Adhesive composition, laminate, and production method for processed semiconductor substrate

Abstract

Provided is an adhesive composition for forming an adhesive layer in a laminate having a first base body that is a semiconductor substrate or an electronic device layer, a second base body that is a support substrate that transmits infrared laser light, and the adhesive layer provided between the first base body and the second base body, the adhesive layer being used in the process in which, after the first base body is processed, the adhesive layer is irradiated with the infrared laser light from the second base body side, and the first base body and the second base body are subsequently separated from each other. The adhesive composition contains an adhesive component having a siloxane bond and a release agent component.

Description

Adhesive composition, laminate, and method for producing processed semiconductor substrate

[0001] The present invention relates to adhesive compositions, laminates, and methods for producing processed semiconductor substrates.

[0002] Semiconductor wafers have traditionally been integrated in a two-dimensional plane, but for the purpose of further integration, semiconductor integration technology is required that integrates (stacks) the plane in a three-dimensional plane as well. 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 to 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), temporary adhesives containing epoxy-modified polysiloxane (Patent Document 2), etc. have been proposed. In these techniques, the support and the semiconductor wafer are separated by inserting a sharp part of a device having a sharp part called a debonder into the layer of the temporary adhesive.

[0005] On the other hand, there have been proposals for peeling a support and a semiconductor wafer using infrared rays. For example, there has been proposed an infrared peeling adhesive composition that can be peeled off by infrared irradiation, and that contains a component (A) that cures by a hydrosilylation reaction and at least one component (B) selected from the group consisting of a component containing an epoxy-modified polyorganosiloxane, a component containing a methyl group-containing polyorganosiloxane, and a component containing a phenyl group-containing polyorganosiloxane (Patent Document 3). Furthermore, a method for peeling a laminate has been proposed, which includes a first step of bonding a first substrate formed of a semiconductor substrate and a second substrate formed of a support substrate transparent to infrared laser light via a first adhesive layer provided on the first substrate side and a second adhesive layer provided on the second substrate side, the first adhesive layer being an adhesive layer obtained by curing an adhesive (A) containing a component that cures via a hydrosilylation reaction, and the second adhesive layer being an adhesive layer obtained using an adhesive (B) that is a polymer adhesive having an aromatic ring in at least one of the main chain and the side chain and that is transparent to infrared laser light, and a second step of irradiating the laminate with an infrared laser from the second substrate side to peel the first adhesive layer from the second adhesive layer (Patent Document 4). In infrared peeling, the infrared irradiation alters the adhesive, making peeling easier.

[0006] International Publication No. 2017 / 221772 Pamphlet International Publication No. 2018 / 216732 Pamphlet International Publication No. 2020 / 100966 Pamphlet International Publication No. 2020 / 100965 Pamphlet

[0007] The techniques described in Patent Documents 1 and 2 require a certain degree of insertion force when using equipment with sharp edges for peeling, which can result in problems such as a long processing time and damage to the semiconductor wafer or supporting substrate. The techniques described in Patent Documents 3 and 4 require sufficient irradiation with an infrared laser to facilitate peeling, but in this case, problems can arise such as a long processing time and deterioration of the adhesive, which can result in reduced cleanability.

[0008] The present invention aims to provide an adhesive composition that does not require a long processing time and causes little damage to a substrate when peeled using an infrared laser, a laminate using the adhesive composition, and a method for producing a processed semiconductor substrate or electronic device layer using the laminate.

[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 encompasses the following: [1] An adhesive composition for forming an adhesive layer used in a laminate having a first substrate which is a semiconductor substrate or an electronic device layer, a second substrate which is a support substrate transparent to an infrared laser, and an adhesive layer provided between the first substrate and the second substrate, the adhesive layer being used to separate the first substrate from the second substrate after processing the first substrate by irradiating the adhesive layer with an infrared laser from the second substrate side, the adhesive composition comprising an adhesive component having a siloxane bond and a release agent component. [2] The adhesive composition according to [1], wherein the adhesive component is a component that cures by a hydrosilylation reaction. [3] The adhesive composition according to [2], wherein the component that cures by a hydrosilylation reaction comprises: a component (A-1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, and a component (A-2) having a Si—H group. [4] The adhesive composition according to [3], wherein the component (A-1) contains a polyorganosiloxane (a1) having an alkenyl group bonded to a silicon atom and having 2 to 40 carbon atoms. [5] The adhesive composition according to [3] or [4], wherein the component (A-2) contains a polyorganosiloxane having a Si—H group. [6] The adhesive composition according to any of [1] to [5], wherein the release agent component is a polyorganosiloxane. [7] The adhesive composition according to any of [1] to [6], wherein the insertion force required to insert a sharp portion of a substrate having a sharp portion between the first substrate and the second substrate and separate the first substrate and the second substrate after irradiating the adhesive layer with the infrared laser is smaller than the insertion force required to insert the sharp portion between the first substrate and the second substrate and separate the first substrate and the second substrate without irradiating the adhesive layer with the infrared laser. [8] A laminate comprising: a first substrate that is a semiconductor substrate or an electronic device layer; a second substrate that is a support substrate that is transparent to an infrared laser; and an adhesive layer provided between the first substrate and the second substrate, wherein the adhesive layer is an adhesive layer formed from the adhesive composition according to any one of [1] to [7].[9] A method for producing a processed semiconductor substrate or electronic device layer, comprising: a processing step in which the first substrate of the laminate described in [8] is processed; and a separation step in which the infrared laser is applied to the adhesive layer from the second substrate side, and then the processed first substrate and the second substrate are separated.

[10] The method for producing a processed semiconductor substrate or electronic device layer described in [9], wherein the infrared laser is applied to the adhesive layer, and the insertion force required to insert the sharp portion of a material having a sharp portion between the first substrate and the second substrate to separate the first substrate and the second substrate is reduced by applying the infrared laser to the adhesive layer, compared to when the infrared laser is not applied to the adhesive layer.

[0011] According to the present invention, it is possible to provide an adhesive composition that does not require a long processing time and causes little damage to a substrate when peeled using an infrared laser, a laminate using the adhesive composition, and a method for producing a processed semiconductor substrate or electronic device layer using the laminate.

[0012] FIG. 1 is a schematic cross-sectional view of an example of a laminate in the first embodiment. FIG. 2A is a schematic cross-sectional view (part 1) illustrating a method for manufacturing a laminate showing an example of the first embodiment. FIG. 2B is a schematic cross-sectional view (part 2) illustrating a method for manufacturing a laminate showing an example of the first embodiment. FIG. 3 is a schematic cross-sectional view of an example of a laminate in the second embodiment. FIG. 4A is a schematic cross-sectional view (part 1) illustrating a method for manufacturing a laminate showing an example of the second embodiment. FIG. 4B is a schematic cross-sectional view (part 2) illustrating a method for manufacturing a laminate showing an example of the second embodiment. FIG. 4C is a schematic cross-sectional view (part 3) illustrating a method for manufacturing a laminate showing an example of the second embodiment. FIG. 5A is a schematic cross-sectional view (part 1) illustrating a method for processing a laminate showing an example of the first embodiment. FIG. 5B is a schematic cross-sectional view (part 2) illustrating a method for processing a laminate showing an example of the first embodiment. FIG. 5C is a schematic cross-sectional view (part 3) illustrating a method for processing a laminate showing an example of the first embodiment. FIG. 5D is a schematic cross-sectional view (part 4) illustrating a method for processing a laminate showing an example of the first embodiment. FIG. 5E is a schematic cross-sectional view (part 5) illustrating a method for processing a laminate showing an example of the first embodiment. FIG. 6A is a schematic cross-sectional view (part 1) illustrating a method for processing a laminate showing an example of the second embodiment. FIG. 6B is a schematic cross-sectional view (part 2) illustrating a method for processing a laminate showing an example of the second embodiment. FIG. 6C is a schematic cross-sectional view (part 3) illustrating a method for processing a laminate showing an example of the second embodiment. FIG. 6D is a schematic cross-sectional view (part 4) illustrating a method for processing a laminate showing an example of the second embodiment. FIG. 6E is a schematic cross-sectional view (part 5) illustrating a method for processing a laminate showing an example of the second embodiment. FIG. 6F is a schematic cross-sectional view (part 6) illustrating a method for processing a laminate showing an example of the second embodiment. FIG. 6G is a schematic cross-sectional view (part 7) illustrating a method for processing a laminate showing an example of the second embodiment.

[0013] (Adhesive Composition) The adhesive composition of the present invention contains an adhesive component having a siloxane bond and a release agent component. The adhesive composition is for forming an adhesive layer that is used to separate the first substrate from the second substrate after processing the first substrate in a laminate and then irradiating the adhesive layer with an infrared laser from the second substrate side. The laminate has a first substrate that is a semiconductor substrate or an electronic device layer, a second substrate that is a support substrate that is transparent to the infrared laser, and an adhesive layer provided between the first substrate and the second substrate.

