Processing liquid and substrate processing method

Abstract

The subject of the present invention is to provide a processing liquid for semiconductor devices, the processing liquid has excellent corrosion resistance to metal-containing layers and removal performance of removal objects and excellent solubility in post-processing liquid. In addition, the subject of the present invention is to provide a substrate processing method using the above-mentioned processing liquid. The processing liquid of the present invention is a processing liquid for semiconductor devices, which contains water, a remover and a copolymer, the copolymer has a first repeating unit and a second repeating unit different from the first repeating unit, and the first repeating unit has at least one group selected from primary amino groups, secondary amino groups, tertiary amino groups and quaternary ammonium cations.

Description

Technical Field

[0001] The invention relates to a processing liquid and a processing method for a substrate. Background Art

[0002] As semiconductor products become increasingly miniaturized, there is an increasing need for a process for efficiently and accurately removing unnecessary metal-containing substances on a substrate in a semiconductor product manufacturing process.

[0003] The semiconductor device is manufactured by, for example, disposing a metal layer as a wiring material and a stacked body having an etching stopper film and an insulating film on a substrate, forming a resist film on the stacked body, and performing a photolithography process and a dry etching process.

[0004] In a photolithography process, a method of etching or removing impurities attached to the surface of a substrate using a processing liquid in which a metal-containing substance is dissolved is widely known.

[0005] For example, in a photolithography process, a metal layer and / or an insulating film on a substrate is sometimes dry-etched using a resist film as a mask. At this time, residues from the metal layer and / or the insulating film may adhere to the substrate, the metal layer and / or the insulating film. In order to remove the attached residues, cleaning using a processing liquid is usually performed.

[0006] In addition, the resist film used as a mask during etching is removed from the laminate by a dry method (dry ashing) or a wet method based on ash. In the laminate from which the resist is removed by the dry ashing method, residues originating from the resist film and the like are sometimes attached. In order to remove the attached residues, cleaning using a treatment liquid is usually performed. On the other hand, as a wet method for removing the resist film, a method of removing the resist film using a treatment liquid can be cited.

[0007] As described above, the processing liquid is used to process metal-containing substances (etching residues and ashing residues) and / or resist films on substrates in the semiconductor device manufacturing process.

[0008] For example, Patent Document 1 describes a cleaning composition for a wiring board, which contains a specific compound having an amino group, a hydroxyl group, and a carboxyl group, and a water-soluble polymer having at least one functional group selected from a carboxyl group, a sulfo group, and an amino group.

[0009] Previous technical literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Publication No. 2018-092960 Summary of the invention

[0012] Technical issues to be solved by the invention

[0013] The inventors of the present invention have studied a semiconductor device processing liquid with reference to Patent Document 1, and found that by applying the processing liquid to a laminate having a metal-containing layer (e.g., a tungsten-containing layer), the component that imparts corrosion resistance may remain on the surface of the metal-containing layer, affecting the subsequent process. That is, for the semiconductor device processing liquid, the corrosion resistance to the metal-containing layer and the removal property of the removal object (i.e., removal selectivity) are clarified, and there is still room for further improvement in the solubility in the post-processing liquid.

[0014] Therefore, an object of the present invention is to provide a semiconductor device processing liquid having excellent corrosion resistance to a metal-containing layer and removal performance of a removal object and excellent solubility in a post-processing liquid.

[0015] Furthermore, an object of the present invention is to provide a method for processing a substrate using the above-mentioned processing liquid.

[0016] Means for solving technical problems

[0017] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by containing a resin having two specific repeating units in a treatment liquid, thereby completing the present invention.

[0018] That is, it was found that the above-mentioned problems can be solved by the following configuration.

[0019] [1] A treatment liquid for semiconductor devices, the treatment liquid containing water, a remover and a resin, wherein the resin has a first repeating unit and a second repeating unit different from the first repeating unit, and the first repeating unit has at least one selected from a primary amino group, a secondary amino group, a tertiary amino group and a quaternary ammonium cation.

[0020] [2] The treatment liquid according to [1], wherein the first repeating unit has a primary amino group.

[0021] [3] The treatment liquid according to [1] or [2], wherein the second repeating unit has at least one hydrophilic group.

[0022] [4] The treatment liquid according to [3], wherein the hydrophilic group is a group selected from a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, a tertiary amino group, an amide group, a polyoxyalkylene group, a sulfone group, and a sulfonyl group.

[0023] [5] The treatment liquid according to any one of [1] to [4], wherein the second repeating unit includes a repeating unit represented by formula (2a) described below.

[0024] [6] The treatment liquid according to any one of [1] to [5], wherein the resin has at least one skeleton structure selected from the group consisting of the following formulae (P-1) to (P-18).

[0025] [7] The treatment liquid according to any one of [1] to [6], wherein a ratio m:n of the number of moles m of the first repeating unit to the number of moles n of the second repeating unit in the resin is 5:1 to 1:5.

[0026] [8] The treatment liquid according to any one of [1] to [7], wherein the weight average molecular weight of the resin is 1000 to 150,000.

[0027] [9] The treatment liquid according to any one of [1] to [8], wherein the content of the resin is 10 to 10,000 ppm by mass relative to the total mass of the treatment liquid.

[0028]

[10] A treatment liquid according to any one of [1] to [9], wherein the above-mentioned removing agent contains at least one selected from hydrofluoric acid, ammonium fluoride, tetramethylammonium fluoride, hydroxylamine compounds, ammonium hydroxide, water-soluble amines, quaternary ammonium compounds, sulfuric acid, hydrochloric acid, phosphoric acid, carboxylic acid, sulfonic acid and phosphonic acid.

[0029]

[11] The treatment liquid according to any one of [1] to

[10] , wherein the removing agent contains a water-soluble amine and at least one organic acid selected from carboxylic acid, sulfonic acid, and phosphonic acid.

[0030]

[12] A treatment liquid according to

[11] , wherein the water-soluble amine is at least one selected from methylamine, ethylamine, propylamine, butylamine, pentylamine, methoxyethylamine, methoxypropylamine, 2-amino-2-methyl-1-propanol and allylamine, and the organic acid is at least one selected from acetic acid, propionic acid, methanesulfonic acid, ethanesulfonic acid, allylglycine, maleic acid, citraconic acid, fumaric acid and itaconic acid.

[0031]

[13] The treatment liquid according to any one of [1] to

[12] , further comprising an oxidizing agent.

[0032]

[14] The treatment liquid according to

[13] , wherein the oxidizing agent contains at least one selected from the group consisting of hydrogen peroxide, nitric acid, peracetic acid, periodic acid, perchloric acid, chloric acid, hypochlorous acid, cerium ammonium nitrate, ferric nitrate and ammonium persulfate.

[0033]

[15] The treatment liquid according to any one of [1] to

[14] , further comprising a corrosion inhibitor.

[0034]

[16] A treatment liquid according to

[15] , wherein the corrosion inhibitor contains at least one compound selected from the group consisting of a compound represented by formula (A) described below, a compound represented by formula (B) described below, a compound represented by formula (C) described below, and substituted or unsubstituted tetrazoles.

[0035]

[17] The treatment liquid according to any one of [1] to

[16] , further comprising a surfactant.

[0036]

[18] The treatment liquid according to

[17] , wherein the surfactant is at least one selected from the group consisting of a phosphate-based surfactant, a carboxylic acid-based surfactant, a sulfonic acid-based surfactant, and a sulfate-based surfactant.

[0037]

[19] The treatment liquid according to

[18] , wherein the phosphate ester surfactant is at least one selected from alkyl phosphate esters, mono- or polyoxyalkyl ether phosphate esters, and salts thereof.

[0038]

[20] The treatment liquid according to

[18] or

[19] , wherein the carboxylic acid-based surfactant is a polyoxyalkylene alkyl ether carboxylic acid.

[0039]

[21] The treatment liquid according to any one of

[18] to

[20] , wherein the sulfonic acid-based surfactant is alkyl diphenyl ether disulfonic acid, and the sulfate-based surfactant is polyoxyalkylene ether sulfate or a salt thereof.

[0040]

[22] The treatment liquid according to any one of [1] to

[21] , further comprising an organic solvent.

[0041]

[23] The treatment liquid according to any one of [1] to

[22] , further comprising a defoaming agent.

[0042]

[24] The treatment liquid according to

[23] , wherein the defoaming agent is a silicon-containing defoaming agent.

[0043]

[25] A treatment liquid according to any one of [1] to

[24] , wherein the treatment liquid is a substrate treatment liquid having a metal-containing substance, and the metal-containing substance contains at least one component selected from copper, cobalt, cobalt alloy, tungsten, tungsten alloy, ruthenium, ruthenium alloy, tantalum, tantalum alloy, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium aluminum, titanium, titanium nitride, titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide and yttrium alloy.

[0044]

[26] A treatment liquid according to any one of [1] to

[25] , which is used as a cleaning liquid for removing etching residues, a solution for removing a resist film used in pattern formation, a cleaning liquid or an etching liquid for removing residues from a substrate after chemical mechanical polishing.

[0045]

[27] A method for processing a substrate, comprising: step A of removing a metal-containing substance on the substrate using the processing liquid described in any one of [1] to

[25] .

[0046]

[28] The method for processing a substrate according to

[27] further comprises: after the step A, a step C of rinsing the substrate obtained in the step A using a rinsing liquid.

[0047]

[29] A method for treating a substrate having a metal-containing layer on its surface, the method comprising: step P, wherein the surface of the substrate is subjected to liquid treatment, ozone treatment in which ozone gas is brought into contact with the substrate, heat treatment of the substrate in an oxygen environment, or plasma treatment of the substrate using oxygen, so that the surface of the metal-containing layer is oxidized to form an oxidized metal layer, wherein the liquid treatment is a treatment in which a chemical solution selected from water, hydrogen peroxide solution, a mixed aqueous solution of ammonia water and hydrogen peroxide solution, a mixed aqueous solution of fluoric acid and hydrogen peroxide solution, a mixed aqueous solution of sulfuric acid and hydrogen peroxide solution, a mixed aqueous solution of hydrochloric acid and hydrogen peroxide solution, dissolved oxygen water, and ozone-dissolved water is brought into contact with the surface of the substrate; and step Q, wherein the treatment solution described in any one of [1] to

[25] is brought into contact with the surface of the oxidized metal layer formed in step P to remove the oxidized metal layer.

[0048]

[30] The treatment method according to

[29] , wherein the step P and the step Q are repeatedly performed.

[0049]

[31] The treatment method according to

[29] or

[30] , wherein the metal-containing layer contains at least one selected from the group consisting of cobalt, copper, tungsten, titanium and aluminum.

[0050] Effects of the Invention

[0051] According to the present invention, it is possible to provide a semiconductor device processing liquid which has excellent corrosion resistance to a metal-containing layer and removal performance of a removal object and excellent solubility in a post-processing liquid.

[0052] Furthermore, the present invention can provide a method for processing a substrate using the processing liquid. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 This is a schematic cross-sectional view showing an example of a stacked body as a processing object in a substrate cleaning method. DETAILED DESCRIPTION

[0054] Hereinafter, the present invention will be described in detail.

[0055] The description of the components described below may be made based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0056] In addition, in this specification, the numerical range expressed with "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0057] Furthermore, in the present invention, the term "preparation" includes not only preparing by synthesizing and mixing specific materials, but also obtaining predetermined materials by purchasing.

[0058] In the present specification, when two or more kinds of a certain component are present, the "content" of the component means the total content of the two or more kinds of components.

[0059] In this specification, "ppm" means "parts-per-million: one millionth (10 -6 )”, “ppb” means “parts-per-billion: one billion (10 -9 )”, “ppt” means “parts-per-trillion: one trillionth (10 -12 )”.

[0060] In this specification, 1A (Angstrom) is equivalent to 0.1 nm.

[0061] In the marking of the group (atom group) in this specification, within the scope of not impairing the effect of the present invention, the marking not marked with substitution and unsubstituted includes not only the group without substitution but also the group with substitution. For example, "hydrocarbon group" includes not only the hydrocarbon group without substitution (unsubstituted hydrocarbon group) but also the hydrocarbon group with substitution (substituted hydrocarbon group). Here, the meaning of each compound is also the same.

[0062] In this specification, "radiation" refers to, for example, far ultraviolet light represented by the bright line spectrum of a mercury lamp, excimer laser, extreme ultraviolet light (EUV light), X-rays, or electron beams. In this specification, "light" refers to active light or radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure based on far ultraviolet light, X-rays, or EUV light represented by mercury lamps and excimer lasers, but also drawing based on particle beams such as electron beams and ion beams.

[0063] [Processing liquid]

[0064] The treatment liquid of the present invention (hereinafter also referred to as "the present treatment liquid") contains water, a removing agent and a copolymer, and the copolymer has a first repeating unit and a second repeating unit different from the first repeating unit, and the first repeating unit has at least one group selected from a primary amino group, a secondary amino group, a tertiary amino group and a quaternary ammonium cation.

[0065] The processing liquid contains water and a removing agent and also contains a resin having two specific repeating units.

[0066] The treatment liquid used in the treatment of a stacked body having a metal-containing layer (especially a tungsten-containing layer) contains the above-mentioned resin. During the treatment, a protective film composed of the resin is formed on the surface of the metal-containing layer, thereby suppressing the dissolution of the metal from the metal-containing layer. At the same time, the protective film can be easily removed by a post-treatment liquid such as a rinse liquid after the treatment. Therefore, it is believed that the residual residue originating from the treatment liquid can be further suppressed.

[0067] Hereinafter, each component of the present treatment liquid will be described in detail.

[0068] 〔water〕

[0069] This treatment solution contains water.

[0070] The content of water is not particularly limited, and is, for example, 1 to 97 mass %, preferably 10 to 98 mass %, and more preferably 10 to 97 mass % relative to the total mass of the treatment liquid.

[0071] As the water, ultrapure water used in the manufacture of semiconductor devices is preferred.

[0072] As water, it is particularly preferred to reduce inorganic anions and metal ions, among which it is more preferred to reduce the ion concentration of metal atoms derived from Fe, Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn. It is further preferred to adjust the water to ppt level or below (in one embodiment, the metal content is less than 0.001 mass ppt) when preparing the treatment solution. As a method of adjustment, it is preferred to use a filter membrane or ion exchange membrane purification or purification by distillation. As a method of adjustment, for example, the method described in paragraphs

[0074] to

[0084] of Japanese Patent Publication No. 2011-110515 and the method described in Japanese Patent Publication No. 2007-254168 can be cited.

[0073] In addition, the water used in the embodiment of the present invention is preferably the water obtained as described above. Moreover, from the viewpoint of significantly obtaining the desired effect of the present invention, it is more preferable that the water is used not only for the treatment liquid but also for washing the storage container. Moreover, the water is preferably also used for the manufacturing process of the treatment liquid, the measurement of the components of the treatment liquid, the measurement of the evaluation of the treatment liquid, etc.

[0074] 〔Resin (A)〕

[0075] The present treatment liquid contains a resin (A) having a first repeating unit containing at least one specific group and a second repeating unit different from the first repeating unit.

[0076] The first repeating unit of the resin (A) has a group selected from the group consisting of a primary amino group (-NH2), a secondary amino group (-NH-), a tertiary amino group (>N-) and a quaternary ammonium cation (>N + At least one group in <) (hereinafter also referred to as "specific amino group").

[0077] The first repeating unit is not particularly limited as long as it has at least one specific amino group and is a repeating unit constituting the main chain of the resin (A).

[0078] The first repeating unit can form a salt with the above-mentioned specific amino group and an acid selected from inorganic acids and organic acids. That is, the first repeating unit of the resin (A) has a primary amino group, a secondary amino group, a tertiary amino group and a quaternary ammonium cation and at least one group selected from salts of these with inorganic acids or organic acids.

[0079] Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, and examples of the organic acid include acetic acid, propionic acid, methanesulfonic acid, ethanesulfonic acid, allylglycine, maleic acid, citraconic acid, fumaric acid, and itaconic acid.

[0080] When the specific amino group is in the form of a salt, a salt with hydrochloric acid, acetic acid, propionic acid, methanesulfonic acid or ethanesulfonic acid is preferred, and a salt with hydrochloric acid, acetic acid or ethanesulfonic acid is more preferred.

[0081] When the specific amino group is a quaternary ammonium cation, a salt is formed with a counter ion corresponding to the above-mentioned inorganic acid or organic acid.

[0082] The number of the specific amino groups contained in the first repeating unit is not particularly limited, but is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0083] Furthermore, when the specific amino group possessed by the first repeating unit is a secondary amino group, a tertiary amino group or a quaternary ammonium cation, there are no particular restrictions on the number of 1, 2 or 3 substituents respectively on the nitrogen atom, but an aliphatic hydrocarbon group is preferred, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group or an ethyl group is further preferred.

[0084] The specific amino group contained in the first repeating unit is preferably a primary amino group, a secondary amino group or a tertiary amino group, and more preferably a primary amino group.

[0085] Examples of the first repeating unit include a repeating unit represented by the following formula (1).

[0086] -(Q1(X1) i)- (1)

[0087] In formula (1), Q1 represents a (2+i)-valent aliphatic hydrocarbon group having 2 to 4 carbon atoms, X1 represents a monovalent group having at least one specific amino group, and i represents 1 or 2. When i represents 2, two X1s are linked to each other and together with at least a portion of Q1, form a ring structure having at least one specific amino group.

[0088] X1 may be a group consisting of only a specific amino group, or may be a group consisting of a specific amino group and a linking group L.

[0089] The linking group L is not particularly limited as long as it is a group having a valence corresponding to the number of specific amino groups, and examples thereof include aliphatic hydrocarbon groups and groups in which the methylene groups contained in the aliphatic hydrocarbon groups are substituted with a group selected from -O-, -CO-, -NH- and -NR- (R represents an aliphatic hydrocarbon group).

[0090] As the linking group L, a linear or branched alkyl group or a methylene group contained in the alkyl group is preferably a group formed by separating the number of hydrogen atoms corresponding to the number of the specific amino groups substituted from the group substituted by -O-, -CO- or -NH-. The number of carbon atoms in the linear or branched alkyl group is preferably 1 to 8, more preferably 1 to 4. As the linking group L, a methylene group or an ethylene group is more preferred, and a methylene group is further preferred.

[0091] Examples of the ring structure formed by two X1s linked to each other and together with at least a part of Q1 include 5- to 7-membered nitrogen-containing heterocyclic rings, preferably a pyrrolidine ring, a pyrrolidinium ring, a 1-pyrroline ring or a piperidine ring, and more preferably a pyrrolidine ring or a pyrrolidinium ring.

[0092] As the aliphatic hydrocarbon group represented by Q1, an ethylene group, a propylene group, a trimethylene group or a tetramethylene group is preferred, and an ethylene group is more preferred.

[0093] The substituent that the aliphatic hydrocarbon group represented by Q1 may have is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0094] Preferably, i represents 1.

[0095] As the first repeating unit, a repeating unit represented by the following formula (1a) is preferred.

[0096] [Chemical formula 1]

[0097]

[0098] In formula (1a), X 11 represents a specific amino group, L1 represents a single bond or a divalent linking group, A11 , A 12 and A 13 Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

[0099] About X 11 Preferred embodiments of the specific amino group represented by are as described above.

[0100] The divalent linking group represented by L1 is as described above in the linking group L, including preferred embodiments. L1 is preferably a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, more preferably a single bond, a methylene group or an ethylene group, and still more preferably a single bond or a methylene group.

[0101] As A 11 , A 12 and A 13 , preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom.

[0102] The content of the first repeating unit is preferably 1 to 99 mol %, more preferably 5 to 95 mol %, further preferably 15 to 85 mol %, particularly preferably 25 to 75 mol % based on all the repeating units in the resin (A).

[0103] The resin (A) has a second repeating unit different from the first repeating unit.

