JP6745362B2 - Kit, semiconductor element manufacturing method, and semiconductor element substrate cleaning method - Google Patents

Description

The present invention relates to a kit, a method for manufacturing a semiconductor device, and a method for cleaning a substrate of a semiconductor device.

Conventionally, a cleaning composition for removing the temporary adhesive has been studied.
For example, Patent Document 1 discloses a stripping composition for stripping an adhesive containing a hydrogenated styrene elastomer, which comprises a cyclic terpene solvent, a nonionic surfactant, and a silicone surfactant. A stripping composition comprising at least one is disclosed.
Patent Document 2 discloses a composition containing A) a water-soluble organic solvent, B) a sulfonic acid or a salt thereof, and C) water.
Further, Patent Document 3 discloses a cleaning liquid composition used for cleaning a semiconductor substrate having a surface contact angle of 70 degrees or more when water is dropped, the composition comprising an aliphatic polycarboxylic acid and a hydroxyl group and/or an ether group. Disclosed is the above-mentioned cleaning liquid composition, which comprises an organic solvent having a contact angle of 40 degrees or less when dropped onto the semiconductor substrate.

JP, 2016-11361, A Japanese Patent Publication No. 2006-505629 JP, 2004-307725, A

However, as a result of examination by the present inventors, a temporary adhesive containing a silicone compound or a precursor of the silicone compound (hereinafter, may be simply referred to as “silicon-containing compound”) was washed with the above-described detergent composition. Attempts to do so revealed that residual carbon atoms and residual silicon atoms derived from the temporary adhesive remained. Therefore, the applicant of the present invention has examined the removal using a composition containing an organic sulfonic acid and an organic solvent. However, it was found that when the temporary adhesive containing the silicon-containing compound was washed with the composition containing the organic sulfonic acid and the organic solvent, the sulfur atom residue derived from the organic sulfonic acid remained. In such a sulfur atom residue, when the substrate to be temporarily bonded has a metal such as copper and the surface of the metal has many irregularities, the acid component causes corrosion of the metal surface or metal wiring. It may cause disconnection. The present invention is intended to solve such a problem, and is a kit including a temporary adhesive containing a silicon-containing compound and a cleaning agent for the temporary adhesive, which can appropriately wash various residues. An object of the present invention is to provide a kit, a method of manufacturing a semiconductor device, and a method of cleaning a substrate of a semiconductor device.

Under the above-mentioned problems, as a result of the present inventor's investigation, a temporary adhesive containing a silicon-containing compound was washed with a detergent composition containing an organic sulfonic acid, and then an organic carboxylic acid and water were further added. It was found that the residue derived from a silicon-containing compound can be effectively removed by washing with a detergent composition containing the same, and further the residue derived from an organic sulfonic acid or the like can be effectively removed, and the present invention has been completed. ..
Specifically, the above problem is solved by the following means <1>, preferably <2> to <29>.
<1> A temporary adhesive containing at least one silicon-containing compound selected from the group consisting of a silicone compound and a precursor of a silicone compound, and an organic acid, wherein the acid group contained in the organic acid is a sulfur atom or A detergent composition B containing at least one organic acid containing a phosphorus atom and an organic solvent, an organic carboxylic acid compound, and a detergent composition B containing water and at least one water-soluble solvent. A kit containing.
<2> The kit according to <1>, wherein the organic acid contains at least one organic acid selected from the group consisting of organic sulfonic acids, organic phosphoric acids, and organic phosphonic acids.
<3> The kit according to <1>, wherein the silicon-containing compound contains silicone oil.
<4> The kit according to any one of <1> to <3>, in which the silicon-containing compound contains a polyether-modified silicone.
<5> The kit according to any one of <1> to <4>, in which the content of the silicon-containing compound in the temporary adhesive is 0.001 to 1.0% by mass.
<6> The kit according to any one of <1> to <5>, in which the temporary adhesive contains an elastomer.
<7> The kit according to <6>, wherein the elastomer is a polystyrene elastomer.
<8> The kit according to any one of <1> to <7>, in which pKa, which is an acid dissociation constant of the organic acid, is −4 to 5.
<9> The organic acid is selected from the group consisting of alkylsulfonic acid, aromatic sulfonic acid, alkylphosphoric acid, aromatic phosphoric acid, alkylphosphonic acid and aromatic phosphonic acid, and the organic acid of <1> to <8> The kit according to any one.
<10> The kit according to any one of <1> to <9>, in which the organic solvent contained in the cleaning composition A contains an aromatic hydrocarbon solvent having an alkyl group.
<11> The kit according to <10>, wherein the aromatic hydrocarbon solvent having an alkyl group is a solvent having a benzene ring and 1 to 3 alkyl groups having 1 to 10 carbon atoms.
<12> The cleaning composition A according to any one of <1> to <11>, in which the mass ratio of the organic acid to the organic solvent is 0.0001:99.9999 to 50:50. Kit.
<13> The kit according to any one of <1> to <12>, wherein the organic carboxylic acid compound is selected from the group consisting of saturated fatty acids, unsaturated fatty acids, hydroxy acids, and aromatic carboxylic acids.
<14> The value of P, which is the 1-octanol/water partition coefficient representing the ratio of the equilibrium concentrations of the organic carboxylic acid compound in 1-octanol and in water, in the form of logarithm logP with respect to the base 10 is -5 to 6 The kit according to any one of <1> to <13>.
<15> The kit according to any one of <1> to <14>, in which the solvent contained in the cleaning composition B contains water.
<16> The kit according to any one of <1> to <15>, wherein the organic carboxylic acid compound has an acid dissociation constant pKa of 1 to 7.
<17> In any one of <1> to <16>, in the cleaning composition B, the mass ratio of the organic carboxylic acid compound to the solvent is 0.0001:99.9999 to 50:50. The described kit.
<18> The kit according to any one of <1> to <17>, further including a rinse composition C containing at least one kind of water and alcohol.
<19> A step of cleaning a substrate having a silicone compound on its surface with a cleaning composition A, and a step of cleaning the cleaned substrate with a cleaning composition B,
The cleaning composition A contains an organic acid, and at least one organic acid whose acid group contained in the organic acid contains a sulfur atom or a phosphorus atom; and an organic solvent. Is a method for producing a semiconductor device, which contains an organic carboxylic acid compound and at least one of water and a water-soluble solvent.
<20> The method for producing a semiconductor element according to <19>, wherein the organic acid contains at least one organic acid selected from the group consisting of organic sulfonic acids, organic phosphoric acids, and organic phosphonic acids.
<21> A temporary adhesive layer formed from a temporary adhesive is provided on the substrate, at least a part of the temporary adhesive layer is washed with the organic acid, and the temporary adhesive is the silicone compound and the silicone. <19> or the manufacturing method of a semiconductor device given in <20> containing at least 1 sorts of compound precursors.
<22> The step of washing with the detergent composition A and the step of washing with the detergent composition B are performed in a single-wafer manner, in any one of <19> to <21>. A method for manufacturing a semiconductor device as described above.
<23> Any one of <19> to <22>, which includes a drying step after the step of cleaning with the cleaning composition A and after the step of cleaning with the cleaning composition B. 1. A method for manufacturing a semiconductor device according to one.
<24> The time from the start of the step of cleaning the single substrate using the cleaning composition A to the end of the step of cleaning the cleaning composition B is 30 to 300 seconds. , <19> to <23>.
<25> Any of <19> to <24>, which includes a step of rinsing with a rinse composition C containing at least one of water and alcohol after the step of cleaning with the cleaning composition B. 2. A method of manufacturing a semiconductor device according to any one of the above.
<26> The method for manufacturing a semiconductor element according to any one of <19> to <25>, which uses the kit according to any one of <1> to <18>.
<27> A step of cleaning a substrate having a silicone compound on its surface with a cleaning composition A, and a step of cleaning the above-cleaned substrate with a cleaning composition B, the cleaning agent The composition A is an organic acid, and at least one organic acid whose acid group contained in the organic acid contains a sulfur atom or a phosphorus atom, and an organic solvent, and the cleaning composition B is an organic acid. A method for cleaning a substrate of a semiconductor device, which comprises a carboxylic acid compound and at least one of water and a water-soluble solvent.
<28> The semiconductor device according to <27>, which comprises performing a rinse treatment with a rinse composition C containing at least one of water and alcohol after the step of cleaning with the cleaning composition B. Substrate cleaning method.
<29> The method for cleaning a semiconductor element substrate according to <27> or <28>, which uses the kit according to any one of <1> to <18>.

According to the present invention, a kit including a temporary adhesive containing a silicon-containing compound and a cleaning agent for the temporary adhesive, the kit being capable of appropriately cleaning various residues, a method for manufacturing a semiconductor device, and a method for cleaning a substrate of a semiconductor device. Is now available.

The details of the present invention will be described below. In the present specification, “to” is used to mean that the numerical values described before and after the “to” are included as a lower limit value and an upper limit value.
In the description of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not included includes not only those having no substituent but also those having a substituent. For example, an “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth)acrylate” represents acrylate and methacrylate, “(meth)acrylic” represents acrylic and methacrylic, and “(meth)acryloyl” represents “acryloyl” and “methacryloyl”. ..
In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values by gel permeation chromatography (GPC) measurement. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, inner diameter) as a column. It can be determined by using (ID) 6.0 mm×15.0 cm) and using a 10 mmol/L lithium bromide NMP (N-methylpyrrolidone) solution as an eluent.

Kit The kit of the present invention comprises a temporary adhesive containing at least one silicon-containing compound selected from the group consisting of a silicone compound and a precursor of a silicone compound, an organic acid, and an acid group contained in the organic acid. Containing at least one organic acid containing a sulfur atom or a phosphorus atom (hereinafter, may be simply referred to as “organic acid”), an organic solvent, an organic carboxylic acid compound, water, and And a cleaning composition B containing at least one water-soluble solvent. Various residues can be effectively removed by using such a composition. In a semiconductor process, a residue derived from a silicon-containing compound on a metal causes peeling of an insulating layer and poor adhesion of solder, and therefore it is required to be appropriately removed. As such a detergent, it is possible to use a detergent composition containing the above organic acid. However, when the metal surface of the substrate to be processed has irregularities, sulfur and phosphorus derived from the detergent composition containing the organic acid are likely to remain in the concave portions. If sulfur or phosphorus remains in the recesses, it may cause corrosion of the metal surface or disconnection of the wiring. Therefore, it is necessary to immediately clean the sulfur and phosphorus components.
In the present invention, the residue derived from the silicon-containing compound is appropriately removed by using the detergent composition A containing an organic acid and an organic solvent, and the residue derived from the organic acid is washed with an organic carboxylic acid compound and water. By properly removing the agent composition B, the above problems have been solved and succeeded. Furthermore, by using the kit of the present invention, discoloration of the copper layer can be effectively suppressed. It is presumed that the discoloration of the copper layer is due to the surface of the copper layer being protected by the coordination of the organic carboxylic acid compound.
The kit of the present invention may further contain a rinse composition C containing at least one of water and alcohol.
Hereinafter, the kit of the present invention will be described in detail.

<Temporary adhesive>
<<Silicone Compound or Silicone Compound Precursor>>
The temporary adhesive used in the present invention contains at least one silicon-containing compound selected from the group consisting of silicone compounds and precursors of silicone compounds. The silicon-containing compound acts as a release agent, and makes it possible to easily remove the temporary adhesive from the substrate to be processed.
Silicone oil is preferred as the silicon-containing compound. Silicone oil refers to a compound that is liquid at 25°C.
Further, the silicon-containing compound preferably does not contain a reactive group such as a polymerizable group.
The silicon-containing compound is preferably a polyether-modified silicone.

