Stacked body, method for manufacturing stacked body, and method for manufacturing semiconductor substrate

Abstract

A laminate comprising: a support substrate; a semiconductor substrate having a bump on the support substrate side; an inorganic material layer interposed between the support substrate and the semiconductor substrate and adjoining the semiconductor substrate; and an adhesive layer interposed between the support substrate and the inorganic material layer and adjoining the support substrate and the inorganic material layer. The laminate is used for applications where, after the semiconductor substrate of the laminate are processed, the support substrate and the semiconductor substrate are separated from each other. When the support substrate and the semiconductor substrate are separated, the adhesive force between the inorganic material layer and the adhesive layer is smaller than the adhesive force between the inorganic material layer and the semiconductor substrate.

Description

[Technical Field]

[0001] The present invention relates to a laminate, a method for manufacturing a laminate, and a method for manufacturing a semiconductor substrate. [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. In order to polish an unthinned semiconductor wafer (also simply referred to as a wafer here) with a polishing apparatus, the unthinned semiconductor wafer is adhered to a support. The adhesive used in this process must be easily peeled off after polishing, and is therefore called a temporary adhesive. This temporary adhesive 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 adhesive 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 adhesive is that it can withstand the stress during polishing and be easily removed after polishing. For example, the required performance is high stress (strong adhesive strength) in the planar direction during polishing, and low stress (weak adhesive strength) in the vertical direction during removal.

[0003] As an example of such an adhesion process, a wafer support structure has been proposed, which has, from the wafer (1) side, a silicone oil layer, a separation layer (4) which is a plasma polymer layer, and a layer (5) of a partially cured or curable elastomer material between a semiconductor wafer (1) and a support layer (6) which is a support, and in which the adhesive bond between the support layer system and the separation layer (4) after the elastomer material has completely cured is greater than the adhesive bond between the wafer (1) and the separation layer (4) (see, for example, the examples in Patent Document 1).

[0004] In recent years, the following technology has been developed to reduce the number of layers between the semiconductor wafer and the support: (1) forming a film by applying an addition reaction curable adhesive composition to a first substrate; optionally, (2) heating the product of step (1); (3) attaching a second substrate to the film, at least one of the first and second substrates being a semiconductor wafer; (4) curing the film to form a cured film; (5) processing the semiconductor wafer; (6) removing the cured film with an etching solution; A method including the following has been proposed (see Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 5335443 [Patent Document 2] Special Publication No. 2008-532313 Summary of the Invention [Problem to be solved by the invention]

[0006] In the technology described in the examples of Patent Document 1, there are three layers interposed between the semiconductor substrate and the support substrate. On the other hand, in the technology described in Patent Document 2, there is only one layer interposed between the semiconductor substrate and the support substrate, and the technology described in Patent Document 2 achieves a simplified system. However, when the layer interposed between the semiconductor substrate and the support substrate is a single adhesive layer as in the technology described in Patent Document 2, the bumps on the semiconductor substrate may be deformed during processing of the semiconductor substrate.

[0007] Therefore, an object of the present invention is to provide a laminate that can suppress deformation of bumps while reducing the number of layers interposed between a semiconductor substrate and a support substrate when manufacturing a processed semiconductor substrate, a method for manufacturing a semiconductor substrate using the laminate, and a method for manufacturing the laminate. [Means for solving the problem]

[0008] 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.

[0009] That is, the present invention includes the following. [1] a support substrate; a semiconductor substrate having bumps on the support substrate side; an inorganic material layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate; an adhesive layer interposed between the support substrate and the inorganic material layer and in contact with the support substrate and the inorganic material layer; A laminate having the stack is used in an application in which the support substrate and the semiconductor substrate are separated after processing of the semiconductor substrate in the stack, a laminate in which, when the support substrate and the semiconductor substrate are separated, the adhesive strength between the inorganic material layer and the adhesive layer is smaller than the adhesive strength between the inorganic material layer and the semiconductor substrate. [2] The laminate according to [1], wherein the adhesive layer is a layer formed from an adhesive composition. [3] The laminate according to [2], wherein the adhesive composition contains a polyorganosiloxane. [4] The laminate according to [3], wherein the adhesive composition contains the polyorganosiloxane as a curable component (A) and a non-curable component (B). [5] The laminate according to [4], wherein the component (A) is a component that cures via a hydrosilylation reaction. [6] 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 platinum group metal catalyst (A2); The laminate according to [4] or [5], [7] The laminate according to any one of [4] to [6], wherein the component (B) is an optionally modified polydimethylsiloxane. [8] The laminate according to any one of [1] to [7], wherein the inorganic material layer is a layer obtained by plasma polymerizing an organosilicon compound on the semiconductor substrate. [9] A step of processing the semiconductor substrate in the laminate according to any one of [1] to [8]; separating the inorganic material layer from the adhesive layer to separate the support substrate from the processed semiconductor substrate; removing the inorganic material layer; A method for manufacturing a semiconductor substrate, comprising:

[10] The method for manufacturing a semiconductor substrate according to [9], wherein the processing step includes a process of polishing the surface of the semiconductor substrate opposite to the surface on which the bumps are present, to thin the semiconductor substrate.