[0104] Here, “different from the first repeating unit” means, for example, that the first repeating unit does not have a group as the specific amino group and / or the structure of the main chain in the first repeating unit or the structure of the linking group connecting the main chain and the specific amino group is different.

[0105] The second repeating unit may have a specific amino group different from the specific amino group currently possessed by the first repeating unit. Furthermore, as long as the structure of the main chain or the side chain is different from that of the first repeating unit, the second repeating unit may have the same specific amino group as that of the first repeating unit. The second repeating unit preferably has a hydrophilic group different from the specific amino group currently possessed by the first repeating unit.

[0106] The second repeating unit preferably has at least one hydrophilic group.

[0107] The number of hydrophilic groups in the second repeating unit is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.

[0108] Examples of the hydrophilic group include a specific amino group, a carboxyl group, a hydroxyl group, an alkoxy group, a polyoxyalkylene group, an amide group, a carbamoyl group, a nitrile group, a sulfo group, a sulfonyl group, a sulfonamide group, and a sulfamoyl group.

[0109] Examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, and a polyoxyalkylene group in which an oxyethylene group and an oxypropylene group are block-bonded or randomly bonded. A polyoxyethylene group or a polyoxypropylene group is preferred, and a polyoxyethylene group is more preferred.

[0110] The number of repetitions of the oxyalkylene group in the polyoxyalkylene group is not particularly limited, but is preferably 1 to 30, more preferably 1 to 10.

[0111] The above hydrophilic group may form a salt. The salt of the specific amino group is as described in the first repeating unit. Examples of the salt of the carboxyl group and the sulfonic group include their alkali metal salts and salts with the basic compound described below.

[0112] The hydrophilic group may further have a substituent. Examples of the substituent that the hydrophilic group may have include an aliphatic hydrocarbon group and the hydrophilic group described above, preferably a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

[0113] The hydrophilic group possessed by the second repeating unit is preferably a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, a tertiary amino group, an amide group, a polyoxyalkylene group, a sulfo group or a sulfonyl group, more preferably a primary amino group, a carboxyl group, a hydroxyl group or a polyoxyethylene group, and still more preferably a carboxyl group.

[0114] Examples of the second repeating unit include a repeating unit represented by the following formula (2).

[0115] -(Q2(X2) j )- (2)

[0116] In formula (1), Q2 represents a (2+j)-valent aliphatic hydrocarbon group having 2 to 4 carbon atoms. X2 represents a monovalent group having at least one hydrophilic group, and j represents 1 or 2. When j represents 2, two X2s may be connected to each other and may form a ring structure having at least one hydrophilic group together with at least a portion of Q2.

[0117] X2 may be a group consisting of a hydrophilic group alone, or may be a group consisting of a hydrophilic group and a linking group L.

[0118] The linking group L has the same meaning as the linking group L in the above formula (1) including preferred embodiments thereof.

[0119] Examples of the ring structure formed by two X2s linked to each other and together with at least a part of Q2 include 5- to 7-membered nitrogen-containing heterocyclic rings, preferably a pyrrolidine ring, a pyrrolidinium ring, a 1-pyrroline ring or a piperidine ring, and more preferably a pyrrolidine ring or a pyrrolidinium ring.

[0120] As the aliphatic hydrocarbon group represented by Q2, an ethylene group, a propylene group, a trimethylene group or a tetramethylene group is preferred, and an ethylene group is more preferred.

[0121] Examples of the substituent that the aliphatic hydrocarbon group represented by Q2 may have include aliphatic hydrocarbon groups, preferably a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

[0122] Preferably, j represents 1.

[0123] The second repeating unit may be a divalent hydrophilic group. Examples of the divalent hydrophilic group serving as the second repeating unit include a sulfonyl group.

[0124] As the second repeating unit, a repeating unit represented by the following formula (2a) is preferred.

[0125] [Chemical formula 2]

[0126]

[0127] In formula (2a), A 21 , A 22 and A 23 Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or -L2-X 21 , X 21 represents a hydrophilic group, L2 represents a single bond or a divalent linking group, when X 21 When there are two or more L2, they may be the same or different.

[0128] About X 21 Preferred embodiments of the hydrophilic group represented by are as described above.

[0129] The divalent linking group represented by L2, including preferred embodiments, is as described above for the linking group L. L2 is preferably a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, more preferably a single bond, a methylene group or an ethylene group, and still more preferably a single bond or a methylene group.

[0130] And, preferably A 21 , A 22 and A 23 Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms or A 21 , A 22 and A 23 1 of them means -L2-X 21 The remaining two represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

[0131] Among them, A is more preferred 21 , A22 and A 23 Each independently represents a hydrogen atom, a methyl group or an ethyl group or A 21 , A 22 and A 23 One of them represents a hydrophilic group and the remaining two represent a hydrogen atom, a methyl group or an ethyl group, and more preferably A 21 , A 22 and A 23 Each independently represents a hydrogen atom or a methyl group or A 21 , A 22 and A 23 One of them represents a carboxyl group and the remaining two represent a hydrogen atom or a methyl group.

[0132] The content of the second repeating unit is preferably 1 to 99 mol %, more preferably 5 to 95 mol %, further preferably 15 to 85 mol %, particularly preferably 25 to 75 mol % based on all the repeating units in the resin (A).

[0133] The second repeating unit may be a single type or a combination of two or more types. When the resin (A) has two or more types of the second repeating unit, it preferably has at least one repeating unit represented by the above formula (2) or formula (2a).

[0134] The content of the repeating unit represented by the above formula (2) or formula (2a) is preferably 1 to 99 mol %, more preferably 5 to 95 mol %, further preferably 15 to 85 mol %, and particularly preferably 25 to 75 mol % relative to all repeating units in the resin (A).

[0135] The ratio of the first repeating unit to the second repeating unit in the resin (A) is not particularly limited, but from the viewpoint of better corrosion resistance with a metal-containing layer (especially a tungsten-containing layer), the ratio of the molar number m of the first repeating unit to the molar number n of the second repeating unit (m:n) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, further preferably 5:1 to 1:5, and particularly preferably 3:1 to 1:3.

[0136] Specific examples of resin (A) include resins having skeleton structures represented by the following formulae (P-1) to (P-23). ​​In the formulae (P-1) to (P-23), the repeating unit marked with the symbol m is the first repeating unit, and the repeating unit marked with the symbol n is the second repeating unit.

[0137] In addition, the skeleton structure represented by formula (P-1) to (P-23) contains multiple repeating units, and the bonding method of the multiple repeating units is not particularly limited. For example, the multiple repeating units can be randomly bonded (so-called random copolymer), can be alternately bonded (so-called alternating copolymer), or can be bonded in blocks (so-called block copolymer).

[0138] [Chemical formula 3]

[0139]

[0140]

[0141] [Chemical formula 4]

[0142]

[0143] [Chemical formula 5]

[0144]

[0145] In the above formulae (P-1) to (P-25), the ratio of the number of moles m of the first repeating unit to the number of moles n of the second repeating unit (m:n) is 1:20 to 20:1.

[0146] In formula (P-7), l represents the number of repetitions of the oxyalkylene unit and represents an integer of 1 to 30.

[0147] Furthermore, in the formula (P-20), X represents an amide group, a nitrile group, an amino hydrochloride group or a formamide group.

[0148] Among them, it is preferred to select at least one of the skeleton structures represented by formulas (P-1) to (P-18), more preferably to select at least one of the skeleton structures represented by formulas (P-8), (P-9), (P-10) and (P-11), and further preferably to select at least one of the skeleton structures represented by formulas (P-8), (P-10) and (P-11).

[0149] In addition, the structure and composition ratio (mol %) of each repeating unit in the resin (A) can be determined by 13 C-NMR measurement.

[0150] The weight average molecular weight of the resin (A) is not particularly limited, but is preferably 500 to 200,000, more preferably 1,000 to 100,000, further preferably 2,000 to 50,000, and particularly preferably 3,000 to 10,000.

[0151] In addition, in this specification, "weight average molecular weight" means the weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

[0152] The resin (A) may be used alone or in combination of two or more.

[0153] The content of the resin (A) is preferably 1 to 10 mass ppm, more preferably 10 to 10,000 mass ppm, and further preferably 50 to 1,000 mass ppm, relative to the total mass of the treatment liquid.

[0154] 〔Removal agent〕

[0155] This treatment solution contains a remover.

[0156] The remover is not particularly limited as long as it is a compound having a function of removing residues such as etching residues and ashing residues, and examples thereof include fluorine-containing compounds, hydroxylamine compounds, basic compounds, and acidic compounds.

[0157] <Fluorinated compounds>

[0158] The fluorine-containing compound is not particularly limited as long as it is a compound containing fluorine atoms, and may be an inorganic compound containing fluorine atoms or an organic compound containing fluorine atoms.

[0159] As the fluorine-containing compound, for example, hydrofluoric acid (fluoric acid), ammonium fluoride, tetramethylammonium fluoride and tetrabutylammonium fluoride can be cited. The fluorine-containing compound has the function of removing residues in the treatment liquid. As a result, when the treatment liquid contains the fluorine-containing compound, the residue removal property is more excellent.

[0160] As the fluorine-containing compound, hydrofluoric acid, ammonium fluoride or tetramethylammonium fluoride is preferred, and hydrofluoric acid or ammonium fluoride is more preferred.

[0161] The fluorine-containing compound may be used alone or in combination of two or more.

[0162] The content of the fluorine-containing compound in the treatment liquid is preferably 0.01 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, based on the total mass of the treatment liquid.

[0163] <Hydroxyamine compounds>

[0164] The processing liquid may contain a hydroxylamine compound as a removing agent.

[0165] The hydroxylamine compound is at least one compound selected from the group consisting of hydroxylamine (NH2OH), hydroxylamine derivatives, and salts thereof.

[0166] The hydroxylamine compound has the function of promoting the decomposition and solubilization of residues and removing residues such as etching residues and ashing residues. Therefore, the processing liquid preferably contains the hydroxylamine compound as a removing agent.

[0167] The hydroxylamine derivatives are not particularly limited, and examples thereof include O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,O-dimethylhydroxylamine, N-ethylhydroxylamine, N,N-diethylhydroxylamine, N,O-diethylhydroxylamine, O,N,N-trimethylhydroxylamine, N,N-dicarboxyethylhydroxylamine and N,N-disulfoethylhydroxylamine.

[0168] Examples of salts of hydroxylamine and hydroxylamine derivatives include inorganic acid salts or organic acid salts, preferably inorganic acid salts in which a non-metal atom such as Cl, S, N or P can be bonded to a hydrogen atom, and more preferably salts of any of hydrochloric acid, sulfuric acid or nitric acid.

[0169] As the inorganic acid salt of hydroxylamine and hydroxylamine derivatives, hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine phosphate, N,N-diethylhydroxylamine sulfate, N,N-diethylhydroxylamine nitrate or a mixture thereof is preferred.

[0170] Examples of organic acid salts of hydroxylamine and hydroxylamine derivatives include hydroxylammonium citrate, hydroxylammonium oxalate, and hydroxylammonium fluoride.

[0171] From the viewpoint of more excellent residue removability, the hydroxylamine compound is preferably hydroxylamine or hydroxylamine sulfate.

[0172] The hydroxylamine compound may be used alone or in combination of two or more.

[0173] The content of the hydroxylamine compound is not particularly limited, but is preferably 0.01 to 30% by mass, more preferably 0.5 to 25% by mass, based on the total mass of the treatment liquid.

[0174] <Basic Compounds>

[0175] The treatment liquid may contain a basic compound as a removing agent. The basic compound refers to a compound whose solution pH exceeds 7 when dissolved in water. The basic compound also functions as a pH adjuster for adjusting the pH of the treatment liquid.

[0176] In addition, in this specification, the compound contained in the corrosion inhibitor mentioned later is not included in the basic compound.

[0177] As described above, the basic compound can form a salt with the hydrophilic group contained in the second repeating unit of the resin (A).

[0178] The basic compound is not particularly limited, and examples thereof include ammonium hydroxide, water-soluble amines, and quaternary ammonium compounds.

[0179] Hereinafter, ammonium hydroxide, water-soluble amines, and quaternary ammonium compounds are described in detail, respectively.

[0180] (Ammonium Hydroxide)

[0181] The treatment liquid may contain ammonium hydroxide (NH 4 OH) as the alkaline compound.

[0182] When the treatment liquid contains ammonium hydroxide, the content thereof is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 5.0% by mass, relative to the total mass of the treatment liquid.

[0183] (Water-soluble amine)

[0184] In the present specification, a water-soluble amine refers to a compound having an amino group in a molecule and capable of dissolving 50 g or more in 1 L of water.

[0185] Examples of the water-soluble amine include primary amines having a primary amino group (—NH 2 ) in the molecule, secondary amines having a secondary amino group (>NH) in the molecule, tertiary amines having a tertiary amino group (>N—) in the molecule, and salts thereof.

[0186] Examples of the salt of the amine include salts of inorganic acids formed by hydrogen bonding with at least one non-metal selected from Cl, S, N and P, and preferably hydrochlorides, sulfates or nitrates.

[0187] The water-soluble amine is preferably a low molecular weight compound. In this specification, "low molecular weight compound" refers to a compound that does not substantially have a molecular weight distribution. As a low molecular weight compound, the molecular weight is preferably 1000 or less. The specific examples of the following water-soluble amines are all low molecular weight compounds with a molecular weight of 1000 or less.

[0188] The water-soluble amine may be an alicyclic amine compound having a ring structure in the molecule, or may be an alkanolamine having at least one hydroxyalkyl group in the molecule.

[0189] Examples of the alicyclic amine compound include 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), ε-caprolactam, the following compound 1, the following compound 2, the following compound 3, 1,4-diazabicyclo[2.2.2]octane (DABCO), tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, 2-piperidinol, cyclohexylamine, and 1,5-diazabicyclo[4,3,0]-5-nonene.

[0190] [Chemical formula 6]

[0191]

[0192] The alkanolamine may have any of a primary amino group, a secondary amino group, and a tertiary amino group, but preferably has a primary amino group.

[0193] Examples of the alkanolamine include monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), diethylene glycolamine (DEGA), trishydroxymethylaminomethane (Tris), 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-dipropanol (AMPD), 2-amino-2-ethyl-1,3-dipropanol (AEPD), 2-(methylamino)-2-methyl-1-propanol (N-MAMP), 2-(aminoethoxy)ethanol (AEE), 2-(2-aminoethylamino)ethanol (CAS registration number: 111-41-1) (AEEA) and N-(3-aminopropyl)diethanolamine (APDA), and AEE or AEEA is preferred.

[0194] Examples of primary amines other than alicyclic amine compounds and alkanolamines among water-soluble amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, methoxyethylamine, methoxypropylamine, 2-amino-2-methyl-1-propanol (AMP), and allylamine.

[0195] As a secondary amine other than an alicyclic amine compound and an alkanolamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine (DBA) are mentioned, for example.

[0196] Examples of the tertiary amine other than the alicyclic amine compound and the alkanolamine include trimethylamine, triethylamine, and tributylamine (TBA).

[0197] The water-soluble amines may be used alone or in combination of two or more.

[0198] The content of the water-soluble amine is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.1 to 5.0% by mass, based on the total mass of the treatment liquid.

[0199] (Quaternary Ammonium Compounds)

[0200] The treatment liquid may contain, as a removing agent, a compound having one quaternary ammonium cation in the molecule or a quaternary ammonium compound as a salt thereof.

[0201] The quaternary ammonium compound is not particularly limited as long as it is a compound having one quaternary ammonium cation in which four hydrocarbon groups (preferably alkyl groups) are substituted with a nitrogen atom, or a salt thereof.

[0202] Examples of the quaternary ammonium compound include quaternary ammonium hydroxides, quaternary ammonium fluorides, quaternary ammonium bromides, quaternary ammonium iodides, quaternary ammonium acetates, and quaternary ammonium carbonates.

[0203] As the quaternary ammonium compound, a quaternary ammonium hydroxide is preferred, and a compound represented by the following formula (a1) is more preferred.

[0204] [Chemical formula 7]

[0205]

[0206] In the above formula (a1), R a1 ~R a4 R each independently represents an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or a hydroxyalkyl group having 1 to 16 carbon atoms. a1 ~R a4 At least two of them may be bonded to each other to form a ring structure.

[0207] As the compound represented by the above formula (a1), from the viewpoint of easy availability, at least one selected from tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, tetrabutylammonium hydroxide (TBAH), methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide (BzTMAH), hexadecyltrimethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide and spiro-(1,1′)-bipyrrolidinium hydroxide is preferred, and TMAH, TEAH, TBAH or BzTMAH is more preferred, and TMAH, TEAH or TBAH is further preferred.

[0208] The quaternary ammonium compound may be used alone or in combination of two or more.

[0209] The content of the quaternary ammonium compound is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the treatment liquid.

[0210] The basic compound may be used alone or in combination of two or more.

[0211] When the treatment liquid contains a basic compound, the content thereof is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total mass of the treatment liquid.

[0212] <Acidic compounds>

[0213] The treatment liquid may contain an acidic compound as a remover. The acidic compound refers to a compound whose solution pH is less than 7 when dissolved in water. The acidic compound also functions as a pH adjuster for adjusting the pH of the treatment liquid.

[0214] In the present specification, the compounds included in any of the above-mentioned fluorine-containing compounds, the oxidizing agents described later, and the anionic surfactants are not included in the acidic compounds.

[0215] The acidic compound may be an inorganic acid or an organic acid.

[0216] As described above, the inorganic acid or organic acid can form a salt with the specific amino group contained in the first repeating unit or the second repeating unit of the resin (A).

[0217] (Inorganic Acid)

[0218] Examples of the inorganic acid include sulfuric acid, hydrochloric acid and phosphoric acid, and sulfuric acid is preferred.

[0219] The inorganic acid may be used alone or in combination of two or more.

[0220] When the treatment liquid contains an inorganic acid, the content thereof is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total mass of the treatment liquid.

[0221] (Organic Acid)

[0222] The organic acid is an organic compound having an acidic functional group and being acidic (pH less than 7.0) in an aqueous solution. Examples of the acidic functional group include a carboxyl group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a mercapto group.

[0223] The organic acid is not particularly limited, and examples thereof include carboxylic acids having a carboxyl group in the molecule (organic carboxylic acids), phosphonic acids having a phosphonic acid group in the molecule (organic phosphonic acids), and sulfonic acids having a sulfonic group in the molecule (organic sulfonic acids). Carboxylic acids are preferred.

[0224] The number of acidic functional groups possessed by the organic acid is not particularly limited, but is preferably 1 to 4, and more preferably 1 to 3.

[0225] Furthermore, the organic acid is preferably a compound having a chelating function with the metal contained in the residue, and preferably a compound having two or more functional groups (ligands) that coordinate and bond with metal ions in the molecule. Examples of the ligands include the above-mentioned acidic functional groups and amino groups.

[0226] -carboxylic acid-

[0227] Examples of the carboxylic acid include polyaminopolycarboxylic acids, amino acids, polycarboxylic acids, and monocarboxylic acids.

[0228] The polyaminopolycarboxylic acid is a compound having a plurality of amino groups and a plurality of carboxyl groups in one molecule, and examples thereof include mono- or polyalkylene polyamine carboxylic acids, polyaminoalkane carboxylic acids, polyaminoalkanol carboxylic acids, and hydroxyalkyl ether polyamine carboxylic acids.

[0229] More specifically, examples of the polyaminopolycarboxylic acid include butanediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraaminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid (Cy-DTA), ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6-hexamethylene-diamine-N,N,N',N'-tetraacetic acid, N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclododecane-tetraacetic acid, diaminopropanoltetraacetic acid, and (hydroxyethyl)ethylenediaminetriacetic acid.