The polyether-modified silicone used in the present invention has a ratio represented by the formula (A) of 80% or more.
Formula (A) {(MO+EO)/AO}×100
In the above formula (A), MO is mol% of methylene oxide contained in the polyether structure in the polyether-modified silicone, and EO is mol% of ethylene oxide contained in the polyether structure in the polyether-modified silicone. Yes, AO refers to the mol% of alkylene oxide contained in the polyether structure in the polyether-modified silicone.
The ratio represented by the above formula (A) is preferably 90% or more, more preferably 95% or more, further preferably 98% or more, and further preferably 99% or more. , 100% is even more preferable.

The weight average molecular weight of the polyether-modified silicone is preferably 500 to 100,000, more preferably 1,000 to 50,000, and even more preferably 2,000 to 40,000.

In the present invention, the polyether-modified silicone is obtained by heating the polyether-modified silicone at a temperature rising rate of 20° C./min from 20° C. to 280° C. under a nitrogen stream of 60 mL/min, and at a temperature of 280° C. for 30 minutes. The mass reduction rate when held is preferably 50 mass% or less. The use of such a compound tends to further improve the surface texture of the substrate after heating. The mass reduction rate of the polyether-modified silicone is preferably 45% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and further preferably 30% by mass or less. The lower limit of the mass reduction rate of the polyether-modified silicone may be 0% by mass, but 15% by mass or more, and even 20% by mass or more is a sufficiently practical level.

In the invention, the refractive index of light of the polyether-modified silicone is preferably 1.440 or less. The lower limit is not particularly specified, but a value of 1.400 or more is at a practical level.

上記式（１０１）中、Ｒ^１１およびＲ^１６は、それぞれ独立に、置換基であり、Ｒ^１２およびＲ^１４は、それぞれ独立に、２価の連結基であり、Ｒ^１３およびＲ^１５は、水素原子または炭素数１〜５のアルキル基であり、ｍ１１、ｍ１２、ｎ１およびｐ１は、それぞれ独立に０〜２０の数であり、ｘ１およびｙ１は、それぞれ独立に２〜１００の数である。
式（１０２）

上記式（１０２）中、Ｒ^２１、Ｒ^２５およびＲ^２６は、それぞれ独立に、置換基であり、Ｒ^２２は、２価の連結基であり、Ｒ^２３は、水素原子または炭素数１〜５のアルキル基であり、ｍ２およびｎ２は、それぞれ独立に０〜２０の数であり、ｘ２は、２〜１００の数である。
式（１０３）

上記式（１０３）中、Ｒ^３１およびＲ^３６は、それぞれ独立に、置換基であり、Ｒ^３２およびＲ^３４は、それぞれ独立に、２価の連結基であり、Ｒ^３３およびＲ^３５は、水素原子または炭素数１〜５のアルキル基であり、ｍ３１、ｍ３２、ｎ３およびｐ３は、それぞれ独立に０〜２０の数であり、ｘ３は、２〜１００の数である。
式（１０４）

上記式（１０４）中、Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４、Ｒ^４５およびＲ^４６は、それぞれ独立に、置換基であり、Ｒ^４７は、２価の連結基であり、Ｒ^４８は、水素原子または炭素数１〜５のアルキル基であり、ｍ４およびｎ４は、それぞれ独立に０〜２０の数であり、ｘ４およびｙ４は、それぞれ独立に２〜１００の数である。The polyether-modified silicone used in the present invention is preferably a polyether-modified silicone represented by any of the following formulas (101) to (104).
Formula (101)

In the above formula (101), R ¹¹ and R ¹⁶ are each independently a substituent, R ¹² and R ¹⁴ are each independently a divalent linking group, and R ¹³ and R ¹⁵ are hydrogen. It is an atom or an alkyl group having 1 to 5 carbon atoms, m11, m12, n1 and p1 are each independently a number of 0 to 20, and x1 and y1 are each independently a number of 2 to 100.
Expression (102)

In the above formula (102), R ²¹ , R ^25, and R ²⁶ are each independently a substituent, R ²² is a divalent linking group, and R ²³ is a hydrogen atom or a carbon number of 1 to 5. Is an alkyl group, m2 and n2 are each independently a number of 0 to 20, and x2 is a number of 2 to 100.
Formula (103)

In the above formula (103), R ³¹ and R ³⁶ are each independently a substituent, R ³² and R ³⁴ are each independently a divalent linking group, and R ³³ and R ³⁵ are hydrogen. It is an atom or an alkyl group having 1 to 5 carbon atoms, m31, m32, n3 and p3 are each independently a number of 0 to 20, and x3 is a number of 2 to 100.
Expression (104)

In the formula (104), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ^45, and R ⁴⁶ are each independently a substituent, R ⁴⁷ is a divalent linking group, and R ⁴⁸ is , A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m4 and n4 each independently represent a number of 0 to 20, and x4 and y4 each independently represent a number of 2 to 100.

In the formula (101), R ¹¹ and R ¹⁶ are each independently a substituent, preferably an alkyl group having 1 to 5 carbon atoms or a phenyl group, and more preferably a methyl group.
In the above formula (101), R ¹² and R ¹⁴ are each independently a divalent linking group, and include a carbonyl group, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, and a cycloalkylene group having 6 to 16 carbon atoms. , An alkenylene group having 2 to 8 carbon atoms, an alkynylene group having 2 to 5 carbon atoms, and an arylene group having 6 to 10 carbon atoms are preferable, and an oxygen atom is more preferable.
In formula (101), R ¹³ and R ¹⁵ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Alkyl groups are more preferred.

In the above formula (102), R ²¹ , R ²⁵ and R ²⁶ are each independently a substituent, have the same meaning as R ¹¹ and R ¹⁶ in the formula (101), and the preferred range is also the same.
In the formula (102), R ²² is a divalent linking group, has the same meaning as R ¹² in the formula (101), and the preferred range is also the same.
In the above formula (102), R ²³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, has the same meaning as R ¹³ and R ¹⁵ in the formula (101), and the preferred range is also the same.

In the formula (103), R ³¹ and R ³⁶ each independently represent a substituent, have the same meaning as R ¹¹ and R ¹⁶ in the formula (101), and the preferred range is also the same.
In the formula (103), R ³² and R ³⁴ each independently represent a divalent linking group, have the same meaning as R ¹² in the formula (101), and the preferred range is also the same.
In the above formula (103), R ³³ and R ³⁵ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, have the same meanings as R ¹³ and R ¹⁵ in the formula (101), and the preferred ranges are also the same.

In the above formula (104), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are each independently a substituent and have the same meaning as R ¹¹ and R ¹⁶ in the formula (101), The preferable range is also the same.
In the above formula (104), R ⁴⁷ is a divalent linking group, has the same meaning as R ¹² in formula (101), and the preferred range is also the same.
In the formula (104), R ⁴⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, has the same meaning as R ¹³ and R ¹⁵ in the formula (101), and the preferred range is also the same.

In formulas (101) to (104), formula (103) or formula (104) is preferable, and formula (104) is more preferable.

The content of the polyoxyalkylene group in the molecule of the polyether-modified silicone used in the present invention is not particularly limited, but the content of the polyoxyalkylene group is preferably more than 1% by mass based on the total molecular weight.
The content of the polyoxyalkylene group is defined by “{(formula weight of polyoxyalkylene group in one molecule)/molecular weight of one molecule}×100”.

Examples of the silicone compound precursor include silane coupling agents. Examples of the silane coupling agent include fluorine atom-containing silane coupling agents, and triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane is preferable.
Further, examples of silane coupling agents include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, and JP-A-63-34540. The surfactants described in JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, and JP-A-2001-330953 can also be used.

The silicon-containing compound used in the present invention may be a commercially available product.
For example, ADVALON FA33, FLUID L03, FLUID L033, FLUID L051, FLUID L053, FLUID L060, FLUID L066, IM22, WACKER-Belsil DMC 6038 (above, Asahi Kasei Wacker Silicone Co., Ltd.), KF-353A, KF-352A, KF-352A, KF-352A, KF-352A, KF-352A, KF-352A. KF-615A, KP-112, KP-341, X-22-4515, KF-354L, KF-355A, KF-6004, KF-6011, KF-6011P, KF-6012, KF-6013, KF-6015, KF-6016, KF-6017, KF-6017P, KF-6020, KF-6028, KF-6028P, KF-6038, KF-6043, KF-6048, KF-6123, KF-6204, KF-640, KF- 642, KF-643, KF-644, KF-945, KP-110, KP-355, KP-369, KS-604, Polon SR-Conc, X-22-4272, X-22-4952 (above, Shin-Etsu) Chemical Industry Co., Ltd.), 8526 ADDITIVE, FZ-2203, FZ-5609, L-7001, SF 8410, 2501 COSMETIC WAX, 5200 FORMULATION AID, 57 ADDITIVE, 8019 ADDITIVE, 8029 ADDITIVE-8036, 8054 ADDITIVE, 8054, 8054 ADDITIVE, 8054, 8054 ADDITIVE, 8054, 8054. BY16-201, ES-5612 FORMULATION AID, FZ-2104, FZ-2108, FZ-2123, FZ-2162, FZ-2164, FZ-2191, FZ-2207, FZ-2208, FZ-2222, FZ-7001, FZ-77, L-7002, L-7604, SF8427, SF8428, SH28 PAINR ADDITIVE, SH3749, SH3773M, SH8400, SH8700 (above, manufactured by Toray Dow Corning Co., Ltd.), BYK-378, BYK-302, BYK. -307, BYK-331, BYK-345, BYK-B, BYK-347, BYK-348, BYK-349, BYK-377 (above, manufactured by Big Chemie Japan KK), Silwet L-7001, Silwet L-. 7002, Silwet L-720, Silwet L-7200, Silwet L-7210, Silwet L-7220, Silwet L-72. 30, Silwet L-7605, TSF4445, TSF4446, TSF4452, Silwet Hydrostable 68, Silwet L-722, Silwet L-7280, Silwet L-7500, Silwet L-7550, Silwet L-7L-Swet76, Silwet. 7604, Silwet L-7607, Silwet L-7608, Silwet L-7622, Silwet L-7650, Silwet L-7657, Silwet L-77, Silwet L-8500, Silwet L-8610, TSF4440, TSF4441, TSF4441, TSF4441, TSF4441, TSF4441, TSF4441, TSF4441 Above, Momentive Performance Materials Japan GK) is exemplified.
Further, as the silicon-containing compound, trade names “BYK-300”, “BYK-306”, “BYK-310”, “BYK-315”, “BYK-313”, “BYK-320”, “BYK-322” are used. , "BYK-323", "BYK-325", "BYK-330", "BYK-333", "BYK-337", "BYK-341", "BYK-344", "BYK-370", "BYK-375", "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "BYK-3550", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720" (above, Big Chemie Japan Co., Ltd.) Product), product names “AC FS 180”, “AC FS 360”, “AC S 20” (all manufactured by Algin Chemie), product names “Polyflow KL-400X”, “Polyflow KL-400HF”, “Polyflow KL-”. 401", "Polyflow KL-402", "Polyflow KL-403", "Polyflow KL-404", "Polyflow KL-700" (above, Kyoeisha Chemical Co., Ltd. product), brand name "KP-301", ""KP-306","KP-109","KP-310","KP-310B","KP-323","KP-326","KP-341","KP-104","KP-"110","KP-112","KP-360A","KP-361","KP-354","KP-357","KP-358","KP-359","KP-362". , "KP-365", "KP-366", "KP-368", "KP-330", "KP-650", "KP-651", "KP-390", "KP-391", "KP-392" (above, manufactured by Shin-Etsu Chemical Co., Ltd.), trade names "LP-7001", "LP-7002", "8032 ADDITIVE", "FZ-2110", "FZ-2105", "67 ADDITIVE". , "8618 ADDITIVE", "3 ADDITIVE", "56 ADDITIVE" (above, manufactured by Toray Dow Corning Co., Ltd.), "TEGO WET 270" (manufactured by Evonik Degussa Japan Co., Ltd.), "NBX-15". (Neos Co., Ltd.) and the like can also be used.

