Composition of dissolved metal-containing substances, substrate treatment methods

Abstract

This invention provides a composition with excellent solubility for metal contents (especially Ru contents) and also excellent solubility for oxidized metal contents (especially RuO2 contents). Furthermore, a method for processing a substrate using the above composition is provided. The composition comprises one or more periodic acid compounds selected from the group consisting of periodic acid and its salts, an amine compound as a compound represented by a specific formula (1) or a salt thereof, and water.

Description

Technical Field

[0001] This invention relates to a method for processing a component and a substrate. Prior Technology

[0002] In the process of miniaturization of semiconductor products, the demand for efficient and high-precision processes to remove unnecessary metal contents from the substrate during semiconductor product manufacturing is gradually increasing.

[0003] Patent Document 1 describes an invention relating to a solution for removing transition metal contents from a substrate, the solution comprising, in a specific amount, one or more periodic acids selected from the group consisting of periodic acid and its salts, and a compound containing one or more anions selected from the group consisting of IO3-, I- and I3-.

[0004] [Patent Document 1] International Publication No. 2019 / 138814

[0005] In recent years, when removing unwanted metal inclusions from substrates, there has been a growing demand for etchants with excellent dissolving power (etching performance) for these inclusions. In particular, there is a need for a composition with excellent etching performance for substrates containing ruthenium (Ru) inclusions.

[0006] On the other hand, in processes such as substrate treatment prior to the removal of metal inclusions, there is a possibility that the metal inclusions are oxidized from their surface to form oxides. While conventional etching solutions may have the ability to dissolve the target metal inclusion, they may not also have the ability to dissolve the oxides of the metal contained within that metal inclusion. Therefore, a composition is required that also has sufficient dissolving ability for inclusions of such oxidized metals (especially ruthenium oxide (RuO2)). Summary of the Invention

[0007] Therefore, the objective of this invention is to provide a composition that has excellent solubility for metal contents (especially Ru contents) and also excellent solubility for oxidized metal contents (especially RuO2 contents).

[0008] Furthermore, the objective of this invention is to provide a method for processing a substrate using the composition.

[0009] As a result of in-depth research conducted by the inventors in order to solve the above-mentioned problems, they discovered that the above-mentioned problems can be solved by the following configuration.

[0010] [1] A composition comprising one or more periodic acid compounds selected from the group consisting of periodic acid and its salts, an amine compound as a compound represented by the formula (1) below or a salt thereof, and water.

[0011] [2] The composition as described in [1] is a composition for processing a substrate having at least one selected from the group consisting of ruthenium inclusions and ruthenium oxide inclusions.

[0012] [3] The composition described in [1] is a composition used for processing substrates containing ruthenium and ruthenium oxide.

[0013] [4] The composition as described in any one of [1] to [3], wherein the amine compound has 1 to 8 carbon atoms.

[0014] [5] A composition as described in any one of [1] to [4], wherein the aliphatic hydrocarbon group represented by R has a substituent and further has at least one functional group selected from the group consisting of carboxyl, amino, lateral oxygen, phosphonic acid and sulfonyl.

[0015] [6] A composition as described in any one of [1] to [5], wherein the amine compound is selected from at least one of the group consisting of β-alanine, 4-butanine, 5-pentanine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, succinylamine, malonic acid, acrylamide, butylamine and hexanediamine.

[0016] [7] The composition as described in any one of [1] to [6], wherein the ratio of the content of the periodic acid compound to the content of the amine compound is 1 to 95 by mass.

[0017] [8] A composition as described in any one of [1] to [7], wherein the pH of the composition is 10.0 or less.

[0018] [9] A composition as described in any one of [1] to [8], wherein the pH of the composition is 3.5 or higher.

[0019]

[10] A composition as described in any one of [1] to [9], wherein the pH of the composition is 3.5 to 6.0.

[0020]

[11] The composition described in any of [1] to

[10] does not substantially contain abrasive particles.

[0021]

[12] A method for processing a substrate, comprising: process A, using any one of the components described in [1] to

[11] to remove at least one of the components selected from the group consisting of metal inclusions and metal oxide inclusions from the substrate.

[0022]

[13] The substrate processing method as described in

[12] , wherein the metal inclusions include ruthenium inclusions and the metal oxide inclusions include ruthenium oxide inclusions.

[0023]

[14] A substrate processing method as described in

[12] or

[13] , wherein process A is process A1, in which the above-mentioned composition is used to perform recess etching on wiring disposed on the substrate and composed of metal inclusions or metal oxide inclusions; process A2, in which the above-mentioned composition is used to remove the film on the outer edge of the substrate on which the film composed of metal inclusions or metal oxide inclusions is disposed; process A3, in which the above-mentioned composition is used to remove the metal inclusions or metal oxide inclusions attached to the back side of the substrate on which the film composed of metal inclusions or metal oxide inclusions is disposed; process A4, in which the above-mentioned composition is used to remove the metal inclusions or metal oxide inclusions on the substrate after dry etching; or process A5, in which the above-mentioned composition is used to remove the metal inclusions or metal oxide inclusions on the substrate after chemical mechanical polishing.

[0024]

[15] The substrate processing method described in any one of

[12] to

[14] further includes an oxidation process in which an oxidant is brought into contact with a metal content on the substrate, and the above process A is performed on a substrate having at least a metal oxide content produced in the above oxidation process. Simple Explanation of the Diagram

[0025] Figure 1 is a schematic diagram of the upper part of a cross-section of an example of the workpiece used in process A1.

[0026] Figure 2 is a schematic diagram of the upper part of a cross-section of an example of a workpiece after process A1 has been performed.

[0027] FIG. 3 is a schematic view showing an example of an object to be processed used in Process A2.

[0028] FIG. 4 is a cross-sectional schematic view showing an example of an object to be processed used in Process A4. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION

[0029] MEANS FOR SOLVING THE PROBLEM

[0030] EFFECT OF THE INVENTION

[0031] According to the present invention, it is possible to provide a composition having excellent solubility for metal inclusions and also excellent solubility for metal oxide inclusions.

[0032] Furthermore, according to the present invention, it is possible to provide a method for processing a substrate using the composition. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of the upper part of a cross-section showing an example of an object to be processed used in Process A1. FIG. 2 is a schematic view of the upper part of a cross-section showing an example of an object to be processed after Process A1 has been carried out. FIG. 3 is a schematic view showing an example of an object to be processed used in Process A2. FIG. 4 is a cross-sectional schematic view showing an example of an object to be processed used in Process A4. EMBODIMENT

[0033] Hereinafter, the present invention will be described in detail.

[0034] The description of the constituent elements described below is based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0035] When there are two or more components in this specification, the "content" of the component represents the total content of these two or more components.

[0036] In this specification, the description of groups (atomic groups) without specifying substitution and non-substitution includes, without prejudice to the effects of the invention, those without substituents and those with substituents. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). This meaning applies to all compounds.

[0037] Unless otherwise specified, “exposure” in this specification refers not only to exposure based on the bright line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, X-rays, and EUV (Extreme ultraviolet) light, but also to depiction based on particle beams such as electron beams and ion beams.

[0038] In this specification, the numerical range represented by "~" indicates the range included by the values ​​recorded before and after "~" as the lower and upper limits.

[0039] In this specification, unless otherwise specified, the term "metal" refers to a monomer of an unoxidized metal, "metal inclusion" refers to a material containing a monomer of a metal as its main component, and "metal oxide inclusion" refers to a material containing an oxide of a metal as its main component. Furthermore, taking "metal inclusion" as an example, "containing as a main component" means that the content of the monomer of the metal (or the total content of monomers containing two or more metals or alloys) is greater than the content of each of the other components, such as metal oxides, metal nitrides, metal oxynitrides, and metal-free components.

[0040] [Composition]

[0041] The composition of the present invention comprises one or more periodic acid compounds selected from the group including periodic acid and its salts, an amine compound (hereinafter also referred to as "specific amine" in this specification) as a compound represented by formula (1) described below, and water.

[0042] The mechanism by which the problem of the present invention is solved by using the composition of the present invention is not yet certain, but the inventors speculate as follows: the composition achieves excellent solubility for metal contents by including periodic acid compound, and the composition achieves excellent solubility for oxidized metal contents by forming complex compounds with specific amines included together with periodic acid compound.

[0043] The composition of the present invention has excellent dissolving ability for metal contents and excellent dissolving ability for metal oxide contents. Therefore, for example, when the composition of the present invention is applied in the processing of substrates, the same composition can be preferably applied to any one of a substrate having only metal contents, a substrate having only metal oxide contents, and a substrate having both metal contents and metal oxide contents.

[0044] <Periodic acid compounds>

[0045] The composition of this invention contains periodic acid compounds.

[0046] In this specification, periodic acid compounds are a collective term for compounds selected from the group consisting of periodic acid and its salts.

[0047] There are no particular limitations on the periodic acid compound. However, considering its excellent solubility for transition metals such as ruthenium, it is preferable to select one or more compounds from the group consisting of orthoperiodic acid (H5IO6), salts of orthoperiodic acid, metaperiodic acid (HIO4), and salts of metaperiodic acid. Orthoperiodic acid or metaperiodic acid is more preferred. In particular, orthoperiodic acid is preferred from the viewpoints of not containing alkali metals such as sodium (Na) and for its compositional stability.

[0048] Periodic acid compounds can be used alone or in combination of two or more.

[0049] From the perspective of superior solubility for metal contents, the content of periodic acid compound relative to the total mass of the composition is preferably 0.1% by mass or more, even better 0.5% by mass or more, further better 1.5% by mass or more, and especially better 2.0% by mass or more.

[0050] There is no particular upper limit to the content of periodic acid compounds. Relative to the total mass of the composition, it is preferred to be below 40.0% by mass, even better to be below 30.0% by mass, further preferred to be below 20.0% by mass, and especially preferred to be below 10.0% by mass.

[0051] Specific amines

[0052] The composition of the present invention comprises an amine compound (specific amine) as a compound represented by the following formula (1) or a salt thereof.

[0053] R-NH2 formula (1)

[0054] In formula (1), R represents an aliphatic hydrocarbon group that may have substituents. The aliphatic hydrocarbon group may have at least one linker selected from the group consisting of -O-, -S-, and -NR1- in the carbon chain. R1 represents a hydrogen atom or an aliphatic hydrocarbon group that may have substituents. Wherein, the substituents that the aliphatic hydrocarbon group represented by R may have or that the aliphatic hydrocarbon group represented by R1 may have do not contain a hydroxyl group.

[0055] The aliphatic hydrocarbon group represented by R can be any of straight-chain, branched, and cyclic, and can have unsaturated carbon bonds. As an aliphatic hydrocarbon group, straight-chain or branched alkyl or cycloalkyl groups are preferred, straight-chain or branched alkyl groups are more preferred, and straight-chain alkyl groups are even more preferred.

