TW201831667A - Kit, method for producing semiconductor element, and method for cleaning substrate of semiconductor element - Google Patents

Abstract

Provided are: a kit which comprises a temporary adhesive containing a silicone compound and a cleaning agent for the temporary adhesive, and which is capable of adequately removing various residues; a method for producing a semiconductor element; and a method for cleaning a substrate of a semiconductor element. A kit which comprises: a cleaning agent composition A that contains a temporary adhesive which contains at least one silicon-containing compound selected from the group consisting of silicone compounds and precursors of silicone compounds, at least one organic acid which has an acid group containing a sulfur atom or a phosphorus atom, and an organic solvent; and a cleaning agent composition B that contains an organic carboxylic acid compound and at least one of water and a water-soluble solvent.

Description

Kit, method of manufacturing semiconductor element, and method of cleaning substrate of semiconductor element

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

Research into cleaning agent compositions for removing temporary adhesives has been conducted to date. For example, Patent Document 1 discloses a composition for peeling off, which is a composition for peeling off a binder containing a hydrogenated styrene-based elastomer, and the composition for peeling is characterized by containing a cyclopentene solvent. At least one of a nonionic surfactant and a lanthanoid surfactant. Further, Patent Document 2 discloses a composition comprising A) a water-soluble organic solvent, B) a sulfonic acid or a salt corresponding thereto, and C) water. Further, Patent Document 3 discloses that a cleaning liquid composition used as a semiconductor substrate having a contact angle of 70 degrees or more on a surface when water is dripped, contains an aliphatic polycarboxylic acid and has a hydroxyl group and/or an ether group. The organic solvent is a cleaning liquid composition having a contact angle of 40 degrees or less when dropped onto the semiconductor substrate. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2006-307725 (Patent Document 3) JP-A-2004-307725

However, as a result of research by the inventors of the present invention, it has been found that when a temporary binder containing a ruthenium compound or a ruthenium compound (hereinafter sometimes simply referred to as "ruthenium-containing compound") is washed with the above-mentioned detergent composition, it is known. This results in the residue of a carbon atom residue or a ruthenium atom residue derived from a temporary binder. Therefore, the applicant has studied a method of removing a composition containing an organic sulfonic acid and an organic solvent. However, the temporary binder containing a ruthenium-containing compound is washed with a composition containing an organic sulfonic acid and an organic solvent, and it is found that a residue of a sulfur atom derived from an organic sulfonic acid remains. When the sulfur atom residue has a metal such as copper on a substrate to be processed which is a temporary adhesion, and the surface of the metal has a large amount of irregularities, the acid component may cause corrosion of the metal surface or disconnection of the metal wiring. The present invention has an object of solving the problem, and an object of the invention is to provide a kit, a method for producing a semiconductor device, and a method for cleaning a substrate of a semiconductor device, the kit comprising a temporary binder containing a bismuth compound and a cleaning comprising the temporary binder An agent capable of properly washing various residues.

According to the results of the study by the present inventors, it has been found that a temporary binder containing a ruthenium-containing compound is washed with a detergent composition containing an organic sulfonic acid or the like, and further, a detergent composition containing an organic carboxylic acid and water is further used. The cleaning is carried out to effectively remove the residue derived from the cerium-containing compound, and further, the residue derived from the 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 mechanism <1>, and it is preferable to solve the above problem by <2> to <29>. <1> A kit comprising: a temporary binder containing at least one selected from the group consisting of a ruthenium compound and a precursor of a ruthenium compound; and a detergent composition A containing an organic acid and an organic compound The solvent is at least one of an organic acid containing a sulfur atom or a phosphorus atom in the acid group contained in the organic acid, and the cleaning agent composition B contains at least one of an organic carboxylic acid compound and at least water and a water-soluble solvent. <2> The kit according to <1>, wherein the organic acid contains at least one selected from the group consisting of organic sulfonic acids, organic phosphoric acids, and organic phosphonic acids. <3> The kit according to <1>, wherein the above-mentioned hydrazine-containing compound contains eucalyptus oil. The kit according to any one of <1> to <3> wherein the ruthenium-containing compound contains a polyether-modified oxime. The kit according to any one of <1> to <4> wherein the content of the cerium-containing compound in the temporary binder is 0.001 to 1.0% by mass. The kit according to any one of <1> to <5> wherein the temporary adhesive contains an elastomer. <7> The kit according to <6>, wherein the elastomer is a polystyrene elastomer. The kit according to any one of <1> to <7> wherein the organic acid has an acid dissociation constant pKa of -4 to 5. The kit according to any one of <1> to <8> wherein the organic acid is selected from the group consisting of an alkylsulfonic acid, an aromatic sulfonic acid, an alkylphosphonic acid, an aromatic phosphoric acid, an alkylphosphonic acid, and A group of aromatic phosphonic acids. The kit according to any one of the above aspects, wherein the organic solvent contained in the cleaning agent composition A contains an aromatic hydrocarbon solvent having an alkyl group. <11> The kit according to <10>, wherein the aromatic hydrocarbon solvent having the alkyl group is a solvent of a benzene ring and 1 to 3 alkyl groups having 1 to 10 carbon atoms. The kit according to any one of <1> to <11> wherein the mass ratio of the organic acid to the organic solvent in the cleaning agent composition A is 0.0001:99.9999 to 50:50. The kit according to any one of <1> to <12> wherein the organic carboxylic acid compound is selected from the group consisting of a saturated fatty acid, an unsaturated fatty acid, a hydroxy acid, and an aromatic carboxylic acid. The kit according to any one of <1> to <13> wherein the ratio of the equilibrium concentration of the 1-octanol in the above-mentioned organic carboxylic acid compound to water is 1-octanol/water distribution. The value of the coefficient P is expressed in the form of a logarithm logP relative to the base of 10 to -5 to 6. The kit according to any one of <1> to <14> wherein the solvent contained in the cleaning agent composition B contains water. The kit according to any one of <1> to <15> wherein the organic carboxylic acid compound has an acid dissociation constant pKa of from 1 to 7. The kit according to any one of <1> to <16> wherein the mass ratio of the organic carboxylic acid compound to the solvent in the cleaning agent composition B is 0.0001:99.9999 to 50:50. The kit according to any one of <1> to <17>, further comprising a rinse composition C containing at least one of water and alcohol. <19> A method of manufacturing a semiconductor device, comprising: a process of cleaning a substrate having a ruthenium compound on a surface using a cleaning agent composition A; and a process of further cleaning the cleaned substrate using a cleaning agent composition B, the cleaning agent composition The substance A contains: an organic acid containing at least one of an organic acid containing a sulfur atom or a phosphorus atom in an acid group contained in the organic acid; and an organic solvent, wherein the cleaning agent composition B contains an organic carboxylic acid compound, at least water and One of the water-soluble solvents. The method for producing a semiconductor device according to the above aspect, wherein the organic acid contains at least one selected from the group consisting of organic sulfonic acids, organic phosphoric acids, and organic phosphonic acids. The method of manufacturing a semiconductor device according to the above aspect, wherein the substrate comprises a temporary adhesive layer formed of a temporary adhesive, and at least a portion of the temporary adhesive layer is cleaned by the organic acid. Further, the temporary binder contains at least one of the above-mentioned hydrazine compound and a precursor of the above hydrazine compound. The method for producing a semiconductor device according to any one of <19> to <21> wherein the cleaning process using the cleaning agent composition A and the cleaning process using the cleaning agent composition B are performed in a single piece manner. Cleaning. The method for producing a semiconductor device according to any one of <19> to <22> wherein after the cleaning process using the cleaning agent composition A and after the cleaning process using the cleaning agent composition B Each includes a drying process. The method of manufacturing a semiconductor device according to any one of <19>, wherein one of the substrates is cleaned from a process of cleaning using the cleaning agent composition A to cleaning using the cleaning agent composition B. The time until the end of the process is 30 to 300 seconds. The method for producing a semiconductor device according to any one of <19> to <24> which, after the cleaning process using the cleaning agent composition B described above, is performed using at least one of water and alcohol. Composition C is subjected to a process of rinsing. The method for producing a semiconductor device according to any one of the above aspects of the present invention, wherein the kit according to any one of <1> to <18> is used. <27> A method for cleaning a substrate of a semiconductor device, comprising: a process of cleaning a substrate having a ruthenium compound on the surface using a cleaning agent composition A; and further cleaning the process of the cleaned substrate using the cleaning agent composition B, the cleaning agent The composition A contains at least one organic acid, an acid acid contained in the organic acid containing a sulfur atom or a phosphorus atom, and an organic solvent. The cleaning agent composition B contains an organic carboxylic acid compound, at least water and water. One of the solvents. <28> The method for cleaning a substrate of a semiconductor device according to <27>, which comprises rinsing with a rinsing composition C containing at least one of water and alcohol after the cleaning process using the cleaning agent composition B Process of processing. The method of cleaning the substrate of the semiconductor device according to the <27> or <28>, wherein the kit according to any one of <1> to <18> is used. [Effect of the invention]

According to the present invention, it is possible to provide a kit, a method of manufacturing a semiconductor device, and a method of cleaning a substrate of a semiconductor element, the kit comprising a temporary binder containing a cerium-containing compound and a cleaning agent of the temporary binder, which can be appropriately cleaned Various residues.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, "to" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit. In the labeling of the group (atomic group) in the present specification, the unlabeled and unsubstituted labeling group includes a group having no substituent and a substituent. For example, "alkyl" 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" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acrylic acid" means propylene oxime and methacrylic acid. Hey. In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-converted values measured by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by TOSOH CORPORATION) and using TSKgel Super AWM-H (TOSOH) as a column. Made of CORPORATION, inner diameter (ID) 6.0 mm × 15.0 cm), 10 mmol/L lithium bromide NMP (N-methylpyrrolidone) solution was used as the eluent.