[11] A method for producing a laminate according to any one of [1] to [8], forming the inorganic material layer on the surface of the semiconductor substrate where the bumps are present; forming an adhesive coating layer on the inorganic material layer to provide the adhesive layer; a step of heating the adhesive coating layer while the support substrate and the adhesive coating layer are in contact with each other and the adhesive coating layer and the inorganic material layer are in contact with each other to form the adhesive layer; A method for producing a laminate, comprising: [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a laminate that can suppress deformation of bumps while reducing the number of layers interposed between a semiconductor substrate and a support substrate when manufacturing a processed semiconductor substrate, a method for manufacturing a semiconductor substrate using the laminate, and a method for manufacturing the laminate. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic cross-sectional view of an example of a laminate. [Figure 2A] FIG. 1 is a diagram (part 1) for explaining one embodiment of manufacturing a laminate and a thinned wafer. [Figure 2B] FIG. 2 is a diagram (part 2) for explaining one embodiment of manufacturing a laminate and a thinned wafer. [Figure 2C] FIG. 3 is a diagram (part 3) for explaining one embodiment of manufacturing a laminate and a thinned wafer. [Figure 2D] FIG. 4 is a diagram (part 4) for explaining one embodiment of manufacturing a laminate and a thinned wafer. [Figure 2E] FIG. 5 is a diagram (part 5) for explaining one embodiment of manufacturing a laminate and a thinned wafer. [Figure 2F] FIG. 6 is a diagram (part 6) for explaining one embodiment of manufacturing a laminate and a thinned wafer. [Figure 2G] FIG. 7 is a diagram (part 7) for explaining one embodiment of manufacturing a laminate and a thinned wafer. [Figure 2H] FIG. 8 is a diagram (part 8) for explaining one embodiment of manufacturing a laminate and a thinned wafer. [Figure 2I] FIG. 9 is a diagram (part 9) for explaining one embodiment of manufacturing a laminate and a thinned wafer. DETAILED DESCRIPTION OF THE INVENTION

[0012] (Laminate) The laminate of the present invention has a support substrate, a semiconductor substrate, an inorganic material layer, and an adhesive layer. The semiconductor substrate has bumps on the support substrate side. The inorganic material layer is interposed between the support substrate and the semiconductor substrate. The inorganic material layer contacts the semiconductor substrate. The adhesive layer is interposed between the support substrate and the inorganic material layer. The adhesive layer contacts the support substrate and the inorganic material layer. The stack is used in applications where the support substrate and the semiconductor substrate are separated after processing of the semiconductor substrate in the stack. When the support substrate and the semiconductor substrate are separated, the adhesive force between the inorganic material layer and the adhesive layer is smaller than the adhesive force between the inorganic material layer and the semiconductor substrate. Here, "when the support substrate and the semiconductor substrate are separated, the adhesive force between the inorganic material layer and the adhesive layer is smaller than the adhesive force between the inorganic material layer and the semiconductor substrate" means that when the support substrate and the semiconductor substrate are separated by mechanical peeling, for example, when mechanically peeling and separating the support substrate and the semiconductor substrate using a material with a sharp portion, the inorganic material layer and the adhesive layer are separated, not the semiconductor substrate.

[0013] In the laminate, the inorganic material layer is formed in contact with the semiconductor substrate, so that deformation of the bumps can be suppressed when manufacturing a processed semiconductor substrate. This is thought to be because the bumps, which are likely to melt or deform due to the heat and pressure when processing the semiconductor substrate, are protected by the inorganic material layer, which is resistant to melting and deformation, and as a result, their shape is maintained. Furthermore, since the inorganic material layer and the adhesive layer can be separated when the support substrate and the semiconductor substrate are separated, there is no need to provide a peeling layer between the semiconductor substrate and the inorganic material layer, which reduces the number of layers interposed between the semiconductor substrate and the support substrate, and as a result, improved production efficiency can be expected.

[0014] <Support substrate> The support substrate is not particularly limited as long as it is a member that can support the semiconductor substrate when the semiconductor substrate is processed, and examples thereof include a glass support substrate and a silicon support substrate.

[0015] The shape of the support substrate is not particularly limited, but may be, for example, a disk. Note that the surface of a disk-shaped support substrate does not necessarily have to be a perfect circle, and for example, the outer periphery of the support substrate may have a straight portion called an orientation flat or a notch. The thickness of the disk-shaped support substrate may be appropriately determined depending on the size of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 μm. The diameter of the disk-shaped support substrate may be appropriately determined depending on the size of the semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.

[0016] An example of the support substrate is a glass wafer or a silicon wafer with a diameter of about 300 mm and a thickness of about 700 μmm.

[0017] <Semiconductor substrate> The semiconductor substrate has bumps, which are protruding terminals. In the stack, the semiconductor substrate has 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.

[0018] 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 disc-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 may be, for example, 100 to 1,000 mm.

[0019] An example of a semiconductor substrate is a silicon wafer with a diameter of about 300 mm and a thickness of about 770 μm.

[0020] 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, diameter and pitch of the bumps are determined appropriately based on the conditions of a bump height of about 1 to 200 μm, a bump diameter 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.

[0021] <Inorganic material layer> The inorganic material layer is not particularly limited as long as it is a layer made of an inorganic material, and examples thereof include layers formed from compounds such as oxides, nitrides, and carbides of at least one element selected from the group consisting of silicon, boron, titanium, zirconium, and aluminum, and mixtures thereof. Preferably, the inorganic material layer is a layer obtained by plasma polymerization of an organosilicon compound.

[0022] The inorganic material layer is formed, for example, by chemical vapor deposition (CVD), which involves, for example, plasma polymerization coating. Examples of materials used in plasma polymerization coating include organosilicon compounds. For example, by performing plasma polymerization coating of an organosilicon compound on a semiconductor substrate, a source gas containing the organosilicon compound is decomposed, and an inorganic material layer, which is a thin film containing Si-O bonds, can be formed on the surface of the semiconductor substrate. It is preferable to blend an oxygen-containing gas such as O2 or N2O into the source gas containing the organosilicon compound. Alternatively, a rare gas such as argon or helium may be blended into the source gas as a carrier gas. In a preferred example of a method for decomposing the source gas, a plasma generator is used to generate plasma under appropriate pressure conditions, and the source gas is decomposed by the plasma. The technique of using plasma to decompose the source gas and form a film (layer) is generally referred to as plasma polymerization.