[0056] There is no particular limitation on the number of carbons in the aliphatic hydrocarbon group represented by R, with 1 to 15 being preferred. From the viewpoint of superior solubility for metal inclusions (especially Ru inclusions), 1 to 8 is even better. From the viewpoint of superior solubility for metal oxide inclusions (especially RuO2 inclusions), 1 to 7 is further preferred, 2 to 7 is further preferred, and 2 to 7 is even better. From the viewpoint of further superior solubility for both metal inclusions (especially Ru inclusions) and metal oxide inclusions (especially RuO2 inclusions), 2 to 6 is particularly preferred, and 3 to 6 is optimal.

[0057] As for the substituents in the aliphatic hydrocarbon group represented by R, there are no particular limitations as long as they do not contain a hydroxyl group or an aromatic ring. For example, at least one functional group selected from the group consisting of carboxyl, amino, oxy, phosphonic, sulfonyl, and mercapto groups can be cited. It is preferable that the aliphatic hydrocarbon group represented by R further has at least one of the above-mentioned functional groups.

[0058] As the aforementioned functional groups, carboxyl, amino, lateral oxygen, phosphonic acid, or sulfonyl are preferred, with carboxyl, amino, or lateral oxygen being even more preferred.

[0059] There is no particular limitation on the number of the aforementioned functional groups in the aliphatic hydrocarbon group represented by R, but 1 to 5 is preferred, and 1 to 3 is even better.

[0060] R can be an aliphatic hydrocarbon group having a linker selected from the group consisting of -O-, -S-, and -NR1- in the carbon chain. R1 represents a hydrogen atom or an aliphatic hydrocarbon group that may have substituents.

[0061] The aliphatic hydrocarbon group represented by R1 can be any of the following: straight-chain, branched, and cyclic; and it can have unsaturated carbon bonds. It is more preferred that the aliphatic hydrocarbon group represented by R1 is a straight-chain or branched alkyl group, and a straight-chain alkyl group is even more preferred.

[0062] There is no particular limitation on the number of carbons in the aliphatic hydrocarbon group represented by R1, but 1 to 5 is preferred, and 1 to 3 is even better.

[0063] As R1, hydrogen atom or straight-chain alkyl group having 1 to 3 carbon atoms is preferred, with hydrogen atom being even more preferred.

[0064] There is no particular limitation on the number of the aforementioned linking groups in the aliphatic hydrocarbon group represented by R, but 1 to 3 are preferred, and 1 or 2 are even better.

[0065] It is preferable that the aliphatic hydrocarbon group represented by R does not have the above-mentioned linking group in the carbon chain or has -NH-, and it is even more preferable that it does not have the above-mentioned linking group in the carbon chain.

[0066] Furthermore, there are no particular limitations on the salt of the compound represented by formula (1). For example, salts of inorganic acids formed by hydrogen bonding of at least one nonmetal from the group including Cl, S, N and P can be cited, with hydrochloride, sulfate or nitrate being preferred.

[0067] There is no particular limitation on the number of carbon atoms in a specific amine, but 1 to 15 is preferred. From the viewpoint of superior solubility for metal inclusions (especially Ru inclusions), 1 to 8 is even better. From the viewpoint of superior solubility for metal oxide inclusions (especially RuO2 inclusions), 2 to 7 is further preferred. From the viewpoint of further superior solubility for both metal inclusions (especially Ru inclusions) and metal oxide inclusions (especially RuO2 inclusions), 3 to 6 is particularly preferred.

[0068] The following are specific examples of certain amines.

[0069] Examples of specific amines that do not have substituents include methylamine, ethylamine, propylamine, n-butylamine, tert-butylamine, n-hexylamine, cyclohexylamine, n-octylamine, and 2-ethylhexylamine.

[0070] Examples of specific amines that have a carboxyl group as a substituent in an aliphatic hydrocarbon group represented by R include glycine, α-alanine (2-aminopropionic acid), β-alanine (3-aminopropionic acid), 4-butanine, 5-pentanine, 7-heptaneine, lysine, cysteine, aspartic acid, glutamic acid, and their salts.

[0071] As a specific amine represented by R, which is an aliphatic hydrocarbon group having an amino group as a substituent, that is, a specific amine having two or more amino groups in the compound as a whole, examples include ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,5-pentanediamine, 2,2-dimethyl-1,3-propanediamine, 1,6-hexanediamine, 1,7-heptanediamine and 1,8-octanediamine, as well as polyalkyl polyamines such as diethylenetriamine, dihexamethylenetriamine, triethylenetetramine, bis(aminopropyl)ethylenediamine and tetraethylenepentamine.

[0072] Aliphatic hydrocarbon groups represented by R have side oxygen groups as substituents, which are specific amines with amide structures. Examples include succinamide, malondiamide, propionamide, butylamide, hexamethylenediamide, methyl carbamate, and urea.

[0073] Examples of specific amines other than those mentioned above include 2-aminoethylphosphonic acid, taurine, aminomethanesulfonic acid, aminomethylphosphonic acid, N-methyl-1,3-propanediamine, N-ethylethylenediamine, and N-(2-aminoethyl)piperazine. .

[0074] From the viewpoint of superior solubility for metal inclusions (especially Ru inclusions), the following are considered as specific amines: β-alanine, 4-butanine, 5-pentanine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, succinylamine, propanediamine, acrylamide, butylamine, hexanediamine, 2-aminoethylphosphonic acid, taurine, glycine, 7-heptane, 1,8-octanediamine, aminomethanesulfonic acid, and amines. Fosinate or methyl carbamate are preferred. From the viewpoint of superior solubility for metal oxides (especially RuO2), β-alanine, 4-butanine, 5-pentanine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, succinylamine, malondiamine, acrylamide, butylamine, hexanediamine, 2-aminoethylphosphonic acid, taurine, glycine, or 7-heptane are even better.

[0075] From the viewpoint of further improving the solubility of metal contents (especially Ru contents) and metal oxide contents (especially RuO2 contents), β-alanine, 4-butanine, 5-pentanine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, succinylamine, propylenediamine, acrylamide, butanediamine or hexanediamine are further preferred, and 4-butanine, 1,3-propanediamine or 1,4-butanediamine are particularly preferred.

[0076] A specific amine can be used alone or in combination with two or more.

[0077] From the viewpoint of superior solubility for metal oxide contents (especially RuO2 contents), the content of the specific amine relative to the total mass of the composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably greater than 0.06% by mass. There is no particular upper limit to the content of the specific amine, but it is preferably 30% by mass or less relative to the total mass of the composition. From the viewpoint of superior solubility for metal oxide contents (especially RuO2 contents), it is more preferably 0.90% by mass or less, and further preferably 0.50% by mass or less.

[0078] Furthermore, the ratio of periodic acid compound content to specific amine content (periodic acid compound content / specific amine content) is preferably 200 or less by mass. From the viewpoint of superior solubility for metal contents (especially Ru contents), 95 or less is even better. From the viewpoint of superior solubility for oxidized metal contents (especially RuO2 contents), 50 or less is further better. From the viewpoint of further superior solubility for metal contents (especially Ru contents), less than 45 is particularly good. From the viewpoint of further superior solubility for oxidized metal contents (especially RuO2 contents), less than 40 is optimal.

[0079] There is no particular limitation on the lower limit of the above-mentioned content ratios, but it is preferred to be 0.01 or more by mass. From the viewpoint of excellent solubility for metal contents (especially Ru contents), 1 or more is even better. From the viewpoint of excellent solubility for both metal contents (especially Ru contents) and metal oxide contents (especially RuO2 contents), 3 or more is further preferred. From the viewpoint of excellent solubility for metal oxide contents (especially RuO2 contents), 5 or more is particularly preferred.

[0080] <Water>

[0081] As for water, there are no particular restrictions, but purified water such as distilled water, ion-exchanged water, or ultrapure water is preferred, with ultrapure water used in semiconductor manufacturing being even better. The water contained in the composition may contain unavoidable trace amounts of mixed components.

[0082] There is no particular limitation on the water content in the composition, but 50% by mass or more is preferred, 65% by mass or more is even more preferred, and 75% by mass or more is further preferred. Furthermore, there is no particular limitation on the upper limit, but 99.5% by mass or less is preferred, 99% by mass or less is even more preferred, and 98% by mass or less is further preferred.

[0083] <Any ingredient>

[0084] The composition may contain any other components besides those mentioned above. The following describes any such components.

[0085] (pH adjuster)

[0086] The composition may include a pH adjuster. Furthermore, the pH adjuster is configured not to contain the specific amines mentioned above.

[0087] As pH adjusters, both basic and acidic compounds can be used, and the appropriate choice can be made according to the pH of the target component.

[0088] -Alkaline compounds-

[0089] The composition may include a basic compound that exhibits alkalinity (pH greater than 7.0) in aqueous solution as a pH adjuster. Examples of basic compounds include inorganic bases and organic bases (other than the specific amines mentioned above).

[0090] As an organic base, for example, quaternary ammonium compounds can be cited. There are no particular limitations as long as the quaternary ammonium compound is a compound or its salt having a quaternary ammonium cation formed by substituting four hydrocarbon groups (preferably alkyl) on the nitrogen atom.

[0091] Examples of quaternary ammonium compounds include, for example, quaternary ammonium hydroxide, quaternary ammonium fluoride, quaternary ammonium bromide, quaternary ammonium iodide, acetates of quaternary ammonium, and carbonates of quaternary ammonium.

[0092] As a quaternary ammonium compound, quaternary ammonium hydroxide is preferred, and the compound represented by the following formula (2) is even more preferred.

[0093]

[0094] In formula (2), R4A to R4D independently represent alkyl groups having 1 to 6 carbon atoms (preferably methyl, ethyl, propyl, or butyl), hydroxyalkyl groups having 1 to 6 carbon atoms (preferably hydroxymethyl, hydroxyethyl, or hydroxybutyl), benzyl, or aryl (preferably phenyl, naphthyl, or naphthalene). Among these, alkyl groups having 1 to 6 carbon atoms, hydroxyethyl groups having 1 to 6 carbon atoms, or benzyl groups having 1 to 6 carbon atoms are preferred.

[0095] As compounds represented by formula (2), tetramethylammonium hydroxide (TMAH), ethyltrimethylammonium hydroxide (ETMAH), tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), dimethyldipropylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methyltri(hydroxyethyl)ammonium hydroxide, tetra(hydroxyethyl)ammonium hydroxide, trimethylbenzylammonium hydroxide, dihydroxyethyldimethylammonium hydroxide, or choline are preferred, with TMAH, ETMAH, TEAH, or TBAH being even more preferred.

[0096] Furthermore, considering the removal effect of metal contents, the amount of metal residue after use, economic efficiency, and the stability of the components, TMAH, ETMAH, TEAH, dimethyl dipropylammonium hydroxide, dihydroxyethyl dimethylammonium hydroxide, or trimethyl (hydroxyethyl) ammonium hydroxide are preferred.

[0097] Alternatively, the quaternary ammonium hydroxide compound described in Japanese Patent Publication No. 2015-518068 may also be used.