[0230] Among them, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA) or trans-1,2-diaminocyclohexanetetraacetic acid (Cy-DTA) is preferred.

[0231] Amino acids are compounds having one or more amino groups and one or more carboxyl groups in one molecule. However, the above-mentioned polyamino-polycarboxylic acids are not included in amino acids.

[0232] As amino acid, for example, glycine, allylglycine, serine, α-alanine (2-aminopropionic acid), β-alanine (3-aminopropionic acid), lysine, leucine, isoleucine, cystine, cysteine, methionine, ethionine, threonine, tryptophan, tyrosine, valine, histidine, histidine derivatives, asparagine, glutamine, arginine, proline, phenylalanine, Japanese Patent Publication No. 2016-086094

[0021] ~

[0023] described in paragraphs and their salts. In addition, as histidine derivatives, Japanese Patent Publication No. 2015-165561 and Japanese Patent Publication No. 2015-165562 can be used, and these contents are incorporated into this specification. And, as salt, alkali metal salts such as sodium salts and potassium salts, ammonium salts, carbonates and acetates can be mentioned.

[0233] Furthermore, examples of the amino acid having a plurality of amino groups and one carboxyl group include compounds represented by the following formula (I) or salts thereof.

[0234] (R 3 NH)C(R 1 )(R 2 )CO2H (I)

[0235] In formula (I), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group having at least one nitrogen-containing group, and R 3It represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group having at least one nitrogen-containing group.

[0236] Among them, R 1 , R 2 and R 3 At least one of means a group having at least one nitrogen-containing group.

[0237] Examples of the compound represented by formula (I) include the following compounds.

[0238] R 1 represents a group having at least one nitrogen-containing group, R 2 and R 3 Compounds representing hydrogen atoms: lysine, 2,3-diaminobutyric acid, 2,4-diaminobutyric acid, ornithine, 2,3-diaminopropionic acid, 2,6-diaminoheptanoic acid, 4-methyllysine, 3-methyllysine, 5-hydroxylysine, 3-methyl-L-arginine, arginine, homoarginine, N 5 -Monomethyl-L-arginine, N 5 -[Imino(methylamino)methyl]-D-ornithine, canavanine and histidine.

[0239] R 1 and R 2 represents a hydrogen atom, R 3 Compounds representing a group having at least one nitrogen-containing group: N-(2-aminoethyl)glycine and N-(2-aminopropyl)glycine.

[0240] R 1 represents a group having at least one nitrogen-containing group, R 2 represents a hydrogen atom, R 3 Compounds representing an alkyl group having 1 to 10 carbon atoms: N 2 -Methyl lysine and N 2 -Methyl-L-arginine.

[0241] R 1 and R 3 represents a group having at least one nitrogen-containing group, R 2 Compounds that represent hydrogen atoms: N 2 -(2-aminoethyl)-D-arginine and N 2 -(2-aminoethyl)-L-arginine.

[0242] R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 represents a group having at least one nitrogen-containing group, R 3 Compounds representing hydrogen atoms: 2-methyllysine and 2-methyl-L-arginine.

[0243] Polycarboxylic acid is a compound having a plurality of carboxyl groups in one molecule. However, the above-mentioned polyaminopolycarboxylic acid is not included in the polycarboxylic acid.

[0244] Examples of the polycarboxylic acid include oxalic acid, citric acid, malonic acid, maleic acid, succinic acid, malic acid, tartaric acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, citraconic acid, fumaric acid and itaconic acid, and citric acid is preferred.

[0245] A monocarboxylic acid is a compound having only one carboxyl group in one molecule. However, the above-mentioned amino acids are not included in the monocarboxylic acid.

[0246] Examples of the monocarboxylic acid include lower (having 1 to 4 carbon atoms) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid.

[0247] -Phosphonic acid-

[0248] The phosphonic acid may be a monophosphonic acid having only one phosphonic acid group in the molecule, or may be a polyphosphonic acid having two or more phosphonic acid groups in the molecule.

[0249] The number of phosphonic acid groups contained in the phosphonic acid is preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 or 3.

[0250] As phosphonic acid, compounds represented by general formulas [1] to [3] described in paragraphs

[0013] to

[0023] of the specification of International Publication No. 2013 / 162020, compounds described in paragraphs

[0026] to

[0036] of the specification of International Publication No. 2018 / 020878, and compounds ((co)polymers) described in paragraphs

[0031] to

[0046] of the specification of International Publication No. 2018 / 030006 can be cited, and these contents are incorporated into this specification.

[0251] Examples of the phosphonic acid include ethylenediphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDEPO), 1-hydroxypropylene-1,1'-diphosphonic acid, 1-hydroxybutylene-1,1'-diphosphonic acid, ethylaminobis(methylenephosphonic acid), dodecylaminobis(methylenephosphonic acid), nitrilotri(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylenephosphonic acid) (EDDPO), 1,3-propylenediaminebis(methylenephosphonic acid), ethylenediaminetetrakis( 1,3-propylenediaminetetrakis(methylenephosphonic acid) (PDTMP), 1,2-diaminopropanetetrakis(methylenephosphonic acid), 1,6-hexamethylenediaminetetrakis(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) (DEPPO), diethylenetriaminepenta(ethylenephosphonic acid), triethylenetetraaminehexa(methylenephosphonic acid) and triethylenetetraaminehexa(ethylenephosphonic acid), preferably HEDEPO.

[0252] -Sulfonic acid-

[0253] The sulfonic acid may be a monosulfonic acid having only one sulfonic group in the molecule, or may be a polysulfonic acid having two or more sulfonic groups in the molecule.

[0254] The number of sulfonic groups contained in the sulfonic acid is preferably 1 or 2, and more preferably 1.

[0255] Examples of the sulfonic acid include methanesulfonic acid (MSA), ethanesulfonic acid, isethionic acid (2-hydroxyethanesulfonic acid), benzenesulfonic acid, and p-toluenesulfonic acid (toluenesulfonic acid), and methanesulfonic acid or isethionic acid is preferred.

[0256] The organic acid preferably has a low molecular weight. Specifically, the molecular weight of the organic acid is preferably 600 or less, and more preferably 450 or less. The lower limit is not particularly limited, but is preferably 85 or more.

[0257] Furthermore, the number of carbon atoms in the organic acid is preferably 15 or less, more preferably 12 or less, and further preferably 8 or less. The lower limit is not particularly limited, but is preferably 2 or more.

[0258] As the organic acid, the above-mentioned polyaminopolycarboxylic acids, the above-mentioned polycarboxylic acids, the above-mentioned monocarboxylic acids, the above-mentioned phosphonic acids or the above-mentioned sulfonic acids are preferred, and DTPA, EDTA, Cy-DTA, citric acid, acetic acid, HEDEPO, MSA or isethionic acid is preferred.

[0259] The organic acid may be used alone or in combination of two or more.

[0260] When the treatment liquid contains an organic acid, the content of the organic acid is not particularly limited, but is preferably 0.001 to 90% by mass, more preferably 0.005 to 70% by mass, based on the total mass of the treatment liquid.

[0261] The treatment liquid may contain other removers other than those mentioned above. As other removers, for example, compounds having at least two nitrogen-containing groups and no carboxyl group can be cited. As specific examples of these compounds, at least one biguanide compound selected from compounds having a biguanide group and salts thereof can be cited.

[0262] Furthermore, as a removing agent, a chelating agent described in JP-A-2017-504190 can also be used, and the contents described in the above document are incorporated into this specification.

[0263] As the remover, it is preferred to select at least one of fluorine-containing compounds, hydroxylamine compounds, alkaline compounds and acidic compounds, and more preferably selected from at least one of hydrofluoric acid, ammonium fluoride, tetramethylammonium fluoride, hydroxylamine compounds, ammonium hydroxide, water-soluble amines, quaternary ammonium compounds, sulfuric acid, hydrochloric acid, phosphoric acid, carboxylic acid, sulfonic acid and phosphonic acid.

[0264] Furthermore, from the viewpoint of further improving the removal performance of dry etching residues when used as a cleaning liquid, the treatment liquid as a remover preferably contains a water-soluble amine and at least one organic acid selected from carboxylic acid (more preferably amino acid or polycarboxylic acid), sulfonic acid and phosphonic acid, and further preferably contains at least one water-soluble amine selected from methylamine, ethylamine, propylamine, butylamine, pentylamine, methoxyethylamine, methoxypropylamine, 2-amino-2-methyl-1-propanol and allylamine and at least one organic acid selected from acetic acid, propionic acid, methanesulfonic acid, ethanesulfonic acid, allylglycine, maleic acid, citraconic acid, fumaric acid and itaconic acid.

[0265] The remover may be used alone or in combination of two or more.

[0266] The content of the removing agent is not particularly limited, but is preferably 0.001 to 90% by mass, more preferably 0.005 to 70% by mass, based on the total mass of the treatment liquid.

[0267] [Optional ingredients]

[0268] The treatment liquid may further contain components other than the above-mentioned components. Optional components that may be contained in the treatment liquid are described in detail below.

[0269] <Oxidant>

[0270] The processing liquid may contain an oxidizing agent. When the processing liquid is an etching solution, the processing liquid preferably contains an oxidizing agent.

[0271] Examples of the oxidizing agent include peroxides such as hydrogen peroxide and peracetic acid, nitric acid, iodic acid, periodic acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, persulfuric acid, dichromic acid, permanganic acid, ozone water, silver (II) salts, and iron (III) salts such as ferric nitrate. The above oxidizing agents may form salts with counter ions.

[0272] The oxidizing agent contained in the treatment liquid is preferably hydrogen peroxide, nitric acid, peracetic acid, periodic acid, perchloric acid, chloric acid, hypochlorous acid, cerium ammonium nitrate, ferric nitrate or ammonium persulfate, and more preferably hydrogen peroxide, nitric acid, peracetic acid, periodic acid or perchloric acid.

[0273] The oxidizing agent may be used alone or in combination of two or more.

[0274] When the treatment liquid contains an oxidizing agent, the content of the oxidizing agent is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, based on the total mass of the treatment liquid.

[0275] <Corrosion Inhibitor>

[0276] The treatment liquid may contain a corrosion inhibitor, and preferably contains a corrosion inhibitor.

[0277] The corrosion inhibitor has a function of preventing corrosion of the metal-containing layer due to overetching or the like by coordinating with the surface of the metal-containing layer such as wiring of a semiconductor device to form a film.

[0278] In addition, in this specification, the above-mentioned chelating agent (compound having a chelating ability) is not included in the corrosion inhibitor.

[0279] The corrosion inhibitor is not particularly limited, and examples thereof include 1,2,4-triazole (TAZ), 5-aminotetrazolyl (ATA), 5-amino-1,3,4-thiadiazole-2-thiol, 3-amino-1H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methoxy-1H-1,2,4-triazole, and the like. 1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, naphthalenetriazole, 1H-tetrazolyl-5-acetic acid, 2-mercaptobenzothiazole (2-MBT), 1-phenyl-2-tetrazoline-5-thione, 2-mercaptobenzimidazole (2-MBI), 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, imidazole, benzimidazole, triazine, methyl tetrazole, bismuthiothiol I, 1,3-dimethyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, imidazolinethione, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol, naphthotriazole, tricresyl phosphate, indazole, adenine, cytosine, guanine, thymine, phosphate inhibitor, pyrazoles, propanethiol, silanes, benzohydroxamic acid class, heterocyclic nitrogen inhibitors, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, uric acid, potassium ethyl xanthate, boric acid, 2,3,5-trimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, quinoxaline, acetylpyrrole, pyridazine, histidine (histadine), pyrazine, glutathione (reduced form), thiophene, mercaptopyridine N-oxide, thiamine HCl, tetramethylthiuram disulfide, catechol, tert-butylcatechol, phenol and gallol.

[0280] As the corrosion inhibitor, substituted or unsubstituted benzotriazole (hereinafter also referred to as "benzotriazole compound") is preferred. As the substituted benzotriazole, benzotriazole substituted with an alkyl group, an aryl group, a halogen group, an amino group, a nitro group, an alkoxy group or a hydroxyl group is preferred. Substituted benzotriazoles also include benzotriazoles fused with one or more aryl groups (e.g., phenyl) or heteroaryl groups.

[0281] Examples of benzotriazole compounds suitable for the corrosion inhibitor include benzotriazole (BTA), 5-aminotetrazolyl, 1-hydroxybenzotriazole, 5-phenylmercapto-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthotriazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-benzotriazole, 5-methyl-1H-benzotriazole (5MBTA), benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole. benzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole, 5-isopropylbenzotriazole, 4-n-butylbenzotriazole, 5-n-butylbenzotriazole, 4-isobutylbenzotriazole, 5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole, 4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-methoxybenzotriazole, 5-hydroxybenzotriazole , dihydroxypropylbenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-tert-butylbenzotriazole, 5-(1',1'-dimethylpropyl)-benzotriazole, 5-(1',1',3'-trimethylbutyl)benzotriazole, 5-n-octylbenzotriazole and 5-(1',1',3',3'-tetramethylbutyl)benzotriazole.

[0282] In addition, examples of benzotriazole compounds include 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol, 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}diethane or 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}dipropane and N,N-bis(2-ethylhexyl)-(4 or 5)-methyl-1H-benzotriazole-1-methylamine.

[0283] The corrosion inhibitor preferably contains at least one compound selected from the group consisting of a compound represented by the following formula (A), a compound represented by the following formula (B), a compound represented by the following formula (C), and a substituted or unsubstituted tetrazole.

[0284] [Chemical formula 8]

[0285]

[0286] In the above formula (A), R 1A ~R 5AEach independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amino group, wherein the structure contains at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, and a substituted or unsubstituted amino group.

[0287] In the above formula (B), R 1B ~R 4B Each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

[0288] In the above formula (C), R 1C , R 2C and R N Each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. 1C With R 2C They may be bonded to form a ring.

[0289] In the above formula (A), R 1A and R 5A Examples of the hydrocarbon group represented include alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, and further preferably 2 to 6 carbon atoms), alkynyl groups (preferably having 2 to 12 carbon atoms, and further preferably 2 to 6 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and further preferably 6 to 10 carbon atoms), and aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms, and further preferably 7 to 11 carbon atoms).

[0290] In addition, examples of the substituent in the case of substituted hydrocarbon groups include hydroxyl groups, carboxyl groups, and substituted or unsubstituted amino groups (in the case of substituted amino groups, the substituent is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms).

[0291] In formula (A), the structure contains at least one group selected from hydroxyl, carboxyl and substituted or unsubstituted amino (the substituent in the case of substituted amino is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms).

[0292] In formula (A), as R 1A ~R 5A Examples of the substituted or unsubstituted hydrocarbon group represented by include hydrocarbon groups having 1 to 6 carbon atoms substituted with a hydroxyl group, a carboxyl group or an amino group.

[0293] Examples of the compound represented by formula (A) include 1-thioglycerol, L-cysteine, and thiomalic acid.

[0294] In formula (B), R 1B ~R 4BThe meaning of the substituted or unsubstituted hydrocarbon group represented by R in the above formula (A) is the same as that of 1A ~R 5A The substituted or unsubstituted hydrocarbon groups represented have the same meanings.

[0295] As R 1B ~R 4B Examples of the substituted or unsubstituted hydrocarbon group represented by include hydrocarbon groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl and tert-butyl.

[0296] Examples of the compound represented by formula (B) include catechol and tert-butylcatechol.

[0297] In formula (C), as R 1C , R 2C and R N The substituted or unsubstituted hydrocarbon group represented by R 1A ~R 5A The substituted or unsubstituted hydrocarbon groups represented have the same meanings.

[0298] As R 1C , R 2C and R N Examples of the substituted or unsubstituted hydrocarbon group represented by include hydrocarbon groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, and butyl.

[0299] And, R 1C With R 2C They may be bonded to form a ring. 1C With R 2C An example of a ring formed by bonding is a benzene ring. 1C With R 2C When they are bonded to form a ring, they may further have a substituent (for example, a hydrocarbon group having 1 to 5 carbon atoms).

[0300] Examples of the compound represented by formula (C) include 1H-1,2,3-triazole, benzotriazole, 5-methyl-1H-benzotriazole, tolyltriazole, 2,2′-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol (product name “IRGAMET 42”, manufactured by BASF), N,N-bis(2-ethylhexyl)-(4 or 5)-methyl-1H-benzotriazole-1-methylamine (product name “IRGAMET 39”, manufactured by BASF), etc. From the viewpoint of more excellent effects of the present invention, benzotriazole, 5-methyl-1H-benzotriazole or tolyltriazole is preferred, and 5-methyl-1H-benzotriazole is more preferred.

[0301] Examples of substituted or unsubstituted tetrazoles include unsubstituted tetrazoles and tetrazoles having a hydroxyl group, a carboxyl group or a substituted or unsubstituted amino group as substituents. Among them, when the amino group is substituted, the substituent is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

[0302] The corrosion inhibitors may be used alone or in combination of two or more.

[0303] When the treatment liquid contains a corrosion inhibitor, the content of the corrosion inhibitor is preferably 0.001 to 10 mass %, more preferably 0.002 to 5 mass %, and further preferably 0.05 to 1 mass % relative to the total mass of the treatment liquid. When two or more corrosion inhibitors are used in combination, the total amount thereof is preferably within the above range.

[0304] The corrosion inhibitor is preferably used in a high purity grade, and more preferably used after further purification.

[0305] The method for purifying the corrosion inhibitor is not particularly limited, and for example, known methods such as filtration, ion exchange, distillation, adsorption purification, recrystallization, reprecipitation, sublimation, and purification using a column may be used, and these methods may be used in combination.

[0306] <Surfactant>

[0307] The treatment liquid may contain a surfactant.

[0308] The treatment liquid preferably contains a surfactant from the viewpoint of excellent corrosion resistance (particularly corrosion resistance to a Ti alloy metal film described later).

[0309] As a surfactant, there is no particular limitation as long as it is a compound having a hydrophilic group and a hydrophobic group (lipophilic group) in the molecule. For example, anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants can be mentioned. From the viewpoint of better corrosion resistance (especially corrosion resistance of Ti alloy metal film), anionic surfactants are preferred.

[0310] Surfactants are mostly hydrophobic groups selected from aliphatic hydrocarbon groups, aromatic hydrocarbon groups and combinations thereof. The hydrophobic group possessed by the surfactant is not particularly limited. When the hydrophobic group contains an aromatic hydrocarbon group, it is preferably 6 or more carbon atoms, and more preferably 10 or more carbon atoms. When the hydrophobic group does not contain an aromatic hydrocarbon group and is composed only of an aliphatic hydrocarbon group, it is preferably 10 or more carbon atoms, and more preferably 12 or more carbon atoms. The upper limit of the carbon number of the hydrophobic group is not particularly limited, and is preferably 20 or less.

[0311] (Anionic surfactant)

[0312] Examples of the anionic surfactant contained in the treatment liquid include a phosphate surfactant, a phosphonic acid surfactant, a sulfonic acid surfactant, a carboxylic acid surfactant, and a sulfate surfactant.

[0313] Examples of the phosphate surfactant include phosphates (alkyl phosphates and aryl phosphates), mono- or polyoxyalkylene ether phosphates (mono- or polyoxyalkylene alkyl ether phosphates and mono- or polyoxyalkylene aryl ether phosphates), and salts thereof. Among them, at least one selected from alkyl phosphates, mono- or polyoxyalkylene ether phosphates, and salts thereof is preferred.

[0314] Examples of the salt of the phosphate ester surfactant include sodium salts, potassium salts, ammonium salts, and organic amine salts.

[0315] Examples of the monovalent alkyl group contained in the alkyl phosphate and the mono- or polyoxyalkylene alkyl ether phosphate include an alkyl group having 6 to 22 carbon atoms, and an alkyl group having 10 to 20 carbon atoms is preferred.

