Treatment liquid and method for treating object to be treated

Abstract

Provided is a treatment liquid having excellent organic residue removal properties and excellent stability. Also provided is a method for treating an object to be treated using the treatment liquid. The treatment liquid contains water, hydroxylamine, and one or more hydrazine compounds selected from the group consisting of hydrazine, hydrazine salts, and hydrazine derivatives, and the total hydrazine compound content is 1 part by mass or less per 100 parts by mass of hydroxylamine.

Description

[0001] This application is a divisional application of the application number 202080092116.6 filed by the applicant and entitled “Method for treating a treatment liquid and a treated object.” The filing date of the parent application is December 24, 2020, and the priority date is January 28, 2020. Technical Field

[0002] The present invention relates to a treatment liquid and a treatment method for a treated object. Background Art

[0003] As semiconductor devices become increasingly miniaturized, there is a growing demand for performing processes such as etching and cleaning efficiently and accurately using processing liquids used in the semiconductor device manufacturing process.

[0004] For example, Patent Document 1 discloses a cleaning composition, etc., characterized by containing N-hydroxyformamide.

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2004-101849 Summary of the Invention

[0008] Technical issues to be solved by the invention

[0009] Research is underway on technologies for treating an object to be treated, such as a substrate, using a treatment liquid.

[0010] The processing liquid used for treating such a treatment object is required to have, for example, excellent removal properties of organic residues generated by prior treatment of the treatment object (such as dry etching) (hereinafter referred to as "excellent organic residue removal properties"). Furthermore, the processing liquid is required to maintain certain performance even over time and to have excellent stability.

[0011] In view of the above circumstances, an object of the present invention is to provide a treatment liquid having excellent organic residue removal performance and excellent stability.

[0012] Furthermore, another object of the present invention is to provide a method for treating an object using the above-mentioned treatment liquid.

[0013] Means for solving technical problems

[0014] The present inventors conducted intensive studies to solve the above-mentioned problems and found that the above-mentioned problems can be solved by the following configuration.

[0015] [1]

[0016] A treatment fluid comprising:

[0017] water;

[0018] Hydroxylamine; and

[0019] One or more hydrazines selected from hydrazine, hydrazine salts and hydrazine derivatives,

[0020] The total content of the hydrazines is 1 part by mass or less relative to 100 parts by mass of the hydroxylamine.

[0021] [2]

[0022] The treatment liquid according to [1], wherein

[0023] The total content of the hydrazines is 0.0001 parts by mass or more relative to 100 parts by mass of the hydroxylamine.

[0024] 〔3〕

[0025] The treatment liquid according to [1] or [2], wherein

[0026] The total content of the hydrazines is 0.005 to 0.5 parts by mass relative to 100 parts by mass of the hydroxylamine.

[0027] [4]

[0028] The treatment liquid according to any one of [1] to [3], wherein

[0029] The hydrazine derivative is one or more selected from the group consisting of compounds represented by the general formula (A), compounds represented by the general formula (B), compounds having a pyrazole ring, and salts thereof.

[0030] H2N-NR N 2 (A)

[0031] H2N-N=X (B)

[0032] In the general formula (A), two R N Each independently represents a hydrogen atom or a substituent, and the two R N can be bonded to each other to form a ring, wherein two R N At least one of them is not a hydrogen atom,

[0033] In the general formula (B), X represents a divalent group.

[0034] 〔5〕

[0035] The treatment liquid according to any one of [1] to [4], wherein

[0036] The above-mentioned hydrazines contain hydrazine.

[0037] [6]

[0038] The treatment liquid according to any one of [1] to [5], further comprising a - 、NO2 - and NO3 - One or more first anions.

[0039] [7]

[0040] The treatment liquid according to [6] contains Cl - 、NO2 - and NO3 - The three types of the above-mentioned first anions are constituted.

[0041] 〔8〕

[0042] The treatment liquid according to [6] or [7], wherein

[0043] The total content of the first anion is 0.0001 to 30 parts by mass relative to 100 parts by mass of the hydroxylamine.

[0044] 〔9〕

[0045] The treatment liquid according to any one of [6] to [8] further contains SO4 2- and PO4 3- One or more second anions in

[0046] The total content of the first anion and the second anion is 0.0001 to 30 parts by mass relative to 100 parts by mass of the hydroxylamine.

[0047]

[10]

[0048] The treatment liquid according to any one of [6] to [9], wherein

[0049] NO2 - and NO3 - The total mass of Cl - Contains quality.

[0050]

[11]

[0051] The treatment liquid according to any one of [1] to

[10] , further comprising a chelating agent.