[0098] Examples of organic bases other than quaternary ammonium compounds include amine oxides, nitro compounds, nitroso compounds, oximes, ketoximes, aldoximes, lactamines, and isonitriles.

[0099] Examples of inorganic bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, and ammonium hydroxide.

[0100] As a basic compound, salts of the above-mentioned compounds can be used as long as they are either bases or non-ionic in aqueous solution.

[0101] Furthermore, among the aforementioned specific amines, compounds that exhibit basicity (pH greater than 7.0) in aqueous solution can also function as basic compounds.

[0102] As an alkaline compound, considering the removal effect of metal contents, the low metal residue after use, economy and stability of the composition, ammonium quaternary hydroxide is better, TMAH, ETMAH, TEAH or dimethyl dipropylammonium hydroxide is better, and ETMAH or TEAH is even better.

[0103] -Acidic compounds-

[0104] The composition may include acidic compounds that exhibit acidity (pH less than 7.0) in aqueous solution as pH adjusters. Examples of acidic compounds include inorganic acids and organic acids (other than the specific amines mentioned above).

[0105] Examples of inorganic acids include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, hydrofluoric acid, perchloric acid, and hypochlorous acid. Sulfuric acid, hydrochloric acid, phosphoric acid, or nitric acid are preferred, and sulfuric acid, hydrochloric acid, or phosphoric acid are even better.

[0106] Examples of organic acids include carboxylic acids and sulfonic acids.

[0107] Examples of carboxylic acids include formic acid, acetic acid, propionic acid, and butyric acid, which are lower (1-4 carbon atoms) aliphatic monocarboxylic acids.

[0108] Examples of sulfonic acids include methanesulfonic acid (MSA), benzenesulfonic acid, and tosic acid.

[0109] As an acidic compound, salts of the above-mentioned compounds can be used as long as they are acidic or acidic ions (anions) in aqueous solution.

[0110] Furthermore, among the aforementioned specific amines, compounds having ligands such as carboxyl, sulfonyl, and phosphonic acid groups and exhibiting acidity (pH less than 7.0) in aqueous solution and / or the anionic surfactants described later can also function as acidic compounds.

[0111] As acidic compounds, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, or sulfonic acid or their salts are preferred, with sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, or p-toluenesulfonic acid being even more preferred.

[0112] pH adjusters can be used alone or in combination of two or more.

[0113] Furthermore, pH adjusters can be commercially available products or synthesized appropriately using known methods.

[0114] The content of the pH adjuster relative to the total mass of the composition is preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. There is no particular upper limit, but it is preferred to be 20.0% by mass or less relative to the total mass of the composition.

[0115] Adjusting the pH adjuster content within the above-mentioned preferred range to achieve a preferred pH range for the components described later is also preferable.

[0116] (surfactants)

[0117] The composition may contain surfactants.

[0118] As a surfactant, there are no particular limitations as long as it is a compound having both a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule. For example, anionic surfactants, cationic surfactants, and nonionic surfactants can be mentioned.

[0119] There are no particular limitations on the hydrophobic group present in a surfactant; for example, aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof can be mentioned. When the hydrophobic group includes an aromatic hydrocarbon group, it is preferable to have 6 or more carbon atoms, and even more preferably 10 or more carbon atoms. When the hydrophobic group does not contain an aromatic hydrocarbon group but consists only of an aliphatic hydrocarbon group, it is preferable to have 8 or more carbon atoms, and even more preferably 10 or more carbon atoms. There is no particular upper limit on the number of carbon atoms in the hydrophobic group, but 24 or less is preferable, and 20 or less is even more preferred.

[0120] Examples of anionic surfactants include those having at least one hydrophilic group selected from the group consisting of sulfonic acid groups, carboxyl groups, sulfate ester groups, and phosphonic acid groups within their molecules.

[0121] Examples of anionic surfactants having an intramolecular sulfonic acid groups include alkyl sulfonic acids, alkylbenzene sulfonic acids, alkylnaphthalene sulfonic acids, alkyl diphenyl ether sulfonic acids, fatty acid amide sulfonic acids, and their salts.

[0122] Examples of anionic surfactants having a carboxylic acid group within the molecule include polyoxyethylene alkyl ether carboxylic acid, polyoxyethylene alkyl ether acetic acid, polyoxyethylene alkyl ether propionic acid, fatty acids, and their salts.

[0123] Furthermore, there are no particular limitations on the salts used as such anionic surfactants; for example, ammonium salts, sodium salts, potassium salts, and tetramethylammonium salts can be cited.

[0124] As a cationic surfactant, there are no particular limitations as long as it is a compound with a cationic hydrophilic group and the aforementioned hydrophobic group. For example, quaternary ammonium salt surfactants and alkylpyridine surfactants can be cited.

[0125] A single surfactant can be used alone, or two or more surfactants can be used.

[0126] When the composition contains a surfactant, the surfactant content relative to the total mass of the composition is preferably 0.01% by mass or more, and more preferably 0.03% by mass or more. There is no particular upper limit, but from the viewpoint of inhibiting foaming of the composition, 10% by mass or less is preferred, and 5% by mass or less is even better.

[0127] (Water-soluble organic solvent)

[0128] The composition may include a water-soluble organic solvent as a solvent. Furthermore, the water-soluble organic solvent is configured not to contain the specific amines mentioned above.

[0129] Examples of water-soluble organic solvents include ether-based solvents, alcohol-based solvents, ketone-based solvents, amide-based solvents, sulfur-containing solvents, and lactone-based solvents. Water-soluble organic solvents that can be mixed with water in any proportion are preferred.

[0130] As an ether solvent, there are no particular limitations as long as the compound has an ether bond (-O-). Examples include diethyl ether, diisopropyl ether, dibutyl ether, tributyl methyl ether, cyclohexyl methyl ether, tetrahydrofuran, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, alkyl glycol monoalkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether and diethylene glycol monobutyl ether), and alkyl glycol dialkyl ethers (diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether).

[0131] There is no particular limitation on the number of carbon atoms in ether-based solvents, but 3 to 16 is preferred, 4 to 14 is even better, and 6 to 12 is even more preferred.

[0132] Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, propylene glycol, glycerol, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.

[0133] There is no particular limitation on the number of carbon atoms in alcohol solvents, but 1 to 8 is preferred, and 1 to 4 is even better.

[0134] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0135] Examples of acetamide solvents include methylamine, monomethylmethylamine, dimethylmethylamine, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0136] Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfene, and cyclobutane.

[0137] Examples of lactone solvents include γ-butyrolactone and δ-valerolactone.

[0138] One water-soluble organic solvent may be used alone, or two or more may be used. When using two or more water-soluble organic solvents, it is preferable that the total content be within the above-mentioned range.

[0139] When the composition contains a water-soluble organic solvent, there is no particular limitation on the content of the water-soluble organic solvent, but 0.1 to 10% by mass is preferred.

[0140] (Grinding particles)

[0141] It is preferable that the composition does not actually contain abrasive particles.

[0142] In this specification, polishing particles refer to particles contained in the polishing slurry used in the polishing process of semiconductor substrates, and whose average primary particle size is 5 nm or more.

[0143] Furthermore, "the composition does not substantially contain abrasive particles" means that, when the composition is measured using a commercially available measuring device for particle size distribution in liquids using light scattering, the number of abrasive particles with an average primary diameter of 5 nm or greater per 1 mL of the composition is 10 or less. It is preferable that the number of abrasive particles with an average primary diameter of 5 nm or greater per 1 mL of the composition is 8 or less, and even more preferable that it is 5 or less.

[0144] Examples of abrasive particles include inorganic abrasive particles such as silicon dioxide (including colloidal silicon dioxide and fumed silicon dioxide), alumina, zirconium dioxide, cerium dioxide, titanium dioxide, germanium dioxide, manganese oxide, and silicon carbide; and organic abrasive particles such as polystyrene, polyacrylic acid, and polyvinyl chloride.

[0145] The content of abrasive particles contained in the composition was determined using a commercially available measuring device that uses a laser as a light scattering liquid particle measurement method.

[0146] Furthermore, the average primary particle size of the grinding particles is determined as follows: the particle size (equivalent circle diameter) of 1000 randomly selected primary particles from an image taken using a JEOL Ltd. transmission electron microscope TEM2010 (with a voltage of 200 kV) is measured, and these are then arithmetically averaged. Furthermore, the equivalent circle diameter refers to the diameter of a circle assuming it has a projected area equal to the projected area of ​​the particle at the time of observation.

[0147] Methods for removing abrasive particles from a composition include, for example, purification processes such as filtration.

[0148] Provided that the effects of the present invention and the functions of each component are not impaired, the composition may contain other components besides those mentioned above.

[0149] <ph>

[0150] There are no particular limitations on the pH of the composition; for example, a range of 1.0 to 13.0 is acceptable. Regarding the pH of the composition, from the viewpoint of superior solubility for metal contents (especially Ru contents), a pH of 10.0 or lower is preferred; from the viewpoint of superior solubility for oxidized metal contents (especially RuO2 contents), a pH of 8.0 or lower is better; from the viewpoint of further superior solubility for metal contents (especially Ru contents), a pH of 7.0 or lower is further preferred; and from the viewpoint of further superior solubility for oxidized metal contents (especially RuO2 contents), a pH of 6.0 or lower is particularly preferred.

[0151] Regarding the lower limit of pH of the composition, from the viewpoint of superior solubility for metal contents (especially Ru contents) and for oxidized metal contents (especially RuO2 contents), pH 3.3 and above is preferred, pH 3.4 and above is even better, and pH 3.5 and above is further preferred.

[0152] The optimal pH range for the composition is 3.5 to 6.0.

[0153] In this specification, the pH of the composition is obtained by measuring it at 25°C using a pH meter (HORIBA, Ltd., F-51 (trade name)).

[0154] <Set>

[0155] The composition can be set by dividing each component (raw material) into multiple parts.

[0156] As a method of setting the components as a set, for example, the following can be described: preparing a liquid composition containing a periodic acid compound and a specific amine as a first liquid, and preparing a liquid composition containing other components as a second liquid.

[0157] There are no particular restrictions on the method of manufacturing the kit. For example, the kit for preparing the composition can be made by preparing the first liquid and the second liquid and then storing them in different containers.

[0158] There are no particular restrictions on the preparation method of the first solution. For example, the following method can be used: after adding periodic acid compound and a specific amine to purified water obtained by purification, the first solution is prepared as a homogeneous aqueous solution by stirring.

[0159] There are no particular restrictions on the preparation method of the second solution; it can be prepared in the same way as the first solution.

[0160] <container>

[0161] The components, as well as the first and second liquids contained in the kit, can be filled into any container for storage, transportation, and use. Containers with high cleanliness and minimal leaching of impurities are preferred. Examples of containers for filling the components include the "CLEAN BOTTLES" series manufactured by AICELLO CHEMICAL CO.,LTD. and the "PURE BOTTLES" manufactured by KODAMA PLASTICS Co.,Ltd., but are not limited to these.