[0023] Examples of the organosilicon compound include a siloxane compound, a disilazane compound, and a silane compound. Examples of siloxane compounds include 1,1,3,3-tetramethyldisiloxane, pentamethyldisiloxane, hexamethyldisiloxane, 1,1,3,3-tetraphenyl-1,3-dimethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, octamethyltrisiloxane, and 1,1,1,3,5,7,7,7-octamethyl Examples of the siloxane include linear siloxanes such as tetrasiloxane, decamethyltetrasiloxane, and 1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane; and cyclic siloxanes such as hexamethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane. Examples of disilazane compounds include 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, heptamethyldisilazane, hexamethylcyclotrisilazane, and 1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane. Examples of silane compounds include methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, trimethoxysilane, triethylsilane, trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, tetramethoxysilane, trimethoxymethylsilane, ethyltrimethoxysilane, dimethoxydimethylsilane, methoxytrimethylsilane, tetraethoxysilane, triethoxymethylsilane, triethoxyethylsilane, diethoxydimethylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethoxydimethylsilane, acetoxytrimethylsilane, allyloxytrimethylsilane, allyltrimethylsilane, butoxytrimethylsilane, butyltrimethoxysilane, diacetoxydimethylsilane, dimethoxydiphenylsilane, and diethoxytrimethylsilane. Examples of the silane include diphenylsilane, dimethoxymethylphenylsilane, ethoxydimethylvinylsilane, diphenylsilanediol, triacetoxymethylsilane, triacetoxyethylsilane, 3-glycidyloxypropyltrimethoxysilane, hexyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, octadecyltriethoxysilane, triethoxyoctylsilane, triethoxyphenylsilane, trimethylphenylsilane, propoxytrimethylsilane, triethoxypropylsilane, tetraacetoxysilane, tetrabutoxysilane, tetrapropoxysilane, triacetoxyvinylsilane, triethoxyvinylsilane, trimethoxyvinylsilane, triphenylsilanol, trimethylvinylsilane, and tris(2-methoxyethoxy)vinylsilane.

[0024] The inorganic material layer is formed on the semiconductor substrate, which allows the layer to conform to the shape of the bumps on the semiconductor substrate, thereby providing a superior effect of suppressing deformation of the bumps.

[0025] The thickness of the inorganic material layer is not particularly limited, but is usually 1 to 1,000 nm, and from the viewpoint of realizing reproducible suppression of bump deformation, it is preferably 100 to 500 nm.

[0026] <Adhesive layer> The adhesive layer is interposed between the support substrate and the inorganic material layer. The adhesive layer is a layer that contacts the support substrate and the inorganic material layer.

[0027] The adhesive layer is not particularly limited, but is preferably a layer formed from an adhesive composition.

[0028] <<Adhesive composition>> Examples of adhesive compositions include, but are not limited to, polysiloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives. Among these, polysiloxane adhesives are preferred as adhesive compositions because they exhibit suitable adhesive properties when processing semiconductor substrates and the like, can be easily peeled off after processing, and also have excellent heat resistance.

[0029] In a preferred embodiment, the adhesive composition used in the present invention contains a polyorganosiloxane. In another preferred embodiment, the adhesive composition used in the present invention contains a curable component (A) that serves as the adhesive component and a component (B) that does not undergo a curing reaction. An example of the component (B) that does not undergo a curing reaction is polyorganosiloxane. Note that, in the present invention, "does not undergo a curing reaction" does not mean that any curing reaction does not occur, but rather that the curing reaction occurring in the curable component (A) does not occur. In another preferred embodiment, component (A) may be a component that cures via a hydrosilylation reaction, or may be 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 platinum group metal 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 hydroxyl 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 platinum group metal 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 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 "R5 "SiO 2 / 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).

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] Specific examples of the optionally substituted cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a 1,2-dimethylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, a cyclohexyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1-ethylcyclobutyl group, a 2-ethylcyclobutyl group, a 3-ethylcyclobutyl group, a 1,2-dimethylcyclobutyl group, a 1,3-dimethylcyclobutyl group, a 2,2-dimethylcyclobutyl group, a 2,3-dimethylcyclobutyl group, a 2,4-dimethylcyclobutyl group, a 3,3-dimethylcyclobutyl group, a cyclohexyl ... Examples of cycloalkyl groups include methyl-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 is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0036] 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.

[0037] 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.

[0038] As described above, the polysiloxane (A1) contains the polyorganosiloxane (a1') and the polyorganosiloxane (a2'), and the alkenyl group contained in the polyorganosiloxane (a1') and the hydrogen atom (Si-H group) contained in the polyorganosiloxane (a2') undergo a hydrosilylation reaction with the platinum group metal catalyst (A2) to form a crosslinked structure and cure, resulting in the formation of a cured film.

[0039] 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.

[0040] 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).

[0041] 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.

[0042] 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.

[0043] 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).

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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 the polyorganosiloxane can be measured using, for example, a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (manufactured by Sigma-Aldrich) as a standard sample.

[0048] 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.

[0049] 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.

[0050] In a preferred embodiment of the present invention, the adhesive composition contains a platinum group metal catalyst (A2) together with the polyorganosiloxane component (A'). 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).

[0051] 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. The amount of the platinum group metal 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).

[0052] 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-propion-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.

[0053] An example of the adhesive composition used in the present invention may contain, in addition to the curable component (A), a component (B) that does not undergo a curing reaction and becomes a release agent component. By including such component (B) in the adhesive composition, the adhesive strength between the inorganic material layer and the adhesive layer can be made smaller than the adhesive strength between the inorganic material layer and the semiconductor substrate, and the resulting adhesive layer can be suitably peeled off with good reproducibility. Such component (B) typically includes polyorganosiloxanes, 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.

[0054] 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.

[0055] 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 by the methods described above for polysiloxane. 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:

[0056] Examples of epoxy group-containing polyorganosiloxanes include R 11 R 12 SiO 2 / 2 The siloxane unit (D 10 Examples include those containing units.

[0057] R 11 is a group bonded to a silicon atom and represents an alkyl group; R 12 is a group bonded to a silicon atom, and represents an epoxy group or an organic group containing an epoxy group, 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.

[0058] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 10 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.

[0059] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. Furthermore, its weight average molecular weight is not particularly limited, but is usually 1,500 to 500,000, and from the viewpoint of suppressing precipitation in the adhesive, it is preferably 100,000 or less.

[0060] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0061] [ka] (m1 and n1 represent the number of each repeating unit and are positive integers.)

[0062] [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.)

[0063] [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.)

[0064] 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.

[0065] 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.

[0066] 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.

