesive layer thickness.

[0362] In this invention, a load in the thickness direction of the semiconductor substrate and the support substrate can be applied while performing heat treatment or depressurization treatment, or both, followed by post-heat treatment, thereby obtaining the laminate of this invention. It should be noted that the choice between heat treatment, depressurization treatment, and which of the two treatment conditions is appropriate, taking into account various factors such as the type of adhesive composition, film thickness, and required adhesive strength.

[0363] From the viewpoint of removing solvent from the composition, the heat treatment is generally appropriately determined within the range of 20 to 160°C. In particular, from the viewpoint of suppressing or avoiding over-curing and unnecessary deterioration of the adhesive component (A), it is preferably 150°C or lower, more preferably 130°C or lower, and the heating time is appropriately determined according to the heating temperature and the type of adhesive. From the viewpoint of reliably achieving proper adhesion, it is generally 30 seconds or more, preferably 1 minute or more, and from the viewpoint of suppressing deterioration of the adhesive layer and other components, it is generally 10 minutes or less, preferably 5 minutes or less.

[0364] The decompression treatment involves exposing the adhesive coating layers that are in contact with each other to a pressure of 10–10000 Pa. The decompression treatment time is usually 1–30 minutes.

[0365] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the support substrate and the layers between them, and can make them firmly and tightly bonded. It is usually in the range of 10 to 50,000 N.

[0366] From the viewpoint of achieving sufficient curing speed, the post-heating temperature is preferably 120°C or higher, and from the viewpoint of preventing deterioration of the substrate and each layer, the post-heating temperature is preferably 260°C or lower.

[0367] From the viewpoint of achieving proper bonding between the substrate and the layers constituting the laminate, the post-heating time is usually 1 minute or more, preferably 5 minutes or more. From the viewpoint of suppressing or avoiding adverse effects on each layer caused by excessive heating, the post-heating time is usually 180 minutes or less, preferably 120 minutes or less.

[0368] Heating can be performed using a heating plate, oven, or similar equipment. When using a heating plate for post-heating, either the semiconductor substrate or the support substrate of the laminate can be heated with the substrate facing downwards. From the viewpoint of achieving proper peeling with good reproducibility, it is preferable to heat the substrate with the semiconductor substrate facing downwards.

[0369] It should be noted that one of the purposes of the post-heat treatment is to achieve an adhesive layer that functions as a more suitable self-supporting film, particularly to achieve proper curing based on the hydrosilanization reaction.

[0370] Figure 3A Figure 3C is a diagram illustrating one method for manufacturing a laminated body.

[0371] First, a laminate with an adhesive coating layer 2a is prepared on a semiconductor substrate 1. Figure 3A This laminate can be obtained, for example, by applying an adhesive composition onto a semiconductor substrate 1 and heating it.

[0372] Next, Figure 3A The laminate and support substrate 4 shown are bonded together with the adhesive coating layer 2a in contact with the support substrate 4. Then, after applying a load in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure, a heating device (not shown; heating plate) is placed on the side of the semiconductor substrate 1 opposite to the side in contact with the adhesive coating layer 2a. The adhesive coating layer 2a is heated by the heating device to cure it, transforming it into adhesive layer 2 ( Figure 3B ).

[0373] pass Figures 3A-3B The process shown can yield Figure 1 The layered structure shown.

[0374] <Second Implementation> A laminate with an electronic device layer is used for the fabrication of the electronic device layer. During the fabrication of the electronic device layer, the electronic device layer is bonded to a support substrate. After the fabrication of the electronic device layer, the electronic device layer is separated from the support substrate.

[0375] <<Electronic Devices Layer>> The electronic device layer refers to a layer containing electronic devices. In this invention, it refers to a layer in which multiple semiconductor chip substrates are embedded in the encapsulation resin. That is, it refers to a layer composed of multiple semiconductor chip substrates and encapsulation resin disposed between the semiconductor chip substrates.

[0376] Here, "electronic device" refers to a component that constitutes at least a part of an electronic component. There are no particular limitations on the electronic device; it can be any electronic device with various mechanical structures and circuits formed on the surface of a semiconductor substrate. Preferably, the electronic device is a composite of a component made of metal or semiconductor and a resin that encapsulates or insulates that component. The electronic device can be an electronic device formed by encapsulating or insulating the redistribution layer and / or semiconductor elements or other components described later with encapsulation or insulating materials, and has a single-layer or multi-layer structure.

[0377] <<Support substrate>> As a support substrate, an example of a support substrate that is the same as the support substrate described in the "Support Substrate" section of the above-described "First Embodiment" can be shown.

[0378] <<Release Agent Layer>> The stripper layer is formed using the photo-irradiation stripper composition of the present invention described above.

[0379] The detailed description of the release agent layer is as described in the "Release Agent Layer" section of the above-mentioned "First Embodiment".

[0380] <<Adhesive Layer>> The adhesive layer is formed using the adhesive composition described above.

[0381] The adhesive layer is described in detail in the "Adhesive Layer" section of the above-mentioned "First Embodiment".

[0382] The following description uses the accompanying drawings to illustrate an example of the structure of the laminate in the second embodiment.

[0383] Figure 4 The laminate sequentially comprises: a support substrate 24, an adhesive layer 22, and an electronic device layer 26.

[0384] The electronic device layer 26 has: a plurality of semiconductor chip substrates 21 and an encapsulation resin 25 disposed between the semiconductor chip substrates 21 as an encapsulation material.

