Method for manufacturing processed semiconductor substrate, and method for manufacturing laminate

Abstract

To provide a method for manufacturing a processed semiconductor substrate in which a process for processing a semiconductor substrate is shortened.SOLUTION: The method for manufacturing a processed semiconductor substrate includes the steps of: preparing a laminate having a semiconductor substrate and a resin layer formed on the semiconductor substrate, a surface of the resin layer opposite to the semiconductor substrate side being exposed; processing the semiconductor substrate of the laminate, the resin layer being a resin layer formed from a resin composition including a component (A) as a component cured by a hydrosilylation reaction.SELECTED DRAWING: Figure 2B

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a processed semiconductor substrate and a method for manufacturing a stack. [Background technology]

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

[0003] Semiconductor wafers (herein simply referred to as wafers) before thinning are bonded to a support in preparation for polishing with a polishing device. This bond must be easily peeled off after polishing, and is therefore called a temporary bond. This temporary bond must be easily removed from the support; applying a large force to remove it can cause the thinned semiconductor wafer to break or deform, so it must be easily removed to prevent this from happening. However, it is undesirable for the temporary bond to become dislodged or shifted due to the polishing stress during polishing of the backside of the semiconductor wafer. Therefore, the performance required of the temporary bond is that it can withstand the stress during polishing and be easily removed after polishing.

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

[0005] [Patent Document 1] International Publication No. 2017 / 221772 Brochure [Patent Document 2] International Publication No. 2018 / 216732 Brochure Summary of the Invention [Problem to be solved by the invention]

[0006] In Patent Documents 1 and 2, when processing a semiconductor wafer (semiconductor substrate), a laminate in which a semiconductor wafer, an adhesive layer, and a support are laminated is used.

[0007] As semiconductor integration advances and the number of steps in semiconductor manufacturing increases, problems arise such as longer manufacturing times and higher manufacturing costs. Therefore, from the perspective of shortening manufacturing times and reducing manufacturing costs, simplification of each process is required.

[0008] An object of the present invention is to provide a technology that enables shortening of the process steps when processing a semiconductor substrate. That is, an object of the present invention is to provide a method for manufacturing a processed semiconductor substrate that shortens the process steps when processing a semiconductor substrate, and a method for manufacturing a laminate that produces a laminate that enables shortening of the process steps when processing a semiconductor substrate. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0010] That is, the present invention includes the following. [1] A method for manufacturing a processed semiconductor substrate, comprising: a step of preparing a laminate having a semiconductor substrate and a resin layer formed on the semiconductor substrate, the surface of the resin layer opposite to the semiconductor substrate being exposed; a step in which the semiconductor substrate of the stack is processed; Including, The resin layer is a resin layer formed from a resin composition containing a component (A) that cures by a hydrosilylation reaction. A method for manufacturing a processed semiconductor substrate. [2] The component (A) is a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom; a polyorganosiloxane (a2) having Si-H groups; a catalyst (A2); The method for producing a processed semiconductor substrate according to [1], comprising: [3] The method for producing a processed conductor-laminated substrate according to [1] or [2], wherein the resin layer in the laminate subjected to the processing step has a thickness of 100 μm to 500 μm. [4] The method for manufacturing a processed semiconductor substrate according to any one of [1] to [3], wherein the processing step includes grinding the surface of the semiconductor substrate opposite to the resin layer side to thin the semiconductor substrate. [5] A method for manufacturing a processed semiconductor substrate according to any one of [1] to [4], wherein in the processing step, the surface of the resin layer opposite to the semiconductor substrate side is brought into contact with a fixing member, thereby fixing the laminate to the fixing member. [6] The method for manufacturing a processed semiconductor substrate according to [5], wherein the fixing member is a vacuum chuck. [7] The step of preparing the laminate applying the resin composition onto the semiconductor substrate to form a coating layer; a step of flattening the surface of the coating layer to form the resin layer; A method for producing a processed semiconductor substrate according to any one of [1] to [6], comprising: [8] A method for manufacturing a laminate having a semiconductor substrate and a resin layer formed on the semiconductor substrate, comprising: a step of applying a resin composition onto the semiconductor substrate to form a coating layer; a step of flattening the surface of the coating layer to form the resin layer; A method for producing a laminate, comprising: [9] The method for producing a laminate according to [8], wherein the resin composition contains a component (A) that cures by a hydrosilylation reaction.

[10] The component (A) a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom; a polyorganosiloxane (a2) having Si-H groups; a catalyst (A2); The method for producing a laminate according to [9], comprising:

[11] The method for manufacturing a laminate according to any one of [8] to

[10] , wherein the laminate is a laminate for processing the semiconductor substrate.

[12] The method for manufacturing a laminate according to

[11] , wherein the processing of the semiconductor substrate includes grinding the surface of the semiconductor substrate opposite to the resin layer side to thin the semiconductor substrate.

[13] The method for producing a laminate according to any one of [8] to

[12] , wherein the difference (Tc-Tr) between the thickness (Tc) of the coating layer and the thickness (Tr) of the resin layer is 5 μm to 200 μm. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a technique that enables the shortening of the process steps when processing a semiconductor substrate. That is, according to the present invention, it is possible to provide a method for manufacturing a processed semiconductor substrate that shortens the process steps when processing a semiconductor substrate, and a method for manufacturing a stack that manufactures a stack that enables the shortening of the process steps when processing a semiconductor substrate. [Brief explanation of the drawings]

[0012] [Figure 1A] FIG. 1A is a schematic cross-sectional view (part 1) illustrating an example of a method for producing a laminate. [Figure 1B] FIG. 1B is a schematic cross-sectional view (part 2) illustrating an example of a method for producing a laminate. [Figure 1C] FIG. 1C is a schematic cross-sectional view for explaining one example of a method for producing a laminate (part 3). [Figure 1D] FIG. 1D is a schematic cross-sectional view for explaining one example of a method for producing a laminate (part 4). [Figure 2A]FIG. 2A is a schematic cross-sectional view (part 1) for explaining an example of a method for manufacturing a processed semiconductor substrate. [Figure 2B] FIG. 2B is a schematic cross-sectional view (part 2) for explaining one example of a method for manufacturing a processed semiconductor substrate. [Figure 2C] FIG. 2C is a schematic cross-sectional view (part 3) for explaining one example of a method for manufacturing a processed semiconductor substrate. DETAILED DESCRIPTION OF THE INVENTION

[0013] (Method for manufacturing a processed semiconductor substrate and a laminate) The method of manufacturing a processed semiconductor substrate of the present invention includes a preparation step and a processing step. The preparation step is a step of preparing a laminate having a semiconductor substrate and a resin layer, with the surface of the resin layer opposite to the semiconductor substrate side being exposed. The processing step is a step in which the semiconductor substrate of the stack is processed. In the method for producing a processed semiconductor substrate, the resin layer is a resin layer formed from a resin composition containing component (A) that cures by a hydrosilylation reaction.