[0162] <Manufacturing Method>

[0163] There are no particular limitations on the method of manufacturing the composition. For example, the composition can be manufactured by mixing the above-mentioned components. There are no particular limitations on the order and / or timing of mixing the above-mentioned components. For example, the composition can be manufactured by mixing the components by sequentially adding a periodic acid compound, a specific amino compound, and any other component to a mixer or other stirrer containing purified pure water and then stirring thoroughly.

[0164] As a method for manufacturing the components, examples include methods such as pre-adjusting the pH of the cleaning solution with a pH adjuster before mixing the components, and methods such as adjusting the pH of the mixture with a pH adjuster to the set pH after mixing the components.

[0165] Alternatively, the composition can be manufactured by producing a concentrate with a lower water content than intended for use, which is then diluted with a diluent (preferably water) to adjust the content of each component to the specified level before use. The composition can also be manufactured by diluting the above-mentioned concentrate with a diluent and then adjusting the pH to the set level using a pH adjuster. When diluting the concentrate, a specified amount of diluent can be added to the concentrate, or a specified amount of concentrate can be added to the diluent.

[0166] [The object being processed]

[0167] The uses of the above-mentioned components are not particularly limited. For example, the components can be used to remove metal inclusions and / or metal oxide inclusions from a substrate (semiconductor substrate) as the object to be processed. Hereinafter, the term "object to be removed" refers to at least one type selected from the group consisting of metal inclusions and metal oxide inclusions, which exists on the substrate and is the object to be removed using the components.

[0168] In this specification, "on the substrate" means, for example, all parts including the surface, back, sides, and grooves of the substrate. Furthermore, "object to be removed on the substrate" means not only that the object to be removed exists on the surface of the substrate, but also that the object to be removed exists on the substrate through other layers.

[0169] Metallic materials are materials whose main components are monomers containing metals (metal atoms).

[0170] Regarding the metals contained in the metal inclusions, examples include metals M selected from Ru (ruthenium), Ti (titanium), Ta (tantalum), Co (cobalt), Cr (chromium), Hf (hafnium), Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Cu (copper), Zr (zirconium), Mo (molybdenum), La (lanthanum), W (tungsten), and Ir (iridium).

[0171] As a metal inclusion, metal M inclusion is preferred.

[0172] Examples of metallic inclusions include monomers of metal M and alloys containing metal M.

[0173] The metal inclusions can be a mixture containing two or more of these compounds.

[0174] Furthermore, as long as it contains a metal as the main component, the metal content can be an oxide, nitride, or complex oxide, complex nitride, or complex nitride containing a metal (preferably metal M).

[0175] The content of metal atoms in the metal inclusion relative to the total mass of the metal inclusion is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. Since the metal inclusion can be the metal monomer itself, the upper limit is 100% by mass.

[0176] As a metallic inclusion, Ru inclusion is preferred.

[0177] Examples of Ru inclusions include Ru monomers and Ru alloys. As long as Ru is a main component, Ru inclusions can contain Ru oxides, nitrides, or oxynitrides.

[0178] The Ru atom content in the Ru-containing compound is preferably 10% by mass or more relative to the total mass of the Ru-containing compound, more preferably 30% by mass or more, and more preferably 50% by mass or more. There is no particular upper limit, and since the Ru-containing compound can be a Ru monomer, it is 100% by mass.

[0179] Metal oxides contain materials in which the oxides of metals are the main components.

[0180] Metal M can be cited as an example of a metal atom constituting an oxide contained in a metal oxide inclusion. It is preferable that the metal oxide inclusion contains an oxide of metal M.

[0181] Metal oxides can be mixtures containing two or more metal oxides.

[0182] Furthermore, as long as it contains metal oxides as the main component, the metal oxide inclusions can contain metal monomers and / or metal nitrides.

[0183] The content of metal oxides in metal oxide inclusions relative to the total mass of the metal oxide inclusions is preferably 5% by mass or more, and even more preferably 20% by mass or more. There is no particular upper limit, and it can be below 100% by mass.

[0184] As a metal oxide inclusion, ruthenium oxide (RuO2) inclusion is preferred.

[0185] As long as RuO2 is included as the main component, RuO2 inclusions may contain Ru monomers and / or Ru nitrides.

[0186] The RuO2 content in the RuO2 inclusions is preferably 5% by mass or more relative to the total mass of the RuO2 inclusions, and even more preferably 20% by mass or more. There is no particular upper limit, and it can be below 100% by mass.

[0187] As an object to be processed, for example, a substrate having metal inclusions and / or metal oxide inclusions can be cited. That is, the object to be processed includes at least a substrate and at least one of the following present on the substrate: metal inclusions and metal oxide inclusions.

[0188] There are no particular restrictions on the type of substrate, but semiconductor substrates are preferred.

[0189] Examples of substrates include semiconductor wafers, photomask glass substrates, liquid crystal display glass substrates, plasma display glass substrates, FED (Field Emission Display) substrates, optical disc substrates, magnetic disc substrates, and magneto-optical disc substrates.

[0190] Materials constituting semiconductor substrates include group III-V compounds such as silicon, silicon germanium, and GaAs, or any combination thereof.

[0191] The types of objects to be removed from the substrate (metal contents and / or metal oxide contents) are as described above.

[0192] There are no particular limitations on the shape of the object to be removed on the substrate. For example, it can be any of the following: a film-like shape (object to be removed film), a wire-like shape (object to be removed wire), or a particle-like shape.

[0193] As described above, Ru (ruthenium) is preferred as a metal, and RuO2 (ruthenium oxide) is preferred as a metal oxide. That is, as the work to be processed, it is preferable to have a substrate and a removal object (removal object film, removal object wiring, or particulate removal object) disposed on the substrate, and each removal object is selected from at least one of the group consisting of Ru-containing substances and RuO2-containing substances.

[0194] Furthermore, as a metal, Cu (copper) or Co (cobalt) is preferred; as an oxide metal, Cu or Co oxide is preferred; as a workpiece to be processed, it is preferred to have a substrate and a removal target film, a removal target wiring or a particle-shaped removal target disposed on the substrate, and each removal target is selected from at least one of the group including Co or Cu inclusions and Co or Cu oxide inclusions.

[0195] The object to be removed on the substrate can be a single type, or two or more types. That is, the substrate can contain only metal inclusions, only metal oxide inclusions, or both metal inclusions and metal oxide inclusions. More specifically, it can be a substrate containing both Ru inclusions (Ru films, Ru wirings, and / or particulate Ru inclusions, etc.) and RuO2 inclusions (RuO2 films, RuO2 wirings, and / or particulate RuO2 inclusions, etc.).

[0196] When two or more objects to be removed exist on a substrate, these objects may exist in the same form or in different forms. For example, Ru-containing wiring and RuO2-containing films may exist on the substrate.

[0197] Furthermore, as an example of configuring the object to be removed in a particle-like form, as described below, examples include a substrate with particle-like removed object adhering as residue after dry etching of a substrate having removed object, and a substrate with particle-like removed object adhering as residue after CMP (chemical mechanical polishing) of removed object.

[0198] When the workpiece contains a film composed of a metal inclusion (metal-containing film) on a substrate, the thickness of the metal-containing film is not particularly limited and can be appropriately selected according to the application, but 50 nm or less is preferred, 20 nm or less is even better, and 10 nm or less is further preferred. There is no particular limitation on the lower limit, but 1 nm or more is preferred.

[0199] When the workpiece contains a film composed of metal oxide inclusions (metal oxide film) on a substrate, there is no particular limitation on the thickness of the metal oxide film; it can be selected appropriately according to the application, but 50 nm or less is preferred, and 20 nm or less is even better. There is no particular limitation on the lower limit, but 0.3 nm or more is preferred.

[0200] Metallic and / or non-metallic films can be disposed on only one side of the main surface of the substrate, or on both sides of the main surface. Furthermore, metallic and / or non-metallic films can be disposed on the entire main surface of the substrate, or on a portion of the main surface of the substrate.

[0201] <Method for manufacturing the work being processed>

[0202] There are no particular limitations on the manufacturing method of the processed object having metallic and / or non-metallic contents on the substrate.

[0203] Methods for manufacturing a substrate containing metal inclusions include, for example, known methods such as sputtering, physical vapor deposition (PVD), atomic layer deposition (ALD), chemical vapor deposition (CVD), and molecular beam epitaxy (MBE) to form a metal-containing film on the substrate. Furthermore, when forming a metal-containing film using sputtering, PVD, ALD, and CVD methods, metal inclusions sometimes also adhere to the back side of the substrate (the surface opposite to the metal-containing film side).

[0204] Alternatively, the above method can be performed through a specified shield to form metal wiring on the substrate.

[0205] Furthermore, after forming a metal-containing film or metal-containing wiring on the substrate, the substrate can be used as the workpiece in this processing method after undergoing different processes or treatments.

[0206] For example, a substrate containing a metal film or metal wiring can be subjected to dry etching to produce a substrate with dry etching residue containing metal. Dry etching residue is a byproduct generated during dry etching (e.g., plasma etching), and examples include organic residues derived from photoresist, Si-containing residues, and metal-containing residues. Furthermore, a substrate containing a metal film or metal wiring can be subjected to CMP to produce a substrate with metal inclusions.

[0207] Methods for manufacturing a substrate containing metal oxide can include, for example, forming a metal oxide film on a substrate by sputtering and performing an oxidation treatment (hereinafter also simply referred to as "oxidation treatment") that brings an oxidant into contact with a substrate containing metal oxide (e.g., a substrate containing metal oxide manufactured in the above method).

[0208] The oxidized metal inclusions formed by oxidation treatment can be at least a portion of the metal inclusions on the substrate that are oxidized. That is, oxidation treatment can be used to oxidize only the surface layer of the metal inclusions, or the entire metal inclusions can be oxidized.

[0209] The oxide metal-containing layer formed by oxidation treatment that oxidizes only the surface of the metal-containing substance can be a layer formed by oxidizing only a part of the surface of the metal-containing substance, or a layer formed by oxidizing the entire surface of the metal-containing substance.

[0210] There is no particular limitation on the thickness of the oxide metal layer formed by oxidation treatment that only oxidizes the surface of the metal-containing material; for example, it can be 1 to 10 atomic layers. In addition, the thickness of 1 atomic layer of metal and metal oxide is less than 1 nm (e.g., 0.3 nm to 0.4 nm).

[0211] There are no particular limitations on the object of oxidation treatment, as long as it is a substrate containing metal. For example, a substrate containing metal can be described as the object to be treated. More specifically, by performing oxidation treatment on a substrate containing a metal film, a metal wiring, and a particle-like metal inclusion, a substrate containing an oxide metal film, an oxide metal wiring, and a particle-like oxide metal inclusion can be obtained, respectively.