[0385] An adhesive layer 22 is disposed between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with both the electronic device layer 26 and the support substrate 24.

[0386] Figure 5 A schematic cross-sectional view showing another example of a laminated body according to the second embodiment.

[0387] Figure 5 The laminate sequentially comprises: a support substrate 24, a release agent layer 23, an adhesive layer 22, and an electronic device layer 26.

[0388] The electronic device layer 26 has: a plurality of semiconductor chip substrates 21 and an encapsulation resin 25 disposed between the semiconductor chip substrates 21 as an encapsulation material.

[0389] An adhesive layer 22 and a release agent layer 23 are disposed between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device layer 26. The release agent layer 23 is in contact with both the adhesive layer 22 and the support substrate 24.

[0390] <<Manufacturing Method of an Example of a Laminated Body in the Second Embodiment>> In the laminated body of the second embodiment Figure 4 The laminate shown is an example. The manufacturing method of the laminate is described below.

[0391] The laminate of the present invention can be manufactured, for example, by a method including the following first to fourth steps.

[0392] The first step is to apply an adhesive composition to the surface of the support substrate to form an adhesive coating layer (and, if necessary, further heat to form the adhesive layer).

[0393] The second process involves placing a semiconductor chip substrate on an adhesive coating layer or adhesive layer, and bonding the semiconductor chip substrate to the adhesive coating layer or adhesive layer while performing at least one of the heat treatment and depressurization treatment.

[0394] The third step is to cure the adhesive coating layer by post-heating.

[0395] The fourth step is to encapsulate the semiconductor chip substrate fixed on the adhesive layer using encapsulating resin.

[0396] If the second step is described in more detail, the steps of the following embodiment (i) can be listed, for example.

[0397] (i) The semiconductor chip substrate is placed on the adhesive coating layer or adhesive layer, and while performing at least one of the heat treatment and the decompression treatment, a load in the thickness direction of the semiconductor chip substrate and the support substrate is applied to make them fit together, thereby attaching the semiconductor chip substrate to the adhesive coating layer or adhesive layer.

[0398] It should be noted that the third step can be performed after the second step of bonding the semiconductor chip substrate to the adhesive coating layer, or it can be performed simultaneously with the second step. For example, the semiconductor chip substrate can be placed on the adhesive coating layer, and while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, the adhesive coating layer can be heated to cure it. This allows for the simultaneous bonding of the semiconductor chip substrate and the adhesive coating layer, as well as the curing of the adhesive coating layer into an adhesive layer, thereby bonding the adhesive layer to the semiconductor chip substrate.

[0399] In addition, the third process can be performed before the second process, or the semiconductor chip substrate can be placed on the adhesive layer, and the adhesive layer can be bonded to the semiconductor chip substrate while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate.

[0400] The coating method, the heating temperature of the coated adhesive composition, the heating method, etc., are as described in the above-described "Manufacturing Method of an Example of a Laminate in the First Embodiment" of the above-described "First Embodiment".

[0401] The manufacturing method of the laminate according to the second embodiment will be further described in detail below with reference to the accompanying drawings. This manufacturing method is used to manufacture... Figure 4 The layered structure shown.

[0402] like Figure 6A As shown, an adhesive coating layer 22' formed of an adhesive composition is formed on the support substrate 24. At this time, the adhesive coating layer 22' can also be formed by heating the adhesive coating layer 22'.

[0403] Next, as Figure 6B As shown, a semiconductor chip substrate 21 is placed on an adhesive layer 22 or an adhesive coating layer 22'. While performing at least one of a heat treatment and a depressurization treatment, a load in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 is applied to bring them into close contact, thus attaching the semiconductor chip substrate 21 to the adhesive layer 22 or the adhesive coating layer 22'. When the semiconductor chip substrate 21 is attached to the adhesive coating layer 22', the adhesive layer 22 is formed by performing a post-heat treatment on the adhesive coating layer 22' to cure it, thereby fixing the semiconductor chip substrate 21 to the adhesive layer 22.

[0404] Next, as Figure 6C As shown, the semiconductor chip substrate 21, which is fixed to the adhesive layer 22, is encapsulated using encapsulating resin 25. Figure 6CIn this process, multiple semiconductor chip substrates 21, which are temporarily bonded to a support substrate 24 by means of an adhesive layer 22, are encapsulated using an encapsulating resin 25. An electronic device layer 26 is formed on the adhesive layer 22, having semiconductor chip substrates 21 and encapsulating resin 25 disposed between the semiconductor chip substrates 21. Thus, the electronic device layer 26 becomes a substrate layer in which multiple semiconductor chip substrates are embedded in the encapsulating resin.

[0405] <<<Packaging Process>>> The semiconductor chip substrate 21 is encapsulated using encapsulation materials.

[0406] As a packaging material for encapsulating a semiconductor chip substrate 21, a component capable of insulating or encapsulating a component made of metal or semiconductor is used.

[0407] In this invention, a resin composition (encapsulating resin) is used as the encapsulation material. There are no particular limitations on the type of encapsulating resin, as long as it can encapsulate and / or insulate a metal or semiconductor; for example, epoxy resins or silicone resins are preferred.

[0408] In addition to resin components, encapsulation materials may also contain other components such as fillers. Examples of fillers include spherical silica particles.

