Temporary adhesive material composition and method for cleaning substrate

Abstract

Provided is a temporary adhesive material composition for releasably adhering a substrate and a support, the temporary adhesive material composition containing (A) an organopolysiloxane mixture that crosslinks by a hydrosilylation reaction, (B) an organopolysiloxane that does not induce a hydrosilylation reaction, (C) a catalyst, and (D) an organic solvent, the temporary adhesive material composition is passed through a filter having a pore diameter of 100 nm or less, and the number of particles remaining after the filtration having a particle diameter of 100-1000 nm or less is 20 particles / ml or less. As a result, it is possible to provide a temporary adhesive material composition having few particles that may cause poor connection on a substrate surface (circuit-forming surface) after cleaning.

Description

TECHNICAL FIELD

[0001] The present application relates to a temporary adhesive material composition and a substrate cleaning method. BACKGROUND

[0002] For achieving further higher density and larger capacity, three-dimensional semiconductor mounting becomes indispensable. The three-dimensional mounting technology refers to a semiconductor manufacturing technology in which one semiconductor chip is thinned, further connected through a through silicon via (TSV), and stacked in multiple layers. In order to achieve this technology, a process is required in which a substrate on which a semiconductor circuit is formed is thinned by polishing a non-circuit formation surface (hereinafter also referred to as "back surface") and further an electrode including a TSV is formed on the back surface. In the past, in the back surface polishing process of a silicon substrate, a back surface protection tape is attached to the opposite side of the polished surface to prevent the wafer from being damaged during polishing. However, this tape uses an organic resin film in the base material, and although it has flexibility, the strength and heat resistance are not sufficient, and it is not suitable for the TSV formation process or the process of forming a wiring layer on the back surface.

[0003] Therefore, a system is proposed in which a semiconductor substrate is joined to a support such as silicon or glass through an adhesive layer, and is able to sufficiently withstand the processes of back surface polishing, TSV, and back surface electrode formation. At this time, it is important to have an adhesive layer when joining the substrate to the support. It is required to be able to join the substrate to the support without gaps, and to have sufficient durability that can only withstand subsequent processes. Further, it is also required to be able to easily peel off the thin wafer from the support at the end. In addition, since this adhesive layer is peeled off at the end, it is also referred to as a "temporary adhesive layer" in this specification.

[0004] As a temporary adhesive layer and a peeling method thereof known so far, a technology is proposed in which a hot-melt hydrocarbon compound is used as an adhesive, and joining / peeling is performed in a heated and molten state (Patent Literature 1).

[0005] After the support is peeled off, a part of the temporary adhesive material remains on the circuit formation surface (hereinafter also referred to as "surface") of the substrate on which the semiconductor circuit is formed. Usually, this remaining temporary adhesive layer is removed in a cleaning process.

[0006] In recent years, a method has been developed for connecting copper electrodes formed on the same surface of thinned semiconductor chips during the lamination process. Compared to conventional methods that connect protruding connecting electrodes on the chip surfaces, this method reduces the void ratio between chips, promising further densification and reduced power consumption. However, this method of connecting copper electrodes formed on the same surface of chips can cause poor connections between chips if large particles remain between the thinned chips.

[0007] Under the above background, there is a demand for the development of a temporary adhesive material composition having fewer particles that may cause poor connection on the substrate surface (circuit formation surface) after cleaning, and a method for cleaning the same.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 2013-243350 Summary of the Invention

[0011] (1) Technical issues to be resolved

[0012] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a temporary adhesive material composition having fewer particles that may cause poor connection on the substrate surface (circuit formation surface) after cleaning.

[0013] (2) Technical solution

[0014] In order to solve the above-mentioned technical problems, the present invention provides a temporary adhesive material composition for bonding a substrate and a support in a releasable manner, characterized in that it contains: (A) an organopolysiloxane mixture that undergoes crosslinking by a hydrosilylation reaction, (B) an organopolysiloxane that does not trigger a hydrosilylation reaction, (C) a catalyst, and (D) an organic solvent. When the temporary adhesive material composition is passed through a filter with a pore size of 100 nm or less, the number of particles with a particle size of 100 nm or more and 1000 nm or less remaining after the filtration is 20 or less per ml.

[0015] The temporary adhesive material composition described above can reduce particles that may cause poor connection on the substrate surface (circuit formation surface) after cleaning.

[0016] In this case, it is preferred that the constituent (A) is a mixture of different organopolysiloxanes (A-1) and organopolysiloxanes (A-2), wherein the constituent (A-1) is composed of R1R2R3SiO 1 / 2 The M unit represented by R4R5SiO 2 / 2at least one of a D unit represented by R6SiO 3 / 2 a T unit represented by SiO 4 / 2 a Q unit represented by SiO 1 / 2 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 10 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 11 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 2 / 2 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 12 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 3 / 2 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 4 / 2 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 10 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 11 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 12 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group.

[0017] Further, it is preferable that the component (B) be a platinum catalyst. 13 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 14 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 15 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 1 / 2 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 16 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 17 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 2 / 2 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 18 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 3 / 2 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 4 / 2 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 13 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 14 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 15 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 16 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 17 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group. 18 R1, R2, R3, R4, R5, R6are a methyl group, a -CH=CH2 group, or a phenyl group.

[0018] Further, it is preferable that the component (C) be a platinum catalyst.

[0019] Further, it is preferable that the component (D) be an organic solvent containing at least one or more saturated hydrocarbons having 8 to 12 carbon atoms and not containing a hetero atom.

[0020] As long as the temporary adhesive composition is the above-described component, it is possible to more certainly reduce particles that can cause connection failure on the surface of the substrate (circuit formation surface) after cleaning.

[0021] Further, the present application provides a substrate cleaning method characterized by comprising: a process of attaching an adhesive sheet so as to cover the entire temporary adhesive material composition on the substrate, and peeling the adhesive sheet, thereby removing the temporary adhesive material composition; a process of cleaning the substrate with cleaning liquid A; a process of rinsing the substrate with cleaning liquid B; and a process of rinsing the substrate with cleaning liquid C.

[0022] By the cleaning method of the above process, a substrate with fewer particles that can cause connection failure on the substrate surface (circuit formation surface) after cleaning can be produced.

[0023] At this time, it is preferable that the cleaning liquid A be a cleaning liquid containing a quaternary ammonium salt, and that the cleaning liquid A pass through a filter having a pore diameter of 100 nm or less, and that the number of particles having a particle diameter of 100 nm or more and 1000 nm or less remaining after filtration be 3.0 particles / ml or less.

[0024] Further, it is preferable that the cleaning liquid B be a cleaning liquid containing a water-soluble organic solvent, and that the cleaning liquid B pass through a filter having a pore diameter of 100 nm or less, and that the number of particles having a particle diameter of 100 nm or more and 1000 nm or less remaining after filtration be 3.0 particles / ml or less.

[0025] Further, it is preferable that the cleaning liquid C be water, and that the cleaning liquid C pass through a filter having a pore diameter of 100 nm or less, and that the number of particles having a particle diameter of 100 nm or more and 1000 nm or less remaining after filtration be 3.0 particles / ml or less.

[0026] By using the above cleaning liquid, a substrate with fewer particles that can cause connection failure on the substrate surface (circuit formation surface) after cleaning can be produced more effectively.

[0027] Further, in the substrate cleaning method of the present application, it is preferable that, after the substrate having the above temporary adhesive material composition is cleaned by the above cleaning method, the distribution of particles having a particle diameter of 100 nm or more and 1000 nm or less remaining on the cleaned surface be 15 particles / cm 2 The following.

[0028] According to the above substrate cleaning method, a substrate with fewer particles that can cause connection failure on the substrate surface (circuit formation surface) after cleaning can be produced more reliably.

[0029] (Three) Advantageous Effects

[0030] The temporary adhesive composition of the present application can reduce the number of particles that can cause connection failure on the surface of the substrate (circuit formation surface) after cleaning, and particularly can provide a temporary adhesive composition that has a number of particles with a particle size of 100 nm or more and 1000 nm or less of 20 particles / ml or less after filtration through a filter with a pore size of 100 nm or less, and a distribution of particles with a particle size of 100 nm or more and 1000 nm or less on the surface of the substrate after cleaning of 15 particles / cm 2 The following cleaning method. DETAILED DESCRIPTION

[0031] Hereinafter, the present application will be described in detail, but the present application is not limited thereto.

[0032] First, the temporary adhesive composition of the present application will be described.