[0014] According to the method for manufacturing a processed semiconductor substrate of the present invention, when processing a semiconductor substrate, a laminate having a semiconductor substrate and a resin layer is used, rather than a laminate having a semiconductor substrate, an adhesive layer, and a support (e.g., a silicon wafer or a glass wafer). By doing so, the support is no longer necessary, and the process of laminating the support is not required when manufacturing the laminate. Furthermore, the need for an expensive support is eliminated, thereby reducing costs. Furthermore, the process of separating the semiconductor substrate from the support after processing the semiconductor substrate is no longer necessary. The process of separating the semiconductor substrate from the support is performed, for example, by mechanical peeling using a debonder.

[0015] The method for manufacturing a processed semiconductor substrate may include other steps, such as a cleaning step.

[0016] The method for producing a laminate of the present invention includes a coating layer forming step and a resin layer forming step. The laminate to be manufactured includes a semiconductor substrate and a resin layer formed on the semiconductor substrate. The coating layer forming step is a step of applying a resin composition onto a semiconductor substrate to form a coating layer. The resin layer forming step is a step of flattening the surface of the coating layer to form a resin layer.

[0017] In the laminate used in the method for manufacturing a processed semiconductor substrate of the present invention, the surface of the resin layer opposite the semiconductor substrate side is preferably flat. This is because if the surface of the resin layer is not flat, the flatness of the processed surface of the semiconductor substrate will be reduced when the semiconductor substrate is processed (particularly thinned). For example, if the surface of the resin layer is not flat and has recessed (thin) areas, the areas of the processed surface of the semiconductor substrate corresponding to the recessed (thin) areas will be recessed during processing (thinning) due to the influence of the thin resin layer. Because the grinding stone has difficulty contacting the recessed areas of the processed surface during grinding, the recessed areas are less likely to be thinned compared to other areas. As a result, the recessed areas of the processed surface will be relatively thicker than other areas, reducing the flatness of the processed surface of the semiconductor substrate. If the flatness of the processed surface of the semiconductor substrate is reduced, poor bonding will occur when the processed semiconductor substrate is bonded to another substrate. On the other hand, simply applying a resin composition often does not result in a flat coating layer, for example, the thickness of the coating layer on the edge of the semiconductor substrate tends to be thicker than the thickness of the coating layer on the center of the semiconductor substrate. Therefore, in the method for producing a laminate of the present invention, the surface of the coating layer is flattened when the resin composition is applied to form a resin layer, thereby producing a laminate suitable for use in a method for producing a processed semiconductor substrate. When the method for manufacturing a processed semiconductor substrate of the present invention is carried out using a planarized resin layer, the flatness of the processed surface of the semiconductor substrate is improved, and as a result, when the processed semiconductor substrate is bonded to another substrate, bonding defects due to unevenness can be prevented. Furthermore, when the method for manufacturing a processed semiconductor substrate of the present invention is carried out using a planarized resin layer, it is expected that the flatness of the processed surface of the semiconductor substrate will be better than when a method for manufacturing a semiconductor substrate is carried out using a laminate in which a semiconductor substrate, an adhesive layer, and a support are laminated in this order, because the adhesive layer is not usually planarized when manufacturing a laminate in which a semiconductor substrate, an adhesive layer, and a support are laminated in this order.

[0018] Below, the method for manufacturing the laminate will be described in detail as the method for manufacturing the processed semiconductor substrate is described.

[0019] <Preparation process> The preparation step is a step in which a laminate is prepared. The laminate includes a semiconductor substrate and a resin layer. In the laminate, the surface of the resin layer opposite to the semiconductor substrate side is exposed. "Exposed" means that the surface of the resin layer opposite to the semiconductor substrate side is not in contact with a solid (e.g., a support). In other words, the laminate does not include a support. The laminate can be prepared, for example, by manufacturing the laminate. The method for producing the laminate includes, for example, a coating layer forming step and a resin layer forming step.

[0020] <<Coating layer formation process>> The coating layer forming step is a step of applying a resin composition onto a semiconductor substrate to form a coating layer.

[0021] The method for applying the resin composition is not particularly limited, but is usually a spin coating method. When the resin composition contains a solvent, the applied resin composition is usually heated. The heating temperature cannot be generally defined because it varies depending on the types and amounts of components contained in the resin composition, whether a solvent is contained, the boiling point of the solvent used, the desired thickness of the coating layer, etc., but is usually 80 to 250°C, and the heating time is usually 30 seconds to 15 minutes. The heating temperature may be increased in stages. Heating can be carried out using a hot plate, an oven, or the like.

[0022] When the resin composition is a curable resin composition, the curing component may be cured by heating when forming the coating layer, or the coating layer may be flattened and then heated to cure the curing component. It is preferable to harden the hardening component by heating when forming the coating layer. If the coating layer is soft, the coating layer will deform when flattening the surface of the coating layer, making flattening difficult. If the hardening component is hardened by heating when forming the coating layer, the coating layer will become hard. Therefore, if the coating layer is hardened, the surface of the coating layer will be more easily flattened when flattening.

[0023] The thickness of the coating layer is not particularly limited, but is preferably 50 μm to 500 μm, more preferably 100 μm to 450 μm, and particularly preferably 150 μm to 400 μm. In the present invention, the thickness of the coating layer is the average thickness of the entire coating layer measured using a non-contact, spectral interference film thickness measuring device (for example, an optical film thickness meter manufactured by Otsuka Electronics Co., Ltd., SF-3000M). The same applies to the thickness of the resin layer. Using an Otsuka Electronics optical film thickness meter (SF-3000M), the thickness of the entire coating layer or resin layer on the semiconductor substrate can be mapped by scanning the measurement probe from the edge of the semiconductor substrate toward the center while rotating the semiconductor substrate.

[0024] If the thickness of the coating layer obtained by applying and heating the resin composition once does not reach the desired thickness, the resin composition may be applied and heated multiple times to form a coating layer of the desired thickness.

[0025] <<<Semiconductor substrates>>> The main material constituting the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, but examples thereof include silicon, silicon carbide, and compound semiconductors. The shape of the semiconductor substrate is not particularly limited, but may be, for example, a disk shape. Note that the disk-shaped semiconductor substrate does not need to have a perfectly circular surface, and for example, the outer periphery of the semiconductor substrate may have a straight portion called an orientation flat or a notch. The thickness of the disk-shaped semiconductor substrate may be appropriately determined depending on the intended use of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 μm. The diameter of the disk-shaped semiconductor substrate may be appropriately determined depending on the intended use of the semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.