[0409] In the encapsulation process, encapsulating resin, heated to, for example, 130–170°C to maintain a high viscosity, is supplied onto the adhesive layer 22 to cover the semiconductor chip substrate 21, and then compressed and molded, thereby forming a layer of encapsulating resin 25 on the adhesive layer 22. At this time, the temperature conditions are, for example, 130–170°C. Furthermore, the pressure applied to the semiconductor chip substrate 21 is, for example, 50–500 N / cm. 2 .

[0410] (Method for manufacturing processed semiconductor substrates or electronic device layers) If the laminate of the present invention is used, a method for manufacturing a processed semiconductor substrate or a method for manufacturing a processed electronic device layer can be provided.

[0411] The "method for manufacturing a processed semiconductor substrate" uses the laminate described in the "First Embodiment" section above. Furthermore, the "method for manufacturing a processed electronic device layer" uses the laminate described in the "Second Embodiment" section above.

[0412] The method for manufacturing a processed semiconductor substrate will be described in the following <Third Embodiment>, and the method for manufacturing a processed electronic device layer will be described in the following <Fourth Embodiment>.

[0413] <Third Implementation Method> The method for manufacturing the processed semiconductor substrate of the present invention includes steps 5A and 6A as described below. The method for manufacturing the processed semiconductor substrate may further include step 7A as described below.

[0414] Here, step 5A is the process of processing the semiconductor substrate in the laminate described in the <First Embodiment> section above.

[0415] In addition, step 6A is a process that separates the semiconductor substrate processed in step 5A from the support substrate.

[0416] In addition, step 7A is a process of cleaning the processed semiconductor substrate after step 6A.

[0417] The processing performed on the semiconductor substrate in step 5A refers, for example, processing on the opposite side of the circuit surface of the wafer, such as wafer thinning achieved by grinding the back side of the wafer. Then, for example, through-silicon via (TSV) electrodes are formed, and the thinned wafer is peeled from the support substrate to form a wafer stack, which is then three-dimensionally packaged. Furthermore, for example, back-side electrodes are formed before and after this process. During the wafer thinning and TSV processes, the wafer is bonded to the support substrate and subjected to heat of approximately 250–350°C. The stack of the present invention typically includes an adhesive layer and possesses heat resistance to this load.

[0418] It should be noted that the processing is not limited to the above-mentioned processing, and also includes, for example, the semiconductor component mounting process performed when the substrate is temporarily bonded to a support substrate for supporting the semiconductor component.

[0419] In process 6A, there are no particular limitations on the method for separating (peeling) the semiconductor substrate from the support substrate.

[0420] For example, a method of mechanical peeling using a device with a pointed tip (a so-called debonder) can be cited. Specifically, for example, the semiconductor substrate and the support substrate are separated after the pointed tip is inserted between them.

[0421] Furthermore, if the laminate has a release agent layer, in step 6A, the method for separating (peeling) the semiconductor substrate from the support substrate may be to peel it off between the semiconductor substrate and the support substrate after irradiating the release agent layer with light.

[0422] By irradiating the release agent layer with light from the support substrate side, the release agent layer deteriorates as described above (e.g., the release agent layer separates or decomposes). Then, for example, by pulling up either substrate, the semiconductor substrate can be easily separated from the support substrate.

[0423] Irradiation of the release agent layer by light does not necessarily require irradiation of the entire release agent layer. Even if irradiated and unirradiated areas are mixed, as long as the overall release agent layer's peeling ability is sufficiently improved, the semiconductor substrate can be separated from the support substrate by a slight external force, such as pulling up the support substrate. The ratio and positional relationship between the irradiated and unirradiated areas vary depending on the type and specific composition of the adhesive used, the thickness of the adhesive layer, the thickness of the release agent layer, the intensity of the irradiated light, etc., and those skilled in the art can set appropriate conditions without excessive experimentation. Because of this, the method for manufacturing the processed semiconductor substrate according to the present invention, for example when the support substrate of the laminate used is light-transmitting, can shorten the light irradiation time when peeling by irradiating light from the support substrate side. As a result, not only can improved throughput be expected, but physical stress caused by peeling can also be avoided, and the semiconductor substrate can be easily and efficiently separated from the support substrate by light irradiation alone.

[0424] Typically, the light dose used for stripping is 50–3000 mJ / cm². 2 The irradiation time should be determined appropriately based on the wavelength and the amount of irradiation.

[0425] The wavelength of the light used for stripping is preferably 250–600 nm, more preferably 250–370 nm. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The amount of light required for stripping is an amount that can cause appropriate deterioration (e.g., decomposition) of the specific compound and polymer.

[0426] The light used for stripping can be a laser or a non-laser light emitted from a light source such as an ultraviolet lamp.

[0427] The substrate can be cleaned by spraying a cleaning agent composition onto the surface of at least either of the separated semiconductor substrate and the support substrate, or by immersing the separated semiconductor substrate or the support substrate in the cleaning agent composition.

[0428] In addition, adhesive tape or similar materials can be used to clean the surface of processed semiconductor substrates and the like.

[0429] As an example of cleaning the substrate, step 7A can be performed after step 6A to clean the processed semiconductor substrate.

[0430] The following substances are examples of cleaning agent compositions used for cleaning.

[0431] Cleaning agent compositions typically contain solvents.

[0432] Examples of solvents include: lactones, ketones, polyols, compounds with ester bonds, derivatives of polyols, cyclic ethers, esters, and aromatic organic solvents.

[0433] Examples of lactones include γ-butyrolactone.

[0434] Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone.

[0435] Examples of polyols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol.