[0067] In one embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include D 200 Polyorganosiloxane consisting of only units, D 200 polyorganosiloxanes containing D units and Q units; 200 Polyorganosiloxanes containing D units and M units, 200 Polyorganosiloxanes containing D units and T units, 200 polyorganosiloxanes containing units, Q units and M units, D 200 Polyorganosiloxanes containing units, M units and T units, D 200 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0068] 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.

[0069] Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1).

[0070] [ka] (n4 represents the number of repeating units and is a positive integer.)

[0071] 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.

[0072] R 31 is a group bonded to a silicon atom and represents a phenyl group or an alkyl group; R 32 is a group bonded to a silicon atom, and represents a phenyl group. Specific examples of the alkyl group include those listed above, with a methyl group being preferred.

[0073] 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.

[0074] 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.

[0075] Specific examples of the methyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

[0076] [ka] (m5 and n5 each represent the number of repeating units and are positive integers.)

[0077] [ka] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0078] In a preferred embodiment, the adhesive composition used in the present invention contains a component (A) that hardens and a component (B) that does not undergo a curing reaction, and in a more preferred embodiment, component (B) contains a polyorganosiloxane.

[0079] An example of the adhesive composition used in the present invention can contain component (A) and component (B) in any ratio. However, taking into consideration the balance between adhesion and releasability, 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.

[0080] The adhesive composition used in the present invention may contain a solvent for the purpose of adjusting the viscosity, etc., and specific examples of the solvent include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.

[0081] 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.

[0082] When the adhesive composition used in the present invention contains a solvent, the content of the solvent is appropriately set taking into consideration the desired viscosity of the composition, the coating method to be used, the thickness of the film to be produced, etc., but is in the range of about 10 to 90 mass % of the entire composition.

[0083] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is typically 500 to 20,000 mPa·s, and preferably 1,000 to 5,000 mPa·s at 25° C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the types of solvents used, their ratios, the concentrations of the film-constituting components, etc., taking into consideration various factors such as the coating method used and the desired film thickness.

[0084] An example of an adhesive composition for use 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 an adhesive 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 adhesive composition, heating may be performed as appropriate within a range that does not cause the components to decompose or deteriorate. In the present invention, in order to remove foreign matter, the solvent, solution, etc. used may be filtered using a submicrometer-order filter during the production of the adhesive composition or after all of the components have been mixed.

[0085] The thickness of the adhesive layer provided in the laminate of the present invention is not particularly limited, but is usually 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 due to a 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 70 μm or less.

[0086] An example of the laminate will be described below with reference to the drawings. FIG. 1 is a schematic cross-sectional view of an example of a laminate. The laminate in FIG. 1 includes a semiconductor substrate 1 having bumps 1a, an inorganic material layer 2, an adhesive layer 3, and a support substrate 4 in this order. The bumps 1a of the semiconductor substrate 1 are disposed on the support substrate 4 side. The inorganic material layer 2 is interposed between the semiconductor substrate 1 and the support substrate 4. The inorganic material layer 2 is in contact with the semiconductor substrate 1. The inorganic material layer 2 covers the bumps 1a. The adhesive layer 3 is interposed between the inorganic material layer 2 and the support substrate 4. The adhesive layer 3 is in contact with the inorganic material layer 2 and the support substrate 4.

[0087] The laminate of the present invention is preferably produced, for example, by the following method for producing the laminate of the present invention.

[0088] (Method of manufacturing laminate) The method for producing the laminate of the present invention includes an inorganic material layer forming step, an adhesive coating layer forming step, and an adhesive layer forming step, and may further include other steps such as a lamination step, if necessary.

[0089] <Inorganic material layer formation process> The inorganic material layer forming process is not particularly limited as long as it is a process in which an inorganic material layer is formed on the surface of a semiconductor substrate on which bumps are present, and examples thereof include a process including the inorganic material layer forming method described above in the description of the inorganic material layer.

[0090] <Adhesive Coating Layer Forming Process> The adhesive coating layer forming step is not particularly limited as long as it is a step of forming an adhesive coating layer that ultimately provides an adhesive layer that contacts the support substrate and the inorganic material layer, and examples thereof include a step of applying an adhesive composition onto the inorganic material layer or the support substrate, followed by heating (preheating treatment) to form an adhesive coating layer that is an uncured or incompletely cured adhesive layer. In this way, the adhesive coating layer is formed on the inorganic material layer formed on the semiconductor substrate, or on the support substrate.

[0091] The coating method is not particularly limited, but is usually a spin coating method. Alternatively, a method may be employed in which a coating film is formed separately by a spin coating method or the like, and the sheet-like coating film is attached as an adhesive coating layer. The thickness of the adhesive coating layer is determined appropriately taking into consideration the thickness of the adhesive layer in the laminate, etc. When the adhesive composition contains a solvent, the applied adhesive composition is usually heated. The heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc., but is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes. Heating can be carried out using a hot plate, an oven, or the like.

[0092] <Adhesive layer formation process> The adhesive layer forming step is not particularly limited as long as it is a step of heating the adhesive coating layer while the support substrate and the adhesive coating layer are in contact with each other and the adhesive coating layer and the inorganic material layer are in contact with each other to form an adhesive layer (post-heat treatment). For example, using a semiconductor substrate and a support substrate on which an inorganic material layer and an adhesive coating layer are formed, or using a semiconductor substrate and a support substrate on which an inorganic material layer is formed and an adhesive coating layer, the two substrates (semiconductor substrate and support substrate) are arranged so as to sandwich the two layers (inorganic material layer and adhesive coating layer), so that the support substrate and the adhesive coating layer are in contact with each other and the adhesive coating layer and the inorganic material layer are in contact with each other, and then heat treatment may be performed. The heating temperature and time are not particularly limited as long as the temperature and time are such that the adhesive coating layer is converted into an adhesive layer. The heating temperature is preferably 120°C or higher from the viewpoint of achieving a sufficient curing rate, and is preferably 260°C or lower from the viewpoint of preventing deterioration of each layer (including the support substrate and semiconductor substrate) that constitutes the laminate. The heating time is preferably 1 minute or more, more preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of each layer (including the support substrate and semiconductor substrate) constituting the laminate, and is preferably 180 minutes or less, more preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be carried out using a hot plate, an oven, or the like.