Kit The kit of the present invention is characterized in that it comprises: a temporary binder containing at least one selected from the group consisting of a ruthenium compound and a precursor of a ruthenium compound; and a detergent composition A containing An organic acid and an organic solvent, at least one of an organic acid containing a sulfur atom or a phosphorus atom in an acid group contained in the organic acid (hereinafter sometimes referred to simply as "organic acid"); and a cleaning agent composition B containing an organic carboxylic acid One of an acid compound, at least water, and a water-soluble solvent. By using such a composition, various residues can be effectively removed. In the semiconductor process, the residue derived from the ruthenium-containing compound on the metal causes a cause of peeling of the insulating layer and a cause of poor adhesion of the solder, and therefore it is required to be appropriately removed. As such a cleaning agent, it is recommended to use a cleaning agent composition containing the above organic acid. However, when the surface of the metal of the substrate to be processed has irregularities, sulfur and phosphorus derived from the cleaning agent composition containing the organic acid are likely to remain in the concave portion. If sulfur and phosphorus remain in the concave portion, the metal surface is corroded, the wiring is broken, and the like, and therefore it is necessary to immediately wash the sulfur and phosphorus components. In the present invention, the detergent composition A containing an organic acid and an organic solvent is used to appropriately remove the residue derived from the ruthenium-containing compound, and further, the detergent composition B containing an organic carboxylic acid compound and water is appropriately removed from the organic component. The residue of acid has been used to solve the above problems and has been successful. Further, by using the kit of the present invention, discoloration of the copper layer can be effectively suppressed. The reason why the discoloration of the copper layer is inferred is that the surface of the copper layer is protected by the coordination of the organic carboxylic acid compound. The kit of the present invention may further comprise a rinse composition C containing at least one of water and alcohol. Hereinafter, the kit of the present invention will be described in detail.

<Temperary binder> <<Precursor of ruthenium compound or ruthenium compound>> The temporary binder used in the present invention contains at least one kind of ruthenium-containing compound selected from the group consisting of ruthenium compounds and precursors of ruthenium compounds. The ruthenium-containing compound functions as a release agent, and the temporary adhesive can be easily removed from the substrate to be processed. As the cerium-containing compound, eucalyptus oil is preferred. Oyster sauce refers to a liquid compound at 25 °C. Further, the ruthenium-containing compound does not preferably contain a reactive group such as a polymerizable group. The ruthenium-containing compound is preferably a polyether modified oxime.

The polyether modified hydrazine 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 means the mole % of the methylene oxide contained in the polyether structure in the polyether modified oxime, EO system It refers to the mole % of ethylene oxide contained in the polyether structure in the polyether modified oxime, and the mole % of the alkylene oxide contained in the polyether structure in the AO-based polyether modified oxime. The ratio represented by the above formula (A) is preferably 90% or more, more preferably 95% or more, more preferably 98% or more, still more preferably 99% or more, and still more preferably 100%.

The weight average molecular weight of the polyether modified ruthenium is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, still more preferably from 2,000 to 40,000.

In the present invention, the polyether modified oxime is preferably a polyether modified ruthenium, and even if the polyether modified ruthenium is heated at a temperature of 20 ° C/min from 20 ° C to 280 ° C under a nitrogen gas flow rate of 60 mL/min. The temperature was raised, and the mass reduction rate at the temperature of 280 ° C for 30 minutes was 50% by mass or less. By using such a compound, the surface properties after processing of the substrate to be heated tend to be further improved. The mass reduction rate of the polyether modified ruthenium is preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, and still more preferably 30% by mass or less. The lower limit of the mass reduction rate of the polyether modified ruthenium may be 0% by mass, and 15% by mass or more and even 20% by mass or more may be sufficient for practical use.

In the present invention, the refractive index of the light of the polyether-modified ruthenium is preferably 1.440 or less. The lower limit value is not particularly limited, and the actual use can be sufficiently satisfied with 1.400 or more.

The polyether-modified oxime used in the present invention is preferably a polyether-modified oxime represented by any one of the following formulas (101) to (104). Formula (101) [Chemical Formula 1] In the above formula (101), R ¹¹ and R ¹⁶ are each independently a substituent, and R ¹² and R ¹⁴ are each independently a divalent linking group, and R ¹³ and R ¹⁵ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The bases, m11, m12, n1, and p1 are independent numbers of 0 to 20, and x1 and y1 are independent numbers of 2 to 100, respectively. Formula (102) [Chemical Formula 2] 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 an alkyl group having 1 to 5 carbon atoms, and m2 and n2 are The numbers of 0 to 20 are independent, and x2 is a number of 2 to 100. Formula (103) [Chemical Formula 3] 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 a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The bases, m31, m32, n3, and p3 are independent numbers of 0 to 20, and x3 is a number of 2 to 100. Formula (104) [Chemical Formula 4] In the above 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 a carbon number of 1 to The alkyl group of 5, m4 and n4 are independent numbers of 0 to 20, and x4 and y4 are each independently 2 to 100.

In the above formula (101), R ¹¹ and R ¹⁶ are each independently a substituent, and an alkyl group having 1 to 5 carbon atoms or a phenyl group is preferred, and a methyl group is more preferred. In the above formula (101), R ¹² and R ¹⁴ are each independently a divalent linking group, and a carboxyl group, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 16 carbon atoms, and a carbon number. The alkenyl group having 2 to 8 carbon atoms, the alkynyl group having 2 to 5 carbon atoms, and the exoaryl group having 6 to 10 carbon atoms are preferred, and an oxygen atom is more preferred. In the formula (101), R ¹³ and R ¹⁵ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. For better.

In the above formula (102), R ²¹ , R ²⁵ and R ²⁶ are each independently a substituent, and have the same meanings as R ¹¹ and R ¹⁶ in the formula (101), and the preferred ranges are also the same. In the above formula (102), R ²² is a divalent linking group, and 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, and has the same meaning as R ¹³ and R ¹⁵ in the formula (101), and the preferred range is also the same.

In the above formula (103), R ³¹ and R ³⁶ are each independently a substituent, and have the same meanings as R ¹¹ and R ¹⁶ in the formula (101), and the preferred ranges are also the same. In the above formula (103), R ³² and R ³⁴ are each independently a divalent linking group, and 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, and 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 meanings as R ¹¹ and R ¹⁶ in the formula (101), and a preferred range. The same is true. In the above formula (104), R ⁴⁷ is a divalent linking group, and has the same meaning as R ¹² in the formula (101), and the preferred range is also the same. In the above formula (104), R ⁴⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and has the same meaning as R ¹³ and R ¹⁵ in the formula (101), and the preferred range is also the same.

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

The content of the polyoxyalkylene group in the polyether-modified oxime used in the present invention is not particularly limited, and 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 as "{(the formula amount of polyoxyalkylene group in one molecule) / molecular weight of one molecule} x 100".

As a precursor of the ruthenium compound, a decane coupling agent is exemplified. Examples of the decane coupling agent include a fluorine atom-containing decane coupling agent, and triethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) decane is preferred. In addition, as an example of the decane coupling agent, Japanese Patent Laid-Open No. 62-36663, Japanese Patent Laid-Open No. 61-226746, Japanese Patent Laid-Open No. 61-226745, Japanese Patent Laid-Open No. 62-170950, Japan JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, and JP-A-2001-330953 The surfactant described in the above.

A commercially available product can be used as the ruthenium-containing compound used in the present invention. For example, ADVALON FA33, FLUID L03, FLUID L033, FLUID L051, FLUID L053, FLUID L060, FLUID L066, IM22, WACKER-Belsil DMC 6038 (above, manufactured by Wacker Asahikasei Silicone Co., Ltd.), KF-352A, KF-353, 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, manufactured by Shin-Etsu Chemical Co., Ltd.), 8526 ADDITIVE, FZ-2203, FZ-5609, L-7001, SF 8410, 2501 COSMETIC WAX, 5200 FORMULATION AID, 57 ADDITIVE, 8019 ADDITIVE, 8029 ADDITIVE, 8054 ADDITIVE, BY16-036, 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, SH 28 PAINR ADDITIVE, SH3749, S H3773M, SH8400, SH8700 (above, manufactured by Dow Corning Corporation), BYK-378, BYK-302, BYK-307, BYK-331, BYK-345, BYK-B, BYK-347, BYK-348, BYK-349, BYK-377 (above, BYK JAPAN CO., LTD.), Silwet L-7001, Silwet L-7002, Silwet L-720, Silwet L-7200, Silwet L-7210, Silwet L-7220, Silwet L-7230 , Silwet L-7605, TSF4445, TSF4446, TSF4452, Silwet Hydrostable 68, Silwet L-722, Silwet L-7280, Silwet L-7500, Silwet L-7550, Silwet L-7600, Silwet L-7602, Silwet L-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, TSF4450, TSF4460 (above , manufactured by Momentive Performance Materials Japan LLC). Further, as the ruthenium-containing compound, the trade names "BYK-300", "BYK-306", "BYK-310", "BYK-315", "BYK-313", "BYK-320", "BYK-" can also be used. 322", "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, BYK JAPAN CO., LTD.), trade name "AC FS 180", "AC FS 360", "AC S 20" (above, manufactured by Algin Chemie), trade name "POLYFLOWKL-400X", "POLYFLOWKL-400HF", "POLYFLOWKL-401" ", "POLYFLOWKL-402", "POLYFLOWKL-403", "POLYFLOWKL-404", "POLYFLOWKL-700" (above, manufactured by KYOEISHA CHEMICAL Co., LTD.), trade 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 name "LP-7001", " LP-7002", "8032 ADDITIVE", "FZ-2110", "FZ-2105", "67 ADDITIVE", "8618 ADDITIVE", "3 ADDITIVE", "56 ADDITIVE" (above, manufactured by Dow Corning Corporation), "TEGO WET 270" (manufactured by Evonik Japan Co., Ltd.), "NBX-15" (manufactured by NEOS COMPANY LIMITED), and the like.

The content of the cerium-containing compound in the temporary binder used in the present invention is preferably 0.001 to 1.0% by mass based on the solid content of the temporary binder. The lower limit of the content of the ruthenium-containing compound is more preferably 0.004% by mass or more, more preferably 0.006% by mass or more, still more preferably 0.008% by mass or more, and still more preferably 0.009% by mass or more. The upper limit of the content of the ruthenium-containing compound is preferably 0.8% by mass or less, more preferably 0.6% by mass or less, more preferably 0.3% by mass or less, still more preferably 0.15% by mass or less, and even more preferably 0.09% by mass or less. Further preferred. The temporary binder used in the present invention may contain only one type of ruthenium-containing compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

<<Other release agent>> In the present invention, a release agent other than the ruthenium-containing compound may be contained. A fluorine-based liquid compound is exemplified as another mold release agent. When other mold release agents are contained, the content is preferably in the range of 0.001 to 0.005% by mass. These other release agents may be contained alone or in combination of two or more. When two or more types are contained, the total amount is preferably in the above range. Further, in the present invention, it is possible to adopt a structure which does not substantially contain another mold release agent. The substance is not substantially contained in an amount of 1% by mass or less based on the content of the cerium-containing compound.