[0436] Examples of compounds containing ester bonds include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate.

[0437] Examples of polyol derivatives include monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, and other monoalkyl ethers or monophenyl ethers, which are monoalkyl ethers or monophenyl ethers, of the aforementioned polyols or compounds having ester bonds. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred.

[0438] Examples of cyclic ethers include dioxane.

[0439] Examples of esters include: methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc.

[0440] Examples of aromatic organic solvents include: anisole, benzyl ethyl ether, methyl anisole, diphenyl ether, dibenzyl ether, phenethyl ether, phenylbutyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, isopropyltoluene, mesitylene, etc.

[0441] They can be used individually or in combination of two or more.

[0442] Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0443] Furthermore, a mixed solvent prepared by mixing PGMEA with a polar solvent is preferred. The mixing ratio (mass ratio) can be appropriately determined by taking into account the compatibility of PGMEA with the polar solvent, etc. Preferably, it is set in the range of 1:9 to 9:1, and more preferably in the range of 2:8 to 8:2.

[0444] For example, when using EL as a polar solvent, the mass ratio of PGMEA to EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Furthermore, when using PGME as a polar solvent, the mass ratio of PGMEA to PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. Moreover, when using PGME and cyclohexanone as polar solvents, the mass ratio of PGMEA to (PGME + cyclohexanone) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.

[0445] The cleaning agent composition may or may not contain salt. From the perspective of increasing versatility when processing semiconductor substrates using laminates and reducing costs, it is preferable to not contain salt.

[0446] As an example of a cleaning agent composition containing salt, a cleaning agent composition containing quaternary ammonium salt and solvent can be cited.

[0447] Quaternary ammonium salts are composed of quaternary ammonium cations and anions, and there are no particular limitations as long as they are used for this purpose.

[0448] Typical examples of such quaternary ammonium cations include tetra(hydrocarbon)ammonium cations. On the other hand, examples of their paired anions include hydroxide ions (OH-). － ); Fluoride ions (F) － ), chloride ions (Cl) － ), bromide ions (Br) － ), iodide ions (I － Halogen ions such as tetrafluoroborate ions (BF4) － ); hexafluorophosphate ions (PF6) － (etc.), but not limited to these.

[0449] The quaternary ammonium salt is preferably a halogenated quaternary ammonium salt, and more preferably a fluorine-containing quaternary ammonium salt.

[0450] In quaternary ammonium salts, halogen atoms can be contained in cations or anions, preferably in anions.

[0451] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride.

[0452] Specific examples of hydrocarbon groups in tetra(hydrocarbon)ammonium fluoride include: alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, alkynyl groups with 2 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms.

[0453] In a more preferred embodiment, the tetra(hydrocarbon) fluoride comprises tetraalkyl fluoride.

[0454] Specific examples of tetraalkylammonium fluoride include: tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride), etc., but are not limited to these. Among them, tetrabutylammonium fluoride is preferred.

[0455] Quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride can also be used in hydrate form. In addition, quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride can be used alone or in combination of two or more.

[0456] There are no particular limitations on the amount of quaternary ammonium salt, as long as it is dissolved in the solvent contained in the cleaning agent composition, which is typically 0.1 to 30% by mass relative to the cleaning agent composition.

[0457] When the cleaning agent composition contains salt, there are no particular limitations on the solvent used, as long as it is used for this purpose and dissolves salts such as quaternary ammonium salts. From the viewpoint of obtaining a cleaning agent composition with excellent cleaning properties with good reproducibility, and from the viewpoint of obtaining a cleaning agent composition with excellent uniformity by good dissolution of salts such as quaternary ammonium salts, the cleaning agent composition preferably contains one or more amide solvents.

[0458] As a preferred example of an amide solvent, an amide derivative represented by formula (Z) can be cited. In the formula, R 0 The symbol represents ethyl, propyl, or isopropyl, with ethyl or isopropyl being preferred, and ethyl being more preferred. R A and R B Each alkyl group independently represents an alkyl group having 1 to 4 carbon atoms. Alkyl groups having 1 to 4 carbon atoms can be any type of linear, branched, or cyclic form, specifically including: methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, etc. Among these, R... A and R B Preferably, it is methyl or ethyl, more preferably both are methyl or ethyl, and even more preferably both are methyl.

[0459] Examples of amide derivatives represented by formula (Z) include: N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyramide, N,N-diethylbutyramide, N-ethyl-N-methylbutyramide, N,N-dimethylisobutyramide, N,N-diethylisobutyramide, and N-ethyl-N-methylisobutyramide. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyramide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

[0460] The amide derivatives shown in formula (Z) can be synthesized by substitution reaction of the corresponding carboxylic acid ester with an amine, or by using commercially available products.

[0461] Another example of a preferred amide solvent is a lactam compound represented by formula (Y). In formula (Y), R 101 R represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms. 102 This refers to alkylene groups having 1 to 6 carbon atoms. Specific examples of alkyl groups having 1 to 6 carbon atoms include: methyl, ethyl, n-propyl, n-butyl, etc. Specific examples of alkylene groups having 1 to 6 carbon atoms include: methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc., but are not limited to these.

[0462] Specific examples of the lactam compounds represented by formula (Y) include: α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc., which can be used alone or in combination of two or more.

[0463] In a preferred embodiment, the lactam compound represented by formula (Y) comprises 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment it comprises N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in a further preferred embodiment it comprises N-methylpyrrolidone (NMP).