[0052]

[12]

[0053] The treatment liquid according to

[11] , wherein

[0054] The chelating agent contains a functional group selected from the group consisting of a carboxylic acid group, a phosphonic acid group, and a sulfonic acid group.

[0055]

[13]

[0056] The treatment liquid according to

[11] or

[12] , wherein

[0057] The chelating agent is one or more selected from diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, oxalic acid, malonic acid, succinic acid, citric acid, methanesulfonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and nitrilotrimethylenephosphonic acid.

[0058]

[14]

[0059] The treatment liquid according to any one of [1] to

[13] , further comprising an antiseptic.

[0060]

[15]

[0061] The treatment liquid according to

[14] , wherein

[0062] The above-mentioned preservative is a benzotriazole.

[0063]

[16]

[0064] The treatment liquid according to

[15] , wherein

[0065] The benzotriazoles are benzotriazoles which may be substituted with one or more substituents selected from an alkyl group which may be substituted, an aryl group which may be substituted, a halogen atom, an amino group which may be substituted, a nitro group, an alkoxy group which may be substituted, and a hydroxyl group.

[0066]

[17]

[0067] The treatment liquid according to

[14] , wherein

[0068] The preservative is selected from benzotriazole, 5-aminotetrazolyl, 1-hydroxybenzotriazole, 5-phenylmercapto-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphtholtriazole, 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, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole, One or more of propylbenzotriazole, 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.

[0069]

[18]

[0070] The treatment liquid according to any one of [1] to

[17] , further comprising one or more organic solvents selected from alcohol solvents, ketone solvents, ester solvents, and ether solvents.

[0071]

[19]

[0072] The treatment liquid according to any one of [1] to

[18] , wherein the pH thereof is 6 to 11.

[0073] 〔20〕

[0074] The treatment liquid according to any one of [1] to

[19] is used for a treatment object containing a cobalt-containing substance containing cobalt atoms and a metal-containing substance containing metal atoms other than cobalt atoms.

[0075] 〔twenty one〕

[0076] The treatment liquid according to

[20] , wherein

[0077] The cobalt-containing substance is cobalt monomer, cobalt alloy, cobalt oxide or cobalt nitride.

[0078] 〔twenty two〕

[0079] A method for treating an object to be treated, wherein:

[0080] A treatment object containing a cobalt-containing substance containing cobalt atoms is brought into contact with the treatment solution described in any one of [1] to

[21] to dissolve the cobalt-containing substance.

[0081] 〔twenty three〕

[0082] A method for treating an object to be treated, comprising:

[0083] Step A: subjecting a workpiece containing a metal layer to a treatment to oxidize a surface of the metal layer to form a metal oxide layer, the treatment comprising:

[0084] Liquid treatment in contact with a solution selected from water, hydrogen peroxide solution, a mixed aqueous solution of ammonia and hydrogen peroxide solution, a mixed aqueous solution of hydrofluoric 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, oxygen-dissolved water, and ozone-dissolved water,

[0085] Ozone treatment in contact with ozone gas,

[0086] Heat treatment in oxygen atmosphere, or

[0087] Plasma treatment using oxygen; and

[0088] In step B, the object to be treated obtained in step A is brought into contact with the treatment solution described in any one of [1] to

[19] to dissolve the metal oxide layer.

[0089] 〔twenty four〕

[0090] The method for processing an object to be processed according to

[23] , wherein:

[0091] The above-mentioned step A and the above-mentioned step B are repeated alternately.

[0092] 〔25〕

[0093] The method for treating an object to be treated according to

[23] or

[24] , wherein:

[0094] The metal layer is composed of a cobalt-containing substance that is cobalt alone or a cobalt alloy.

[0095] 〔26〕

[0096] A method for treating an object to be treated, wherein:

[0097] After dry etching is performed on the workpiece containing metal materials,

[0098] The above-mentioned object to be processed is brought into contact with the processing liquid described in any one of [1] to

[19] to remove dry etching residue.

[0099] 〔27〕

[0100] The method for treating an object to be treated according to

[26] , wherein:

[0101] The above-mentioned metal-based material is a cobalt-containing substance containing cobalt atoms.

[0102] Effects of the Invention

[0103] According to the present invention, a treatment liquid having excellent organic residue removal performance and excellent stability can be provided.

[0104] Furthermore, according to the present invention, a method for treating an object to be treated using the above-mentioned treatment liquid can also be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0105] Figure 1 It is a cross-sectional view showing one embodiment of a processed object.

[0106] Figure 2 It is a cross-sectional view showing another embodiment of the object to be processed.

[0107] Figure 3 This is a schematic cross-sectional view showing an example of a laminate that can be applied to the method for treating an object to be treated according to one embodiment of the present invention. DETAILED DESCRIPTION

[0108] Hereinafter, the present invention will be described in detail.

