Semiconductor substrate cleaning composition and cleaning method

Abstract

A semiconductor substrate cleaning composition containing: hydrogen peroxide (A), a hydrogen peroxide stabilizer (B) which is at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-1H-tetrazole, triethylenetetraminehexaacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+) -isoleucine, DL-valine, L(-) -proline, hydroxyethylethylenediaminetriacetic acid, N,N-bis(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine, an alkali compound (C) which is at least one selected from the group consisting of quaternary ammonium hydroxide (C1) and potassium hydroxide (C2), and water.

Description

TECHNICAL FIELD

[0001] The present application relates to a composition for cleaning a semiconductor substrate and a cleaning method. BACKGROUND

[0002] In the production of a semiconductor substrate in which a semiconductor element is highly integrated, after a conductive thin film such as a metal film that becomes a conductive wiring material, an interlayer insulating film for insulating between the conductive thin films, a hard mask, and the like are formed on a substrate such as a silicon wafer, a photosensitive layer is provided by uniformly applying a photoresist on the surface thereof, selective exposure and development processing are performed thereon, and a desired photoresist pattern is produced. Then, the photoresist pattern is used as a mask, and dry etching processing is performed on the substrate on which the interlayer insulating film, the hard mask, and the like are laminated, and a desired pattern is formed on the substrate. Then, the residue (hereinafter referred to as "dry etching residue") generated by the photoresist pattern and the dry etching processing is removed by ashing using an oxygen plasma, a cleaning liquid, or the like.

[0003] In recent years, the current density of the metal wiring has increased in accordance with the progress of the miniaturization of the design rule, and thus, when the current flows in the metal wiring material, the atoms constituting the metal wiring move, and a countermeasure against electromigration in which a hole is formed in the metal wiring is more strongly required. As the countermeasure, there are a method in which a layer of cobalt or a cobalt alloy is formed around the copper wiring as a cap metal, and a method in which cobalt or a cobalt alloy is used as the metal wiring material. Therefore, in the production of a semiconductor element on a substrate such as a silicon wafer, a method in which a hard mask is removed in the presence of copper or a copper alloy, and cobalt or a cobalt alloy has been proposed.

[0004] For example, in Patent Literature 1, as a cleaning liquid composition for suppressing damage to copper or a copper alloy, cobalt or a cobalt alloy, and removing a titanium nitride hard mask, a cleaning liquid composition is disclosed, which respectively contains specific amounts of hydrogen peroxide, potassium hydroxide, aminopolymethylenephosphonic acid, a zinc salt, and water.

[0005] In addition, in Patent Literatures 2 to 18, an etchant, a cleaning agent, and a peeling agent for a semiconductor substrate containing an oxidizing agent mainly of hydrogen peroxide are disclosed.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

[0008] Patent Literature 1: Japanese Patent Application Laid-Open No. 2017-076783

[0009] Patent Literature 2: Japanese Patent Application Laid-Open No. 2020-017732

[0010] Patent Literature 3: Japanese Patent Application Laid-Open No. 2018-093225

[0011] Patent Literature 4: Japanese Patent Application Laid-Open (JP A) No. 2017-031502

[0012] Patent Literature 5: Japanese Patent Application Laid-Open (JP A) No. 2018-093225

[0013] Patent Literature 6: Japanese Patent Application Laid-Open (JP A) No. 2015-156171

[0014] Patent Literature 7: Japanese Patent Application Laid-Open (JP A) No. 2016-176126

[0015] Patent Literature 8: Japanese Patent Application Laid-Open (JP A) No. 2015-506583

[0016] Patent Literature 9: Japanese Patent Application Laid-Open (JP A) No. 2013-199702

[0017] Patent Literature 10: Japanese Patent Application Laid-Open (JP A) No. 2011-228517

[0018] Patent Literature 11: Japanese Patent Application Laid-Open (JP A) No. 2009-512194

[0019] Patent Literature 12: Japanese Patent Application Laid-Open (JP A) No. 2009-505388

[0020] Patent Literature 13: Japanese Patent Application Laid-Open (JP A) No. 2009-041112

[0021] Patent Literature 14: Japanese Patent Application Laid-Open (JP A) No. 2009-120870

[0022] Patent Literature 15: Japanese Patent Application Laid-Open (JP A) No. 2008-285508

[0023] Patent Literature 16: Japanese Patent Application Laid-Open (JP A) No. 2004-317584

[0024] Patent Literature 17: Japanese Patent Application Laid-Open (JP A) No. 2004-212818

[0025] Patent Literature 18: Japanese Patent Application Laid-Open (JP A) No. 2005-201100 SUMMARY

[0026] PROBLEMS TO BE SOLVED BY THE INVENTION

[0027] For example, the cleaning agent in the related art represented by Patent Literature 1 aims at suppressing damage to copper or a copper alloy or cobalt or a cobalt alloy when a semiconductor substrate is cleaned. However, in a process of cleaning a semiconductor substrate containing various metals such as copper or a copper alloy, cobalt or a cobalt alloy, hydrogen peroxide in a cleaning solution easily decomposes, and there arises a problem that cleaning cannot be performed for a long time and the cleaning solution cannot be reused.

[0028] Therefore, a semiconductor substrate cleaning composition in which hydrogen peroxide is stable even in the presence of various metals such as copper and cobalt, cleaning can be performed for a long time, and the cleaning solution can be reused is sought.

[0029] The present application provides a semiconductor substrate cleaning composition in which hydrogen peroxide is stable even in the presence of various metals including cobalt, cleaning can be performed for a long time, and the cleaning solution can be reused.

[0030] In particular, the first problem to be solved by the present application is to provide a semiconductor substrate cleaning composition in which hydrogen peroxide is stable even in the presence of copper and cobalt, cleaning can be performed for a long time, and the cleaning solution can be reused.

[0031] In addition, the second problem to be solved by the present application is to provide a semiconductor substrate cleaning composition in which hydrogen peroxide is stable even in the presence of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt, cleaning can be performed for a long time, and the cleaning solution can be reused.

[0032] Solution to the problem

[0033] The present application provides the following semiconductor substrate cleaning composition.

[0034] <1> A semiconductor substrate cleaning composition comprising: hydrogen peroxide (A), a hydrogen peroxide stabilizer (B), an alkali compound (C), and water,

[0035] The hydrogen peroxide stabilizer (B) is at least one selected from the group consisting of oxalic acid, diethylenetriamine pentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-1H-tetrazole, triethylenetetramine hexaacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-di(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine,

[0036] The alkali compound (C) is at least one selected from the group consisting of quaternary ammonium hydroxide (C1) and potassium hydroxide (C2).

[0037] <2> The semiconductor substrate cleaning composition according to the aforementioned <1>, wherein the content of the hydrogen peroxide stabilizer (B) is 0.0001 to 5 mass% in the semiconductor substrate cleaning composition.

[0038] <3> The semiconductor substrate cleaning composition according to any one of the preceding <1> or <2>, wherein the content of the hydrogen peroxide (A) is 10 to 30 mass% in the semiconductor substrate cleaning composition.

[0039] <4> The semiconductor substrate cleaning composition according to any one of the preceding <1> to <3>, wherein the pH is 7 to 12.

[0040] <5> The semiconductor substrate cleaning composition according to any one of the preceding <1> to <4>, further comprising an aminopolymethylene phosphonic acid (D).

[0041] <6> The semiconductor substrate cleaning composition according to the preceding <5>, wherein the content of the aminopolymethylene phosphonic acid (D) is 0.00005 to 0.005 mass% in the semiconductor substrate cleaning composition.

[0042] <7> The semiconductor substrate cleaning composition according to any one of the preceding <1> to <6>, wherein the content of the quaternary ammonium hydroxide (C1) is 0.005 to 10 mass% in the semiconductor substrate cleaning composition.

[0043] <8> The semiconductor substrate cleaning composition according to any one of the preceding <1> to <7>, wherein the content of the potassium hydroxide (C2) is 0.005 to 5 mass% in the semiconductor substrate cleaning composition.

[0044] <9> The semiconductor substrate cleaning composition according to any one of the preceding <1> to <8>, wherein the quaternary ammonium hydroxide (C1) is at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide.

[0045] <10> The semiconductor substrate cleaning composition according to any one of the preceding <5> to <9>, wherein the aminopolymethylene phosphonic acid (D) is at least one selected from the group consisting of amino-tris(methylene phosphonic acid), ethylenediamine-tetra(methylene phosphonic acid), diethylenetriamine-penta(methylene phosphonic acid), and 1,2-propanediamine-tetra(methylene phosphonic acid).

[0046] <11> The semiconductor substrate cleaning composition according to any one of the preceding <1> to <10>, wherein the hydrogen peroxide stabilizer (B) is at least one selected from the group consisting of oxalic acid, diethylenetriamine-pentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, triethylenetetramine-hexaacetic acid, trans-1,2-cyclohexanediamine-tetraacetic acid, 8-hydroxyquinoline, hydroxyethylethylenediaminetriacetic acid, 5-phenyl-1H-tetrazole, N,N-bis(2-hydroxyethyl)glycine, and benzothiazole.

[0047] <12> The semiconductor substrate cleaning composition according to any one of the preceding <1> to <11>, wherein the semiconductor substrate cleaning composition is substantially free of any of ammonia and ammonium ion (NH4 + ).

[0048] <13> The semiconductor substrate cleaning composition according to any one of the preceding <1> to <12>, which is used for cleaning a semiconductor substrate having a hard mask comprising at least 1 selected from the group consisting of titanium and titanium nitride.

[0049] <14> The semiconductor substrate cleaning composition according to any one of the preceding <1> to <13>, which is used for cleaning a semiconductor substrate comprising cobalt and copper.

[0050] <15> The semiconductor substrate cleaning composition according to any one of the preceding <1> to <14>, wherein, relative to the total amount of the semiconductor substrate cleaning composition, 400 mass ppb of cobalt ions and 1000 mass ppb of copper ions are added, and the residual rate of hydrogen peroxide (A) after 6 hours of treatment at 50°C is 50% or more, with the content of hydrogen peroxide before the treatment as a reference.

[0051] <16> The semiconductor substrate cleaning composition according to any one of the preceding <1> to <13>, which is used for cleaning a semiconductor substrate comprising at least 1 metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt.

[0052] <17> The semiconductor substrate cleaning composition according to the preceding <16>, wherein the at least 1 metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum is at least 1 metal selected from the group consisting of titanium, zirconium, hafnium, tantalum, tungsten, manganese, ruthenium, magnesium, and aluminum.