[0026] The semiconductor substrate may have bumps, which are protruding terminals. In the laminate, when the semiconductor substrate has bumps, the semiconductor substrate has the bumps on the support substrate side. In a semiconductor substrate, bumps are usually formed on the surface on which a circuit is formed. The circuit may be a single layer or a multilayer. There are no particular limitations on the shape of the circuit. In the semiconductor substrate, the surface opposite to the surface having the bumps (back surface) is the surface to be processed. The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited. Examples of the bumps include ball bumps, printed bumps, stud bumps, and plated bumps. Generally, the height, radius and pitch of the bumps are determined appropriately based on the conditions of a bump height of about 1 to 200 μm, a bump radius of 1 to 200 μm and a bump pitch of 1 to 500 μm. Examples of materials for the bumps include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bumps may be composed of a single component or multiple components. More specifically, alloy platings mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps, may be used. The bump may also have a laminated structure including a metal layer made of at least one of these components.

[0027] An example of a semiconductor substrate is a silicon wafer with a diameter of about 300 mm and a thickness of about 770 μm.

[0028] <<<Resin composition>>> The resin composition is not particularly limited as long as it can form a coating layer by coating, but a curable resin composition is preferred.

[0029] Examples of the resin composition include, but are not limited to, a polysiloxane-based resin composition, an acrylic resin-based resin composition, an epoxy-based resin composition, a polyamide-based resin composition, a polystyrene-based resin composition, a polyimide resin composition, and a phenolic resin-based resin composition. Among these, the polysiloxane-based resin composition containing polyorganosiloxane is preferred as the resin composition because it has excellent heat resistance and can be suitably removed by a cleaning composition.

[0030] The resin composition preferably contains a component (A) that cures via a hydrosilylation reaction. The resin composition may or may not contain a resin component (B) that does not undergo a hydrosilylation reaction. The resin composition preferably contains a polyorganosiloxane.

[0031] In a preferred embodiment, the component (A) that cures via a hydrosilylation reaction is a polyorganosiloxane component (A') that cures via a hydrosilylation reaction. In another preferred embodiment, component (A) contains, for example, a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom (as an example of component (A')), a polyorganosiloxane (a2) having a Si-H group, and a catalyst (A2). Here, the alkenyl group having 2 to 40 carbon atoms may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group. In another preferred embodiment, the polyorganosiloxane component (A') that cures via a hydrosilylation reaction contains siloxane units (Q units) represented by SiO, R 1 R 2 R 3 SiO 1 / 2 Siloxane unit (M unit) represented by R 4 R 5 SiO 2 / 2 Siloxane units (D units) represented by the formula 6 SiO 3 / 2 and a catalyst (A2), wherein the polysiloxane (A1) contains one or more units selected from the group consisting of siloxane units (Q' units) represented by SiO2, R 1 'R 2 'R 3 'SiO 1 / 2 Siloxane unit (M' unit) represented by R 4 'R 5 'SiO 2 / 2 Siloxane units (D' units) represented by the formula: and R 6 'SiO 3 / 2 and a polyorganosiloxane (a1') containing one or more units selected from the group consisting of siloxane units (T' units) represented by the following formula: and at least one unit selected from the group consisting of M' units, D' units and T' units; a polyorganosiloxane (a1') containing siloxane units (Q" units) represented by the following formula: 1 "R 2 "R 3 "SiO 1 / 2 Siloxane unit (M" unit) represented by R 4 "R 5 "SiO2 / 2 Siloxane units (D" units) represented by and R 6 "SiO 3 / 2 and a polyorganosiloxane (a2') containing one or more units selected from the group consisting of siloxane units (T" units) represented by the following formula: and containing at least one unit selected from the group consisting of M" units, D" units, and T" units. Note that (a1') is an example of (a1), and (a2') is an example of (a2).

[0032] R 1 ~R 6 are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0033] R 1 '~R 6 R ' is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group. 1 '~R 6 At least one of the groups ' is an alkenyl group which may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

[0034] R 1 ”~R 6 " are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group or a hydrogen atom, but R 1 ”~R 6 At least one of " is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

[0035] The alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0036] Specific examples of the optionally substituted straight-chain or branched-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a tertiary butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 4-methyl-n-pentyl group, a 5-methyl-n-pentyl group, a 6-methyl-n-pentyl group, a 7-methyl-n-pentyl group, a 8-methyl-n-pentyl group, a 9-methyl-n-pentyl group, a 10-methyl-n-pentyl group, a 11-methyl-n-pentyl group, a 12-methyl-n-pentyl group, a 13-methyl-n-pentyl group, a 14-methyl-n-pentyl group, a 15-methyl-n-pentyl group, a 16-methyl-n-pentyl group, a 17-methyl-n-pentyl group, a 18-methyl-n-pentyl group, a 19-methyl-n-pentyl group, a 20-methyl-n-pentyl group, a 21-methyl-n-pentyl group, a 22-methyl-n-pentyl group, a 23-methyl-n-pentyl group, a 24-methyl-n-pentyl group, a 25-methyl-n-pentyl group, a 26-methyl-n-pentyl group, a 27-methyl-n-pentyl group, a 2 Examples of such alkyl groups include, but are not limited to, a methyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group, and the number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Of these, a methyl group is particularly preferred.

[0037] Specific examples of the optionally substituted cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a 1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a 3-ethyl-cyclobutyl group, a 1,2-dimethyl-cyclobutyl group, a 1,3-dimethyl-cyclobutyl group, a 2,2-dimethyl-cyclobutyl group, a 2,3-dimethyl-cyclobutyl group, a 2,4-dimethyl-cyclobutyl group, a 3,3-dimethyl-cyclobutyl group, a cyclohexyl ... Examples of cycloalkyl groups include cycloalkyl groups such as 1-n-ethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group; and bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group, but are not limited to these. The number of carbon atoms in the cycloalkyl groups is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0038] The alkenyl group may be either linear or branched, and the number of carbon atoms therein is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0039] Specific examples of the optionally substituted linear or branched alkenyl group include, but are not limited to, a vinyl group, an allyl group, a butenyl group, and a pentenyl group, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Of these, an ethenyl group and a 2-propenyl group are particularly preferred. Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl and cyclohexenyl, and the number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0040] As described above, polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'), and the alkenyl group contained in polyorganosiloxane (a1') and the hydrogen atom (Si-H group) contained in polyorganosiloxane (a2') undergo a hydrosilylation reaction in the presence of catalyst (A2) to form a crosslinked structure and cure, resulting in the formation of a cured film.