[0014] In the present invention, an adhesive composition (adhesive composition containing a release agent component) that can be peeled using a substrate having sharp portions is used to form an adhesive layer in a laminate having a first substrate, a second substrate, and an adhesive layer provided between the first substrate and the second substrate. By using such an adhesive composition to separate the first substrate and the second substrate using an infrared laser, separation of the first substrate and the second substrate becomes possible with a small amount of infrared laser irradiation. This reduces processing time. Furthermore, since peeling using a substrate having sharp portions is not required, damage to the substrate adjacent to the adhesive layer is minimal. Note that the adhesive compositions in the techniques described in Patent Documents 3 and 4 contain, for example, a component including an epoxy-modified polyorganosiloxane, but are not necessarily adhesive compositions that can be peeled using a substrate having sharp portions, and therefore differ from the adhesive composition of the present invention.

[0015] In the present invention, it is preferable that the penetration force (Fb) required to insert the sharp portion of a substrate having a sharp portion between the first and second substrates to separate the first and second substrates after irradiating the adhesive layer with an infrared laser is smaller than the penetration force (Fa) required to insert the sharp portion between the first and second substrates without irradiating the adhesive layer with an infrared laser. The penetration force is expressed as an absolute value. Examples of the penetration force (Fa) include 0.1 N to 100 N.

[0016] The ratio (Fb / Fa) of the insertion force (Fa) to the insertion force (Fb) is not particularly limited, but is preferably less than 1.0, more preferably 0.9 or less, and even more preferably 0.6 or less. The lower limit of the ratio (Fb / Fa) is not particularly limited, but the ratio (Fb / Fa) may be 0.01 or more, 0.05 or more, or 0.1 or more. The insertion force is measured, for example, as follows. After a laminate is obtained by temporarily bonding a semiconductor substrate or electronic device layer and a support substrate via an adhesive layer, peeling is performed using a peeling device. During peeling, a scraper blade (manufactured by Esco Corporation; blade thickness 0.2 mm) is attached to the tip of a Newton meter, and the blade is inserted parallel to the substrate into the adhesive layer bonding the semiconductor substrate or electronic device layer and the support substrate, forming a trigger for peeling. At this time, the maximum force required to insert the blade is measured with a force gauge and used as the insertion force. The insertion force can be measured using, for example, a force gauge or a texture analyzer. The force gauge value representing the insertion force is an absolute value.

[0017] <Adhesive Component> The adhesive component has a siloxane bond. Since the siloxane bond has infrared absorption, it is not necessary to add an additive for absorbing infrared to the adhesive composition.

[0018] The adhesive component is not particularly limited, but is preferably a component that cures, and more preferably a component that cures by a hydrosilylation reaction. The component that cures by a hydrosilylation reaction is not particularly limited, but preferably contains a component having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom (hereinafter sometimes referred to as "component (A-1)"), a component having a Si—H group (hereinafter sometimes referred to as "component (A-2)"), and a platinum group metal catalyst (A-3).

[0019] <<Component (A-1) and Component (A-2)>> The adhesive composition preferably contains component (A-1). The adhesive composition preferably contains component (A-2). Hereinafter, the combination of component (A-1), component (A-2), and platinum group metal catalyst (A-3) may be referred to as "curable component (A)" or "component (A)."

[0020] From the viewpoint of optimally achieving the effects of the present invention, component (A-1) preferably contains a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom. From the viewpoint of optimally achieving the effects of the present invention, component (A-2) preferably contains a polyorganosiloxane (a2) having a Si—H group. 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.

[0021] In another preferred embodiment, the adhesive composition that cures by a hydrosilylation reaction is ２ Siloxane units (Q units) represented by R １ R ２ R ３ SiO １／２ Siloxane units (M units) 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 platinum group metal catalyst (A-3), wherein the polysiloxane (A1) contains one or more units selected from the group consisting of siloxane units (T units) represented by the following formula: ２ Siloxane units (Q′ units) represented by R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M′ units) represented by R ４ 'R ５ 'SiO ２／２ Siloxane units (D′ units) represented by the formula: ６ 'SiO３／２ and a polyorganosiloxane (a1') containing at least one unit selected from the group consisting of M' units, D' units, and T' units, and SiO ２ Siloxane units (Q″ units) represented by R １ "R ２ "R ３ "SiO １／２ Siloxane units (M″ units) represented by R ４ "R ５ "SiO ２／２ Siloxane units (D″ units) represented by the formula: 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).

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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, and a 4-methyl-n-pentyl group. Examples of such alkyl groups include, but are not limited to, 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.

[0027] 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 cyclopropyl ... Examples of such cycloalkyl groups include cycloalkyl groups such as 1-n-propyl-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.

[0028] 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.

[0029] Specific examples of optionally substituted linear or branched alkenyl groups include, but are not limited to, vinyl, allyl, butenyl, and pentenyl groups, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Of these, ethenyl and 2-propenyl groups are particularly preferred. Specific examples of optionally substituted cyclic alkenyl groups 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.

[0030] 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') form a crosslinked structure through a hydrosilylation reaction with the platinum group metal catalyst (A-3), and the crosslinked structure is cured. As a result, a cured film is formed.

[0031] 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.

[0032] 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).

[0033] In addition, when two or more types of polyorganosiloxanes are included in the polyorganosiloxane (a1'), a combination of (Q' units and M' units) and (D' units and M' units), a combination of (T' units and M' units) and (D' units and M' units), a combination of (Q' units, T' units and M' units) and (T' units and M' units) is preferred, but is not limited to these.

[0034] 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.

[0035] 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).

[0036] The polyorganosiloxane (a1') is composed of siloxane units in which alkyl groups and / or alkenyl groups are bonded to the silicon atoms thereof. １ '~R ６ The proportion of alkenyl groups in all the substituents represented by R ′ is preferably 0.1 to 50.0 mol %, more preferably 0.5 to 30.0 mol %, and the remaining R １ '~R ６ ' can be an alkyl group.

[0037] The polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to the silicon atom. １ "~R ６ The proportion of hydrogen atoms in all the substituents and substituted atoms represented by R １ "~R ６ " can be an alkyl group.

[0038] When the adhesive composition contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of the alkenyl groups contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si—H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0039] 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, it 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 (Shodex manufactured by Showa Denko K.K.) as a standard sample.

[0040] The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are not particularly limited, but are usually 10 to 1,000,000 (mPa s), and from the viewpoint of realizing 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.

[0041] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via a hydrosilylation reaction, and therefore the curing mechanism is different from that via, for example, silanol groups, and therefore neither siloxane needs to contain a silanol group or a functional group that forms a silanol group upon hydrolysis, such as an alkyloxy group.

[0042] <<Platinum Group Metal Catalyst (A-3)>> The platinum group metal catalyst is a platinum-based metal catalyst that promotes the hydrosilylation reaction between an alkenyl group and a Si—H group.

[0043] Specific examples of platinum-based metal catalysts that can be used include known platinum-based compounds (platinum or compounds containing platinum). Specific examples include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and diolefins, platinum-olefin complexes, platinum-carbonyl complexes (platinum bis(acetoacetate), platinum bis(acetylacetonate), etc.), chloroplatinic acid-alkenylsiloxane complexes (chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex, etc.), platinum-alkenylsiloxane complexes (platinum-divinyltetramethyldisiloxane complex, platinum-tetravinyltetramethylcyclotetrasiloxane complex, etc.), and complexes of chloroplatinic acid and acetylene alcohols. Among these, platinum-alkenylsiloxane complexes are particularly preferred due to their high hydrosilylation reaction-accelerating effect. These hydrosilylation reaction catalysts may be used either individually or in combination of two or more.

[0044] The alkenylsiloxane used in the platinum-alkenylsiloxane complex is not particularly limited, and examples thereof include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxane oligomers in which some of the methyl groups of these alkenylsiloxanes have been substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxane oligomers in which the vinyl groups of these alkenylsiloxanes have been substituted with allyl groups, hexenyl groups, etc. 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is particularly preferred because the resulting platinum-alkenylsiloxane complex has good stability.

[0045] The content of the platinum group metal catalyst (A-3) in the adhesive composition is not particularly limited, but is, for example, in the range of 0.1 to 50.0 ppm relative to the total mass of component (A-1) and component (A-2).

[0046] <<Polymerization Inhibitor>> The adhesive component may contain a polymerization inhibitor 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, for example, typically 1,000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and 10,000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0047] The content of the adhesive component in the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 70% by mass or more, relative to the non-volatile content of the adhesive composition. The upper limit is not particularly limited, but may be, for example, 95% by mass or less, 90% by mass or less, or 85% by mass or less. The non-volatile content of the adhesive composition refers to components other than the solvent in the adhesive composition.