[0053] <18> A cleaning method of cleaning a semiconductor substrate with the semiconductor substrate cleaning composition according to any one of the preceding <1> to <15> in the presence of cobalt ions and copper ions.

[0054] <19> A cleaning method of cleaning a semiconductor substrate comprising cobalt and copper with the semiconductor substrate cleaning composition according to any one of the preceding <1> to <15>.

[0055] <20> A cleaning method of cleaning a semiconductor substrate with the semiconductor substrate cleaning composition according to any one of the preceding <1> to <13>, the preceding <16>, and <17> in the presence of ions of at least 1 metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt ions.

[0056] <21> A cleaning method for cleaning a semiconductor substrate containing at least one metal selected from the group consisting of a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, magnesium, and aluminum, and cobalt, with the composition for cleaning a semiconductor substrate according to any one of <1> to <13>, <16>, and <17>.

[0057] <22> The cleaning method according to any one of <18> to <21>, wherein a semiconductor substrate having a hard mask containing at least one selected from the group consisting of titanium and titanium nitride is cleaned.

[0058] <23> A cleaning method for removing at least one selected from the group consisting of a dry etching residue in a semiconductor substrate and a hard mask, with the composition for cleaning a semiconductor substrate according to any one of <1> to <17>.

[0059] <24> A method for stabilizing hydrogen peroxide, wherein hydrogen peroxide (A) is stabilized with a hydrogen peroxide stabilizer (B) in a liquid containing hydrogen peroxide (A), cobalt ions, copper ions, and water, the hydrogen peroxide stabilizer (B) being at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-lH-tetrazole, triethylenetetraminehexaacetic acid, trans-l,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-bis(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine.

[0060] <25> The method for stabilizing hydrogen peroxide according to <24>, wherein the liquid containing hydrogen peroxide (A), cobalt ions, copper ions, and water has a pH of 7 to 12.

[0061] <26> A method for stabilizing hydrogen peroxide, wherein hydrogen peroxide (A) is stabilized with a hydrogen peroxide stabilizer (B) in a liquid containing hydrogen peroxide (A), ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, cobalt ions, and water, the hydrogen peroxide stabilizer (B) being at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-lH-tetrazole, triethylenetetraminehexaacetic acid, trans- 1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-di(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine.

[0062] <27> The method for stabilizing hydrogen peroxide according to the preceding <26>, wherein the pH of the liquid containing hydrogen peroxide (A), ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, cobalt ions, and water is 7 to 12.

[0063] <28> A method for manufacturing a semiconductor substrate, comprising a step of removing at least one selected from the group consisting of dry etching residues and hard masks in a semiconductor substrate, using the semiconductor substrate cleaning composition according to any one of <1> to <17>.

[0064] Effects of the Invention

[0065] The semiconductor substrate cleaning composition of the present invention also has high stability of hydrogen peroxide in the presence of a plurality of metals including cobalt, and can perform long-term cleaning and the cleaning solution can be reused.

[0066] In particular, the semiconductor substrate cleaning composition of the present invention also has high stability of hydrogen peroxide in the presence of copper and cobalt, and can perform long-term cleaning and the cleaning solution can be reused.

[0067] In addition, the semiconductor substrate cleaning composition of the present invention also has high stability of hydrogen peroxide in the presence of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt, and can perform long-term cleaning and the cleaning solution can be reused. DETAILED DESCRIPTION

[0068] The present application is a semiconductor substrate cleaning composition containing: hydrogen peroxide (A), a hydrogen peroxide stabilizer (B), an alkali compound (C), and water, the hydrogen peroxide stabilizer (B) being at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-1H-tetrazole, triethylenetetraminehexaacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-di(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine, the alkali compound (C) being at least one selected from the group consisting of quaternary ammonium hydroxide (C1) and potassium hydroxide (C2), a cleaning method using the semiconductor substrate cleaning composition, a manufacturing method of a semiconductor substrate, and a hydrogen peroxide stabilization method using the aforementioned hydrogen peroxide stabilizer (B) to stabilize hydrogen peroxide (A).

[0069] [Semiconductor substrate cleaning composition]

[0070] The semiconductor substrate cleaning composition of the present application contains: hydrogen peroxide (A), a hydrogen peroxide stabilizer (B), an alkali compound (C), and water, the hydrogen peroxide stabilizer (B) being at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-1H-tetrazole, triethylenetetraminehexaacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-di(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine, the alkali compound (C) being at least one selected from the group consisting of quaternary ammonium hydroxide (C1) and potassium hydroxide (C2).

[0071] <Hydrogen peroxide (A)>

[0072] The semiconductor substrate cleaning composition of the present application contains hydrogen peroxide (A).

[0073] Hydrogen peroxide (A) is usually mixed with other components as an aqueous solution of a moderate concentration. The concentration of hydrogen peroxide (A) in the hydrogen peroxide aqueous solution used in the production of the semiconductor substrate cleaning composition of the present application is not particularly limited, and is preferably, for example, 10 to 90 mass%, more preferably 30 to 60 mass% in accordance with an industrial standard.

[0074] Further, the hydrogen peroxide (A) can contain a stabilizer used at the time of production thereof. The method of producing the hydrogen peroxide (A) is not limited, and for example, one produced by an anthraquinone method or the like is suitably used. Further, the hydrogen peroxide (A) can also be purified by a method such as passing a liquid through an ion exchange resin.

[0075] The content of the hydrogen peroxide (A) is preferably 10 to 30% by mass, and more preferably 10 to 20% by mass in the semiconductor substrate cleaning composition from the viewpoint of cleaning properties.

[0076] <Hydrogen Peroxide Stabilizer (B)>

[0077] The semiconductor substrate cleaning composition of the present application contains a hydrogen peroxide stabilizer (B) which is at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-lH-tetrazole, triethylenetetraminehexaacetic acid, trans- 1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-di(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine.

[0078] The semiconductor substrate cleaning composition of the present application contains the aforementioned hydrogen peroxide stabilizer (B), and thus the stability of hydrogen peroxide is also high in the presence of a plurality of metals including cobalt, and cleaning can be performed for a long period of time and reused. The semiconductor substrate cleaning composition of the present application contains the aforementioned hydrogen peroxide stabilizer (B), and thus the stability of hydrogen peroxide is also high especially in the presence of both copper and cobalt, and cleaning can be performed for a long period of time and reused. Further, the semiconductor substrate cleaning composition of the present application contains the aforementioned hydrogen peroxide stabilizer (B), and thus the stability of hydrogen peroxide is also high in the presence of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt, and cleaning can be performed for a long period of time and reused.

[0079] As a result of research by the present inventors and the like, it has been found that, in cleaning of a semiconductor substrate using a semiconductor substrate cleaning composition, decomposition of hydrogen peroxide is particularly likely to occur in the presence of a plurality of metals including cobalt, and especially in the presence of both copper and cobalt, that is, in the presence of both copper and cobalt. Specifically, stabilizers of hydrogen peroxide against metal ions such as copper ions or cobalt ions are described in the aforementioned Patent Documents 2 to 18 as prior art, but decomposition of hydrogen peroxide in the presence of both copper ions and cobalt ions cannot be inhibited.

[0080] On the other hand, the present inventors and others have repeatedly and intensively studied, and as a result, have found a semiconductor substrate cleaning composition in which the stability of hydrogen peroxide is also high in the presence of both copper ions and cobalt ions, as described above. Further, they have found a semiconductor substrate cleaning composition in which the stability of hydrogen peroxide is also high in the presence of both ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt ions, as described above.

[0081] The reason why the stability of hydrogen peroxide is improved particularly in the presence of both copper and cobalt in the semiconductor substrate cleaning composition of the present application, as described above, is not clear, but it is believed that the compound exemplified here exhibits a strong chelating ability to either of copper ions or cobalt ions, or both, in the presence of two kinds of metals and in an alkaline solution, due to its structure, particularly the balance of amino groups and carboxyl groups. In addition, copper ions and cobalt ions alone also have a certain hydrogen peroxide decomposition ability, but as described above, the decomposition rate becomes a problem by the simultaneous presence of copper ions and cobalt ions. As a mechanism thereof, it is believed that, in addition to the catalytic effect based on copper ions and cobalt ions, a Fenton-like reaction proceeds due to the presence of copper ions, and the generated hydroxyl radicals participate therein. It is believed that, in the hydrogen peroxide stabilizer (B) of the present application, in addition to the chelating ability, there is also an ability to capture hydroxyl radicals, thereby further improving the stability of hydrogen peroxide.

[0082] The hydrogen peroxide stabilizer (B) is at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-1H-tetrazole, triethylenetetraminehexaacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-di(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine.

[0083] In the hydrogen peroxide stabilizer (B), from the viewpoint of inhibiting corrosion of metals and the like that constitute the semiconductor substrate, at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, triethylenetetraminehexaacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, hydroxyethylethylenediaminetriacetic acid, 5-phenyl-lH-tetrazole, N,N-bis(2-hydroxyethyl)glycine, and benzothiazole is preferred, from the viewpoint of inhibiting corrosion of metals and further improving stability of hydrogen peroxide, at least one selected from the group consisting of diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, 8-hydroxyquinoline, hydroxyethylethylenediaminetriacetic acid, and trans-1,2-cyclohexanediaminetetraacetic acid is more preferred, and trans-1,2-cyclohexanediaminetetraacetic acid is further preferred.

[0084] The semiconductor substrate contains a metal portion such as a metal wiring, but it is considered that the hydrogen peroxide stabilizer (B) described herein has a specific property of capturing metal ions in a solution and not contributing to ionization of the metal, stabilizes hydrogen peroxide without corroding the metal wiring and the like, and improves cleaning properties. It is further considered that it also has the ability to capture hydroxyl radicals.

[0085] As the hydrogen peroxide stabilizer (B), the aforementioned compounds can be given, but hydrates, salts, and derivatives of these compounds and the like generated in the cleaning composition can also be used. For example, for trans-1,2-cyclohexanediaminetetraacetic acid, it is preferred to use a monohydrate in terms of availability and ease of compounding.

[0086] The content of the hydrogen peroxide stabilizer (B) in the semiconductor substrate cleaning composition is preferably 0.0001 to 5% by mass, and more preferably 0.001 to 1% by mass.