[0316] Examples of the monovalent aryl group contained in the aryl phosphate and the mono- or polyoxyalkylene aryl ether phosphate include an aryl group having 6 to 14 carbon atoms which may have an alkyl group, and a phenyl group which may have an alkyl group is preferred.

[0317] Examples of the divalent alkylene group contained in the mono- or poly-oxyalkylene alkyl ether phosphate and the mono- or poly-oxyalkylene aryl ether phosphate include alkylene groups having 2 to 6 carbon atoms, preferably ethylene or propylene, more preferably ethylene. The number of repetitions of the oxyalkylene group is preferably 1 to 12, more preferably 1 to 10.

[0318] More specific examples of phosphate surfactants include octyl phosphate, lauryl phosphate, tridecyl phosphate, tetradecyl phosphate, hexadecyl phosphate, stearyl phosphate, mono- or polyoxyethylene octyl ether phosphate, mono- or polyoxyethylene lauryl ether phosphate, and mono- or polyoxyethylene tridecyl ether phosphate. Among them, lauryl phosphate or mono- or polyoxyethylene lauryl ether phosphate is preferred.

[0319] Furthermore, as the phosphate-based surfactant, compounds described in paragraphs

[0012] to

[0019] of JP-A-2011-040502 can also be used, and these contents are incorporated into the present specification.

[0320] Examples of the phosphonic acid-based surfactant include alkylphosphonic acid, polyvinylphosphonic acid, and aminomethylphosphonic acid described in JP-A-2012-057108.

[0321] Examples of the sulfonic acid-based surfactant include alkylsulfonic acid, alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, alkyldiphenyl ether disulfonic acid, alkylmethyltaurine, sulfosuccinic acid diesters, polyoxyalkylene alkyl ether sulfonic acid, and salts thereof.

[0322] Specific examples of the sulfonic acid surfactant include hexylsulfonic acid, octanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid (DBS), dinitrobenzenesulfonic acid (DNBSA), lauryl dodecylphenyl ether disulfonic acid (LDPEDSA), and salts thereof, preferably dodecylbenzenesulfonic acid.

[0323] Examples of the carboxylic acid-based surfactant include alkyl carboxylic acids, alkylbenzene carboxylic acids, polyoxyalkylene alkyl ether carboxylic acids, and salts thereof.

[0324] Specific examples of the carboxylic acid-based surfactant include lauric acid, myristic acid, palmitic acid, stearic acid, polyoxyethylene lauryl ether acetic acid, and polyoxyethylene tridecyl ether acetic acid.

[0325] Examples of the sulfate-based surfactant include sulfate (alkyl ether sulfate), polyoxyalkylene ether sulfate, and salts thereof.

[0326] Specific examples of the sulfate ester surfactant include lauryl sulfuric acid, myristyl sulfuric acid, and polyoxyethylene lauryl ether sulfuric acid.

[0327] As the anionic surfactant, a phosphate surfactant, a sulfonic acid surfactant, a phosphonic acid surfactant or a carboxylic acid surfactant is preferred, and a sulfonic acid surfactant is more preferred.

[0328] Furthermore, from the viewpoint of better corrosion resistance of the TiAlC film, the anionic surfactant is preferably a phosphate surfactant, a sulfonic acid surfactant, a carboxylic acid surfactant or a sulfate surfactant, more preferably a phosphate surfactant or a carboxylic acid surfactant, and further preferably a phosphate surfactant.

[0329] (Cationic surfactant)

[0330] Examples of the cationic surfactant include primary and tertiary alkylamine salts (for example, monostearylammonium chloride, distearyllammonium chloride, tristearylammonium chloride, etc.) and modified aliphatic polyamines (for example, polyethylene polyamine, etc.).

[0331] (Nonionic surfactant)

[0332] Examples of the nonionic surfactant include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyalkylene glycols, polyoxyalkylene monoalkylates, polyoxyalkylene dialkylates, bispolyoxyalkylene alkylamides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerol fatty acid esters, oxyethylene oxypropylene block copolymers, acetylene glycol surfactants, and acetylene polyoxyethylene oxides.

[0333] (amphoteric surfactant)

[0334] Examples of the amphoteric surfactant include carboxybetaines (e.g., alkyl-N,N-dimethylaminoacetic acid betaine and alkyl-N,N-dihydroxyethylaminoacetic acid betaine), sulfobetaines (e.g., alkyl-N,N-dimethylsulfonylvinyl ammonium betaine), and imidazolinium betaines (e.g., 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine).

[0335] As surfactants, compounds described in paragraphs

[0092] to

[0096] of JP-A-2015-158662, paragraphs

[0045] to

[0046] of JP-A-2012-151273, and paragraphs

[0014] to

[0020] of JP-A-2009-147389 can also be used, and these contents are incorporated into the present specification.

[0336] The surfactant may be used alone or in combination of two or more. When the treatment liquid contains a surfactant, the content thereof is preferably 0.001 to 1% by mass, more preferably 0.005 to 0.5% by mass, relative to the total mass of the treatment liquid from the viewpoint of a more excellent effect of the present invention.

[0337] <Defoaming agent>

[0338] The treatment liquid may contain a defoaming agent. Surfactants may generate bubbles depending on the method of use. Therefore, the treatment liquid containing a surfactant preferably contains a defoaming agent that suppresses the generation of bubbles and shortens the life of the generated bubbles to suppress the residual bubbles.

[0339] The defoamer is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include silicone defoamers, acetylene glycol defoamers, fatty acid ester defoamers, long-chain aliphatic alcohol defoamers, and polyether defoamers. Among them, silicone defoamers are preferred from the viewpoint of having a more excellent effect of suppressing the residual bubbles, and silicone defoamers having a high molecular weight are more preferred.

[0340] In addition, the defoaming agent does not contain compounds included in the above-mentioned surfactants.

[0341] The silicone-based defoaming agent is a defoaming agent composed of a compound having a silane structure.

[0342] Examples of silicone defoamers include oil-based, oil compound-based, solution-based, emulsion-based, and self-emulsifying defoamers. Examples of silicone defoamers include polydimethylsiloxane, siloxane glycol, and fluorosilicone. Examples of long-chain aliphatic alcohol-based defoamers include aliphatic alcohols having 7 to 22 carbon atoms.

[0343] Examples of commercially available defoamers include KM-73A, KA-540, and KF-6701 (all silicone defoamers) manufactured by Shin-Etsu Chemical Co., Ltd.; KS-508, KS-531, KM-72, and KM-85 manufactured by Shin-Etsu Chemical Co., Ltd.; and Evonic Surfynol (registered trademark) MD20 (acetylene glycol defoamer) manufactured by Chemicals; BYK-012 (polydimethylsiloxane defoamer), BYK-014 (polydimethylsiloxane defoamer), BYK-019, BYK-020, BYK-025, BYK-080A, BYK-094, BYK-1650 and BYK-1660 (all silicone defoamers) manufactured by BYK-Chemie; Q-23183A and SH5510 (both silicone defoamers) manufactured by Dow Corning Toray Co., Ltd.; SAG30 (silicone defoamer) manufactured by ENEOS NUC Corporation; and Adecaneate series (silicone defoamers) manufactured by ADEKACORPORATION.

[0344] The defoaming agent may be used alone or in combination of two or more. When the treatment liquid contains a defoaming agent, the amount thereof is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and further preferably 0.005 to 0.1% by mass relative to the total mass of the treatment liquid from the viewpoint of better residual suppression of bubbles.

[0345] <Organic Solvents>

[0346] The treatment liquid may contain an organic solvent, and preferably contains an organic solvent.

[0347] The organic solvent is preferably a water-soluble organic solvent. The organic solvent being water-soluble means that water at 25° C. and the organic solvent are miscible (dissolved) in any proportion.

[0348] Examples of the organic solvent include alcohol solvents, ketone solvents, ester solvents, ether solvents (eg, glycol diethers), sulfone solvents, sulfoxide solvents, nitrile solvents, and amide solvents.

[0349] These solvents may be water-soluble.

[0350] Among them, the treatment liquid preferably contains one or more organic solvents selected from the group consisting of alcohol solvents, ketone solvents, ester solvents, and ether solvents.

[0351] Examples of the alcohol solvent include alkanediols (including, for example, alkylene glycols), alkoxy alcohols (including, for example, glycol monoethers), saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, and low-molecular-weight alcohols containing a ring structure.

[0352] Among them, the alcohol solvent is preferably a glycol monoether or a saturated aliphatic monohydric alcohol.

[0353] Examples of the alkanediol include glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycol.

[0354] Examples of the alkylene glycol include ethylene glycol, propylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol, and propylene glycol or hexylene glycol is preferred.

[0355] Examples of the alkoxy alcohol include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and glycol monoethers, and glycol monoethers are preferred.

[0356] Examples of the glycol monoethers include ethylene glycol mono-C1-C4 alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether and ethylene glycol mono-butyl ether; diethylene glycol mono-C1-C4 alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol mono-butyl ether; triethylene glycol mono-C1-C4 alkyl ethers such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and triethylene glycol mono-butyl ether; 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether and diethylene glycol monobenzyl ether.

[0357] Among them, ethylene glycol mono C1-C4 alkyl ether is preferred, and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol monobutyl ether is more preferred.

[0358] Examples of the saturated aliphatic monohydric alcohol include methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 2-pentanol, tert-pentanol, and hexanol.

[0359] Examples of the unsaturated non-aromatic monohydric alcohol include allyl alcohol, propargyl alcohol, 2-butenol, 3-butenol, and 4-penten-2-ol.

[0360] Examples of the low-molecular-weight alcohol having a ring structure include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

[0361] Examples of the ketone solvent include acetone, propanone, cyclobutanone, cyclopentanone, cyclohexanone, diacetone alcohol, 2-butanone, 5-hexanedione, 1,4-cyclohexanedione, 3-hydroxyacetophenone, 1,3-cyclohexanedione, and cyclohexanone.

[0362] Examples of the ester solvent include glycol monoesters such as ethyl acetate (ethyl acetate), butyl acetate (butyl acetate), ethylene glycol monoacetate, and diethylene glycol monoacetate; and glycol monoether monoesters such as propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol monoethyl ether acetate.

[0363] Examples of the sulfone solvent include sulfolane, 3-methylsulfolane, and 2,4-dimethylsulfolane, and sulfolane is preferred.

[0364] Examples of the sulfoxide-based solvent include dimethyl sulfoxide and the like.

[0365] Examples of the nitrile solvent include acetonitrile and the like.

[0366] Examples of the amide solvent include N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone, ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide and hexamethylphosphoric triamide.

[0367] The organic solvent may be used alone or in combination of two or more.

[0368] When the treatment liquid contains an organic solvent, the content of the organic solvent is preferably 0.1 to 99% by mass, more preferably 1 to 90% by mass, based on the total mass of the treatment liquid.

[0369] <Metal component>

[0370] The treatment liquid may contain a metal component.

[0371] Examples of the metal component include metal particles and metal ions. For example, when referring to the content of the metal component, it refers to the total content of the metal particles and the metal ions.

[0372] The processing liquid may contain either metal particles or metal ions, or both.

[0373] Examples of metal atoms contained in the metal component include metal atoms selected from Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sn, Sr, Ti and Zn.

[0374] The metal component may contain one type of metal atom or two or more types.

[0375] The metal particles may be a single substance or an alloy, and the metal may exist in a form of association with an organic substance.

[0376] The metal component may be a metal component inevitably contained in each component (raw material) contained in the treatment liquid, may be a metal component inevitably contained during the production, storage and / or transfer of the treatment liquid, or may be intentionally added.

[0377] When the treatment liquid contains a metal component, the content of the metal component is often 0.01 mass ppt to 10 mass ppm, preferably 0.1 mass ppt to 1 mass ppm, and more preferably 0.1 mass ppt to 100 mass ppb relative to the total mass of the treatment liquid.

[0378] In addition, the type and content of the metal component in the treatment liquid can be measured by SP-ICP-MS (Single Nanoparticle Inductively Coupled Plasma Mass Spectrometry).

[0379] The SP-ICP-MS method uses the same apparatus as the conventional ICP-MS method (inductively coupled plasma mass spectrometry), and only the data analysis is different. The data analysis of the SP-ICP-MS method can be performed using commercially available software.

[0380] In the ICP-MS method, the content of the metal component to be measured is measured regardless of its existence form. Therefore, the total mass of the metal particles and metal ions to be measured is quantified as the content of the metal component.

[0381] On the other hand, the SP-ICP-MS method can measure the content of metal particles, and thus the content of metal ions in the sample can be calculated by subtracting the content of metal particles from the content of metal components in the sample.

[0382] As a measurement method based on the SP-ICP-MS method, for example, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies Japan, Ltd. can be used, and the measurement can be performed by the method described in the embodiment. As other devices besides the above, in addition to NexION350S manufactured by PerkinElmer Co., Ltd., Agilent8900 manufactured by Agilent Fechnologies Japan, Ltd. can also be used.

[0383] The method for adjusting the content of each metal component in the treatment liquid is not particularly limited. For example, the content of the metal component in the treatment liquid can be reduced by performing a known treatment to remove metals from the treatment liquid and / or from the raw materials containing each component used to prepare the treatment liquid. In addition, the content of the metal component in the treatment liquid can be increased by adding a compound containing metal ions to the treatment liquid.

[0384] The treatment liquid may contain additives other than the above-mentioned components. Examples of the additives include surfactants, defoamers, rust inhibitors, and antiseptics.

[0385] In addition, the content of the above-mentioned components (excluding metal components) in the treatment liquid can be measured by well-known methods such as gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS) and ion exchange chromatography (IC).

[0386] [Physical properties of treatment fluid]

[0387] <ph>

[0388] The pH of the treatment liquid is not particularly limited, but is preferably 0 to 14, more preferably 6 to 12. When the pH of the treatment liquid is 6 or more, the corrosion resistance of the cobalt-containing layer is further improved, and when the pH of the treatment liquid is 12 or less, the corrosion resistance of the tungsten-containing layer is further improved.

[0389] The pH of the treatment liquid is a value measured at 25° C. using a known pH meter.

[0390] <Coarse particles>

[0391] It is preferred that the treatment liquid does not contain substantially any coarse particles.

[0392] Coarse particles refer to particles with a diameter of 0.2 μm or more when the particle shape is regarded as a sphere, for example. Also, substantially free of coarse particles means that when the treatment liquid is measured using a commercially available measuring device in a light scattering liquid particle measurement method, there are 10 or less particles with a diameter of 0.2 μm or more in 1 mL of the treatment liquid.

[0393] In addition, the coarse particles contained in the treatment liquid are particles of dust, dirt, organic solid matter, inorganic solid matter, etc. contained in the raw materials as impurities, and particles of dust, dirt, organic solid matter, inorganic solid matter, etc. brought in as contaminants during the preparation of the treatment liquid, which are equivalent to substances that are not dissolved in the final treatment liquid and exist as particles.

[0394] The amount of coarse particles present in the treatment liquid can be measured in a liquid phase using a commercially available measuring device of a light scattering type in-liquid particle measuring method using laser light as a light source.

[0395] As a method for removing coarse particles, for example, there is filtration or the like.

[0396] [Kit and Concentrate]

[0397] The above-mentioned treatment liquid can be used as a kit for preparing the treatment liquid by dividing its raw materials into a plurality of parts. There is no particular limitation, and as a specific method of setting the treatment liquid as a kit, for example, a method of preparing a liquid composition containing water and a remover as the first liquid and preparing a liquid composition containing the resin (A) as the second liquid can be cited.

[0398] The content of each component contained in the first liquid and the second liquid included in the kit is not particularly limited, but the content of each component in the treatment liquid prepared by mixing the first liquid and the second liquid is preferably the above-mentioned preferred content.

[0399] The pH of the first liquid and the second liquid included in the kit is not particularly limited, and the pH of each liquid may be adjusted so that the pH of the treatment liquid prepared by mixing the first liquid and the second liquid becomes a desired value.

[0400] Furthermore, the treatment solution may be prepared as a concentrated solution. In this case, it can be diluted with a diluent before use. That is, the kit may include the treatment solution in the form of a concentrated solution and the diluent.

[0401] The diluent is preferably a liquid selected from the group consisting of water, isopropanol, a mixture of water and isopropanol, and a solvent of ammonium hydroxide (more preferably water, isopropanol, or a mixture of water and isopropanol).

[0402] The dilution ratio of the concentrate is not particularly limited, but is preferably 1 to 2000 times, more preferably 1 to 100 times.

[0403] [use]

[0404] Next, the use of the processing liquid of the above-mentioned embodiment will be described.

[0405] The above-mentioned treatment liquid is a treatment liquid for semiconductor devices. In this specification, "for semiconductor devices" means for manufacturing semiconductor devices. The above-mentioned treatment liquid can be used in any process for manufacturing semiconductor devices, for example, it can be used to treat insulating films, resists, anti-reflective films, etching residues and ashing residues on substrates. In addition, in this specification, etching residues and ashing residues are collectively referred to as residues. In addition, the above-mentioned treatment liquid can be used for etching treatment to remove metal-containing substances on the substrate, and can also be used for processing the substrate after chemical mechanical polishing.

[0406] The processing liquid can be used as the following solutions before the process of forming a resist film using an active light-sensitive or radiation-sensitive composition: a pre-wetting liquid applied to a substrate to improve the coating properties of the composition, a cleaning liquid for removing residues attached to a metal layer, a solution for removing various resist films for pattern formation (e.g., a removal liquid and a stripping liquid, etc.), and a solution for removing permanent films (e.g., color filters, transparent insulating films, and resin lenses) from semiconductor substrates (e.g., a removal liquid and a stripping liquid, etc.). In addition, the semiconductor substrate after the permanent film is removed may be used again in the use of a semiconductor device, so the removal of the permanent film is also included in the manufacturing process of the semiconductor device.

[0407] Furthermore, the processing liquid can also be used as a cleaning liquid for removing residues such as metal impurities and fine particles from a substrate after chemical mechanical polishing.

[0408] Furthermore, the above-mentioned processing liquid can also be used as an etching liquid for metal-containing substances (including metal oxides and composite oxides composed of a plurality of metal oxides) on a substrate.

[0409] Among the above-mentioned uses, the present invention can be particularly preferably used as a cleaning solution for removing etching residues, a solution for removing a resist film used in pattern formation, and a cleaning solution or etching solution for removing residues from a substrate after chemical mechanical polishing.

[0410] The treatment liquid may be used for only one of the above purposes, or may be used for two or more purposes.

[0411] The above treatment liquid can also be used for treating a semiconductor device having a metal layer containing Co, a semiconductor device having a metal layer containing W, or a semiconductor device having a metal layer containing Cu. In addition, the above treatment liquid has excellent corrosion resistance to insulating films, and thus can also be used for treating a semiconductor device having a substrate containing a layer selected from SiO X , SiN and SiOC (x represents a number from 1 to 3).

[0412] [Method for producing treatment solution, concentrated solution, and kit]

[0413] <Processing Liquid Preparation Step>

[0414] The method for producing the treatment liquid is not particularly limited, and a known method can be used. For example, the method for producing the treatment liquid includes at least a treatment liquid preparation step of mixing the above-mentioned components to prepare the treatment liquid.

[0415] In the treatment solution preparation step, the order of mixing the components is not particularly limited. The concentrate and the liquids included in the kit are also preferably produced by the same method as described above.

[0416] The method for preparing the kit is not particularly limited. For example, the kit for preparing the treatment solution may be prepared by separately preparing the first liquid and the second liquid and then storing the first liquid and the second liquid in different containers.

[0417] <Filtration process>

[0418] In order to remove foreign matter, coarse particles, and the like from the liquid, the production method preferably includes a filtering step of filtering the liquid.