[0041] The polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units, and T' units. As the polyorganosiloxane (a1'), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0042] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units and M' units).

[0043] Furthermore, when the polyorganosiloxane (a1') contains two or more types of polyorganosiloxane, combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but are not limited to these.

[0044] The polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units, and T" units, and also contains at least one unit selected from the group consisting of M" units, D" units, and T" units. As the polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0045] Preferred combinations of two or more selected from the group consisting of Q" units, M" units, D" units and T" units include, but are not limited to, (M" units and D" units), (Q" units and M" units), and (Q" units, T" units and M" units).

[0046] The polyorganosiloxane (a1') is composed of siloxane units in which alkyl groups and / or alkenyl groups are bonded to the silicon atoms thereof, and R 1 '~R 6 The proportion of alkenyl groups in all the substituents represented by R 1 '~R 6 ' can be an alkyl group.

[0047] The polyorganosiloxane (a2') is composed of siloxane units in which alkyl groups and / or hydrogen atoms are bonded to the silicon atoms. 1 ”~R 6 The proportion of hydrogen atoms in all the substituents and substituted atoms represented by R 1 ”~R6 " can be an alkyl group.

[0048] When component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in polyorganosiloxane (a1) to hydrogen atoms constituting Si-H bonds contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0049] The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of realizing the effects of the present invention with good reproducibility, is preferably 5,000 to 50,000. In the present invention, the weight average molecular weight, number average molecular weight and dispersity of polyorganosiloxane (excluding the organosiloxane polymer) can be measured using, for example, a GPC apparatus (Tosoh Corporation EcoSEC, HLC-8320GPC) and a GPC column (Tosoh Corporation TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Showa Denko K.K., Shodex) as a standard sample.

[0050] The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are not particularly limited, but are typically 10 to 1,000,000 (mPa·s), and from the viewpoint of achieving the effects of the present invention with good reproducibility, are preferably 50 to 10,000 (mPa·s). The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are values measured at 25°C using an E-type rotational viscometer.

[0051] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other to form a film by hydrosilylation, and therefore the curing mechanism is different from that via, for example, silanol groups, and therefore neither siloxane needs to contain a functional group that forms a silanol group upon hydrolysis, such as an alkyloxy group.

[0052] In a preferred embodiment of the present invention, the resin composition contains a catalyst (A2) together with the polyorganosiloxane component (A'). The catalyst (A2) is preferably a platinum group metal catalyst. Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl groups of the polyorganosiloxane (a1) and the Si—H groups of the polyorganosiloxane (a2).

[0053] Specific examples of platinum-based metal catalysts include, but are not limited to, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, and platinum bisacetoacetate. Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum.

[0054] The amount of the catalyst (A2) is not particularly limited, but is usually in the range of 1.0 to 50.0 ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0055] The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of inhibiting the progress of the hydrosilylation reaction. The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol. The amount of the polymerization inhibitor is not particularly limited, but is usually 1000.0 ppm or more relative to the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0056] An example of the resin composition used in the present invention may contain a resin component (B) that does not undergo a hydrosilylation reaction together with a curable component (A). Component (B) is typically a non-curable polyorganosiloxane, and specific examples thereof include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes. Component (B) may also include polydimethylsiloxane. The polydimethylsiloxane may be modified. Examples of the optionally modified polydimethylsiloxane include, but are not limited to, epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, and phenyl group-containing polydimethylsiloxane.

[0057] Preferred examples of the polyorganosiloxane of component (B) include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes.

[0058] The weight-average molecular weight of the polyorganosiloxane of component (B) is not particularly limited, but is usually 100,000 to 2,000,000. From the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000. Its dispersity is also not particularly limited, but is usually 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable release, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight-average molecular weight and dispersity can be measured using the methods described above for polyorganosiloxane. The viscosity of the polyorganosiloxane, component (B), is not particularly limited, but is usually 1,000 to 2,000,000 mm 2 The viscosity value of the polyorganosiloxane, which is component (B), is expressed as a kinematic viscosity, and is expressed in centistokes (cSt) = mm 2 / s. Viscosity (mPa s) is converted to density (g / cm 3 ) can be calculated by dividing the viscosity and density measured with an E-type rotational viscometer at 25°C. 2 / s)=viscosity (mPa s) / density (g / cm 3 ) can be calculated from the formula:

[0059] Examples of epoxy group-containing polyorganosiloxanes include R 11 R 12 SiO 2 / 2 The siloxane unit (D 10 Examples include those containing units.

[0060] R 11 is a group bonded to a silicon atom and represents an alkyl group, and R 12 is a group bonded to a silicon atom, and represents an epoxy group or an organic group containing an epoxy group, and specific examples of the alkyl group include those listed above. The epoxy group in the epoxy group-containing organic group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group. Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl. In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but is not limited thereto.

[0061] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D10 units), but D 10 In addition to units, Q units, M units and / or T units may be included. In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include D 10 Polyorganosiloxane consisting of only units, D 10 polyorganosiloxanes containing D units and Q units; 10 Polyorganosiloxanes containing D units and M units, 10 Polyorganosiloxanes containing D units and T units, 10 polyorganosiloxanes containing units, Q units and M units, D 10 Polyorganosiloxanes containing units, M units and T units, D 10 Examples of suitable organosiloxanes include polyorganosiloxanes containing Q units, M units, and T units.

[0062] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. The weight average molecular weight thereof is not particularly limited, but is usually 1,500 to 500,000, and from the viewpoint of suppressing precipitation in the composition, it is preferably 100,000 or less.

[0063] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0064] [ka] (m1 and n1 represent the number of each repeating unit and are positive integers.)

[0065] [ka] (m2 and n2 each represent the number of repeating units and are positive integers, and R represents an alkylene group having 1 to 10 carbon atoms.)

[0066] [ka] (m3, n3, and o3 each represent the number of repeating units and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0067] Examples of the methyl group-containing polyorganosiloxane include R 210 R 220 SiO 2 / 2 The siloxane unit (D 200 units), preferably R 21 R 21 SiO 2 / 2 The siloxane unit (D 20 Examples include those containing units.

[0068] R 210 and R 220 are groups bonded to a silicon atom, and each independently represents an alkyl group, with at least one being a methyl group. Specific examples of the alkyl group include those listed above. R 21 is a group bonded to a silicon atom, and represents an alkyl group. Specific examples of the alkyl group include those listed above. 21 As the alkyl group, a methyl group is preferred. In the present invention, a preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.