[0087] If examples are cited using the following specific compounds, for example, for the content of trans-1,2-cyclohexanediaminetetraacetic acid, as trans-1,2-cyclohexanediaminetetraacetic acid monohydrate, it is preferable that the content in the semiconductor substrate cleaning composition be 0.0001 to 5 mass%, more preferable 0.001 to 1 mass%, further preferable 0.001 to 0.5 mass%, more further preferable 0.002 to 0.3 mass%, more further preferable 0.003 to 0.2 mass%, more further preferable 0.003 to 0.1 mass%, more further preferable 0.005 to 0.05 mass%, more further preferable 0.005 to 0.01 mass% in terms of a balance between cost and effect. Also, the content of diethylenetriaminepentaacetic acid in the semiconductor substrate cleaning composition is preferably 0.0001 to 5 mass%, more preferably 0.001 to 1 mass%, further preferably 0.01 to 1 mass%, more further preferably 0.02 to 0.8 mass%, more further preferably 0.02 to 0.1 mass%. The content of hydroxyethyliminodiacetic acid in the semiconductor substrate cleaning composition is preferably 0.001 to 5 mass%, more preferably 0.01 to 3 mass%, further preferably 0.05 to 1 mass%, more further preferably 0.05 to 0.5 mass%. The content of triethylenetetraminehexaacetic acid in the semiconductor substrate cleaning composition is preferably 0.0001 to 5 mass%, more preferably 0.001 to 1 mass%, further preferably 0.005 to 0.5 mass%, more further preferably 0.01 to 0.1 mass%. The content of 8-hydroxyquinoline in the semiconductor substrate cleaning composition is preferably 0.0001 to 5 mass%, more preferably 0.0005 to 1 mass%, further preferably 0.001 to 0.1 mass%, more further preferably 0.001 to 0.01 mass%. The content of hydroxyethylethylenediaminetriacetic acid in the semiconductor substrate cleaning composition is preferably 0.001 to 5 mass%, more preferably 0.01 to 3 mass%, further preferably 0.05 to 1 mass%, more further preferably 0.05 to 0.5 mass%.

[0088] By the content of the hydrogen peroxide stabilizer (B) being within the aforementioned range, the semiconductor substrate cleaning composition of the present application has high stability of hydrogen peroxide in the presence of a plurality of metals including cobalt, particularly in the presence of copper and cobalt, and can perform cleaning for a long time and be reused. Also, corrosion of metals and the like that constitute a semiconductor substrate can be inhibited. Further, the semiconductor substrate cleaning composition of the present application also has high stability of hydrogen peroxide in the presence of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt, and can perform cleaning for a long time and be reused.

[0089] <Alkali compound (C)>

[0090] The semiconductor substrate cleaning composition of the present application contains an alkali compound (C).

[0091] The alkali compound (C) is at least one selected from the group consisting of a quaternary ammonium hydroxide (C1) and a potassium hydroxide (C2). By the alkali compound (C), hard mask and dry etching residue can be effectively removed, and damage to low dielectric constant interlayer insulating film and metal wiring can be suppressed. The quaternary ammonium hydroxide (C1) and the potassium hydroxide (C2) can be compounded alone or in combination of two or more.

[0092] It is particularly preferable that the alkali compound (C) contain both the quaternary ammonium hydroxide (C1) and the potassium hydroxide (C2).

[0093] The quaternary ammonium hydroxide (C1) is not particularly limited, and is preferably at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide, more preferably at least one selected from the group consisting of tetramethylammonium hydroxide, tetrapropylammonium hydroxide, and benzyltrimethylammonium hydroxide, and further preferably tetramethylammonium hydroxide, from the viewpoints of economy and easiness of raw material procurement.

[0094] The content of the quaternary ammonium hydroxide (C1) in the semiconductor substrate cleaning composition is preferably 0.005 to 10 mass%, more preferably 0.05 to 5 mass%, and further preferably 0.1 to 3 mass%.

[0095] The content of the potassium hydroxide (C2) in the semiconductor substrate cleaning composition is preferably 0.005 to 5 mass%, more preferably 0.01 to 5 mass%, and further preferably 0.1 to 1 mass%.

[0096] If the content of the alkali compound (C) is within the aforementioned range, the etching rate of titanium and titanium nitride becomes good, and it is preferable.

[0097] < Amino Poly-methylene Phosphonic Acid (D) >

[0098] The semiconductor substrate cleaning composition of the present application can contain an amino poly-methylene phosphonic acid (D).

[0099] By containing the amino poly-methylene phosphonic acid (D), copper ions present are chelated to form a complex, and thus the stability of hydrogen peroxide is improved, and it is preferable.

[0100] The amino poly-methylene phosphonic acid (D) is preferably at least one selected from the group consisting of amino tri(methylene phosphonic acid), ethylenediamine tetra(methylene phosphonic acid), diethylenetriamine penta(methylene phosphonic acid), and 1,2-propanediamine tetra(methylene phosphonic acid).

[0101] When the semiconductor substrate cleaning composition of the present application contains the aminopolymethylenephosphonic acid (D), the content of the aminopolymethylenephosphonic acid (D) is preferably 0.00005 to 0.005% by mass, more preferably 0.0005 to 0.004% by mass, and further preferably 0.001 to 0.003% by mass in the semiconductor substrate cleaning composition.

[0102] The content of the aminopolymethylenephosphonic acid (D) is preferably within the above range, whereby the stability of hydrogen peroxide can be maintained, and the cost can be suppressed.

[0103] <Water>

[0104] The semiconductor substrate cleaning composition of the present application contains water.

[0105] The water is not particularly limited, and is preferably water from which metal ions, organic impurities, fine particles, and the like are removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, and the like, and is more preferably pure water, and particularly preferably ultrapure water.

[0106] The content of the water is the balance of the semiconductor substrate cleaning composition of the present application, excluding the components (A) to (D) described above, the optional azole compound, and other components, and is preferably 50% by mass or more, more preferably 73 to 89.9385% by mass, further preferably 75 to 89.798% by mass, more preferably 75 to 85% by mass, and more preferably 80 to 85% by mass in the semiconductor substrate cleaning composition. The content of the water is preferably within the above range, whereby the effects of the present application can be exhibited, and the composition is further economical.

[0107] <Properties of the Semiconductor Substrate Cleaning Composition>

[0108] The pH of the semiconductor substrate cleaning composition of the present application is preferably 7 to 12, more preferably 7.5 to 11, and further preferably 8 to 10.

[0109] By having the pH within the above range, the stability of hydrogen peroxide can be maintained at a high level, and the cleaning performance can be improved.

[0110] The pH can be measured according to the method described in the Examples.

[0111] (Semiconductor substrate cleaning composition for cleaning of semiconductor substrate containing cobalt and copper)

[0112] The semiconductor substrate cleaning composition of the present application is preferably used for cleaning a semiconductor substrate containing cobalt and copper. That is, the semiconductor substrate cleaning composition of the present application is preferably used for cleaning a semiconductor substrate containing both of cobalt and copper. In the case of cleaning a semiconductor substrate containing both of cobalt and copper, the semiconductor substrate cleaning composition of the present application also has high stability of hydrogen peroxide. Note that cobalt and copper are used as metal wiring and the like of a semiconductor substrate.

[0113] In the semiconductor substrate, cobalt and copper can be used as these metals as such (pure metals) or as alloys.

[0114] The semiconductor substrate cleaning composition of the present application, to which 400 mass ppb of cobalt ions and 1000 mass ppb of copper ions are added with respect to the total amount of the semiconductor substrate cleaning composition, has a residual rate of hydrogen peroxide (A) after 6 hours of treatment at 50°C of preferably 50% or more, more preferably 60% or more, further preferably 70% or more, and still further preferably 80% or more, with the hydrogen peroxide content before treatment as a reference.

[0115] The residual rate of hydrogen peroxide (A) can be measured, for example, according to the method described in the Examples.

[0116] With the semiconductor substrate cleaning composition of the present application, in the case where cobalt ions and copper ions coexist in the cleaning solution, hydrogen peroxide also stably exists for a long time, and can be used for long-term cleaning of a semiconductor substrate, repeated cleaning of a semiconductor substrate.

[0117] That is, the semiconductor substrate cleaning composition of the present application, in the presence of cobalt and copper, hydrogen peroxide also stably exists for a long time, and can be used for long-term cleaning of a semiconductor substrate, repeated cleaning of a semiconductor substrate.

[0118] (Semiconductor substrate cleaning composition for cleaning a semiconductor substrate containing at least one metal selected from the group consisting of a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, magnesium, and aluminum, and cobalt)

[0119] The semiconductor substrate cleaning composition of the present application is also preferably used for cleaning a semiconductor substrate containing at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt. That is, the semiconductor substrate cleaning composition of the present application is preferably used for cleaning a semiconductor substrate containing both at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt. In the case of cleaning a semiconductor substrate containing both at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt, the semiconductor substrate cleaning composition of the present application also has high stability of hydrogen peroxide. Note that at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt are used as materials for semiconductor substrates such as metal wiring.

[0120] For the semiconductor substrate cleaning composition of the present application, in the case where ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt ions coexist in the cleaning solution, hydrogen peroxide also stably exists for a long time, and can be used for long-term cleaning of semiconductor substrates, repeated cleaning of semiconductor substrates.

[0121] That is, the semiconductor substrate cleaning composition of the present application, in the presence of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt, hydrogen peroxide also stably exists for a long time, and can be used for long-term cleaning of semiconductor substrates, repeated cleaning of semiconductor substrates.

[0122] The aforementioned at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum can be used as these metals in the form of a single substance (pure metal), or can be used as an alloy.

[0123] The aforementioned at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum is preferably at least one metal selected from the group consisting of titanium, zirconium, hafnium, tantalum, tungsten, manganese, ruthenium, magnesium, and aluminum.

[0124] The aforementioned at least one metal selected from the group consisting of titanium, zirconium, hafnium, tantalum, tungsten, manganese, ruthenium, magnesium, and aluminum can be used as these metals in the form of a single substance (pure metal), or can be used as an alloy.

[0125] (A composition for cleaning semiconductor substrates having a hard mask containing titanium and titanium nitride)

[0126] Furthermore, the semiconductor substrate cleaning composition of the present invention is preferably used for cleaning semiconductor substrates having a hard mask comprising at least one of the group consisting of titanium and titanium nitride, and more preferably for cleaning semiconductor substrates having a hard mask comprising titanium nitride. Additionally, it is preferably used for cleaning semiconductor substrates having a hard mask formed from at least one of the group consisting of titanium and titanium nitride, and more preferably for cleaning semiconductor substrates having a hard mask formed from titanium nitride.

[0127] (Other ingredients)

[0128] In the semiconductor substrate cleaning composition of the present invention, in addition to the aforementioned components, other components may be mixed within a range that does not impair the purpose of the present invention. For example, surfactants, defoamers, etc., may be added.