[0419] The filtering method is not particularly limited, and a known filtering method can be used. Among them, filtration using a filter is preferred.

[0420] The filter used for filtering can be used without particular limitation as long as it is used for filtering purposes in the past. As the material constituting the filter, for example, fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight) can be cited. Among them, polyamide resins, PTFE and polypropylene (including high-density polypropylene) are preferred.

[0421] By using a filter formed of these materials, highly polar foreign matter that is likely to cause defects can be removed more effectively from the processing liquid.

[0422] The critical surface tension of the filter is preferably 70 mN / m or more as a lower limit and 95 mN / m or less as an upper limit. In particular, the critical surface tension of the filter is preferably 75 to 85 mN / m.

[0423] The critical surface tension is a nominal value of the manufacturer. By using a filter having a critical surface tension within the above range, highly polar foreign matter that is likely to cause defects can be more effectively removed from the treatment liquid.

[0424] The pore size of the filter is preferably about 0.001 to 1.0 μm, more preferably about 0.02 to 0.5 μm, and further preferably about 0.01 to 0.1 μm. By setting the pore size of the filter within the above range, clogging of the filter can be suppressed and fine foreign matter contained in the treatment liquid can be reliably removed.

[0425] When using filters, different filters may be combined. In this case, the filtration of the first filter may be performed only once or twice or more. When different filters are combined to perform filtration twice or more, the filters may be of the same type or different types, but preferably of different types. Typically, the first filter and the second filter preferably differ in at least one of the pore size and the constituent raw materials.

[0426] It is preferred that the pore size after the second filtration is the same as or smaller than the pore size of the first filtration. In addition, a first filter with different pore sizes within the above range can also be combined. The pore size can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL Corporation, Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (Formerly Nippon Mykrolis Corporation) or KITZMICROFILTER CORPORATION. In addition, polyamide "P-nylon filter (pore size 0.02μm, critical surface tension 77mN / m)" (manufactured by NIHON PALL Corporation), high-density polyethylene "PE·clean filter (pore size 0.02μm)" (manufactured by NIHON PALL Corporation) and high-density polyethylene "PE·clean filter (pore size 0.01μm)" (manufactured by NIHON PALL Corporation) can also be used.

[0427] The second filter can be a filter formed of the same material as the first filter. A filter having the same pore size as the first filter can be used. When the pore size of the second filter is smaller than that of the first filter, the ratio of the pore size of the second filter to the pore size of the first filter (pore size of the second filter / pore size of the first filter) is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and further preferably 0.3 to 0.9. By setting the pore size of the second filter within the above range, fine foreign matter mixed in the treatment liquid can be more reliably removed.

[0428] For example, a mixed liquid containing a part of the components of the treatment liquid may be filtered through a first filter, and the remaining components may be mixed therewith to prepare a treatment liquid, followed by second filtration.

[0429] Furthermore, the filter used is preferably treated before filtering the treatment liquid. The liquid used in the treatment is not particularly limited, but the treatment liquid, the concentrated liquid, and the liquid containing the components contained in the treatment liquid are preferred.

[0430] When filtering, the upper limit of the temperature during filtration is preferably room temperature (25°C) or lower, more preferably 23°C or lower, and further preferably 20°C or lower. The lower limit of the temperature during filtration is preferably 0°C or higher, more preferably 5°C or higher, and further preferably 10°C or higher.

[0431] During filtration, particulate foreign matter and / or impurities can be removed. However, if the filtration is performed at the above temperature, the amount of particulate foreign matter and / or impurities dissolved in the treatment liquid decreases, so filtration can be performed more efficiently.

[0432] <Electrical elimination process>

[0433] The production method may further include a static elimination step of eliminating static electricity from at least one selected from the group consisting of a liquid, a concentrated solution, and a kit. The specific method for eliminating static electricity will be described later.

[0434] In addition, all the steps of the above-mentioned manufacturing method are preferably carried out in a clean room. The clean room preferably meets the 14644-1 clean room standard. It is preferred to meet any one of ISO (International Organization for Standardization) grade 1, ISO grade 2, ISO grade 3, and ISO grade 4, more preferably ISO grade 1 or ISO grade 2, and further preferably ISO grade 1.

[0435] <Container>

[0436] The container for storing the above-mentioned treatment liquid, concentrated solution or reagent kit is not particularly limited as long as the corrosiveness of the liquid does not pose a problem, and a known container can be used.

[0437] As the container, for semiconductor applications, a container having high cleanliness inside the container and little elution of impurities is preferred.

[0438] Specific examples of the above-mentioned containers include, for example, the "Clean-Bottle" series manufactured by AICELLO CHEMICAL CO., LTD. and the "Pure bottle" manufactured by KODAMA PLASTICS Co., Ltd. In addition, in order to prevent impurities from being mixed into (contaminated) raw materials and liquid medicines, it is also preferred to use a multilayer container having a six-layer structure with six kinds of resins forming the inner wall of the container and a multilayer container having a seven-layer structure with six kinds of resins forming the inner wall of the container. As these containers, for example, the containers described in Japanese Patent Publication No. 2015-123351 can be cited, but they are not limited to these.

[0439] The inner wall of the container is preferably formed or coated with one or more resins selected from polyethylene resin, polypropylene resin and polyethylene-polypropylene resin, a resin different from these, and a metal such as stainless steel, Hastelloy, Inconel and Monel.

[0440] As the above-mentioned different resins, fluorine-based resins (perfluorinated resins) can be preferably used. Thus, by using a container whose inner wall is formed of or coated with a fluorine-based resin, the occurrence of undesirable conditions such as the dissolution of oligomers of ethylene or propylene can be suppressed, compared with the case of using a container whose inner wall is formed of or coated with a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin.

[0441] Specific examples of containers having such inner walls include, for example, FluoroPure PFA composite columns manufactured by Entegris, Inc. In addition, containers described in Japanese Unexamined Patent Application Publication No. 3-502677, page 4, etc., International Publication No. 2004 / 016526, page 3, etc., and International Publication No. 99 / 046309, pages 9 and 16, etc., can also be used.

[0442] Furthermore, the inner wall of the container is preferably made of quartz or an electrolytically polished metal material (ie, an electrolytically ground metal material) in addition to the above-mentioned fluorine-based resin.

[0443] The metal material used for producing the electrolytically polished metal material contains at least one selected from chromium and nickel, and preferably contains chromium and nickel in a total amount exceeding 25% by mass relative to the total mass of the metal material. Examples thereof include stainless steel and nickel-chromium alloys.

[0444] The total content of chromium and nickel in the metal material is preferably 25% by mass or more, more preferably 30% by mass or more, based on the total mass of the metal material.

[0445] The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is usually preferably 90 mass % or less.

[0446] As stainless steel, there is no particular limitation, and known stainless steel can be used. Among them, preferably an alloy containing more than 8% by mass of nickel, more preferably an austenitic stainless steel containing more than 8% by mass of nickel. As austenitic stainless steel, for example, SUS (Steel Use Stainless) 304 (Ni content: 8% by mass, Cr content: 18% by mass), SUS304L (Ni content: 9% by mass, Cr content: 18% by mass), SUS316 (Ni content: 10% by mass, Cr content: 16% by mass), and SUS316L (Ni content: 12% by mass, Cr content: 16% by mass) can be cited.

[0447] The nickel-chromium alloy is not particularly limited, and a known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferred.

[0448] Examples of nickel-chromium alloys include Hastelloy (the same product name below), Monel (the same product name below), and Inconel (the same product name below). More specifically, Hastelloy C-276 (Ni content: 63 mass%, Cr content: 16 mass%), Hastelloy-C (Ni content: 60 mass%, Cr content: 17 mass%), and Hastelloy C-22 (Ni content: 61 mass%, Cr content: 22 mass%) are included.

[0449] Furthermore, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like in addition to the above-mentioned alloys as necessary.

[0450] There is no particular limitation on the method for electrolytically polishing the metal material, and a known method can be used. For example, the method described in paragraphs

[0011] to

[0014] of Japanese Patent Application Laid-Open No. 2015-227501 and paragraphs

[0036] to

[0042] of Japanese Patent Application Laid-Open No. 2008-264929 can be used.

[0451] It is speculated that the chromium content in the passivation layer on the surface of the metal material becomes higher than the chromium content in the parent phase due to electrolytic polishing. Therefore, it is speculated that it is difficult for metal elements to flow into the treatment liquid from the inner wall coated with the electrolytically polished metal material, so that a treatment liquid with reduced specific metal elements can be obtained.

[0452] In addition, the metal material is preferably polished. The polishing method is not particularly limited, and a known method can be used. The size of the abrasive grains used for fine polishing is not particularly limited, and from the viewpoint that the concavity and convexity of the surface of the metal material are more likely to become smaller, preferably less than #400.

[0453] In addition, polishing is preferably performed before electrolytic grinding.

[0454] Furthermore, the metal material may be processed by combining one or more of polishing, pickling, and magnetic fluid polishing in multiple stages by changing the size and number of abrasive grains.

[0455] The inside of these containers is preferably cleaned before filling. The liquid used for cleaning may be appropriately selected according to the application, but is preferably the above-mentioned treatment liquid, a liquid obtained by diluting the above-mentioned treatment liquid, or a liquid containing at least one of the components added to the above-mentioned treatment liquid.

[0456] In order to prevent the change of the components in the treatment liquid during storage, the container can also be replaced with an inert gas (nitrogen or argon, etc.) with a purity of 99.99995% by volume or more. In particular, a gas with a low water content is preferred. In addition, the liquid container can be transported and stored at room temperature, but in order to prevent deterioration, the temperature can also be controlled within the range of -20°C to 20°C.

[0457] [Substrate processing method]

[0458] In a substrate treatment method using a treatment liquid (hereinafter referred to as "the present treatment method"), the treatment liquid is typically used in contact with a substrate having a metal-containing substance as a material containing metal (hereinafter also referred to as "the object to be treated"). In this case, the object to be treated may contain a plurality of metal-containing substances.

[0459] 〔Object to be processed〕

[0460] The object to be processed using the processing liquid is not particularly limited as long as it is a substrate having a substance containing a metal.

[0461] In addition, "on the substrate" in this specification includes, for example, any place on the surface, inside, side, and groove of the substrate. Furthermore, the metal-containing substance on the substrate includes not only the case where the metal-containing substance exists directly on the surface of the substrate, but also the case where the metal-containing substance exists on the substrate through other layers.

[0462] Furthermore, the “substrate” in this specification includes, for example, a semiconductor substrate composed of a single layer and a semiconductor substrate composed of a multilayer.

[0463] In addition, the term "removal target" in this specification refers to at least one selected from metal-containing substances (particularly metal oxide-containing substances) that is present on the substrate and is a target for removal using the processing liquid.

[0464] The metal-containing substance is a material containing a simple substance of a metal (metal atom) as a main component.

[0465] Examples of the metal contained in the metal-containing substance include at least one metal M selected from the group consisting of Cu (copper), Co (cobalt), W (tungsten), Ti (titanium), Ta (tantalum), Ru (ruthenium), Cr (chromium), Hf (hafnium), Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Zr (zirconium), Mo (molybdenum), La (lanthanum) and Ir (iridium).

[0466] The metal-containing substance may be any substance containing a metal (metal atom), and examples thereof include a simple substance of metal M, an alloy containing metal M, an oxide of metal M, a nitride of metal M, and a nitride oxide of metal M.

[0467] As more specific metal-containing substances, there can be mentioned metal-containing substances containing at least one component selected from copper, cobalt, cobalt alloys, tungsten, tungsten alloys, ruthenium, ruthenium alloys, tantalum, tantalum alloys, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium aluminum, titanium, titanium nitride, titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide and yttrium alloys.

[0468] Furthermore, the metal-containing substance may be a mixture containing two or more of these compounds.

[0469] In addition, the oxides, nitrides and oxynitrides may be composite oxides, composite nitrides and composite oxynitrides containing metals. Furthermore, the metal-containing substance may contain: at least one selected from a single metal, an alloy, a metal oxide and a metal nitride; and at least one element selected from carbon, nitrogen, boron and phosphorus as a dopant material.

[0470] The content of metal atoms in the metal-containing substance is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more relative to the total mass of the metal-containing substance. The metal-containing substance may be the metal itself, so the upper limit is 100% by mass.

[0471] When the metal-containing substance contains the above-mentioned dopant, the content of the dopant is preferably 0.1 to 50% by mass, more preferably 10 to 40% by mass, relative to the total mass of the metal-containing substance. In this case, the content of the metal atoms in the metal-containing substance is preferably 30 to 99.9% by mass, more preferably 60 to 90% by mass, relative to the total mass of the metal-containing substance.

[0472] The metal oxide-containing substance is a material containing a metal oxide as a main component.

[0473] Examples of the metal atom constituting the metal oxide contained in the metal oxide-containing substance include the above-mentioned metal M. The metal oxide-containing substance preferably contains an oxide of the metal M, and more preferably contains tungsten oxide (WOx), cobalt oxide (CoOx), or ruthenium oxide (RuOx).

[0474] The substance containing metal oxides may be a mixture containing oxides of two or more metals.

[0475] Furthermore, the substance containing metal oxide may contain a simple substance of the metal and / or a nitride of the metal as long as it contains a metal oxide as a main component.

[0476] The content of the metal oxide in the metal oxide-containing substance is preferably 5% by mass or more, more preferably 20% by mass or more, relative to the total mass of the metal oxide-containing substance. The upper limit is not particularly limited and may be 100% by mass or less.

[0477] The form of the metal-containing substance is not particularly limited, and may be, for example, a film (layer) form, a wiring form, or a particle form.

[0478] The metal-containing substance may be disposed on only one main surface of the substrate or on both main surfaces. Furthermore, the metal-containing substance may be disposed on the entire main surface of the substrate or on a portion of the main surface of the substrate.

[0479] The substrate preferably has a metal-containing substance containing metal M, more preferably has a metal-containing substance (containing at least one metal selected from Cu, Co, W, Ti, Ta and Ru), and further preferably has a metal-containing substance (containing at least one metal selected from Cu, W and Co).

[0480] In particular, the substrate preferably has a film containing copper, a film containing Co, or a film containing W.

[0481] Examples of the copper-containing film include a wiring film composed only of metallic copper (copper wiring film) and a wiring film made of an alloy composed of metallic copper and other metals (copper alloy wiring film).

[0482] Specific examples of the copper alloy wiring film include wiring films made of an alloy consisting of copper and one or more metals selected from Al, Ti, Cr, Mn, Ta, and W. More specifically, there are CuAl alloy wiring films, CuTi alloy wiring films, CuCr alloy wiring films, CuMn alloy wiring films, CuTa alloy wiring films, and CuW alloy wiring films.

[0483] Examples of the film containing Co include a metal film composed only of metal cobalt (Co metal film) and a metal film made of an alloy composed of metal cobalt and other metals (Co alloy metal film).

[0484] Specific examples of the Co alloy metal film include metal films made of an alloy consisting of cobalt and one or more metals selected from Ti, Cr, Fe, Ni, Mo, Pd, Ta, and W. More specifically, CoTi alloy metal films, CoCr alloy metal films, CoFe alloy metal films, CoNi alloy metal films, CoMo alloy metal films, CoPd alloy metal films, CoTa alloy metal films, and CoW alloy metal films are included.

[0485] Among films containing Co, Co metal films are often used as wiring films, and Co alloy metal films are often used as barrier metals.

[0486] Examples of the W-containing film include a metal film composed only of tungsten (W metal film) and a metal film composed of an alloy composed of tungsten and other metals (W alloy metal film). Specific examples of the W alloy metal film include a WTi alloy metal film and a WCo alloy metal film.

[0487] Films containing tungsten are often used as wiring films or barrier metals.

[0488] Examples of the titanium-containing film include a metal film containing an alloy of titanium and other metals such as aluminum and a Ti alloy metal film that may further contain the above-mentioned dopant. Specific examples of the Ti alloy metal film include a TiAl film, a TiAlC film, and a TiAlN film.

[0489] Ti alloy metal films are mostly used for gates and their surrounding structures.

[0490] As a more specific example of the object to be processed, there can be cited a laminate having at least a metal layer, an insulating film, and a metal hard mask in sequence on a substrate. The laminate can also have a hole formed from the surface (opening) of the metal hard mask toward the substrate in a manner that exposes the surface of the metal layer through a dry etching process or the like.

[0491] There is no particular limitation on the method for manufacturing a stack having holes as described above, and a common method is to perform a dry etching process on a pre-processed stack having a substrate, a metal layer, an insulating film and a metal hard mask in sequence using a metal hard mask as a mask, and to etch the insulating film in such a way that the surface of the metal layer is exposed, thereby providing holes that penetrate the metal hard mask and the insulating film.

[0492] In addition, the method for manufacturing the metal hard mask is not particularly limited, and for example, the following method can be cited: first, a metal layer containing a predetermined component is formed on an insulating film, and a resist film having a predetermined pattern is formed thereon. Then, the metal layer is etched using the resist film as a mask, thereby manufacturing a metal hard mask (i.e., a film in which the metal layer is patterned).

[0493] Furthermore, the laminate may have layers other than the above-mentioned layers, for example, an etching stopper film, an antireflection layer, etc. may be mentioned.

[0494] Figure 1 Schematic cross-sectional view showing an example of a laminated body as a processed object is shown in FIG.

[0495] Figure 1 The stacked body 10 shown in the figure has a metal layer 2, an etching stop layer 3, an insulating film 4 and a metal hard mask 5 in this order on a substrate 1, and a hole 6 exposing the metal layer 2 is formed at a predetermined position by a dry etching process or the like. That is, Figure 1 The object to be processed shown is a laminated body which includes a substrate 1, a metal layer 2, an etching stop layer 3, an insulating film 4, and a metal hard mask 5 in order, and includes a hole 6 which penetrates from the surface of the metal layer 2 to the surface of the metal layer 2 at the position of the opening of the metal hard mask 5. The inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a composed of the etching stop layer 3, the insulating film 4, and the metal hard mask 5, and a bottom wall 11b composed of the exposed metal layer 2, and has a dry etching residue 12 attached thereto.

[0496] This processing method can be suitably used for removing the dry etching residue 12. That is, it has excellent removal performance (residue removal property) of the dry etching residue 12 and excellent corrosion resistance to the inner wall 11 (for example, the metal layer 2, etc.) of the object to be processed.

[0497] Furthermore, the above-mentioned substrate cleaning method can be performed on a stacked body that has been subjected to a dry ashing step after a dry etching step.

[0498] Hereinafter, the constituent materials of each layer of the above-mentioned laminate will be described.

[0499] <Metal Hard Mask>

[0500] The metal hard mask preferably contains at least one component selected from copper, cobalt, cobalt alloy, tungsten, tungsten alloy, ruthenium, ruthenium alloy, tantalum, tantalum alloy, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium aluminum, titanium, titanium nitride, titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide and yttrium alloy (preferably YSiOx). In which, x and y are preferably numbers represented by x=1 to 3 and y=1 to 2, respectively.

[0501] Examples of the material of the metal hard mask include TiN, WO 2 , and ZrO 2 .

[0502] <Insulating film>

[0503] The material of the insulating film is not particularly limited, and examples thereof include materials having a dielectric constant k of preferably 3.0 or less, and more preferably 2.6 or less.

[0504] Specific examples of the material of the insulating film include SiOx, SiN, SiOC, and organic polymers such as polyimide.

[0505] The insulating film may be composed of a plurality of films. Examples of the insulating film composed of a plurality of films include an insulating film in which a film containing silicon oxide and a film containing silicon carbide oxide are combined.

[0506] <Etch Stop Layer>

[0507] The material of the etching stop layer is not particularly limited. Specific examples of the material of the etching stop layer include SiN, SiON, SiOCN-based materials, and metal oxides such as AlOx.