[0048] <Release Agent Component> The release agent component is not particularly limited, but from the viewpoint of more suitably obtaining the effects of the present invention, polyorganosiloxane is preferred. The polyorganosiloxane as the release agent component usually does not react with the adhesive component. For example, the polyorganosiloxane as the release agent component is a component that does not undergo a hydrosilylation reaction.

[0049] Polyorganosiloxane usually contains siloxane units (D units), but may also contain Q units, M units, and T units. For example, when consisting of only D units, when a combination of D units and Q units, when a combination of D units and M units, when a combination of D units and T units, when a combination of D units, Q units, and M units, when a combination of D units, M units, and T units, when a combination of D units, Q units, M units, and T units, and when a combination of D units, Q units, M units, and T units, etc. can be mentioned.

[0050] The polyorganosiloxane is not particularly limited, and examples thereof include polydimethylsiloxane, epoxy group-containing polyorganosiloxane, phenyl group-containing polyorganosiloxane, and carbinol-modified polyorganosiloxane.

[0051] <<Polydimethylsiloxane>> The “polydimethylsiloxane” in the present invention is an unmodified polyorganosiloxane that differs from epoxy group-containing polydimethylsiloxanes, phenyl group-containing polydimethylsiloxanes, carbinol-modified polyorganosiloxanes, and the like, and is a polyorganosiloxane that has methyl groups as organic groups bonded to silicon atoms.

[0052] Specific examples of polydimethylsiloxane include, but are not limited to, those represented by formula (M1).

[0053] (n ４ indicates the number of repeating units and is a positive integer.)

[0054] The weight-average molecular weight of the polydimethylsiloxane is not particularly limited, but is typically 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, and more preferably 300,000 to 900,000. The dispersity is also not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable release, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. The weight-average molecular weight and dispersity can be measured using the method described above for polyorganosiloxane. The viscosity of the polydimethylsiloxane is not particularly limited, but is typically 1,000 to 2,000,000 mm. ２ The viscosity value of polydimethylsiloxane is expressed as kinematic viscosity, and is expressed as centistokes (cSt) = mm ２ Viscosity (mPa s) is converted to density (g / cm ３ That is, the value can be calculated from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm ２ / s)=viscosity (mPa・s) / density (g / cm ３ ) can be calculated using the formula:

[0055] <<Epoxy Group-Containing Polyorganosiloxane>> Examples of the epoxy group-containing polyorganosiloxane include R １１ R １２ SiO ２／２ The siloxane unit (D １０ Examples include those containing units.

[0056] 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 organic group containing an epoxy group may be an independent epoxy group that is not condensed with another ring, or may be an epoxy group that forms a condensed ring with another ring, 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, but is not limited to, epoxy group-containing polydimethylsiloxane.

[0057] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D １０ units), but D １０ In addition to the units, the epoxy group-containing polyorganosiloxane may contain Q units, M units and / or T units. In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include D １０ Polyorganosiloxane consisting only of 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, １０Polyorganosiloxanes containing units, M units and T units, D １０ Examples of suitable organosiloxanes include polyorganosiloxanes containing Q units, M units, and T units.

[0058] The epoxy group-containing polyorganosiloxane may have an epoxy group on a side chain, may have an epoxy group at one end, or may have epoxy groups at both ends.

[0059] 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.

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

[0061] (m １ and n １ indicates the number of each repeating unit and is a positive integer.)

[0062] (m ２ and n ２ indicates the number of each repeating unit and is a positive integer, and R is an alkylene group having 1 to 10 carbon atoms which may be interrupted by at least one of an oxygen atom and an unsaturated bond (e.g., a carbon-carbon double bond, a carbon-carbon triple bond, or -N=N-).

[0063] (m ３ , n ３ and ３ indicates the number of each repeating unit and is a positive integer, and R is an alkylene group having 1 to 10 carbon atoms which may be interrupted by at least one of an oxygen atom and an unsaturated bond (e.g., a carbon-carbon double bond, a carbon-carbon triple bond, or -N=N-).

[0064] In the above general formula, m １ , m ２ , m ３ , and O３ When the number of repeating units is two or more, the repeating units may be arranged adjacent to each other to form a block, or may be arranged randomly.

[0065] Since the polyorganosiloxane represented by formula (E3) has an epoxy group and a phenyl group, it is an epoxy group-containing polyorganosiloxane and also a phenyl group-containing polyorganosiloxane. The epoxy group-containing polyorganosiloxane may or may not have a phenyl group.

[0066] The weight-average molecular weight of the epoxy group-containing polyorganosiloxane is not particularly limited, but is typically 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. Furthermore, its dispersity is not particularly limited, but is typically 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 method described above for polyorganosiloxane. The viscosity of the epoxy group-containing polyorganosiloxane is not particularly limited, but is typically 1,000 to 2,000,000 mm. ２ The viscosity value of the epoxy group-containing polyorganosiloxane is expressed as a kinematic viscosity, and is expressed as centistokes (cSt) = mm ２ Viscosity (mPa s) is converted to density (g / cm ３ That is, the value can be calculated from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm ２ / s)=viscosity (mPa・s) / density (g / cm ３ ) can be calculated using the formula:

[0067] <<Phenyl Group-Containing Polyorganosiloxane>> Examples of the phenyl group-containing polyorganosiloxane include R ３１ R ３２ SiO ２／２ The siloxane unit (D ３０Examples include those containing units.

[0068] 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.

[0069] 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.

[0070] In a preferred embodiment, specific examples of the phenyl group-containing polyorganosiloxane include D ３０ Polyorganosiloxane consisting only of 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, ３０ Polyorganosiloxanes containing units, M units and T units, D ３０ Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0071] Specific examples of the phenyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

[0072] (m5 and n5 represent the number of each repeating unit and are positive integers.)

[0073] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0074] In the above general formula, m ５ , and m ６ When the number of repeating units is two or more, the repeating units may be arranged adjacent to each other to form a block, or may be arranged randomly.

[0075] <<Carbinol-modified polyorganosiloxane>> The carbinol-modified polyorganosiloxane is not particularly limited. The carbinol-modified polyorganosiloxane is a polyorganosiloxane having a hydroxy group directly bonded to a carbon atom. Thus, the carbinol in "carbinol-modified polyorganosiloxane" is not limited to methanol in the narrow sense, but also includes methanol derivatives.

[0076] The carbinol-modified polyorganosiloxane is, for example, a carbinol-modified polydimethylsiloxane.

[0077] The number of hydroxy groups directly bonded to carbon atoms in the carbinol-modified polyorganosiloxane is not particularly limited, and may be one or two or more.

[0078] The carbinol-modified polyorganosiloxane may have a hydroxy group bonded directly to a carbon atom in the side chain, or may have a hydroxy group bonded directly to a carbon atom at one end, or may have hydroxy groups bonded directly to a carbon atom at both ends. The carbinol-modified polyorganosiloxane preferably has a hydroxy group bonded directly to a carbon atom in the side chain. In this case, even if the content of the carbinol-modified polyorganosiloxane is small, the adhesive layer formed from the adhesive composition can be imparted with good releasability.

[0079] The carbinol-modified polyorganosiloxane has, for example, a group represented by the following formula (Cg) as a group directly bonded to a silicon atom.

[0080] (In formula (Cg), R １ represents a group having one or more carbon atoms. * represents a bond bonded to a silicon atom. However, the hydroxy group in formula (Cg) is directly bonded to a carbon atom.

[0081] The number of hydroxy groups directly bonded to a carbon atom in the group represented by formula (Cg) may be 1 or 2 or more. Examples of 2 or more include 2, 3, and 4.

[0082] R １ The number of carbon atoms is not particularly limited, and may be, for example, 1 to 30, 1 to 20, or 1 to 10.

[0083] Examples of the group represented by formula (Cg) include groups represented by the following formulae (Cg-1) to (Cg-4). (In formula (Cg-1), R １１ represents an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 3 carbon atoms. １２ represents an alkylene group having 1 to 6 carbon atoms. １３ represents an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 3 carbon atoms or a hydroxy group. １４ represents an alkylene group having 1 to 6 carbon atoms. １５ represents an alkylene group having 1 to 3 carbon atoms, and m represents an integer of 1 to 10. In formula (Cg-4), R １６ ~R １８ each independently represents an alkylene group having 1 to 6 carbon atoms. In formulas (Cg-1) to (Cg-4), * represents a bond bonded to a silicon atom.

[0084] R １１ ~R １８ The alkylene group may be linear, branched, or cyclic.

[0085] Examples of the group represented by formula (Cg) include the following groups. (In the formula, m1 represents an integer of 2 to 10. * represents a bond bonded to a silicon atom.)