[0033] [Temporary adhesive composition]

[0034] In the process of backgrinding a substrate on which a semiconductor circuit is formed, for example, the substrate and the support are joined by a temporary adhesive layer containing a temporary adhesive for a substrate. The temporary adhesive for a substrate of the present application uses the following silicone-based adhesive.

[0035] The present application is a temporary adhesive composition that adheres a substrate and a support in a releasable manner, characterized by containing: (A) an organopolysiloxane mixture that crosslinks by hydrosilylation, (B) an organopolysiloxane that does not cause hydrosilylation, (C) a catalyst, and (D) an organic solvent, and passing the temporary adhesive composition through a filter with a pore size of 100 nm or less, and the number of particles with a particle size of 100 nm or more and 1000 nm or less remaining after filtration being 20 particles / ml or less.

[0036] The organopolysiloxane (A) that crosslinks by hydrosilylation is provided as a mixture, and at this time, a mixture of different organopolysiloxanes (A-1) and (A-2) is preferable.

[0037] Further, it is preferable that the constituent component (A-1) is composed of at least one of an M unit represented by R1R2R3SiO 1 / 2 a D unit represented by R4R5SiO 2 / 2 a T unit represented by R6SiO 3 / 2 or a Q unit represented by SiO 4 / 2 , and the substituents R1, R2, R3, R4, R5, and R6 are a methyl group, -CH=CH2, or a phenyl group, and the constituent component (A-2) is composed of an M unit represented by R7R8R9SiO 1 / 2 a D unit represented by R 10R 11 SiO 2 / 2 D unit represented by R 12 SiO 3 / 2 T unit represented by SiO 4 / 2 Q unit represented by SiO 10 R7, R8, R9, R 11 , R 12 , R 4 / 2 are methyl, phenyl or hydrogen.

[0038] If further specified, component (A-1) is an organic polysiloxane having 2 or more alkenyl groups in 1 molecule. As component (A-1), for example, a linear or branched diorganopolysiloxane having 2 or more alkenyl groups in 1 molecule, an organic polysiloxane having 2 or more alkenyl groups in 1 molecule and having a resin structure of siloxane units (Q units) represented by SiO 31 , etc. can be exemplified. Component (A-1) preferably has an alkenyl group content of 0.6 to 9 mol%. In the present application, the alkenyl group content means the proportion of siloxane units having alkenyl groups among all siloxane units.

[0039] As the above organic polysiloxane, specifically, an organic polysiloxane represented by the following formula (1), (2) or (3) can be exemplified. These organic polysiloxanes can be used alone or two or more can be used simultaneously.

[0040] [Chemical Formula 1]

[0041]

[0042] In formulae (1) to (3), R 31 to R 46 are each independently a hydrocarbon group having no aliphatic unsaturated bond, X 1 to X 5 are each independently an alkenyl group-containing monovalent organic group.

[0043] In formula (1), a and b are each independently an integer of 0 to 3.

[0044] In formulae (1) and (2), c 1 , c 2 , d 1 and d 2 are integers satisfying 0 ≤ c 1 ≤ 10, 2 ≤ c 2 ≤ 10, 0 ≤ d 1 ≤ 100 and 0 ≤ d 2 ≤ 100. Among them, a + b + c 1 ≥ 2. a, b, c 1 , c 2 , d1 and d 2 The combination of the content of the alkenyl group is preferably a number of 0.6 to 9 mol%.

[0045] In formula (3), e is an integer of 1 to 3.f 1 , f 2 , and f 3 is a number such that (f 2 + f 3 ) / f 1 is 0.3 to 3.0, and f 3 / (f 1 + f 2 + f 3 ) is 0.01 to 0.6.

[0046] As the hydrocarbon group not having the aliphatic unsaturated bond, a hydrocarbon group having 1 to 10 carbon atoms is preferred. As specific examples thereof, an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, and the like; a cycloalkyl group having 4 to 10 carbon atoms such as cyclohexyl, and the like; and an aryl group having 6 to 10 carbon atoms such as phenyl, tolyl, and the like can be given. Among them, methyl or phenyl is preferred.

[0047] As the monovalent organic group containing an alkenyl group, a monovalent organic group containing an alkenyl group having 2 to 10 carbon atoms is preferred. As specific examples thereof, an alkenyl group having 2 to 10 carbon atoms such as vinyl, allyl, hexenyl, octenyl, and the like; a (meth)acryloylalkyl group having 3 to 10 carbon atoms such as acryloylpropyl, acryloylmethyl, methacryloylpropyl, and the like; a (meth)acryloxyalkyl group having 3 to 10 carbon atoms such as acryloxypropyl, acryloxy methyl, methacryloxypropyl, methacryloxy methyl, and the like; and cyclovinylethyl, vinyloxypropyl, and the like can be given. Among them, from the industrial viewpoint, vinyl is preferred.

[0048] In formula (1), a and b are preferably 1 to 3 because the molecular chain ends are capped with alkenyl groups, and thus the reaction can be completed in a short time by the alkenyl groups of the molecular chain ends which have a high reactivity. From the industrial viewpoint and the cost aspect, a and b are each preferably 1. The diorganopolysiloxane containing an alkenyl group represented by formula (A-1) is preferably in the form of an oil or a raw rubber, and is more preferably in the form of an oil from the viewpoint of filterability.

[0049] The compound represented by formula (3) is an organopolysiloxane having a resin structure (three-dimensional network structure). In formula (3), from the industrial viewpoint and the cost aspect, e is preferably 1. Further, the product of the average value of e and f3 / (f1+f2+f3) is preferably 0.02 to 1.5, and more preferably 0.03 to 1.0. The organopolysiloxane represented by formula (3) can also be dissolved in an organic solvent and used in the form of a solution.

[0050] Component (A-2) is a crosslinking agent, which is an organohydrogenpolysiloxane containing at least 2, preferably 3 or more silicon atom-bonded hydrogen atoms (Si-H groups) in one molecule. The organohydrogenpolysiloxane can be any of linear, branched, or cyclic. Furthermore, the organohydrogenpolysiloxane can be used alone or in combination with two or more.

[0051] The viscosity of component (A-2) at 25°C is preferably 1 to 5000 mPa-s, more preferably 5 to 500 mPa-s. In the present application, the viscosity is a measured value obtained using a rotational viscometer at 25°C.

[0052] Component (A-2) is preferably blended so that the total of Si-H groups in component (A-2) is in the range of 0.3 to 10 in terms of molar ratio (Si-H groups / alkenyl groups) relative to the total of alkenyl groups in component (A-1), more preferably so that the total of Si-H groups in component (A-2) is in the range of 1.0 to 8.0 in terms of molar ratio (Si-H groups / alkenyl groups) relative to the total of alkenyl groups in component (A-1). If the molar ratio is 0.3 or more, the crosslinking density does not become too low, and it is also possible to sufficiently cure the uncured composition layer. If the molar ratio is 10 or less, the crosslinking density does not become too high, and sufficient adhesion and tack can be obtained. Furthermore, if the molar ratio is 10 or less, it is possible to extend the usable time of the temporary adhesive composition.

[0053] The organopolysiloxane (B) that does not initiate a hydrosilylation reaction is composed of at least one of an M unit represented by R 13 R 14 R 15 SiO 1 / 2 a D unit represented by R 16 R 17 SiO 2 / 2 a T unit represented by R 18 SiO 3 / 2 or a Q unit represented by SiO 4 / 2 . As the functional group bonded to a silicon atom, a hydrocarbon group having 1 to 10 carbon atoms is preferred. As specific examples thereof, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and the like; a cycloalkyl group having 4 to 10 carbon atoms such as a cyclohexyl group, and the like; an aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, and the like can be listed. Among these, a methyl group or a phenyl group is preferred. That is, the above substituents R 13 , R 14 , R 15 , R 16 , R 17 , R 18The organic group is preferably a methyl group or a phenyl group. Furthermore, the organopolysiloxane can be one alone or a mixture of two or more.

[0054] The component (B) is preferably added in an amount of 0.1 to 80 mass% relative to the organopolysiloxane mixture (A) which is crosslinked by hydrosilation reaction, but is not particularly limited.