The content of the silicon-containing compound in the temporary adhesive used in the present invention is preferably 0.001 to 1.0 mass% of the solid content of the temporary adhesive. The lower limit of the content of the silicon-containing compound is more preferably 0.004% by mass or more, further preferably 0.006% by mass or more, further preferably 0.008% by mass or more, and further preferably 0.009% by mass or more. preferable. The upper limit of the content of the silicon-containing compound is preferably 0.8% by mass or less, more preferably 0.6% by mass or less, further preferably 0.3% by mass or less, more preferably 0.15% by mass or less, It is even more preferably 0.09 mass% or less.
The temporary adhesive used in the present invention may include only one type of silicon-containing compound, or may include two or more types of silicon-containing compounds. When two or more kinds are contained, the total amount is preferably within the above range.

<<other release agents>>
In the present invention, a release agent other than the silicon-containing compound may be included. Examples of other release agents include fluorine-based liquid compounds.
When other release agent is contained, its content is preferably in the range of 0.001 to 0.005 mass %. These other release agents may be contained alone or in combination of two or more. When two or more kinds are contained, the total amount is preferably within the above range.
Further, in the present invention, it is possible to adopt a configuration in which other release agent is not substantially included. The term "substantially free" means that the content of the silicon-containing compound is 1% by mass or less.

<< resin >>
The temporary adhesive used in the present invention preferably contains at least one resin.
Examples of the resin include a block copolymer, a random copolymer and a graft copolymer, and a block copolymer is preferable. Since the block copolymer can suppress the flow of the temporary adhesive during the heating process, it is expected that the adhesion can be maintained even during the heating process and that the peelability does not change even after the heating process.

In the temporary adhesive used in the present invention, the resin is preferably an elastomer. By using the elastomer as the resin, it is possible to follow the fine irregularities of the substrate (the substrate to be processed such as a carrier substrate or a device wafer) and form a temporary adhesive having excellent adhesiveness by an appropriate anchor effect. The elastomer may be used alone or in combination of two or more.
In this specification, the elastomer means a polymer compound that exhibits elastic deformation. That is, it is defined as a polymer compound having a property of being instantly deformed according to the external force when an external force is applied, and recovering the original shape in a short time when the external force is removed.

<<<<Elastomer>>>>
In the present invention, the weight average molecular weight of the elastomer is preferably 2,000 to 200,000, more preferably 10,000 to 200,000, and further preferably 50,000 to 100,000. Elastomers having a weight average molecular weight in this range are excellent in solubility in a solvent, so after peeling the carrier substrate from the substrate to be processed, the solvent is used to derive the elastomer derived from the elastomer remaining on the substrate to be processed or the carrier substrate. When removing the residue, the residue is easily dissolved in the solvent and removed. Therefore, there is an advantage that a residue does not remain on the substrate to be processed or the carrier substrate.

In the present invention, the elastomer is not particularly limited, and an elastomer containing a repeating unit derived from styrene (polystyrene elastomer), a polyester elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyamide elastomer, a polyacrylic elastomer, a silicone elastomer. Elastomer, polyimide elastomer, etc. can be used. In particular, polystyrene-based elastomers, polyester-based elastomers and polyamide-based elastomers are preferable, and polystyrene-based elastomers are more preferable from the viewpoint of heat resistance and peelability.

In the present invention, the elastomer is preferably a hydrogenated product. In particular, hydrogenated products of polystyrene elastomer are preferable. When the elastomer is a hydrogenated product, thermal stability and storage stability are improved. Furthermore, the peelability and the removability of the temporary adhesive after peeling are improved. When a hydrogenated product of polystyrene-based elastomer is used, the above effect is remarkable. The hydrogenated product means a polymer having a structure in which an elastomer is hydrogenated.

In the present invention, the 5% thermal mass reduction temperature of the elastomer when heated from 25° C. at a heating rate of 20° C./min is preferably 250° C. or higher, and more preferably 300° C. or higher. The temperature is preferably 350° C. or higher, more preferably 400° C. or higher. The upper limit value is not particularly limited, but is preferably 1000° C. or lower, more preferably 800° C. or lower. According to this aspect, a temporary adhesive having excellent heat resistance can be obtained.
The elastomer of the present invention can be deformed up to 200% with a small external force at room temperature (20° C.) when the original size is 100%, and when the external force is removed, it is 130% or less in a short time. It is preferable to have a property of returning to.

<<<<<polystyrene elastomer>>>>
The polystyrene elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polystyrene-poly(ethylene-propylene) diblock copolymer (SEP), polystyrene-poly(ethylene -Propylene)-polystyrene triblock copolymer (SEPS), polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer (SEBS), polystyrene-poly(ethylene/ethylene-propylene)-polystyrene triblock copolymer At least one polystyrene elastomer selected from (SEEPS) is preferable.

In the polystyrene-based elastomer, the proportion of repeating units derived from styrene is preferably 90% by mass or less, more preferably 55% by mass or less, further preferably 48% by mass or less, further preferably 35% by mass or less, and more preferably 33% by mass or less. More preferable. The lower limit of the proportion of the repeating unit derived from styrene may be 0% by mass, but may be 10% by mass or more. By setting such a range, it is possible to more effectively suppress the warpage of the laminate formed by bonding the substrates to each other with a temporary adhesive.

As one embodiment of the polystyrene-based elastomer in the present invention, an elastomer A containing a repeating unit derived from styrene in a proportion of 10% by mass or more and 55% by mass or less in all repeating units, and a repeating unit derived from styrene in all repeating units In addition, it may be used in combination with the elastomer B contained in a proportion of more than 55% by mass and less than 95% by mass. The combined use of Elastomer A and Elastomer B can effectively suppress the occurrence of warpage. It can be inferred that the mechanism for obtaining such an effect is as follows. That is, since the elastomer A is a relatively soft material, it is easy to form a layered temporary adhesive (temporary adhesive layer) having elasticity. For this reason, when a laminated body of a substrate and a carrier substrate is manufactured using a temporary adhesive, and when the substrate is polished into a thin film, the temporary adhesive (temporary adhesive The layer easily deforms elastically and returns to its original shape. As a result, excellent flat polishability can be obtained. Further, even if the laminated body of the carrier substrate, the substrate to be processed and the temporary adhesive after polishing is heat-treated and then cooled, the internal stress generated at the time of cooling can be relaxed by the temporary adhesive (temporary adhesive layer), The occurrence of warpage can be effectively suppressed.
Further, since the elastomer B is a relatively hard material, the provision of the elastomer B makes it possible to provide a temporary adhesive having excellent releasability.

When blending the elastomer A and the elastomer B, the mass ratio is preferably elastomer A: elastomer B=1:99 to 99:1, more preferably 3:97 to 97:3, and 5:95 to 95:5. Is more preferable, and 10:90 to 90:10 is more preferable. Within the above range, the occurrence of warpage can be suppressed more effectively.

The polystyrene elastomer is preferably a block copolymer of styrene and another monomer, more preferably a block copolymer in which one end or both ends are styrene blocks, and both ends are styrene blocks. Is particularly preferable. When both ends of the polystyrene-based elastomer are styrene blocks (repeating units derived from styrene), heat resistance tends to be further improved. This is because the repeating unit derived from styrene having high heat resistance is present at the terminal. In particular, when the block portion of the repeating unit derived from styrene is a reactive polystyrene-based hard block, heat resistance and chemical resistance tend to be superior, which is preferable. In addition, such an elastomer is more preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.
When the polystyrene-based elastomer is a hydrogenated product, the stability to heat is improved, and deterioration such as decomposition or polymerization is less likely to occur. Further, it is more preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.
The amount of unsaturated double bonds of the polystyrene-based elastomer is preferably less than 15 mmol, more preferably less than 5 mmol, and less than 0.5 mmol, per 1 g of the polystyrene-based elastomer, from the viewpoint of releasability. More preferable. The amount of unsaturated double bonds mentioned here does not include the amount of unsaturated double bonds in the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by NMR (nuclear magnetic resonance) measurement.

In the present specification, the “styrene-derived repeating unit” is a styrene-derived structural unit contained in the polymer when styrene or a styrene derivative is polymerized, and may have a substituent. Examples of the styrene derivative include α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene and the like. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 2 to 5 carbon atoms, an acetoxy group, a carboxyl group and the like.

Examples of commercially available polystyrene-based elastomers include Tuffprene A, Tuffprene 125, Tuffprene 126S, Soprene T, Asaprene T-411, Asaprene T-432, Asaprene T-437, Asaprene T-438, Asaprene T-439, Tuftec H1272. , Tuftec P1500, Tuftec H1052, Tuftec H1062, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftec H1053, Tuftech P2000, Tuftec H1043 (above, Asahi Kasei Co., Ltd. C-50), elastomer. , Elastomer AR-815C, Elastomer AR-840C, Elastomer AR-830C, Elastomer AR-860C, Elastomer AR-875C, Elastomer AR-885C, Elastomer AR-SC-15, Elastomer AR-SC-0, Elastomer AR-SC- 5, elastomer AR-710, elastomer AR-SC-65, elastomer AR-SC-30, elastomer AR-SC-75, elastomer AR-SC-45, elastomer AR-720, elastomer AR-741, elastomer AR-731, Elastomer AR-750, Elastomer AR-760, Elastomer AR-770, Elastomer AR-781, Elastomer AR-791, Elastomer AR-FL-75N, Elastomer AR-FL-85N, Elastomer AR-FL-60N, Elastomer AR-1050. Elastomer AR-1060, Elastomer AR-1040 (all manufactured by Aron Kasei Co., Ltd.), Clayton D1111, Clayton D1113, Clayton D1114, Clayton D1117, Clayton D1119, Clayton D1124, Clayton D1126, Clayton D1161, Clayton D1162, Clayton D1163. Clayton D1164, Clayton D1165, Clayton D1183, Clayton D1193, Clayton DX406, Clayton D4141, Clayton D4150, Clayton D4153, Clayton D4158, Clayton D4270, Clayton D4271, Clayton D4433, Clayton D1170, Clayton D1171, Clayton D1173. , Califlex IR0307, Califlex IR 0310, Califlex IR 0401, Clayton D0242, Clayton D1101, Clayton D1102, Clayton D1116, Clayton D1118, Clayton D1133, Clayton D1152, Clayton D1153, Clayton D1155, Clayton D1184, Clayton D1186, Clayton D1192, Clayton D1191, Clayton D1192, Clayton D1192. DX405, Clayton DX408, Clayton DX410, Clayton DX414, Clayton DX415, Clayton A1535, Clayton A1536, Clayton FG1901, Clayton FG1924, Clayton G1640, Clayton G1641, Clayton G1642, Clayton G1633, Clayton G1633, Clayton G1633, Clayton G1633, Clayton G1633, Clayton G1633, Clayton G1633, Clayton G1633, Clayton G1633 Clayton G1652 (G1652MU-1000), Clayton G1654, Clayton G1657, Clayton G1660, Clayton G1726, Clayton G1701, Clayton G1702, Clayton G1730, Clayton G1750, Clayton G1765, Clayton G4609, Clayton G4610 (above, made by Clayton Polymer Japan Co., Ltd.) ), TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynaron 6100P, Dynaron 4600P, Dynaron 6200P, Dynaron 4630P, Dynaron 8601P, Dynaron 8630P, Dynaron 8600P, Dynaron 8903P, Dynaron 6201B, Dynaron 1321P, Dynaron 1320P, Dynaron 2324P, Dynaron 9901P (all manufactured by JSR Corporation), Denka STR series (manufactured by Denka Corporation), Quintac 3520, Quintac 3433N. , Quintac 3421, Quintac 3620, Quintac 3450, Quintac 3460 (above, manufactured by Nippon Zeon), TPE-SB series (Sumitomo Chemical Co., Ltd.), Lavalon series (Mitsubishi Chemical Co., Ltd.), Septon 1001 , Septon 1020, Septon 2002, Septon 2004, Septon 2005, Septon 2006, Septon 2007, Septon 2063, Septon 2104, Septon 4033, Septon 4044, Septon 4055, Septon 4077, Septon 4099, Septon HG252, Septon 8004, Septon 8006, Septon 8007, Septon 8076, Septon 8104, Septon V9461, Septon V9475, Septon V9827, Examples include Hybler 7311, Hibler 7125, Hibler 5127, Hibler 5125 (all manufactured by Kuraray Co., Ltd.), Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (all manufactured by Riken Technos Co., Ltd.).