[0086] The carbinol-modified polyorganosiloxane is represented, for example, by the following formula (CPS-1) or formula (CPS-2). (In formula (CPS-1), R５１ Each of X independently represents a hydrocarbon group. １ represents a group represented by the above formula (Cg). n1 represents an integer of 0 or more. n2 represents an integer of 1 or more. In formula (CPS-2), R ５２ each independently represents a hydrocarbon group. ２ represents a group represented by the above formula (Cg). ３ represents a hydrocarbon group or a group represented by the above formula (Cg); and n3 represents an integer of 0 or more.

[0087] R ５１ , R ５２ , and X ３ Examples of the hydrocarbon group in the formula (CPS-1a) include alkyl groups having 1 to 8 carbon atoms. As the alkyl group having 1 to 8 carbon atoms, a methyl group is preferred. That is, the carbinol-modified polyorganosiloxane is preferably a polydimethylsiloxane represented by the following formula (CPS-1a) or formula (CPS-2a). (In formula (CPS-1a), X １ represents a group represented by the above formula (Cg). n1 represents an integer of 0 or more. n2 represents an integer of 1 or more. In formula (CPS-2a), X ２ represents a group represented by the above formula (Cg). ３ represents a methyl group or a group represented by the above formula (Cg); and n3 represents an integer of 0 or more.

[0088] The carbinol-modified polyorganosiloxane represented by formula (CPS-1) and the carbinol-modified polydimethylsiloxane represented by formula (CPS-1a) have hydroxy groups directly bonded to carbon atoms in their side chains. The carbinol-modified polyorganosiloxane represented by formula (CPS-2) and the carbinol-modified polydimethylsiloxane represented by formula (CPS-2a) have hydroxy groups directly bonded to carbon atoms at one or both ends.

[0089] In the carbinol-modified polyorganosiloxane represented by formula (CPS-1), when n2 is 2 or more, -Si(R ５１ ) (X １The siloxane units represented by —Si(CH )—O— may be arranged adjacent to each other to form a block, or may be arranged randomly. In the carbinol-modified polydimethylsiloxane represented by formula (CPS-1a), when n2 is 2 or more, ３ ) (X １ The siloxane units represented by —O— may be arranged adjacent to each other to form a block, or may be arranged randomly.

[0090] The weight average molecular weight of the carbinol-modified polyorganosiloxane is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of reproducibly realizing the effects of the present invention, it is preferably 5,000 to 50,000. The degree of dispersion is also not particularly limited, but is usually 1.0 to 10.0, and from the viewpoint of reproducibly realizing suitable release, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The viscosity of the carbinol-modified polyorganosiloxane is not particularly limited, but is usually 100 to 200,000 mm ２ The viscosity value of polydimethylsiloxane is expressed as kinematic viscosity, and is expressed as centistokes (cSt) = mm ２ Viscosity (mPa s) is converted to density (g / cm ３ That is, the value can be calculated from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm ２ / s)=viscosity (mPa・s) / density (g / cm ３ ) can be calculated using the formula:

[0091] The polyorganosiloxane as a release agent component can be used alone or in combination of two or more. Here, the two or more polyorganosiloxanes referred to as "two" refer to, for example, a combination of polydimethylsiloxane and epoxy group-containing polyorganosiloxane, or a combination of polydimethylsiloxane and phenyl group-containing polyorganosiloxane, but do not refer to a combination of two epoxy group-containing polyorganosiloxanes that differ in molecular weight, viscosity, type of epoxy group, etc.

[0092] The polyorganosiloxane that is the release agent component (B) may be a commercially available product or may be synthesized. Commercially available polyorganosiloxanes include, for example, WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST GUM, manufactured by Wacker Chemie, dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy group-containing polyorganosiloxane (trade names CMS-227, ECMS-327, EMS-622) manufactured by Gelest, and Shin-Etsu Chemical Co., Ltd. Epoxy group-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343), epoxy group-containing polyorganosiloxanes (DOWSIL BY16-839, DOWSIL8413, DOWSIL8411) manufactured by Dow-Toray Industries, Inc.; 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, but are not limited to these.

[0093] Commercially available carbinol-modified polyorganosiloxanes include, for example, KF6000, KF6001, KF6002, KF6003, X-22-4039, and X-22-4015 manufactured by Shin-Etsu Silicone Co., Ltd.; DMS-C15, DMS-C16, DMS-C21, DMS-C23, DBE-C25, DBE-C22, DMS-CA21, DMS-CS26, CMS-221, CMS-222, CMS-832, CMS-626, MCR-C12, MCR-C18, MCR-C22, MCS-C11, MCS-C13, MCR-C61, MCR-C62, and MCR-C63 manufactured by Gelest; and DOWSIL BY 16-201, DOWSIL SF 8427 Fluid, DOWSIL SF 8428 Fluid, etc.

[0094] The content of the release agent component in the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more, relative to the non-volatile content of the adhesive composition. The upper limit is not particularly limited, but is, for example, preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

[0095] <Solvent> The adhesive composition may contain a solvent for purposes such as adjusting viscosity. Specific examples include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones. More specific examples include, but are not limited to, hexane, heptane, octane, nonane, isononane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, cyclohexanone, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. Such solvents may be used alone or in combination of two or more.

[0096] When the adhesive composition 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 thin film to be produced, etc., but is, for example, in the range of about 10 to 90 mass % with respect to the entire composition.

[0097] The viscosity of the adhesive 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.

[0098] An example of the adhesive composition used in the present invention can be produced by mixing component (A), release agent component (B), and a solvent. The order of mixing is not particularly limited, and 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 release agent component (B) in a solvent, or a method of dissolving a portion of component (A) and a portion of release agent 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 decomposition or deterioration of the components. In the present invention, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the adhesive composition or after all components have been mixed, in order to remove foreign matter.

[0099] Examples of adhesive compositions that can be used include the adhesives described in WO2017 / 221772, the temporary adhesives described in WO2018 / 216732, the temporary adhesives described in WO2019 / 009365, the adhesive compositions described in WO2020 / 111069, and the adhesive compositions described in WO2021 / 131925. The contents of these publications are incorporated herein by reference to the same extent as if expressly set forth herein.

[0100] (Laminate) The laminate according to the present invention includes a first substrate, a second substrate, and an adhesive layer. The first substrate is a semiconductor substrate or an electronic device layer. The second substrate is a support substrate that transmits infrared laser light.

[0101] The adhesive layer is disposed between the first substrate and the second substrate, and the adhesive layer is in contact with the first substrate and the second substrate.

[0102] The laminate of the present invention is used for temporary bonding when processing a semiconductor substrate or an electronic device layer, and can be suitably used for processing such as thinning of a semiconductor substrate or an electronic device layer. While the semiconductor substrate is being processed such as thinning, the semiconductor substrate is supported by a support substrate. On the other hand, after processing of the semiconductor substrate, the support substrate and the semiconductor substrate are separated. Also, while the electronic device layer is being processed such as thinning, the electronic device layer is supported by a support substrate. On the other hand, after processing of the electronic device layer, the support substrate and the electronic device layer are subsequently separated. Residues of the adhesive layer remaining on the semiconductor substrate, electronic device layer, or support substrate after the semiconductor substrate or electronic device layer and the support substrate are separated can be removed, for example, with a cleaning composition for cleaning semiconductor substrates, etc.

[0103] The laminate will be described in detail below, with respect to cases where the laminate has a semiconductor substrate and cases where the laminate has an electronic device layer. The case where the laminate has a semiconductor substrate will be described in the following <First embodiment>, and the case where the laminate has an electronic device layer will be described in the following <Second embodiment>.

[0104] <First embodiment> A stacked body having a semiconductor substrate is used for processing the semiconductor substrate. While the semiconductor substrate is being processed, the semiconductor substrate is adhered to a support substrate. After the semiconductor substrate is processed, the semiconductor substrate is separated from the support substrate.

[0105] <<Semiconductor Substrate>> The main material constituting the entire semiconductor substrate is not particularly limited as long as it is suitable for this type of application, and examples thereof include silicon, silicon carbide, compound semiconductors, and glass substrates with organic resins. The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disk. Note that the surface of a disk-shaped semiconductor substrate does not need to be perfectly circular; for example, the outer periphery of the semiconductor substrate may have a straight line portion called an orientation flat or a notch. The thickness of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 500 to 1,000 μm. The diameter of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 100 to 1,000 mm.