[0508] <Metal Layer>

[0509] The material forming the metal layer as a wiring material and / or a plug material is not particularly limited, but preferably contains at least one selected from cobalt, tungsten and copper. Furthermore, the material forming the metal layer may be an alloy of cobalt, tungsten or copper and other metals.

[0510] The metal layer may further contain metals, metal nitrides and / or alloys other than cobalt, tungsten and copper. Examples of metals other than cobalt, tungsten and copper that may be contained in the metal layer include titanium, titanium-tungsten, titanium nitride, tantalum, tantalum compounds, chromium, chromium oxide and aluminum.

[0511] The metal layer may further contain at least one dopant selected from the group consisting of carbon, nitrogen, boron and phosphorus in addition to at least one selected from the group consisting of cobalt, tungsten and copper.

[0512] <Substrate>

[0513] Specific examples of chips constituting the substrate include silicon (Si) chips, silicon carbide (SiC) chips, silicon-containing resin chips (glass epoxy chips), and other chips made of silicon-based materials, gallium phosphide (GaP) chips, gallium arsenide (GaAs) chips, and indium phosphide (InP) chips.

[0514] The silicon wafer may be an n-type silicon wafer doped with pentavalent atoms (e.g., phosphorus (P), arsenic (As), and antimony (Sb)) or a p-type silicon wafer doped with trivalent atoms (e.g., boron (B) and gallium (Ga)). The silicon used in the silicon wafer may be, for example, amorphous silicon, single crystal silicon, polycrystalline silicon, or polycrystalline silicon (polysilicon).

[0515] The above-mentioned processed object may contain various layers and / or structures as desired in addition to the above-mentioned. For example, the substrate may contain metal wiring, a gate electrode, a source electrode, a drain electrode, an insulating layer, a ferromagnetic layer and / or a non-magnetic layer, etc.

[0516] The substrate may contain exposed integrated circuit structures, such as interconnects such as metal wiring and dielectric materials. Examples of metals and alloys used for the interconnects include aluminum, copper-aluminum alloys, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. The substrate may contain a layer of silicon oxide, silicon nitride, silicon carbide, and / or carbon-doped silicon oxide.

[0517] The method for producing the object to be processed is not particularly limited as long as it is a method generally performed in the field.

[0518] As a method for forming the above-mentioned insulating film on a wafer constituting a substrate, for example, there is a method of forming a silicon oxide film by heat treating the wafer constituting the substrate in the presence of oxygen, and then flowing silane and ammonia gas and forming a silicon nitride film by chemical vapor deposition (CVD) method.

[0519] As a method for forming the above-mentioned metal-containing layer on a chip constituting a substrate, for example, there is a method of forming a circuit on a chip having the above-mentioned insulating film by a known method such as a resist, and then forming a metal-containing layer by a method such as gold plating, sputtering, CVD, and molecular beam epitaxy (MBE: Molecular Beam Epitaxy).

[0520] The object to be processed may be a substrate on which an insulating film, a barrier metal and a metal-containing film are provided on a wafer and then subjected to a planarization process such as a CMP process. The CMP process is a process for planarizing the surface of a substrate having a metal-containing film, a barrier metal and an insulating film by a chemical action using a polishing slurry containing polishing particles (abrasive grains) and a composite action of mechanical polishing.

[0521] Impurities such as abrasive grains (such as silicon dioxide and aluminum oxide) used in the CMP process, a polished metal-containing film, and metal impurities (metal residues) derived from barrier metals may remain on the surface of the substrate subjected to the CMP process. These impurities may, for example, cause short circuits between wirings and deteriorate the electrical characteristics of the substrate, so the substrate subjected to the CMP process is subjected to a cleaning process for removing these impurities from the surface.

[0522] As a specific example of a substrate subjected to CMP processing, a substrate subjected to CMP processing described in Journal of Precision Engineering Vol. 84, No. 3, 2018 can be cited, but the present invention is not limited to this.

[0523] [Process A]

[0524] As an example of the present treatment method, there can be mentioned a step A of removing the metal-containing substance on the substrate by bringing the above-mentioned treatment liquid into contact with a treatment object containing the metal-containing substance.

[0525] The treatment liquid used in step A is as described above.

[0526] Furthermore, the substrate having the metal-containing substance as the object to be processed in step A is also as described above.

[0527] The method of bringing the treatment liquid into contact with the treated object is not particularly limited, and examples thereof include a method of immersing the treated object in the treatment liquid placed in a tank, a method of spraying the treatment liquid on a substrate, a method of flowing the treatment liquid over a substrate, or any combination thereof. Among them, a method of immersing a substrate having a metal-containing substance as the treated object in the treatment liquid is preferred.

[0528] In order to further improve the cleaning ability of the treatment liquid, a mechanical stirring method may also be used.

[0529] Examples of the mechanical stirring method include a method of circulating the processing liquid on the substrate, a method of flowing or spraying the processing liquid on the substrate, and a method of stirring the processing liquid with ultrasound or megasonic waves.

[0530] Furthermore, the treatment by immersion may be a batch method in which a plurality of objects to be treated are immersed in a treatment tank for treatment, or may be a single wafer method.

[0531] The treatment time of step A can be adjusted by the method of bringing the treatment liquid into contact with the substrate, the temperature of the treatment liquid, etc. The treatment time (contact time between the treatment liquid and the object to be treated) is not particularly limited, but is preferably 0.25 to 10 minutes, more preferably 0.5 to 2 minutes.

[0532] The temperature of the treatment liquid during treatment is not particularly limited, but the lower limit is preferably 15°C or higher, more preferably 20°C or higher, and further preferably 30°C or higher. The upper limit of the temperature is preferably 80°C or lower, more preferably 75°C or lower, and further preferably 70°C or lower.

[0533] Specific methods of process A include process A1 for etching a wiring arranged on a substrate and composed of a metal-containing substance using a processing liquid, process A2 for removing a film at the outer edge of a substrate arranged with a film composed of a metal-containing substance using a processing liquid, process A3 for removing the metal-containing substance attached to the back side of the substrate arranged with a film composed of a metal-containing substance using a processing liquid, process A4 for removing the metal-containing substance on the substrate after dry etching using a processing liquid, and process A5 for removing the metal-containing substance on the substrate after chemical mechanical polishing using a processing liquid.

[0534] Regarding the above-mentioned steps A1 to A5, the descriptions in paragraphs

[0049] to

[0072] of the specification of International Publication No. 2019 / 138814 can be cited, and these contents are incorporated into this specification.

[0535] 〔Rinsing process〕

[0536] The substrate cleaning method of the present invention may further include, after step A, a step of washing and cleaning the object to be processed with a solvent (hereinafter referred to as "step B").

[0537] Step B is performed continuously with step A, and preferably the step of rinsing with a rinsing solvent (rinsing liquid) for 5 seconds to 5 minutes. Step B can also be performed using the above-mentioned mechanical stirring method.

[0538] Examples of the rinse solvent include deionized (DI: De Ionized) water, methanol, ethanol, isopropanol, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate.

[0539] The solvent of the rinse liquid is preferably DI water, methanol, ethanol, isopropanol or a mixture thereof, and more preferably DI water, isopropanol or a mixture of DI water and isopropanol.

[0540] As a method of bringing the rinse solvent into contact with the object to be processed, the method of bringing the above-mentioned processing liquid into contact with the object to be processed can also be applied in the same manner.

[0541] The temperature of the rinse solvent in step B is preferably 16 to 27°C.

[0542] 〔Drying process〕

[0543] This treatment method may include, after step B, step C of drying the treated object.

[0544] There are no particular restrictions on the drying method, and examples thereof include a rotary drying method, a method of passing a dry gas over the object to be processed, a method of heating the substrate by a heating mechanism such as a hot plate or an infrared lamp, a Marangoni drying method, a Rotagoni drying method, an IPA (isopropyl alcohol) drying method, and any combination thereof.

[0545] The drying time in step C depends on the specific method used, but is preferably 20 seconds to 5 minutes.

[0546] In step C, from the viewpoint of excellent removal of the processing liquid in the SiOx layer, it is preferred to dry the substrate by heating it with a heating mechanism.

[0547] The heating temperature in this case is not particularly limited, but from the viewpoint of achieving a better balance between the removal of the processing liquid in the SiOx layer and the film loss in the Co film and the SiOx layer, it is preferably 50 to 350°C, more preferably greater than 100°C and less than 400°C, and from the viewpoint of achieving better removal of the processing liquid in the Co film and the SiOx layer, it is further preferably 150 to 250°C.

[0548] [Method 2]

[0549] As another aspect of the present treatment method, the following second aspect can be mentioned.

[0550] That is, a method for treating a treated object includes the following steps: step P, performing oxidation treatment on a treated object (substrate) having a metal-containing layer to oxidize the surface of the above-mentioned metal-containing layer to obtain an oxidized metal layer; and step Q, bringing a treatment liquid into contact with the surface of the oxidized metal layer of the treated object formed in the above-mentioned step P to dissolve the above-mentioned metal oxide layer.

[0551] The metal-containing layer is preferably, for example, a metal monomer or alloy. Furthermore, the metal-containing layer preferably contains at least one selected from cobalt, copper, tungsten, titanium and aluminum. That is, as the metal-containing layer, preferably, a cobalt-containing substance (cobalt monomer or cobalt alloy, etc.), a copper-containing substance (monomer or alloy, etc.), a tungsten-containing substance (tungsten monomer or tungsten alloy, etc.), a titanium-containing substance (titanium monomer or titanium alloy, etc.) or an aluminum-containing substance (aluminum monomer or aluminum alloy, etc.), more preferably a tungsten-containing substance.

[0552] The metal oxide layer is a layer formed by oxidizing the surface layer of the metal-containing layer. A part of the surface layer of the metal-containing layer may be the metal oxide layer, or the entire surface layer of the metal-containing layer may be the metal oxide layer.

[0553] The oxidized metal layer is a layer composed of an oxide of a metal monomer or an alloy, preferably a layer composed of cobalt oxide, cobalt alloy oxide, copper oxide, copper alloy oxide, tungsten oxide, tungsten alloy oxide, titanium oxide, titanium alloy oxide, aluminum oxide or aluminum alloy oxide, more preferably a layer composed of tungsten oxide or tungsten alloy oxide, and even more preferably a layer composed of tungsten oxide.

[0554] The thickness of the metal oxide layer is, for example, 1 to 10 atomic layers. The thickness of one atomic layer of the metal and the metal oxide is 1 nm or less (for example, 0.3 to 0.4 nm).

[0555] The metal oxide layer generally has higher solubility in the processing liquid than the metal-containing layer (is easily etched).

[0556] That is, in the second method, the surface of the metal-containing layer is treated as a thin metal oxide layer in step P, and a treatment liquid is used in step Q to remove only the above-mentioned metal oxide layer (and the portion of the metal-containing layer present in the lower layer of the metal oxide layer that can inevitably be dissolved), thereby removing (dissolving) only the extremely thin surface of the metal-containing layer contained in the treated object.

[0557] Furthermore, by repeatedly performing step P and step Q alternately, the etching amount can be controlled with high accuracy.

[0558] As the number of times each step is performed when step P and step Q are performed alternately, for example, step P and step Q are combined as one cycle and performed for 1 to 20 cycles. From the viewpoint of excellent control of the amount of depression, the number of times each step is performed when step P and step Q are performed alternately is preferably 3 cycles or more, and more preferably 5 cycles or more.

[0559] The object to be processed to which the second embodiment can be applied may contain only one metal-containing layer or two or more metal-containing layers. Furthermore, the object to be processed to which the second embodiment can be applied may contain metal-containing layers or metal-containing materials other than the metal-containing layer or the metal oxide layer, and part or all of such metal-containing materials may be removed intentionally or inevitably through steps P and Q.

[0560] Step P is a step of subjecting the object to be treated including the metal-containing layer to oxidation treatment to oxidize the surface layer of the metal-containing layer to obtain an oxidized metal layer.

[0561] The oxidation treatment method is not limited to the method for oxidizing the surface layer of the metal-containing layer to obtain the oxidized metal layer. For example, the above-mentioned object can be subjected to liquid treatment in which an oxidizing liquid is contacted, gas treatment in which an oxidizing gas is contacted (ozone treatment in which the ozone gas described later is contacted with the substrate or heat treatment in oxygen in an oxygen environment, etc.), or plasma treatment using oxygen.

[0562] The oxidation treatment may be carried out alone or in combination of two or more.

[0563] Among them, as the oxidation treatment, it is preferable to perform at least a liquid treatment in which a predetermined oxidizing liquid is brought into contact with the above-mentioned object to be treated.

[0564] The oxidizing liquid may be any liquid that oxidizes the surface of the metal-containing layer. The oxidizing liquid is preferably an oxidizing liquid other than the present treatment liquid.

[0565] The above-mentioned oxidizing liquid is preferably selected from water, hydrogen peroxide solution, a mixed aqueous solution of ammonia and hydrogen peroxide (APM), a mixed aqueous solution of fluoric acid and hydrogen peroxide solution (FPM), a mixed aqueous solution of sulfuric acid and hydrogen peroxide solution (SPM), a mixed aqueous solution of hydrochloric acid and hydrogen peroxide solution (HPM), dissolved oxygen water, ozone dissolved water, perchloric acid and a liquid in nitric acid (hereinafter also recorded as "specific liquid").

[0566] Regarding the composition of the hydrogen peroxide solution, for example, the content of H 2 O 2 is 0.5 to 31% by mass, more preferably 3 to 15% by mass, relative to the total mass of the hydrogen peroxide solution.

[0567] The composition of APM is preferably within the range of, for example, "ammonia water: hydrogen peroxide water: water = 1:1:1" to "ammonia water: hydrogen peroxide water: water = 1:3:45" (mass ratio).

[0568] The composition of FPM is preferably within the range of, for example, "fluoric acid: hydrogen peroxide solution: water = 1:1:1" to "fluoric acid: hydrogen peroxide solution: water = 1:1:200" (mass ratio).

[0569] The composition of SPM is preferably within the range of, for example, "sulfuric acid: hydrogen peroxide solution: water = 3:1:0" to "sulfuric acid: hydrogen peroxide solution: water = 1:1:10" (mass ratio).

[0570] The composition of HPM is preferably within the range of, for example, "hydrochloric acid: hydrogen peroxide solution: water = 1:1:1" to "hydrochloric acid: hydrogen peroxide solution: water = 1:1:30" (mass ratio).

[0571] The description of these preferred composition ratios refers to the composition ratios when ammonia water is 28 mass % ammonia water, hydrofluoric acid is 49 mass % hydrofluoric acid, sulfuric acid is 98 mass % sulfuric acid, hydrochloric acid is 37 mass % hydrochloric acid, and hydrogen peroxide water is 30 mass % hydrogen peroxide water.

[0572] Also, the volume ratio is based on the volume at room temperature.

[0573] The description of [referred to as "A∶B∶C=x∶y∶z" ~ "A∶B∶C=X∶Y∶Z"] as a suitable range indicates that at least one (preferably two, more preferably all) of the ranges of ["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 preferably satisfied.

[0574] The composition of the dissolved oxygen water is, for example, an aqueous solution having an O 2 content of 20 to 500 ppm by mass relative to the total mass of the dissolved oxygen water.

[0575] The composition of the ozone-dissolved water is, for example, an aqueous solution in which the content of O 3 is 1 to 60 ppm by mass based on the total mass of the ozone-dissolved water.

[0576] Perchloric acid is, for example, an aqueous solution in which the content of HClO 4 is 0.001 to 60% by mass relative to the total mass of the solution.

[0577] Nitric acid is, for example, an aqueous solution in which the content of HNO 3 is 0.001 to 60% by mass relative to the total mass of the solution.

[0578] In liquid treatment, there is no particular limitation on the method of bringing the object to be treated into contact with an oxidizing liquid (preferably a specific liquid). Examples include a method of immersing the object to be treated in the oxidizing liquid placed in a tank, a method of spraying the oxidizing liquid on the object to be treated, a method of flowing the oxidizing liquid over the object to be treated, and any combination thereof.

[0579] The contact time between the object to be treated and the oxidizing liquid is, for example, preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes.

[0580] The temperature of the oxidizing liquid is preferably 20 to 75°C, more preferably 20 to 60°C.

[0581] In the gas treatment, examples of the oxidizing gas that comes into contact with the object to be treated include dry air, oxygen, ozone gas, and mixed gases thereof. The oxidizing gas may contain gases other than the above gases.

[0582] In the gas treatment, the oxidizing gas contacting the treated object is preferably oxygen gas or ozone gas. When oxygen gas or ozone gas is contacted with the treated object, it is also preferably contacted in an oxygen atmosphere, an ozone atmosphere, or a mixed gas atmosphere of oxygen and ozone.

[0583] In the gas treatment, a method of heating the object to be treated (for example, heating at 40 to 200° C.) while contacting the object with an oxidizing gas is also preferred.

[0584] Among them, the gas treatment is preferably an ozone treatment in which ozone gas is brought into contact with the object to be treated, or a heat treatment in oxygen in which the object to be treated is heated in an oxygen atmosphere.

[0585] In the above-mentioned ozone treatment, the ozone gas may be brought into contact with the treated object in an ozone environment or in a mixed gas environment of ozone gas and other gases (such as oxygen). Furthermore, the ozone treatment may be a treatment in which the treated object is heated while being brought into contact with the ozone gas.

[0586] In process P (especially when liquid treatment is performed), the object to be treated may contain metal-based materials other than the metal-containing layer that is oxidized by oxidation treatment and the surface layer becomes an oxidized metal layer. Part or all of this metal-based material may also be intentionally or inevitably removed by process P (especially liquid treatment).

[0587] Furthermore, in step P (particularly when liquid treatment is performed), a portion of the metal-containing layer of the object to be treated may be removed intentionally or inevitably.

[0588] Step Q is a method for treating an object to be treated, including the step of bringing the object to be treated obtained in the above step P into contact with a treatment liquid to dissolve the above oxide metal layer.

[0589] The method of bringing the object to be treated into contact with the treatment liquid in step Q is not particularly limited, and examples thereof include the same methods as those for bringing the object to be treated into contact with the oxidizing liquid.

[0590] The contact time between the treatment object and the treatment liquid is, for example, preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes.

[0591] The temperature of the treatment liquid is preferably 20 to 75°C, more preferably 20 to 60°C.

[0592] In step Q, the oxide metal layer may be removed partially or entirely.

[0593] In step Q, a part or the whole of the metal-containing layer (for example, the metal oxide layer covering the surface is removed to expose the metal-containing layer on the surface layer) may be removed intentionally or unavoidably.

[0594] In step Q, the object to be processed may contain other metallic materials in addition to the oxidized metal layer and the metal-containing layer having the oxidized metal layer formed on the surface, and a part or the whole of such metallic materials may be removed intentionally or inevitably.

[0595] Furthermore, when the metal-containing layer and / or the other metal-based material are intentionally not dissolved, it is preferred that the amount of the metal-containing layer and / or the other metal-based material that is inevitably dissolved is small.

[0596] The treatment liquid provided to step Q may be degassed in advance to reduce the amount of dissolved oxygen. The metal-containing layer exposed by removing the oxidized metal layer with the treatment liquid is oxidized by the dissolved oxygen in the treatment liquid to form a new oxidized metal layer, and this oxidized metal layer is further removed by the treatment liquid. As a result, the removal of an excessive amount of the metal-containing layer can be suppressed by reducing the amount of dissolved oxygen in the treatment liquid.

[0597] The processing method can be implemented in combination before or after other steps performed in the method for manufacturing a semiconductor device. The processing method can be incorporated into other steps when implementing the processing method, and the processing method can be incorporated into other steps when implementing the processing method.