[0212] There are no limitations on the oxidation treatment methods for oxidizing metal contents. For example, the following treatments can be performed on the above-mentioned objects: liquid treatment in contact with an oxidizing liquid, gas treatment in contact with an oxidizing gas (ozone treatment in which ozone gas is brought into contact with the substrate, and oxygen heating treatment in an oxygen environment, etc.), and dry etching treatment and plasma ashing treatment using plasma.

[0213] In oxidation processes, there are no particular restrictions on the oxidizing agent that comes into contact with the metal inclusions; any substance capable of oxidizing the metal inclusions can be selected depending on the oxidation process. Examples of oxidizing agents include oxidizing liquids, oxidizing gases, and oxygen plasma.

[0214] Furthermore, the processed object containing metal oxide on the substrate can be obtained by placing the substrate containing metal oxide in an environment where oxygen is present, such as in the atmosphere, and oxidizing a portion of the metal oxide.

[0215] Oxidation treatment can be performed in one or more ways.

[0216] Among these, liquid treatment in which a specified oxidizing solution comes into contact with the object to be treated is preferred as an oxidation treatment.

[0217] The aforementioned oxidizing solution can be a liquid containing a compound that has the function of oxidizing the aforementioned metal contents.

[0218] There are no particular limitations on the compounds mentioned above, including hydrogen peroxide (H2O2), FeCl3, FeF3, Fe(NO3)3, Sr(NO3)2, CoF3, MnF3, potassium persulfate (2KHSO5‧KHSO4‧K2SO4), periodic acid, iodic acid, vanadium oxide (V), vanadium oxide (IV, V), ammonium vanadate, and polyatomic ammonium salts (e.g., ammonium persulfate, ammonium hypochlorite (NH4ClO2), ammonium chlorate (NH4ClO3), ammonium iodate (NH4IO3), ammonium nitrate (NH4NO3), ammonium perborate (NH4BO3), and ammonium perchlorate. Ammonium periodate (NH4IO4), ammonium persulfate ((NH4)2S2O8), ammonium hypochlorite (NH4ClO), ammonium tungstate ((NH4)10H2(W2O7)), polyatomic sodium salts {e.g., sodium persulfate (Na2S2O8), sodium hypochlorite (NaClO), sodium perborate}, polyatomic potassium salts {e.g., potassium iodate (KIO3), potassium permanganate (KMnO4), potassium nitrate (KNO3), potassium persulfate (K2S) 2O8), potassium hypochlorite (KClO), polyatomic tetramethylammonium salts {e.g., tetramethylammonium hypochlorite ((N(CH3)4)ClO2), tetramethylammonium chlorate ((N(CH3)4)ClO3), tetramethylammonium iodate ((N(CH3)4)IO3), tetramethylammonium perborate ((N(CH3)4)BO3), tetramethylammonium perchlorate ((N(CH3)4)ClO4), tetramethylammonium periodoate ((N(CH3)4)IO4), persulfate Tetramethylammonium ((N(CH3)4)S2O8)}, polyatomic tetrabutylammonium salts {e.g., tetrabutylammonium persulfate}, persulfate, ferric nitrate (Fe(NO3)3), hydrogen peroxide ((CO(NH2)2)H2O2), peracetic acid (CH3(CO)OOH), 1,4-benzoquinone, formquinone, dimethyl-1,4-benzoquinone, chloroquinone, alloxan, N-methylmorphofolin N-oxide, trimethylamine N-oxide, and combinations thereof.

[0219] When the above-mentioned compounds are salts, the water and anhydrides of the salts can also be used.

[0220] In addition to the compounds mentioned above, the oxidizing liquid may also contain additives such as acids and bases.

[0221] The preferred oxidizing solution is selected from the group consisting of water, hydrogen peroxide solution, ammonium and hydrogen peroxide mixed aqueous solution (APM), hydrofluoric acid and hydrogen peroxide solution (FPM), sulfuric acid and hydrogen peroxide solution (SPM), hydrochloric acid and hydrogen peroxide solution (HPM), dissolved oxygen water, ozone water, perchloric acid and nitric acid.

[0222] Regarding the composition of hydrogen peroxide water, for example, the content of H2O2 relative to the total mass of hydrogen peroxide water is 0.5~31% by mass, and 3~15% by mass is preferred.

[0223] Regarding the composition of APM, it is preferable to have a mass ratio within the range of "ammonia water: hydrogen peroxide water: water = 1:1:1" to "ammonia water: hydrogen peroxide water: water = 1:3:45".

[0224] Regarding the composition of FPM, it is preferable to have a mass ratio in the range of "fluoric acid:hydrogen peroxide water:water = 1:1:1" to "fluoric acid:hydrogen peroxide water:water = 1:1:200".

[0225] Regarding the composition of SPM, it is preferable to have a mass ratio within the range of "sulfuric acid:hydrogen peroxide water:water = 3:1:0" to "sulfuric acid:hydrogen peroxide water:water = 1:1:10".

[0226] Regarding the composition of HPM, it is preferable to have a mass ratio in the range of "hydrochloric acid:hydrogen peroxide water:water = 1:1:1" to "hydrochloric acid:hydrogen peroxide water:water = 1:1:30".

[0227] Furthermore, the preferred composition ratios described herein represent the composition ratios in the case of 28% by mass of ammonia water, 49% by mass of hydrofluoric acid, 98% by mass of sulfuric acid, 37% by mass of hydrochloric acid, and 30% by mass of hydrogen peroxide water.

[0228] The record ["A:B:C=x:y:z”~"A:B:C=X:Y:Z”] as a preferred range indicates that at least one (preferably two, more preferably all) of the ranges ["A:B=x:y”~"A:B=X:Y”], ["B:C=y:z”~"B:C=Y:Z”] and ["A:C=x:z”~"A:C=X:Z”] is preferred.

[0229] Regarding the composition of dissolved oxygen water, for example, it is an aqueous solution with an O2 content of 20 to 500 ppm by mass relative to the total mass of dissolved oxygen water.

[0230] Regarding the composition of ozone water, for example, it is an aqueous solution with an O3 content of 1 to 60 ppm by mass relative to the total mass of ozone water.

[0231] For example, perchloric acid is an aqueous solution containing 0.001 to 60% by mass of HClO4 relative to the total mass of the solution.

[0232] Regarding nitric acid, for example, it is an aqueous solution with a HNO3 content of 0.001 to 60% by mass relative to the total mass of the solution.

[0233] In liquid processing, there are no particular limitations on the method of bringing the workpiece into contact with the oxidizing liquid. For example, methods such as immersing the workpiece in the oxidizing liquid contained in a tank, spraying the oxidizing liquid onto the workpiece, allowing the oxidizing liquid to flow over the workpiece, and any combination thereof can be mentioned.

[0234] Regarding the contact time between the treated material and the oxidizing solution, for example, 0.25 to 10 minutes is preferred, and 0.5 to 5 minutes is even better.

[0235] The optimal temperature for the oxidation solution is 20-75℃, with 20-60℃ being even better.

[0236] In gas processing, oxidizing gases that come into contact with the processed material include, for example, dry air, oxygen, ozone gas, and mixtures thereof. Oxidizing gases may also include gases other than those mentioned above.

[0237] In gas treatment, oxygen or ozone gas is preferred as the oxidizing gas system that comes into contact with the treated material. When oxygen or ozone gas comes into contact with the treated material, it is also preferable to have the contact environment be oxygen-rich, ozone-rich, or a mixture of oxygen and ozone.

[0238] In gas treatment, it is also preferable to heat the workpiece while it is in contact with an oxidizing gas (e.g., heating at 40~200°C).

[0239] Regarding gas treatment, ozone treatment in which ozone gas comes into contact with the object being treated, or heating treatment in oxygen in an oxygen environment, is preferred.

[0240] In the above-mentioned ozone treatment, ozone gas can be brought into contact with the object being treated in an ozone environment, or in a mixed gas environment containing ozone gas and other gases (such as oxygen). Furthermore, ozone treatment can be a process in which the object being treated is heated while being brought into contact with ozone gas.

[0241] In the above-mentioned oxidation treatment (especially liquid treatment), the treated material may further have other metal contents that are different from the metal contents that are oxidized to become metal oxide contents by the oxidation treatment. Some or all of such other metal contents may be intentionally or unavoidably removed by the oxidation treatment (especially liquid treatment).

[0242] Furthermore, in the above-mentioned oxidation treatment (especially liquid treatment), a portion of the metal contents contained in the treated material may be intentionally or unavoidably removed.

[0243] In addition to removing the object, the substrate of the object being processed can also have various layers and / or structures as needed. For example, the substrate can have metal wiring, gate electrodes, source electrodes, drain electrodes, insulating layers, strongly magnetic layers, and / or non-magnetic layers, etc.

[0244] The substrate may have exposed integrated circuit structures, such as interconnects of metal wiring and dielectric materials. Examples of metals and alloys used for the interconnects include aluminum, aluminum-copper alloys, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. The substrate may have layers of silicon oxide, silicon nitride, silicon carbide, and / or carbon-doped silicon oxide.

[0245] There are no particular restrictions on the size, thickness, shape, and layer structure of the substrate; it can be selected appropriately according to needs.

[0246] [Substrate processing methods]

[0247] The substrate processing method of the present invention (hereinafter also referred to as "the processing method") includes a process A of removing metal contents and / or metal oxide contents (objects to be removed) on the substrate using the above-described composition (hereinafter also referred to as "the composition").

[0248] As described above, this treatment method is particularly suitable when removing an object containing at least one of the group consisting of Ru-containing substances and RuO2-containing substances.

[0249] Furthermore, this processing method can be better applied to substrates containing metal oxides, which are obtained by oxidizing the substrate containing the metal oxides.

[0250] The components used in this treatment method are as described above.

[0251] Furthermore, the object to be processed in this processing method, namely the substrate having the object to be removed, is also as described above.

[0252] As a specific method of process A, one example is a method of bringing the constituent into contact with the object being processed, that is, a substrate containing metal.

[0253] The contact method is not particularly limited. Examples include immersing the object to be treated in a composition contained in a container, spraying the composition onto a substrate, allowing the composition to flow over the substrate, or any combination thereof. Among these, immersing the object to be treated, i.e., the substrate with the object to be removed, in the composition is preferred.

[0254] Furthermore, mechanical stirring methods can be used to further enhance the cleaning ability of the components.

[0255] Examples of mechanical stirring methods include circulating the composition on a substrate, flowing or spraying the composition on a substrate, and stirring the composition by ultrasonic or mega-frequency means.

[0256] The processing time of process A can be adjusted according to the method of contacting the component with the substrate and the temperature of the component. There is no particular limitation on the processing time (the contact time between the component and the object being processed), but 0.25 to 10 minutes is preferred, and 0.5 to 2 minutes is even better.

[0257] There are no particular restrictions on the temperature of the components during processing, but 20~75℃ is preferred, and 20~60℃ is even better.

[0258] In process A, the object to be removed from the substrate can be only one type or more types.