[0106] The semiconductor substrate may have bumps. Bumps are protruding terminals. Bumps are, for example, electrodes. When the semiconductor substrate has bumps in a laminate, the bumps are located on the supporting substrate side. In a semiconductor substrate, the bumps are usually formed on the surface on which a circuit is formed. The circuit may be single-layered or multi-layered. The shape of the circuit is not particularly limited. In a semiconductor substrate, the surface opposite to the surface having the bumps (the back surface) is the surface used for processing. The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited. Examples of bumps include ball bumps, printed bumps, stud bumps, and plated bumps. The height, radius, and pitch of the bumps are usually determined appropriately based on the following conditions: a bump height of approximately 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 bump include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bump may be composed of only a single component, or may be composed of multiple components. More specifically, examples include alloy platings mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. The bump may also have a layered structure including a metal layer composed of at least one of these components.

[0107] An example of a semiconductor substrate is a silicon wafer with a diameter of about 300 mm and a thickness of about 770 μm.

[0108] <<Support Substrate>> The support substrate is not particularly limited as long as it is a member that can support a semiconductor substrate when the semiconductor substrate is processed and is transparent to an infrared laser, and examples thereof include a silicon support substrate.

[0109] The shape of the support substrate is not particularly limited, but may be, for example, a disk shape. The disk-shaped support substrate does not need to have a perfectly circular surface; for example, the outer periphery of the support substrate may have a straight line portion called an orientation flat, or a notch. The thickness of the disk-shaped support substrate may be determined appropriately depending on the size of the semiconductor substrate, etc., and is not particularly limited, but is, for example, 500 to 1,000 μm. The diameter of the disk-shaped support substrate may be determined appropriately depending on the size of the semiconductor substrate, etc., and is not particularly limited, but is, for example, 100 to 1,000 mm.

[0110] An example of the support substrate is a silicon wafer with a diameter of about 300 mm and a thickness of about 700 μm.

[0111] <<Adhesive Layer>> The adhesive layer is provided between the support substrate and the semiconductor substrate. The adhesive layer is in contact with, for example, the semiconductor substrate. The adhesive layer may be in contact with, for example, the support substrate. The adhesive layer is an adhesive layer formed from an adhesive composition.

[0112] 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 100 μm or less.

[0113] The method for forming the adhesive layer from the adhesive composition will be described in detail below in the section entitled "Example of method for producing the laminate in the first embodiment."

[0114] An example of the configuration of the laminate of the first embodiment will be described below with reference to the drawings. Fig. 1 shows a schematic cross-sectional view of an example of the laminate of the first embodiment. The laminate of Fig. 1 has a semiconductor substrate 1, an adhesive layer 2, and a support substrate 4, in this order. That is, the adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 contacts the semiconductor substrate 1 and the support substrate 4.

[0115] <<Manufacturing Method of an Example of the Laminate in the First Embodiment>> A manufacturing method of a laminate will be described below using the laminate shown in Fig. 1 as an example of the laminate in the first embodiment. An example of the laminate of the present invention can be manufactured, for example, by a method including the following first and second steps. First step: A step of applying an adhesive composition onto a semiconductor substrate to form an adhesive coating layer. Second step: A step of heating the adhesive coating layer to form an adhesive layer.

[0116] The method for applying the adhesive composition is not particularly limited, but is typically spin coating. Alternatively, a method can be employed in which a coating film is formed separately by spin coating or the like, a sheet-like coating film is formed, and the sheet-like coating film is then applied as an adhesive coating layer. 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, and other factors. However, it is typically 80 to 150°C, and the heating time is typically 30 seconds to 5 minutes. When the adhesive composition contains a solvent, the applied adhesive composition is typically heated. The thickness of the adhesive coating layer obtained by applying the adhesive composition and, if necessary, heating it is typically about 5 to 500 μm, and is appropriately determined so as to ultimately achieve the above-mentioned range of adhesive layer thickness.

[0117] In the present invention, the laminate of the present invention can be obtained by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing a heat treatment, a decompression treatment, or both, and then performing a post-heat treatment. The treatment conditions to be adopted, whether heat treatment, decompression treatment, or a combination of both, are appropriately determined taking into consideration various factors such as the type of adhesive composition, the film thickness, and the desired adhesive strength.

[0118] The heat treatment temperature is determined appropriately from the viewpoint of removing the solvent from the composition, etc., usually within the range of 20 to 160° C. In particular, from the viewpoint of suppressing or avoiding excessive curing or unnecessary deterioration of the adhesive component (A), the heat treatment temperature is preferably 150° C. or lower, more preferably 130° C. or lower, and the heating time is determined appropriately depending on the heating temperature and the type of adhesive, but is usually 30 seconds or longer, preferably 1 minute or longer, from the viewpoint of reliably achieving suitable adhesion, and is usually 10 minutes or shorter, preferably 5 minutes or shorter, from the viewpoint of suppressing deterioration of the adhesive layer and other components.

[0119] The reduced pressure treatment can be carried out by exposing the adhesive coated layers in contact with each other to an atmospheric pressure of 10 to 10,000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

[0120] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate, and the layers therebetween and can firmly adhere them to each other, but is usually within the range of 10 to 50,000 N.

[0121] The post-heating temperature is preferably 120°C or higher from the viewpoint of achieving a sufficient curing rate, and preferably 260°C or lower from the viewpoint of preventing deterioration of the substrate and each layer. The post-heating time is usually 1 minute or longer, preferably 5 minutes or longer, from the viewpoint of achieving suitable bonding of the substrate and layers constituting the laminate, and usually 180 minutes or shorter, preferably 120 minutes or shorter, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be performed using a hot plate, oven, or the like. When post-heating is performed using a hot plate, either the semiconductor substrate or the support substrate of the laminate may be heated facing down, but from the viewpoint of achieving suitable peeling with good reproducibility, post-heating with the semiconductor substrate facing down is preferred. Note that one purpose of the post-heating treatment is to achieve an adhesive layer that is a more suitable free-standing film, and in particular to achieve suitable curing by a hydrosilylation reaction.

[0122] 2A to 2C are diagrams illustrating one embodiment of manufacturing a laminate. First, a laminate is prepared in which an adhesive coating layer 2a is formed on a semiconductor substrate 1 (FIG. 2A). This laminate can be obtained, for example, by applying an adhesive composition to the semiconductor substrate 1 and heating it. Next, the laminate shown in FIG. 2A is bonded to a support substrate 4 so that the adhesive coating layer 2a contacts the support substrate 4. Then, a load is applied in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure. After that, a heating device (not shown; hot plate) is placed on the surface of the semiconductor substrate 1 opposite the surface where the adhesive coating layer 2a contacts. The adhesive coating layer 2a is heated and cured by the heating device, converting it into the adhesive layer 2 (FIG. 2B). The laminate shown in FIG. 1 is obtained by the steps shown in FIGS. 2A and 2B.

[0123] Second Embodiment The laminate having an electronic device layer is used for processing the electronic device layer. While the electronic device layer is being processed, the electronic device layer is adhered to a support substrate. After the electronic device layer is processed, the electronic device layer is separated from the support substrate.

[0124] <<Electronic Device Layer>> The electronic device layer refers to a layer having an electronic device. In the present invention, it refers to a layer in which multiple semiconductor chip substrates are embedded in a sealing resin, that is, a layer consisting of multiple semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates. Here, "electronic device" refers to a member that constitutes at least a part of an electronic component. The electronic device is not particularly limited and can be a semiconductor substrate having various mechanical structures or circuits formed on the surface thereof. The electronic device is preferably a composite of a member made of metal or semiconductor and a resin that seals or insulates the member. The electronic device may have a rewiring layer (described later) and / or a semiconductor element or other element sealed or insulated with a sealing material or insulating material, and may have a single-layer or multi-layer structure.

[0125] <<Support Substrate>> Examples of the support substrate include those similar to those explained in the section <<Support Substrate>> of the <First Embodiment>> above.

[0126] <<Adhesive Layer>> The adhesive layer is formed using the adhesive composition described above. Details of the adhesive layer are as described above in the <<Adhesive Layer>> section of the <First Embodiment>>.

[0127] An example of the configuration of the laminate of the second embodiment will be described below with reference to the drawings. The laminate of Fig. 3 has a support substrate 24, an adhesive layer 22, and an electronic device layer 26, in this order. The electronic device layer 26 includes a plurality of semiconductor chip substrates 21 and sealing resin 25, which is a sealing material, disposed between the semiconductor chip substrates 21. The adhesive layer 22 is provided between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 contacts the electronic device layer 26 and the support substrate 24.