[0129] In the semiconductor substrate cleaning composition of the present invention, azoles other than 5-phenyl-1H-tetrazole and benzothiazole may be mixed without impairing the purpose of the present invention.

[0130] As an azole, it is preferably selected from at least one of the group consisting of imidazole compounds, pyrazole compounds, and triazole compounds, and more preferably a triazole compound.

[0131] As an azole, at least one azole is particularly preferred from the group consisting of 1-methylimidazole, 1-vinylimidazole, 2-phenylimidazole, 2-ethyl-4-imidazole, N-benzyl-2-methylimidazole, 2-methylbenzimidazole, pyrazole, 4-methylpyrazole, 3,5-dimethylpyrazole, 1H-benzotriazole, 5-methyl-1H-benzotriazole, and 1H-tetrazole; more preferably, at least one azole is preferred from the group consisting of 1-methylimidazole, pyrazole, 1H-benzotriazole, and 5-methyl-1H-benzotriazole; and even more preferably, 5-methyl-1H-benzotriazole.

[0132] In the semiconductor substrate cleaning composition of the present invention, ammonia and ammonium ions (NH4+) + These substances have the effect of increasing the corrosion of copper and cobalt; therefore, it is preferable that they are substantially not contained. Here, "substantially not contained" means not contained, or contained to a extent that does not impair the effects of the invention. Specifically, ammonia and ammonium ions (NH4+) have the effect of increasing the corrosion of copper and cobalt; therefore, they are preferably not contained. + The total content of ammonia and ammonium ions (NH4+) in the semiconductor substrate cleaning composition is preferably less than 0.01% by mass, more preferably less than 10 ppm by mass, and even more preferably free of ammonia and ammonium ions (NH4+). + ).

[0133] [Cleaning Method]

[0134] The cleaning method of the present application is a cleaning method in which the aforementioned semiconductor substrate cleaning composition is used to clean a semiconductor substrate, and preferably a cleaning method in which the aforementioned semiconductor substrate cleaning composition is used to clean a semiconductor substrate containing a plurality of metals including cobalt.

[0135] The cleaning method of the present application is preferably a cleaning method in which a semiconductor substrate having a hard mask including at least one selected from the group consisting of titanium and titanium nitride is cleaned, and more preferably a cleaning method in which a semiconductor substrate having a hard mask including titanium nitride is cleaned. In addition, it is preferable that the cleaning method be one in which a semiconductor substrate having a hard mask formed from at least one selected from the group consisting of titanium and titanium nitride is cleaned, and more preferably a cleaning method in which a semiconductor substrate having a hard mask formed from titanium nitride is cleaned.

[0136] (Cleaning method in which a semiconductor substrate containing cobalt and copper is cleaned)

[0137] In the aforementioned cleaning method, it is preferable that the cleaning method be one in which the aforementioned semiconductor substrate cleaning composition is used to clean a semiconductor substrate containing both cobalt and copper. In the case of cleaning a semiconductor substrate containing both cobalt and copper, the semiconductor substrate cleaning composition also has high stability of hydrogen peroxide. Note that cobalt and copper are used as metal wiring and the like of a semiconductor substrate.

[0138] Cobalt and copper can be used as these metals in the elemental state (pure metals), or as alloys.

[0139] In addition, the cleaning method of the present application is preferably one in which the aforementioned semiconductor substrate cleaning composition is used to clean a semiconductor substrate in the presence of both cobalt ions and copper ions.

[0140] Hydrogen peroxide also remains stable for a long time in the presence of both cobalt ions and copper ions, and thus long-term cleaning of a semiconductor substrate, and repeated cleaning of a semiconductor substrate, can also be performed.

[0141] In the cleaning method of the present application, cobalt and copper exist in the cleaning as metal wiring and the like of a semiconductor substrate, in addition to existing as ions dissolved in the cleaning solution, and further existing as metal residues.

[0142] The cleaning method of the present application can also maintain the hydrogen peroxide content in the semiconductor substrate cleaning composition for a long time in the presence of both cobalt ions and copper ions, and thus can efficiently remove dry etching residues and hard masks in a semiconductor substrate. That is, it is preferable that the cleaning method be one in which at least one selected from the group consisting of dry etching residues and hard masks in a semiconductor substrate is removed using the aforementioned semiconductor substrate cleaning composition.

[0143] Further, the temperature at the time of cleaning in the cleaning method of the present application is not particularly limited, and is preferably 20 to 80°C, more preferably 25 to 70°C. Further, ultrasonic waves can be used at the time of cleaning.

[0144] The cleaning time in the cleaning method of the present application is not particularly limited, and is preferably 0.3 to 20 minutes, more preferably 0.5 to 10 minutes.

[0145] The pH of the cleaning solution in the cleaning method of the present application is preferably 7 to 12, more preferably 7.5 to 11, further preferably 8 to 10.

[0146] In the cleaning method of the present application, it is further preferable to perform rinsing with a rinsing solution containing water, alcohol, or the like after cleaning.

[0147] The method of contacting the semiconductor substrate cleaning composition of the present application with a semiconductor substrate in the cleaning method of the present application is not particularly limited. For example, a method of contacting the semiconductor substrate cleaning composition of the present application with a semiconductor substrate in the form of dropwise addition (single spin coating treatment) or spray coating (spray treatment), or a method of immersing a semiconductor substrate in the semiconductor substrate cleaning composition of the present application, or the like can be employed. In the present application, any method can be employed.

[0148] (Cleaning method for cleaning a semiconductor substrate containing at least one metal selected from the group consisting of a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, magnesium, and aluminum, and cobalt)

[0149] It is further preferable to use the aforementioned semiconductor substrate cleaning composition in a cleaning method for cleaning a semiconductor substrate containing both at least one metal selected from the group consisting of a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, magnesium, and aluminum, and cobalt. In the case of cleaning a semiconductor substrate containing both at least one metal selected from the group consisting of a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, magnesium, and aluminum, and cobalt, the semiconductor substrate cleaning composition also has high stability of hydrogen peroxide. Note that at least one metal selected from the group consisting of a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, magnesium, and aluminum, and cobalt are used as materials for semiconductor substrates such as metal wiring.

[0150] The aforementioned at least one metal selected from the group consisting of a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, magnesium, and aluminum can be used as these metals as such (pure metals), or can be used as alloys.

[0151] Further, the cleaning method of the present application is preferably a cleaning method in which a semiconductor substrate is cleaned with the aforementioned semiconductor substrate cleaning composition in the presence of ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt ions.

[0152] Hydrogen peroxide also remains stable for a long time in the presence of ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt ions, and thus, long-time cleaning of a semiconductor substrate, repeated cleaning of a semiconductor substrate can also be performed.

[0153] In the cleaning method of the present application, at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt exist in the cleaning as a material of a semiconductor substrate such as a metal wiring, further exist as ions dissolved in a cleaning solution, and further exist as a metal residue.

[0154] The cleaning method of the present application can maintain the hydrogen peroxide content in the semiconductor substrate cleaning composition stably for a long time in the presence of ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt ions, and thus, dry etching residues and hard masks in a semiconductor substrate can be removed efficiently. That is, a cleaning method in which at least one of dry etching residues and hard masks in a semiconductor substrate is removed using the aforementioned semiconductor substrate cleaning composition is preferred.

[0155] The at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum in the cleaning method of the present application is preferably at least one metal selected from the group consisting of titanium, zirconium, hafnium, tantalum, tungsten, manganese, ruthenium, magnesium, and aluminum.

[0156] The aforementioned at least one metal selected from the group consisting of titanium, zirconium, hafnium, tantalum, tungsten, manganese, ruthenium, magnesium, and aluminum can be used as these metals as such (pure metals) or as alloys.

[0157] Further, the temperature at the time of cleaning in the cleaning method of the present application is not particularly limited, and is preferably 20 to 80°C, more preferably 25 to 70°C. Further, ultrasonic waves can be used at the time of cleaning.

[0158] The cleaning time in the cleaning method of the present application is not particularly limited, and is preferably 0.3 to 20 minutes, more preferably 0.5 to 10 minutes.

[0159] The pH of the cleaning solution in the cleaning method of the present application is preferably 7 to 12, more preferably 7.5 to 11, and further preferably 8 to 10.

[0160] In the cleaning method of the present application, it is further preferable to perform rinsing with a rinsing solution containing water, alcohol, or the like after cleaning.

[0161] The method of contacting the semiconductor substrate cleaning composition of the present application with a semiconductor substrate in the cleaning method of the present application is not particularly limited. For example, a method of contacting the semiconductor substrate cleaning composition of the present application with a semiconductor substrate in the form of dropwise addition (single spin coating treatment) or spray coating (spray treatment), or a method of immersing a semiconductor substrate in the semiconductor substrate cleaning composition of the present application, or the like can be employed. In the present application, any method can be employed.

[0162] [Method for manufacturing semiconductor substrate]

[0163] The method for manufacturing a semiconductor substrate of the present application includes a step of removing at least one selected from the group consisting of dry etching residues and hard masks in a semiconductor substrate, using the aforementioned semiconductor substrate cleaning composition. A specific method for manufacturing a semiconductor substrate is described below.

[0164] First, after laminating a barrier insulating film, a low dielectric constant interlayer insulating film, a hard mask, and a photoresist on a substrate of silicon or the like having a barrier metal, a metal wiring, a low dielectric constant interlayer insulating film, a cap metal as necessary, selective exposure and development treatment are performed on the photoresist to form a photoresist pattern. Then, the photoresist pattern is transferred to the hard mask by dry etching. Thereafter, the photoresist pattern is removed, and dry etching treatment is performed on the low dielectric constant interlayer insulating film and the barrier insulating film using the aforementioned hard mask as an etching mask. Then, the step of removing at least one selected from the group consisting of dry etching residues and hard masks in a semiconductor substrate using the aforementioned semiconductor substrate cleaning composition, which is the aforementioned step, is performed to obtain a semiconductor substrate having a desired metal wiring pattern.

[0165] Here, as the substrate material, silicon, amorphous silicon, polysilicon, glass, or the like is used. As the barrier metal, tantalum, tantalum nitride, ruthenium, manganese, magnesium, cobalt, oxides thereof, or the like is used. As the metal wiring, copper or copper alloy, copper or copper alloy on which cobalt or cobalt alloy is formed as a cap metal, cobalt or cobalt alloy, or the like is used. As the low dielectric constant interlayer insulating film, OCD (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), Black Diamond (trade name, manufactured by Applied Materials, Inc.) of a carbon-doped silicon oxide (SiOC) system, or the like is used.