[0093] <Lamination process> Between the adhesive layer forming steps, a bonding step is preferably carried out to ensure sufficient bonding between the semiconductor substrate and the support substrate. The bonding step is not particularly limited as long as it allows the substrate and the layer to be bonded together and does not damage the substrate or the layer, but is typically a step in which a load is applied in the thickness direction of the support substrate and the semiconductor substrate, and more preferably a step in which a load is applied in the thickness direction of the support substrate and the semiconductor substrate under reduced pressure. The load is not particularly limited as long as it allows the substrate and layer to be bonded together and does not damage the substrate or layer, but is, for example, 10 to 1,000 N. The degree of reduced pressure is not particularly limited as long as it allows bonding of the substrate and the layer and does not damage the substrate or the layer, but is, for example, 10 to 10,000 Pa.

[0094] (Method of manufacturing semiconductor substrate) The method for manufacturing a semiconductor substrate of the present invention includes at least a processing step, a peeling step, and a removing step, and may further include other steps as necessary.

[0095] <Processing process> The processing step is not particularly limited as long as it is a step in which the semiconductor substrate in the laminate of the present invention is processed, and includes, for example, a polishing process, a through electrode formation process, and the like.

[0096] <<Polishing process>> The polishing process is not particularly limited as long as it is a process for polishing the surface of the semiconductor substrate opposite to the surface on which the bumps are present, thereby thinning the semiconductor substrate. For example, physical polishing using an abrasive or a grinding stone may be used. The polishing process can be carried out using a general polishing device used for polishing semiconductor substrates. The polishing process reduces the thickness of the semiconductor substrate, resulting in a semiconductor substrate thinned to a desired thickness. The thickness of the thinned semiconductor substrate is not particularly limited, but may be, for example, 30 to 300 μm or 30 to 100 μm.

[0097] <<Through electrode formation process>> In some cases, through electrodes are formed in the polished semiconductor substrate to realize electrical continuity between the thinned semiconductor substrates when a plurality of thinned semiconductor substrates are stacked. Therefore, the method for manufacturing a semiconductor substrate may include a through electrode forming process for forming a through electrode in the polished semiconductor substrate after the polishing process and before the peeling step. The method for forming a through electrode in a semiconductor substrate is not particularly limited, but may include, for example, forming a through hole and filling the formed through hole with a conductive material. The through holes are formed by, for example, photolithography. The through holes are filled with a conductive material by, for example, plating techniques.

[0098] <Peeling process> The peeling step is not particularly limited as long as it is a step in which the inorganic material layer and the adhesive layer are separated from each other after the processing step, thereby separating the support substrate and the processed semiconductor substrate, and examples thereof include a method of mechanically peeling the inorganic material layer and the adhesive layer using a tool having a sharp portion. Specifically, for example, the sharp portion is inserted between the support substrate and the semiconductor substrate to separate the inorganic material layer and the adhesive layer. The peeling step can be performed using a general peeling device that is used for peeling a support substrate from a semiconductor substrate.

[0099] <Removal process> The removal step is not particularly limited as long as it is a step in which the inorganic material layer is removed after the peeling step, and examples thereof include dissolution removal. Removal may also be performed using removal tape or the like. Note that if there is residue of the adhesive layer on the inorganic material layer after the peeling step, the residue is also removed in the removal step. When using the cleaning composition, for example, the semiconductor substrate with the inorganic material layer can be immersed in the cleaning composition or sprayed with the cleaning composition.

[0100] A suitable example of the cleaning composition used in the present invention is a cleaning 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.

[0101] In the present invention, 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.

[0102] 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.

[0103] 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.

[0104] The solvent contained in the cleaning composition used in the present invention is not particularly limited as long as it is used for this type of application and can dissolve salts such as the quaternary ammonium salt. However, from the viewpoint of reproducibly obtaining a cleaning composition having excellent cleaning properties and from the viewpoint of satisfactorily dissolving salts such as the quaternary ammonium salt to obtain a cleaning composition with excellent uniformity, the cleaning composition used in the present invention preferably contains one or more amide solvents.

[0105] A suitable example of the amide solvent is an acid amide derivative represented by formula (Z). [ka]

[0106] In the formula, R 0 represents an ethyl group, a propyl group, or an isopropyl group, and an ethyl group is preferred. 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.

[0107] 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. Of these, N,N-dimethylpropionamide is particularly preferred.

[0108] 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.

[0109] Another example of a preferred amide solvent is a lactam compound represented by formula (Y). [ka]

[0110] In the formula, R 101 represents an alkyl group having 1 to 6 carbon atoms. 102 represents an alkylene group having 1 to 6 carbon atoms. In the formula (Y), 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.

[0111] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, and δ-lactam compounds, which can be used alone or in combination of two or more.

[0112] In a preferred embodiment of the present invention, the lactam compound represented by formula (Y) includes 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, it includes N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it includes N-methylpyrrolidone (NMP).

[0113] The cleaning composition used in the present invention may contain one or more other organic solvents different from the above-mentioned amide compound. Such other organic solvents are not particularly limited as long as they are used for this type of application and are compatible with the above-mentioned amide compounds. Other preferred solvents include, but are not limited to, alkylene glycol dialkyl ethers, aromatic hydrocarbon compounds, and ether compounds containing a ring structure. The amount of the organic solvent other than the above-mentioned amide compound is usually determined appropriately so as to be 95 mass % or less of the solvent contained in the cleaning composition, as long as the quaternary ammonium salt contained in the cleaning composition does not precipitate or separate and is uniformly mixed with the above-mentioned amide compound. 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.