[0128] <<Example of Manufacturing Method of Laminate in Second Embodiment>> A method for manufacturing a laminate will be described below using the laminate shown in Fig. 3 as an example of the laminate in the second embodiment. The laminate of the present invention can be manufactured, for example, by a method including the following first to fourth steps. First step: a step of applying an adhesive composition to the surface of the support substrate to form an adhesive coating layer (and, if necessary, further heating to form an adhesive layer); Second step: a step of placing a semiconductor chip substrate on the adhesive coating layer or adhesive layer, and bonding the semiconductor chip substrate to the adhesive coating layer or adhesive layer while performing at least one of a heat treatment and a decompression treatment; Third step: a step of curing the adhesive coating layer by post-heat treatment to form an adhesive layer; Fourth step: a step of sealing the semiconductor chip substrate fixed on the adhesive layer with a sealing resin. Step two will be described in more detail, for example, as step (i) of the following embodiment. (i) A semiconductor chip substrate is placed on the adhesive coating layer or adhesive layer, and while performing at least one of a heat treatment and a decompression treatment, a load is applied in the thickness direction of the semiconductor chip substrate and the support substrate to bring them into close contact, and the semiconductor chip substrate is bonded to the adhesive coating layer or adhesive layer.

[0129] The third step may be performed after bonding the semiconductor chip substrate to the adhesive coating layer in the second step, or may be performed in conjunction with the second step. For example, the semiconductor chip substrate may be placed on the adhesive coating layer, and the adhesive coating layer may be heated and cured while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, thereby simultaneously achieving close contact between the semiconductor chip substrate and the adhesive coating layer and curing the adhesive coating layer to the adhesive layer, thereby bonding the adhesive layer to the semiconductor chip substrate. The third step may also be performed before the second step, in which the semiconductor chip substrate is placed on the adhesive layer, and the adhesive layer may be bonded to the semiconductor chip substrate while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate.

[0130] The application method, the heating temperature of the applied adhesive composition, the heating means, etc. are as described above in <<An example of the method for producing the laminate in the first embodiment>> of the <First embodiment>>.

[0131] The procedure for manufacturing a laminate according to the second embodiment will be described in more detail below with reference to the accompanying drawings. This manufacturing method produces the laminate shown in FIG. 3 . As shown in FIG. 4A , an adhesive coating layer 22′ made of an adhesive composition is formed on a support substrate 24. The adhesive coating layer 22′ may be heated to form the adhesive layer 22. Next, as shown in FIG. 4B , a semiconductor chip substrate 21 is placed on the adhesive layer 22 or the adhesive coating layer 22′. While performing at least one of a heat treatment and a decompression treatment, a load is applied in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 to bring them into close contact, bonding the semiconductor chip substrate 21 to the adhesive layer 22 or the adhesive coating layer 22′. When the semiconductor chip substrate 21 is bonded to the adhesive coating layer 22′, the adhesive coating layer 22′ is post-heat treated to harden it into the adhesive layer 22, and the semiconductor chip substrate 21 is then fixed to the adhesive layer 22. Next, as shown in FIG. 4C , the semiconductor chip substrate 21 fixed on the adhesive layer 22 is sealed with a sealing resin 25. 4C , a plurality of semiconductor chip substrates 21 temporarily adhered to a support substrate 24 via an adhesive layer 22 are sealed with a sealing resin 25. An electronic device layer 26 having semiconductor chip substrates 21 and sealing resin 25 disposed between the semiconductor chip substrates 21 is formed on the adhesive layer 22. In this manner, the electronic device layer 26 is a base material layer in which a plurality of semiconductor chip substrates are embedded in the sealing resin.

[0132] <<<Encapsulating Step>>> The semiconductor chip substrate 21 is encapsulated using an encapsulant. The encapsulant used for encapsulating the semiconductor chip substrate 21 is a material capable of insulating or encapsulating metal or semiconductor components. In the present invention, for example, a resin composition (encapsulating resin) is used as the encapsulant. The type of encapsulating resin is not particularly limited as long as it is capable of encapsulating and / or insulating metal or semiconductor components. For example, epoxy-based resins or silicone-based resins are preferably used. The encapsulating material may contain other components, such as fillers, in addition to the resin component. Examples of fillers include spherical silica particles. In the encapsulating step, the encapsulating resin, heated to, for example, 130 to 170°C, is supplied onto the adhesive layer 22 while maintaining a high viscosity, covering the semiconductor chip substrate 21. The encapsulating resin is then compression-molded to form a layer of encapsulating resin 25 on the adhesive layer 22. The temperature conditions are, for example, 130 to 170°C. The pressure applied to the semiconductor chip substrate 21 is, for example, 50 to 500 N / cm. ２ is.

[0133] (Method for manufacturing a processed semiconductor substrate or an electronic device layer) Using the laminate of the present invention, a method for manufacturing a processed semiconductor substrate or a method for manufacturing a processed electronic device layer can be provided. The "method for manufacturing a processed semiconductor substrate" uses the laminate described in the <First embodiment> section of the above (Laminate). The "method for manufacturing a processed electronic device layer" uses the laminate described in the <Second embodiment> section of the above (Laminate). The "method for manufacturing a processed semiconductor substrate" will be explained in the <Third embodiment> below, and the "method for manufacturing a processed electronic device layer" will be explained in the <Fourth embodiment> below.

[0134] The method for producing a processed semiconductor substrate or electronic device layer includes the following steps: a processing step in which the first substrate of the laminate of the present invention is processed; and a separation step in which an infrared laser is irradiated onto the adhesive layer from the second substrate side, and then the processed first substrate and the second substrate are separated.

[0135] Examples of infrared lasers include lasers with wavelengths of 1 μm to 20 μm. The wavelength of the infrared laser is preferably 9.2 to 10.8 μm. Examples of light sources for infrared lasers include semiconductor lasers, He—Ne lasers, Ar lasers, carbon dioxide lasers, YAG lasers, and fiber lasers. The output of infrared light from the infrared laser is preferably 10 W to 100 W, and more preferably 30 W to 90 W.

[0136] The infrared laser irradiation of the adhesive layer does not necessarily have to be performed on the entire area of ​​the adhesive layer. Even if there are areas irradiated with the infrared laser and areas not irradiated with the infrared laser, as long as the adhesive strength of a portion of the adhesive layer is sufficiently reduced, the second substrate can be peeled off from the laminate by applying a slight external force and lifting the second substrate. The ratio and positional relationship of the areas irradiated with the infrared laser and the areas not irradiated with the infrared laser vary depending on the adhesive composition forming the adhesive layer, the thickness of the adhesive layer, the intensity of the irradiated infrared laser, etc., but those skilled in the art can set appropriate conditions without requiring excessive testing. For example, a non-irradiated area with the same width as the infrared line width may be provided adjacent to the area irradiated with the infrared laser. Furthermore, the infrared laser irradiation of the adhesive layer may be limited to the edge of the adhesive layer sandwiched between the first and second substrates.

[0137] After irradiating the adhesive layer with an infrared laser, a material having a sharp edge may be inserted between the first substrate and the second substrate to make it easier to separate the first substrate and the second substrate.

[0138] The first and second substrates can be separated by, for example, holding the first and second substrates with holders after the adhesive strength of the adhesive layer is reduced by irradiating the adhesive layer with an infrared laser, and then moving one or both of the holders in a direction that separates the first and second substrates. Examples of the holder include an adsorption plate.

[0139] In the separation step, preferably, irradiating the adhesive layer with an infrared laser reduces the penetration force required to insert the sharp portion of a substrate having a sharp portion between the first and second substrates to separate the first and second substrates, compared to when the adhesive layer is not irradiated with an infrared laser. In other words, the penetration force (Fb) required to insert the sharp portion of a substrate having a sharp portion between the first and second substrates after irradiating the adhesive layer with an infrared laser to separate the first and second substrates is preferably smaller than the penetration force (Fa) required to insert the sharp portion of a substrate having a sharp portion between the first and second substrates without irradiating the adhesive layer with an infrared laser. The penetration force is expressed as an absolute value. Examples of the penetration force (Fa) include 0.1 N to 100 N.

[0140] The ratio (Fb / Fa) of the insertion force (Fa) to the insertion force (Fb) is not particularly limited, but is preferably less than 1.0, more preferably 0.9 or less, and even more preferably 0.6 or less. The lower limit of the ratio (Fb / Fa) is not particularly limited, but the ratio (Fb / Fa) may be 0.01 or more, 0.05 or more, or 0.1 or more. The insertion force is measured, for example, as described above.

[0141] <Third embodiment> The method for producing a processed semiconductor substrate of the present invention includes the following step 5A and step 6A. The method for producing a processed semiconductor substrate may further include the following step 7A. Here, step 5A is a step of processing the semiconductor substrate in the stack described in the above <First embodiment> section. Furthermore, step 6A is a step of separating the semiconductor substrate processed in step 5A from the support substrate. Furthermore, step 7A is a step of cleaning the processed semiconductor substrate after step 6A.