[0166] As the barrier insulating film, silicon nitride, silicon carbide, silicon carbonitride, or the like is used. As the hard mask, titanium, titanium nitride, or the like is used.

[0167] The manufacturing method of a semiconductor substrate according to the present application has a step of removing unnecessary components with the aforementioned composition for cleaning a semiconductor substrate, and thus can manufacture a semiconductor substrate with high precision and high quality at a high yield.

[0168] [Method for stabilizing hydrogen peroxide]

[0169] As the composition for cleaning a semiconductor substrate of the present application, decomposition of hydrogen peroxide (A) can be inhibited even in the presence of various metals including cobalt at the time of cleaning, and the content of hydrogen peroxide (A) can be stably maintained for a long time, and particularly, this effect can be exhibited by using the aforementioned hydrogen peroxide stabilizer (B).

[0170] [Method for stabilizing hydrogen peroxide in a liquid containing cobalt ions and copper ions]

[0171] As the composition for cleaning a semiconductor substrate of the present application, decomposition of hydrogen peroxide (A) can be inhibited even in the presence of cobalt and copper at the time of cleaning, and the content of hydrogen peroxide (A) can be stably maintained for a long time, and particularly, this effect can be exhibited by using the aforementioned hydrogen peroxide stabilizer (B).

[0172] That is, the method for stabilizing hydrogen peroxide of the present application is a method for stabilizing hydrogen peroxide in which hydrogen peroxide (A) is stabilized in a liquid containing hydrogen peroxide (A), cobalt ions, copper ions, and water, by using a hydrogen peroxide stabilizer (B) selected from at least one of the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-1H-tetrazole, triethylenetetraminehexaacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-di(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine.

[0173] The hydrogen peroxide stabilizer (B) in the hydrogen peroxide stabilizing method of the present application is at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-lH-tetrazole, triethylenetetraminehexaacetic acid, trans- 1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-di(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine, preferably at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, triethylenetetraminehexaacetic acid, trans- 1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, hydroxyethylethylenediaminetriacetic acid, 5-phenyl-lH-tetrazole, N,N-di(2-hydroxyethyl)glycine, and benzothiazole, more preferably at least one selected from the group consisting of diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and trans- 1,2-cyclohexanediaminetetraacetic acid, further preferably trans- 1,2-cyclohexanediaminetetraacetic acid.

[0174] The amount of the hydrogen peroxide stabilizer (B) used in the liquid used in the hydrogen peroxide stabilizing method of the present application, which contains hydrogen peroxide (A), cobalt ions, copper ions, and water, is preferably 0.0001 to 5 mass%, more preferably 0.001 to 1 mass%.

[0175] If examples are cited using the following specific compounds, for example, for the amount of trans-1,2-cyclohexanediaminetetraacetic acid, as trans-1,2-cyclohexanediaminetetraacetic acid monohydrate, in the liquid used in the hydrogen peroxide stabilizing method of the present application comprising hydrogen peroxide (A), cobalt ions, copper ions, and water, it is preferably 0.0001 to 5 mass%, more preferably 0.001 to 1 mass%, further preferably 0.001 to 0.5 mass%, more further preferably 0.002 to 0.3 mass%, more further preferably 0.003 to 0.2 mass%, more further preferably 0.003 to 0.1 mass%, more further preferably 0.005 to 0.05 mass%, more further preferably 0.005 to 0.01 mass% in terms of a balance between cost and effect. Also, for the amount of diethylenetriaminepentaacetic acid, in the liquid used in the hydrogen peroxide stabilizing method of the present application comprising hydrogen peroxide (A), cobalt ions, copper ions, and water, it is preferably 0.0001 to 5 mass%, more preferably 0.001 to 1 mass%, further preferably 0.01 to 1 mass%, more further preferably 0.02 to 0.8 mass%, more further preferably 0.02 to 0.1 mass%. For the amount of hydroxyethyliminodiacetic acid, in the liquid used in the hydrogen peroxide stabilizing method of the present application comprising hydrogen peroxide (A), cobalt ions, copper ions, and water, it is preferably 0.001 to 5 mass%, more preferably 0.01 to 3 mass%, further preferably 0.05 to 1 mass%, more further preferably 0.05 to 0.5 mass%. For the amount of triethylenetetraminehexaacetic acid, in the liquid used in the hydrogen peroxide stabilizing method of the present application comprising hydrogen peroxide (A), cobalt ions, copper ions, and water, it is preferably 0.0001 to 5 mass%, more preferably 0.001 to 1 mass%, further preferably 0.005 to 0.5 mass%, more further preferably 0.01 to 0.1 mass%. For the amount of 8-hydroxyquinoline, in the liquid used in the hydrogen peroxide stabilizing method of the present application comprising hydrogen peroxide (A), cobalt ions, copper ions, and water, it is preferably 0.0001 to 5 mass%, more preferably 0.0005 to 1 mass%, further preferably 0.001 to 0.1 mass%, more further preferably 0.001 to 0.01 mass%. For the amount of hydroxyethylethylenediaminetriacetic acid, in the liquid used in the hydrogen peroxide stabilizing method of the present application comprising hydrogen peroxide (A), cobalt ions, copper ions, and water, it is preferably 0.001 to 5 mass%, more preferably 0.01 to 3 mass%, further preferably 0.05 to 1 mass%, more further preferably 0.05 to 0.5 mass%.

[0176] The amount of hydrogen peroxide (A) used in the hydrogen peroxide stabilizing method of the present application is not limited, and in the liquid used in the hydrogen peroxide stabilizing method of the present application comprising hydrogen peroxide (A), cobalt ions, copper ions, and water, the amount is preferably 10 to 30 mass%, more preferably 10 to 20 mass%.

[0177] In the hydrogen peroxide stabilizing method of the present application, the pH of the liquid comprising hydrogen peroxide (A), cobalt ions, copper ions, and water is preferably 7 to 12, more preferably 7.5 to 11, further preferably 8 to 10.

[0178] (In a method for stabilizing hydrogen peroxide in a liquid comprising hydrogen peroxide (A), ions of at least one metal selected from the group consisting of a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, magnesium, and aluminum, and cobalt ions)

[0179] As described above, in the semiconductor substrate cleaning composition of the present application, the decomposition of hydrogen peroxide (A) can be inhibited in the presence of at least one metal selected from the group consisting of a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, magnesium, and aluminum, and cobalt at the time of cleaning, and the content of hydrogen peroxide (A) can be stably maintained for a long period of time, and this effect can be exhibited in particular by using the aforementioned hydrogen peroxide stabilizer (B).

[0180] That is, the hydrogen peroxide stabilizing method of the present application is a hydrogen peroxide stabilizing method in which hydrogen peroxide (A) is stabilized by a hydrogen peroxide stabilizer (B) in a liquid comprising hydrogen peroxide (A), ions of at least one metal selected from the group consisting of a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, magnesium, and aluminum, cobalt ions, and water, the hydrogen peroxide stabilizer (B) being at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-1H-tetrazole, triethylenetetraminehexaacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-di(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine.

[0181] The hydrogen peroxide stabilizer (B) in the hydrogen peroxide stabilization method of the present application is at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-lH-tetrazole, triethylenetetraminehexaacetic acid, trans- 1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-di(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine, preferably at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, triethylenetetraminehexaacetic acid, trans- 1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, hydroxyethylethylenediaminetriacetic acid, 5-phenyl-lH-tetrazole, N,N-di(2-hydroxyethyl)glycine, and benzothiazole, more preferably at least one selected from the group consisting of diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and trans- 1,2-cyclohexanediaminetetraacetic acid, further preferably trans- 1,2-cyclohexanediaminetetraacetic acid.

[0182] The amount of the hydrogen peroxide stabilizer (B) used in the hydrogen peroxide stabilization method of the present application comprising hydrogen peroxide (A), ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, cobalt ions, and water, in the liquid used is preferably 0.0001 to 5% by mass, more preferably 0.001 to 1% by mass.

[0183] If examples are cited using the following specific compounds, for example, for the amount of trans-1,2-cyclohexanediaminetetraacetic acid, as trans-1,2-cyclohexanediaminetetraacetic acid monohydrate, in the liquid used in the hydrogen peroxide stabilizing method of the present application containing hydrogen peroxide (A), an ion of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium and aluminum, a cobalt ion and water, it is preferably 0.0001 to 5 mass%, more preferably 0.001 to 1 mass%, further preferably 0.001 to 0.5 mass%, more further preferably 0.002 to 0.3 mass%, more further preferably 0.003 to 0.2 mass%, more further preferably 0.003 to 0.1 mass%, more further preferably 0.005 to 0.05 mass%, more further preferably 0.005 to 0.01 mass% in terms of a balance between cost and effect. Also, for the amount of diethylenetriaminepentaacetic acid, in the liquid used in the hydrogen peroxide stabilizing method of the present application containing hydrogen peroxide (A), an ion of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium and aluminum, a cobalt ion and water, it is preferably 0.0001 to 5 mass%, more preferably 0.001 to 1 mass%, further preferably 0.01 to 1 mass%, more further preferably 0.02 to 0.8 mass%, more further preferably 0.02 to 0.1 mass%. For the amount of hydroxyethyliminodiacetic acid, in the liquid used in the hydrogen peroxide stabilizing method of the present application containing hydrogen peroxide (A), an ion of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium and aluminum, a cobalt ion and water, it is preferably 0.001 to 5 mass%, more preferably 0.01 to 3 mass%, further preferably 0.05 to 1 mass%, more further preferably 0.05 to 0.5 mass%. For the amount of triethylenetetraminehexaacetic acid, in the liquid used in the hydrogen peroxide stabilizing method of the present application containing hydrogen peroxide (A), an ion of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium and aluminum, a cobalt ion and water, it is preferably 0.0001 to 5 mass%, more preferably 0.001 to 1 mass%, further preferably 0.005 to 0.5 mass%, more further preferably 0.01 to 0.1 mass%.The amount of 8-hydroxyquinoline is preferably 0.0001 to 5% by mass, more preferably 0.0005 to 1% by mass, further preferably 0.001 to 0.1% by mass, and more further preferably 0.001 to 0.01% by mass, in the liquid used in the hydrogen peroxide stabilizing method of the present application which contains hydrogen peroxide (A), ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium and aluminum, cobalt ions, and water. The amount of hydroxyethylethylenediaminetriacetic acid is preferably 0.001 to 5% by mass, more preferably 0.01 to 3% by mass, further preferably 0.05 to 1% by mass, and more further preferably 0.05 to 0.5% by mass, in the liquid used in the hydrogen peroxide stabilizing method of the present application which contains hydrogen peroxide (A), ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium and aluminum, cobalt ions, and water.