[0464] It should be noted that the cleaning agent composition used in this invention may also contain water as a solvent, but from the viewpoint of avoiding substrate corrosion, etc., it is generally intentionally used only as an organic solvent. It should be noted that in this case, the presence of hydrated water containing salt in the cleaning agent composition or trace amounts of water contained in the organic solvent is not excluded. The water content of the cleaning agent composition used in this invention is generally 5% by mass or less.

[0465] Regarding the constituent elements and methodological elements related to the above-described steps of the method for manufacturing the processed semiconductor substrate of the present invention, various modifications can be made as long as they do not depart from the spirit of the present invention.

[0466] The manufacturing method of the processed semiconductor substrate of the present invention may also include steps other than those described above.

[0467] One example of the peeling method of the present invention is that, when the semiconductor substrate or support substrate of the laminate of the present invention is transparent, the semiconductor substrate of the laminate is separated from the support substrate by irradiating the peeling agent layer with light from the semiconductor substrate side or the support substrate side.

[0468] In one example of the laminate of the present invention, the semiconductor substrate and the support substrate are appropriately and temporarily bonded in a peelable manner by an adhesive layer and a release agent layer. Therefore, for example, if the support substrate is light-transmitting, the semiconductor substrate and the support substrate can be easily separated by irradiating the release agent layer from the support substrate side of the laminate. Typically, the peeling is performed after the semiconductor substrate of the laminate has been processed.

[0469] use Figures 7A to 7D An example of the third embodiment will be described. This example is an example of manufacturing a thinned semiconductor substrate.

[0470] First, prepare the stacked body ( Figure 7A This laminate is with Figure 1 and Figure 3B The stack shown is the same as the stack shown.

[0471] Next, a polishing apparatus (not shown) is used to polish the side of the semiconductor substrate 1 opposite to the side in contact with the adhesive layer 2, thereby thinning the semiconductor substrate 1. Figure 7B It should be noted that through-electrodes can also be formed on the thinned semiconductor substrate 1.

[0472] Next, using a peeling device (not shown), the thinned semiconductor substrate 1 is separated from the support substrate 4. Figure 7C ).

[0473] Thus, a thinned semiconductor substrate 1 is obtained. Figure 7D ).

[0474] Sometimes, residue of the adhesive layer 2 remains on the thinned semiconductor substrate 1. Therefore, it is preferable to clean the thinned semiconductor substrate 1 with a cleaning agent composition to remove the residue of the adhesive layer 2 from the semiconductor substrate 1.

[0475] <Fourth Implementation> The method for manufacturing the processed electronic device layer of the present invention includes steps 5B and 6B as described below. The method for manufacturing the processed electronic device layer may further include step 7B as described below.

[0476] Here, step 5B is the process of processing the electronic device layer in the laminate described in the <Second Embodiment> section above.

[0477] In addition, step 6B is a process that separates the electronic device layer processed in step 5B from the support substrate.

[0478] In addition, step 7B is the process of cleaning the processed electronic device layer after step 6B.

[0479] The following uses Figures 8A to 8F Specific examples of the fourth implementation method will be described.

[0480] The processing performed on the electronic device layer in process 5B can include, for example, grinding and wiring layer formation.

[0481] <<Grinding Process>> The grinding process is a process of grinding the resin portion of the encapsulation resin 25 layer in the electronic device layer 26 with a portion of the semiconductor chip substrate 21 exposed.

[0482] Grinding of the encapsulating resin portion, for example, Figure 8B As shown, by Figure 8A The encapsulating resin 25 of the laminate shown is ground to a thickness approximately the same as that of the semiconductor chip substrate 21. It should be noted that... Figure 8A The stacked body shown is with Figure 4 and Figure 6C The stack shown is the same as the stack shown.

[0483] <<Wireline Layer Formation Process>> The wiring layer formation process is a process of forming a wiring layer on the exposed semiconductor chip substrate 21 after the above-mentioned grinding process.

[0484] exist Figure 8C In this process, a wiring layer 28 is formed on an electronic device layer 26, which is composed of a semiconductor chip substrate 21 and an encapsulating resin 25.

[0485] The wiring layer 28, also known as the RDL (Redistribution Layer), is a thin-film wiring structure that forms the wiring for connection to the substrate. It can have a single-layer or multi-layer structure. The wiring layer can utilize a conductor (such as metals like aluminum, copper, titanium, nickel, gold, and silver, as well as alloys like silver-tin alloys) on a dielectric (silicon oxide (SiO2)). x It is formed by wiring between photosensitive resins such as photosensitive epoxy resin, but is not limited to this.

[0486] The following methods can be listed as examples of methods for forming the wiring layer 28.

[0487] First, silicon oxide (SiO2) is formed on the layer of encapsulating resin 25. xThe dielectric layer consists of a photosensitive resin and other dielectric layers. The dielectric layer formed from silicon oxide can be formed, for example, by sputtering or vacuum evaporation. The dielectric layer formed from photosensitive resin can be formed, for example, by applying the photosensitive resin onto the encapsulating resin 25 layer using methods such as spin coating, dip coating, roller blade coating, spraying, or slot coating.

[0488] Next, wiring is formed on the dielectric layer using a conductive material such as a metal. Methods for forming the wiring include, for example, well-known semiconductor processes such as photolithography (resist photolithography) and etching. Examples of such photolithography processes include photolithography using a positive resist material and photolithography using a negative resist material.