[0055] The catalyst component (C) is suitably a platinum-based catalyst (i.e., a platinum group metal catalyst). As the platinum-based catalyst, there can be mentioned chloroplatinic acid, an alcoholic solution of chloroplatinic acid, a reaction product of chloroplatinic acid with an alcohol, a reaction product of chloroplatinic acid with an olefin compound, a reaction product of chloroplatinic acid with a siloxane containing a vinyl group, and the like. The platinum-based catalyst can be used alone as one kind or two or more kinds can be used simultaneously.

[0056] The catalyst component (C) is preferably incorporated in an amount of 1 to 5000 ppm in terms of platinum group metal component (mass conversion) relative to the total of components (A-1) and (A-2), and more preferably in an amount of 5 to 2000 ppm in terms of platinum group metal component (mass conversion) relative to the total of components (A-1) and (A-2). If it is 1 ppm or more, the curability of the uncured composition layer is not easily decreased, so that it is possible to suppress the lowering of crosslinking density and the lowering of retention. If it is 5000 ppm or less, it is possible to extend the usable time of the temporary adhesive composition.

[0057] As the organic solvent (D), a saturated hydrocarbon having 8 to 12 carbon atoms which does not contain a hetero atom is suitably used. For example, there can be mentioned hydrocarbon-based solvents such as pentane, hexane, cyclohexane, isooctane, nonane, decane, p-mentane, pinene, isododecane, limonene, and silicone-based solvents. However, there is no particular limitation as long as the components of the temporary adhesive composition can be dissolved.

[0058] The content of the organic solvent in the temporary adhesive composition is preferably 10 to 900 parts by mass, more preferably 25 to 400 parts by mass, and further preferably 40 to 300 parts by mass, relative to 100 parts by mass of the total of component (A-1) and component (A-2). The organic solvent can be used alone as one kind or two or more kinds can be used simultaneously.

[0059] The temporary adhesive composition can also contain a reaction control agent. The reaction control agent is an ingredient which is arbitrarily added as needed in order to suppress the tackification or gelling of the uncured composition before heat curing, when the uncured composition is prepared or when the uncured composition is applied to a substrate.

[0060] As the reaction control agent, for example, 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexene-3-ol, 1-ethynylcyclohexanol, 3-methyl-3-trimethylsilyloxy-1-butyne, 3-methyl-3-trimethylsilyloxy-1-pentyne, 3,5-dimethyl-3-trimethylsilyloxy-1-hexyne, 1-ethynyl-1-trimethylsilyloxycyclohexane, bis(2,2-dimethyl-3-butylnyloxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-divinyl disiloxane, and the like can be exemplified. Among them, 1-ethynylcyclohexanol and 3-methyl-1-butyne-3-ol are preferred.

[0061] When the temporary adhesive material composition contains the reaction control agent, the content thereof is preferably 0.01 to 8.0 parts by mass, more preferably 0.05 to 2.0 parts by mass, relative to 100 parts by mass of the total of components (A-1) and (A-2). If it is 0.01 parts by mass or more, the effect of controlling the reaction can be sufficiently exerted. If it is 8.0 parts by mass or less, the curability of the uncured composition layer is not easily decreased. One kind of the reaction control agent can be used alone, or two or more kinds thereof can be used simultaneously.

[0062] The temporary adhesive material composition can further contain other components. As the other components, fillers such as silica; non-reactive organopolysiloxanes such as polydimethylsiloxane and polydimethylphenylsiloxane; antioxidants such as phenol-based, quinone-based, amine-based, phosphorus-based, phosphite-based, sulfur-based, and sulfide-based antioxidants; light stabilizers such as triazole-based and benzophenone-based light stabilizers; flame retardants such as phosphate-based, halogen-based, phosphorus-based, and antimony-based flame retardants; antistatic agents such as cationic, anionic, and nonionic active agents; and the like can be exemplified. One kind of each of the other components can be used alone, or two or more kinds thereof can be used simultaneously.

[0063] When the temporary adhesive material composition contains other components, the other components can be blended within an appropriate range. For example, when a filler is used in order to improve heat resistance, the content thereof is preferably 50 parts by mass or less, relative to 100 parts by mass of the total of components (A-1) and (A-2).

[0064] The temporary adhesive material composition of the present application has the above composition, but is further characterized in that, when the temporary adhesive material composition is filtered through a filter having a pore size of 100 nm or less, the number of particles having a particle size of 100 nm or more and 1000 nm or less remaining after the filtration is 20 particles / ml or less. The number of particles can be achieved by filtration or the like of the temporary adhesive material composition.

[0065] [Filtering of temporary adhesive material composition]

[0066] The insoluble impurities such as the gel-like particles or solid-like particles in the temporary adhesive material composition are removed before the composition is applied to the substrate. As a method for removing these insoluble impurities, for example, a method of passing them through a filter can be cited.

[0067] The filter used for the temporary adhesive material composition can cite a fluororesin such as polytetrafluoroethylene or polyvinylidene fluoride, or a polyolefin resin such as polyethylene or polypropylene, a polyamide resin such as nylon 66, and the like, and is not particularly limited. From the viewpoint of stability and elution of the filter, a fluorine-based resin filter is suitably used.

[0068] The shape of the filter can cite a filter paper or a disc, a box, and the like, and is not particularly limited. As a material other than the filter portion, from the viewpoint of stability and elution, a fluorine-based resin is suitably used.

[0069] The pore size of the filter needs to be a pore size as much as possible to remove small insoluble impurities contained in the temporary adhesive material composition having high viscosity, and the lower limit is not particularly limited, and can be 0.5 nm or more, more preferably 1 to 100 nm, and further preferably a filter having a pore size of 10 to 70 nm is used.

[0070] The filtration speed is not limited as long as the temporary adhesive material can pass through, and is preferably 10 ml / minute or more, more preferably 30 ml / minute or more, and further preferably 50 ml / minute or more.

[0071] The number of particles contained in the temporary adhesive material composition that has passed through the filter is 20 particles / ml or less, more preferably 10 particles / ml or less, further preferably 3.0 particles / ml or less, and most preferably 0 particles / ml, for particles having a particle size of 100 nm or more.

[0072] [Preparation stage of the substrate cleaning method of the present application]

[0073] The substrate cleaning method of the present application is characterized by comprising a process of attaching an adhesive sheet so as to cover the entire temporary adhesive material composition on the substrate, and peeling off the adhesive sheet, thereby removing the temporary adhesive material composition; a process of cleaning the substrate with cleaning liquid A; a process of rinsing the substrate with cleaning liquid B; and a process of rinsing the substrate with cleaning liquid C. First, the substrate to which this cleaning can be applied and the process up to obtaining the substrate will be described.

[0074] [Process (a)]

[0075] As described above, in the back surface grinding process or the like for forming a substrate with a semiconductor circuit, for example, the substrate and the support are joined through a temporary adhesive layer containing a temporary adhesive for a substrate. In the cleaning method for a substrate of the present application, first, it is preferable to perform the treatment by the filtration method described above before the substrate and the support are adhered using the temporary adhesive.

[0076] [Method for manufacturing a laminate]

[0077] In the manufacture of a thin wafer, the temporary adhesive material composition is used in the manufacture of a laminate in which the circuit-formed surface of a substrate and a support are joined in a manner such that the two face each other by the temporary adhesive material composition. The thinning process of the substrate is performed, for example, by a method including the following processes: (b) a process for manufacturing a substrate laminate, (c) a process for grinding or polishing the back surface of the substrate in the substrate laminate, (d) a process for performing processing on the back surface of the substrate, and (e) a process for peeling the support from the substrate laminate.

[0078] [Process (b)]

[0079] In process (b), specifically, the circuit-formed surface of a substrate having a circuit-formed surface on the surface and a non-circuit-formed surface on the back surface is joined to the support through a temporary adhesive layer (hereinafter, referred to as a cured layer (a)). The cured layer (a) is not particularly limited, and as an organic silicon-based adhesive, it is preferable to be an adhesive formed by heat-curing an uncured composition of a thermosetting organopolysiloxane or a thermoplastic organopolysiloxane, and from the viewpoint of reducing post-cleaning particles, it is particularly preferable to be a substance formed by heat-curing the temporary adhesive material composition through a filter. More specifically, process (b) includes: (b-1) a process for laminating the temporary adhesive material composition as an organic silicon-based adhesive on the support; (b-2) a process for joining the support and the substrate having a circuit-formed surface on the surface and a non-circuit-formed surface on the back surface through the temporary adhesive material composition layer in a manner such that the surface of the substrate having the circuit-formed surface faces the temporary adhesive material composition layer; and (b-3) a process for heat-curing the temporary adhesive material composition layer to thereby produce the cured layer (a). Or includes: (b-1') a process for laminating the temporary adhesive material composition layer on the circuit-formed surface of the substrate having a circuit-formed surface on the surface and a non-circuit-formed surface on the back surface; (b-2) a process for joining the substrate and the support through the temporary adhesive material composition layer; and (b-3) a process for heat-curing the temporary adhesive material composition layer to thereby produce the cured layer (a).