[0114] An example of an embodiment in which the production of a laminate and the production of a thinned wafer are carried out in succession will be described with reference to FIGS. 2A to 2I. 2A to 2I are diagrams for explaining an embodiment of manufacturing a laminate and a thinned wafer. First, a wafer 1 having bumps 1a is prepared (FIG. 2A). Next, an inorganic material layer 2 is formed on the surface of the wafer 1 where the bumps 1a are present by plasma polymerization coating of an organosilicon compound 11 (FIG. 2B). Next, an adhesive composition is applied onto the inorganic material layer 2 by spin coating using a coating device 12 to form an adhesive coating layer 3a (FIG. 2C). Next, a heating device (hot plate) 13 is placed on the side of the wafer 1 opposite to the side on which the bumps 1a are present, and the adhesive coating layer 3a is heated by the heating device 13 to remove volatile components from the adhesive coating layer 3a (Figure 2D). Next, a support substrate 4 is placed on the adhesive coating layer 3a (FIG. 2E). Next, a load is applied in the thickness direction of the wafer 1 and the support substrate 4 under reduced pressure, and then a heating device (hot plate) 14 is placed on the side of the wafer 1 opposite to the side on which the bumps 1a are present, and the adhesive coating layer 3a is heated and hardened by the heating device 14, converting it into an adhesive layer 3 (Figure 2F). A laminate is obtained through the steps shown in FIGS. 2A to 2F. Next, an example of manufacturing a thinned wafer will be described. Next, a polishing machine (not shown) is used to polish the surface of the wafer 1 opposite to the surface on which the bumps 1a are present, thereby thinning the wafer 1 (FIG. 2G). Note that the thinned wafer 1 may be subjected to the formation of through electrodes, etc. Next, a peeling device (not shown) is used to peel the thinned wafer 1 from the support substrate 4 (FIG. 2H). At this time, the inorganic material layer 2 and the adhesive layer 3 are peeled off, and the thinned wafer 1 is thereby peeled off from the support substrate 4. Next, the thinned wafer 1 is cleaned by using a cleaning device 15 to dissolve and remove the inorganic material layer 2 from the thinned wafer 1 with a cleaning agent composition 16 (FIG. 2I). In this way, a thinned wafer 1 is obtained. [Example]

[0115] 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.

[0116] (1) Mixer: Thinky Corporation Rotating and Revolving Mixer ARE-500 (2) Vacuum bonding device: SUSS MicroTec Autobonder (3) Peeling device: Manual debonder manufactured by SUSS Microtec Co., Ltd. (4) Optical film thickness meter (film thickness measurement): Filmetrics F-50 (5) High-rigidity grinder: HRG300 manufactured by Tokyo Seimitsu Co., Ltd. (6) Dicing machine: SS30 manufactured by Tokyo Seimitsu Co., Ltd. (7) Heat and pressure bonding device: Ayumi Industries Co., Ltd., pasting device

[0117] [1] Preparation of adhesive composition [Preparation Example 1] Into a 600 mL stirring vessel dedicated to the stirrer, 104.14 g of a p-menthane solution (concentration 80.6% by mass) of an MQ resin (manufactured by Wacker Chemical Co.) having a polysiloxane skeleton and a vinyl group as component (a1), and 104.14 g of a polyorganosiloxane represented by the following formula (M1-1) (manufactured by Wacker Chemical Co., trade name AK1000000, viscosity 1000000 mm) as component (B) were added. 2 58.11 g of ethanol (manufactured by Nippon Terpene Chemical Co., Ltd.) and 34.94 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) and 6.20 g of n-decane (manufactured by Sankyo Chemical Co., Ltd.) as solvents were added, and the mixture was stirred for 5 minutes with the stirrer to obtain a mixture (I). To the resulting mixture (I), 16.79 g of component (a2), a linear polydimethylsiloxane containing SiH groups and having a viscosity of 100 mPa·s (manufactured by Wacker Chemical Co.), and 24.54 g of component (a1), a linear polydimethylsiloxane containing vinyl groups and having a viscosity of 200 mPa·s (manufactured by Wacker Chemical Co.), were added to obtain mixture (II). 1.61 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.61 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) as component (A3) and 3.23 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) as a solvent were stirred in the stirrer for 60 minutes to obtain a mixture (III). 1.29 g of the obtained mixture (III) was added to the mixture (II), and the mixture was stirred for 5 minutes with the stirrer to obtain a mixture (IV). 0.65 g of a platinum catalyst (manufactured by Wacker Chemie) as component (A2) and 19.37 g of a vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1000 mPa·s as component (a1) were stirred for 5 minutes in the stirrer to obtain mixture (V). 4.00 g of the obtained mixture (V) was added to the mixture (IV), and the mixture was stirred for 5 minutes with the stirrer to obtain a mixture (VI). Finally, the resulting mixture (VI) was filtered through a 300-mesh nylon filter to obtain an adhesive composition having a viscosity of 3000 mPa·s.

[0118] [ka] (In the formula, a represents the number of repeating units.)

[0119] [2] Preparation of cleaning composition [Preparation Example 2] 6 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Inc.) was mixed with 94 g of N,N-dimethylpropionamide and stirred thoroughly to obtain a detergent composition.

[0120] [3] Evaluation of adhesion and peelability [3-1] [Example 1-1] A plasma polymer layer (320 nm thick) derived from hexamethyldisiloxane (HMDSO) was formed as an inorganic material layer by CVD on the circuit side of a 300 mm silicon wafer (770 μm thick) used as the device wafer. CVD was performed under conditions of 40 W, 65 mTorr, and an HMDSO flow rate of 15 sccm. The adhesive composition obtained in Preparation Example 1 was applied to the plasma polymer layer by spin coating and heated at 120°C for 1.5 minutes (pre-heat treatment), forming an adhesive coating layer on the plasma polymer layer such that the adhesive layer in the resulting laminate would be approximately 65 μm thick. Then, in a vacuum bonding apparatus, the silicon wafer having the plasma polymer layer and adhesive coating layer was bonded to a 300 mm glass wafer (thickness: 700 μm) as a carrier-side wafer (support) so that the plasma polymer layer and adhesive coating layer were sandwiched between them, and the wafer was heated on a hot plate with the device side facing down at 200°C for 10 minutes (post-heat treatment) to produce a laminate. The bonding was performed at a temperature of 23°C, a vacuum level of 1,000 Pa, and a load of 100 N.