<<Resin>> The temporary adhesive used in the present invention preferably contains at least one type of resin. The resin may, for example, be a block copolymer, a random copolymer or a graft copolymer, and a block copolymer is preferred. When the block copolymer is used, the flow of the temporary binder in the heating process can be suppressed, so that the adhesion can be maintained even in the heating process, and the effect that the peeling property does not change after the heating process can be expected.

Among the temporary binders used in the present invention, the resin is preferably an elastomer. By using an elastomer as a resin, even fine concavities and convexities of a substrate (a substrate to be processed such as a carrier substrate or a device wafer) can be traced, and a temporary adhesive having excellent adhesion can be formed by an appropriate anchoring effect. One or two or more kinds of the elastomers can be used in combination. Further, in the present specification, the elastic system means a polymer compound which exhibits elastic deformation. That is, it is defined as a polymer compound having a property of instantaneously deforming according to the external force when the external force is applied and returning to 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, still more preferably 50,000 to 100,000. Since the weight average molecular weight is excellent in solubility in the solvent in this range, the carrier substrate is peeled off from the substrate to be processed, and after removing the residue derived from the elastomer remaining on the surface of the substrate to be processed or the carrier substrate using a solvent. The residue is easily dissolved in a solvent and removed. Therefore, there is an advantage that the 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 (polystyrene elastomer) containing a repeating unit derived from styrene, a polyester elastomer, a polyolefin elastomer, or a polyurethane elastomer can be used. A polyamine-based elastomer, a polypropylene-based elastomer, a fluorene-based elastomer, or a polyimide-based elastomer. In particular, a polystyrene-based elastomer, a polyester-based elastomer, and a polyamide-based elastomer are preferable, and a polystyrene-based elastomer is more preferable from the viewpoint of heat resistance and peelability.

In the present invention, the elastomer is preferably a hydrogenated product. In particular, a hydrogenated product of a polystyrene elastomer is preferred. If the elastomer is a hydrogenated product, thermal stability and storage stability are improved. Further, the releasability and the removability of the temporary adhesive after peeling are improved. When the hydrogenated product of the polystyrene elastomer is used, the above effects are remarkable. Further, the hydrogenated product means a polymer in which the elastomer is hydrogenated.

In the present invention, the 5% thermal mass reduction temperature when the elastomer is heated at a temperature elevation rate of 20 ° C /min at 25 ° C is preferably 250 ° C or higher, more preferably 300 ° C or higher, and even more preferably 350 ° C or higher. Above °C is even further preferred. Further, the upper limit is not particularly limited, and is preferably, for example, 1000 ° C or less, more preferably 800 ° C or less. According to this aspect, a temporary adhesive which is excellent in heat resistance can be used. The elastomer of the present invention is preferably one which is capable of being deformed to 200% with a small external force at room temperature (20 ° C) when the original size is regarded as 100%, and when the external force is removed Recovered to below 130% in a short time.

<<<<Polyester-Based Elastomer>>>> The polystyrene-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, it is selected from the group consisting of styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polystyrene-poly(ethylene-propylene) II. Block copolymer (SEP), polystyrene-poly(ethylene-propylene)-polystyrene triblock copolymer (SEPS), polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymerization At least one polystyrene elastomer of the composition (SEBS) or polystyrene-poly(ethylene/ethylene-propylene)-polystyrene triblock copolymer (SEEPS) is preferred.

The proportion of the repeating unit derived from styrene in the polystyrene-based elastomer is preferably 90% by mass or less, more preferably 55% by mass or less, more preferably 48% by mass or less, and still more preferably 35% by mass or less. Further preferably, 33% by mass or less is more preferably further. The lower limit of the ratio of the repeating unit derived from styrene may be 0% by mass, but may be 10% by mass or more. By setting it as such a range, it is possible to more effectively suppress the warpage of the laminated body in which the substrates are bonded together with the temporary adhesive.

In one embodiment of the polystyrene-based elastomer of the present invention, the elastomer A and the elastomer B may be used in combination, and the elastomer A contains 10% by mass or more of 55 in the total repeating unit. A repeating unit derived from styrene in a ratio of mass% or less; and an elastomer B system containing a repeating unit derived from styrene in a ratio of more than 55% by mass and 95% by mass or less in the total repeating unit. By using the elastomer A and the elastomer B in combination, the occurrence of warpage can be effectively suppressed. The mechanism for obtaining such an effect can be estimated based on the following. That is, the elastomer A is a relatively soft material, and thus it is easy to form a layered temporary adhesive (temporary adhesive layer) having elasticity. Therefore, when a laminate of a substrate and a carrier substrate is produced by using a temporary adhesive, and the substrate is polished to become a film, the temporary adhesive (temporary adhesive layer) is easily elastically deformed and restored even if it is locally applied. shape. As a result, excellent flat polishing property can be obtained. Further, even if the laminated body obtained by polishing the carrier substrate, the substrate to be processed, and the temporary adhesive is subjected to heat treatment, and then cooled, the internal stress generated during cooling can be alleviated by the temporary adhesive (temporary adhesive layer). Therefore, the occurrence of warpage can be effectively suppressed. Further, since the elastic body B is a relatively hard material, the elastic body B can be used as a temporary adhesive having excellent peelability.

The mass ratio when the elastomer A and the elastomer B are blended is Elastomer A: Elastomer B = 1:99 to 99:1 is preferred, and 3:97 to 97:3 is more preferred, 5:95 to 95. Further, 5 is further preferred, and 10:90 to 90:10 is further more preferable. If it is in the above range, the occurrence of warpage can be more effectively suppressed.

The polystyrene elastomer is preferably a block copolymer of styrene and other monomers, and a block copolymer having a styrene block at one end or both ends is more preferable, and a styrene block at both ends is particularly preferred. . When both ends of the polystyrene-based elastomer are styrene blocks (repeating units derived from styrene), heat resistance tends to be further improved. The reason for this is that a repeating unit derived from styrene having high heat resistance exists at the terminal. In particular, the block portion of the repeating unit derived from styrene is a reactive polystyrene-based hard block, and thus heat resistance and chemical resistance are more excellent, which is preferable. Further, such an elastomer is more preferable from the viewpoints of solubility in a solvent and resistance to a resist solvent. Further, when the polystyrene elastomer is a hydrogenated product, the stability with respect to heat is improved, and denaturation such as decomposition or polymerization is less likely to occur. Further, it is also more preferable from the viewpoints of solubility in a solvent and resistance to a resist solvent. The amount of the unsaturated double bond of the polystyrene-based elastomer is preferably less than 15 mmol per 1 g of the polystyrene-based elastomer, more preferably less than 5 mmol, and even more preferably less than 0.5 mmol. Further, the amount of the unsaturated double bond herein does not include the amount of the unsaturated double bond 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 "repeating unit derived from styrene" means a structural unit derived from styrene contained in a polymer when a styrene or a styrene derivative is polymerized, and may have a substituent. Examples of the styrene derivative include α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene. The substituent may, for example, be 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 ethoxy group or a carboxyl group.

Examples of commercially available polystyrene elastomers include Tufprenea, Tufprene 125, Tufprene 126S, Solprene T, Asaprene T-411, Asaprene T-432, Asaprene T-437, Asaprene T-438, Asaprene T-439, Tuftec H 1272, Tuftec P1500, Tuftec H 1052. Tuftec H1062, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftec H1053, Tuftec P2000, Tuftec H1043 (above, manufactured by Asahi Kasei Chemicals Corp.), elastomer AR-850C, 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 (above, ARONKASEYI CO., LTD ., Ltd.), KratonD1111, KratonD1113, KratonD1114, KratonD1117, KratonD1119, KratonD1124, KratonD1126, KratonD1161, KratonD1162, KratonD1163, KratonD1164, KratonD1165, KratonD1183, KratonD1193, KratonDX406, KratonD4141, KratonD4150, KratonD4153, KratonD4158, KratonD4270, KratonD4271, KratonD4433, KratonD1170, KratonD1171, KratonD1173, CarifelxIR0307, CarifelxIR0310, CarifelxIR0401, KratonD0242, KratonD1101, KratonD1102, KratonD1116, KratonD1118, KratonD1133, KratonD1152, KratonD1153, KratonD1155, KratonD1184, KratonD1186, KratonD1189, KratonD1191, KratonD1192, KratonDX405, KratonDX408, KratonDX410, KratonDX414, KratonDX415, KratonA1535, KratonA1536, KratonFG1901, KratonFG1924, KratonG1640, KratonG1641, KratonG1642, KratonG1643, KratonG1645, KratonG1633, KratonG1650, KratonG1651, KratonG1652 (G1652MU-1000), KratonG1654, KratonG1657, KratonG1660, KratonG1726, KratonG1701, KratonG1702, KratonG1730, KratonG1750, KratonG17 65, Kraton G4609, Kraton G4610 (above, manufactured by Kraton Polymer Japan Co., Ltd.), TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505 DYNARON6100P, DYNARON4600P, DYNARON6200P, DYNARON4630P, DYNARON8601P, DYNARON8630P, DYNARON8600P, DYNARON8903P, DYNARON6201B, DYNARON1321P, DYNARON1320P, DYNARON2324P, DYNARON9901P (above, manufactured by JSR Corporation), Denka STRseries (manufactured by Denka Company Limited), Quintac3520, Quintac3433N, Quintac3421, Quintac3620 , Quintac 3450, Quintac 3460 (above, manufactured by Zeon Corporation), TPE-SBseries (manufactured by Sumitomo Chemical Company, Limited), rabalonseries (manufactured by Mitsubishi Chemical Corporation), SEPTON 1001, SEPTON 1020, SEPTON 2002, SEPTON 2004, SEPTON 2005, SEPTON 2006, SEPTON 2007, SEPTON 2063, SEPTON 2104, SEPTON4033, SEPTON4044, SEPTON4055, SEPTON4077, SEPTON4099, SEPTONHG252, SEPTON8004, SEPTON8006, SEPTON8007, SEPTON8076, SEPTON8104, SEPTON V9461, SEPTON V9475, SEPTON V9827, HYBRAR7311, HYBRAR7125, HYBRAR5127, HYBRAR5125 (above, manufactured by KURARAY CO., LTD.), Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), LEOSTOMER, ACTYMER (above, RIKEN TECHNOS CORPORATION) )Wait.

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 polypropylene-based elastomer, or the like can be used.