[0184] The amount of hydrogen peroxide (A) is not limited in the hydrogen peroxide stabilizing method of the present application, and is preferably 10 to 30% by mass, and more preferably 10 to 20% by mass, in the liquid used in the hydrogen peroxide stabilizing method of the present application which contains hydrogen peroxide (A), ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium and aluminum, cobalt ions, and water.

[0185] The pH of the liquid which contains hydrogen peroxide (A), ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium and aluminum, cobalt ions, and water is preferably 7 to 12, more preferably 7.5 to 11, and further preferably 8 to 10, in the hydrogen peroxide stabilizing method of the present application.

[0186] Examples

[0187] Hereinafter, the present application will be described in further detail based on Examples, but the present application is not limited to these Examples.

[0188] <Analysis method and evaluation method (1)>

[0189] (1) pH

[0190] The pH of the semiconductor substrate cleaning composition was measured by a glass electrode method (F-55S benchtop pH meter manufactured by HORIBA; standard ToupH electrode 9165S-10D; temperature: 25°C).

[0191] (2) Evaluation of hydrogen peroxide stability

[0192] As a substitute for metal residues mixed after cleaning of a semiconductor substrate, each standard solution (ICP standard solution Cu1000 (1000 mass ppm) and Co1000 (1000 mass ppm), manufactured by FUJIFILM and Otsuka Pharmaceutical Co., Ltd.) of copper ions and cobalt ions was added to the semiconductor substrate cleaning compositions of Examples and Comparative Examples to be amounts shown in Tables 1 to 5, and the amount of hydrogen peroxide immediately after the addition and the amount of hydrogen peroxide after 6 hours of incubation at 50°C were measured with potassium permanganate according to the method described in JIS K 1463:2007, and the hydrogen peroxide residual rate (unit: %) was calculated. The higher the hydrogen peroxide residual rate, the higher the stability of hydrogen peroxide.

[0193] (3) Metal corrosion evaluation

[0194] A silicon wafer on which electroplated copper having a thickness of 6000 angstroms was formed on a PVD seed layer having a thickness of 600 angstroms and on which annealing treatment was performed, and a silicon wafer on which cobalt having a thickness of 2000 angstroms was formed by PVD (manufactured by Advantec Co., Ltd.) were measured for film thickness with fluorescent X-ray analysis (SEA 1200VX manufactured by Hitachi), immersed in a semiconductor substrate cleaning composition at 50°C for a prescribed time (copper: 60 minutes, cobalt: 5 minutes), then washed with ultrapure water at room temperature, and measured for film thickness with fluorescent X-ray analysis again, and thereby the amount of reduction in film thickness per unit time of copper and cobalt was determined.

[0195] The results of the evaluation were determined with the following criteria.

[0196] A: For copper, the amount of reduction in film thickness was 1 angstrom / minute or less. For cobalt, the amount of reduction in film thickness was 3 angstrom / minute or less.

[0197] B: For copper, the amount of reduction in film thickness exceeded 1 angstrom / minute and was 2 angstrom / minute or less. For cobalt, the amount of reduction in film thickness exceeded 3 angstrom / minute and was 10 angstrom / minute or less.

[0198] C: For copper, the amount of reduction in film thickness exceeded 2 angstrom / minute. For cobalt, the amount of reduction in film thickness exceeded 10 angstrom / minute.

[0199] < Semiconductor substrate cleaning composition >

[0200] Example 1

[0201] A semiconductor substrate cleaning composition was obtained by diluting, with ultrapure water, so as to become 100 parts by mass in total, hydrogen peroxide 15 parts by mass (diluted in the aforementioned manner with 31% hydrogen peroxide aqueous solution 48.39 parts by mass), potassium hydroxide 0.15 parts by mass, tetramethylammonium hydroxide 0.5 parts by mass, and trans-1,2-cyclohexanediaminetetraacetic acid monohydrate 0.005 parts by mass as the hydrogen peroxide stabilizer (B). The evaluations shown in Table 1 were performed. In each table, the compounding amount of each component is expressed in "mass %".

[0202] Example 2

[0203] A semiconductor substrate cleaning composition was obtained by diluting, with ultrapure water, so as to become 100 parts by mass in total, hydrogen peroxide 20 parts by mass (diluted in the aforementioned manner with 31% hydrogen peroxide aqueous solution 64.52 parts by mass), potassium hydroxide 0.15 parts by mass, tetramethylammonium hydroxide 0.5 parts by mass, and trans-1,2-cyclohexanediaminetetraacetic acid monohydrate 0.005 parts by mass as the hydrogen peroxide stabilizer (B). The evaluations shown in Table 1 were performed.

[0204] Example 3

[0205] A semiconductor substrate cleaning composition was obtained by diluting, with ultrapure water, so as to become 100 parts by mass in total, hydrogen peroxide 25 parts by mass (diluted in the aforementioned manner with 31% hydrogen peroxide aqueous solution 80.65 parts by mass), potassium hydroxide 0.15 parts by mass, tetramethylammonium hydroxide 0.5 parts by mass, and trans-1,2-cyclohexanediaminetetraacetic acid monohydrate 0.005 parts by mass as the hydrogen peroxide stabilizer (B). The evaluations shown in Table 1 were performed.

[0206] Example 4

[0207] A semiconductor substrate cleaning composition was obtained by diluting, with ultrapure water, so as to become 100 parts by mass in total, hydrogen peroxide 15 parts by mass (diluted in the aforementioned manner with 31% hydrogen peroxide aqueous solution 48.39 parts by mass), potassium hydroxide 0.30 parts by mass, tetramethylammonium hydroxide 0.5 parts by mass, and trans-1,2-cyclohexanediaminetetraacetic acid monohydrate 0.005 parts by mass as the hydrogen peroxide stabilizer (B). The evaluations shown in Table 1 were performed.

[0208] Example 5

[0209] A semiconductor substrate cleaning composition was obtained by diluting with ultrapure water so as to become 100 parts by mass in total, compounding hydrogen peroxide 15 parts by mass (in the aforementioned manner, compounding 31% hydrogen peroxide aqueous solution 48.39 parts by mass), potassium hydroxide 0.15 parts by mass, tetramethylammonium hydroxide 1.0 parts by mass, and trans-1,2-cyclohexanediaminetetraacetic acid monohydrate 0.005 parts by mass as the hydrogen peroxide stabilizer (B). The evaluations shown in Table 1 were performed.

[0210] Example 6

[0211] A semiconductor substrate cleaning composition was obtained by diluting with ultrapure water so as to become 100 parts by mass in total, compounding hydrogen peroxide 15 parts by mass (in the aforementioned manner, compounding 31% hydrogen peroxide aqueous solution 48.39 parts by mass), potassium hydroxide 0.15 parts by mass, and trans-1,2-cyclohexanediaminetetraacetic acid monohydrate 0.005 parts by mass as the hydrogen peroxide stabilizer (B). The evaluations shown in Table 1 were performed.

[0212] Example 7

[0213] A semiconductor substrate cleaning composition was obtained by diluting with ultrapure water so as to become 100 parts by mass in total, compounding hydrogen peroxide 15 parts by mass (in the aforementioned manner, compounding 31% hydrogen peroxide aqueous solution 48.39 parts by mass), tetramethylammonium hydroxide 0.5 parts by mass, and trans-1,2-cyclohexanediaminetetraacetic acid monohydrate 0.005 parts by mass as the hydrogen peroxide stabilizer (B). The evaluations shown in Table 1 were performed.

[0214] Example 8

[0215] A semiconductor substrate cleaning composition was obtained by diluting with ultrapure water so as to become 100 parts by mass in total, compounding hydrogen peroxide 15 parts by mass (in the aforementioned manner, compounding 31% hydrogen peroxide aqueous solution 48.39 parts by mass), potassium hydroxide 0.15 parts by mass, tetraethylammonium hydroxide 0.5 parts by mass, and trans-1,2-cyclohexanediaminetetraacetic acid monohydrate 0.005 parts by mass as the hydrogen peroxide stabilizer (B). The evaluations shown in Table 1 were performed.

[0216] Example 9

[0217] A semiconductor substrate cleaning composition was obtained by diluting with ultrapure water, in such a manner that the total becomes 100 parts by mass, 15 parts by mass of hydrogen peroxide (in the aforementioned manner, 48.39 parts by mass of a 31% hydrogen peroxide aqueous solution was compounded), 0.15 parts by mass of potassium hydroxide, 0.5 parts by mass of tetraalkylammonium hydroxide, and 0.005 parts by mass of trans-1,2-diaminocyclohexane tetraacetic acid monohydrate as the hydrogen peroxide stabilizer (B). The evaluations shown in Table 1 were performed.

[0218] Example 10

[0219] A semiconductor substrate cleaning composition was obtained by diluting with ultrapure water, in such a manner that the total becomes 100 parts by mass, 15 parts by mass of hydrogen peroxide (in the aforementioned manner, 48.39 parts by mass of a 31% hydrogen peroxide aqueous solution was compounded), 0.15 parts by mass of potassium hydroxide, 0.5 parts by mass of tetrabutylammonium hydroxide, and 0.005 parts by mass of trans-1,2-diaminocyclohexane tetraacetic acid monohydrate as the hydrogen peroxide stabilizer (B). The evaluations shown in Table 1 were performed.

[0220] Example 11

[0221] A semiconductor substrate cleaning composition was obtained by diluting with ultrapure water, in such a manner that the total becomes 100 parts by mass, 15 parts by mass of hydrogen peroxide (in the aforementioned manner, 48.39 parts by mass of a 31% hydrogen peroxide aqueous solution was compounded), 0.15 parts by mass of potassium hydroxide, 0.5 parts by mass of benzyltrimethylammonium hydroxide, and 0.005 parts by mass of trans-1,2-diaminocyclohexane tetraacetic acid monohydrate as the hydrogen peroxide stabilizer (B). The evaluations shown in Table 1 were performed.

[0222] Example 12

[0223] A semiconductor substrate cleaning composition was obtained by diluting with ultrapure water, in such a manner that the total becomes 100 parts by mass, 15 parts by mass of hydrogen peroxide (in the aforementioned manner, 48.39 parts by mass of a 31% hydrogen peroxide aqueous solution was compounded), 0.15 parts by mass of potassium hydroxide, 0.5 parts by mass of tetramethylammonium hydroxide, 0.002 parts by mass of amino tris(methylene phosphonic acid), and 0.005 parts by mass of trans-1,2-diaminocyclohexane tetraacetic acid monohydrate as the hydrogen peroxide stabilizer (B). The evaluations shown in Table 1 were performed.