[0080] In the process (b-1) or (b-1'), a film of the adhesive material composition can be used when laminating the adhesive material composition layer. Alternatively, a solution of the adhesive material composition can be laminated by a method such as spin coating, slit coating, spray coating, and the like. Lamination is preferably performed by spin coating. At this time, a pre-bake is preferably performed at a temperature of 80 to 250°C, more preferably 100 to 230°C, after spin coating according to the volatilization conditions of the solvent contained in the adhesive material composition.

[0081] In the process (b-1) or (b-1'), the adhesive material composition layer is preferably formed so as to have a film thickness of 10 to 150 μm. If it is 10 μm or more, the substrate and the support can be bonded without gaps, and can sufficiently withstand the lapping process described later. If it is 150 μm or less, the resin can be inhibited from deforming in the heat treatment process such as the TSV formation process described later, and can withstand actual use.

[0082] In the process (b-2) or (b-2'), as a method of bonding the substrate and the support, for example, a method of uniformly pressing the substrate under reduced pressure at a temperature of preferably 40 to 250°C, more preferably 60 to 200°C can be exemplified. At the time of bonding, a commercially available wafer bonding device such as EVG520IS, 850TB (product names) manufactured by EV Group, XBC300 (product name) manufactured by SUSS Group, Synapse V (product name) manufactured by Tokyo Electron Limited, and the like can be used.

[0083] In the process (b-3), the curing of the uncured composition layer is performed, for example, by heating the uncured composition layer at a temperature of preferably 120 to 250°C, more preferably 140 to 200°C for a time of preferably 10 minutes or more and 4 hours or less, more preferably 30 minutes or more and 2 hours or less.

[0084] The substrate used in the process (b) is typically a semiconductor wafer. As the semiconductor wafer, a silicon wafer, a germanium wafer, a gallium-arsenic wafer, a gallium-phosphorus wafer, and a gallium-arsenic-aluminum wafer can be exemplified. The thickness of the wafer is not particularly limited, and is typically 600 to 800 μm, more typically 625 to 775 μm.

[0085] Further, as the support used in the process (b), a substrate such as a silicon wafer, a glass plate, a quartz wafer, and the like can be exemplified.

[0086] [Temporary adhesive layer (cured layer (a))]

[0087] As described above, the cured layer (a) is obtained by heat-curing the temporary adhesive material composition layer.

[0088] The peeling force when the cured layer (a) laminated on the support is subjected to interfacial peeling from the support is preferably 10 to 500 mN / 25 mm, more preferably 30 to 500 mN / 25 mm, and further preferably 50 to 200 mN / 25 mm. Here, the peeling force is the pull-off peeling force obtained in a 180° peeling test in which a 25 mm wide test piece is pulled and peeled off at 5 mm / second. As long as the peeling amount is more than 10 mN / 25 mm, peeling in the processing steps described later can be suppressed. As long as it is less than 500 mN / 25 mm, the cured layer (a) can be easily peeled off from the support.

[0089] In addition, the peeling force when the cured layer (a) stacked on the substrate is peeled off from the substrate is, for example, preferably 50 to 1000mN / 25mm, more preferably 70 to 1000mN / 25mm, and further preferably 80 to 500mN / 25mm or less. Here, the peeling force is the pull-off peeling force obtained in the 180° peeling test in which a 25mm wide test piece is pulled off at 5mm / second. As long as the peeling amount is more than 50mN / 25mm, it is possible to suppress the peeling in the processing steps described later, especially even if peeling is not easy to occur by a high temperature process. As long as it is less than 1000mN / 25mm, the cured layer (a) can be peeled off from the substrate by tape.

[0090] Furthermore, the storage modulus of the cured layer (a) at 25°C is preferably 1×10 6 ~1×10 9 Pa. As long as the storage elastic modulus is within the above range, it can fully withstand the grinding process described later and reduce the warping of the substrate. Therefore, it is less likely to cause problems such as the device being unable to start during the process.

[0091] [Step (c)]

[0092] Step (c) is a step of grinding or polishing the back side of the substrate in the substrate laminate. In step (c), the thickness of the substrate is reduced by grinding or polishing the back side (non-circuit forming side) of the substrate bonded to the support. The thickness of the thinned substrate is typically 5 to 300 μm, preferably 10 to 100 μm. The grinding method is not particularly limited and can be implemented in a known manner. Grinding is preferably implemented while applying water to the substrate and the grindstone (diamond, etc.) for cooling. As an apparatus for grinding the back side of the substrate, for example, DAG-810 (product name) manufactured by DISCO Corporation can be cited. In addition, chemical mechanical polishing (CMP) can be performed on the back side of the substrate.

[0093] [Step (d)]

[0094] The step (d) is a step of applying processing to the back surface of the substrate. In the step (d), processing is applied to the back surface (non-circuit formation surface) of the substrate that has been thinned by the back surface grinding or back surface polishing in the step (c). This step includes various processes that can be used at the wafer level. As the processes, electrode formation, metal wiring formation, protective film formation, and the like can be listed. More specifically, metal sputtering for forming an electrode or the like, wet etching for etching a metal sputtered layer, coating of resist for making a mask for forming a metal wiring, pattern formation by exposure and development, resist peeling, dry etching, formation of a metal plating layer, silicon etching for forming a TSV, oxide film formation on a silicon surface, and the like, which are conventionally known processes, can be listed. Further, the wafer that has been thinned is cut into a chip size by dicing or the like.

[0095] [Step (e)]

[0096] The step (e) is a step of peeling the support from the substrate laminate. In the step (e), the support is peeled from the substrate laminate on which processing has been applied in the step (d). The peeling step is usually performed at a relatively low temperature of room temperature to about 60°C. It can be performed by horizontally fixing one of the substrate or the support of the substrate laminate in advance and lifting the other at a certain angle from the horizontal direction. Further, a protective film can be attached to the ground surface of the substrate, and the substrate and the protective film can be peeled together in a peel-off manner.

[0097] This peel-off manner includes, for example, (e-1) a step of bonding a dicing tape to the processed surface of the substrate on which processing has been applied, (e-2) a step of vacuum-adsorbing the surface of the dicing tape to an adsorption surface, and (e-3) a step of peeling the support from the substrate by peel-off at a temperature of the adsorption surface in a range of 10°C or higher and 100°C or lower. At this time, the support can be easily peeled from the substrate, and the subsequent dicing step can be easily performed.

[0098] By the above peeling step, in addition to the case where the cured layer (a) is peeled from the substrate laminate together with the support, so that only the substrate is obtained, there is a case where only the support is peeled from the substrate laminate, so that the substrate with the cured layer (a) laminated is obtained. In the latter case, as shown in the step (f) (described later), for example, a step of peeling the cured layer (a) from the substrate by tape peel-off is performed, and only the substrate is obtained.

[0099] [Substrate cleaning method]

[0100] A substrate cleaning method is used, for example, when a substrate is cleaned in manufacturing a thin wafer. That is, a process of removing the temporary adhesive layer remaining on the substrate from a substrate layer stack having a support, a temporary adhesive layer formed on the support, and a substrate layered on the temporary adhesive layer in a manner that a surface having a circuit surface faces the temporary adhesive layer, peeling the support.

[0101] The temporary adhesive material remaining on the substrate is removed by, for example, a method including the following processes: (f) a process of attaching an adhesive sheet in a manner that covers the entire temporary adhesive layer on the substrate, and peeling the adhesive sheet, thereby removing the temporary adhesive layer; (g) a process of cleaning the substrate with cleaning liquid A; (h) a process of cleaning the substrate with cleaning liquid B; and (i) a process of cleaning the substrate with cleaning liquid C.

[0102] [Process (f)]

[0103] Process (f) is a process of removing the temporary adhesive layer remaining on the substrate by tape peeling. The temporary adhesive layer is removed by attaching an adhesive sheet in a manner that covers the entire temporary adhesive layer on the substrate, and peeling the adhesive sheet, thereby obtaining only the substrate. As a tape used in the tape peeling, a tape using a silicone adhesive material is preferably used. For example, polyester film adhesive tape No. 646S, No. 648, and the like manufactured by Teraoka Seisakusho co., Ltd. are suitably used.