<<<Polymer blending amount>> The temporary binder used in the present invention is preferably contained in a ratio of 50.00 to 99.99% by mass based on the total solid content of the temporary binder, and is contained in a ratio of 70.00 to 99.99% by mass. For better, the ratio of 88.00 to 99.99% by mass is particularly preferable. 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 a proportion of 50.00 to 99.99% by mass in the total solid content of the temporary binder, and more preferably in a ratio of 70.00 to 99.99% by mass, and preferably 88.00 to 99.99% by mass. It is especially good. When the content of the elastomer is in the above range, the adhesiveness and the peeling property are excellent. When two or more kinds of elastomers are used, the total amount is preferably in the above range. Further, when an elastomer is used as the resin, the content of the elastomer in the total mass of the resin is preferably from 50 to 100% by mass, more preferably from 70 to 100% by mass, still more preferably from 80 to 100% by mass, and further preferably from 90 to 100%. The mass % is even further preferred. Further, the resin may be substantially only an elastomer. Further, when the resin is substantially only an 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 an elastomer.

<<Plasticizer>> The temporary binder used in the present invention may contain a plasticizer as needed. By blending the plasticizer, it is possible to provide a temporary adhesive layer which satisfies the above various properties. As the plasticizer, a phthalic acid ester, a fatty acid ester, an aromatic polycarboxylic acid ester, a polyester, or the like can be used.

Examples of the phthalic acid esters include DMP, DEP, DBP, #10, BBP, DOP, DINP, DIDP (above, manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD.), PL-200, and DOIP (above, Manufactured by CG ESTER CORPORATION, Sansosaiza DUP (manufactured by New Japan Chemical Co., Ltd.). Examples of the fatty acid esters include butyl stearate, Unistar M-9676, Unistar M-2222SL, Unistar H-476, Unistar H-476D, Panasee 800B, Panasee 875, Panaseate 810 (above, manufactured by NOF Corporation), DBA, DIBA, DBS, DOA, DINA , DIDA, DOS, BXA, DOZ, DESU (above, manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD.). Examples of the aromatic polycarboxylic acid esters include TOTM (manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD.), Monocizer W-705 (manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD.), UL-80, and UL-100 (manufactured by ADEKA Company). )Wait. Examples of the polyester include Porisaiza TD-1720, Porisaiza S-2002, Porisaiza S-2010 (above, 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 Porisaiza TD-1720 are preferably used, and DIDA and TOTM are more preferable, and TOTM is particularly preferable. The plasticizer may be used alone or in combination of two or more.

From the viewpoint of preventing sublimation in heating, it is preferable to reduce the weight by 1% by mass to a temperature of 250 ° C or more when the weight change is measured under a nitrogen gas stream at a constant temperature of 20 ° C /min. More preferably, it is 270 ° C or more, and more preferably 300 ° C or more. The upper limit is not specifically specified, and for example, it can be set to 500 ° C or lower.

The amount of the plasticizer to be added is preferably from 0.01% by mass to 5.0% by mass based on the total solid content of the temporary binder, and more preferably from 0.1% by mass to 2.0% by mass.

<<Solvent>> The temporary binder used in the present invention preferably contains a solvent. The solvent can be used without limitation as long as it is known, and an organic solvent is preferred. As an organic solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, lactate Ester, ethyl lactate, alkoxyalkyl acetate (eg methyl alkoxyalkyl acetate, ethyl alkoxyalkyl acetate, butyl alkoxyalkyl acetate (eg, methoxyacetic acid) Methyl ester, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate (Example: 3-oxygen) Methyl propyl propionate, ethyl 3-alkoxyalkyl propionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-ethoxypropionate ethyl ester, etc.), 2-oxypropionic acid alkyl ester, etc. (Example: methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-alkoxy group Alkyl propionate or the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate)), methyl 2-alkoxyalkyl-2-methylpropanoate and 2-oxy-2-methylpropionic acid Esters (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate Ethyl acetate, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1-methoxy-2-propyl acetate, etc.; Glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl fiber solvent acetate, ethyl fiber solvent acetate, diethylene glycol monomethyl ether, diethylene glycol Ethers such as diethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate; methyl ethyl ketone, cyclohexanone, 2- Ketones such as heptanone, 3-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone; toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, N-butylbenzene, t-butylbenzene, isobutylbenzene, tert-butylbenzene, pentylbenzene, isopentylbenzene, (2,2-dimethylpropyl)benzene, 1-phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenyldecane, 1-phenylnonane, ring Benzobenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-cymene, indoline, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, Umbellifera, 1,3-diisopropyl stupid, 4-ethyltoluene, 1,4-diethylbenzene, p-cymene, 1,4-diisopropyl stupid, 4-tert-butyltoluene , 1,4-di-tert-butylbenzene, 1,3-diethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl-ortho Xylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 5-tert-butyl-m-xylene, 3,5 An aromatic hydrocarbon such as di-tert-butyltoluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene or pentamethylbenzene; Hydrocarbons such as limonene, p-menthane, decane, decane, dodecane, decahydronaphthalene, and the like. Among these, mesitylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, methyl 3-ethoxypropionate, 3-ethyl Ethyl oxypropionate, ethyl cellulose solvent 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.

It is also preferable that these solvents are mixed in two or more types from the viewpoint of improving the coating surface properties and the like. In this case, it is selected from the group consisting of mesitylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl cellulose solvent acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, A mixed solution of two or more kinds of cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is particularly preferable.

The content of the solvent of the temporary binder is preferably from 5 to 80% by mass based on the total solid content of the temporary binder, and more preferably from 10 to 50% by mass in terms of the coating amount. The proportion meter is preferably 15 to 40% by mass. The solvent may be used alone or in combination of two or more. When the solvent is two or more kinds, the total amount thereof is preferably in the above range. Further, the temporary binder is applied in a layer form, and the content of the solvent in the temporary adhesive layer obtained by 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 binder used in the present invention may contain an antioxidant. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a lanthanoid antioxidant, an amine-based antioxidant, or the like can be used. Examples of the phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox 1010, Irganox 1330, Irganox 3114, Irganox 1035 (above, manufactured by BASF JAPAN LTD.), and Sumilizer. MDP-S, Sumilizer GA-80 (above, manufactured by Sumitomo Chemical Company, Limited), and the like. Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate distearyl ester, Sumilizer TPL-R, Sumilizer TPM, Sumilizer TPS, Sumilizer MB, and Sumilizer TP-D (above, Sumitomo Chemical Company). , Limited system) and so on. Examples of the phosphorus-based antioxidant include tris(2,4-di-tert-butylphenyl)phosphoric acid, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphoric acid, and poly(dipropylene glycol). Phenylphosphoric acid, diphenylisodecyl ester phosphorous acid, 2-ethylhexyl diphenylphosphite, triphenylphosphite, Irgafos 168, Irgafos 38 (above, manufactured by BASF JAPAN LTD.), Sumilizer GP (Sumitomo) Chemical Company, Limited) and the like. Examples of the oxime-based antioxidant include p-benzoquinone, 2-tert-butyl-1,4-benzoquinone, and the like. Examples of the amine-based antioxidant include dimethylaniline or phenothiazine. The antioxidants are Irganox 1010, Irganox 1330, 3,3'-thiodipropionate distearyl, Sumilizer TP-D, Irgonox 1010, Irganox 1330 is more preferred, and Irganox 1010 is particularly preferred. Further, among the above antioxidants, a phenol-based antioxidant, a sulfur-based antioxidant or a phosphorus-based antioxidant is preferably used together, and a phenol-based antioxidant and a sulfur-based antioxidant are preferred. In particular, when a polystyrene-based elastomer is used as the elastomer, a phenol-based antioxidant and a sulfur-based antioxidant are preferably used. By such a combination, an effect of effectively suppressing deterioration of the temporary binder caused by the oxidation reaction can be expected. When a phenol-based antioxidant and a sulfur-based antioxidant are used together, the mass ratio of the phenol-based antioxidant to the sulfur-based antioxidant is a phenol-based antioxidant: a sulfur-based antioxidant = 95:5 to 5:95 is preferable, and 25: 75 to 75:25 is better. As a combination of antioxidants, Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D and Sumilizer GA-80 and Sumilizer TP-D are preferred, Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D are better. Irganox1010 and Sumilizer TP-D are especially good.

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

When the temporary binder contains an antioxidant, the content of the antioxidant is preferably 0.001 to 20.0% by mass based on the total solid content of the temporary binder, and more preferably 0.005 to 10.0% by mass. The antioxidant may be used alone or in combination of two or more. When the amount of the antioxidant is two or more, the total amount thereof is preferably in the above range.

<<Other Additives>> In the range which does not impair the effect of the present invention, various additives such as a surfactant, a curing agent, a curing catalyst, a filler, and the like can be blended in the temporary adhesive used in the present invention as needed. Adhesion promoter, ultraviolet absorber, agglutination inhibitor, and the like. When these additives are blended, the total blending amount is preferably 3% by mass or less based on the total solid content of the temporary binder.

<<Formation of Temporary Adhesive Layer>> Temporary adhesive layer can be applied by spin coating method, spray coating method, slit coating method, roll coating method, flow coating method, blade coating method, dipping method, etc. Formed above the substrate. The temporary adhesive layer is formed on the surface of at least one of the two substrates to be temporarily bonded. The temporary adhesive layer may be formed only on one surface of the substrate to be bonded to the other substrate, or a temporary adhesive layer may be provided on both of the substrates to bond the two. Next, the temporary adhesive usually contains a solvent, so heating is performed to volatilize the solvent. The heating temperature is preferably a temperature higher than the boiling point of the solvent, more preferably 110 ° C or more, still more preferably 130 ° C to 200 ° C, and particularly preferably 160 ° C to 190 ° C.

<<Preparation of Temporary Binder>> The temporary binder used in the present invention can be prepared by mixing the above components. The mixing of the components is usually carried out in the range of 0 °C to 100 °C. Further, after mixing the components, for example, filtration using a filter is preferred. Filtration can be carried out in multiple stages, or it can be repeated multiple times. Moreover, the filtered liquid can also be refiltered. The filter is not particularly limited as long as it is used as a filter or the like. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a nylon urethane resin such as nylon 6, nylon 6, or the like, or a filter made of a polyolefin resin such as polyethylene or polypropylene (PP) may be used. Among these materials, polypropylene and nylon are preferred. The pore diameter of the filter is, for example, 0.003 to 5.0 μm. By setting it as the range, it is possible to suppress the clogging of the filter and to reliably remove fine foreign matter such as impurities and aggregates contained in the composition. When using filters, you can combine different filters. At this time, the filtration by the first filter may be one time or two times or more. When the filters are combined for two or more times, it is preferable that the pore diameters of the second and subsequent passes are the same or smaller than the pore sizes of the first filter. Further, a plurality of first filters of different apertures may be combined within the above range. The aperture here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD., Toyo Roshi Kaisha, Ltd., Nihon Entegris K.K., or KITZ MICROFILTER CORPORATION.