[0489] In the manufacturing method of the laminate according to the fourth embodiment, bumps may be further formed or components may be mounted on the wiring layer 28. Components may be mounted on the wiring layer 28, for example, using a pick-and-place machine.

[0490] The laminate in the fourth embodiment can be a laminate manufactured in a process based on the following technique: a fan-out technique in which terminals provided on a semiconductor chip substrate are mounted on a wiring layer that extends beyond the chip area.

[0491] In process 6B, methods for separating (peeling) the electronic device layer from the support substrate include, but are not limited to, mechanical peeling using a tool with a sharp point, tearing and peeling between the support and the electronic device layer.

[0492] When the laminate has a release agent layer, for example, by irradiating the release agent layer with light from the support substrate side, the release agent layer deteriorates as described above (e.g., the release agent layer separates or decomposes), and then, for example, by pulling up either substrate, the electronic device layer can be easily separated from the support substrate.

[0493] Figures 8D to 8E This is a schematic cross-sectional view used to illustrate the separation method of laminated bodies. Figure 8F This is a schematic cross-sectional view used to illustrate the cleaning method after the separation of laminates. It can be viewed through... Figures 8D to 8F An embodiment of a method for manufacturing a semiconductor package (electronic component) will be described.

[0494] like Figure 8D and Figure 8E As shown, the process of separating the laminate is a process of using a peeling device (not shown) to separate the electronic device layer 26 from the support substrate 24.

[0495] The substrate can be cleaned by spraying a cleaning agent composition onto the surface of at least one of the separated electronic device layer and the support substrate, or by immersing the separated electronic device layer or the support substrate in the cleaning agent composition.

[0496] In addition, it can also be used to clean the surface of processed electronic device layers, etc., by removing adhesive tape.

[0497] For example, in Figure 8E In the process, after the separation step, an adhesive layer 22 is attached to the electronic device layer 26. The adhesive layer 22 can be removed by decomposing it using a cleaning agent composition such as an acid or alkali. By removing the adhesive layer, a suitable product can be obtained... Figure 8F The processed electronic device layer (electronic component) is shown.

[0498] Regarding the constituent elements and method elements related to the above-described steps of the method for manufacturing the processed electronic device layer of the present invention, various modifications can be made as long as they do not depart from the spirit of the present invention.

[0499] The manufacturing method of the processed electronic device layer of the present invention may also include processes other than those described above.

[0500] Example The present invention will be described in more detail below with reference to specific embodiments, but the present invention is not limited to the embodiments described below. It should be noted that the apparatus used is as described below.

[0501] [Apparatus] (1) Stirring rotor: AS ONE Corporation VMR-5R stirring rotor.

[0502] (2) Mixer: ARE-500 self-rotating and revolution-rotating mixer manufactured by THINKY Corporation.

[0503] (3) Vacuum bonding device: SUSS MicroTec Co., Ltd., XBS300.

[0504] (4) Manual stripping device: SUSS MicroTec Co., Ltd., manual debonding machine.

[0505] (5) Contact angle meter: Kyowa Interface Science Co., Ltd., DM701.

[0506] [1] Preparation of adhesive composition [Preparation Example 1] Add 2.54 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.54 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie Co., Ltd.), and 5.09 g of p-menthane to a 50 ml screw tube, and stir with a stirring rotor for 10 minutes to obtain mixture (I).

[0507] Mixture (II) was prepared by mixing vinyl-containing MQ resin (manufactured by Wacker Chemie) (S1), vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 200 mPa·s (S2), and SiH-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 100 mPa·s (S3).

[0508] 1.70 g of mixture (I), 117.1 g of vinyl-containing MQ resin (manufactured by Wacker Chemie) dissolved in menthol at a solid content of 86.0% by mass, 38.3 g of mixture (II), and 15.9 g of SiH-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 100 mPa·s were added to a 300 mL mixing container for a rotary mixer. The mixture was stirred for 5 minutes to obtain mixture (III). 0.07 g of platinum catalyst (manufactured by Wacker Chemie) and 21.5 g of epoxy-containing polyorganosiloxane X-22-343 (manufactured by Shin-Etsu Chemical) were added to mixture (III). The mixture was stirred for 5 minutes to obtain adhesive composition (1).

[0509] [Preparation Example 2] Add 2.54 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.54 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie Co., Ltd.), and 5.09 g of p-menthane to a 50 ml screw tube, and stir with a stirring rotor for 10 minutes to obtain mixture (I).

[0510] Mixture (II) was prepared by mixing vinyl-containing MQ resin (manufactured by Wacker Chemie) (S1), vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 200 mPa·s (S2), and SiH-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 100 mPa·s (S3).

[0511] 1.70 g of mixture (I), 117.1 g of vinyl-containing MQ resin (manufactured by Wacker Chemie) dissolved in menthol (with a solid content of 86.0% by mass), 38.3 g of mixture (II), and 15.9 g of SiH-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 100 mPa·s were added to a 300 mL mixing container for a rotary mixer. The mixture was stirred for 5 minutes to obtain mixture (III). 0.07 g of platinum catalyst (manufactured by Wacker Chemie) and 21.5 g of phenyl-containing polyorganosiloxane PMM-1043 (manufactured by Gelest) were added to mixture (III). The mixture was stirred for 5 minutes to obtain adhesive composition (2).