[0142] The processing performed on the semiconductor substrate in step 5A is, for example, processing of the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the back surface of the wafer. Thereafter, for example, through-silicon vias (TSVs) are formed, and then the thinned wafer is peeled off from the support substrate to form a wafer stack, which is then three-dimensionally mounted. Also, for example, before or after this, formation of wafer backside electrodes is also performed. During the wafer thinning and TSV process, a heat load of approximately 250 to 350°C is applied while the wafer is adhered to the support substrate. The laminate of the present invention, including the adhesive layer, typically has heat resistance to this load. Note that the processing is not limited to the above-described processing, and also includes, for example, the implementation of a semiconductor component mounting process when the wafer is temporarily adhered to a support substrate to support the substrate for mounting the semiconductor component.

[0143] In the 6A step, the method for separating (peeling) the semiconductor substrate and the support substrate is the above-mentioned separation step.

[0144] The substrate can be cleaned by spraying the cleaning composition onto the surface of at least one of the separated semiconductor substrate and the support substrate, or by immersing the separated semiconductor substrate or the support substrate in the cleaning composition. The surface of the processed semiconductor substrate or the like may also be cleaned using a removal tape or the like. As an example of cleaning the substrate, after the step 6A, a step 7A of cleaning the processed semiconductor substrate may be performed. Examples of cleaning compositions used for cleaning include the following.

[0145] The cleaning agent composition usually contains a solvent. 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 the lactones include γ-butyrolactone. Examples of the ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples of the 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 compounds having an ether bond, such as monoalkyl ethers or monophenyl ethers of the above polyhydric alcohols or compounds having an ester bond, such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether. 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, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, etc. These can 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.

[0146] Also preferred are mixed solvents containing PGMEA and a polar solvent. The blending ratio (mass ratio) can be determined appropriately taking into account the compatibility of the PGMEA and the polar solvent, but 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, and 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.

[0147] 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.

[0148] 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, the anion paired with the quaternary ammonium cation is a hydroxide ion (OH － ) ; fluorine ion (F － ), chloride ions (Cl － ), bromine ion (Br － ), iodine ion (I － ) and other halogen ions; tetrafluoroborate ion (BF４ － ) ; hexafluorophosphate ion (PF ６ － ) and the like, but are not limited to these.

[0149] 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.

[0150] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is 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 includes tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride). Of these, tetrabutylammonium fluoride is preferred.

[0151] The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of a hydrate. 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 cleaning composition, but is usually 0.1 to 30 mass% based on the cleaning composition.

[0152] 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 to obtain a cleaning composition having excellent uniformity, the cleaning composition preferably contains one or two or more amide solvents.

[0153] A suitable example of the amide solvent is an acid amide derivative represented by formula (Z).

[0154] 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.

[0155] 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.

[0156] The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

[0157] Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

[0158] In formula (Y), R １０１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, 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.

[0159] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, and δ-lactam compounds, and these can be used alone or in combination of two or more.

[0160] In a preferred embodiment, 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).

[0161] The cleaning composition used in the present invention may contain water as a solvent, but usually only an organic solvent is used as the solvent from the viewpoint of avoiding corrosion of the substrate, etc. In this case, 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 usually 5 mass% or less.

[0162] The components and methodological elements of 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 of the present invention. The method for manufacturing a processed semiconductor substrate of the present invention may include steps other than those described above.

[0163] An example of the third embodiment will be described with reference to FIGS. 5A to 5E. This example is an example of manufacturing a thinned semiconductor substrate. First, a laminate is prepared (FIG. 5A). This laminate is the same as the laminate shown in FIGS. 1 and 2B. Next, a polishing device (not shown) is used to polish the surface of the semiconductor substrate 1 opposite to the surface in contact with the adhesive layer 2, thereby thinning the semiconductor substrate 1 (FIG. 5B). The thinned semiconductor substrate 1 may also be subjected to the formation of through-hole electrodes, etc. Next, an infrared laser L is irradiated onto the adhesive layer 2 from the support substrate 4 side (FIG. 5C). The infrared laser irradiation may be performed on the entire surface of the adhesive layer 2, or may be performed on only a portion of the adhesive layer 2. Next, a peeling device (not shown) is used to separate the thinned semiconductor substrate 1 from the support substrate 4 (FIG. 5D). This results in the thinned semiconductor substrate 1 (FIG. 5E). Residues of the adhesive layer 2 may remain on the thinned semiconductor substrate 1. Therefore, it is preferable to clean the thinned semiconductor substrate 1 using a cleaning composition to remove the residue of the adhesive layer 2 from the semiconductor substrate 1.

[0164] <Fourth embodiment> The method for producing a processed electronic device layer of the present invention includes the following step 5B and step 6B. The method for producing a processed electronic device layer may further include the following step 7B. Here, step 5B is a step of processing the electronic device layer in the laminate described in the above <Second embodiment> section. Furthermore, step 6B is a step of separating the electronic device layer processed in step 5B from the support substrate. Furthermore, step 7B is a step of cleaning the processed electronic device layer after step 6B. Specific examples of the fourth embodiment will be described below with reference to FIGS. 6A to 6G.

[0165] Examples of the processing performed on the electronic device layer in the step 5B include a grinding step and a wiring layer forming step.

[0166] <<Grinding Process>> The grinding process is a process of grinding away the resin portion of the layer of sealing resin 25 in the electronic device layer 26 so as to expose a portion of the semiconductor chip substrate 21. Grinding of the sealing resin portion is performed by grinding away the layer of sealing resin 25 of the stack shown in Fig. 6A until it has a thickness substantially equal to that of the semiconductor chip substrate 21, as shown in Fig. 6B, for example. The stack shown in Fig. 6A is the same stack as the stacks shown in Figs. 3 and 4C.

[0167] <<Wiring Layer Forming Process>> The wiring layer forming process is a process of forming a wiring layer on the exposed semiconductor chip substrate 21 after the grinding process. In FIG. 6C , a wiring layer 28 is formed on an electronic device layer 26 consisting of the semiconductor chip substrate 21 and a layer of sealing resin 25. The wiring layer 28 is also called an RDL (Redistribution Layer), and is a thin-film wiring body that constitutes wiring connected to the substrate, and can have a single-layer or multi-layer structure. The wiring layer is made of a dielectric (silicon oxide (SiO ｘ The wiring layer 28 may be formed by forming wiring between a conductive material (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys) and a layer of a sealing resin 25 (for example, a photosensitive resin such as photosensitive epoxy, photosensitive epoxy, etc.). The wiring layer 28 may be formed by, for example, forming wiring between a conductive material (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys, etc. ...). The wiring layer 28 may be formed by, for example, forming wiring between a conductive material (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys, etc.). The wiring layer 28 may be formed by, for example, forming wiring between a conductive material (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys, etc.). ｘ), a dielectric layer made of a photosensitive resin or the like is formed. The dielectric layer made of silicon oxide can be formed by, for example, sputtering, vacuum deposition, or the like. The dielectric layer made of a photosensitive resin can be formed by applying the photosensitive resin onto the layer of sealing resin 25 by, for example, spin coating, dipping, roller blade, spray coating, slit coating, or the like. Next, wiring is formed on the dielectric layer using a conductor such as metal. Methods for forming wiring can include, for example, known semiconductor process techniques such as lithography processes such as photolithography (resist lithography) and etching processes. Examples of such lithography processes include lithography processes using a positive resist material and lithography processes using a negative resist material. In the manufacturing method of the laminate according to the fourth embodiment, bumps can be formed on the wiring layer 28, or elements can be mounted on the wiring layer 28. Elements can be mounted on the wiring layer 28 using, for example, a chip mounter. The stack according to the fourth embodiment may be a stack produced in a process based on fan-out technology, in which terminals provided on a semiconductor chip substrate are mounted on a wiring layer extending outside the chip area.

[0168] In Step 6B, the method for separating (peeling) the electronic device layer from the support substrate is the separation step described above.

[0169] 6D to 6F are schematic cross-sectional views illustrating a method for separating the laminate, and FIG. 6G is a schematic cross-sectional view illustrating a cleaning method after separation of the laminate. FIGS. 6D to 6G illustrate one embodiment of a method for manufacturing a semiconductor package (electronic component). The step of separating the laminate is a step of separating the electronic device layer 26 and the support substrate 24, as shown in FIGS. 6D to 6F. Specifically, an infrared laser L is irradiated onto the adhesive layer 22 from the support substrate 24 side ( FIG. 6D ). The infrared laser irradiation may be performed on the entire adhesive layer 22, or may be performed on a portion of the adhesive layer 22. Next, a peeling device (not shown) is used to separate the thinned electronic device layer 26 from the support substrate 24 ( FIG. 6E ).