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

<<Organic acid>> The organic acid used in the present invention may be a low molecular compound (for example, a molecular weight of less than 1,000, a molecular weight of 500 or less, and a lower limit, for example, 98 or more), and a polymer compound (for example, a molecular weight of 1,000 or more, Further, it is 2,000 or more, and the upper limit is, for example, 5,000 or less. The organic acid used in the present invention is preferably a low molecular compound. The organic acid used in the present invention has an acid dissociation constant pKa of -4 to 5, more preferably -3 to 4. The organic acid used in the present invention is a ratio of the equilibrium concentration of 1-octanol in the organic acid to the concentration of 1-octanol/water partition coefficient P in the form of logarithm logP relative to the base of 10 - 5 to 6 are preferred, and -3 to 5 is more preferred. The organic acid used in the present invention is preferably selected from the group consisting of alkylsulfonic acid, aromatic sulfonic acid, alkylphosphonic acid, aromatic phosphoric acid, alkylphosphonic acid and aromatic phosphonic acid. Here, the aromatic group may be an aromatic hydrocarbon system or an aromatic heterocyclic ring, and an aromatic hydrocarbon system is preferred. The organic acid used in the present invention preferably contains at least one selected from the group consisting of organic sulfonic acids, organic phosphoric acids, organic phosphonic acids, organic sulfinic acids, and organic phosphinic acids, and is preferably selected from organic At least one of the organic acids in the group consisting of sulfonic acid, organic phosphoric acid and organic phosphonic acid is more preferred, and at least one of the organic sulfonic acids is further preferred, and the alkylsulfonic acid having a cyclic group is contained. At least one of the aromatic sulfonic acids and the aromatic sulfonic acid is more preferably further. 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 preferred, and an organic acid having no acid radical other than sulfonate, phosphate or phosphonate is more preferred.

As the organic sulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, butanesulfonic acid, vinylsulfonic acid, 1,5-propane disulfonic acid, 3-hydroxypropanesulfonic acid, benzenesulfonic acid, and the like are shown. Toluenesulfonic acid, p-ethylbenzenesulfonic acid, dodecylbenzenesulfonic acid, 2,4,5-trimethylbenzenesulfonic acid, nonafluoro-1-butanesulfonic acid, 2-naphthalenesulfonic acid, 1, 5-naphthalenedisulfonic acid, heptadecafluorooctanesulfonic acid, camphorsulfonic acid, 3-cyclohexylaminopropanesulfonic acid, m-xylene-4-sulfonic acid, p-xylene-2-sulfonic acid, tannic acid ( DANSIC ACID), 4,4'-biphenyldisulfonic acid, 8-anilino-1-naphthalenesulfonic acid, 2-morpholinoethanesulfonic acid, 3-morpholinepropanesulfonic 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, picryl sulfonic acid. The organic sulfonic acid is preferably an alkylsulfonic acid or an aromatic sulfonic acid, and the aromatic sulfonic acid is more preferred.

Examples of the organic phosphoric acid include alkyl phosphates such as methyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, butyl phosphate, dibutyl phosphate, butoxyethyl phosphate, and 2-ethylhexyl phosphate. An aromatic phosphoric acid such as phenylphosphoric acid or diphenylphosphoric acid. The organic phosphoric acid is preferably an alkylphosphoric acid or an aromatic phosphoric acid, more preferably an aromatic phosphoric acid, and further preferably a diarylphosphoric acid. Examples of the organic phosphonic acid include vinylphosphonic acid, methylene diphosphonic acid, ethylphosphonic acid, propylphosphonic acid, 1,3-propylene diphosphonic acid, butylphosphonic acid, and 1,4-butylene. Diphosphonic acid, pentylphosphonic acid, 1,5-pentylene and phosphonic acid, hexylphosphonic acid, 1,6-dihexylenephosphonic acid, octylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid Equivalent alkylphosphonic acid, phenylphosphonic acid, phenylene diphosphonic acid, xylylene diphosphonic acid, (4-hydroxyphenyl) phosphonic acid, (2-phenylethyl) phosphonic acid, o-xylene An aromatic phosphonic acid such as bisphosphonic acid, diphenylmethylphosphonic acid, cinnamylphosphonic acid or (4-hydroxybenzyl)phosphonic acid. The organic phosphonic acid is preferably an alkylphosphonic acid or an aromatic phosphonic acid, and more preferably an aromatic phosphonic acid.

The content of the organic acid in the cleaning agent composition A is preferably from 0.08 mg to 0.8 g based on 1 L of the organic solvent contained in the cleaning agent composition A. In addition, the content of the organic acid in the cleaning agent composition A is preferably 0.000088% by mass or more, more preferably 0.000080% by mass or more, more preferably 0.000800% by mass or more, and still more preferably 0.008000% by mass or more. Further preferably, 0.08% by mass or more is more preferably further. The content of the organic acid in the detergent composition of the present invention is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, even more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less. Further preferred. The cleaning agent composition A may contain only one type, and may contain two or more types of organic acids. When two or more types are contained, the total amount is preferably in the above range.

<<Organic solvent>> The cleaning agent composition A contains an organic solvent. In the organic solvent, when the temporary binder contains an elastomer, the organic solvent in which the elastomer is dissolved is preferable, and at least one selected from the group consisting of an aromatic compound, a saturated alicyclic compound, a cyclic ketone, and a cyclic oxime is more preferable. At least one selected from the group consisting of an aromatic compound, an alicyclic compound, and a cyclic oxime is more preferably further selected from at least one selected from the group consisting of aromatic compounds. The organic solvent of the aromatic compound is preferably an aromatic hydrocarbon-based solvent having an alkyl group, and more preferably a solvent having a benzene ring and 1 to 3 alkyl groups each having 1 to 10 carbon atoms.

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, and a linear or branched alkyl group is preferred. The number of carbon atoms constituting the alkyl group is preferably from 1 to 10, more preferably from 1 to 6, and further preferably from 1 to 4. The aromatic hydrocarbon-based 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 a solvent represented by the following formula (X) is more preferable. Formula (X) [Chemical Formula 5] 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 a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or a t-butyl group. Further, the total number of carbon atoms constituting R is preferably 2 to 5, and more preferably 3 or 4.

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

Specific examples of the aromatic hydrocarbon-based solvent having an alkyl group used in the present invention include toluene, xylene, and trimethylbenzene (preferably 1,3,5-trimethylbenzene (mesitylene), 1, 2). , 4-trimethylbenzene (pseudoene), ethylbenzene, propylbenzene, 1-methylethylbenzene, butylbenzene (preferably n-butylbenzene, second butylbenzene, isobutylbenzene) , tert-butylbenzene, more preferably tert-butylbenzene), pentylbenzene, isoamylbenzene, (2,2-dimethylpropyl)benzene, 1-phenylhexane, 1-phenylheptane , 1-phenyloctane, 1-phenyldecane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-cymene (2-dipropyltoluene), 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 selected from the group consisting of toluene, xylene, trimethylbenzene (preferably mesitylene), butylbenzene (preferably t-butylbenzene), and diethylbenzene. More preferably, it is at least one of xylene and trimethylbenzene and butylbenzene.

Examples of the saturated alicyclic compound include cyclopropane, cyclobutane, cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclodecane, and cycloundecane. Cyclododecane, cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, cyclooctene, dicycloundecane, decalin, norbornene, norbornadiene, cubane, sulphane , alkane. Examples of the cyclic ketone include cyclohexanone, cyclopentanone, isophorone, acetophenone, and benzophenone. Examples of cyclic guanidines are wild chrysanthemum alcohol, deco-enol, junionone, grapefruit thiol, iridoid oxime, split iridoid oxime, menthane, limonene, hydrocelene, terpinolene, terpinene, umbrella Flower hydrocarbon, menthol, menthol, piperitol, terpineol, carvacrol, thymol, dihydrocarvacenol, menthone, menthol, celery aldehyde, fragrant Celanone, carvone, piperone, 1,8-nonyl phenol, 1,4-nonyl phenol, dysparin, monocyclic guanidine, decane, sane, decane, bornane, Fenchane, isobornane, isocamphane, 3-decene, sapene, cedarene, ketone, thujanol, decene, whipenol, Bicyclic guanidines such as whey ketene, carvone, ketone, borneol, isobornyl, anthrone, and Fenchol fenchane.

The content of the organic solvent in the cleaning agent composition A is preferably from 0.000000 to 99.9999% by mass of the cleaning agent composition A, and more preferably from 99.0000 to 99.9990% by mass. The cleaning agent composition of the present invention may contain only one type, or may contain two or more types of organic solvents. When two or more types are contained, the total amount is preferably in the above range. Further, in the cleaning agent composition A, the mass ratio of the organic acid to the organic solvent is 0.0001: 99.9999 to 50:50, preferably 0.0010: 99.9990 to 10:90, and more preferably 0.0100: 99.9900 to 1.0000: 99.0000. Preferably. By setting it as such a range, the removal property of a temporary adhesive is more effectively improved.