[0512] [2] Preparation of the composition for contact angle evaluation [Preparation Example 3] 0.3 g of epoxy-containing polyorganosiloxane (X-22-343, Shin-Etsu Chemical) and 29.3 g of hexamethyldisiloxane were placed in a 50 ml screw tube and stirred for 10 minutes with a stirring rotor to obtain the evaluation sample (1).

[0513] [Preparation Example 4] 0.3 g of phenyl-containing polyorganosiloxane (PMM-1043, manufactured by Gelest) and 29.3 g of hexamethyldisiloxane were placed in a 50 ml screw tube and stirred for 10 minutes with a stirring rotor to obtain the evaluation sample (2).

[0514] [3] Contact angle evaluation [Determination 1-1: Surface free energy B-1 of the stripping agent component] For a 4-inch bare silicon wafer spin-coating evaluation sample (1), an epoxy-containing polyorganosiloxane (X-22-343, manufactured by Shin-Etsu Chemical) was formed into a film. The contact angles of the formed wafers were evaluated using a contact angle meter (Kyowa Interface Science Co., Ltd.), with water and diiodomethane added separately. Based on the results obtained here, the surface free energy of the epoxy-containing polyorganosiloxane (X-22-343, manufactured by Shin-Etsu Chemical), which is a component of the stripping agent, was calculated.

[0515] Specifically, in an environment of 23°C and 55% RH, water or diiodomethane is placed in the syringe of the contact angle meter, and one drop is added from a height of 1.0 cm onto the wafer after film formation. The contact angle meter's automatic resolution function is used to calculate the contact angle 10 seconds after the drop.

[0516] The surface free energy is determined based on the contact angle between water and diiodomethane. The surface free energy is calculated using a static method. The theoretical formula for the surface free energy is the Owens and Wendt equation.

[0517] The surface free energy of the epoxy-containing polyorganosiloxane (X-22-343, manufactured by Shin-Etsu Chemical) is 55 mN / m.

[0518] [Determination 1-2: Surface free energy B-2 of the stripping agent component] Evaluation sample (2) was used. In addition, the surface free energy of the phenyl-containing polyorganosiloxane (PMM-1043, manufactured by Gelest) which is a stripping agent component was determined by the same method as determination 1-1.

[0519] The surface free energy of the phenyl-containing polyorganosiloxane (PMM-1043, manufactured by Gelest) is 37 mN / m.

[0520] [Measurement 2-1: Surface free energy A-1 of the device substrate] The contact angles of the bare silicon wafer (device substrate No. 1) were evaluated using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) by adding water and diiodomethane respectively. Based on the results obtained here, the surface free energy of the device substrate was calculated.

[0521] Specifically, in an environment of 23°C and 55% RH, water or diiodomethane is placed in the syringe of a contact angle meter, and one drop is dropped onto the device substrate from a height of 1.0 cm. The contact angle is then calculated 10 seconds after the drop is dropped using the automatic resolution function of the contact angle meter.

[0522] The surface free energy is determined based on the contact angle between water and diiodomethane. The surface free energy is calculated using a static method. The theoretical formula for the surface free energy is the Owens and Wendt equation.

[0523] The surface free energy of a bare silicon wafer is 64 mN / m.

[0524] [Measurement 2-2: Surface free energy A-2 of the device substrate] A silicon wafer with SiN vapor deposited (device substrate No. 2) was used. Otherwise, the surface free energy of the device substrate was determined by the same method as that used in determination 2-1.

[0525] The surface free energy of a silicon wafer coated with SiN is 62 mN / m.

[0526] [Measurement 2-3: Surface free energy A-3 of the device substrate] A silicon wafer with electrodes coated with SiN (device substrate No. 3) was used. Otherwise, the surface free energy of the device substrate was determined by the same method as that used in determination 2-1.

[0527] The surface free energy of a silicon wafer with electrodes coated with SiN is 66 mN / m.

[0528] It should be noted that the silicon wafer with electrodes coated with SiN has an area ratio of 91% for the SiN deposition surface and 9% for the electrode surface, consisting of a SiN deposition surface without electrodes and an electrode surface with electrodes on the SiN deposition surface. Therefore, regarding the surface free energy of the silicon wafer with electrodes coated with SiN, the surface free energy of the SiN deposition surface (68 mN / m) and the surface free energy of the electrode surface (42 mN / m) are calculated separately, and then weighted by the area ratio of the SiN deposition surface to the electrode surface. Specifically, this is calculated using the following formula.

[0529] Surface free energy (66 mN / m) = 68 mN / m × 0.91 + 42 mN / m × 0.09 [Measurement 2-4: Surface free energy A-4 of the device substrate] A silicon wafer coated with Cu (device substrate No. 4) was used. Otherwise, the surface free energy of the device substrate was determined by the same method as that used in determination 2-1.

[0530] The surface free energy of a silicon wafer coated with Cu is 34 mN / m.

[0531] [Measurement 2-5: Surface free energy A-5 of the device substrate] A silicon wafer with polyimide film (device substrate No. 5) was used. Otherwise, the surface free energy of the device substrate was determined by the same method as that used in determination 2-1.

[0532] The surface free energy of the silicon wafer with polyimide film is 44 mN / m.