[0069] The methyl group-containing polyorganosiloxane is a polyorganosiloxane having the above-mentioned siloxane unit (D 200 Unit or D 20 units), but D 200 Units and D 20 In addition to units, Q units, M units and / or T units may be included.

[0070] In one embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include D 200 Polyorganosiloxane consisting of only units, D 200polyorganosiloxanes containing D units and Q units; 200 Polyorganosiloxanes containing D units and M units, 200 Polyorganosiloxanes containing D units and T units, 200 polyorganosiloxanes containing units, Q units and M units, D 200 Polyorganosiloxanes containing units, M units and T units, D 200 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0071] In a preferred embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include D 20 Polyorganosiloxane consisting of only units, D 20 polyorganosiloxanes containing D units and Q units; 20 Polyorganosiloxanes containing D units and M units, 20 Polyorganosiloxanes containing D units and T units, 20 polyorganosiloxanes containing units, Q units and M units, D 20 Polyorganosiloxanes containing units, M units and T units, D 20 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0072] Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1).

[0073] [ka] (n4 represents the number of repeating units and is a positive integer.)

[0074] Examples of the phenyl group-containing polyorganosiloxane include R 31 R 32 SiO 2 / 2 The siloxane unit (D 30 Examples include those containing units.

[0075] R 31is a group bonded to a silicon atom and represents a phenyl group or an alkyl group; R 32 is a group bonded to a silicon atom, and represents a phenyl group. Specific examples of the alkyl group include those listed above, with a methyl group being preferred.

[0076] The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 30 units), but D 30 In addition to units, Q units, M units and / or T units may be included.

[0077] In a preferred embodiment of the present invention, specific examples of the phenyl group-containing polyorganosiloxane include D 30 Polyorganosiloxane consisting of only units, D 30 polyorganosiloxanes containing D units and Q units; 30 Polyorganosiloxanes containing D units and M units, 30 Polyorganosiloxanes containing D units and T units, 30 polyorganosiloxanes containing units, Q units and M units, D 30 Polyorganosiloxanes containing units, M units and T units, D 30 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0078] Specific examples of the phenyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

[0079] [ka] (m5 and n5 each represent the number of repeating units and are positive integers.)

[0080] [ka] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0081] The polyorganosiloxane that is component (B) may be a commercially available product or may be synthesized. Commercially available polyorganosiloxanes include, for example, Wacker Chemical's WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST GUM, Shin-Etsu Chemical Co., Ltd.'s dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), and cyclic dimethyl silicone oil (KF-995); Gelest's epoxy group-containing polyorganosiloxanes (product names CMS-227, ECMS-327), Shin-Etsu Chemical Co., Ltd.'s epoxy group-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343), and Dow Corning's Examples of suitable polyorganosiloxanes include, but are not limited to, epoxy group-containing polyorganosiloxane (BY16-839); phenyl group-containing polyorganosiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest, phenyl group-containing polyorganosiloxane (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd., and phenyl group-containing polyorganosiloxanes (TSF431, TSF433) manufactured by Momentive.

[0082] An example of the resin composition used in the present invention can contain component (A) and component (B) in any ratio, but the ratio of component (A) to component (B) in mass ratio [(A):(B)] is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25. That is, when a polyorganosiloxane component (A') that cures by a hydrosilylation reaction is included, the mass ratio of component (A') to component (B) [(A'):(B)] is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25.

[0083] The viscosity of the resin composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s, and preferably 1,000 to 1,0000 mPa·s at 25°C.

[0084] The resin composition used in the present invention may contain a solvent for the purpose of adjusting the viscosity, etc., and specific examples of the solvent include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but are not limited to these.

[0085] More specifically, examples of the solvent include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc. Such solvents may be used alone or in combination of two or more.

[0086] When the resin composition used in the present invention contains a solvent, the content of the solvent is appropriately determined taking into consideration the desired viscosity of the composition, the coating method to be used, the thickness of the film to be produced, etc., but is in the range of about 10 to 90 mass % of the entire composition.

[0087] An example of the resin composition used in the present invention can be prepared by mixing component (A) with component (B), if used, and a solvent. The order of mixing is not particularly limited, but examples of methods that can easily and reproducibly produce a resin composition include, but are not limited to, a method of dissolving component (A) and component (B) in a solvent, or a method of dissolving a portion of component (A) and a portion of component (B) in a solvent and the remaining portion in a solvent, and then mixing the resulting solutions. When preparing the resin composition, the composition may be heated as appropriate within a range that does not cause decomposition or deterioration of the components. In the present invention, in order to remove foreign matter, the solvent, solution, etc. used may be filtered using a filter during the production of the resin composition or after all components have been mixed.

[0088] <<Resin layer formation process>> The resin layer forming step is a step of flattening the surface of the coating layer to form a resin layer. The method for flattening the surface of the coating layer is not particularly limited, but may include a method of flattening the surface of the coating layer by grinding the surface of the coating layer.

[0089] The surface of the coating layer may be ground, for example, using a device for grinding (backgrinding) the surface of a semiconductor substrate. For example, the surface of the coating layer is ground by rotating and pressing a grinding wheel having a grinding stone on the contact surface.

[0090] The surface of the coating layer is ground, for example, by fixing the semiconductor substrate to a fixing member. When grinding the surface of the coating layer, the semiconductor substrate is fixed, for example, by bringing the surface of the semiconductor substrate (the surface of the semiconductor substrate opposite to the coating layer side) into contact with a fixing member. The fixing member may be, for example, a vacuum chuck. A vacuum chuck is a device that holds a member to be fixed (for example, a semiconductor substrate) by reducing the pressure on one side of the member to be fixed (for example, a semiconductor substrate) and using the resulting suction force.

[0091] The thickness of the resin layer obtained in the resin layer forming step and subjected to the processing step is not particularly limited, but is preferably 50 μm or more, more preferably 100 μm to 500 μm, and particularly preferably 100 μm to 350 μm. If the resin layer is too thin, warping or the like may occur in the semiconductor substrate when the semiconductor substrate is processed. By making the resin layer thicker than 50 μm, the resin layer can be suitably used as a support for the semiconductor substrate when the semiconductor substrate is subjected to a processing step.

[0092] The difference (Tc-Tr) between the thickness (Tc) of the coating layer and the thickness (Tr) of the resin layer before and after the surface of the coating layer is flattened is not particularly limited, but is preferably more than 0 μm, and is preferably 5 μm to 200 μm, and more preferably 10 μm to 100 μm.