[0170] The substrate can be cleaned by spraying the cleaning composition onto at least one surface of the separated electronic device layer and / or the supporting substrate, or by immersing the separated electronic device layer or the supporting substrate in the cleaning composition. Alternatively, the surface of the processed electronic device layer, etc., may be cleaned using a removal tape or the like. For example, in FIG. 6F , after the separation step, an adhesive layer 22 is attached to the electronic device layer 26. The adhesive layer 22 can be removed by decomposing the adhesive layer 22 using a cleaning composition such as an acid or alkali. By removing the adhesive layer, a processed electronic device layer (electronic component) such as that shown in FIG. 6G can be suitably obtained.

[0171] The constituent elements and methodological elements of the above-described steps of the method for producing a processed electronic device layer 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 electronic device layer of the present invention may include steps other than those described above.

[0172] 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.

[0173] [Apparatus] (1) Mixer A: ARE-500, a planetary centrifugal mixer manufactured by Thinky Corporation (2) Mixer B: VMR-5R, a mix rotor manufactured by AS ONE Corporation (3) Viscosity measurement: TVE-22H, a rotational viscometer manufactured by Toki Sangyo Co., Ltd. (4) Spin coating device: Coater manufactured by APOGEE Corporation (5) Vacuum heating lamination device: VE09-07, manufactured by Ayumi Kogyo Co., Ltd. (6) Force gauge: RZE-10, manufactured by Aiko Engineering Co., Ltd. (7) Infrared laser peeling device: AFS-MCTII-FX, manufactured by Aflair Corporation

[0174] The structures and properties of the polysiloxanes (formula (V) and formula (W)) used are shown below.

[0175] (In formula (V), n represents the number of repeating units and is a positive integer.) Polysiloxanes having the structure represented by formula (V) and exhibiting the properties shown in Table 1 below were used.

[0176]

[0177] (In formula (W), n and m represent the number of repeating units and are each independently a positive integer.) The copolymer also has 2.7 mol / kg of vinyl groups and a number average molecular weight (Mn) of 9,000 as determined by GPC.

[0178] [1] Preparation of Adhesive Composition [Preparation Example 1] 1.0 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.0 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) were added to a 50 mL screw tube and stirred for 5 minutes with Stirrer A to obtain mixture (I). 210.71 g of a p-menthane solution (concentration 81.2% by mass) of vinyl group-containing MQ resin (manufactured by Wacker Chemie) and 0.05 g of a platinum catalyst (valence 0, platinum content 1 wt%) diluted with polysiloxane of the above formula (W) were added to a 650 mL stirring vessel dedicated to planetary centrifugal mixers and stirred for 5 minutes with Stirrer A to obtain mixture (II). 0.17 g of the obtained mixture (I) and 60.22 g of the obtained mixture (II) were added to a 200 mL stirring vessel dedicated to the planetary centrifugal mixer, and the mixture was stirred for 5 minutes with Stirrer A to obtain a mixture (III). To the obtained mixture (III), 16.84 g of the following mixture A, 13.01 g of the following mixture B, 0.80 g of epoxy-modified silicone (X-22-343, manufactured by Shin-Etsu Silicones Co., Ltd.), and 2.17 g of p-menthane were added, and the mixture was stirred for 5 minutes with Stirrer A to obtain a mixture (IV). Mixture A: 16.84 g of a mixture obtained by mixing a vinyl group-containing MQ resin (manufactured by Wacker Chemical Co.), a vinyl group-containing linear polydimethylsiloxane having a viscosity of 200 mPa·s and represented by the above formula (V) (V1 in Table 1), and a SiH group-containing linear polydimethylsiloxane having a viscosity of 100 mPa·s (manufactured by Wacker Chemical Co.), in a mass ratio of 54.1:36.4:9.5. Mixture B: A mixture obtained by mixing GENIOPLAST GUM (manufactured by Wacker Chemical Co.), a SiH group-containing linear polydimethylsiloxane having a viscosity of 100 mPa·s (manufactured by Wacker Chemical Co.), and p-menthane, in a mass ratio of 30.31:63.50:6.19. Finally, the resulting mixture (IV) was filtered through a 300-mesh nylon filter to obtain an adhesive composition.

[0179] [2] Preparation of Laminate [Example 1] The adhesive composition obtained in Preparation Example 1 was applied to a 4 cm square silicon substrate by spin coating at 950 rpm for 30 seconds, and then heated at 90 ° C for 1.5 minutes (pre-heat treatment) to form an adhesive coating layer. Then, in a vacuum heating and laminating apparatus, the silicon substrate having this adhesive coating layer and a 4 cm square silicon substrate were bonded together with the adhesive coating layer sandwiched between them, and the substrate with the adhesive coating layer formed on it was 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 lamination was performed using a vacuum heating and laminating apparatus at a temperature of 70 ° C, a vacuum of 1000 Pa, and a load of 150 kg for 3 minutes.

[0180] [3] Laser Irradiation [Example 2] Using an infrared laser peeling device, the laminate produced in Example 1 was irradiated with a laser having a wavelength of 9.3 μm from a direction perpendicular to the silicon wafer on the carrier side, only on a 5 mm portion of the outer periphery of a 4 cm square substrate. The laser irradiation conditions were as follows: Scan speed: 1000 nm / sec, Laser power: 60 W, Frequency: 20 Hz.

[0181] [4] Evaluation of Adhesion Strength [Example 3] The device side of the laminate produced in Example 2 was fixed on a workbench with double-sided tape. Next, the blade of a force gauge with a razor blade attached to the tip was inserted into the adhesive layer of the fixed laminate, and the maximum absolute value of the force gauge at this time was taken as the insertion force.

[0182] Comparative Example 1 The insertion force was evaluated in the same manner as in Example 3, except that the laminate produced in Example 1 was used without laser irradiation.

[0183] The evaluation results of Example 3 and Comparative Example 1 are shown in Table 2.

[0184]

[0185] The results of Example 3 and Comparative Example 1 revealed that when infrared laser irradiation was performed, it was possible to insert a substrate having a sharp part between substrates with a low insertion force. This confirmed that when the composition and process according to the present invention were used, the substrates were less damaged when the laminate was separated, and peeling was possible.

[0186] REFERENCE SIGNS LIST 1 semiconductor substrate 2 adhesive layer 2a adhesive coating layer 4 support substrate 21 semiconductor chip substrate 22 adhesive layer 22' adhesive coating layer 24 support substrate 25 sealing resin 26 electronic device layer 28 wiring layer L infrared laser

Claims

1. An adhesive composition for forming an adhesive layer used to separate the first and second substrates after processing the first substrate in a laminate having a first substrate that is a semiconductor substrate or an electronic device layer, a second substrate that is a support substrate that is transparent to infrared laser light, and an adhesive layer provided between the first and second substrates, and then irradiating the adhesive layer with an infrared laser from the second substrate side, the adhesive composition comprising an adhesive component having a siloxane bond and a release agent component.

2. The adhesive composition according to claim 1, wherein the adhesive component is a component that cures by a hydrosilylation reaction.

3. The adhesive composition according to claim 2, wherein the component that cures by a hydrosilylation reaction comprises: a component (A-1) having a silicon-bonded alkenyl group having 2 to 40 carbon atoms; and a component (A-2) having a Si—H group.

4. The adhesive composition according to claim 3, wherein the component (A-1) contains a polyorganosiloxane (a1) having a silicon-bonded alkenyl group having 2 to 40 carbon atoms.

5. The adhesive composition according to claim 3, wherein the component (A-2) contains a polyorganosiloxane having Si—H groups.

6. The adhesive composition of claim 1, wherein the release agent component is a polyorganosiloxane.

7. The adhesive composition according to claim 1, wherein the insertion force required when inserting the sharp portion of a substrate having a sharp portion between the first substrate and the second substrate to separate the first substrate and the second substrate after irradiating the adhesive layer with the infrared laser is smaller than the insertion force required when inserting the sharp portion between the first substrate and the second substrate without irradiating the adhesive layer with the infrared laser to separate the first substrate and the second substrate.

8. A laminate comprising: a first substrate which is a semiconductor substrate or an electronic device layer; a second substrate which is a support substrate that is transparent to infrared laser; and an adhesive layer provided between the first substrate and the second substrate, wherein the adhesive layer is an adhesive layer formed from the adhesive composition according to any one of claims 1 to 7.

9. A method for producing a processed semiconductor substrate or electronic device layer, comprising: a processing step in which the first substrate of the laminate described in claim 8 is processed; and a separation step in which the infrared laser is irradiated onto the adhesive layer from the second substrate side, and then the processed first substrate and second substrate are separated.

10. The method for producing a processed semiconductor substrate or electronic device layer according to claim 9, wherein irradiating the adhesive layer with the infrared laser reduces the insertion force required to insert the sharp portion of a material having a sharp portion between the first substrate and the second substrate to separate the first substrate from the second substrate, compared to when the infrared laser is not irradiated on the adhesive layer.

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