[0104] [Process (g)]

[0105] Process (g) is a process of cleaning the surface of the substrate with cleaning liquid A. In process (g), the surface (circuit formation surface) of the substrate is cleaned with cleaning liquid A, and the remaining cured layer (a) (cured product of the uncured composition) is removed. Thus, after the support and the cured layer (a) are peeled by process (e), the cured layer (a) remaining on the surface of the substrate can also be sufficiently removed.

[0106] The cleaning can also be performed by immersing the substrate in cleaning liquid A. The immersion time is preferably 10 seconds or more and 30 minutes or less, and more preferably 30 seconds or more and 10 minutes or less. In addition, the cleaning can also be performed by spraying cleaning liquid A on the substrate. Further, the cleaning can also be performed using cleaning liquid A with a paddle, and oscillation, ultrasonic cleaning can also be performed. The temperature at the time of performing the cleaning is preferably 10 to 50°C, and more preferably 20 to 40°C.

[0107] The cleaning liquid A can be used without particular limitation as long as it can dissolve the cured layer (a) of the temporary adhesive material composition, and specifically, pentane, hexane, cyclohexane, decane, isododecane, limonene, and the like as aliphatic hydrocarbon compounds; benzene, toluene, xylene, mesitylene, and the like as aromatic hydrocarbon compounds; N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N-methylpyrrolidone, and the like as heteroatom-containing compounds can be exemplified. These solvents can be used alone or in combination of two or more. In addition, when it is difficult to remove, an alkali or an acid can be added to the above solvent. As examples of the alkali, amine such as ethanolamine, diethanolamine, triethanolamine, triethylamine, ammonia, and the like; ammonium salt such as tetramethylammonium hydroxide can be used. As the acid, organic acid such as acetic acid, oxalic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, and the like can be used. The amount of addition is 0.01 to 10% by mass, and preferably 0.1 to 5% by mass in terms of the concentration in the cleaning liquid. The cleaning liquid A is particularly preferably a cleaning liquid containing a quaternary ammonium salt. The quaternary ammonium salt is a compound represented by R A R B R C R D N + X - , R A ~R D are each independently selected from an alkyl group, an aryl group, an aralkyl group, and the like. In addition, X - is selected from a fluoride ion or a hydroxide ion.

[0108] [Step (h)]

[0109] Step (h) is a step of rinsing the surface of the substrate with the cleaning liquid B. In step (h), the surface (circuit formation surface) of the substrate is rinsed with the cleaning liquid B to remove the cleaning residue and the cleaning liquid A.

[0110] The cleaning liquid B can be used without particular limitation as long as it can dissolve the cured layer (a) of the temporary adhesive material composition and the cleaning liquid A, and specifically, pentane, hexane, cyclohexane, decane, isododecane, limonene, and the like can be exemplified. In particular, when an ammonium salt is used as an additive of the cleaning liquid A, a water-soluble organic solvent is preferably used. Specifically, methanol, ethanol, 1-propanol, 2-propanol, and the like can be exemplified. These solvents can be used alone or in combination of two or more.

[0111] The rinsing with the cleaning liquid B is preferably a method in which the substrate is held horizontally and rotated at a certain speed while the cleaning liquid B is caused to flow onto the substrate. The flow can be to only the center of the substrate, or can be in a manner that goes back and forth between the center and the periphery. The rotation speed of the substrate is not particularly limited, and is preferably 1 to 500 rpm, more preferably 200 to 300 rpm. Further, the flow rate of the flow is not particularly limited, and is preferably 1 to 100 mL / sec, more preferably 10 to 30 mL / sec. The temperature of the cleaning liquid B is preferably 10 to 50°C, more preferably 20 to 40°C.

[0112] [Step (i)]

[0113] Step (i) is a step of rinsing the surface of the substrate with the cleaning liquid C. In step (i), the surface (circuit formation surface) of the substrate is rinsed with the cleaning liquid C to remove the cleaning residue and the cleaning liquid B.

[0114] The cleaning liquid C preferably uses water, more preferably pure water, and most preferably ultrapure water.

[0115] The rinsing with the cleaning liquid C is preferably a method in which the substrate is held horizontally and rotated at a certain speed while the cleaning liquid C is caused to flow onto the substrate. The flow can be to only the center of the substrate, or can be in a manner that goes back and forth between the center and the periphery. The rotation speed of the substrate is not particularly limited, and is preferably 1 to 500 rpm, more preferably 200 to 300 rpm. Further, the flow rate of the flow is not particularly limited, and is preferably 1 to 100 mL / sec, more preferably 10 to 30 mL / sec. The temperature of the cleaning liquid C is preferably 10 to 50°C, more preferably 20 to 40°C.

[0116] In order to reduce the number of particles remaining after cleaning, the above cleaning liquids A, B, and C are preferably passed through a filter in advance. The number of particles contained in the cleaning liquid that has passed through the filter is further preferably 3.0 or less, 2 or less, 1 or less, and most preferably 0 or less per ml, of particles having a particle diameter of 100 nm or more. The number of particles remaining after cleaning is preferably 15 or less per cm 2 , and more preferably 10 or less per cm 2 .

[0117] The substrate after cleaning can be dried by air blowing or spin-drying.

[0118] Example

[0119] Hereinafter, the present application will be specifically described by Examples, but the present application is not limited to the following Examples. The following shows [1] residual particles in the temporary adhesive composition and [2] particles after cleaning of the substrate. In addition, in order to measure the post-cleaning particles on the substrate, a silicon wafer (mirror surface) having no circuit formation surface was used. Furthermore, in order to prevent the mixing of particles other than the temporary adhesive composition and the cleaning process, the process (c) (a process of polishing or grinding the back surface of the substrate in the substrate laminate) and the process (d) (a process of performing processing on the back surface of the substrate) were omitted. In addition, in the following examples, the molecular weight is the weight average molecular weight (Mw), which is a polystyrene conversion measurement value obtained by GPC using toluene as a solvent. Furthermore, for the filtration speed, the specific gravity of the substrate with the temporary adhesive composition is set to d [g / ml], the weight of the composition obtained by filtration is set to m [g], and the time required for filtration is set to t [minutes], and m / (d*t) is obtained.

[0120] [1] Residual particles in the temporary adhesive composition for substrate

[0121] Preparation of temporary adhesive composition for substrate

[0122] (Process [a])

[0123] [Example 1-1]

[0124] To 100 parts by mass of (CH3)2SiO 2 / 2 units (D units) were 98.0 mol% and (CH2=CH)(CH3)SiO 2 / 2A solution composed of 2.0 mole% of a linear polydimethylsiloxane having a vinyl group on a side chain of a molecule (molecular weight: 50,000, manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 parts by mass of isododecane, 50 parts by mass of an organohydrogenpolysiloxane represented by the following (M-1) as an organopolysiloxane (A-2), 30 parts by mass of a linear polydimethylsiloxane (molecular weight: 80,000, manufactured by Shin-Etsu Chemical Co., Ltd.) as an organopolysiloxane (B), and 0.7 parts by mass of ethynylcyclohexanol was prepared, and the mixture was sufficiently mixed. Then, 0.2 parts by mass of a platinum catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed. In the resin solution, the molar ratio of the Si-H groups of the organohydrogenpolysiloxane to the alkenyl groups of the organopolysiloxane was 1.0. Next, the mixed solution was filtered using a filter having a pore size of 30 nm (manufactured by Pall Corporation, capsule filter) to obtain a temporary adhesive composition N. The filtration was performed at room temperature and the filtration pressure was 0.1 MPa.

[0125] In addition, the value of the molar ratio of the Si-H groups of the organohydrogenpolysiloxane to the alkenyl groups of the organopolysiloxane (Si-H / Si-Vi) in this Example 1 was calculated from the following calculation formula.

[0126] (1) Si-Vi amount (mole) from the component (A-1)

[0127] (PDMS addition amount / PDMS molecular weight) x {PDMS molecular weight / (D unit molecular weight x D unit mole% / 100 + D Vi unit mole% / 100) x D Vi unit mole% / 100

[0128] (2) Si-H amount (mole) from the component (A-2)

[0129] (POHS addition amount / POHS molecular weight) x number of siloxane units bonded to H in 1 molecule

[0130] (3) Value of Si-H / Si-Vi

[0131] Si-H amount (mole) from the component (A-2) / Si-Vi amount (mole) from the component (A-1)

[0132] [Chemical Formula 2]

[0133]

[0134] [Example 1-2]

[0135] A temporary adhesive material composition M was obtained in the same manner except that the mixed solution was filtered using a filter with a pore size of 50 nm (manufactured by TOYO ROSHI KAISHA, LTD., PTFE capsule filter) in Example 1-1.