[0259] When removing two or more objects in process A, the objects can be removed simultaneously in one process or they can be removed separately. In process A, which removes two or more objects from a substrate by means of multiple removal processes, it is preferable to use this composition in the removal process performed to remove at least one object.

[0260] Examples of combinations of two or more target substances include combinations of metal inclusions or metal oxide inclusions containing two or more metals from the aforementioned metal M, and combinations of metal inclusions and metal oxide inclusions containing the same type of metal atoms. Since the above composition allows for the removal of two or more target substances in a single removal process, combinations of metal inclusions and metal oxide inclusions containing the same type of metal atoms are preferred, and combinations of Ru inclusions and RuO2 inclusions are even better.

[0261] In process A, the content of periodic acid compounds, specific amines, and / or any other components in the composition can be determined while simultaneously adding a solvent (preferably water) to the composition as needed. By performing this treatment, the content of the components in the composition can be stably maintained within a specified range.

[0262] Ion chromatography is an example of a method for determining the content of periodic acid compounds, specific amines, and arbitrary components in a composition. A specific apparatus example is the Dionex ICS-2100 from Thermo Fisher Scientific KK.

[0263] As a specific preferred embodiment of process A, the following can be cited: process A1, using the composition to perform recess etching on wiring disposed on a substrate and composed of metal inclusions or metal oxide inclusions; process A2, using the composition to remove the film on the outer edge of the substrate on which the film composed of metal inclusions or metal oxide inclusions is disposed; process A3, using the composition to remove metal inclusions or metal oxide inclusions attached to the back side of the substrate on which the film composed of metal inclusions or metal oxide inclusions is disposed; process A4, using the composition to remove metal inclusions or metal oxide inclusions on the substrate after dry etching; and process A5, using the composition to remove metal inclusions or metal oxide inclusions on the substrate after chemical mechanical polishing.

[0264] Among them, process A1 or A4 is preferred as process A, with process A1 being even better.

[0265] The following describes the processing methods used in the above processes.

[0266] <Process A1>

[0267] As a process A, process A1 can be cited as an example, in which a component is used to perform a recess etching process on a metal wiring disposed on a substrate.

[0268] Figure 1 shows a schematic diagram of the upper part of a cross section of an example of a substrate (hereinafter also referred to as "wiring substrate") having wiring (hereinafter also referred to as "wiring to be removed") consisting of metal inclusions or metal oxide inclusions in the recess etching process A1.

[0269] The wiring substrate 10a shown in Figure 1 has a substrate (not shown), an insulating film 12 with trenches disposed on the substrate, a barrier metal layer 14 disposed along the inner wall of the trench, and a removal target wiring 16 filled into the trench.

[0270] The substrate and the wiring to be removed in the wiring board are as described above.

[0271] As for the wiring to be removed, a composite containing Ru wiring (wiring with Ru as the principal component), RuO2 wiring (wiring with RuO2 as the principal component), or a composite containing both Ru wiring and RuO2 wiring is preferred. For example, a laminate containing Ru wiring and a RuO2 layer formed on the surface of Ru wiring can be cited as such a composite.

[0272] There are no particular limitations on the materials used to form the barrier metal layer in the wiring substrate; for example, titanium nitride (TiN) and tantalum nitride (TaN) are examples.

[0273] Furthermore, Figure 1 illustrates a wiring substrate with a barrier metal layer, but it can also be a wiring substrate without a barrier metal layer.

[0274] Furthermore, although not shown in Figure 1, a liner layer can be disposed between the barrier metal layer 14 and the metal-containing wiring 16. There are no particular limitations on the material constituting the liner layer; for example, Ru-containing, Cu-containing, and Co-containing materials can be cited.

[0275] There are no particular limitations on the manufacturing method of the wiring board. For example, methods including the following processes can be cited: forming an insulating film on the substrate; forming trenches on the insulating film; forming a barrier metal layer on the insulating film; forming a metal-containing film or a metal oxide-containing film by filling the trenches; and performing a planarization process on the metal-containing film or the metal oxide-containing film.

[0276] In process A1, the above-mentioned components are used to perform a recess etching process on the wires to be removed in the wiring substrate, thereby removing a portion of the wires to be removed to form a recess.

[0277] More specifically, if process A1 is implemented, as shown in the wiring substrate 10b of FIG2, the barrier metal layer 14 and a portion of the wiring to be removed 16 are removed to form a recess 18.

[0278] As a specific method of process A1, one example is a method of bringing the components into contact with the wiring substrate.

[0279] The contact method between the components and the wiring board is as described above.

[0280] The preferred ranges for the contact time between the component and the wiring board and the temperature of the component are as described above.

[0281] (Processes A1a and A1b)

[0282] As process A1, process A1a can be implemented to remove at least one of two or more objects to be removed disposed on the substrate; and process A1b can be implemented to remove objects to be removed that are different from the objects to be removed in process A1a.

[0283] Processes A1a and A1b are performed, for example, on a wiring substrate in which a liner layer is disposed between the wiring to be removed and the barrier metal layer, and the wiring to be removed and the liner layer are different objects to be removed.

[0284] When the target wiring and the liner layer are composed of different materials, the solubility of the processing solution varies depending on the type of material. In this case, it is preferable to perform process A1a (removing the target wiring using solution A, which has better solubility for the target wiring than for the liner layer) and process A1b (removing the liner layer using solution B, which has better solubility for the liner layer than for the target wiring). This is because by performing a two-stage removal process including processes A1a and A1b, the degree of removal of the target wiring and the liner layer can be finely adjusted, and in-wafer uniformity can be ensured.

[0285] As a wiring substrate having the above-mentioned removal target wiring and liner layer, it is preferable that the removal target wiring is a combination of Cu-containing wiring or Co-containing wiring and the liner layer is Ru-containing, or that the removal target wiring is a combination of Ru-containing wiring and the liner layer is a combination of Cu-containing or Co-containing. It is even more preferable that the removal target wiring is a combination of Cu-containing wiring or Co-containing wiring and the liner layer is Ru-containing.

[0286] When removing wiring containing Ru and with a lining layer containing Cu or Co, this composition is preferably used as solution A in process A1a for removing the wiring. When removing wiring containing Cu or Co and with a lining layer containing Ru, this composition is preferably used as solution B in process A1b for removing the lining layer.

[0287] Furthermore, when performing processes A1a and A1b as process A1, one of the aforementioned solutions A or B is the composition itself, and the other is a solution other than the composition itself. There are no particular limitations on the solution other than the composition itself that can be used as solution A or B in process A1a or A1b, and known solutions can be used depending on the types of two or more objects to be removed disposed on the substrate and the etching selectivity of the composition itself.

[0288] For example, when performing process A1b to remove the liner layer using this composition on a wiring substrate whose target wiring is Cu-containing wiring or Co-containing wiring and whose liner layer contains Ru, solutions other than this composition that can be used in process A1a to remove the target wiring include, for example, a mixture of sulfuric acid and hydrogen peroxide water (SPM), a mixture of ammonia water and hydrogen peroxide water (SC-1 or APM), and repeated treatment with hydrogen peroxide and acidic aqueous solution.

[0289] In this processing method, process A1a and process A1b can be performed alternately.

[0290] When alternating between processes A1a and A1b, it is preferable to perform each process A1a and A1b 1 to 10 times.

[0291] Process B

[0292] In addition, process B, which involves treating the wiring board with a specified solution (hereinafter also referred to as "specific solution"), can be performed before or after process A1 as needed.

[0293] In particular, as described above, when a barrier metal layer is disposed on a substrate, there are cases where the solubility of the components constituting the wiring to be removed and the components constituting the barrier metal layer varies depending on their type. In such cases, it is preferable to use a solution with superior solubility for the barrier metal layer to adjust the degree of solubility of the wiring to be removed and the barrier metal layer.

[0294] From this perspective, a particular solution is better if it has poor solubility for the target wiring to be removed but excellent solubility for the substance that constitutes the barrier metal layer.

[0295] Examples of specific solutions include a mixture of hydrofluoric acid and hydrogen peroxide water (FPM), a mixture of sulfuric acid and hydrogen peroxide water (SPM), a mixture of ammonia water and hydrogen peroxide water (APM), and a mixture of hydrochloric acid and hydrogen peroxide water (HPM).

[0296] The compositions of FPM, SPM, APM, and HPM are the same as those of the solutions in the above-mentioned oxidizing solution, including the preferred range.

[0297] In process B, a method of contacting the substrate with a specific solution is preferred as a method of treating the substrate with a specific solution. There are no particular limitations on the method of contacting the specific solution with the substrate; for example, methods similar to those used to contact the composition with the substrate can be cited.

[0298] The contact time between the specific solution and the substrate is preferably 0.25 to 10 minutes, and even more preferably 0.5 to 5 minutes.

[0299] In this process, process A1 and process B can be performed alternately.

[0300] When alternating processes, it is preferable to perform process A1 and process B 1 to 10 times each.

[0301] When process A1 includes processes A1a and A1b, process B can be performed before or after processes A1a and A1b. Alternatively, process A1, which includes processes A1a and A1b, and process B can be performed alternately.

[0302] <Process A2>

[0303] As process A, process A2 can be cited as an example of removing the target film from the outer edge of a substrate on which a film composed of metal inclusions or metal oxide inclusions (hereinafter also referred to as "target film") is disposed.

[0304] Figure 3 shows a schematic diagram (top view) of an example of the object to be processed in process A2, namely, a substrate with the film to be removed.

[0305] The workpiece 20 in process A2 shown in Figure 3 is a laminate having a substrate 22 and a removal target film 24 disposed on a main surface of one side of the substrate 22 (the entire area surrounded by solid lines). As described below, in process A2, the removal target film 24 located at the outer edge 26 (outer area of ​​dashed lines) of the workpiece 20 is removed.

[0306] The substrate in the work to be processed, as well as the metal-containing film and the metal oxide-containing film that are the film to be removed, are as described above.

[0307] As the membrane to be removed, a Ru-containing membrane (a membrane containing Ru as the main component), a RuO2-containing membrane (a membrane containing RuO2 as the main component), or a composite of a Ru-containing membrane and a RuO2-containing membrane are preferred. As an example of the above-mentioned composite, a laminate of a Ru-containing membrane and a RuO2-containing membrane formed on the surface of the Ru-containing membrane can be cited.

[0308] The specific method of process A2 is not particularly limited. For example, a method in which the composition is supplied from the nozzle in such a way that the composition only contacts the removal target film on the outer edge of the substrate can be cited.

[0309] When performing process A2, the substrate processing apparatus and substrate processing method described in Japanese Patent Application Publication No. 2010-267690, Japanese Patent Application Publication No. 2008-080288, Japanese Patent Application Publication No. 2006-100368 and Japanese Patent Application Publication No. 2002-299305 are more applicable.

[0310] The contact method between the components and the processed object is as described above.

[0311] The preferred ranges for the contact time between the composition and the processed material and the temperature of the composition are as described above.