As the elastomer other than the polystyrene-based elastomer, a polyester-based elastomer, a polyolefin-based elastomer, a polyurethane-based elastomer, a polyamide-based elastomer, a polyacrylic-based elastomer, or the like can be used.

<<<resin content>>>
The temporary adhesive used in the present invention preferably contains the resin in a proportion of 50.00 to 99.99 mass% in the total solid content of the temporary adhesive, and in a proportion of 70.00 to 99.99 mass %. It is more preferable to contain, and it is particularly preferable to contain it in a ratio of 88.0 to 99.99 mass %. When the content of the resin is in the above range, the adhesiveness and the peeling property are excellent.
When an elastomer is used as the resin, the elastomer is preferably contained in the total solid content of the temporary adhesive in a proportion of 50.00 to 99.99 mass %, and in a proportion of 70.00 to 99.99 mass %. Is more preferable, and it is particularly preferable that the content is 88.0 to 99.99 mass %. When the content of the elastomer is within the above range, the adhesive property and the peeling property are excellent. When two or more elastomers are used, the total is preferably within the above range.
When an elastomer is used as the resin, the content of the elastomer in the total mass of the resin is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and 80 to 100% by mass. Is more preferable, and 90 to 100 mass% is even more preferable. Further, the resin may be substantially only the elastomer. When the resin is substantially only the elastomer, the content of the elastomer in the total mass of the resin is preferably 99% by mass or more, more preferably 99.9% by mass or more, and even more preferably only the elastomer.

<< plasticizer >>
The temporary adhesive used in the present invention may contain a plasticizer, if necessary. By blending a plasticizer, a temporary adhesive layer that satisfies the above-mentioned various properties can be obtained.
As the plasticizer, phthalic acid ester, fatty acid ester, aromatic polycarboxylic acid ester, polyester and the like can be used.

Examples of the phthalic acid ester include DMP, DEP, DBP, #10, BBP, DOP, DINP, DIDP (all manufactured by Daihachi Chemical Industry Co., Ltd.), PL-200, DOIP (all manufactured by CG Esther Corporation). ), Sanso Sizer DUP (manufactured by Shin Nippon Rika Co., Ltd.) and the like.
Examples of the fatty acid ester include butyl stearate, Unistar M-9676, Unistar M-2222SL, Unistar H-476, Unistar H-476D, Panasate 800B, Panasate 875, Panasate 810 (above, NOF Corporation), DBA. , DIBA, DBS, DOA, DINA, DIDA, DOS, BXA, DOZ, DESU (above, manufactured by Daihachi Kagaku) and the like.
Examples of aromatic polycarboxylic acid esters include TOTM (manufactured by Daihachi Chemical Industry Co., Ltd.), Monosizer W-705 (manufactured by Daihachi Chemical Industry Co., Ltd.), UL-80, UL-100 (ADEKA Corporation). Manufactured) and the like.
Examples of the polyester include Polysizer TD-1720, Polysizer S-2002, Polysizer S-2010 (above, manufactured by DIC Corporation), BAA-15 (manufactured by Daihachi Chemical Industry Co., Ltd.) and the like.
Among the above plasticizers, DIDP, DIDA, TOTM, Unistar M-2222SL, and Polycizer TD-1720 are preferable, DIDA and TOTM are more preferable, and TOTM is particularly preferable.
As the plasticizer, only one kind may be used, or two or more kinds may be combined.

From the viewpoint of preventing sublimation during heating, the plasticizer has a temperature at which the weight decreases by 1% by mass when the weight change is measured under a nitrogen stream under a temperature rising condition of a constant rate of 20° C./min. It is preferably 250°C or higher, more preferably 270°C or higher, and particularly preferably 300°C or higher. The upper limit is not particularly limited, but may be, for example, 500° C. or lower.

The addition amount of the plasticizer is preferably 0.01% by mass to 5.0% by mass, more preferably 0.1% by mass to 2.0% by mass, based on the total solid content of the temporary adhesive. %.

<<solvent>>
The temporary adhesive used in the present invention preferably contains a solvent. Known solvents can be used without limitation, and organic solvents are preferable.
Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and alkyl oxyacetate alkyl (eg, alkyl Methyl oxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-oxypropionic acid alkyl esters (eg Methyl 3-oxypropionate, ethyl 3-alkyloxypropionate and the like (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate and the like), 2 -Oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-alkyloxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example 2-methoxy 2-Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-oxobutane Esters such as ethyl acid and 1-methoxy-2-propylacetate;
Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Ethers such as monoethyl ether acetate and propylene glycol monopropyl ether acetate;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and γ-butyrolactone;
Toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert-butylbenzene, amylbenzene, isoamylbenzene, (2,2-dimethylpropyl)benzene, 1 -Phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-cymene, indane, 1 , 2,3,4-Tetrahydronaphthalene, 3-ethyltoluene, m-cymene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-cymene, 1,4-diisopropylbenzene, 4- tert-butyltoluene, 1,4-di-tert-butylbenzene, 1,3-diethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl-o-xylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 5-tert-butyl-m-xylene, 3,5-di-tert-butyltoluene, 1 , 2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene and other aromatic hydrocarbons;
Hydrocarbons such as limonene, p-menthane, nonane, decane, dodecane, decalin and the like are preferable.
Among these, mesitylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate. , Diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate are preferred.

From the viewpoint of improving the properties of the coated surface, it is preferable to mix two or more of these solvents. In this case, particularly preferably, mesitylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate. , Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate. It is a mixed solution composed of two or more kinds.

From the viewpoint of coatability, the content of the solvent of the temporary adhesive is preferably such that the total solid content concentration of the temporary adhesive is 5 to 80% by mass, and more preferably 10 to 50% by mass. It is particularly preferable that the content is 15 to 40% by mass.
Only one type of solvent may be used, or two or more types may be used. When two or more kinds of solvents are used, it is preferable that the total thereof is within the above range.
The content of the solvent in the temporary adhesive layer obtained by applying the temporary adhesive in layers and drying is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably not contained at all. ..

<< Antioxidant >>
The temporary adhesive used in the present invention may contain an antioxidant. As the antioxidant, phenol-based antioxidant, sulfur-based antioxidant, phosphorus-based antioxidant, quinone-based antioxidant, amine-based antioxidant and the like can be used.
Examples of the phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox1010, Irganox1330, Irganox3114, Irganox1035 (above, manufactured by BASF Japan Ltd.), Sumilizer MDP-. S, Sumilizer GA-80 (above, Sumitomo Chemical Co., Ltd. make) etc. are mentioned.
Examples of sulfur antioxidants include 3,3′-thiodipropionate distearyl, Sumilizer TPL-R, Sumilizer TPM, Sumilizer TPS, Sumilizer MB, and Sumilizer TP-D (above, Sumitomo Chemical Co., Ltd.). Is mentioned.
Examples of the phosphorus-based antioxidant include tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, poly(dipropylene glycol)phenyl. Examples include phosphite, diphenylisodecylphosphite, 2-ethylhexyldiphenylphosphite, triphenylphosphite, Irgafos168, Irgafos38 (all manufactured by BASF Japan Ltd.) and Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.).
Examples of the quinone-based antioxidant include p-benzoquinone, 2-tert-butyl-1,4-benzoquinone and the like.
Examples of amine-based antioxidants include dimethylaniline and phenothiazine.
As the antioxidant, Irganox 1010, Irganox 1330, 3,3′-thiodipropionate distearyl, and Sumilizer TP-D are preferable, Irganox 1010 and Irganox 1330 are more preferable, and Irganox 1010 is particularly preferable.
Further, among the above antioxidants, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant or a phosphorus-based antioxidant in combination, and a phenol-based antioxidant and a sulfur-based antioxidant are used in combination. Is most preferred. Particularly, when a polystyrene-based elastomer is used as the elastomer, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant together. With such a combination, the effect of efficiently suppressing the deterioration of the temporary adhesive due to the oxidation reaction can be expected. When the phenolic antioxidant and the sulfur antioxidant are used in combination, the mass ratio of the phenolic antioxidant and the sulfur antioxidant is as follows: phenolic antioxidant:sulfur antioxidant=95:5 5:95 is preferable, and 25:75 to 75:25 is more preferable.
As the combination of the antioxidants, Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D, and Sumilizer GA-80 and Sumilizer TP-D are preferable, and Irganox 1010 and Sumilizer TP-D, Izir30Sg 13g and 13g, and Imiloxer TP-D and Irmioxer TP-D. More preferably, Irganox 1010 and Sumilizer TP-D are particularly preferable.

From the viewpoint of preventing sublimation during heating, the molecular weight of the antioxidant is preferably 400 or more, more preferably 600 or more, and particularly preferably 750 or more.

When the temporary adhesive contains an antioxidant, the content of the antioxidant is preferably 0.001 to 20.0 mass% with respect to the total solid content of the temporary adhesive, More preferably, it is contained in a proportion of 005 to 10.0 mass %.
The antioxidant may be only one kind or two or more kinds. When two or more antioxidants are used, it is preferable that the total amount thereof be within the above range.

<<Other additives>>
In the temporary adhesive used in the present invention, various additives, such as a surfactant, a curing agent, a curing catalyst, a filler, an adhesion promoter, and an ultraviolet absorbing agent, may be added as necessary within a range that does not impair the effects of the present invention. Agents, anti-aggregation agents and the like can be added. When these additives are blended, the total blending amount thereof is preferably 3% by mass or less of the total solid content of the temporary adhesive.

<<Formation of temporary adhesive layer>>
The temporary adhesive layer is formed by applying a temporary adhesive onto the substrate by spin coating, spraying, slit coating, roller coating, flow coating, doctor coating, dipping, or the like. You can
The temporary adhesive layer is formed on the surface of at least one of the two substrates to be temporarily bonded. A temporary adhesive layer may be formed on only one of the substrates and bonded to the other substrate, or a temporary adhesive layer may be provided on both substrates to bond the two.
Next, since the temporary adhesive usually contains a solvent, it is heated to volatilize the solvent. The heating temperature is preferably higher than the boiling point of the solvent, more preferably 110°C or higher, further preferably 130°C to 200°C, particularly preferably 160°C to 190°C.