[0598] Other processes include, for example, processes for forming structures such as metal wiring, gate structure, source structure, drain structure, insulating layer, ferromagnetic layer and / or non-magnetic layer (layer formation, etching, chemical mechanical polishing, metamorphism, etc.), processes for forming resist, exposure process and removal process, heat treatment process, cleaning process and inspection process, etc.

[0599] The processing method can be performed at any stage of the back end of the line (BEOL), middle of the line (MOL) and front end of the line (FEOL).

[0600] Example

[0601] Below, the present invention is further described in detail based on examples. The materials, usage, ratio, processing content and processing sequence etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. However, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0602] [Raw materials of treatment fluid]

[0603] The following compounds were used to prepare the processing liquid. In addition, each component used in this embodiment was classified as a semiconductor grade component or a compound classified as a high-purity grade corresponding thereto.

[0604] <Copolymer>

[0605] As the copolymer, compounds CP-1 to CP-37 shown in the following Table 1 were used.

[0606] The "Structural Formula" column of Table 1 shows the structural formulas of the corresponding compounds in the following formulas (P-1) to (P-25). The "m" and "n" columns of Table 1 show the ratio (m:n) of the number of moles m of the first repeating unit to the number of moles n of the second repeating unit in each compound. In addition, the composition ratio (molar % ratio) of each repeating unit in the resin is given by 13 C-NMR measurement.

[0607] The “weight average molecular weight Mw” in Table 1 represents the weight average molecular weight of each compound in terms of polystyrene measured by the above-mentioned GPC (gel permeation chromatography) method.

[0608] [Table 1]

[0609] Compound Structural formula m n Weight-average molecular weight Mw CP-1 (P-19) 1 1 60,000 CP-2 (P-19) 2 1 60,000 CP-3 (P-1) 1 1 1,000 CP-4 (P-2) 1 2 15,000 CP-5 (P-20) 1 2 60,000 CP-6 (P-21) 2 1 60,000 CP-7 (P-14) 1 1 5,000 CP-8 (P-22) 1 1 2,000 CP-9 (P-18) 1 2 40,000 CP-10 (P-13) 1 1 3,000 CP-11 (P-15) 2 1 10,000 CP-12 (P-8) 2 1 10,000 CP-13 (P-17) 1 1 150,000 CP-14 (P-16) 2 1 25,000 CP-15 (P-23) 2 1 25,000 CP-16 (P-4) 1 1 15,000 CP-17 (P-5) 1 1 15,000 CP-18 (P-6) 1 1 15,000 CP-19 (P-7) 1 1 2,500 CP-20 (P-8) 2 1 4,000 CP-21 (P-3) 3 1 15,000 CP-22 (P-10) 1 1 100,000 CP-23 (P-10) 2 1 100,000 CP-24 (P-11) 1 1 15,000 CP-25 (P-12) 1 1 12,000 CP-26 (P-7) 2 1 2,000 CP-27 (P-11) 2 1 30,000 CP-28 (P-12) 1 2 15,000 CP-29 (P-12) 1 2 15,000 CP-30 (P-3) 1 1 15,000 CP-31 (P-3) 1 3 15,000 CP-32 (P-3) 1 5 15,000 CP-33 (P-8) 2 1 10,000 CP-34 (P-8) 2 1 15,000 CP-35 (P-9) 2 1 10,000 CP-36 (P-24) 1 1 10,000 CP-37 (P-25) 1 1 10,000

[0610] [Chemical formula 9]

[0611]

[0612] [Chemical formula 10]

[0613]

[0614]

[0615] [Chemical formula 11]

[0616]

[0617]

[0618] In both Compound CP-19 and Compound CP-26, the number of repeating units represented by 1 in Formula (P-7) was an average of 10.5 per repeating unit surrounded by [ ]n.

[0619] Furthermore, in the formula (P-20), X represents an amide group, a nitrile group, an amino hydrochloride group or a formamide group.

[0620] <Water>

[0621] Ultrapure water

[0622] <Removal Agent>

[0623] ·Hydrofluoric acid (equivalent to fluorine-containing compounds.)

[0624] Phosphoric acid (equivalent to inorganic acid.)

[0625] ·TEAH: Tetraethylammonium hydroxide (equivalent to quaternary ammonium compounds.)

[0626] · HAS: Hydroxylamine sulfate ((NH2OH)2H2SO4) (equivalent to hydroxylamine compound.)

[0627] HA: Hydroxylamine (NH2OH) (equivalent to hydroxylamine compound.)

[0628] Cy-DTA: trans-1,2-cyclohexanediaminetetraacetic acid (equivalent to polyaminopolycarboxylic acid.)

[0629] HEDEPO: 1-Hydroxyethylidene-1,1'-diphosphonic acid (equivalent to phosphonic acid.)

[0630] NH4F: Ammonium fluoride (equivalent to fluorine-containing compounds.)

[0631] ·Acetic acid (equivalent to monocarboxylic acid.)

[0632] ·TMAH: Tetramethylammonium hydroxide (equivalent to quaternary ammonium compounds.)

[0633] ·Methanesulfonic acid (equivalent to sulfonic acid.)

[0634] AEEA: 2-(2-aminoethylamino)ethanol (CAS registration number: 111-41-1) (equivalent to alkanolamine.)

[0635] ·Citric acid (equivalent to polycarboxylic acid.)

[0636] ·Isethionic acid (equivalent to sulfonic acid.)

[0637] · Sulfuric acid (equivalent to inorganic acid.)

[0638] DTPA: Diethylenetriaminepentaacetic acid (equivalent to polyaminopolycarboxylic acid.)

[0639] ·TBAH: Tetrabutylammonium hydroxide (equivalent to quaternary ammonium compounds.)

[0640] APDA: N-(3-aminopropyl)diethanolamine (equivalent to alkanolamine.)

[0641] ·Allylamine (equivalent to water-soluble amine.)

[0642] ·Allylglycine (equivalent to amino acid.)

[0643] ·Maleic acid (equivalent to polycarboxylic acid.)

[0644] ·Citraconic acid (equivalent to polycarboxylic acid.)

[0645] Fumaric acid (equivalent to polycarboxylic acid.)

[0646] ·Itaconic acid (equivalent to polycarboxylic acid.)

[0647] <Oxidant>

[0648] ·Nitric acid

[0649] Periodic acid

[0650] Hydrogen peroxide

[0651] Peracetic acid

[0652] <Corrosion Inhibitor>

[0653] 5MBTA: 5-methyl-1H-benzotriazole (corresponding to the compound represented by formula (C))

[0654] ·DBS: Dodecylbenzenesulfonic acid (equivalent to anionic surfactant.)

[0655] <Organic Solvents>

[0656] PG: Propylene glycol

[0657] ·HG: Hexanediol

[0658] Sulfolane

[0659] EGME: Ethylene glycol methyl ether

[0660] EGBE: Ethylene glycol butyl ether

[0661] <Surfactant (anionic surfactant)>

[0662] ·S-1: NIKKOL (registered trademark) Phosten HLP (lauryl phosphoric acid, manufactured by Nikko Chemicals Co., Ltd.)

[0663] ·S-2: NIKKOL Phosten HLP-1 (POE (1) lauryl ether phosphoric acid, manufactured by Nikko Chemicals Co., Ltd.)

[0664] ·S-3: Plysurf (registered trademark) A208B (POE lauryl ether phosphate, manufactured by DKS Co. Ltd.)

[0665] S-4: NIKKOL ECT-3NEX (POE (3) tridecyl ether sodium acetate, manufactured by Nikko Chemicals Co., Ltd.)

[0666] S-5: NIKKOL ECT-7 (POE (7) tridecyl ether acetic acid, manufactured by Nikko Chemicals Co., Ltd.)

[0667] ·S-6: NIKKOL SBL-2A-27 (POE (2) ammonium lauryl ether sulfate, manufactured by Nikko Chemicals Co., Ltd.)

[0668] ·S-7: Takesurf (registered trademark) A-43-NQ (alkyl diphenyl ether disulfonate, manufactured by TAKEMOTO OIL & FAT CO., LTD.)

[0669] <Defoaming agent>

[0670] ·E-1: KM-73A (silicone-based defoaming agent, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0671] · E-2: KA-540 (silicone-based defoaming agent, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0672] · E-3: Surfynol (registered trademark) MD20 (acetylene glycol defoamer, manufactured by Evonic Chemicals)

[0673] ·E-4: BYK-012 (polydimethylsiloxane defoamer, manufactured by BYK-Chemie)

[0674] ·E-5: BYK-014 (polydimethylsiloxane defoamer, manufactured by BYK-Chemie)

[0675] E-6: KS-508 (self-emulsifying silicone defoamer, manufactured by Shin-etsu Astec Co., Ltd.)

[0676] · E-7: KM-85 (emulsion type silicone defoamer, manufactured by Shin-etsu Astec Co., Ltd.)

[0677] ·E-8: Q-23183A (silicone-based defoaming agent, manufactured by Dow Corning Toray Co., Ltd.)

[0678] E-9: SH5510 (emulsion type silicone defoamer, manufactured by Dow Corning Toray Co., Ltd.)

[0679] · E-10: SAG30 (silicone-based defoaming agent, manufactured by ENEOS NUC Corporation)

[0680] ·E-11: BYK-1650 (silicone defoamer, manufactured by BYK-Chemie)

[0681] [Example A]

[0682] 〔Preparation of etching solution〕

[0683] In Examples A-1 to A-11 and Comparative Examples A-1 to A-11, etching solutions were prepared. The method for preparing the etching solution will be described using Example A-1 as an example.

[0684] The compound CP-1, hydrofluoric acid, and ultrapure water were mixed in amounts to give the contents shown in Table 2, and the obtained mixed solution was sufficiently stirred using a stirrer to prepare an etching solution of Example A-1.

[0685] According to the preparation method of the etching solution of Example A-1, etching solutions of Examples A-2 to A-11 and Comparative Examples A-1 to A-11 having the compositions shown in Table 2 were prepared. The contents of the components in each etching solution (all based on mass) are as shown in the table.

[0686] The pH of the treatment solutions prepared in Examples A-1 to A-11 were all within the range of 0-12.

[0687] 〔Evaluation of etching solution〕

[0688] The following tests were performed using the prepared etching solutions of Examples or Comparative Examples.

[0689] <Evaluation of solubility and dissolution selectivity>

[0690] A substrate in which a film composed of tungsten boride (WBx, W:B=4:1 (element ratio)) (WBx film) with a film thickness of 100 nm was stacked and a substrate in which a film composed of tungsten oxide (WOx, W:O=4:1 (element ratio)) (WOx film) with a film thickness of 100 nm was stacked was made, and the prepared substrates were cut into 2×2 cm squares to prepare test samples.

[0691] The obtained test samples were immersed in the etching solution of each example or each comparative example for 10 minutes. The temperature of the etching solution at that time is shown in Table 2.

[0692] Before and after the immersion test, the film thickness of each film was measured using an optical film thickness meter Ellipsometer M-2000 (manufactured by JA Woollam). The dissolution rate of each film when using each etching solution was calculated from the measured film thickness before and after immersion.

[0693] Table 2 shows the calculated dissolution rates of the WBx films.

[0694] In addition, in each of the Examples and Comparative Examples, the ratio of the dissolution rate of the WOx film to the dissolution rate of the WBx film (WOx film / WBx film dissolution rate ratio) was calculated from the dissolution rates of each film obtained by the above method. Based on the calculated dissolution rate ratios, the dissolution selectivity of the WOx film relative to the WBx film was evaluated based on the following evaluation criteria.

[0695] (Evaluation criteria for dissolution selectivity)

[0696] A: The dissolution rate ratio of WOx film / WBx film is 20 or more

[0697] B: The dissolution rate ratio of WOx film / WBx film is 1 or more and less than 20

[0698] C: The dissolution rate ratio of WOx film / WBx film is less than 1

[0699] Table 2 shows the composition of the etching solution in each Example and each Comparative Example and each evaluation result.

[0700] In the table, the "Amount" column indicates the content of the corresponding component (unit: mass %), and the "Amount [ppm]" column indicates the content of the corresponding component (unit: mass ppm).

[0701] [Table 2]

[0702] [Table 2(1)]

[0703]

[0704] [Table 3]

[0705] [Table 2(2)]

[0706]

[0707] From the results in Table 2, it was confirmed that the present treatment solution (etching solution) was excellent in the dissolution selectivity of the WOx film with respect to the WBx film and the corrosion resistance with respect to the WBx film.

[0708] In Examples A-1 to A-11, instead of the WOx film described in Table 2, a film composed of silicon oxide (SiO2), a film composed of aluminum oxide (Al2O3), a Ru film, a film composed of cobalt oxide (CoO), a film composed of copper oxide (CuO), and a film composed of silicon germanium (Si:Ge=75:25 (element ratio)) were used, respectively, and the dissolution selectivity of the etching solutions of Examples A-1 to A-11 was evaluated according to the above method. As a result, it was confirmed that the dissolution selectivity of the etching solutions of Examples A-1 to A-11 for films other than the WOx film with respect to the WBx film was also excellent as in the case of each target film.

[0709] In addition, in Examples A-1 to A-11, instead of the WBx film, a film composed of a tungsten monomer and a film composed of a W-based metal material in which one element selected from carbon, nitrogen and phosphorus was added to tungsten were stacked on a substrate to prepare test samples, and the dissolution rate and dissolution selectivity of the etching solutions of Examples A-1 to A-11 were evaluated according to the above method. As a result, it was confirmed that the etching solutions of Examples A-1 to A-11 had excellent dissolution rates and dissolution selectivities for the film composed of tungsten monomer and the film composed of the W-based metal material containing the above elements, as well as the WBx film.

[0710] [Example B]

[0711] 〔Preparation of cleaning solution〕

[0712] In Examples B-1 to B-66 and Comparative Examples B-1 to B-2, cleaning liquids were prepared. The preparation method of the cleaning liquid will be described using Example B-1 as an example.

[0713] After mixing compound CP-1, hydroxylamine (HA), diethylenetriaminepentaacetic acid (DTPA), tetrabutylammonium hydroxide (TBAH), ethylene glycol butyl ether (EGBE) and ultrapure water in amounts as shown in Table 3, the obtained mixed solution was fully stirred using a stirrer to prepare the cleaning solution of Example B-1.

[0714] According to the preparation method of the cleaning solution of Example B-1, cleaning solutions of Examples B-2 to B-66 and Comparative Examples B-1 to B-2 were prepared respectively having the compositions shown in Table 3. The contents of the components in each cleaning solution (all based on mass) are as shown in the table.

[0715] Table 3 shows the pH values ​​of the cleaning solutions prepared in Examples B-1 to B-66.

[0716] [Evaluation of cleaning fluid]

[0717] The following tests were performed using the prepared cleaning solutions of Examples or Comparative Examples.

[0718] <Evaluation of solubility and dissolution selectivity>

[0719] According to the method described in <Evaluation of solubility> of the above [Example A], substrates in which a Co film composed of cobalt monomer (Co), a W film composed of tungsten monomer (W), a WBx film composed of tungsten boride (WBx), a CoO film composed of cobalt oxide (CoO) or a WOx film composed of tungsten oxide (WOx) were stacked with a film thickness of 100 nm were prepared, and these substrates were cut into square shapes of 2em×2cm to prepare test samples.

[0720] The obtained test samples were immersed in the cleaning solution of each example or each comparative example for 10 minutes. The temperature of the cleaning solution at that time is shown in Table 3.

[0721] Before and after the immersion test, the film thickness of each film was measured using an optical film thickness meter Fllipsometer M-2000 (manufactured by JA Woollam). The dissolution rate of each film when using each cleaning solution was calculated from the measured film thickness before and after immersion.

[0722] Table 3 shows the calculated dissolution rates of the Co film, the W film, and the WBx film.

[0723] In each example and each comparative example, the ratio of the dissolution rate of the WOx film to the dissolution rate of the WBx film was calculated based on the dissolution rate of the WBx film and the dissolution rate of the WOx film obtained by the above method. Based on the calculated dissolution rate ratio, the dissolution selectivity of the WOx film with respect to the WBx film was evaluated based on the following evaluation criteria.

[0724] (Evaluation criteria for dissolution selectivity)

[0725] A: The dissolution rate ratio of WOx film / WBx film is 20 or more

[0726] B: The dissolution rate ratio of WOx film / WBx film is 5 or more and less than 20

[0727] C: The dissolution rate ratio of WOx film / WBx film is greater than 1 and less than 5

[0728] D: The dissolution rate ratio of WOx film / WBx film is less than 1

[0729] In each example and each comparative example, the ratio of the dissolution rate of the CoOx film to the dissolution rate of the Co film was calculated based on the dissolution rate of the Co film and the dissolution rate of the CoOx film obtained by the above method. Based on the calculated dissolution rate ratio, the dissolution selectivity of the CoOx film with respect to the Cox film was evaluated based on the following evaluation criteria.

[0730] (Evaluation criteria for dissolution selectivity)

[0731] A: The dissolution rate ratio of CoOx film / Co film is 20 or more

[0732] B: The dissolution rate ratio of CoOx film / Co film is 5 or more and less than 20

[0733] C: The dissolution rate ratio of CoOx film / Co film is greater than 1 and less than 5

[0734] D: The dissolution rate ratio of CoOx film / Co film is less than 1

[0735] <Evaluation of Residue Removability>

[0736] A stacked body (equivalent to the stacked body before treatment) having a WBx film, a SiO2 film, and a metal hard mask (TiN) having a predetermined opening in sequence on a substrate (Si) was formed. Using the obtained stacked body, dry etching was performed using the metal hard mask as a mask, and the SiO2 film was etched until the WBx film surface was exposed to form a hole, thereby producing Sample 1 (reference Figure 1 ). When the cross section of the laminate was confirmed by a scanning electron microscope (SEM), dry etching residue was observed on the hole wall surface.

[0737] The residue removal property was evaluated by the following procedure. First, the prepared slices of the above-mentioned sample 1 (square shape of about 2.0 cm×2.0 cm) were immersed in each cleaning solution adjusted to 60°C. After 5 minutes from the start of immersion, the slices of sample 1 were taken out, immediately washed with ultrapure water and dried with N2. After that, the surface of the slices of the immersed sample 1 was observed by SEM to confirm the presence or absence of dry etching residue. Similarly, after the slices of sample 1 that had been immersed for 10 minutes were washed with ultrapure water and dried with N2, the surface of the slices was observed by SEM to confirm the presence or absence of dry etching residue.

[0738] Based on the observation results of the slices of each sample 1, the removability of the dry etching residue ("residue removability") was evaluated according to the following criteria.

[0739] (Evaluation criteria for residue removability)

[0740] A: The dry etching residue was completely removed by immersion for 5 minutes.

[0741] B: The dry etching residue was not completely removed by immersion for 5 minutes, but was completely removed by immersion for 10 minutes.

[0742] C: The dry etching residue was not completely removed by immersion for 10 minutes.

[0743] <Evaluation of Residual Rate of Cleaning Liquid after Rinsing>

[0744] The laminate having the WBx membrane was immersed in each cleaning solution of the Example and the Comparative Example according to the method described in the above <Evaluation of Solubility and Dissolution Selectivity>. Then, the laminate having the immersion treatment was immersed in a rinse solution composed of isopropyl alcohol for 0.5 minutes, thereby performing a rinse treatment of the WBx membrane.

[0745] The surface of the WBx film after the rinsing treatment was analyzed by X-ray photoelectron spectroscopy, and the ratio of the number of nitrogen atoms derived from the cleaning solution of each embodiment or comparative example to the number of all atoms on the surface of the WBx film was measured (unit: atom %).

[0746] In addition, the measurement conditions of X-ray photoelectron spectroscopy are shown below.

[0747] (Measurement conditions)

[0748] · Device: Quantera SXMTM manufactured by ULVAC-PHI, INCORPORATED.