[0136] [Example 1-3]

[0137] A temporary adhesive material composition O was obtained in the same manner except that the mixed solution was filtered using a filter with a pore size of 100 nm (manufactured by TOYO ROSHI KAISHA, LTD., PTFE capsule filter) in Example 1-1.

[0138] [Example 1-4]

[0139] To a solution composed of 100 parts by mass of (CH3)2SiO 2 / 2 units (D units) were 97.5 mole%, and (CH2=CH)(CH3)SiO 2 / 2 units (DVi units) were 2.5 mole%, a solution composed of 100 parts by mass of isododecane, 2 parts by mass of an organohydrogenpolysiloxane represented by the following (M-2) as an organopolysiloxane (A-2), 30 parts by mass of a linear polydimethylsiloxane (molecular weight: 50,000, manufactured by Shin-Etsu Chemical Co., Ltd.) as an organopolysiloxane (B), and 0.7 parts by mass of ethynylcyclohexanol were mixed sufficiently. Then, 0.2 parts by mass of a platinum catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added and further mixed sufficiently. In the resin solution, the mole ratio of the Si-H groups of the organohydrogenpolysiloxane having Si-H groups to the alkenyl groups of the organopolysiloxane having alkenyl groups was 1.1. Next, the above mixed solution was filtered using a filter with a pore size of 50 nm (manufactured by TOYO ROSHI KAISHA, LTD., PTFE capsule filter) to obtain a temporary adhesive material composition P.

[0140] [Chemical Formula 3]

[0141]

[0142] [Example 1-5]

[0143] A temporary adhesive material composition Q was obtained in the same manner except that the mixed solution was filtered using a filter with a pore size of 100 nm (manufactured by TOYO ROSHI KAISHA, LTD., PTFE capsule filter) in Example 1-3.

[0144] [Example 1-6]

[0145] The production of the substrate laminate and the cleaning of the substrate were carried out in the same manner as in Example 1-1 except that the temporary adhesive material composition shown below was used. A solution composed of 100 parts by mass of a linear polydimethylsiloxane (molecular weight: 50,000, manufactured by Shin-Etsu Chemical Co., Ltd.) having a vinyl group on a side chain of a molecule, 97.0 parts by mole of a unit (D unit) of (CH2=CH)(CH3)SiO 2 / 2 a unit (D unit) of (CH2=CH)(CH3)SiO 2 / 2 a unit (D Vi unit) of 3.0 mole % was added to a solution composed of 100 parts by mass of isododecane, 5.5 parts by mass of an organohydrogenpolysiloxane represented by the following (M-3) as an organopolysiloxane (A-2), 30 parts by mass of a linear polydimethylsiloxane (molecular weight: 100,000, manufactured by Shin-Etsu Chemical Co., Ltd.) as an organopolysiloxane (B), and 0.7 parts by mass of ethynylcyclohexanol, and the mixture was sufficiently mixed, and then 0.2 parts by mass of a platinum catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added and further mixed. In the resin solution, the molar ratio of the Si-H group of the organohydrogenpolysiloxane having the Si-H group to the alkenyl group of the organopolysiloxane having the alkenyl group was 1.1. Next, the above mixed solution was filtered using a filter with a pore size of 50 nm (manufactured by TOYO ROSHI KAISHA, LTD., PTFE capsule filter) to obtain a temporary adhesive material composition R.

[0146] [Chemical Formula 4]

[0147]

[0148] [Comparative Example 1-1]

[0149] A temporary adhesive material composition S was obtained in the same manner except that the mixed solution was filtered using a filter with a pore size of 200 nm (manufactured by TOYO ROSHI KAISHA, LTD., PTFE membrane filter) in Example 1-1.

[0150] [Comparative Example 1-2]

[0151] A temporary adhesive material composition T was obtained in the same manner except that the mixed solution was filtered using a filter with a pore size of 200 nm (manufactured by TOYO ROSHI KAISHA, LTD., PTFE membrane filter) in Examples 1-3.

[0152] [Comparative Examples 1-3]

[0153] A temporary adhesive material composition U was obtained in the same manner except that the mixed solution was filtered using a filter with a pore size of 200 nm (manufactured by TOYO ROSHI KAISHA, LTD., PTFE membrane filter) in Examples 1-5.

[0154] Evaluation of Residual Particles after Filtration

[0155] For the temporary adhesive material compositions of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-3 filtered using filters with different pore sizes, the number of particles with a particle size of 100 nm or more and 1000 nm or less (average of 5 samples) was measured. If the number of residual particles is 20 or less per ml, it can be considered that the temporary adhesive material composition is excellent in that the number of particles to be introduced into the substrate is small. In addition, the measurement was performed using a particle counter (product name: KS-42A, manufactured by RION Co., Ltd.).

[0156] [Table 1]

[0157]

[0158] For Table 1, the number of particles with a particle size of 100 nm or more and 1000 nm or less in the temporary adhesive material compositions of Examples 1-1 to 1-6 after filtration using a filter with a pore size of 100 nm or less was 20 or less per ml. On the other hand, the number of particles with a particle size of 100 nm or more and 1000 nm or less in the temporary adhesive material compositions of Comparative Examples 1-1 to 1-3 after filtration using a filter with a pore size of 200 nm was more than 20 per ml. Therefore, it can be considered that the temporary adhesive material composition of the present application is a temporary adhesive material composition in which the number of particles to be introduced into the substrate is small.

[0159] [2] Particles after Substrate Cleaning

[0160] [Example 2-1]

[0161] A substrate laminate was produced using the temporary adhesive material composition N. With respect to the cured layer (a) of the temporary adhesive material composition N, which was coated on a substrate by the above-described method and subjected to heat curing, the peel strength was measured at room temperature in accordance with JIS K 6854, and the result was 98 mN / 25 mm. In addition, the storage modulus of the cured layer (a) at 25°C was 2.9 x 107Pa. Further, with respect to the storage modulus, the storage modulus of the cured product was measured using Rheogel-E4000 manufactured by UBM Co., Ltd. under conditions of a frequency of 1 Hz and a temperature of 25°C. 7 Pa. Further, with respect to the storage modulus, the storage modulus of the cured product was measured using Rheogel-E4000 manufactured by UBM Co., Ltd. under conditions of a frequency of 1 Hz and a temperature of 25°C.

[0162] <Production of substrate laminate>

[0163] After spin coating the above-prepared temporary adhesive material composition on a 300 mm silicon wafer (mirror surface, thickness 725 μm) as a substrate, a temporary adhesive material composition layer (thickness 25 μm) was formed by heating at 50°C for 3 minutes using a hot plate. Subsequently, the wafer was joined to a 300 mm glass wafer (thickness 700 μm) as a support. The joining was performed using a wafer bonding apparatus (EVG520IS (product name) manufactured by EV Group). Further, the joining was performed under conditions of a joining temperature of 50°C, a pressure in the chamber during joining of 10 mbar or less, and a load of 10 kN. After the joining, the substrate on which the joining was completed was heated at 200°C for 2 hours using an oven, the temporary adhesive material composition layer was cured, and the temperature was cooled to room temperature. Thus, the substrate laminate was obtained. -3

[0164] <Peeling of substrate laminate>

[0165] (Step [e])

[0166] The support was peeled from the substrate laminate. Specifically, a dicing tape was attached to the silicon wafer side of the above-described laminate using a dicing frame, and the dicing tape surface was mounted on a suction plate by vacuum suction. Then, one point of the glass wafer was lifted with a pair of tweezers at room temperature, whereby the glass wafer was peeled.

[0167] <Substrate cleaning step>

[0168] (Step [f])

[0169] The remaining temporary adhesive material composition on the substrate was peeled by tape peeling. Specifically, a polyester film adhesive tape No. 648 manufactured by Teraoka Seisakusho co., Ltd. was attached to the temporary adhesive layer exposed on the surface, and tape peeling was performed. Thus, the remaining temporary adhesive layer was peeled from the silicon wafer substrate.