<<Preparation of temporary adhesive>>
The temporary adhesive used in the present invention can be prepared by mixing the above components. Mixing of each component is usually performed in the range of 0°C to 100°C. Moreover, it is preferable to filter each component after mixing, for example, with a filter. Filtration may be performed in multiple stages or may be repeated many times. Further, the filtered liquid can be refiltered.
The filter can be used without particular limitation as long as it has been conventionally used for filtration and the like. Examples thereof include filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon 6, nylon 6,6, and polyolefin resins such as polyethylene and polypropylene (PP). Among these materials, polypropylene and nylon are preferable.
A suitable pore size of the filter is, for example, about 0.003 to 5.0 μm. Within this range, it is possible to reliably remove fine foreign substances such as impurities and agglomerates contained in the composition while suppressing filter clogging.
When using the filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once, or may be performed twice or more. When different filters are combined and filtering is performed twice or more, it is preferable that the pore diameters of the second and subsequent times are the same or smaller than the pore diameters of the first filtering. Further, a plurality of first filters having different pore diameters within the above-mentioned range may be combined. For the pore size here, the nominal value of the filter manufacturer can be referred to. The commercially available filter can be selected from various filters provided by, for example, Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd., or Kits Micro Filter Co., Ltd.

<Cleaning composition A>
The cleaning composition A in the present invention is an organic acid, and contains at least one organic acid whose acid group contained in the organic acid contains a sulfur atom or a phosphorus atom, and an organic solvent. With such a structure, the residue derived from the silicon-containing compound can be effectively removed, and peeling of the insulating layer to be laminated thereafter can be effectively suppressed.

<< organic acid >>
The organic acid used in the present invention may be a low molecular weight compound (for example, a molecular weight of less than 1000, further 500 or less, and the lower limit is, for example, 98 or more), or a high molecular compound (for example, a molecular weight of 1000 or more). Further, it may be 2000 or more, and the upper limit thereof may be, for example, 5000 or less). The organic acid used in the present invention is preferably a low molecular weight compound.
The organic acid used in the present invention preferably has an acid dissociation constant pKa of -4 to 5, more preferably -3 to 4.
The organic acid used in the present invention has a value of P, which is a 1-octanol/water partition coefficient representing the ratio of the equilibrium concentrations of the organic acid in 1-octanol and water, in the form of logarithmic log P with respect to the base 10. It is preferable that it is -6, and it is more preferable that it is -3-5.
The organic acid used in the present invention is preferably selected from alkylsulfonic acid, aromatic sulfonic acid, alkylphosphoric acid, aromatic phosphoric acid, alkylphosphonic acid and aromatic phosphonic acid. The aromatic here may be an aromatic hydrocarbon or an aromatic heterocyclic ring, but is preferably an aromatic hydrocarbon.
The organic acid used in the present invention preferably contains at least one organic acid selected from the group consisting of organic sulfonic acid, organic phosphoric acid, organic phosphonic acid, organic sulfinic acid and organic phosphinic acid, and organic sulfonic acid, It is more preferable to contain at least one kind of organic acid selected from the group consisting of organic phosphoric acid and organic phosphonic acid, and it is more preferable to contain at least one kind of organic sulfonic acid, and alkyl sulfonic acid and aromatic having a cyclic group. It is more preferred to include at least one group sulfonic acid.
The organic acid used in the present invention may or may not have an acid group other than an acid group containing a sulfur atom or a phosphorus atom. In the present invention, an organic acid having no carboxyl group is preferable, and an organic acid having no acid group other than sulfonic acid group, phosphoric acid group and phosphonic acid group is more preferable.

Examples of the organic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, butanesulfonic acid, vinylsulfonic acid, 1,5-propanedisulfonic acid, 3-hydroxypropanesulfonic acid, benzenesulfonic acid and paratoluenesulfonic acid. , P-ethylbenzenesulfonic acid, dodecylbenzenesulfonic acid, 2,4,5-trimethylbenzenesulfonic acid, nonafluoro-1-butanesulfonic acid, 2-naphthalenesulfonic acid, 1,5-naphthalenedisulfonic acid, heptadecafluorooctasulfone Acid, camphorsulfonic acid, 3-cyclohexylaminopropanesulfonic acid, m-xylene-4-sulfonic acid, p-xylene-2-sulfonic acid, dansyl acid, 4,4′-biphenyldisulfonic acid, 8-anilino-1- Naphthalenesulfonic acid, 2-morpholinoethanesulfonic acid, 3-morpholinopropanesulfonic acid, piperazine-1,4-bis(2-hydroxypropanesulfonic acid), 7-anilino-4-hydroxy-2-naphthalenesulfonic acid, 7- Anilino-1-naphthol-3-sulfonic acid, 4-sulfophthalic acid, 2-hydroxy-3-morpholinopropanesulfonic acid, 4-nitrotoluene-2-sulfonic acid and picrylsulfonic acid are exemplified. The organic sulfonic acid is preferably an alkyl sulfonic acid or an aromatic sulfonic acid, more preferably an aromatic sulfonic acid.

As the organic phosphoric acid, an alkyl phosphoric acid such as methyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, butyl phosphate, dibutyl phosphate, butoxyethyl phosphate, 2-ethylhexyl phosphate, phenylphosphoric acid, Aromatic phosphoric acid such as diphenyl phosphoric acid is exemplified. The organic phosphoric acid is preferably alkyl phosphoric acid and aromatic phosphoric acid, more preferably aromatic phosphoric acid, and further preferably diaryl phosphoric acid.
Examples of the organic phosphonic acid include vinylphosphonic acid, methylenediphosphonic acid, ethylphosphonic acid, propylphosphonic acid, 1,3-propylenediphosphonic acid, butylphosphonic acid, 1,4-butylenediphosphonic acid, pentylphosphonic acid, 1 ,5-Pentylenediphosphonic acid, hexylphosphonic acid, 1,6-dihexylenephosphonic acid, octylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, and other alkylphosphonic acids, phenylphosphonic acid, phenylenediphosphonic acid, xylylenediphosphonic acid Aromatic acids such as acid, (4-hydroxyphenyl)phosphonic acid, (2-phenylethyl)phosphonic acid, o-xylenediphosphonic acid, benzhydrylphosphonic acid, cinnamylphosphonic acid, (4-hydroxybenzyl)phosphonic acid A phosphonic acid is illustrated. The organic phosphonic acid is preferably an alkylphosphonic acid and an aromatic phosphonic acid, more preferably an aromatic phosphonic acid.

The content of the organic acid in the cleaning composition A is preferably 0.08 mg to 0.8 g with respect to 1 L of the organic solvent contained in the cleaning composition A.
Further, the content of the organic acid in the cleaning composition A is preferably 0.000008% by mass or more of the cleaning composition, more preferably 0.000080% by mass or more, further preferably 0.000800% by mass or more, 0.008000 mass% or more is more preferable, and 0.08 mass% or more is still more preferable. In the cleaning composition of the present invention, the content of the organic acid is preferably 1.0% by mass or less of the cleaning composition, more preferably 0.8% by mass or less, further preferably 0.5% by mass or less, It is more preferably 0.3% by mass or less.
The cleaning composition A may include only one type of organic acid, or may include two or more types. When two or more kinds are contained, the total amount is preferably within the above range.

<< organic solvent >>
The cleaning composition A contains an organic solvent. When the temporary adhesive contains an elastomer, the organic solvent is preferably an organic solvent capable of dissolving the elastomer, and is at least one selected from aromatic compounds, saturated alicyclic compounds, cyclic ketones and cyclic terpenes. Is more preferable, at least one selected from an aromatic compound, an alicyclic compound and a cyclic terpene is more preferable, and at least one selected from an aromatic compound is even more preferable.
The organic solvent as the aromatic compound preferably contains an aromatic hydrocarbon solvent having an alkyl group, and is more preferably a solvent having 1 to 3 benzene rings and an alkyl group having 1 to 10 carbon atoms. preferable.

上記式（Ｘ）において、Ｒは炭素数１〜４のアルキル基であり、ｎは１〜３の整数である。
Ｒは、直鎖または分岐の炭素数１〜４のアルキル基が好ましく、メチル基、エチル基、ｔｅｒｔ−ブチル基がより好ましい。また、Ｒを構成する炭素数の合計が２〜５の整数であることが好ましく、３または４がより好ましい。The alkyl group constituting the aromatic hydrocarbon solvent having an alkyl group used in the present invention is a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group. The number of carbon atoms constituting the alkyl group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4.
The aromatic hydrocarbon solvent having an alkyl group used in the present invention is preferably a solvent having a benzene ring and 1 to 3 alkyl groups having 1 to 10 carbon atoms, and is represented by the following formula (X). More preferably, it is a solvent.
Formula (X)

In the above formula (X), R is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3.
R is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group, an ethyl group, or a tert-butyl group. Further, the total number of carbon atoms constituting R is preferably an integer of 2 to 5, more preferably 3 or 4.

The boiling point of the alkyl group-containing aromatic hydrocarbon solvent used in the present invention is preferably 50 to 250°C, more preferably 80 to 200°C, and further preferably 120 to 170°C.

Specific examples of the aromatic hydrocarbon solvent having an alkyl group used in the present invention include toluene, xylene, trimethylbenzene (preferably 1,3,5-trimethylbenzene (mesitylene), 1,2,4-trimethylbenzene). (Pseudocumene)), ethylbenzene, propylbenzene, 1-methylethylbenzene, butylbenzene (preferably n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert-butylbenzene, more preferably tert-butylbenzene), amyl Benzene, isoamylbenzene, (2,2-dimethylpropyl)benzene, 1-phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2- Ethyltoluene, 1,2-diethylbenzene, o-cymene (2-isopropyltoluene), 3-ethyltoluene, m-cymene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-cymene, 1,4-diisopropylbenzene, 4-tert-butyltoluene, 1,4-di-tert-butylbenzene, 1,3-diethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4 -Tert-butyl-o-xylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 5-tert-butyl-m-xylene, 3,5 -Di-tert-butyltoluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene and the like.

The aromatic hydrocarbon solvent having an alkyl group is preferably at least one of toluene, xylene, trimethylbenzene (preferably mesitylene), butylbenzene (preferably tert-butylbenzene) and diethylbenzene, and more preferably Is xylene and at least one of trimethylbenzene and butylbenzene.

The saturated alicyclic compound, cyclopropane, cyclobutane, cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, cyclo Examples include octene, bicycloundecane, decahydronaphthalene, norbornene, norbornadiene, cubane, basketane, and hausan.
Examples of cyclic ketones include cyclohexanone, cyclopentanone, isophorone, acetophenone, and benzophenone.
Cyclic terpenes include chrysanthemol, grangesol, junione, thioterpineol, iridoid, secoiridoid, menthane, limonene, ferrandrene, terpinolene, terpinene, simene, menthol, pregol, piperitol, terpineol, carveol, thymol, dihydrocarbe. Monocyclic terpenes such as oar, menthone, pulegone, ferrandral, carvone, carbenone, piperiton, 1,8-cineole, 1,4-cineole, and ascaridol, karan, tujan, pinan, bornan, fencan, isobornane, isocane. Illustrative examples include bicyclic terpenes such as fan, 3-carene, tugen, sabinene, tujon, tujanol, pinene, berbenol, berbenone, pinocarvone, camphor, borneol, isoborneol, fencon and fencorfenken.