[0093] The flatness (total thickness variation: TTV) of the coating layer before the coating layer is flattened may be, for example, 5 μm to 150 μm, 20 μm to 130 μm, or 50 μm to 120 μm. The flatness (total thickness variation: TTV) of the resin layer after the resin layer has been flattened may be, for example, 10 μm or less, or 5 μm or less. The difference (Vc-Vr) between the flatness of the coating layer (Vc) and the flatness of the resin layer (Vr) is not particularly limited, but is preferably more than 0 μm, and is preferably from 1 μm to 120 μm. Regarding the flatness, the smaller the value, the flatter the surface. The flatness of the coating layer is the difference between the maximum and minimum film thicknesses when the thickness of the entire coating layer is mapped using a non-contact, spectral interference film thickness measuring device (for example, an optical film thickness meter manufactured by Otsuka Electronics; SF-3000M). The flatness of the resin layer is the difference between the maximum and minimum film thicknesses when the thickness of the entire resin layer is mapped using a non-contact, spectral interference film thickness measuring device (e.g., Otsuka Electronics optical film thickness meter; SF-3000M).

[0094] An example of a method for manufacturing a laminate will be described below with reference to the drawings. 1A to 1D are schematic cross-sectional views illustrating an example of a method for producing a laminate. First, a semiconductor substrate 1 is prepared (FIG. 1A). Next, a resin composition is applied onto the semiconductor substrate 1 to form a coating layer 2a (FIG. 1B). The resin composition is usually applied onto the circuit surface (the surface opposite to the processed surface) of the semiconductor substrate 1. The coating layer 2a thus formed is thicker at the edges and is not flat. Therefore, the semiconductor substrate 1 is fixed in contact with a vacuum chuck 11, and the surface of the coating layer 2a is ground using a grinding wheel 10 of a grinding device (backgrinding device) (FIG. 1C). The coating layer 2a is flattened by grinding, and a resin layer 2 is formed (FIG. 1D). Usually, grinding flattens the resin layer and makes it thinner than the coating layer. As a result of the above, a laminate is obtained (FIG. 1D) having the semiconductor substrate 1 and the resin layer 2 formed on the semiconductor substrate 1. In the laminate, the surface of the resin layer 2 opposite to the semiconductor substrate 1 side is exposed.

[0095] <Processing process> The processing step is a step in which the semiconductor substrate of the stack is processed. The processing step preferably includes grinding the surface of the semiconductor substrate opposite to the resin layer side to thin the semiconductor substrate.

[0096] The surface of the semiconductor substrate can be ground, for example, using a grinding device. For example, a grinding wheel having a grinding stone on the contact surface is rotated and pressed against the surface of the semiconductor substrate to grind it.

[0097] Grinding of the surface of the semiconductor substrate is carried out, for example, with the stack fixed to a fixing member. When grinding the surface of the semiconductor substrate, for example, the surface of the resin layer (the surface of the resin layer opposite to the semiconductor substrate side) is brought into contact with a fixing member, thereby fixing the stack to the fixing member. The fixing member may be, for example, a vacuum chuck. A vacuum chuck is a device that holds a member to be fixed (for example, a laminate) by reducing the pressure on one side of the member to be fixed (for example, a laminate) and using the resulting suction force. When fixing with a vacuum chuck, it is preferable that the resin layer has excellent flatness. In this respect, the laminate to be subjected to the processing step is preferably a laminate obtained by the laminate manufacturing method of the present invention.

[0098] In the processing step, formation of through silicon vias (TSVs) and the like, formation of back surface electrodes, etc. may be performed.

[0099] During thinning of semiconductor substrates and TSV processes, the substrate may be subjected to heat of approximately 250 to 350° C. in a state where it is bonded to a resin layer. If the resin layer is formed from a polyorganosiloxane resin composition, it can adequately withstand such heat load.

[0100] <Cleaning process> The cleaning step is a step in which the processed semiconductor substrate is cleaned with a cleaning composition. Examples of cleaning methods include a method of spraying the cleaning composition onto the processed semiconductor substrate, and a method of immersing the processed semiconductor substrate in the cleaning composition. The resin layer on the semiconductor substrate is removed by cleaning. After cleaning, rinsing with a solvent and drying may be performed.

[0101] <<Cleaning agent composition>> The resin layer remaining on the processed semiconductor substrate can be suitably removed by a cleaning composition, and such a cleaning composition usually contains a solvent.

[0102] Examples of the solvent include lactones, ketones, polyhydric alcohols, compounds having an ester bond, derivatives of polyhydric alcohols, cyclic ethers, esters, and aromatic organic solvents. Examples of lactones include γ-butyrolactone. Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Examples of compounds having an ester bond include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. Examples of derivatives of polyhydric alcohols include monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the above polyhydric alcohols or compounds having an ester bond, or compounds having an ether bond such as monophenyl ether, etc. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred. Examples of cyclic ethers include dioxane. Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, isopropyl benzene, toluene, xylene, cymene, and mesitylene. These may be used alone or in combination of two or more. Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0103] A mixed solvent of PGMEA and a polar solvent is also preferred. The blending ratio (mass ratio) may be appropriately determined taking into consideration the compatibility of PGMEA with the polar solvent, and is preferably within the range of 1:9 to 9:1, and more preferably 2:8 to 8:2. For example, when EL is blended as the polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. When PGME is blended as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. When PGME and cyclohexanone are blended as the polar solvents, the mass ratio of PGMEA:(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.

[0104] The cleaning composition may or may not contain a salt; however, the absence of a salt is preferred in terms of increasing versatility in processing semiconductor substrates using the laminate and reducing costs.

[0105] An example of a detergent composition containing a salt is a detergent composition containing a quaternary ammonium salt and a solvent. The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for this type of application. A typical example of such a quaternary ammonium cation is a tetra(hydrocarbon)ammonium cation. On the other hand, an anion paired with the quaternary ammonium cation is a hydroxide ion (OH - ); fluorine ion (F - ), chloride ions (Cl - ), bromide ion (Br - ), iodine ion (I - ) and other halogen ions; tetrafluoroborate ion (BF4 - ); Hexafluorophosphate ion (PF6 - ) and the like, but are not limited to these.

[0106] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt. In the quaternary ammonium salt, the halogen atom may be contained in either the cation or the anion, but is preferably contained in the anion.

[0107] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is a tetra(hydrocarbon)ammonium fluoride. Specific examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms. In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also called tetrabutylammonium fluoride), etc. Among these, tetrabutylammonium fluoride is preferred.

[0108] The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of hydrates. The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used singly or in combination of two or more. The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the detergent composition, but is usually 0.1 to 30% by mass relative to the detergent composition.