[0312] <Process A3>

[0313] As process A, process A3 can be cited as an example, in which a component is used to remove the object to be removed from the back of a substrate on which a removal object film is disposed.

[0314] As an example of the workpiece processed in process A3, the workpiece used in process A2 can be cited. When forming the substrate used in process A2 and the workpiece on which a removal target film is disposed on a main surface of one side of the substrate, the removal target film is formed using methods such as sputtering and CVD. At this time, sometimes a removal target material adheres to the surface of the substrate on the side opposite to the removal target film side (the back side). Process A3 is performed to remove the removal target material from this workpiece.

[0315] There are no particular limitations on the specific method of process A3. For example, a method in which the composition is blown in such a way that it only contacts the back side of the substrate can be cited.

[0316] The contact method between the components and the processed object is as described above.

[0317] The preferred ranges for the contact time between the composition and the processed material and the temperature of the composition are as described above.

[0318] <Process A4>

[0319] As a process A, process A4 can be cited as an example, in which the composition is used to remove the object to be removed from the substrate after dry etching.

[0320] Figure 4 shows a schematic diagram of an example of the workpiece being processed in process A4.

[0321] The workpiece 30 shown in Figure 4 has a removal target film 34, an etch stop layer 36, an interlayer insulating film 38, and a metal hard mask 40 sequentially on a substrate 32. Through a dry etching process, holes 42 exposing the removal target film 34 are formed at predetermined locations. That is, the workpiece shown in Figure 4 is a laminate containing a substrate 32, a removal target film 34, an etch stop layer 36, an interlayer insulating film 38, and a metal hard mask 40, with holes 42 penetrating from the surface of the metal hard mask 40 to the surface of the removal target film 34 at the opening of the metal hard mask 40. The inner wall 44 of the hole 42 is composed of a cross-sectional wall 44a including the etch stop layer 36, the interlayer insulating film 38, and the metal hard mask 40, and a bottom wall 44b including the exposed removal target film 34, and is coated with dry etching residue 46.

[0322] Dry etching residue contains the removed object.

[0323] As the membrane to be removed in process A4, a Ru-containing membrane (a membrane containing Ru as the main component), a RuO2-containing membrane (a membrane containing RuO2 as the main component), or a composite of a Ru-containing membrane and a RuO2-containing membrane are preferred. As such a composite, for example, a laminate of a Ru-containing membrane and a RuO2-containing membrane formed on the surface of the Ru-containing membrane can be cited.

[0324] As the object to be removed in process A4, Ru-containing substances are preferred.

[0325] As an interlayer insulating film and a metal hard shield, known materials can be selected.

[0326] Furthermore, Figure 4 illustrates the use of a hard metal mask, but a resist mask formed using known photoresist materials can also be used.

[0327] As a specific method for process A4, one example is a method of bringing the components into contact with the aforementioned material to be processed.

[0328] The contact method between the components and the wiring board is as described above.

[0329] The preferred ranges for the contact time between the component and the wiring board and the temperature of the component are as described above.

[0330] <Process A5>

[0331] As a process A, process A5 can be cited as an example, in which the target material is removed from the substrate after chemical mechanical polishing (CMP) using the composition.

[0332] CMP technology has been incorporated into manufacturing processes such as planarization of insulating films, planarization of interconnects, and inlay wiring. Sometimes, the substrate after CMP becomes contaminated with a large amount of contaminants, including particles from the abrasive particles and metallic impurities. Therefore, these contaminants need to be removed and the substrate cleaned before proceeding to the next processing stage. By implementing process A5, it is possible to remove the contaminants that are generated and adhered to the substrate during CMP processing, specifically when the workpiece has a wire or film to be removed.

[0333] Regarding the material to be processed in process A5, as mentioned above, a substrate with the object to be removed after CMP can be cited as an example.

[0334] As the object to be removed, Ru-containing substances, RuO2-containing substances, or complexes composed of Ru-containing substances and RuO2-containing substances are preferred. As an example of such complexes, a laminate of Ru-containing substances and a RuO2-containing layer formed on the surface of the Ru-containing substances can be cited.

[0335] As a specific method for process A5, one example is a method of bringing the components into contact with the aforementioned material to be processed.

[0336] The contact method between the components and the wiring board is as described above.

[0337] The preferred ranges for the contact time between the component and the wiring board and the temperature of the component are as described above.

[0338] <Process C>

[0339] This processing method can, as needed, include a process C after the above-mentioned process A, in which the substrate obtained in process A is rinsed with a rinsing solution.

[0340] Because this composition comes into contact with the substrate, there is a possibility that iodine compounds derived from this composition may adhere as residual iodine on the surface of the substrate. This residual iodine can be removed from the surface of the substrate by performing a rinsing process.

[0341] As rinsing solutions, preferred options include, for example, hydrofluoric acid, hydrochloric acid, hydrogen peroxide solution, a mixture of hydrofluoric acid and hydrogen peroxide solution, a mixture of sulfuric acid and hydrogen peroxide solution, a mixture of ammonia and hydrogen peroxide solution, a mixture of hydrochloric acid and hydrogen peroxide solution, carbon dioxide solution, ozone solution, hydrogen water, citric acid aqueous solution, sulfuric acid, ammonia solution, isopropanol, hypochlorous acid aqueous solution, aqua regia, ultrapure water, nitric acid, perchloric acid, oxalic acid aqueous solution, or periodic acid aqueous solution. These rinsing solutions can be used in combination without compromising the purpose of the rinsing process.

[0342] In addition, fluoric acid, nitric acid, perchloric acid and hydrochloric acid represent aqueous solutions of HF, HNO3, HClO4 and HCl dissolved in water, respectively.

[0343] Sulfuric acid can be an aqueous solution of H2SO4 dissolved in water.

[0344] Ozone water, carbon dioxide water, and hydrogen water are aqueous solutions in which O3, CO2, and H2 are dissolved in water, respectively.

[0345] Among these, from the viewpoint of further reducing residual iodine on the substrate surface after the rinsing process, carbon dioxide water, ozone water, hydrogen water, hydrofluoric acid, citric acid aqueous solution, hydrochloric acid, sulfuric acid, ammonia water, hydrogen peroxide water, SPM, APM, HPM, IPA, hypochlorous acid aqueous solution, aqua regia or FPM are preferred as rinsing fluids, and hydrofluoric acid, hydrochloric acid, hydrogen peroxide water, SPM, APM, HPM or FPM are even better.

[0346] As a specific method of process C, one example is a method of bringing the rinsing liquid into contact with the object being treated, namely the substrate obtained in process A.

[0347] The contact method can be implemented by immersing the substrate in a rinsing solution contained in a container, spraying the rinsing solution onto the substrate, allowing the rinsing solution to flow over the substrate, or any combination thereof.

[0348] There is no particular limit to the treatment time (the contact time between the rinsing solution and the treated object), which is more than 5 seconds and less than 5 minutes.

[0349] There are no particular restrictions on the temperature of the rinsing solution during treatment, but 16~60℃ is preferred, and 18~40℃ is even better.

[0350] <Process D>

[0351] This processing method can include a drying process D after process C, as needed. The drying method is not particularly limited and can include rotary drying, flow of drying gas on the substrate, heating based on a substrate-based heating element such as a heating plate or infrared lamp, IPA (isopropyl alcohol) vapor drying, marangoni drying, notagononi drying, or combinations thereof.

[0352] The drying time varies depending on the specific method used, and is generally between 30 seconds and several minutes.

[0353] This processing method can be implemented before or after other processes performed on the substrate. It can be integrated into other processes during the implementation of this processing method, or it can be integrated into other processes.

[0354] Other processes include, for example, the formation processes of various structures such as metal wiring, gate structure, source structure, drain structure, insulating layer, strong magnetic layer and / or non-magnetic layer (layer formation, etching, chemical mechanical polishing, modification, etc.), resist formation process, exposure process and removal process, heat treatment process, cleaning process and inspection process, etc.

[0355] This processing method can be performed at any stage of the back end of the line (BEOL), middle end of the line (MOL), and front end of the line (FEOL), but from the viewpoint of further maximizing the effects of the present invention, it is preferable to perform it in the front end or middle end of the line. [Example]

[0356] The present invention will now be described in further detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0357] [Preparation of the composition]

[0358] Compositions having the composition described in Table 1 below were prepared, and the following tests were conducted using the prepared composition.

[0359] The following describes the periodic acid compound (oxidizing agent), specific amine (additive), pH adjuster, and water used to prepare the composition.

[0360] In addition, the following components used to prepare the composition are all commercially available products and are classified as semiconductor grade products or products classified as equivalent high purity grades.

[0361] (Periodic acid compound)

[0362] Orthoperiodic acid

[0363] Periodic acid

[0364] (Oxidizing agents that do not conform to periodic acid compounds)

[0365] Sodium hypochlorite

[0366] (Specific amines)

[0367] 1,3-Propanediamine

[0368] 1,4-Butanediamine

[0369] β-alanine

[0370] 4-Butanine

[0371] 5-Pentaneous acid

[0372] 1,6-Hexanediamine

[0373] succinylamine

[0374] malondiamine

[0375] Acetylmamide

[0376] Butylamine

[0377] hexamethylenediamine

[0378] 2-Aminoethylphosphonic acid

[0379] Taurine

[0380] Glycine

[0381] 7-Heptanediol

[0382] .1,8-Octandiamine

[0383] Aminosulfonic acid

[0384] Amiodarone

[0385] Methyl carbamate

[0386] .dihexamethylenetriamine

[0387] Diethylenetriamine

[0388] N-Methyl-1,3-propanediamine

[0389] 2,2-Dimethyl-1,3-propanediamine

[0390] N-Ethylethylenediamine

[0391] N-(2-aminoethyl)piperazine

[0392] (Additives that do not meet specific amine requirements)

[0393] Diethylene glycolamine

[0394] Monoethanolamine

[0395] succinic acid

[0396] .aniline

[0397] 2,4,6-Trimethylaniline

[0398] (pH adjuster)

[0399] . Sulfuric acid

[0400] . MSA (methanesulfonic acid)

[0401] . ETMAH (ethyltrimethylammonium hydroxide)

[0402] . TEAH (tetraethylammonium hydroxide)

[0403] . Hydrochloric acid

[0404] . Phosphoric acid

[0405] . p-Toluenesulfonic acid

[0406] . Nitric acid

[0407] (Water)

[0408] . Ultrapure water

[0409] In Table 1, the "amount (%)" column represents the content of each component relative to the total mass of the composition (unit: mass%).

[0410] In Table 1, the "carbon number" column represents the carbon number of the component used as a specific amine or additive.

[0411] In Table 1, the value in the "Ratio 1" column represents the ratio (mass ratio) of the content of periodic acid (or oxidant) to the content of a specific amine (or additive).

[0412] In each example and each comparative example, the content of the "pH adjuster" described in Table 1 was adjusted so that the pH of the composition became the value described in the "Composition pH" column of Table 1.