The content of the organic solvent in the detergent composition A is preferably 50.0000 to 99.9999% by mass of the detergent composition A, and more preferably 99.0000 to 99.99990% by mass. ..
The cleaning composition of the present invention may contain only one type of organic solvent, or may contain two or more types. When two or more kinds are contained, the total amount is preferably within the above range.
In the cleaning composition A, the mass ratio of the organic acid and the organic solvent is preferably 0.0001:99.9999 to 50:50, and 0.0010:99.99990 to 10:90. Is more preferable, and it is further preferable that it is 0.0100:99.9900 to 1.0000:99.0000. By setting it as such a range, the removal property of a temporary adhesive agent improves more effectively.

<<other ingredients>>
The cleaning composition A may contain components other than the organic acid and the organic solvent. Other components include sodium tripolyphosphate, 4-sodium pyrophosphate, potassium pyrophosphate, sodium aluminum silicate, sodium nitrilotriacetate, ethylenediaminetetraacetic acid, cleaning aids such as sodium citrate, and micelle enhancement such as sodium sulfate. Agent, IRGAMET 30, IRGAMET 39, IRGAMET 42 (above, manufactured by BASF Japan Ltd.), Belcrene 510, Belcrene 511, Belcrene 512, Belcrene 515 (above manufactured by Pan-Asia Trading Co., Ltd.), BT-120, BT-. LX, CBT-1, TT-LX, TT-LYK, JCL-400 (all manufactured by Johoku Chemical Co., Ltd.), VERZONE Crystal #120, VERZONE MA-10, VERZONE A3-T, VERZONE Crystal #130, VERZONE. Crystal #150, VERZONE Crystal #270, VERZONE Crystal #260, VERZONE SG Powder, VERZONE Grin SH-K, VERZONE Oil #1022, VERZONE Oil OIL OIL #1030 VERZONE OIL OIL #1030, VERZONE Crystal #270, VERZONE Crystal #2702 (Above, manufactured by Daiwa Kasei Co., Ltd.), top rust preventive agent Y, top rust preventive agent 511 (above, manufactured by Okuno Chemical Industries Co., Ltd.) CB Bright (manufactured by Ryobo Chemical Co., Ltd.), and the like. Corrosion inhibitors such as IRGACOR L12, IRGACOR DSS G, IRGACOR NPA, IRGALUBE 349, SARKOSYL O (above, manufactured by BASF Japan Ltd.), VERZONE COR-280, silver lip, VERZONE DA-1, New Dain Silver-1. , New Dain Silver V-2, New Dain Silver, CUE Guard 1000R, CUE Guard 1000N, CUE Guard 1000, CUE Guard D, VERZONE NFS-Oil, VERZONE OA#386, VERZONE C-BTA, VERZONE, VERZONE, VERZONE. (Above, manufactured by Daiwa Kasei Co., Ltd.), Cu-423Y, Ag-422Y, Ag-420Y (above, manufactured by Dipsol Co., Ltd.), Entec CU-560, Ente CU-56, Meldip AG-6801 (all manufactured by Meltex Co., Ltd.), Top rinse CU-5, Top rinse CU-3 (all manufactured by Okuno Chemical Industries Co., Ltd.), BT-5, BT -7, BT-8, BT-14 (above, manufactured by ASAHI Co., Ltd.) and the like, metal surface discoloration inhibitor, CU-500, CU-600 (above, manufactured by ASAHI Co., Ltd.), Esculin S-800, Esculin S-800FR, Esculin S-101PN, Espure SJ-400, Espure SJ Gel, Esculin SK-507, Esculin W-2550, Esculin S-105, Esculin S-109, Esculin AG-301, Esculin S-1000 (above. , Sasaki Chemical Co., Ltd.), pickle 25, pickle 27, Z-2218 (manufactured by Nippon Surface Chemical Co., Ltd.), and the like, metal oxide film removing agents, antistatic agents, antioxidants, and surfactants. R.

<<Preparation of Cleaning Agent Composition A>>
The detergent composition A is preferably prepared by mixing the respective components of the detergent composition A and then filtering. For filtration, it is preferable to use a filter having a pore size of 0.003 to 10 μm. By performing the filtration, it is possible to reduce the contamination of the substrate surface due to the impurities derived from the cleaning composition A. The filter is preferably made of polytetrafluoroethylene.

As a container for the cleaning composition A used in the present invention, a conventionally known container can be used. In addition, as a storage container, a multi-layer bottle in which the inner wall of the container is composed of 6 kinds of 6 layers of resin, or 6 kinds of resin of 7 layers structure is used for the purpose of suppressing the mixing of impurities into raw materials and compositions. It is also preferable to use a bottle. As such a container, for example, the container described in JP-A-2015-123351 can be cited.

<Cleaning composition B>
The cleaning composition of the present invention contains an organic carboxylic acid compound and at least one solvent consisting of water and a water-soluble solvent. With such a structure, the residue derived from the organic acid can be effectively removed.

<<organic carboxylic acid compound>>
The organic carboxylic acid compound used in the present invention may be a low molecular weight compound (for example, a molecular weight of less than 1000, further, a molecular weight of 500 or less, and a lower limit of, for example, 46 or more) or a high molecular weight compound (for example, a molecular weight. 1000 or more, further 2000 or more, and the upper limit may be, for example, 5000 or less). The organic carboxylic acid compound used in the present invention is preferably a low molecular weight compound.
The organic carboxylic acid compound used in the present invention has an acid dissociation constant pKa of preferably 1 to 7, more preferably 2 to 7, even more preferably 2 to 5, and 2 to 4. Good.
The organic carboxylic acid compound used in the present invention has a value of -5, which is the logarithm logP form with respect to the base 10, of P, which is a 1-octanol/water partition coefficient representing the ratio of equilibrium concentrations in 1-octanol and water. It is preferably 2 and more preferably -5 to 1.
The organic carboxylic acid used in the present invention is preferably a monocarboxylic acid, a dicarboxylic acid or a tricarboxylic acid, more preferably a monocarboxylic acid and a dicarboxylic acid.
The organic carboxylic acid compound used in the present invention is preferably selected from the group consisting of saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, oxocarboxylic acids and halogen-containing carboxylic acids, saturated fatty acids, unsaturated fatty acids. , More preferably selected from the group consisting of hydroxy acids and aromatic carboxylic acids, and even more preferably selected from the group consisting of saturated fatty acids and aromatic carboxylic acids.
The saturated fatty acid, unsaturated fatty acid and hydroxy acid are preferably monocarboxylic acids, and the aromatic carboxylic acid is more preferably a monocarboxylic acid or a dicarboxylic acid.
The organic carboxylic acid compound used in the present invention may or may not have an acid group other than the carboxyl group. The organic carboxylic acid compound used in the present invention preferably does not have a sulfonic acid group, a phosphoric acid group and a phosphonic acid group, and more preferably does not have an acid group other than a carboxyl group.

As the organic carboxylic acid compound, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, etc. Saturated fatty acids, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, sorbic acid, unsaturated fatty acids such as aconitic acid, lactic acid, malic acid, hydroxy acids such as citric acid, benzoic acid, phthalic acid Aroma such as, isophthalic acid, terephthalic acid, salicylic acid, 3,4,5-trihydroxybenzoic acid, mellitic acid, cinnamic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid and maleic acid Examples thereof include oxocarboxylic acids such as group carboxylic acids, pyruvic acid and oxaloacetic acid, and halogen-containing carboxylic acids such as chloroacetic acid, dichloroacetic acid, trichloroacetic acid and trifluoroacetic acid.

The content of the organic carboxylic acid compound in the cleaning composition B is preferably 0.8 mg to 1.6 g with respect to 1 L of the solvent contained in the cleaning composition B.
In addition, the content of the organic carboxylic acid compound in the cleaning composition B is preferably 0.0016% by mass or more, more preferably 0.0016% by mass or more, and 0.1600% by mass or more of the cleaning composition B. More preferably, 1.6000 mass% or more is still more preferable. The content of the organic carboxylic acid compound in the cleaning composition B of the present invention is preferably 10.0 mass% or less of the cleaning composition B, more preferably 8.0 mass% or less, and 5.0 mass% or less. Is more preferable, and 4.0% by mass or less is further preferable.
The cleaning composition B may include only one type of organic carboxylic acid compound, or may include two or more types. When two or more kinds are contained, the total amount is preferably within the above range.

<<solvent>>
The solvent contained in the cleaning composition B is at least one of water and a water-soluble solvent, and is preferably water.
The water-soluble solvent means an organic compound having a water solubility of 1000 mg/L or more, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, tert-butyl alcohol, and ethylene glycol.

The content of the solvent in the cleaning composition B is preferably 50.0000 to 99.9999% by mass of the cleaning composition B, and more preferably 99.0000 to 99.9990% by mass.
The cleaning composition B of the present invention may contain only one type of solvent, or may contain two or more types of solvents. When two or more kinds are contained, the total amount is preferably within the above range.
In the cleaning composition B, the mass ratio of the organic carboxylic acid compound and the solvent is preferably 0.0001:99.9999 to 50:50, and 0.0010:99.99990 to 10:90. It is more preferable that it is 0.0100:99.9900 to 1.0000:99.0000. By setting it as such a range, the removal property of the residue originating in cleaning composition A is improved more effectively.

<<other ingredients>>
The cleaning composition B may contain the above-mentioned organic carboxylic acid compound and components other than the solvent. Specifically, the other components described in the detergent composition A can be used.

<<Preparation of Cleaning Agent Composition B>>
The detergent composition B is preferably prepared by mixing the respective components of the detergent composition B and then filtering. For filtration, it is preferable to use a filter having a pore size of 0.003 to 10 μm. By performing the filtration, it is possible to reduce the contamination of the substrate surface due to the impurities derived from the cleaning composition B. The filter is preferably made of polytetrafluoroethylene.

As a container for the cleaning composition B used in the present invention, a conventionally known container can be used. In addition, as a storage container, a multi-layer bottle in which the inner wall of the container is composed of 6 kinds of 6 layers of resin, or 6 kinds of resin of 7 layers structure is used for the purpose of suppressing the mixing of impurities into raw materials and compositions. It is also preferable to use a bottle. As such a container, for example, the container described in JP-A-2015-123351 can be cited.

<Cleaning composition A and cleaning composition B>
In the present invention, the difference between the acid dissociation constant pKa of the organic carboxylic acid compound and the acid dissociation constant pKa of the organic acid is preferably 2 to 10. By setting it as such a range, the effect of this invention is exhibited more effectively.
Further, in the present invention, it is preferable that the equivalent of the acid contained in the detergent composition B is 2 to 100 times the equivalent of the acid contained in the detergent composition A. By setting it as such a range, the effect of this invention is exhibited more effectively.

<Rinse composition C>
The kit of the present invention may further include a rinse composition C.
The rinse composition includes at least one of water and alcohol. As the alcohol, an alcohol composed of a linear or branched alkyl group having 1 to 10 carbon atoms and a hydroxyl group is preferable.
Specific examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, tert-butyl alcohol and ethylene glycol.

<<other ingredients>>
The rinse composition C may include components other than at least one of water and alcohol. Specifically, the other components described in the detergent composition A can be used.

<<Preparation of rinse composition C>>
The rinse composition C is preferably prepared by mixing the components of the rinse composition C and then filtering. For filtration, it is preferable to use a filter having a pore size of 0.003 to 10 μm. By performing the filtration, the removability of the residues derived from the cleaning compositions A and B tends to be further improved. The filter is preferably made of polytetrafluoroethylene.