<<Other Components>> The cleaning agent composition A may contain components other than the above organic acid or organic solvent. Examples of other components include sodium tripolyphosphate, sodium pyrophosphate, sodium pyrophosphate, sodium aluminum citrate, sodium nitrilotriacetate, ethylenediaminetetraacetic acid, sodium citrate, and the like, and sodium sulfate, etc. Micellar enhancer, IRGAMET 30, IRGAMET 39, IRGAMET 42 (above, manufactured by BASF JAPAN LTD.), Belclene 510, Belclene 511, Belclene 512, Belclene 515 (above, manufactured by Pan asian Trading Co., Ltd.), BT- 120, BT-LX, CBT-1, TT-LX, TT-LYK, JCL-400 (above, 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 Green SH-K, VERZONE Oil #1022, VERZONE Origin Oil #1030, VERZONE Origin Oil #220, VERZONE OIL-HD VERZONE OIL-U (above, manufactured by Daiwa Fine Chemicals Co., Ltd.), top rust inhibitor Y, top rust inhibitor 511 (above, manufactured by Okuno Chemical Industries Co., Ltd.) CBBright (RYOKO CHEMICAL CO., Anti-rust agent such as LTD.), IRGACOR L12, IRGACOR DSS G, IRGACOR NPA Preservatives such as IRGALUBE 349, SARKOSYL O (above, manufactured by BASF JAPAN LTD.), VERZONE COR-280, Silver Rip, VERZONE DA-1, New Dain Silver S-1, New Dain Silver V-2, New Dain Silver, CU -Guard 1000R, CU-Guard 1000N, CU-Guard 1000, CU-Guard D, VERZONE NFS-Oil, VERZONE OA-386, VERZONE C-BTA, VERZONE TTA, VERZONE Crystal #120 (above, Daiwa Fine Chemicals Co., Ltd., Cu-423Y, Ag-422Y, Ag-420Y (above, manufactured by DIPSOL CHEMICALS CO., LTD.), Entech CU-560, Entech CU-56, Meldip AG-6801 (above, manufactured by Meltex Inc.) ), top rinseCU-5, top rinse CU-3 (above, manufactured by Okuno Chemical Industries Co., Ltd.), BT-5, BT-7, BT-8, BT-14 (above, ASAHI Co., Ltd.) Discoloration inhibitors on metal surfaces, such as CU-500, CU-600 (above, manufactured by ASAHI Co., Ltd.), S-CLEANS-800, S-CLEANS-800FR, S-CLEANS-101PN, S-PURE SJ-400, S-PURE SJ adhesive, S-CLEANSK-507, S-CLEANW-2550, S-CLEANS-105, S-CLEANS-109, S-CLEANAG-301, S-CLEANS-1000 (above, SASAKI CHEMICAL CO., LTD.), PICKLE25, PICKLE27 A metal oxide film remover such as Z-2218 (NIPPON HYOMEN KAGAKU KABUSHIKI KAISHA), an antistatic agent, an antioxidant, and a surfactant.

<<Preparation of Cleaning Agent Composition A>> Preparation of Cleaning Agent Composition A After mixing the respective components of the cleaning agent composition A, it is preferred to carry out filtration. It is preferred to use a filter having a pore diameter of 0.003 to 10 μm for filtration. By performing filtration, it is possible to reduce contamination of the substrate surface by impurities derived from the cleaning agent composition A. The filter is preferably made of polytetrafluoroethylene.

As the storage container of the cleaning agent composition A used in the present invention, a conventionally known storage container can be used. Further, for the purpose of suppressing the incorporation of impurities into the material and the composition as the storage container, it is also preferable to use a multi-layered bottle made of six kinds of six layers of resin on the inner wall of the container or a bottle having a seven-layer structure of six kinds of resins. As such a container, for example, a container described in JP-A-2015-123351 can be cited.

<Cleaning Agent Composition B> The cleaning agent composition of the present invention contains one of a solvent composed of an organic carboxylic acid compound and at least water and a water-soluble solvent. With such a configuration, 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 compound (for example, a molecular weight of less than 1,000, a molecular weight of 500 or less, a lower limit, for example, 46 or more), or a polymer compound. (For example, the molecular weight is 1000 or more, and 2000 or more, and the upper limit is 5,000 or less, for example). The organic carboxylic acid compound used in the present invention is preferably a low molecular compound. The organic carboxylic acid compound used in the present invention has an acid dissociation constant pKa of preferably 1 to 7, preferably 2 to 7, more preferably 2 to 5, and may be 2 to 4. The organic carboxylic acid compound used in the present invention has a ratio of the 1-octanol/water partition coefficient P to the logarithm of the logarithm of the logarithm of 10 in the ratio of the equilibrium concentration of 1-octyl alcohol to water, and is -5. ～2 is preferred, and -5 to 1 is more preferred. 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 or 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, oxycarboxylic acids and halogenated carboxylic acids, selected from saturated fatty acids, not The group consisting of a saturated fatty acid, a hydroxy acid, and an aromatic carboxylic acid is more preferably selected from the group consisting of a saturated fatty acid and an aromatic carboxylic acid. The saturated fatty acid, the unsaturated fatty acid, and the hydroxy acid are preferably a monocarboxylic acid, and the aromatic carboxylic acid is 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 a carboxyl group. The organic carboxylic acid compound used in the present invention is preferably a sulfonate, a phosphate or a phosphonate, and more preferably has no acid other than a carboxyl group.

Examples of the organic carboxylic acid compound include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, lauric acid, myristic acid, palmitic acid, heptadecanoic acid, and hard. Saturated fatty acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, sorbic acid, aconitic acid, etc.; lactic acid, malic acid, Hydroxy acid such as citric acid; benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, 3,4,5-trihydroxybenzoic acid, mellitic acid, cinnamic acid, oxalic acid, and propylene An aromatic carboxylic acid such as acid, succinic acid, glutaric acid, adipic acid, fumaric acid or maleic acid, oxocarboxylic acid such as pyruvic acid or oxalic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid or trifluoroacetic acid A halogen-containing carboxylic acid such as acetic acid.

The content of the organic carboxylic acid compound in the cleaning agent composition B is preferably 0.8 mg to 1.6 g based on 1 L of the solvent contained in the cleaning agent composition B. Further, the lower limit of the content of the organic carboxylic acid compound in the cleaning agent composition B is preferably 0.0016% by mass or more of the cleaning agent composition B, more preferably 0.0016% by mass or more, and still more preferably 0.1600% by mass or more. More than 1.6000 mass% is further preferred. The content of the organic carboxylic acid compound in the cleaning agent composition B of the present invention is preferably 10.0% by mass or less, more preferably 8.0% by mass or less, even more preferably 5.0% by mass or less, and further preferably 4.0% by mass of the cleaning agent composition B. % below is even further preferred. The cleaning agent composition B may contain only one type of organic carboxylic acid compound, or may contain two or more types of organic carboxylic acid compounds. When two or more types are contained, the total amount is preferably in the above range.

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

The content of the solvent in the cleaning agent composition B is preferably from 0.000000 to 99.9999% by mass of the cleaning agent composition B, more preferably from 99.0000 to 99.9990% by mass. The cleaning agent composition B of the present invention may contain only one type, and may contain two or more types of solvents. When two or more types are contained, the total amount is preferably in the above range. Further, in the cleaning agent composition B, the mass ratio of the organic carboxylic acid compound to the organic solvent is preferably 0.0001: 99.9999 to 50:50, more preferably 0.0010: 99.9990 to 10:90, and 0.0100: 99.9900 to 1.0000: 99.0000. It is further preferred. By setting it as such a range, the removability of the residue derived from the cleaning agent composition A is more effectively improved.

<<Other Components>> The cleaning agent composition B may contain components other than the above organic carboxylic acid compound and solvent. Specifically, other components mentioned in the description of the detergent composition A can be used.

<<Preparation of Cleaning Agent Composition B>> Preparation of Cleaning Agent Composition B of the Present Invention After mixing the respective components of the cleaning agent composition B, it is preferred to carry out filtration. It is preferred to use a filter having a pore diameter of 0.003 to 10 μm for filtration. By performing filtration, it is possible to reduce contamination of the substrate surface by impurities derived from the cleaning agent composition B. The filter is preferably made of polytetrafluoroethylene.

As the storage container of the cleaning agent composition B used in the present invention, a conventionally known storage container can be used. Further, for the purpose of suppressing the incorporation of impurities into the material or the composition as the storage container, it is preferable to use a container having six layers of six layers of resin on the inner wall of the container or a bottle having six layers of six resins. As such a container, for example, a container described in JP-A-2015-123351 can be cited.

<Cleaning Agent Composition A and Cleaning Agent 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 from 2 to 10. By setting it as such a range, the effect of this invention is exerted more effectively. Further, in the present invention, the equivalent of the acid contained in the cleaning agent composition B is preferably from 2 to 100 times the equivalent of the acid contained in the cleaning agent composition A. By setting it as such a range, the effect of this invention is exerted more effectively.

<Rinse Composition C> The kit of the present invention may further comprise a rinse composition C. The rinse composition contains 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 preferred. Specific examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, and ethylene glycol.

<<Other Components>> The rinse composition C may contain components other than at least one of water and alcohol. Specifically, other components mentioned in the description of the detergent composition A can be used.

<<Preparation of Flushing Composition C>> Preparation of Flushing Composition C After mixing the components of the rinse composition C, it is preferred to carry out filtration. It is preferred to use a filter having a pore diameter of 0.003 to 10 μm for filtration. By the filtration, the removability of the residue derived from the cleaning agent compositions A and B tends to be further improved. The filter is preferably made of polytetrafluoroethylene.

Method for Manufacturing Semiconductor Element The method for manufacturing a semiconductor device of the present invention includes: a process of cleaning a substrate having a ruthenium compound on the surface using a cleaning agent composition A; and a process of further cleaning the above-mentioned cleaned substrate using a cleaning agent composition B, the cleaning The agent composition A contains at least one organic acid, an acid acid contained in the organic acid containing a sulfur atom or a phosphorus atom, and an organic solvent. The cleaning agent composition B contains an organic carboxylic acid compound, at least water and One of the water-soluble solvents. The method for producing a semiconductor device of the present invention includes a process of performing a rinsing treatment using at least one of the rinsing composition C containing at least one of water and alcohol after the cleaning process using the cleaning agent composition B.

Further, the substrate includes a temporary adhesive layer formed of a temporary adhesive, at least a portion of the temporary adhesive layer is cleaned by the organic acid, and the temporary adhesive contains at least 1 of the ruthenium compound and the precursor of the ruthenium compound. The species is preferred. Therefore, as a substrate having a ruthenium-containing compound on its surface, a substrate to be processed or a carrier substrate can be exemplified. As a temporary adhesive removal agent containing a ruthenium-containing compound, the temporary adhesive layer in the process of removing the temporary adhesive layer on the substrate to be processed, the temporary adhesion of the substrate to be processed and the carrier substrate is removed, and the carrier substrate is reused. The temporary adhesive or the like remaining on the carrier substrate is removed.