[0413] In Table 1, the "remainder" in the "Water" column indicates that the remainder of the composition other than the periodic acid compound (oxidant), specific amine (additive), and pH adjuster is water.

[0414] [Test]

[0415] <Ru dissolution ability>

[0416] A substrate was prepared by forming a Ru layer (a layer composed of Ru monomers) on one surface of a commercially available silicon wafer (diameter: 12 inches) by PVD method.

[0417] The obtained substrate was placed in a container filled with the composition of each example or each comparative example, the composition was stirred, and a Ru layer removal treatment was carried out for 1 minute. The temperature of the composition was 25°C.

[0418] <RuO2 Dissolving Ability>

[0419] A substrate was prepared by forming a RuO2 layer (a layer composed only of RuO2) on one surface of a commercially available silicon wafer (diameter: 12 inches) by sputtering method.

[0420] The obtained substrate was placed in a container filled with the composition of each example or each comparative example, the composition was stirred, and a RuO2 layer removal treatment was carried out for 1 minute. The temperature of the composition was 25°C.

[0421] [Evaluation]

[0422] <Ru / RuO2 Dissolving Ability>

[0423] Based on the thickness difference of the Ru layer or RuO2 layer before and after the treatment, the etching rate (Å / min) of the Ru layer or RuO2 layer was calculated. The calculated etching rate of the Ru layer or RuO2 layer was evaluated according to the following criteria. The evaluation results are shown in Table 1.

[0424] A: The etching rate is 175 Å / min or more

[0425] B: The etching rate is 100 Å / min or more and less than 175 Å / min

[0426] C: The etching rate is 50 Å / min or more and less than 100 Å / min

[0427] D: The etching rate is less than 50 Å / min

[0428] The results are shown in the following table.

[0429]

[0430]

[0431]

[0432] Based on the results shown in the table, it was confirmed that the composition of the present invention has excellent solubility for both Ru-containing layers and RuO2-containing layers.

[0433] Among them, when the carbon number of a specific amine is 1 to 8, the solubility for Ru-containing compounds is better (comparison of Examples 1 to 25); when the carbon number of a specific amine is 2 to 7, the solubility for RuO2-containing compounds is better (comparison of Examples 1 to 19); and when the carbon number of a specific amine is 3 to 6, the solubility for both Ru-containing compounds and RuO2-containing compounds is further better (comparison of Examples 1 to 11).

[0434] It was confirmed that when the ratio of periodic acid compound content to specific amine content (ratio 1) was 95 or less, the solubility for Ru-containing compounds was superior (comparison of Example 38 and Example 39); when it was 50 or less, the solubility for RuO2-containing compounds was superior (comparison of Example 28 and Example 36); when it was less than 45, the solubility for Ru-containing compounds was further superior (comparison of Example 27 and Example 28); and when it was less than 40, the solubility for RuO2-containing compounds was further superior (comparison of Example 26 and Example 27).

[0435] Furthermore, it was confirmed that when the ratio 1 is 1 or higher, the solubility for Ru-containing compounds is superior (comparison between Example 40 and Example 52); when it is 3 or higher, the solubility for Ru-containing compounds and RuO2-containing compounds is superior (comparison between Example 29 and Example 42); and when it is 5 or higher, the solubility for RuO2-containing compounds is further superior (comparison between Examples 5 and 7 and Example 31).

[0436] It was confirmed that the solubility of Ru-containing compounds was superior when the pH of the composition was below 10.0 (comparison between Example 46 and Example 55), superior when the pH was below 8.0 (comparison between Example 35 and Example 44), further superior when the pH was below 7.0 (comparison between Example 32 and Example 33), and further superior when the pH was below 6.0 (comparison between Examples 5 and 9 and Example 34).

[0437] Furthermore, it was confirmed that the solubility of Ru-containing compounds and RuO2-containing compounds was superior when the pH of the composition was above 3.3 (comparison between Example 3 and Example 59).

[0438] 10a: Wiring substrate before recessed etching treatment

[0439] 10b: Wiring substrate after recessed etching treatment

[0440] 12: Interlayer insulating film

[0441] 14: Barrier Metal Layer

[0442] 16: Remove object wiring

[0443] 18: concave part

[0444] 20, 30: Items to be processed

[0445] 22:Substrate

[0446] 24: Remove the object membrane

[0447] 26: Outer edge

[0448] 32:Substrate

[0449] 34: Remove the object membrane

[0450] 36: Etching Stop Layer

[0451] 38: Interlayer insulating film

[0452] 40: Metal Hard Mask

[0453] 42: Kong

[0454] 44: Inner wall

[0455] 44a: Section wall

[0456] 44b: Bottom wall

[0457] 46: Dry etching residue< / ph>

Claims

1. A composition for dissolving metal-containing substances, comprising: one or more periodic acid compounds selected from the group consisting of periodic acid and its salts; an amine compound as a compound or its salt represented by the following formula (1); and water, wherein the pH of the aforementioned composition is 3.6 or higher and 10.5 or lower, and R-NH2 In formula (1), R represents an aliphatic hydrocarbon group that may have substituents, wherein the aforementioned aliphatic hydrocarbon group may have at least one linker selected from the group consisting of -O-, -S- and -NR1- in the carbon chain, and R1 represents a hydrogen atom or an aliphatic hydrocarbon group that may have substituents, wherein the substituents of the aforementioned R and the aforementioned R1 do not contain hydroxyl groups, and the substituents of the aforementioned R are selected from at least one functional group selected from the group consisting of amine, phosphonic acid and sulfonyl groups, wherein the content of the aforementioned periodic acid compound is 0.1% by mass or more and 40.0% by mass or less relative to the total mass of the aforementioned composition, and the content of the aforementioned amine compound is 0.01% by mass or more and 30% by mass or less relative to the total mass of the aforementioned composition, and the ratio of the content of the aforementioned periodic acid compound to the content of the aforementioned amine compound is 1 to 95 by mass.

2. The composition of dissolved metal contents as described in claim 1, which is a composition for treating a substrate having at least one of the group consisting of ruthenium contents and ruthenium oxide contents.

3. The composition for dissolving metal contents as described in claim 1, which is a composition for treating substrates containing ruthenium and ruthenium oxide.

4. The composition of a dissolved metal-containing compound as described in claim 1, wherein the aforementioned amine compound has 1 to 8 carbon atoms.

5. The composition of a dissolved metal-containing compound as described in claim 1, wherein R represents the aforementioned aliphatic hydrocarbon group having the aforementioned substituents.

6. The composition of a dissolved metal-containing compound as described in any one of claims 1 to 5, wherein the aforementioned amine compound is selected from at least one of the group consisting of 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, propylenediamide and hexamethylenediamine.

7. The composition of the dissolved metal content as described in any one of claims 1 to 5, which substantially does not contain abrasive particles.

8. A composition for dissolving metal-containing substances, comprising: one or more periodic acid compounds selected from the group consisting of periodic acid and its salts; an amine compound selected from the group consisting of a compound represented by formula (1) or its salt, β-alanine, 5-pentanenic acid, succinylamine, malondiamide, acrylamide, butylamine and hexamethylenediamide; and water, R-NH2 In formula (1), R represents an aliphatic hydrocarbon group that may have substituents, wherein the aforementioned aliphatic hydrocarbon group may have at least one linker selected from the group consisting of -O-, -S- and -NR1- in the carbon chain, and R1 represents a hydrogen atom or an aliphatic hydrocarbon group that may have substituents, wherein the substituents of the aforementioned R and the aforementioned R1 do not contain hydroxyl groups, and the substituents of the aforementioned R are selected from at least one functional group selected from the group consisting of amine, phosphonic acid and sulfonyl groups, wherein the content of the aforementioned periodic acid compound is 0.1% by mass or more and 40.0% by mass or less relative to the total mass of the aforementioned composition, and the content of the aforementioned amine compound is 0.01% by mass or more and 30% by mass or less relative to the total mass of the aforementioned composition, and the ratio of the content of the aforementioned periodic acid compound to the content of the aforementioned amine compound is 1 to 95 by mass.

9. The composition of a dissolved metal-containing compound as claimed in claim 8, wherein R represents an aliphatic hydrocarbon group having at least one functional group selected from the group consisting of amino, phosphonic, and sulfonyl groups.

10. A composition for dissolving metal-containing substances, comprising: one or more periodic acid compounds selected from the group consisting of periodic acid and its salts; an amine compound selected from the group consisting of β-alanine, 5-pentanenic acid, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, succinylamine, malondiamine, propanediamine, butanediamine and hexanediamine; and water, wherein the content of the periodic acid compound is 0.1% by mass or more and 40.0% by mass or less relative to the total mass of the aforementioned composition, and the content of the amine compound is 0.01% by mass or more and 30% by mass or less relative to the total mass of the aforementioned composition, and the ratio of the content of the periodic acid compound to the content of the amine compound is 1 to 95 by mass.

11. A composition of dissolved metal-containing material as described in any one of claims 8 to 10, wherein the pH of the aforementioned composition is below 10.

0.

12. A composition of a dissolved metal-containing substance as described in any one of claims 8 to 10, wherein the pH of the aforementioned composition is 3.5 or higher.

13. A composition of dissolved metal contents as described in any one of claims 8 to 10, which is a composition for treating a substrate having at least one of the group consisting of ruthenium contents and ruthenium oxide contents.

14. A method for processing a substrate, comprising: process A, using a composition of dissolved metal contents as described in any one of claims 1 to 13 to remove at least one of the group consisting of metal contents and metal oxide contents from the substrate.

15. The substrate processing method as described in claim 14, wherein the aforementioned metal inclusions include ruthenium inclusions and the aforementioned metal oxide inclusions include ruthenium oxide inclusions.

16. A substrate processing method as described in claim 14 or claim 15, wherein process A is process A1, in which the aforementioned composition for dissolving metal inclusions is used to perform recess etching on wiring disposed on the substrate and composed of metal inclusions or metal oxide inclusions; process A2, in which the aforementioned composition for dissolving metal inclusions is used to remove the aforementioned film on the outer edge of the substrate on which a film composed of metal inclusions or metal oxide inclusions is disposed; process A3, in which the aforementioned composition for dissolving metal inclusions is used to remove metal inclusions or metal oxide inclusions attached to the back side of the substrate on which a film composed of metal inclusions or metal oxide inclusions is disposed; process A4, in which the aforementioned composition for dissolving metal inclusions is used to remove metal inclusions or metal oxide inclusions on the substrate after dry etching; or process A5, in which the aforementioned composition for dissolving metal inclusions is used to remove metal inclusions or metal oxide inclusions on the substrate after chemical mechanical polishing.

17. A substrate processing method as described in claim 14 or claim 15, further comprising an oxidation process in which an oxidant is brought into contact with a metal inclusion on the substrate, wherein the aforementioned processing method performs the aforementioned process A on a substrate having at least a metal oxide inclusion manufactured in the aforementioned oxidation process.