[0749] X-ray source: monochromatized Al Kα ray

[0750] X-ray beam diameter: φ200μm

[0751] Signal capture angle: 45°

[0752] Table 3 shows the compositions of the cleaning solutions used in Examples B-1 to B-66 and Comparative Examples B-1 and B-2 and the results of each evaluation.

[0753] In the table, the "Amount" column indicates the content of the corresponding component (unit: mass %), and the "Amount [ppm]" column indicates the content of the corresponding component (unit: mass ppm).

[0754] In addition, "nd" in the "residual rate after washing" column means that the number of nitrogen atoms is below the detection limit (below the detection limit relative to the total number of atoms).

[0755] [Table 4]

[0756] [Table 3(1-1)]

[0757]

[0758] [Table 5]

[0759] [Table 3(1-2)]

[0760]

[0761] [Table 6]

[0762] [Table 3(2-1)]

[0763]

[0764] [Table 7]

[0765] [Table 3(2-2)]

[0766]

[0767] From the results in Table 3, it was confirmed that the cleaning solution of the present invention was excellent in corrosion resistance to the W-containing film, dissolution selectivity of the removal target film in the W-containing film, and solubility of the cleaning solution in the rinse liquid.

[0768] In addition, in Examples B-1 to B-66, a test sample was prepared in which a film composed of a W-based metal material in which one element selected from the group of carbon, nitrogen and phosphorus was added to tungsten and laminated on a substrate, instead of a W film or a WBx film. In addition, the cleaning solutions of Examples B-1 to B-66 were evaluated for dissolution rate, dissolution selectivity, residue removal property and post-rinsing residual rate according to the above method. As a result, it was confirmed that the cleaning solutions of Examples B-1 to B-66 had excellent dissolution rate, dissolution selectivity, residue removal property and post-rinsing residual rate for each film composed of a W-based metal material containing the above-mentioned elements as well as the W film or the WBx film.

[0769] [Example C]

[0770] 〔Preparation of cleaning solution〕

[0771] After mixing compound CP-1, hydroxylamine (HA), diethylenetriaminepentaacetic acid (DTPA), tetrabutylammonium hydroxide (TBAH), 5-methyl-1H-benzotriazole (5MBTA), ethylene glycol butyl ether (EGBE), surfactant S-1 and ultrapure water in amounts as shown in Table 4, the obtained mixed solution was fully stirred using a stirrer to prepare the cleaning solution of Example C-1.

[0772] According to the preparation method of the cleaning solution of Example C-1, cleaning solutions of Examples C-2 to C-7 having the compositions shown in Table 4 were prepared. The contents of the components in the cleaning solutions (all based on mass) are as shown in the table.

[0773] Table 4 shows the pH values ​​of the cleaning solutions prepared in Examples C-1 to C-7.

[0774] [Evaluation of cleaning fluid]

[0775] According to the method described in <Evaluation of Solubility> of [Example A], substrates each consisting of a Co film, a W film, a WBx film, a CoO film and a TiAlC film composed of titanium aluminum carbide (TiAlC) and stacked with a film thickness of 100 nm were prepared, and these substrates were cut into a square shape of 2 cm×2 cm to prepare test samples.

[0776] Next, according to the method described in <Evaluation of Solubility and Dissolution Selectivity> of [Example B], an evaluation test of the solubility of various films such as Co film, W film, WBx film and TiAlC film was carried out using the prepared cleaning solutions of Examples C-1 to C-7 and Example B-36 (for reference).

[0777] Table 4 shows the calculated dissolution rates (A / min) of the Co film, the W film, the WBx film, and the TiAlC film.

[0778] In addition, according to the methods described in <Evaluation of solubility and dissolution selectivity>, <Evaluation of residue removability> and <Evaluation of residual rate of cleaning liquid after rinsing> of [Example B], evaluation tests of dissolution selectivity, residue removability and residual rate after rinsing were carried out on each cleaning liquid of Examples C-1 to C-7.

[0779] Table 4 shows the compositions of the cleaning solutions of Examples C-1 to C-7 and Example B-36 (for reference) and the results of each evaluation.

[0780] [Table 8]

[0781] [Table 4(1)]

[0782]

[0783] [Table 9]

[0784] [Table 4(2)]

[0785]

[0786] From the results in Table 4, it is confirmed that the cleaning solutions of Examples C-1 to C-7 of the present invention are as excellent as those of the cleaning solution B-36 in terms of corrosion resistance to W-containing films, dissolution selectivity of the removal target film in the W-containing film, removal performance of dry etching residues (residue removability), and solubility of the cleaning solution in the rinse solution.

[0787] Furthermore, it was confirmed that when the cleaning liquid contained a surfactant, the corrosion resistance of the TiAlC film was superior to that when the cleaning liquid did not contain a surfactant (comparison between Examples C-1 to C-7 and Example B-36).

[0788] Among them, it was confirmed that when the cleaning liquid contained a phosphate ester surfactant or a carboxylic acid surfactant, the corrosion resistance of the TiAlC film was better, and when the cleaning liquid contained a phosphate ester surfactant, the corrosion resistance of the TiAlC film was particularly excellent (comparison of Examples C-1 to C-7).

[0789] In addition, a test sample was prepared in which a film composed of a W-based metal material in which one element selected from the group of carbon, nitrogen and phosphorus was added to tungsten and laminated on a substrate, instead of a W film or a WBx film. In addition, the dissolution rate, dissolution selectivity, residue removal property and post-rinsing residual rate of the cleaning solutions of Examples C-1 to C-7 were evaluated according to the above method. As a result, it was confirmed that the dissolution rate, dissolution selectivity, residue removal property and post-rinsing residual rate of the cleaning solutions of Examples C-1 to C-7 were excellent for the films composed of the W-based metal material containing the above-mentioned elements, as well as when applied to the W film or the WBx film.

[0790] [Example D]

[0791] 〔Preparation of cleaning solution〕

[0792] After mixing compound CP-1, hydroxylamine (HA), diethylenetriaminepentaacetic acid (DTPA), tetrabutylammonium hydroxide (TBAH), allylamine, maleic acid, 5-methyl-1H-benzotriazole (5MBTA), ethylene glycol butyl ether (EGBE) and ultrapure water in amounts as shown in Table 5, the obtained mixed solution was fully stirred using a stirrer to prepare the cleaning solution of Example D-1.

[0793] According to the preparation method of the cleaning solution of Example D-1, cleaning solutions of Examples D-2 to D-34 having the compositions shown in Table 5 were prepared. The contents of the components in the cleaning solutions (all based on mass) are as shown in the table.

[0794] Table 5 shows the pH values ​​of the cleaning solutions prepared in Examples D-1 to D-34.

[0795] [Evaluation of cleaning fluid]

[0796] According to the methods described in <Evaluation of solubility and dissolution selectivity>, <Evaluation of residue removability> and <Evaluation of residual rate of cleaning solution after rinsing> of [Example B], the solubility, dissolution selectivity, residue removability and residual rate after rinsing of each membrane such as Co film, W film and WBx film were evaluated by the cleaning solutions of Examples D-1 to D-34.

[0797] Table 5 shows the compositions of the cleaning solutions of Examples D-1 to D-34 and the results of each evaluation.

[0798] [Table 10]

[0799] [Table 5(1)]

[0800]

[0801] [Table 11]

[0802] [Table 5(2)]

[0803]

[0804] [Table 12]

[0805] [Table 5(3)]

[0806]

[0807] From the results in Table 5, it was confirmed that the cleaning solutions of Examples D-1 to D-34 of the present invention were excellent in corrosion resistance to W-containing films, dissolution selectivity of the removal target film in the W-containing film, and solubility of the cleaning solutions in rinse solutions.

[0808] Furthermore, it was confirmed that when the cleaning liquid contained a water-soluble amine, amino acid or polycarboxylic acid as a removing agent, the removal performance of the dry etching residue was further improved (for example, comparison between Examples D-2 to D-6 and Examples B-20 to B-24).

[0809] In addition, a test sample was prepared in which a film composed of a W-based metal material in which one element selected from the group of carbon, nitrogen and phosphorus was added to tungsten and laminated on a substrate, instead of a W film or a WBx film. In addition, the cleaning solutions of Examples D-1 to D-34 were evaluated for dissolution rate, dissolution selectivity, residue removal property and residual rate after rinsing according to the above method. As a result, it was confirmed that the cleaning solutions of Examples D-1 to D-34 were excellent in dissolution rate, dissolution selectivity, residue removal property and residual rate after rinsing for each film composed of a W-based metal material containing the above-mentioned elements as well as when applied to a W film or a WBx film.

[0810] [Example E]

[0811] 〔Preparation of cleaning solution〕

[0812] After mixing compound CP-27, hydroxylamine (HA), diethylenetriaminepentaacetic acid (DTPA), tetrabutylammonium hydroxide (TBAH), 5-methyl-1H-benzotriazole (5MBTA), ethylene glycol butyl ether (EGBE), surfactant S-4, defoaming agent E-1 and ultrapure water in amounts as shown in Table 6, the obtained mixed solution was fully stirred using a stirrer to prepare the cleaning solution of Example E-1.

[0813] According to the preparation method of the cleaning solution of Example E-1, cleaning solutions of Examples E-2 to E-15 having the compositions shown in Table 6 were prepared. The contents of the components in the cleaning solutions (all based on mass) are as shown in the table.

[0814] Table 6 shows the pH values ​​of the cleaning solutions prepared in Examples E-1 to E-15.

[0815] [Evaluation of cleaning fluid]

[0816] According to the method described in <Evaluation of solubility and dissolution selectivity> of [Example B], the solubility evaluation test of each film such as Co film, W film, WBx film and TiAlC film was carried out using each cleaning solution prepared in Examples E-1 to E-15. The calculated dissolution rates (A / min) of each Co film, W film, WBx film and TiAlC film are shown in Table 6.

[0817] In addition, according to the methods described in <Evaluation of solubility and dissolution selectivity>, <Evaluation of residue removability> and <Evaluation of residual rate of cleaning liquid after rinsing> of [Example B], evaluation tests of dissolution selectivity, residue removability and residual rate after rinsing were carried out on each cleaning liquid of Examples E-1 to E-15.

[0818] <Evaluation of Foaming of Cleaning Liquid>

[0819] 70 g of each of the cleaning solutions of Examples E-1 to E-15 and C-4 were filled into 150 mL transparent glass bottles (wide-mouth standard glass bottles PS-No.12), and the transparent glass bottles filled with the cleaning solutions were stirred at 250 rpm for 5 minutes using a vibrator. The height of the bubbles from the liquid surface immediately after the stirring was stopped was recorded (unit: cm).

[0820] The lower the height of the bubbles, the more effective it is to suppress the remaining bubbles in the cleaning liquid.

[0821] Table 6 shows the composition of each cleaning solution of Examples E-1 to E-15 and Example C-4 (for reference) and each evaluation result.

[0822] [Table 13]

[0823] [Table 6(1)]

[0824]

[0825] [Table 14]

[0826] [Table 6(2)]

[0827]

[0828] From the results in Table 4, it was confirmed that the cleaning solutions of Examples E-1 to E-15 were excellent in corrosion resistance to W-containing films, dissolution selectivity of the removal target film in the W-containing film, dry etching residue removal performance (residue removal performance), and solubility of the cleaning solutions in rinse solutions.

[0829] Furthermore, it was confirmed that when the cleaning liquid contained a defoaming agent, the remaining bubbles could be suppressed compared to the case where the cleaning liquid did not contain a defoaming agent (comparison between Examples E-1 to E-15 and Example C-4).

[0830] Among them, it was confirmed that when the cleaning liquid contained a silicone-based defoaming agent having a high molecular weight (defoaming agents E-1 and E-2, etc.), the effect of suppressing the remaining bubbles was more excellent (comparison of Examples E-1 to E-15).

[0831] In addition, a test sample was prepared in which a film composed of a W-based metal material in which one element selected from the group of carbon, nitrogen and phosphorus was added to tungsten and laminated on a substrate, instead of a W film or a WBx film. In addition, the cleaning solutions of Examples E-1 to E-15 were evaluated for dissolution rate, dissolution selectivity, residue removal property and residual rate after rinsing according to the above method. As a result, it was confirmed that the cleaning solutions of Examples E-1 to E-15 were excellent in dissolution rate, dissolution selectivity, residue removal property and residual rate after rinsing for each film composed of a W-based metal material containing the above-mentioned elements as well as when applied to a W film or a WBx film.

[0832] Explanation of symbols

[0833] 1-substrate, 2-metal layer, 3-etching stop layer, 4-insulating film, 5-metal hard mask, 6-hole, 10-laminated body, 11-inner wall, 11a-cross-sectional wall, 11b-bottom wall, 12-dry etching residue.< / ph>

Claims

1. A processing liquid, which is a processing liquid for semiconductor devices, The treatment solution contains: water; removers; and Resin, The resin has a first repeating unit and a second repeating unit different from the first repeating unit, wherein the first repeating unit has at least one selected from a primary amino group, a secondary amino group, a tertiary amino group and a quaternary ammonium cation, The second repeating unit includes a repeating unit represented by the following formula (2a), and the content of the second repeating unit is 5 mol % to 95 mol % relative to all the repeating units in the resin. The resin has a ratio m:n of the number of moles m of the first repeating unit to the number of moles n of the second repeating unit of 5:1 to 1:5, The weight average molecular weight of the resin is 5000 to 150000, The content of the resin is 1 ppm by mass to 500 ppm by mass relative to the total mass of the treatment liquid. The content of water is 10% to 98% by mass relative to the total mass of the treatment liquid. The remover is selected from at least one of a fluorine-containing compound, a hydroxylamine compound, an alkaline compound, and an acidic compound, and the content of the remover is 0.005 mass % to 90 mass % relative to the total mass of the treatment liquid. In formula (2a), A 21 , A 22 and A 23 Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or -L2-X 21 , X 21 represents a hydrophilic group, wherein the hydrophilic group is a group selected from hydroxyl, carboxyl, primary amino, secondary amino, tertiary amino, amide, polyoxyalkylene, sulfonic and sulfonyl groups, L2 represents a single bond or a divalent linking group, when X 21 When there are two or more L2, they may be the same or different.

2. The treatment liquid according to claim 1, wherein The first repeating unit has a primary amino group.

3. The treatment liquid according to claim 1 or 2, wherein The resin has at least one skeleton structure selected from the group consisting of the following formulae (P-1), (P-3) to (P-12), and (P-16), In formulas (P-1), (P-3) to (P-12), and (P-16), the ratio m:n of the number of moles m of the first repeating unit to the number of moles n of the second repeating unit is 5:1 to 1:5, In formula (P-7), l represents an integer of 1 to 30.

4. The treatment liquid according to claim 1 or 2, wherein The remover contains at least one selected from hydrofluoric acid, ammonium fluoride, tetramethylammonium fluoride, hydroxylamine compounds, ammonium hydroxide, water-soluble amines, quaternary ammonium compounds, sulfuric acid, hydrochloric acid, phosphoric acid, carboxylic acid, sulfonic acid and phosphonic acid.

5. The treatment liquid according to claim 1 or 2, wherein The remover contains a water-soluble amine and at least one organic acid selected from carboxylic acid, sulfonic acid and phosphonic acid.

6. The treatment liquid according to claim 5, wherein The water-soluble amine is at least one selected from methylamine, ethylamine, propylamine, butylamine, pentylamine, methoxyethylamine, methoxypropylamine, 2-amino-2-methyl-1-propanol and allylamine, The organic acid is at least one selected from acetic acid, propionic acid, methanesulfonic acid, ethanesulfonic acid, allylglycine, maleic acid, citraconic acid, fumaric acid and itaconic acid. The treatment liquid according to claim 1 or 2, further comprising an oxidizing agent.

8. The treatment liquid according to claim 7, wherein The oxidant contains at least one selected from the group consisting of hydrogen peroxide, nitric acid, peracetic acid, periodic acid, perchloric acid, chloric acid, hypochlorous acid, cerium ammonium nitrate, ferric nitrate and ammonium persulfate.

9. The treatment liquid according to claim 1 or 2, further comprising a corrosion inhibitor.

10. The treatment liquid according to claim 9, wherein The corrosion inhibitor contains at least one compound selected from the group consisting of a compound represented by the following formula (A), a compound represented by the following formula (B), a compound represented by the following formula (C), and a substituted or unsubstituted tetrazole. In formula (A), R 1A ~R 5A Each independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amino group, wherein the structure contains at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, and a substituted or unsubstituted amino group, In formula (B), R 1B ~R 4B Each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, In formula (C), R 1C , R 2C and R N Each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and R 1C With R 2C They are optionally bonded to form a ring. The treatment liquid according to claim 1 or 2, further comprising a surfactant.

12. The treatment liquid according to claim 11, wherein The surfactant is at least one selected from the group consisting of a phosphate surfactant, a carboxylic acid surfactant, a sulfonic acid surfactant, and a sulfate surfactant.

13. The treatment liquid according to claim 12, wherein The phosphate ester surfactant is at least one selected from alkyl phosphates or salts thereof, monooxyalkyl ether phosphates or salts thereof, and polyoxyalkyl ether phosphates or salts thereof.

14. The treatment liquid according to claim 12, wherein The carboxylic acid surfactant is a polyoxyalkylene alkyl ether carboxylic acid.

15. The treatment liquid according to claim 12, wherein The sulfonic acid surfactant is alkyl diphenyl ether disulfonic acid, and the sulfate surfactant is polyoxyalkylene ether sulfate or its salt.

16. The treatment liquid according to claim 1 or 2, further comprising an organic solvent.

17. The treatment liquid according to claim 1 or 2, further comprising a defoaming agent.

18. The treatment liquid according to claim 17, wherein The defoaming agent is a silicone defoaming agent.

19. The treatment liquid according to claim 1 or 2, wherein: The treatment liquid is a substrate treatment liquid containing a metal-containing substance, The metal-containing substance contains at least one component selected from copper, cobalt, cobalt alloys, tungsten, tungsten alloys, ruthenium, ruthenium alloys, tantalum, tantalum alloys, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium aluminum, titanium, titanium nitride, titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide and yttrium alloys.

20. The treatment liquid according to claim 1 or 2, wherein: It is used as a cleaning solution for removing etching residues, a solution for removing a resist film used in pattern formation, and a cleaning solution or etching solution for removing residues from a substrate after chemical mechanical polishing.

21. A method for processing a substrate, comprising: A step A of removing a metal-containing substance on a substrate using the processing liquid according to any one of claims 1 to 19.

22. The method for treating a substrate according to claim 21, further comprising: After the step A, a step C is performed in which the substrate obtained in the step A is rinsed using a rinse liquid.

23. A method for treating a substrate, wherein the method treats a substrate having a metal-containing layer on the surface, the method comprising: Step P, subjecting the surface of the substrate to liquid treatment, ozone treatment in which ozone gas is brought into contact with the substrate, heat treatment of the substrate in an oxygen environment, or plasma treatment of the substrate using oxygen, wherein the liquid treatment is a treatment in which a chemical solution selected from water, hydrogen peroxide solution, a mixed aqueous solution of ammonia water and hydrogen peroxide solution, a mixed aqueous solution of fluoric acid and hydrogen peroxide solution, a mixed aqueous solution of sulfuric acid and hydrogen peroxide solution, a mixed aqueous solution of hydrochloric acid and hydrogen peroxide solution, dissolved oxygen water, and ozone-dissolved water is brought into contact with the surface of the substrate to oxidize the surface layer of the metal-containing layer to form an oxidized metal layer; and In step Q, the processing liquid according to any one of claims 1 to 19 is brought into contact with the surface of the metal oxide layer formed in step P to remove the metal oxide layer. The processing method according to claim 23 , wherein the step P and the step Q are repeatedly performed.

25. The processing method according to claim 23 or 24, wherein: The metal-containing layer contains at least one selected from the group consisting of cobalt, copper, tungsten, titanium, and aluminum.

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