Method for Manufacturing Semiconductor Device A method for manufacturing a semiconductor device according to the present invention comprises a step of cleaning a substrate having a silicone compound on its surface with a cleaning composition A, the above cleaned substrate, and a cleaning composition B. The cleaning composition A is an organic acid, and the acid group contained in the organic acid contains at least one organic acid containing a sulfur atom or a phosphorus atom, and an organic solvent. The cleaning composition B contains an organic carboxylic acid compound and at least one of water and a water-soluble solvent. The method for manufacturing a semiconductor device of the present invention preferably includes a step of rinsing with a rinse composition C containing at least one of water and alcohol after the step of cleaning with the cleaning composition B. ..

In addition, a temporary adhesive layer formed from a temporary adhesive on the substrate, at least a portion of the temporary adhesive layer is washed with the organic acid, and the temporary adhesive is formed of the silicone compound and the silicone compound. It is preferred to include at least one of the precursors. Therefore, the substrate having a silicon-containing compound on its surface is, for example, a substrate to be processed or a carrier substrate.
As a mode of removing the temporary adhesive containing the silicon-containing compound, the temporary adhesive layer on the substrate to be processed is removed, and the excess temporary adhesive in the step of temporarily bonding the substrate to be processed and the carrier substrate is removed. And that the temporary adhesive remaining on the carrier substrate is removed for reuse of the carrier substrate.

In the method for manufacturing a semiconductor device of the present invention, the temporary adhesive is used for temporary adhesion between the carrier substrate and the substrate to be processed, and the cleaning agent composition A is used to remove a part or all of the temporary adhesive, It is preferable to wash the substrate and then further wash the substrate to be processed with the cleaning composition B. The temporary adhesive removed by using the cleaning composition A is a temporary adhesive or a temporary adhesive layer remaining on the substrate to be processed after peeling the carrier substrate, or a carrier substrate, and a temporary adhesive layer. It is preferably a temporary adhesive that remains on the substrate to be processed after peeling off. Peel-off of the temporary adhesive layer is preferably performed at a temperature of 40° C. or lower, more preferably 10 to 40° C. The peeling off of the temporary adhesive layer is preferably manual peeling or mechanical peeling.
Examples of the substrate to be processed include a device wafer in which a substrate is made of silicon, glass, a compound semiconductor such as SiC, GaN, or GaAs, or a mold resin, and a structure is formed on the surface and inside thereof. Particularly, in the present invention, the surface of the substrate to be processed preferably has a metal layer, more preferably a copper layer, as a structure. In the method for manufacturing a semiconductor device of the present invention, the sulfur atom residue and phosphorus atom residue derived from the cleaning composition A, which remain on the surface of the copper layer, are effectively removed by using the cleaning composition B. It will be possible.
Furthermore, the semiconductor element manufacturing method of the present invention is preferably used in an aspect in which a copper layer is provided on the surface of a substrate and solder balls are provided on the surface of the copper layer. When the solder balls are provided, it is highly valuable to use the method for manufacturing a semiconductor device of the present invention in terms of the effect of removing impurities and enhancing the adhesion between the solder balls and the copper layer.
In addition, due to the structure of the semiconductor, there may be uneven steps in the wiring layer including the copper layer. In particular, the residue containing sulfur atoms and phosphorus atoms derived from the cleaning agent composition A is likely to remain on the bottom surface of the copper pad having a depth of 5 to 50 μm, which is formed in the shape of a circular basin having a diameter of 400 to 800 μm.

Further, it is preferable that the step of washing with the above-mentioned detergent composition A and the step of washing with the above-mentioned detergent composition B are performed by a single-wafer method. Furthermore, it is preferable that spin-drying and washing are performed in a single-wafer manner also in the step of rinsing.
In addition, it is preferable to include a drying step after the step of cleaning with the cleaning composition A and after the step of cleaning with the cleaning composition B, respectively. As described above, by providing the drying step after each washing step, the effects of the present invention are more effectively exhibited. Furthermore, it is preferable to include a drying step even after the step of rinsing.
Drying after cleaning with the cleaning composition A is preferably performed at 80 to 200°C. The drying time is preferably 30 to 180 seconds. It is preferable to wash with the detergent composition B within 180 seconds after the drying. Drying after cleaning with the cleaning composition B is preferably performed at 80 to 200°C. The drying time is preferably 30 to 180 seconds. Rinsing with the rinse composition C is preferably performed within 30 seconds after the drying. It is preferable to start the drying within 3 seconds after applying the rinse treatment. Drying after the rinse treatment using the rinse composition C is preferably performed at 80 to 200°C. The drying time is preferably 30 to 180 seconds.

In the method for manufacturing a semiconductor device of the present invention, the time from the start of the step of cleaning the single substrate with the cleaning composition A to the end of the step of cleaning with the cleaning composition B is completed. , 30 to 540 seconds are preferable, and 60 to 240 seconds are more preferable. By setting such time, it is possible to effectively remove the temporary adhesive and the residue of the silicon-containing compound in one step. Furthermore, the time from the start of cleaning with the cleaning composition A to the end of cleaning with the rinse composition C is preferably 60 to 660 seconds, and preferably 90 to 540 seconds. More preferable.
Furthermore, the time A from the start of the step of cleaning with the cleaning composition A to the start of the step of cleaning with the cleaning composition B, and the step of cleaning with the cleaning composition B. The ratio of the time B from the start of step 1 to the start of the step of washing with the rinse composition C is preferably 1:10 to 10:1, and more preferably 4:6 to 6:4. preferable. By setting such a ratio, it is possible to further homogenize the cleaning effect for each substrate in the single-wafer processing.

Regarding the cleaning composition A, the cleaning composition B, the rinse composition C, and the temporary adhesive in the method for manufacturing a semiconductor device of the present invention, the cleaning composition A, the cleaning composition B, and the rinse described above, respectively. It has the same meaning as the composition C and the temporary adhesive. Therefore, the kit of the present invention can be preferably used in the method of manufacturing a semiconductor device of the present invention.
In addition, regarding the manufacturing method of the semiconductor element, in particular, regarding the method of temporary adhesion, the description of paragraphs 0074 to 0099 and FIGS. ..

Method for Cleaning Semiconductor Device Substrate A method for cleaning a semiconductor device substrate according to the present invention comprises a step of cleaning a substrate having a silicone compound on its surface with a cleaning composition A, and further cleaning the cleaned substrate. And a cleaning step using the cleaning agent composition B, wherein the cleaning agent composition A is an organic acid, and the acid group contained in the organic acid contains at least one organic acid containing a sulfur atom or a phosphorus atom. And an organic solvent, and the cleaning composition B contains an organic carboxylic acid compound and at least one of water and a water-soluble solvent.
The method for cleaning a substrate of a semiconductor device of the present invention includes, after the step of cleaning with the cleaning composition B, a rinse treatment with a rinse composition C containing at least one of water and alcohol. Is preferred.

Regarding the cleaning composition A, the cleaning composition B, the rinsing composition C, and the temporary adhesive in the method for cleaning a substrate of a semiconductor device of the present invention, the above-mentioned cleaning composition A and cleaning composition B, respectively. , Rinse composition C, and temporary adhesive. Therefore, the kit of the present invention can be preferably used in the method for cleaning a substrate of a semiconductor device of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded. In addition, "part" and "%" are based on mass unless otherwise specified.

<Preparation of temporary adhesive>
As shown in Table 1 below, each component of the temporary adhesive was mixed to form a uniform solution, which was then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm to prepare a temporary adhesive. ..

Details of the compounds used are as follows.
<<Elastomer>>
P-1: Septon 4033 (Kuraray Co., Ltd., polystyrene elastomer)
P-2: Septon 2104 (Kuraray Co., Ltd., polystyrene elastomer)
P-3: Septon 8004 (Kuraray Co., Ltd., polystyrene elastomer)

<<Silicon-containing compound>>
Si-1: TSF4446 (polyether-modified organopolysiloxane manufactured by Momentive Performance Materials Japan LLC)
Si-2: TSF4445 (polyether-modified organopolysiloxane manufactured by Momentive Performance Materials Japan LLC)
Si-3: Silwet L-7605 (polyether-modified organopolysiloxane manufactured by Momentive Performance Materials Japan LLC)
Si-4: KF-6017 (Shin-Etsu Chemical Co., Ltd., polyether modified organopolysiloxane)
Si-5: Silwet L-7200 (manufactured by Momentive Performance Materials Japan LLC, polyether modified organopolysiloxane)
Si-6: KP-323 (Shin-Etsu Chemical Co., Ltd., silicone single substance)
Si-7: Fluorine atom-containing silane coupling agent (precursor of silicone compound) (Tokyo Chemical Industry Co., Ltd., triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane)

<<Other additives>>
A-1: Irganox1010 (manufactured by BASF Japan Ltd.)
A-2: Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.)

<< organic solvent >>
S-1: 1,3,5-trimethylbenzene (mesitylene, manufactured by Toyo Gosei Co., Ltd.)

<Preparation of detergent composition A>
As shown in Tables 2 and 3 below, after the respective components of the detergent composition A were mixed to form a uniform solution, the detergent was filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm. Composition A was prepared.

<Preparation of detergent composition B>
As shown in Tables 4 and 5 below, the respective components of the detergent composition B were mixed to form a uniform solution, which was then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm to remove the detergent. Composition B was prepared.

<Preparation of rinse composition C>
As shown in Table 6 below, the rinse composition C was prepared by filtering the components of the rinse composition C using a filter made of polytetrafluoroethylene having a pore size of 0.2 μm.

Evaluation method A disk-shaped silicon wafer having a diameter of 12 inches (1 inch is 2.54 cm) was used as a carrier substrate, and the surface thereof was coated with the above-mentioned temporary adhesive (EVG Group Japan Co., Ltd., EVG). 101) was used to form a layer. A temporary adhesive layer was formed on the surface of the carrier substrate by heating at 100° C. for 3 minutes and then at 180° C. for 3 minutes using a hot plate (EVG 105 manufactured by Evigroup Japan Ltd.). A laminate A was obtained. The thickness of the temporary adhesive layer was 60 μm.
The carrier substrate of the obtained laminated body A was set to the lower side and set in a coating device (EVG 101, manufactured by Evigroup Japan KK), and the rotation speed was accelerated from 1250 rpm to 2000 rpm at an acceleration of 50 rpm/s. Meanwhile, the bevel portion of the carrier substrate was subjected to BSR (Back Side Rince) treatment with a mesitylene flow rate of 20 mL/min to wash the temporary adhesive layer attached to the bevel portion.

A 10-nm-thick titanium layer and a 50-nm-thick copper layer were formed in this order by sputtering on the surface of a disk-shaped silicon wafer having a diameter of 12 inches to obtain a substrate to be processed.
The laminated body A obtained above and the substrate to be processed obtained above were subjected to a pressure of 1 Pa, a temperature of 200° C., and a pressure of 0.3 MPa using a wafer bonding apparatus (EVG 540 manufactured by Evigroup Japan Ltd.). Thermocompression bonding was performed for 1 minute under pressure to obtain a laminated body B. During the pressure bonding, the copper layer and the temporary adhesive layer were placed in contact with each other.

The back surface (the side not provided with the temporary adhesive layer) of the substrate to be processed of the laminate B obtained above was polished to a thickness of 40 μm using a back grinder (manufactured by Disco Corporation, DFG8540), and back-ground. A processed (thinned) laminated body C was obtained.

The back-grinded surface of the laminate C was set to the lower side, and the lower silicon wafer was fixed to the center of the dicing tape together with the dicing frame using a dicing tape mounter. Then, using a wafer debonder device (Tokyo Electron Ltd., Synapse Z), at 25° C., the upper silicon wafer is pulled vertically to the lower silicon wafer at a speed of 3 mm/min. A laminate D including a temporary adhesive layer (or a residue derived from the temporary adhesive) and a substrate to be processed was obtained. The upper silicon wafer could be peeled off without the lower silicon wafer cracking.