[0170] <Preparation of cleaning solution for substrate cleaning> ​

[0171] To N,N-dimethylpropanamide was added tetrabutylammonium fluoride, and stirring was performed at room temperature to obtain cleaning solution A. In addition, tetrabutylammonium fluoride was dissolved in cleaning solution A. Among them, cleaning solution A was prepared in such a manner that 100 mass% of tetrabutylammonium fluoride contained tetrabutylammonium fluoride at an amount of 10 mass% in N,N-dimethylpropanamide. The cleaning solution A was filtered using a filter having a pore size of 20 nm (manufactured by TOYO ROSHI KAISHA, LTD., PTFE capsule filter). The number of particles having a particle size of 100 nm or more contained in the filtered cleaning solution A was 2.4 pieces / ml.

[0172] Isopropyl alcohol was filtered using a filter having a pore size of 20 nm (manufactured by Entegris, Inc., cartridge filter) to obtain cleaning solution B. The number of particles having a particle size of 100 nm or more contained in the filtered cleaning solution B was 0.7 pieces / ml.

[0173] Ultrapure water purified using an ultrapure water purification device (product name: MILLIPURE Advntage10 uv, manufactured by Merck) was filtered using a filter having a pore size of 20 nm (manufactured by Pall Corporation, capsule filter) to obtain cleaning solution C. The number of particles having a particle size of 100 nm or more contained in the filtered cleaning solution C was 1.1 pieces / ml.

[0174] (Step [g])

[0175] The substrate was fixed to a wafer cleaning device (product name: Delta, manufactured by SUSS) and liquid cleaning was performed. Specifically, the substrate was immersed in 300 ml of cleaning solution A at room temperature for 5 minutes, and then cleaning was performed while the substrate was rotated at 250 rpm and 10 seconds of cleaning solution A was flowed at a flow rate of 15 ml / sec.

[0176] (Step [h])

[0177] Cleaning was performed while the substrate was rotated at 250 rpm and 10 seconds of cleaning solution B was flowed at a flow rate of 15 ml / sec.

[0178] (Step [i])

[0179] Cleaning was performed while the substrate was rotated at 250 rpm and 10 seconds of cleaning solution C was flowed at a flow rate of 15 ml / sec.

[0180] (Step [j])

[0181] Finally, the substrate was dried by high-speed rotation at 1500 rpm for 1 minute.

[0182] [Example 2-2]

[0183] In addition to using the temporary adhesive material composition M, a substrate laminate was produced in the same manner as in Example 2-1, and was subjected to cleaning. In addition, the peel strength of the cured layer (a) coated on the substrate by the above method and subjected to heat curing was 96 mN / 25 mm. Furthermore, the storage modulus of the cured layer (a) at 25°C was 2.8 x 10 7 Pa.

[0184] [Example 2-3]

[0185] In addition to using the temporary adhesive material composition O, a substrate laminate was produced in the same manner as in Example 2-1, and was subjected to cleaning. In addition, the peel strength of the cured layer (a) coated on the substrate by the above method and subjected to heat curing was 99 mN / 25 mm. Furthermore, the storage modulus of the cured layer (a) at 25°C was 2.8 x 10 7 Pa.

[0186] [Example 2-4]

[0187] In addition to using the temporary adhesive material composition P, a substrate laminate was produced in the same manner as in Example 2-1, and was subjected to cleaning. In addition, the peel strength of the cured layer (a) coated on the substrate by the above method and subjected to heat curing was 99 mN / 25 mm. Furthermore, the storage modulus of the cured layer (a) at 25°C was 3.4 x 10 7 Pa.

[0188] [Example 2-5]

[0189] In addition to using the temporary adhesive material composition Q, a substrate laminate was produced in the same manner as in Example 2-1, and was subjected to cleaning. In addition, the peel strength of the cured layer (a) coated on the substrate by the above method and subjected to heat curing was 102 mN / 25 mm. Furthermore, the storage modulus of the cured layer (a) at 25°C was 3.4 x 10 7 Pa.

[0190] [Example 2-6]

[0191] In addition to using the temporary adhesive material composition R, a substrate laminate was produced in the same manner as in Example 2-1, and was subjected to cleaning. In addition, the peel strength of the cured layer (a) coated on the substrate by the above method and subjected to heat curing was 100 mN / 25 mm. Furthermore, the storage modulus of the cured layer (a) at 25°C was 3.7 x 10 7 Pa.

[0192] [Comparative Example 2-1]

[0193] In addition to using the temporary adhesive material composition S, a substrate laminate was produced and cleaned in the same manner as in Example 2-1. In addition, the peel strength of the cured layer (a) coated on the substrate by the above method and subjected to heat curing was 96 mN / 25 mm. Furthermore, the storage modulus of the cured layer (a) at 25°C was 2.9 x 10 7 Pa.

[0194] [Comparative Example 2-2]

[0195] In addition to using the temporary adhesive material composition T, a substrate laminate was produced and cleaned in the same manner as in Example 2-1. In addition, the peel strength of the cured layer (a) coated on the substrate by the above method and subjected to heat curing was 103 mN / 25 mm. Furthermore, the storage modulus of the cured layer (a) at 25°C was 2.8 x 10 7 Pa.

[0196] [Comparative Example 2-3]

[0197] In addition to using the temporary adhesive material composition U, a substrate laminate was produced and cleaned in the same manner as in Example 2-1. In addition, the peel strength of the cured layer (a) coated on the substrate by the above method and subjected to heat curing was 97 mN / 25 mm. Furthermore, the storage modulus of the cured layer (a) at 25°C was 3.6 x 10 7 Pa.

[0198] [Comparative Example 2-4]

[0199] In addition to not performing the tape peeling of step [f], the production of a substrate laminate and the cleaning of a substrate were performed in the same manner as in Example 2-1.

[0200] [Comparative Example 2-5]

[0201] In addition to not performing the cleaning with cleaning liquid A of step [g], the production of a substrate laminate and the cleaning of a substrate were performed in the same manner as in Example 2-1.

[0202] [Comparative Example 2-6]

[0203] In addition to not performing the cleaning with cleaning liquid B of step [h], the production of a substrate laminate and the cleaning of a substrate were performed in the same manner as in Example 2-1.

[0204] [Comparative Example 2-7]

[0205] In addition to not performing the cleaning with cleaning liquid C of step [i], the production of a substrate laminate and the cleaning of a substrate were performed in the same manner as in Example 2-1.

[0206] <Particle Evaluation after Cleaning>

[0207] The number of particles remaining on the surface of the substrate subjected to cleaning was measured using a substrate surface inspection device (product name: WM-10, manufactured by TAKANO Co., Ltd.). The distribution of particles (average of 5 samples) was calculated by dividing the number of particles by the measurement area. The measurement particle size range R of the particles was set to 100 nm or more and 1000 nm or less. If the average distribution of particles was 15 or more per cm 2 The results are shown in Table 2. In addition, cases in which measurement could not be normally completed due to an excessive number of particles are described as "unable to calculate", and cases in which the temporary adhesive material composition could not be removed are described as "unable to clean".

[0208] [Table 2]

[0209]

[0210] With regard to Table 2, Examples 2-1 to 2-6 used a temporary adhesive material composition in which the number of particles having a particle size of 100 nm or more and 1000 nm or less remaining after filtration through a filter having a pore size of 100 nm or less was 20 particles / ml or less, and as a result, the temporary adhesive material composition was removed by the cleaning method of the present application. The distribution of particles after cleaning was 15 or more per cm 2 below. As a result, the temporary adhesive material composition was removed by the same cleaning method. Since the number of particles after cleaning was excessive in each case, the distribution could not be calculated. Comparative Examples 2-4 to 2-7 used a temporary adhesive material composition in which the average number of particles having a particle size of 100 nm or more and 1000 nm or less remaining after filtration through a filter having a pore size of 100 nm or less was 20 particles / ml or less, and as a result, none of the temporary adhesive material composition was subjected to any one of the tape peeling and cleaning processes using cleaning liquids A, B, and C. The distribution of particles after cleaning in Comparative Example 2-4 was 15 or more per cm 2 above, the temporary adhesive material composition could not be removed in Comparative Example 2-5, the distribution could not be calculated due to an excessive number of particles in Comparative Example 2-6, and the distribution of particles after cleaning increased to 15 or more per cm 2 .