[0121] [Example 1-2] A plasma polymer layer (500 nm thick) derived from HMDSO was formed as an inorganic material layer by CVD on the circuit side of a 300 mm silicon wafer (770 μm thick) used as the device wafer. CVD was performed under conditions of 120 W, 65 mTorr, and an HMDSO flow rate of 15 sccm. The adhesive composition obtained in Preparation Example 1 was applied to the plasma polymer layer by spin coating and heated at 120°C for 1.5 minutes (pre-heat treatment), forming an adhesive coating layer on the plasma polymer layer so that the adhesive layer in the resulting laminate would be approximately 65 μm thick. Then, in a vacuum bonding apparatus, the silicon wafer having the plasma polymer layer and adhesive coating layer was bonded to a 300 mm glass wafer (thickness: 700 μm) as a carrier-side wafer (support) so that the plasma polymer layer and adhesive coating layer were sandwiched between them, and the wafer was heated on a hot plate with the device side facing down at 200°C for 10 minutes (post-heat treatment) to produce a laminate. The bonding was performed at a temperature of 23°C, a vacuum level of 1,000 Pa, and a load of 100 N.

[0122] [Comparative Example 1-1] The adhesive composition obtained in Preparation Example 1 was spin-coated onto a 300 mm silicon wafer (thickness: 770 μm) as the device side wafer, and heated at 120°C for 1.5 minutes (pre-heat treatment) to form an adhesive coating layer on the circuit side of the wafer so that the thickness of the adhesive layer in the resulting laminate would be approximately 65 μm. The silicon wafer with the adhesive coating layer was then bonded to a 300 mm glass wafer (thickness: 700 μm) as a carrier wafer (support) in a vacuum bonding apparatus, sandwiching the adhesive coating layer between them, and then heated on a hot plate with the device side facing down at 200°C for 10 minutes (post-heat treatment) to produce a laminate. The bonding was performed at a temperature of 23°C, a vacuum level of 1,000 Pa, and a load of 100 N.

[0123] [3-2] Evaluation of adhesion and peelability The laminates obtained in Examples 1-1 and 1-2 were used to evaluate the adhesiveness and peelability of the adhesive layer. Adhesion was evaluated by visually checking for the presence or absence of voids from the glass wafer (support) side of the laminate; if no voids were observed, the adhesive was rated as good, and if voids were observed, the adhesive was rated as poor. As a result, no voids were found in the laminates obtained in Examples 1-1 and 1-2. The peelability was evaluated by measuring the force required for peeling, and if peeling was possible with the peeling device, it was rated as good, and if peeling was not possible, it was rated as bad. The peeling point was between the plasma polymer layer and the adhesive layer. As a result, in each of the laminates obtained in Examples 1-1 and 1-2, the plasma polymer layer and the adhesive layer could be satisfactorily peeled off with a force of 16N.

[0124] [3-3] Checking cleaning performance The semiconductor substrate with the plasma polymer layer peeled from the laminate obtained in Example 1-1 was fixed and cut into 4 cm × 4 cm chips using a dicing machine. These chips were immersed in 9 mL of the cleaning composition obtained in Preparation Example 2 for 1 minute, and the presence or absence of adhesive residue and a plasma polymer layer on the chips was confirmed using an optical microscope and an optical film thickness meter. As a result, no adhesive residue or plasma polymer layer was found on the chip, and it was confirmed that these could be successfully removed by immersion in the cleaning composition.

[0125] [4] Preparation of laminate for high-temperature and high-pressure processing test [4-1] Fabrication of laminate [Example 2-1] A plasma polymer layer (320 nm thick) derived from HMDSO was formed as an inorganic material layer on the circuit side of a 300 mm PI TEG silicon wafer (thickness: 770 μm, bump diameter: 0.03 mm, bump height: 0.04 mm, bump pitch: 0.06 × 0.1 mm) by CVD. CVD was performed under conditions of 40 W, 65 mTorr, and an HMDSO flow rate of 15 sccm. The adhesive composition obtained in Preparation Example 1 was spin-coated onto the plasma polymer layer and heated at 120°C for 1.5 minutes (pre-heat treatment), forming an adhesive coating layer on the plasma polymer layer so that the adhesive layer in the resulting laminate would be approximately 65 μm thick. Then, in a vacuum bonding apparatus, the silicon wafer having the plasma polymer layer and adhesive coating layer was bonded to a 300 mm glass wafer (thickness: 700 μm) as a carrier-side wafer (support) so that the plasma polymer layer and adhesive coating layer were sandwiched between them, and the wafer was placed on a hot plate with the device side facing down and heated at 200°C for 10 minutes (post-heat treatment) to produce a laminate. The bonding was performed at a temperature of 23°C, a vacuum level of 1,000 Pa, and a load of 100 N. The silicon wafer of the obtained laminate was thinned to a thickness of 50 μm using a high-rigidity grinder, and then the thinned silicon wafer side was attached and fixed to a dicing tape (DU-300, manufactured by Nitto Denko Corporation) with the thinned silicon wafer side facing downward. The fixed laminate was cut into 4 cm x 4 cm pieces using a dicing machine, and cut out as 4 cm square laminate chips to be used in high-temperature, high-pressure processing tests.

[0126] [Example 2-2] A 500 nm thick plasma polymer layer derived from HMDSO was formed as an inorganic material layer on the circuit side of a 300 mm PI TEG silicon wafer (770 μm thick, 0.03 mm bump diameter, 0.04 mm bump height, 0.06 × 0.1 mm bump pitch) by CVD. CVD was performed at 120 W, 65 mTorr, and an HMDSO flow rate of 15 sccm. The adhesive composition obtained in Preparation Example 1 was spin-coated onto the plasma polymer layer and heated at 120°C for 1.5 minutes (pre-heat treatment). This formed an adhesive layer on the plasma polymer layer, resulting in an adhesive layer thickness of approximately 65 μm in the resulting laminate. Then, in a vacuum bonding apparatus, the silicon wafer having the plasma polymer layer and adhesive coating layer was bonded to a 300 mm glass wafer (thickness: 700 μm) as a carrier-side wafer (support) so that the plasma polymer layer and adhesive coating layer were sandwiched between them, and the wafer was placed on a hot plate with the device side facing down and heated at 200°C for 10 minutes (post-heat treatment) to produce a laminate. The bonding was performed at a temperature of 23°C, a vacuum level of 1,000 Pa, and a load of 100 N. The silicon wafer of the obtained laminate was thinned to a thickness of 50 μm using a high-rigidity grinder, and then the thinned silicon wafer side was attached and fixed to a dicing tape (DU-300, manufactured by Nitto Denko Corporation) with the thinned silicon wafer side facing downward. The fixed laminate was cut into 4 cm x 4 cm pieces using a dicing machine, and cut out as 4 cm square laminate chips to be used in high-temperature, high-pressure processing tests.