[0224] Example 13

[0225] A semiconductor substrate cleaning composition was obtained by diluting with ultrapure water, in such a manner that the total becomes 100 parts by mass, 15 parts by mass of hydrogen peroxide (in the aforementioned manner, 48.39 parts by mass of a 31% hydrogen peroxide aqueous solution), 0.15 parts by mass of potassium hydroxide, 0.5 parts by mass of tetramethylammonium hydroxide, 0.002 parts by mass of ethylenediaminetetra(methylene phosphonic acid), and 0.005 parts by mass of trans-1,2-cyclohexanediaminetetraacetic acid monohydrate as the hydrogen peroxide stabilizer (B), in such a manner that the total becomes 100 parts by mass. The evaluations shown in Table 1 were performed.

[0226] Example 14

[0227] A semiconductor substrate cleaning composition was obtained by diluting with ultrapure water, in such a manner that the total becomes 100 parts by mass, 15 parts by mass of hydrogen peroxide (in the aforementioned manner, 48.39 parts by mass of a 31% hydrogen peroxide aqueous solution), 0.15 parts by mass of potassium hydroxide, 0.5 parts by mass of tetramethylammonium hydroxide, 0.002 parts by mass of diethylenetriaminepenta(methylene phosphonic acid), and 0.005 parts by mass of trans-1,2-cyclohexanediaminetetraacetic acid monohydrate as the hydrogen peroxide stabilizer (B), in such a manner that the total becomes 100 parts by mass. The evaluations shown in Table 1 were performed.

[0228] Example 15

[0229] A semiconductor substrate cleaning composition was obtained by diluting with ultrapure water, in such a manner that the total becomes 100 parts by mass, 15 parts by mass of hydrogen peroxide (in the aforementioned manner, 48.39 parts by mass of a 31% hydrogen peroxide aqueous solution), 0.15 parts by mass of potassium hydroxide, 0.5 parts by mass of tetramethylammonium hydroxide, 0.002 parts by mass of 1,2-propanediaminetetra(methylene phosphonic acid), and 0.005 parts by mass of trans-1,2-cyclohexanediaminetetraacetic acid monohydrate as the hydrogen peroxide stabilizer (B), in such a manner that the total becomes 100 parts by mass. The evaluations shown in Table 1 were performed.

[0230] Example 16

[0231] A semiconductor substrate cleaning composition was obtained by diluting with ultrapure water, in such a manner that the total becomes 100 parts by mass, 15 parts by mass of hydrogen peroxide (in the aforementioned manner, 48.39 parts by mass of a 31% hydrogen peroxide aqueous solution), 0.15 parts by mass of potassium hydroxide, 0.5 parts by mass of tetramethylammonium hydroxide, 0.002 parts by mass of diethylenetriaminepenta(methylene phosphonic acid), and 0.005 parts by mass of trans-1,2-cyclohexanediaminetetraacetic acid monohydrate as the hydrogen peroxide stabilizer (B), in such a manner that the total becomes 100 parts by mass. The evaluations shown in Table 1 were performed.

[0232] Example 17

[0233] A semiconductor substrate cleaning composition was obtained by diluting, with purified water, 15 parts by mass of hydrogen peroxide (diluted in the same manner as described above with 48.39 parts by mass of a 31% hydrogen peroxide aqueous solution), 0.15 parts by mass of potassium hydroxide, 0.5 parts by mass of tetramethylammonium hydroxide, 0.002 parts by mass of diethylenetriaminepenta(methylene phosphonic acid), and 0.0001 parts by mass of trans-1,2-cyclohexanediaminetetraacetic acid monohydrate as a hydrogen peroxide stabilizer (B), in such a manner that the total becomes 100 parts by mass. The evaluations shown in Table 1 were performed.

[0234] Example 18

[0235] Example 14 was changed to 0.50 parts by mass of ammonia instead of tetramethylammonium hydroxide, and the amount of purified water was adjusted in such a manner that the total becomes 100 parts by mass, and otherwise, a semiconductor substrate cleaning composition was obtained in the same manner as Example 14. The evaluations shown in Table 1 were performed.

[0236] Example 19

[0237] Example 14 was changed to 0.50 parts by mass of ammonia instead of tetramethylammonium hydroxide, and 0.002 parts by mass of 5-methyl-lH-tetrazole was compounded, and the amount of purified water was adjusted in such a manner that the total becomes 100 parts by mass, and otherwise, a semiconductor substrate cleaning composition was obtained in the same manner as Example 14. The evaluations shown in Table 1 were performed.

[0238] Comparative Example 1

[0239] Example 16 was changed to 0.10 parts by mass of purified water instead of trans-1,2-cyclohexanediaminetetraacetic acid monohydrate, and the amount of purified water was adjusted in such a manner that the total becomes 100 parts by mass, and otherwise, a semiconductor substrate cleaning composition was obtained in the same manner as Example 16. The evaluation results are shown in Table 1.

[0240] Reference Examples 1 and 2

[0241] As reference examples, the semiconductor substrate cleaning composition of Comparative Example 1 was used, and only cobalt or copper was added, and the stability of hydrogen peroxide was evaluated, and the results are also shown in Table 1.

[0242] [Table 1]

[0243]

[0244] Examples 20 to 35

[0245] Example 16 was changed to 0.10 parts by mass of each compound (compound of the hydrogen peroxide stabilizer (B)) shown in Table 2 and the compounding amount, the amount of ultrapure water was adjusted so as to be 100 parts by mass in total, and otherwise, a semiconductor substrate cleaning composition was obtained in the same manner as in Example 16. The evaluation results are shown in Table 2.

[0246] Example 36

[0247] Example 16 was changed to 0.10 parts by mass of glycine and 0.02 parts by mass of 5-methyl-lH-benzotriazole was compounded, the amount of ultrapure water was adjusted so as to be 100 parts by mass in total, and otherwise, a semiconductor substrate cleaning composition was obtained in the same manner as in Example 16. The evaluation results are shown in Table 2.

[0248] Example 37

[0249] Example 36 was changed to 1.0 parts by mass of pyrazole, the amount of ultrapure water was adjusted so as to be 100 parts by mass in total, and otherwise, a semiconductor substrate cleaning composition was obtained in the same manner as in Example 16. The evaluation results are shown in Table 2.

[0250] Example 38

[0251] Example 36 was changed to 1.0 parts by mass of 1-methylimidazole, the amount of ultrapure water was adjusted so as to be 100 parts by mass in total, and otherwise, a semiconductor substrate cleaning composition was obtained in the same manner as in Example 16. The evaluation results are shown in Table 2.

[0252] Example 39

[0253] Example 36 was changed to 0.02 parts by mass of lH-benzotriazole, the amount of ultrapure water was adjusted so as to be 100 parts by mass in total, and otherwise, a semiconductor substrate cleaning composition was obtained in the same manner as in Example 16. The evaluation results are shown in Table 2.

[0254] [Table 2]

[0255]

[0256] Comparative Examples 2 to 22

[0257] A semiconductor substrate cleaning composition was obtained in the same manner as in Example 16, except that 0.10 parts by mass of trans-1,2-cyclohexanediaminetetraacetic acid monohydrate of Example 16 was changed to each of the compounds shown in the column of the compound and the compounding amount of Table 3, and the pH of the obtained semiconductor substrate cleaning composition was adjusted to 7 by adding sulfuric acid. The evaluation results are shown in Table 3.

[0258] [Table 3]

[0259] Table 3

[0260]

[0261] The semiconductor substrate cleaning compositions (Comparative Examples 2 to 22) of Table 3 contained hydrogen peroxide 15 mass%, potassium hydroxide 0.15 mass%, tetramethylammonium hydroxide 0.5 mass%, and diethylenetriaminepenta(methylene phosphonic acid) 0.002 mass%.

[0262] Example 40

[0263] A semiconductor substrate cleaning composition was obtained in the same manner as in Example 14, except that 5-methyl-lH-benzotriazole 1.0 mass% was compounded, and sulfuric acid was added. The evaluation results are shown in Table 4.

[0264] Example 41

[0265] A semiconductor substrate cleaning composition was obtained in the same manner as in Example 16, except that pyrazole 5.0 mass% was compounded, and sodium hydroxide was added. The evaluation results are shown in Table 4.

[0266] Comparative Example 23

[0267] A semiconductor substrate cleaning composition was obtained in the same manner as in Comparative Example 1, except that 5-methyl-lH-benzotriazole 1.0 mass% was compounded, and sulfuric acid was added. The evaluation results are shown in Table 4.

[0268] Comparative Example 24

[0269] A semiconductor substrate cleaning composition was obtained in the same manner as in Comparative Example 1, except that pyrazole 5.0 mass% was compounded, and sodium hydroxide was added. The evaluation results are shown in Table 4.

[0270] [Table 4]

[0271] Table 4

[0272]

[0273] *) The semiconductor substrate cleaning compositions in Table 4 (Examples 40-41 and Comparative Examples 23-24) contain 15% by mass of hydrogen peroxide, 0.15% by mass of potassium oxyoxide, 0.5% by mass of tetramethylammonium oxyoxide, and 0.002% by mass of diethylenetriaminepenta (methylenephosphonic acid).

[0274] Comparative Examples 25–40

[0275] The composition for cleaning semiconductor substrates was obtained by changing 0.10 parts by mass of trans-1,2-cyclohexanediaminetetraacetic acid monohydrate in Example 16 to the compounds and mixing amounts shown in Table 5 of the aforementioned Patent Documents 2-17, otherwise, the composition was obtained in the same manner as in Example 16. The evaluation results are shown in Table 5.

[0276] [Table 5]

[0277] Table 5

[0278]

[0279] *) The semiconductor substrate cleaning compositions in Table 5 (Comparative Examples 25-40) contain 15% by mass of oxygen peroxide, 0.15% by mass of potassium hydroxide, 0.5% by mass of tetramethylammonium hydroxide, and 0.002% by mass of diethylenetriaminepenta (methylenephosphonic acid).

[0280] As shown in Tables 1-5, the semiconductor substrate cleaning compositions of the embodiments exhibit high stability of hydrogen peroxide in the presence of copper and cobalt metal ions. Furthermore, it can be seen that the semiconductor substrate cleaning compositions using the hydrogen peroxide stabilizer shown in the embodiments also exhibit less corrosion of the metals constituting the semiconductor substrate.