[0109] When the cleaning composition contains a salt, the solvent to be used in combination with the salt is not particularly limited as long as it is used for this type of application and dissolves the salt, such as a quaternary ammonium salt. However, from the viewpoint of reproducibly obtaining a cleaning composition having excellent cleaning properties and from the viewpoint of satisfactorily dissolving the salt, such as a quaternary ammonium salt, and obtaining a cleaning composition with excellent uniformity, the cleaning composition preferably contains one or two or more amide solvents.

[0110] A suitable example of the amide solvent is an acid amide derivative represented by formula (Z). [ka]

[0111] In the formula, R 0 represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group. A and R B each independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group. Of these, R A and R B As the alkyl group, a methyl group or an ethyl group is preferred, and both of them are more preferably methyl groups or ethyl groups, and both of them are even more preferably methyl groups.

[0112] Examples of the acid amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N,N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, N-ethyl-N-methylisobutyric acid amide, etc. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyric acid amide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

[0113] The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between the corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

[0114] Another example of a preferred amide solvent is a lactam compound represented by formula (Y). [ka]

[0115] In formula (Y), R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 102 represents an alkylene group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, but are not limited to these.

[0116] Specific examples of the lactam compound 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.

[0117] In a preferred embodiment of the present invention, the lactam compound represented by formula (Y) comprises 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, N-methylpyrrolidone (NMP).

[0118] The cleaning composition used in the present invention may contain water as a solvent, but typically only an organic solvent is used as the solvent to avoid corrosion of the substrate, etc. In this case, however, it is not excluded that the cleaning composition may contain water of hydration of salts or trace amounts of water contained in the organic solvent. The water content of the cleaning composition used in the present invention is typically 5% by mass or less.

[0119] The constituent elements and methodological elements relating to the above-described steps of the method for manufacturing a processed semiconductor substrate of the present invention may be modified in various ways without departing from the spirit and scope of the present invention. The method for producing a processed semiconductor substrate of the present invention may include steps other than those described above.

[0120] An example of a method for manufacturing a processed semiconductor substrate will be described below with reference to the drawings. 2A to 2C are diagrams for explaining one mode of manufacturing a processed semiconductor substrate. First, a laminate is prepared (FIG. 2A). The laminate shown in FIG. 2A is the laminate shown in FIG. 1D. The laminate has a semiconductor substrate 1 and a resin layer 2 formed on the semiconductor substrate 1. The surface of the resin layer 2 opposite to the semiconductor substrate 1 side is exposed. Next, the resin layer 2 of the laminate is brought into contact with a vacuum chuck 21 to fix the laminate, and a grinding wheel 20 of a grinding device (backgrinding device) is used to grind the surface of the semiconductor substrate 1 opposite to the resin layer 2 side, thereby thinning the semiconductor substrate 1 (FIG. 2B). Note that the thinned semiconductor substrate 1 may be subjected to formation of a through electrode or the like. Next, the resin layer 2 is dissolved and removed from the thinned semiconductor substrate 1 using a cleaning composition, thereby cleaning the thinned semiconductor substrate 1 (FIG. 2C). In this way, a thinned semiconductor substrate 1 is obtained. [Example]

[0121] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The apparatus used is as follows.

[0122] [Device] (1) Mixer A: Thinky Corporation, planetary centrifugal mixer, ARE-500 (2) Agitator B: AS ONE Corporation Mix Rotor VMR-5R (3) Coating device: XBS-300 manufactured by SUSS Microtec Co., Ltd. (4) Back grinding equipment (thinning process): Back grinder SS30 manufactured by Tokyo Seimitsu Co., Ltd. (5) Otsuka Electronics Optical Film Thickness Gauge: Otsuka Electronics, SF-3000M (6) Cleaning equipment: SUSS MicroTec manual debonder (7) Peeling device: Auto Debonder, manufactured by SUSS Microtec Co., Ltd.

[0123] [1] Preparation of curable resin composition [Preparation Example 1] In a 300 mL stirring vessel dedicated to stirrer A, 125.0 g of MQ resin (manufactured by Wacker Chemie) containing polysiloxane and vinyl groups as polyorganosiloxane (a1), 44.5 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 100 mPa·s as polyorganosiloxane (a2), 9.5 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 70 mPa·s as polyorganosiloxane (a2), 0.34 g of 1,1-diphenyl-1,2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.4 g of platinum catalyst (manufactured by Wacker Chemie) as a catalyst were added and stirred with the stirrer for 5 minutes. To the resulting mixture, 0.34 g of 1-ethynylcyclohexanol (manufactured by Wacker Chemie) as a polymerization inhibitor and 23.7 g of p-menthane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a solvent were added, and the mixture was stirred for 5 minutes with a stirrer to obtain a curable resin composition. The proportion of components other than the solvent (non-volatile content) in the resulting composition was 86.6 mass%.

[0124] [Preparation Example 2] In a 600 mL stirring vessel dedicated to Mixer A, 105.26 g of a p-menthane solution (concentration 80.6% by mass) of vinyl group-containing MQ resin (manufactured by Wacker Chemie) as polyorganosiloxane (a1), 35.24 g of a polyorganosiloxane represented by the following formula (G) (complex viscosity 6000 Pa·s, weight average molecular weight 642,000 (dispersity 2.6), trade name GENIOPLASTGUM manufactured by Wacker Chemie), 54.11 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) as a solvent, and 8.35 g of n-decane (manufactured by Sankyo Chemical Co., Ltd.) were added, and stirring was carried out for 5 minutes using Mixer A, with short breaks in between, a total of 8 times (total stirring time 40 minutes). Mixture (I) was obtained. To the obtained mixture (I), 16.97 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 100 mPa·s as polyorganosiloxane (a2) and 24.80 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 200 mPa·s as polyorganosiloxane (a1) were added to obtain mixture (II). 1.63 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.63 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) as polymerization inhibitors and 3.26 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) as a solvent were stirred with a stirrer B for 60 minutes to obtain a mixture (III). 1.31 g of the mixture (III) was added to the mixture (II), and the mixture was stirred with the stirrer A for 5 minutes to obtain the mixture (IV). 0.26 g of platinum catalyst (manufactured by Wacker Chemie) and 19.58 g of vinyl-group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1000 mPa·s as polyorganosiloxane (a1) were stirred for 5 minutes with stirrer A to obtain mixture (V). 3.97 g of the mixture (V) was added to the mixture (IV), and the mixture was stirred with the stirrer A for 5 minutes to obtain the mixture (VI). Finally, the resulting mixture (VI) was filtered through a 300-mesh nylon filter to obtain an adhesive composition having a viscosity of 3900 mPa·s. [ka] (g represents a positive integer.)