The cleaning composition A is supplied to the layered product D obtained by performing the above-mentioned peeling using a wafer debonder device (Tokyo Electron Ltd., Synapse Z) while rotating the substrate to be processed of the layered product D. It was washed. The processed substrate after cleaning was heated at 110° C. for 2 minutes to be dried.

<Surface observation (carbon atom residue and silicon atom residue)>
The surface of the substrate to be processed, which was washed with the cleaning composition A and dried, was used a Quantera SXM apparatus (manufactured by ULVAC-PHI Co., Ltd.) as a monochromatic Al-Kα ray ( The energy value was 1486.6 eV, the output was 25 W, the voltage was 15 kV, and the beam diameter was 200 μm. The measurement area is 1400×700 μm ² , the measurement conditions are Pass Energy=140 eV, the step size=0.1 eV, and the number of integration is 1 to 3 times, and the existence ratio of carbon atoms and silicon atoms (carbon atom residue, silicon atom residue) The evaluation was performed according to the following criteria.
<<carbon atom residue>>
A: Carbon atom is less than 40 mol% B: Carbon atom is 40 mol% or more and less than 50 mol% C: Carbon atom is 50 mol% or more and less than 60 mol% D: Carbon atom is 60 mol% or more <<Silicon atom residue>>
A: Silicon atom is less than 0.1 mol% B: Silicon atom is 0.1 mol% or more and less than 1 mol% C: Silicon atom is 1 mol% or more and less than 3 mol% D: Silicon atom is 3 mol% or more

The surface of the substrate to be processed, which has been cleaned using the cleaning composition A and dried, is cleaned using a wafer debonder device (Tokyo Electron Ltd., Synapse Z) while rotating the substrate to be processed. It was cleaned by supplying the agent composition B. The processed substrate after cleaning was spin-dried.
Next, the surface of the substrate to be processed, which has been washed with the cleaning composition B and dried, is rotated by the laminate D using a wafer debonder device (Tokyo Electron KK, Synapse Z). While rinsing, the rinse composition C was supplied. It was dried by heating at 100°C for 1 minute.

<Surface observation (sulfur atom residue and phosphorus atom residue)>
Using a Quantera SXM apparatus (manufactured by ULVAC-PHI Co., Ltd.), the surface of the substrate to be processed after cleaning with the cleaning composition B was used as an X-ray source, and monochromatic Al-Kα rays (energy value: 1486.6 eV). , Output: 25 W, voltage: 15 kV, beam diameter 200 μm). The measurement area is 1400×700 μm ² , the measurement conditions are Pass Energy=140 eV, the step size=0.1 eV, and the number of integration is 1 to 3 times, and the existence ratios of sulfur atom and phosphorus atom (sulfur atom residue, phosphorus atom residue) The evaluation was performed according to the following criteria.
<<Sulfur atom residue>>
A: Sulfur atom is less than 0.1 mol% B: Sulfur atom is 0.1 mol% or more and less than 1 mol% C: Sulfur atom is 1 mol% or more and less than 3 mol% D: Sulfur atom is 3 mol% or more <<Phosphorus atom residue>>
A: Sulfur atom is less than 0.1 mol% B: Sulfur atom is 0.1 mol% or more and less than 1 mol% C: Sulfur atom is 1 mol% or more and less than 3 mol% D: Sulfur atom is 3 mol% or more

<Improved copper discoloration>
A substrate having a copper layer with a thickness of 50 nm provided on the surface of a disk-shaped silicon wafer having a diameter of 12 inches by sputtering was produced. Using a wafer debonder device (Synapse Z, manufactured by Tokyo Electron Ltd.), the cleaning composition A was supplied while rotating the copper layer of the silicon wafer. The processed substrate after cleaning was heated at 110° C. for 2 minutes to be dried. Then, cleaning was performed by supplying the cleaning composition B. Next, the substrate to be processed after cleaning was rinsed by supplying the rinse composition C. It was dried by heating at 100°C for 1 minute. The time from the start of the step of cleaning with the cleaning composition A to the start of the step of cleaning with the cleaning composition B was 200 seconds. The time from the start of the step of cleaning with the cleaning composition B to the start of the step of cleaning with the rinse composition C was 140 seconds. Furthermore, the time from the start of cleaning with cleaning composition A to the end of cleaning with rinse composition C was 460 seconds.
Then, it was left in a clean room at room temperature of 23° C. and a relative humidity of 55% for 48 hours, visually observed, and evaluated as follows.
A: No discoloration of the copper layer was observed.
B: The copper layer was slightly discolored to light brown.
C: The copper layer had a brown discoloration.

The results are shown in Tables 7 and 8 below.

As is clear from the above results, when the kit of the present invention was used, neither carbon atom residue, silicon atom residue, sulfur atom residue nor phosphorus atom residue was observed. Further, discoloration of the copper layer was not recognized.
On the other hand, when the cleaning composition B was not used (Comparative Examples 1 to 11), neither carbon atom residue nor silicon atom residue was observed, but sulfur atom residue or phosphorus atom residue was observed. Also, some discoloration of the copper layer was observed.
On the other hand, when the cleaning composition A was not used (Comparative Examples 12 to 23), carbon atom residues and silicon atom residues were observed. Also, the copper layer turned brown.
Furthermore, when other detergent compositions were used instead of the detergent composition A (Comparative Examples 24 and 25), any residue of carbon atom residue, silicon atom residue, sulfur atom residue and phosphorus atom residue was observed. Was given. Further, discoloration of the copper layer was also recognized.
On the other hand, when other detergent compositions were used instead of the detergent composition B (Comparative Examples 26 to 28), residues of sulfur atom residues and phosphorus atom residues were observed. Furthermore, some discoloration of the copper layer was observed.

The substrate obtained by the method of the present invention is free of carbon atom residues, silicon atom residues, sulfur atom residues and phosphorus atom residues, and the copper layer is not discolored. Therefore, it can be preferably used as a substrate for semiconductor devices.

Claims (29)

A temporary adhesive containing at least one silicon-containing compound selected from the group consisting of silicone compounds and precursors of silicone compounds;
A cleaning composition A, which is an organic acid, comprising at least one kind of organic acid in which an acid group contained in the organic acid contains a sulfur atom or a phosphorus atom, and an organic solvent.
A kit comprising a detergent composition B containing an organic carboxylic acid compound and at least one of water and a water-soluble solvent. The kit according to claim 1, wherein the organic acid contains at least one organic acid selected from the group consisting of organic sulfonic acids, organic phosphoric acids, and organic phosphonic acids. The kit of claim 1, wherein the silicon-containing compound comprises silicone oil. The kit according to any one of claims 1 to 3, wherein the silicon-containing compound comprises a polyether-modified silicone. The kit according to any one of claims 1 to 4, wherein the content of the silicon-containing compound in the temporary adhesive is 0.001 to 1.0% by mass. The kit according to claim 1, wherein the temporary adhesive contains an elastomer. The kit according to claim 6, wherein the elastomer is a polystyrene elastomer. The kit according to any one of claims 1 to 7, wherein pKa, which is an acid dissociation constant of the organic acid, is -4 to 5. 9. The organic acid according to claim 1, wherein the organic acid is selected from the group consisting of alkylsulfonic acid, aromatic sulfonic acid, alkylphosphoric acid, aromatic phosphoric acid, alkylphosphonic acid and aromatic phosphonic acid. The described kit. The kit according to any one of claims 1 to 9, wherein the organic solvent contained in the cleaning composition A contains an aromatic hydrocarbon solvent having an alkyl group. The kit according to claim 10, wherein the aromatic hydrocarbon solvent having an alkyl group is a solvent having a benzene ring and 1 to 3 alkyl groups having 1 to 10 carbon atoms. The kit according to any one of claims 1 to 11, wherein a mass ratio of the organic acid and the organic solvent in the cleaning composition A is 0.0001:99.9999 to 50:50. The kit according to claim 1, wherein the organic carboxylic acid compound is selected from the group consisting of saturated fatty acids, unsaturated fatty acids, hydroxy acids and aromatic carboxylic acids. A value of P, which is a 1-octanol/water partition coefficient representing the ratio of the equilibrium concentrations of the organic carboxylic acid compound in 1-octanol and in water, in the form of logarithm logP with respect to the base 10 is -5 to 6, The kit according to any one of claims 1 to 13. The kit according to any one of claims 1 to 14, wherein the solvent contained in the detergent composition B contains water. The kit according to any one of claims 1 to 15, wherein pKa, which is an acid dissociation constant of the organic carboxylic acid compound, is 1 to 7. The kit according to any one of claims 1 to 16, wherein a mass ratio of the organic carboxylic acid compound and the solvent in the cleaning composition B is 0.0001:99.9999 to 50:50. The kit according to any one of claims 1 to 17, further comprising a rinse composition C containing at least one of water and alcohol. A step of cleaning a substrate having a silicone compound on its surface with a cleaning composition A; and a step of cleaning the cleaned substrate with a cleaning composition B,
The detergent composition A is an organic acid, and the acid group contained in the organic acid contains at least one organic acid containing a sulfur atom or a phosphorus atom, and an organic solvent,
The detergent composition B contains an organic carboxylic acid compound and at least one of water and a water-soluble solvent,
Manufacturing method of semiconductor device. 20. The method for manufacturing a semiconductor device according to claim 19, wherein the organic acid contains at least one organic acid selected from the group consisting of organic sulfonic acids, organic phosphoric acids, and organic phosphonic acids. A temporary adhesive layer formed of a temporary adhesive is provided on the substrate, at least a part of the temporary adhesive layer is washed with the organic acid, and the temporary adhesive is the silicone compound and a precursor of the silicone compound. 21. The method for manufacturing a semiconductor device according to claim 19, which comprises at least one kind of body. 22. The semiconductor device according to claim 19, wherein the step of cleaning with the cleaning composition A and the step of cleaning with the cleaning composition B are single-wafer cleaning. Production method. The method according to any one of claims 19 to 22, including a drying step after the step of cleaning with the cleaning composition A and after the step of cleaning with the cleaning composition B, respectively. Manufacturing method of semiconductor device. The time from the start of the step of cleaning the single substrate with the cleaning composition A to the end of the step of cleaning with the cleaning composition B is 30 to 300 seconds. 24. The method for manufacturing a semiconductor device according to any one of 19 to 23. The method according to any one of claims 19 to 24, which comprises a step of rinsing with a rinse composition C containing at least one of water and alcohol after the step of cleaning with the detergent composition B. Of manufacturing a semiconductor device of. The method of manufacturing a semiconductor device according to any one of claims 19 to 25, wherein the kit according to any one of claims 1 to 18 is used. A step of cleaning a substrate having a silicone compound on its surface with a cleaning composition A; and a step of cleaning the cleaned substrate with a cleaning composition B,
The detergent composition A is an organic acid, and the acid group contained in the organic acid contains at least one organic acid containing a sulfur atom or a phosphorus atom, and an organic solvent,
The detergent composition B contains an organic carboxylic acid compound and at least one of water and a water-soluble solvent,
A method for cleaning a substrate of a semiconductor device. 28. The cleaning of a substrate of a semiconductor device according to claim 27, comprising a rinsing treatment with a rinsing composition C containing at least one of water and alcohol after the step of cleaning with the cleaning composition B. Method. A method for cleaning a substrate of a semiconductor device according to claim 27 or 28, wherein the kit according to any one of claims 1 to 18 is used.