[0127] [Comparative Example 2-1] The adhesive composition obtained in Preparation Example 1 was spin-coated onto a PI TEG 300 mm silicon wafer (thickness: 770 μm, bump diameter: 0.03 mm, bump height: 0.04 mm, bump pitch: 0.06 × 0.1 mm) as the device wafer, and heated at 120°C for 1.5 minutes (pre-heat treatment) to form an adhesive coating layer on the circuit side of the wafer so that the thickness of the adhesive layer in the resulting laminate was approximately 65 μm. The silicon wafer with the adhesive coating layer was then bonded to a 300 mm glass wafer (thickness: 700 μm) as a carrier wafer (support) in a vacuum bonding apparatus, sandwiching the adhesive coating layer between them, and then heated on a hot plate with the device side facing down at 200°C for 10 minutes (post-heat treatment) to produce a laminate. The bonding was performed at a temperature of 23°C, a vacuum level of 1,000 Pa, and a load of 100 N. The silicon wafer of the obtained laminate was thinned to a thickness of 50 μm using a high-rigidity grinder, and then the thinned silicon wafer side was attached and fixed to a dicing tape (DU-300, manufactured by Nitto Denko Corporation) with the thinned silicon wafer side facing downward. The fixed laminate was cut into 4 cm x 4 cm pieces using a dicing machine, and cut out as 4 cm square laminate chips to be used in high-temperature, high-pressure processing tests.

[0128] [5] High-temperature and high-pressure treatment test Using a thermocompression bonding device, high-temperature and high-pressure treatment was performed on the chips of each of the laminates obtained in Example 2-1, Example 2-2, and Comparative Example 2-1. The treatment was performed according to the following procedure. The glass wafer (support substrate) of the stacked chips was placed face down on a stage set at 60°C, and the temperature was 270°C and the pressure was 160 N / cm. 2 The silicon wafer and the glass wafer were heated while applying pressure from the silicon wafer (semiconductor substrate) side in the direction perpendicular to the silicon wafer and the glass wafer under the thermocompression bonding conditions of 20 seconds and a treatment time of 20 seconds. After processing, the condition of the silicon wafer of each stack was observed through the glass wafer support substrate using an optical microscope, and the presence or absence of bump deformation was visually confirmed. There were 5,044 bumps in one stack chip, and a case where the number of deformed bumps was 200 or less was rated as good, and a case where the number was more than 200 was rated as bad. The results are shown in Table 1.

[0129] [Table 1]

[0130] As shown in Table 1, the laminate including the plasma polymer layer derived from HMDSO as the inorganic material layer was able to suppress the bump deformation caused by the high-temperature and high-pressure treatment. [Industrial Applicability]

[0131] According to the present invention, it is possible to suppress deformation of bumps while reducing the number of layers interposed between a semiconductor substrate and a support substrate, and therefore the present invention is useful in manufacturing processed semiconductor substrates. [Explanation of symbols]

[0132] 1 wafer 1a Bump 2 Inorganic material layer 3 Adhesive layer 3a Adhesive coating layer 4 Support substrate 11 Organosilicon compounds 12 Coating equipment 13 Heating device 14 Heating device 15 Cleaning equipment 16 Cleaning composition

Claims

1. A support substrate; a semiconductor substrate having bumps on the support substrate side; an inorganic material layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate; an adhesive layer interposed between the support substrate and the inorganic material layer and in contact with the support substrate and the inorganic material layer; A laminate having the stack is used in an application in which the support substrate and the semiconductor substrate are separated after processing of the semiconductor substrate in the stack, a laminate in which, when the support substrate and the semiconductor substrate are separated, the adhesive strength between the inorganic material layer and the adhesive layer is smaller than the adhesive strength between the inorganic material layer and the semiconductor substrate.

2. The laminate according to claim 1 , wherein the adhesive layer is a layer formed from an adhesive composition.

3. The laminate according to claim 2 , wherein the adhesive composition contains a polyorganosiloxane.

4. The laminate according to claim 3, wherein the adhesive composition contains a curable component (A) and the polyorganosiloxane as a component (B) that does not undergo a curing reaction.

5. 5. The laminate according to claim 4, wherein the component (A) is a component that cures via a hydrosilylation reaction.

6. 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 platinum group metal catalyst (A2); The laminate according to claim 4 or 5, comprising:

7. 7. The laminate according to claim 4, wherein the component (B) is an optionally modified polydimethylsiloxane.

8. 8. The laminate according to claim 1, wherein the inorganic material layer is a layer obtained by plasma polymerizing an organosilicon compound on the semiconductor substrate.

9. A step of processing the semiconductor substrate in the stack according to any one of claims 1 to 8; separating the inorganic material layer from the adhesive layer to separate the support substrate from the processed semiconductor substrate; removing the inorganic material layer; A method for manufacturing a semiconductor substrate, comprising:

10. The method for manufacturing a semiconductor substrate according to claim 9 , wherein the processing step includes a process of polishing a surface of the semiconductor substrate opposite to a surface on which the bumps are present, to thin the semiconductor substrate.

11. A method for producing a laminate according to any one of claims 1 to 8, comprising the steps of: forming the inorganic material layer on the surface of the semiconductor substrate where the bumps are present; forming an adhesive coating layer on the inorganic material layer to provide the adhesive layer; a step of heating the adhesive coating layer while the support substrate and the adhesive coating layer are in contact with each other and the adhesive coating layer and the inorganic material layer are in contact with each other to form the adhesive layer; A method for producing a laminate, comprising:

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