[0125] [2] Coating film production and grindability confirmation [Example 1] The curable resin composition obtained in Preparation Example 1 was spin-coated onto a 300 mm silicon wafer (775 μm thick) used as a device wafer using a coating device. The wafer was then heated at 90°C for 1.5 minutes, 130°C for 5 minutes, and 200°C for 5 minutes to remove residual solvent and form a coating layer approximately 100 μm thick on the wafer. This process was repeated three times to form a coating layer approximately 350 μm thick on the wafer. The coating layer had a total thickness variation (TTV) of 102 μm. The resulting coating layer was attached to a backgrinding machine with the silicon wafer attached to the bottom. The machine was used to grind approximately 100 μm of the coating layer from its thickest point (approximately 430 μm thick). The entire coating layer was then ground to a uniform thickness, yielding a resin layer. The thickness and in-plane uniformity of the resin layer on the wafer were then measured using an optical film thickness meter manufactured by Otsuka Electronics. The resin layer had a film thickness of 330 μm and a flatness of 4 μm. Next, the silicon wafer was placed on the upper surface and the resin layer on the lower surface, and the bottom of the wafer was attached to a back grinding machine by suction. The silicon wafer was then ground using this machine. The film thickness and in-plane uniformity of the resin layer on the wafer were then measured using an optical film thickness meter manufactured by Otsuka Electronics. Next, the resin layer coated on the silicon wafer was cleaned using a cleaning device, and the film thickness and in-plane uniformity of the silicon wafer were measured again using an optical film thickness meter manufactured by Otsuka Electronics.

[0126] [Reference example 1] The adhesive composition obtained in Preparation Example 2 was spin-coated onto a 300 mm silicon wafer (775 μm thick) serving as the device wafer using a coating device. The wafer was then heated at 90°C for 1.5 minutes (pre-heat treatment) to remove residual solvent and form an adhesive coating layer approximately 60 μm thick on the wafer. The silicon wafer bearing this adhesive coating layer was then bonded to a 300 mm silicon wafer (775 μm thick) serving as the carrier wafer (support) in a vacuum bonding apparatus, sandwiching the adhesive coating layer between them. The device-side wafer was then placed face down on a hot plate and heated at 130°C for 5 minutes and then at 200°C for 5 minutes (post-heat treatment) to produce a laminate. The bonding was performed at 50°C, under a vacuum of 1,000 Pa, and with a load of 500 N applied for 3 minutes. The bonded wafer was then attached to a backgrinding apparatus, and the device-side silicon wafer was then ground using this apparatus. The thickness and in-plane uniformity of the adhesive layer on the device side of the wafer were then measured using an optical film thickness meter manufactured by Otsuka Electronics Co., Ltd. The results showed that the in-plane uniformity was good. Next, the wafers were peeled off using a peeling device, and the adhesive layer formed on the silicon wafer on the device side was cleaned using a cleaning device.Then, the film thickness and in-plane uniformity of the silicon wafer were measured again using an Otsuka Electronics optical film thickness meter.

[0127] After grinding the device wafer, the film thickness and in-plane uniformity of the device wafer were measured using an Otsuka Electronics optical film thickness meter, and those that confirmed a reduction in the film thickness of the device wafer were rated as good, and those with a TTV (Total Thickness Variation: flatness) value of 8 μm or less, which indicates in-plane uniformity, were rated as good. The results are shown in Table 1.

[0128] [Table 1]

[0129] As a result, it was found that the new process of the present invention (Example 1) that does not use a carrier wafer provides good device grinding and in-plane uniformity of the device after grinding, and that device grinding and in-plane uniformity of the device after grinding are comparable to those of the conventional process that uses a carrier wafer (Reference Example 1). [Explanation of symbols]

[0130] 1. Semiconductor substrate 2a Coating layer 2 Resin layer 10 Grinding Wheel 11 Vacuum chuck 20 Grinding Wheel 21 Vacuum chuck

Claims

1. 1. A method for manufacturing a processed semiconductor substrate, comprising: a step of preparing a laminate having a semiconductor substrate and a resin layer formed on the semiconductor substrate, the surface of the resin layer opposite to the semiconductor substrate being exposed; a step in which the semiconductor substrate of the stack is processed; Including, The resin layer is a resin layer formed from a resin composition containing a component (A) that cures by a hydrosilylation reaction. A method for manufacturing a processed semiconductor substrate.

2. The component (A) is A polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, a polyorganosiloxane (a2) having Si—H groups; a catalyst (A2); The method for producing the processed semiconductor substrate of claim 1 , comprising:

3. 2. The method for producing a processed conductor laminate according to claim 1, wherein the resin layer in the laminate subjected to the processing step has a thickness of 100 μm to 500 μm.

4. The method for producing a processed semiconductor substrate according to claim 1 , wherein the processing step includes grinding a surface of the semiconductor substrate opposite to the resin layer side to thin the semiconductor substrate.

5. 2. The method for manufacturing a processed semiconductor substrate according to claim 1, wherein in the processing step, the laminate is fixed to a fixing member by bringing a surface of the resin layer opposite to the semiconductor substrate side into contact with the fixing member.

6. The method of claim 5 , wherein the fixing member is a vacuum chuck.

7. The step of preparing the laminate includes: applying the resin composition onto the semiconductor substrate to form a coating layer; a step of flattening the surface of the coating layer to form the resin layer; The method for producing the processed semiconductor substrate of claim 1 , comprising:

8. A method for manufacturing a laminate including a semiconductor substrate and a resin layer formed on the semiconductor substrate, the method comprising: a step of applying a resin composition onto the semiconductor substrate to form a coating layer; a step of flattening the surface of the coating layer to form the resin layer; A method for producing a laminate, comprising:

9. The method for producing a laminate according to claim 8 , wherein the resin composition contains a component (A) that cures by a hydrosilylation reaction.

10. The component (A) is A polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, a polyorganosiloxane (a2) having Si—H groups; a catalyst (A2); The method for producing a laminate according to claim 9, comprising:

11. The method for manufacturing a laminate according to claim 8 , wherein the laminate is a laminate for processing the semiconductor substrate.

12. The method for manufacturing a laminate according to claim 11 , wherein the processing of the semiconductor substrate includes grinding a surface of the semiconductor substrate opposite to the resin layer side to thin the semiconductor substrate.

13. The method for producing a laminate according to claim 8, wherein the difference (Tc-Tr) between the thickness (Tc) of the coating layer and the thickness (Tr) of the resin layer is 5 μm to 200 μm.

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