[0533] [4] Evaluation of the fabrication of laminated bodies [Example 1] To form a temporary adhesive layer on a 300mm bare silicon wafer (device substrate No. 1, thickness: 775μm) serving as the device-side wafer, the adhesive composition (1) described above was spin-coated and then heated at 120°C for 1 minute to form an adhesive coating layer (1) with a thickness of approximately 50μm on the circuit surface of the wafer. The wafer with the adhesive coating layer (1) was then bonded to a 300mm silicon wafer (thickness: 775μm) serving as the carrier-side wafer (support) in a vacuum bonding apparatus (manufactured by SUSS MicroTec, manual bonding machine) while holding the adhesive coating layer (1). A post-heat treatment was performed at 200°C for 10 minutes to create a laminate. It should be noted that the bonding was performed at a temperature of 23°C and a pressure reduction of 1500Pa. To confirm peelability, the force required for peeling was measured using a peeling apparatus (manufactured by SUSS MicroTec, manual debonding machine). Regarding cases where peeling is successful, a good result is indicated by the force required for peeling, expressed numerically. Cases where peeling fails are considered unsatisfactory and are marked with "×". Furthermore, when verifying peelability, the peeling interface is examined. If the force required for peeling is less than 25 N, it is considered to indicate good peelability and is marked with "0". If the force required for peeling exceeds 25 N, it is considered that a load was applied during peeling and is marked with "×". The results are shown in Table 1.

[0534] [Example 2] A silicon wafer with SiN vapor-deposited coating (device substrate No. 2) was used as the device-side wafer. Apart from this, other experimental procedures were performed using the same methods as in Example 1, including the fabrication and peeling evaluation of the laminate. The results are shown in Table 1.

[0535] [Example 3] A silicon wafer with electrodes coated with SiN (device substrate No. 3) was used as the device-side wafer. Apart from this, other experimental procedures were performed using the same methods as in Example 1, including the fabrication and peeling evaluation of the laminate. The results are shown in Table 1.

[0536] [Comparative Example 1] A silicon wafer with Cu vapor deposition (device substrate No. 4) was used as the device-side wafer. Apart from this, other experimental procedures were performed using the same methods as in Example 1, including the fabrication and peeling evaluation of the laminate. The results are shown in Table 1.

[0537] [Comparative Example 2] Adhesive composition (1) was changed to adhesive composition (2). Apart from this, the laminate was fabricated and peel evaluation was performed using the same method as in Example 1. The results are shown in Table 1.

[0538] [Comparative Example 3] A silicon wafer with SiN vapor-deposited coating (device substrate No. 2) was used as the device-side wafer. Apart from this, the same methods were used as in Comparative Example 2 for the fabrication and peel evaluation of the laminate. The results are shown in Table 1.

[0539] [Comparative Example 4] A silicon wafer with electrodes coated with SiN (device substrate No. 3) was used as the device-side wafer. Apart from this, the same methods were used for fabrication and peel evaluation of the laminate as in Comparative Example 2. The results are shown in Table 1.

[0540] [Example 4] A silicon wafer with polyimide film (device substrate No. 5) was used as the device-side wafer. Apart from this, the same method was used as in Comparative Example 2 for the fabrication and peel evaluation of the laminate. The results are shown in Table 1.

[0541] [Example 5] A silicon wafer with Cu vapor deposition (device substrate No. 4) was used as the device-side wafer. Apart from this, the same methods were used as in Comparative Example 2 for the fabrication and peel evaluation of the laminate. The results are shown in Table 1. Explanation of reference numerals in the attached figures 1: Semiconductor substrate; 2: Adhesive layer; 2a: Adhesive coating layer; 3: Release agent layer; 4: Support substrate; 21: Semiconductor chip substrate; 22: Adhesive layer; 22': Adhesive coating layer; 23: Release agent layer; 24: Support substrate; 25: Encapsulation resin; 26: Electronic device layer; 28: Wiring layer.

Claims

1. An adhesive composition for forming an adhesive layer for temporarily bonding a semiconductor substrate or electronic device layer to a support substrate. The adhesive composition contains a release agent component. The absolute value of the difference between the surface free energy A of the semiconductor substrate or the electronic device layer and the surface free energy B of the stripping agent component, A-B, is less than 20 mN / m.

2. The adhesive composition according to claim 1, wherein, The absolute value of the difference A-B is less than 15 mN / m.

3. The adhesive composition according to claim 1, wherein, The stripping agent contains polyorganosiloxane.

4. The adhesive composition according to claim 1, wherein, The adhesive composition contains adhesive components.

5. The adhesive composition according to claim 4, wherein, The adhesive component is a component that is cured through a hydrogenation silanization reaction.

6. The adhesive composition according to claim 5, wherein, The component cured by the hydrogenation silanization reaction contains: Composition A-1 has an alkenyl group with 2 to 40 carbon atoms bonded to silicon atoms; Component A-2 containing Si-H groups; and Platinum group metal catalyst A-3.

7. The adhesive composition according to claim 6, wherein, The component A-1 contains: a polyorganosiloxane a1 having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms.

8. The adhesive composition according to claim 6, wherein, The component A-2 contains: a polyorganosiloxane having Si-H groups.

9. A laminated body having: Semiconductor substrate or electronic device layer; Support substrate; and An adhesive layer disposed between the semiconductor substrate or the electronic device layer and the support substrate. The adhesive layer is an adhesive layer formed from the adhesive composition as described in any one of claims 1 to 8.

10. A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: A 5A step for processing the semiconductor substrate of the laminate as claimed in claim 9, or a 5B step for processing the electronic device layer of the laminate as claimed in claim 9; and The sixth step is either the process of separating the semiconductor substrate processed by the fifth step from the support substrate, or the sixth step is either the process of separating the electronic device layer processed by the fifth step from the support substrate.

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