In the method for producing a semiconductor device of the present invention, the temporary adhesive is used for temporary bonding between the carrier substrate and the substrate to be processed, and a part or all of the temporary adhesive is removed by using the cleaning agent composition A to clean the substrate to be processed, and then used for cleaning. It is preferred that the agent composition B further cleans the substrate to be processed. The temporary adhesive removed by the cleaning agent composition A is a temporary adhesive or temporary adhesive layer remaining on the substrate to be processed after peeling off the carrier substrate or remaining on the peeling carrier substrate to further peel off the temporary adhesive layer (peel oFF) A temporary adhesive on the substrate to be processed is preferred. The peeling of the temporary adhesive layer is preferably carried out at a temperature of 40 ° C or lower, more preferably at a temperature of 10 to 40 ° C. Further, the peeling of the temporary adhesive layer is preferably manual peeling or mechanical peeling. The substrate to be processed is an element wafer in which a compound semiconductor such as tantalum or glass, SiC, GaN or GaAs, a mold resin or the like is used as a substrate, and a structure is formed on the surface and the inside thereof. In particular, in the present invention, the surface of the substrate to be processed preferably has a metal layer as a structure, and more preferably has a copper layer. In the method for producing a semiconductor device of the present invention, the sulfur atom residue and the phosphorus atom residue derived from the cleaning agent composition A remaining on the surface of the copper layer can be effectively removed by using the cleaning agent composition B. Further, the method of manufacturing a semiconductor element of the present invention is preferably used in the case where a copper layer is provided on the surface of the substrate and a solder ball is provided on the surface of the copper layer. When the solder ball is provided, the method of manufacturing the semiconductor device of the present invention is highly valuable from the viewpoint of removing impurities to improve the adhesion between the solder ball and the copper layer. Further, due to the structure of the semiconductor, there is a case where the unevenness of the wiring layer including the copper layer is present. In particular, the residue containing the sulfur atom and the phosphorus atom derived from the cleaning agent composition A tends to remain on the bottom surface of the copper pad having a circular basin shape of a diameter of 400 to 800 μm and a depth of 5 to 50 μm.

Further, it is preferred to use a cleaning process of the above-mentioned cleaning agent composition A and a process of cleaning using the cleaning agent composition B described above in a single piece. Further, it is preferred that the process for performing the above-described rinsing treatment is also performed by spin drying and washing in a single piece. In addition, after the process of cleaning with the cleaning agent composition A and after the cleaning process using the cleaning agent composition B, it is preferred to include a drying process, respectively. Thus, the effect of the present invention is more effectively exerted by providing a drying process after each cleaning process. In addition, it is preferred to include a drying process after the process of performing the above rinsing treatment. It is preferred to carry out the drying after washing with the cleaning agent composition A at 80 to 200 °C. A drying time of 30 to 180 seconds is preferred. After the above drying, it is preferred to use the cleaning agent composition B for cleaning within 180 seconds. Drying after washing with the cleaning agent composition B is preferably carried out at 80 to 200 °C. A drying time of 30 to 180 seconds is preferred. After the above drying, it is preferred to use the rinse composition C for rinsing within 30 seconds. After applying the rinsing treatment, it is preferred to start drying in 3 seconds. It is preferred to carry out the drying after the rinsing treatment using the rinsing composition C at 80 to 200 °C. A drying time of 30 to 180 seconds is preferred.

In the method for producing a semiconductor device of the present invention, it is preferred that the time from the start of the cleaning process using the cleaning agent composition A to the end of the process of cleaning using the cleaning agent composition B is 30 to 540 seconds. 60 to 240 seconds is better. By setting this time, the removal of the temporary adhesive and the residue removal of the cerium-containing compound can be efficiently performed by one step. Further, the time from the start of the cleaning using the cleaning agent composition A to the completion of the cleaning using the rinse composition C is preferably 60 to 660 seconds, more preferably 90 to 540 seconds. Further, the time A from the start of the cleaning process using the cleaning agent composition A to the start of the cleaning process using the cleaning agent composition B is started from the process of cleaning using the cleaning agent composition B to the use of the above-mentioned rinse composition. The ratio of the time B until the start of the C cleaning process is preferably 1:10 to 10:1, and more preferably 4:6 to 6:4. By setting this ratio, it is possible to make the cleaning effect of each of the substrates in the single-piece process more uniform.

The cleaning agent composition A, the cleaning agent composition B, the rinsing composition C, and the temporary bonding agent in the method for producing a semiconductor device of the present invention are respectively combined with the cleaning agent composition A, the cleaning agent composition B, and the rinsing composition C Temporary adhesives have the same meaning. Therefore, in the method for producing a semiconductor device of the present invention, the kit of the present invention can be preferably used. Further, regarding the method of manufacturing the semiconductor element, in particular, the method of the temporary bonding can be referred to the paragraphs 0074 to 0999 of WO2016/181879 and the descriptions of FIGS. 1 to 3, and the contents are incorporated in the present specification.

Method for cleaning a substrate of a semiconductor device The method for cleaning a substrate of a semiconductor device of the present invention includes: a process of cleaning a substrate having a ruthenium compound on the surface using a cleaning agent composition A; and further cleaning the substrate to be cleaned using a cleaning agent composition B In the process, the cleaning agent composition A contains at least one organic acid, an acid acid contained in the organic acid containing a sulfur atom or a phosphorus atom, and an organic solvent, and the cleaning agent composition B contains an organic carboxylic acid compound. At least one of water and a water-soluble solvent. The method for cleaning the substrate of the semiconductor device of the present invention includes a process of performing a rinsing treatment using at least one of the rinsing composition C containing at least one of water and alcohol after the cleaning process using the cleaning agent composition B.

The cleaning agent composition A, the cleaning agent composition B, the rinsing composition C, and the temporary bonding agent in the method for cleaning the substrate of the semiconductor device of the present invention are respectively combined with the above-mentioned cleaning agent composition A, cleaning agent composition B, and rinsing The composition C and the temporary binder have the same meaning. Therefore, in the method of cleaning a substrate of a semiconductor device of the present invention, the kit of the present invention can be preferably used. [Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples as long as it does not exceed the gist of the invention. In addition, “part” and “%” are quality standards unless otherwise specified.

<Preparation of Temporary Binder> As shown in Table 1 below, each component of the temporary binder was mixed into a uniform solution, and then filtered using a filter made of polytetrafluoroethylene having a pore diameter of 0.2 μm to prepare a temporary binder.

[Table 1]

The details of the compounds used are as follows. <<Elastomer>> P-1: SEPTON4033 (manufactured by KURARAY CO., LTD., polystyrene elastomer) P-2: SEPTON 2104 (manufactured by KURARAY CO., LTD., polystyrene elastomer) P- 3: SEPTON8004 (made by KURARAY CO., LTD., polystyrene elastomer)

<<Indole-containing compound>> Si-1: TSF4446 (polyether-modified polyorganosiloxane manufactured by Momentive Performance Materials Inc.) Si-2: TSF4445 (manufactured by Momentive Performance Materials Inc., polyether-denatured organopolyoxane Si-3: Silwet L-7605 (polyether-modified organic polyoxane manufactured by Momentive Performance Materials Inc.) Si-4: KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd., polyether-denatured organic polymerization)矽 烷 ) Si-5: Silwet L-7200 (polyether-modified polyorganosiloxane manufactured by Momentive Performance Materials Inc.) Si-6: KP-323 (manufactured by Shin-Etsu Chemical Co., Ltd., 矽Si-7: fluorine atom-containing decane coupling agent (precursor of ruthenium compound) (manufactured by Tokyo Chemical Industry Co., Ltd., triethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) decane)

<<Other Additives>> A-1: Irganox 1010 (manufactured by BASF JAPAN LTD.) A-2: Sumilizer TP-D (manufactured by Sumitomo Chemical Company, Ltd.)

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

<Preparation of the cleaning agent composition A> As shown in the following Table 2 and Table 3, after the components of the cleaning agent composition A were mixed into a uniform solution, filtration was carried out using a filter made of polytetrafluoroethylene having a pore diameter of 0.2 μm. The cleaning agent composition A was prepared. [Table 2]

[table 3]

The cleaning agent composition B was prepared as shown in Table 4 and Table 5, and the components of the cleaning agent composition B were mixed into a uniform solution, and then filtered by using a filter made of polytetrafluoroethylene having a pore diameter of 0.2 μm. The cleaning agent composition B.

[Table 4]

[table 5]

<Preparation of Flushing Composition C> As shown in the following Table 6, a component of the rinse composition C was filtered using a filter made of polytetrafluoroethylene having a pore diameter of 0.2 μm to prepare a rinse composition C. [Table 6]

Evaluation method As a carrier substrate, a disk-shaped silicon wafer having a diameter of 12 inches (2.5 inches per 1 inch) was used, and the temporary adhesive was applied to the surface using a coating device (EV Group Japan KK, EVG 101). The film formation is layered. Using a hot plate (EV Group Japan KK, EVG 105), the laminate was heated at 100 ° C for 3 minutes and further heated at 180 ° C for 3 minutes, thereby obtaining a laminate A in which a temporary adhesion layer was formed on the surface of the carrier substrate. The thickness of the temporary adhesive layer was 60 μm. The carrier substrate of the obtained laminate A was placed on the coating device (EV Group Japan KK, EVG 101), and the rotation speed was accelerated to 2000 rpm from an acceleration of 50 rpm at a rotation speed of 1250 rpm, and a flow rate of 20 mL/ was used. Minute mesitylene was subjected to a BSR (Back Side Rince) treatment on the swash plate portion of the carrier substrate, thereby cleaning the temporary adhesion layer adhering to the swash plate portion.

A substrate on which a titanium layer having a thickness of 10 nm and a copper layer having a thickness of 50 nm were sequentially formed by sputtering on a surface of a disk-shaped ruthenium wafer having a diameter of 12 inches was obtained. The laminate A obtained above and the substrate to be processed were subjected to thermocompression bonding for 1 minute under the conditions of a pressure of 1 Pa, a temperature of 200 ° C, and a pressure of 0.3 MPa using a wafer bonding apparatus (EV Group Japan KK, EVG 540). , the laminated body B was obtained. When crimping, the temporary adhesive layer is placed in contact with the copper layer.

The back surface of the substrate (the side on which the temporary adhesion layer was not provided) of the laminate B obtained above was polished to a thickness of 40 μm using a DFG8540 manufactured by Disco Corporation to obtain a laminate which was subjected to back grinding (thinning). C.

The surface of the layered body C subjected to the back grinding process was directed downward, and the lower side silicon wafer was fixed together with the dicing frame at the center of the dicing blue film using a dicing blue film loader. Then, using a wafer bonding apparatus (manufactured by Tokyo Electron Limited, Synapse Z), the upper side silicon wafer was pulled at a speed of 3 mm/min in a direction perpendicular to the lower side of the germanium wafer at 25 ° C, and a temporary adhesive layer was obtained. (or a residue derived from a temporary binder) and a laminate D of the substrate to be processed. The upper silicon wafer can be peeled off without rupturing the underlying germanium wafer.

The laminate D which can be used for the above-described peeling is supplied to the substrate A while being rotated by the wafer bonding apparatus (Synapse Z, manufactured by Tokyo Electron Limited), and is supplied to the substrate A to be cleaned. The substrate to be processed after washing was dried by heating at 110 ° C for 2 minutes.