[0211] Industrial applicability

[0212] After processing a laminate using the temporary adhesive composition of the present application, the temporary adhesive composition is removed by the cleaning method of the present application, whereby the cleanliness of the wafer after processing can be improved. Thus, in a lamination process for thinning semiconductor chips by connecting copper electrodes formed on the same surface of chips to each other, it is expected that the occurrence of connection failure can be suppressed.

[0213] The present specification includes the following aspects.

[0214] [1] A temporary adhesive composition which is a temporary adhesive composition that adheres a substrate to a support in a releasable manner, characterized by containing:

[0215] (A) an organopolysiloxane mixture that crosslinks through hydrosilylation,

[0216] (B) an organopolysiloxane that does not initiate hydrosilylation,

[0217] (C) a catalyst, and

[0218] (D) an organic solvent,

[0219] The temporary adhesive composition is passed through a filter having a pore size of 100 nm or less, and the number of particles having a particle size of 100 nm or more and 1000 nm or less that remain after the filtration is 20 particles / ml or less.

[0220] [2] The temporary adhesive composition according to the above [1], wherein the above constituent component (A) is a mixture of different organopolysiloxanes (A-1) and (A-2),

[0221] The constituent component (A-1) is composed of at least one of an M unit represented by R1R2R3SiO 1 / 2 , a D unit represented by R4R5SiO 2 / 2 , a T unit represented by R6SiO 3 / 2 , or a Q unit represented by SiO 4 / 2 , the substituents R1, R2, R3, R4, R5, and R6 being a methyl group, a -CH=CH2 group, or a phenyl group,

[0222] The constituent component (A-2) is composed of at least one of an M unit represented by R7R8R9SiO 1 / 2 , a D unit represented by R 10 R 11 SiO 2 / 2 , a T unit represented by R 12 SiO 3 / 2 , or a Q unit represented by SiO 4 / 2 , the substituents R7, R8, R9, and R10 R 11 R 12 is methyl, phenyl or hydrogen.

[0223] [3] The temporary adhesive material composition according to any one of the above [1] or the above [2], wherein the component (B) is constituted by at least one of an M unit represented by R 13 R 14 R 15 SiO 1 / 2 a D unit represented by R 16 R 17 SiO 2 / 2 a T unit represented by R 18 SiO 3 / 2 or a Q unit represented by SiO 4 / 2 , and the substituent R 13 R 14 R 15 R 16 R 17 R 18 is methyl or phenyl.

[0224] [4] The temporary adhesive material composition according to any one of the above [1] to the above [3], wherein the component (C) is a platinum catalyst.

[0225] [5] The temporary adhesive material composition according to any one of the above [1] to the above [4], wherein the component (D) is an organic solvent containing at least one or more saturated hydrocarbons having 8 to 12 carbon atoms which do not contain a hetero atom.

[0226] [6] A substrate cleaning method characterized by comprising:

[0227] a step of attaching an adhesive sheet so as to cover the entire temporary adhesive material composition on the substrate, and peeling the adhesive sheet, thereby removing the temporary adhesive material composition;

[0228] a step of cleaning the substrate with a cleaning liquid A;

[0229] a step of rinsing the substrate with a cleaning liquid B; and

[0230] a step of rinsing the substrate with a cleaning liquid C.

[0231] [7] The substrate cleaning method according to the above [6], wherein the cleaning liquid A is set to a cleaning liquid containing a quaternary ammonium salt,

[0232] the cleaning liquid A is filtered through a filter having a pore size of 100 nm or less, and the number of particles having a particle size of 100 nm or more and 1000 nm or less remaining after the filtration is 3.0 pieces / ml or less.

[0233] [8] The substrate cleaning method according to [6] or [7] above, wherein the cleaning liquid B is a cleaning liquid containing a water-soluble organic solvent,

[0234] The cleaning liquid B is filtered through a filter having a pore diameter of 100 nm or less, and the number of particles having a particle size of 100 nm or more and 1000 nm or less remaining after the filtration is 3.0 particles / ml or less.

[0235] [9] The substrate cleaning method according to any one of [6] to [8] above, wherein the cleaning liquid C is water,

[0236] The cleaning liquid C is filtered through a filter having a pore diameter of 100 nm or less, and the number of particles having a particle size of 100 nm or more and 1000 nm or less remaining after the filtration is 3.0 particles / ml or less.

[0237]

[10] A substrate cleaning method, wherein the distribution of particles having a particle size of 100 nm or more and 1000 nm or less remaining on the surface of the substrate after the substrate is cleaned by the cleaning method according to any one of [6] to [9] above, in which the temporary bonding material composition according to any one of [1] to [5] above is present, is 15 particles / cm 2 or less.

[0238] Further, the present application is not limited to the above-described embodiments. The above-described embodiments are merely examples, and technical solutions having substantially the same technical concept as that described in the claims of the present application and having the same technical effects are all included in the technical scope of the present application.

Claims

1. A temporary adhesive material composition for bonding a substrate and a support in a releasable manner, characterized in that: contains: (A) an organopolysiloxane mixture which is crosslinked by hydrosilylation, (B) an organopolysiloxane which does not initiate hydrosilylation, (C) a catalyst, and (D) an organic solvent, the temporary adhesive composition is passed through a filter having a pore size of 100 nm or less, and the number of particles having a particle size of 100 nm or more and 1000 nm or less remaining after filtration is 20 particles / ml or less.

2. The temporary bonding material composition according to claim 1, characterized by The aforementioned component (A) is a mixture of different organopolysiloxanes (A-1) and (A-2), The constitutional unit (A-1) is constituted by at least one of M unit represented by R1R2R3SiO 1 / 2 / 2, D unit represented by R4R5SiO 2 / 2 / 2, T unit represented by R6SiO 3 / 2 / 2 or Q unit represented by SiO 4 / 2 / 2, and R1, R2, R3, R4, R5 and R6 are a methyl group, -CH=CH2 or a phenyl group. The constituent component (A-2) is composed of R7R8R9SiO 1 / 2 The M unit represented by R 10 R 11 SiO 2 / 2 The D unit represented by R 12 SiO 3 / 2 T unit represented by SiO 4 / 2 At least one of the Q units represented by 10 、R 11 、R 12 is methyl, phenyl or hydrogen.

3. The temporary bonding material composition according to claim 1, wherein The constitutional unit represented by R 13 R 14 R 15 SiO 1 / 2 D unit represented by R 16 R 17 SiO 2 / 2 D unit represented by R 18 SiO 3 / 2 T unit represented by R 4 / 2 Q unit represented by SiO 13 , R 14 , R 15 , R 16 , R 17 , R 18 is a methyl group or a phenyl group.

4. The temporary bonding material composition according to claim 1, wherein The aforementioned component (C) is a platinum catalyst.

5. The temporary bonding material composition according to claim 1, wherein The aforementioned component (D) is an organic solvent containing at least one or more saturated hydrocarbons having 8 to 12 carbon atoms and not containing hetero atoms.

6. A substrate cleaning method characterized by, comprises: a step of attaching and peeling an adhesive sheet in a manner of covering the entire temporary adhesive composition on the substrate, thereby removing the temporary adhesive composition; a step of cleaning the substrate with cleaning liquid A; a step of rinsing the substrate with cleaning liquid B; and a step of rinsing the substrate with cleaning liquid C.

7. The substrate cleaning method according to claim 6, wherein The cleaning liquid A is set to a cleaning liquid containing a quaternary ammonium salt, The cleaning liquid A is passed through a filter having a pore size of 100 nm or less, and the number of particles having a particle size of 100 nm or more and 1000 nm or less remaining after filtration is 3.0 particles / ml or less.

8. The substrate cleaning method according to claim 6, wherein The cleaning liquid B is set to a cleaning liquid containing a water-soluble organic solvent, The cleaning liquid B is passed through a filter having a pore size of 100 nm or less, and the number of particles having a particle size of 100 nm or more and 1000 nm or less remaining after filtration is 3.0 particles / ml or less.

9. The substrate cleaning method according to claim 6, wherein The cleaning liquid C is set to water, The cleaning liquid C is passed through a filter having a pore size of 100 nm or less, and the number of particles having a particle size of 100 nm or more and 1000 nm or less remaining after filtration is 3.0 particles / ml or less.

10. A substrate cleaning method, characterized by, The distribution of particles having a particle size of 100 nm or more and 1000 nm or less remaining on the surface of the substrate after cleaning the substrate on which the temporary adhesive material composition according to claim 1 is present by the cleaning method according to claim 6 is 15 pieces / cm 2 The following.

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