[0281] <Analysis Methods·Evaluation Methods (2)>

[0282] (1) Stability evaluation of hydrogen peroxide

[0283] As a substitute for metal residues mixed in after cleaning semiconductor substrates, standard solutions of each metal ion and cobalt ion (ICP standard solution Co1000 (1000 ppm by mass), manufactured by Fujifilm and Koden Chemical Co., Ltd.) were added to the semiconductor substrate cleaning compositions of the examples and comparative examples to the amounts shown in Table 6. The amount of hydrogen peroxide immediately after addition and after incubation at 50°C for 6 hours was determined using potassium permanganate according to the method described in JIS K1463:2007, and the hydrogen peroxide residue rate (unit: %) was calculated. A higher hydrogen peroxide residue rate indicates higher hydrogen peroxide stability.

[0284] Note that the aforementioned each metal ion is an ion of a metal shown below. Tantalum (Group 5 element), ruthenium (Group 8 element), manganese (Group 7 element), magnesium, titanium (Group 4 element), aluminum, tungsten (Group 6 element), zirconium (Group 4 element), hafnium (Group 4 element).

[0285] Example 42

[0286] Hydrogen peroxide 15 parts by mass (diluted with ultrapure water in such a manner that 48.39 parts by mass of 31% hydrogen peroxide aqueous solution becomes the aforementioned, potassium hydroxide 0.2 parts by mass, tetramethylammonium hydroxide 0.5 parts by mass, diethylenetriaminepenta(methylene phosphonic acid) 0.002 parts by mass, and diethylenetriaminepentaacetic acid 0.05 parts by mass as the hydrogen peroxide stabilizer (B) were compounded, diluted with ultrapure water in such a manner that the whole becomes 100 parts by mass, to obtain a semiconductor substrate cleaning composition. The evaluation shown in Table 6 was performed. In each table below, the compounding amount of each component is expressed by "mass%".

[0287] Examples 43 to 45

[0288] The diethylenetriaminepentaacetic acid 0.05 parts by mass of Example 42 was changed to each compound and compounding amount shown in Table 6, and otherwise, a semiconductor substrate cleaning composition was obtained in the same manner as Example 42. The evaluation results are shown in Table 6.

[0289] Examples 46 and 47

[0290] The diethylenetriaminepentaacetic acid 0.05 parts by mass of Example 42 was changed to each compound and compounding amount shown in Table 7, and otherwise, a semiconductor substrate cleaning composition was obtained in the same manner as Example 42. The evaluation results are shown in Table 7.

[0291] Comparative Example 41

[0292] The diethylenetriaminepentaacetic acid 0.05 parts by mass of Example 42 was not used, and the amount of ultrapure water was adjusted in such a manner that the whole becomes 100 parts by mass, and otherwise, a semiconductor substrate cleaning composition was obtained in the same manner as Example 42. The evaluation results are shown in Table 7.

[0293] Reference Example 3

[0294] As a reference example, using the semiconductor substrate cleaning composition of Comparative Example 41, only cobalt ions were added, and the stability of hydrogen peroxide was evaluated, and the results are shown in Table 7.

[0295] [Table 6]

[0296] Table 6

[0297]

[0298] *) The semiconductor substrate cleaning composition of Table 6 (Examples 42 to 47, Comparative Example 41, Reference Example 3) contains hydrogen peroxide 15 mass%, potassium hydroxide 0.2 mass%, tetramethylammonium hydroxide 0.5 mass%, diethylenetriaminepenta(methylene phosphonic acid) 0.002 mass%.

[0299] [Table 7]

[0300] Table 7

[0301]

[0302] *) The semiconductor substrate cleaning composition of Table 7 (Examples 42 to 47, Comparative Example 41, Reference Example 3) contains hydrogen peroxide 15 mass%, potassium hydroxide 0.2 mass%, tetramethylammonium hydroxide 0.5 mass%, diethylenetriaminepenta(methylene phosphonic acid) 0.002 mass%.

[0303] As is apparent from Tables 6 and 7, the semiconductor substrate cleaning composition of the examples also has high stability of hydrogen peroxide in the presence of two kinds of metal ions of a specific metal (Group 4 element, Group 5 element, Group 6 element, Group 7 element, Group 8 element, magnesium, aluminum) and cobalt.

Claims

1. A semiconductor substrate cleaning composition comprising: hydrogen peroxide (A), a hydrogen peroxide stabilizer (B), an alkali compound (C), and water, the hydrogen peroxide stabilizer (B) is at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-lH-tetrazole, triethylenetetraminehexaacetic acid, trans- 1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-di(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine, the alkali compound (C) consists of a quaternary ammonium hydroxide (Cl) and potassium hydroxide (C2), the content of the quaternary ammonium hydroxide (Cl) in the semiconductor substrate cleaning composition is 0.005 to 10 mass%, the content of the potassium hydroxide (C2) in the semiconductor substrate cleaning composition is 0.005 to 5 mass%, the semiconductor substrate cleaning composition further comprises an aminopolymethylene phosphonic acid (D), the content of the aminopolymethylene phosphonic acid (D) in the semiconductor substrate cleaning composition is 0.00005 to 0.005 mass%.

2. The semiconductor substrate cleaning composition according to claim 1, wherein, the content of the hydrogen peroxide stabilizer (B) in the semiconductor substrate cleaning composition is 0.0001 to 5 mass%.

3. The semiconductor substrate cleaning composition according to claim 1 or 2, wherein, the content of the hydrogen peroxide (A) in the semiconductor substrate cleaning composition is 10 to 30 mass%.

4. The semiconductor substrate cleaning composition according to claim 1 or 2, having a pH of 7 to 12.

5. The semiconductor substrate cleaning composition according to claim 1 or 2, wherein the quaternary ammonium hydroxide (Cl) is at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide.

6. The semiconductor substrate cleaning composition according to claim 1 or 2, wherein the aminopolymethylene phosphonic acid (D) is at least one selected from the group consisting of aminotri(methylene phosphonic acid), ethylenediaminetetra(methylene phosphonic acid), diethylenetriaminepenta(methylene phosphonic acid), and 1,2-propanediaminetetra(methylene phosphonic acid).

7. The semiconductor substrate cleaning composition according to claim 1 or 2, wherein the hydrogen peroxide stabilizer (B) is at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, triethylenetetraminehexaacetic acid, trans- 1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, hydroxyethylethylenediaminetriacetic acid, 5-phenyl-lH-tetrazole, N,N-di(2-hydroxyethyl)glycine, and benzothiazole.

8. The semiconductor substrate cleaning composition according to claim 1 or 2, wherein substantially free of any of ammonia and ammonium (NH4 + ) ions.

9. The semiconductor substrate cleaning composition according to claim 1 or 2, which is used for cleaning a semiconductor substrate having a hard mask comprising at least one selected from the group consisting of titanium and titanium nitride.

10. The semiconductor substrate cleaning composition according to claim 1 or 2, which is used for cleaning a semiconductor substrate comprising cobalt and copper.

11. The semiconductor substrate cleaning composition according to claim 1 or 2, wherein The residual rate of the hydrogen peroxide (A) after 6 hours of treatment at 50°C is 50% or more, with respect to the total amount of the semiconductor substrate cleaning composition, with the addition of 400 mass ppb of cobalt ions and 1000 mass ppb of copper ions, with the content of hydrogen peroxide before treatment as a reference.

12. The composition for cleaning a semiconductor substrate according to claim 1 or 2, which is used for cleaning a semiconductor substrate containing at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt.

13. The semiconductor substrate cleaning composition according to claim 12, wherein, The at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum is at least one metal selected from the group consisting of titanium, zirconium, hafnium, tantalum, tungsten, manganese, ruthenium, magnesium, and aluminum.

14. A cleaning method of cleaning a semiconductor substrate with the composition for cleaning a semiconductor substrate according to any one of claims 1 to 11 in the presence of cobalt ions and copper ions.

15. A cleaning method of cleaning a semiconductor substrate containing cobalt and copper with the composition for cleaning a semiconductor substrate according to any one of claims 1 to 11.

16. A cleaning method of cleaning a semiconductor substrate with the composition for cleaning a semiconductor substrate according to any one of claims 1 to 9, claim 12, and claim 13 in the presence of ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt ions.

17. A cleaning method of cleaning a semiconductor substrate containing at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, and cobalt with the composition for cleaning a semiconductor substrate according to any one of claims 1 to 9, claim 12, and claim 13.

18. The cleaning method according to any one of claims 14 to 17, wherein, A semiconductor substrate having a hard mask containing at least one selected from the group consisting of titanium and titanium nitride is cleaned.

19. A cleaning method of removing at least one selected from the group consisting of dry etching residues and a hard mask in a semiconductor substrate with the composition for cleaning a semiconductor substrate according to any one of claims 1 to 13.

20. A method of stabilizing hydrogen peroxide, wherein, In a liquid containing hydrogen peroxide (A), cobalt ions, copper ions, 0.005 to 10 mass% of a quaternary ammonium hydroxide (C1), 0.005 to 5 mass% of potassium hydroxide (C2), 0.00005 to 0.005 mass% of aminomethylenephosphonic acid (D), and water, hydrogen peroxide (A) is stabilized with a hydrogen peroxide stabilizer (B) which is at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-lH-tetrazole, triethylenetetraminehexaacetic acid, trans-l,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-di(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine.

21. A method of stabilizing hydrogen peroxide, wherein, In a liquid containing hydrogen peroxide (A), ions of at least one metal selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements, Group 7 elements, Group 8 elements, magnesium, and aluminum, cobalt ions, 0.005 to 10 mass% of a quaternary ammonium hydroxide (C1), 0.005 to 5 mass% of potassium hydroxide (C2), 0.00005 to 0.005 mass% of an aminopolymethylenephosphonic acid (D), and water, hydrogen peroxide (A) is stabilized with a hydrogen peroxide stabilizer (B) that is at least one selected from the group consisting of oxalic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, potassium oxalate, 5-phenyl-1H-tetrazole, triethylenetetraminehexaacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 8-hydroxyquinoline, L(+)-isoleucine, DL-valine, L(-)-proline, hydroxyethylethylenediaminetriacetic acid, N,N-bis(2-hydroxyethyl)glycine, glycine, L-tryptophan, 2,6-pyridinedicarboxylic acid, benzothiazole, and DL-alanine.

22. A method for producing a semiconductor substrate, comprising a step of removing at least one selected from the group consisting of dry etching residues and hard masks in a semiconductor substrate, using the composition for cleaning a semiconductor substrate according to any one of claims 1 to 13.

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