<Surface observation (carbon atom residue and cesium atom residue)> The surface of the substrate to be processed which was cleaned and dried using the above-mentioned cleaning agent composition A was a Quantera SXM apparatus (manufactured by ULVAC-PHI, INCORPORATED) and used as an X-ray source. Measurements were carried out using monochromated Al-Kα rays (energy value; 1486.6 eV, power; 25 W, voltage; 15 kV, beam diameter: 200 μm). The measurement ratio is 1400 × 700 μm ² , the measurement conditions are Pass Energy = 140 eV, the step length = 0.1 eV, and the cumulative number of times is 1 to 3 times, and the ratio of the presence of carbon atoms to germanium atoms (carbon atom residue, germanium atom residue), The evaluation was performed on the basis of the following criteria. <<Carbon 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 <<矽 atom residue>> A: 矽 atom is less than 0.1 mol% B: 矽 atom is 0.1 mol% or more and less than 1 mol% C: 矽 atom is 1 mol% or more and less than 3 mol% D: 矽 atom is 3 mol %the above

After cleaning with the above-described cleaning agent composition A, a wafer bonding apparatus (Synapse Z, manufactured by Tokyo Electron Limited) is used, and the cleaning agent composition B is supplied while rotating the substrate to be processed on the surface of the substrate to be processed after drying. It was cleaned. The substrate to be processed after washing is spin-dried. Then, the cleaning composition B is cleaned by the above-described cleaning agent composition B, and a wafer bonding apparatus (Synapse Z, manufactured by Tokyo Electron Limited) is used, and the rinse composition is supplied while rotating the laminated body D on the surface of the substrate to be processed after drying. C was flushed. It was dried by heating at 100 ° C for 1 minute.

<Surface observation (sulfur atom residue and phosphorus atom residue)> The surface of the substrate to be processed which has been cleaned by the cleaning agent composition B is a Quantera SXM device (manufactured by ULVAC-PHI, INCORPORATED), and is used as an X-ray source. The coloring Al-Kα ray (energy value; 1486.6 eV, power; 25 W, voltage; 15 kV, beam diameter: 200 μm) was measured. The measurement ratio is 1400 × 700 μm ² , the measurement conditions are Pass Energy = 140 eV, the step length = 0.1 eV, and the cumulative number of times is 1 to 3 times, and the ratio of the sulfur atom to the phosphorus atom (sulfur atom residue, phosphorus atom residue) is The evaluation was performed on the basis of 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: carbon 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: carbon atom More than 3mol%

<Improvement of Copper Discoloration> A substrate provided with a copper layer having a thickness of 50 nm was formed by sputtering on the surface of a disk-shaped ruthenium wafer having a diameter of 12 inches. The cleaning agent composition A was supplied while rotating the copper layer of the ruthenium wafer using a wafer bonding apparatus (manufactured by Tokyo Electron Limited, Synapse Z). The substrate to be processed after washing was dried by heating at 110 ° C for 2 minutes. Next, washing is performed by supplying the cleaning agent composition B. Next, rinsing is performed by supplying the rinse composition C to the substrate to be processed after washing. It was dried by heating at 100 ° C for 1 minute. The time from the start of the cleaning process using the cleaning agent composition A to the start of the process of cleaning using the cleaning agent composition B was 200 seconds. The time from the start of the process of cleaning using the above-mentioned cleaning agent composition B to the start of the process of cleaning using the above-described rinse composition C was 140 seconds. Further, the time from the start of washing using the cleaning agent composition A to the completion of washing using the rinse composition C was 460 seconds. Thereafter, it was allowed to stand in a clean room at room temperature of 23 degrees and a relative humidity of 55% for 48 hours, and the following observation was made by visual observation. A: No discoloration of the copper layer was observed. B: The copper layer slightly changed to a thin brown color. C: The copper layer turned brown.

The results are shown in Tables 7 and 8 below. [Table 7]

[Table 8]

From the above results, it was found that when the kit of the present invention was used, none of the carbon atom residue, the cesium atom residue, the sulfur atom residue, and the phosphorus atom residue was observed. Also, no discoloration of the copper layer was observed. On the other hand, when the cleaning agent composition B was not used (Comparative Examples 1 to 11), the carbon atom residue and the cesium atom residue were not observed, but the sulfur atom residue or the phosphorus atom residue was confirmed. Also, it was confirmed that some copper layers were discolored. On the other hand, when the cleaning agent composition A was not used (Comparative Examples 12 to 23), the carbon atom residue and the cesium atom residue were confirmed. Also, the copper layer turned brown. Further, when other cleaning agent compositions were used instead of the cleaning agent composition A (Comparative Examples 24 and 25), any one of the carbon atom residue, the cesium atom residue, the sulfur atom residue, and the phosphorus atom residue was also confirmed. In addition, the discoloration of the copper layer was also confirmed. On the other hand, when other cleaning agent compositions were used instead of the cleaning agent composition B (Comparative Examples 26 to 28), the residue of the sulfur atom residue and the residue of the phosphorus atom were confirmed. In addition, it was confirmed that the effective copper layer was discolored.

Since the substrate obtained by the method of the present invention has no carbon atom residue, ruthenium atom residue, sulfur atom residue, and phosphorus atom residue, and the copper layer does not change color, it can be preferably used as a substrate of a semiconductor element.

no

no

Claims (29)

A kit comprising: a temporary binder comprising at least one selected from the group consisting of a ruthenium compound and a ruthenium compound-containing precursor; a cleaning agent composition A comprising an organic acid and an organic solvent, At least one of an acid acid contained in the organic acid containing a sulfur atom or a phosphorus atom; and a cleaning agent composition B containing at least one of an organic carboxylic acid compound and at least water and a water-soluble solvent. The kit according to claim 1, wherein the organic acid contains at least one selected from the group consisting of organic sulfonic acids, organic phosphoric acids and organic phosphonic acids. The kit of claim 1, wherein the cerium-containing compound contains eucalyptus oil. The kit according to any one of claims 1 to 3, wherein the ruthenium-containing compound contains a polyether-modified oxime. The kit according to any one of claims 1 to 3, wherein the content of the cerium-containing compound in the temporary binder is 0.001 to 1.0% by mass. The kit according to any one of claims 1 to 3, wherein the temporary adhesive contains an elastomer. The kit of claim 6, wherein the elastomer is a polystyrene elastomer. The kit according to any one of claims 1 to 3, wherein the organic acid has an acid dissociation constant pKa of -4 to 5. The kit according to any one of claims 1 to 3, wherein the organic acid is selected from the group consisting of an alkylsulfonic acid, an aromatic sulfonic acid, an alkylphosphonic acid, an aromatic phosphoric acid, an alkylphosphonic acid, and an aromatic phosphine. A group of acids. The kit according to any one of claims 1 to 3, wherein the organic solvent contained in the detergent composition A contains an aromatic hydrocarbon solvent having an alkyl group. The kit according to claim 10, wherein the aromatic hydrocarbon solvent having the 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 3, wherein a mass ratio of the organic acid to the organic solvent in the detergent composition A is 0.0001: 99.9999 to 50:50. The kit according to any one of claims 1 to 3, 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. The kit according to any one of claims 1 to 3, wherein a ratio of the equilibrium concentration of 1-octanol to water in the organic carboxylic acid compound to 1-octyl alcohol/water partition coefficient P is The logarithm of the logP relative to the base 10 indicates a value of -5 to 6. The kit according to any one of claims 1 to 3, wherein the solvent contained in the detergent composition B contains water. The kit according to any one of claims 1 to 3, wherein the organic carboxylic acid compound has an acid dissociation constant pKa of from 1 to 7. The kit according to any one of claims 1 to 3, wherein a mass ratio of the organic carboxylic acid compound to the solvent in the cleaning agent composition B is 0.0001: 99.9999 to 50:50. The kit according to any one of claims 1 to 3, further comprising a rinse composition C containing at least one of water and alcohol. A method of manufacturing a semiconductor device, comprising: a process of cleaning a substrate having a ruthenium compound on a surface using a cleaning agent composition A; and further cleaning a process of the cleaned substrate using a cleaning agent composition B, the cleaning agent composition A containing : an organic acid, at least one of an acid acid contained in the organic acid containing a sulfur atom or a phosphorus atom; and an organic solvent, the cleaning agent composition B containing an organic carboxylic acid compound, at least water and a water-soluble solvent 1 species. The method for producing a semiconductor device according to claim 19, wherein the organic acid contains at least one selected from the group consisting of organic sulfonic acids, organic phosphoric acids, and organic phosphonic acids. The method of manufacturing a semiconductor device according to claim 19 or 20, wherein the substrate comprises a temporary adhesive layer formed of a temporary adhesive, at least a portion of the temporary adhesive layer being cleaned by the organic acid, and The temporary binder contains at least one of the ruthenium compound and the precursor of the ruthenium compound. The method for producing a semiconductor device according to claim 19 or 20, wherein the cleaning process using the cleaning agent composition A and the cleaning process using the cleaning agent composition B are performed in a single piece. The method of manufacturing a semiconductor device according to claim 19, wherein the cleaning process is performed after the cleaning process using the cleaning agent composition A and the cleaning process using the cleaning agent composition B, respectively. The method of manufacturing a semiconductor device according to claim 19 or 20, wherein a period of time from the start of the process of cleaning using the cleaning agent composition A to the end of the process of cleaning using the cleaning agent composition B is 30 to 300 seconds. The method for producing a semiconductor device according to the invention of claim 19, wherein the process of cleaning with the cleaning agent composition B is followed by rinsing with a rinse composition C containing at least one of water and alcohol. Process. A method of producing a semiconductor device using the kit according to any one of claims 1 to 18. A method for cleaning a substrate of a semiconductor device, comprising: a process of cleaning a substrate having a ruthenium compound on a surface using a cleaning agent composition A; and a process of further cleaning the cleaned substrate using a cleaning agent composition B, the cleaning composition A contains: an organic acid, at least one of an acid acid contained in the organic acid containing a sulfur atom or a phosphorus atom; and an organic solvent, the cleaning agent composition B containing an organic carboxylic acid compound, at least water and water-soluble One of the solvents. The method for cleaning a substrate of a semiconductor device according to claim 27, which comprises rinsing with a rinsing composition C containing at least one of water and alcohol after the cleaning process using the cleaning agent composition B Process of processing. A method of cleaning a substrate of a semiconductor device according to the invention of claim 27 or 28, which uses the kit according to any one of claims 1 to 18.