[0109] Although the description of the constituent elements described below may be made based on representative embodiments of the present invention, the present invention is not limited to such embodiments.

[0110] In addition, in this specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0111] Also, in the present invention, "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 )”.

[0112] In this specification, "room temperature" means "25°C".

[0113] [Processing liquid]

[0114] The treatment liquid of the present invention contains water, hydroxylamine, and one or more hydrazines selected from hydrazine, hydrazine salts, and hydrazine derivatives, wherein the content of the hydrazine is 1 part by mass or less relative to 100 parts by mass of hydroxylamine.

[0115] The mechanism by which the above-mentioned problems are solved by adopting the processing liquid having such a structure is not necessarily clear, but the present inventors believe it to be as follows.

[0116] That is, the treatment liquid of the present invention contains both hydroxylamine and hydrazines in water. Hydrazines have more nitrogen atoms than hydroxylamine, and the number of unshared electron pairs possessed by nitrogen atoms is greater than that of hydroxylamine. It is speculated that hydrazines have a suitably abundant number of unshared electron pairs on nitrogen, so that when coexisting with hydroxylamine, hydrazines and / or hydroxylamine can appropriately interact with organic matter, enabling the treatment liquid to achieve excellent organic residue removal properties. Furthermore, it is speculated that since the hydrazines content is below a specified amount, the decomposition of hydroxylamine that may occur during storage of the treatment liquid is suppressed, contributing to the excellent stability of the treatment liquid.

[0117] Furthermore, when the treatment liquid of the present invention contains anions of a specified type and amount, the object to be treated can further have excellent removal properties of residues containing metal as the main component (hereinafter referred to as "metal residue removal properties of the treatment liquid") and / or the surface smoothness of metal-containing substances (cobalt-containing substances, etc.) that the object to be treated can contain after treatment (hereinafter referred to as "smoothness of the object to be treated").

[0118] Hereinafter, regarding the treatment liquid of the present invention, cases in which the organic residue removal performance is better, the stability is better, the metal residue removal performance is better, and / or the smoothness of the treated object is better will be referred to as "the treatment liquid has better effects."

[0119] Hereinafter, the components contained in the treatment liquid of the present invention will be described in detail.

[0120] <Water>

[0121] The treatment liquid contains water.

[0122] Water is not particularly limited, and examples thereof include distilled water, ion-exchanged water, and pure water.

[0123] The water content in the treatment liquid is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more relative to the total mass of the treatment liquid. The upper limit is less than 100% by mass.

[0124] <Hydroxyamine>

[0125] The treatment solution contains hydroxylamine (NH2OH).

[0126] Hydroxylamine can be ionized in the treatment solution.

[0127] The content of the hydroxylamine compound is not particularly limited, but is preferably 0.001 to 25% by mass relative to the total mass of the treatment liquid in order to achieve a more excellent effect of the treatment liquid.

[0128] When the content of hydroxylamine is 0.001% by mass or more relative to the total mass of the treatment liquid, the cleaning properties of the treatment liquid are further improved, and when it is 25% by mass or less, the smoothness of the treated object is further improved.

[0129] From the viewpoint of excellent balance in the performance of the treatment liquid, the content of hydroxylamine is, for example, preferably 0.05 to 15 mass %, more preferably 0.1 to 10 mass %, and even more preferably 0.5 to 8 mass % relative to the total mass of the treatment liquid.

[0130] The hydroxylamine content in the treatment liquid can be measured by ion chromatography (Dionex ICS-2100 manufactured by Thermo Fisher Scientific K.K., etc.).

[0131] Furthermore, when the components and blending of the raw materials used in the preparation of the treatment liquid are known, the value can be determined by calculation based on the blending amounts.

[0132] <Hydrazines>

[0133] The treatment liquid contains one or more hydrazines selected from the group consisting of hydrazine, hydrazine salts (salts of hydrazine), and hydrazine derivatives (derivatives of hydrazine).

[0134] The hydrazine derivative may or may not be a salt.

[0135] Examples of the hydrazine salt include hydrazine sulfate, hydrazine hydrochloride, and hydrazine acetate.

[0136] Examples of hydrazine derivatives include compounds represented by the general formula (A): N 2), compounds represented by the general formula (B) (compounds represented by H2N-N=X), compounds having a pyrazole ring (pyrazoles) and their salts (sulfates, hydrochlorides or acetates, etc.).

[0137] H2N-NR N 2 (A)

[0138] H2N-N=X (B)

[0139] Furthermore, the hydrazine derivative is preferably not an azole (such as benzotriazole) other than pyrazoles.

[0140] General formula (A)(H2N-NR N 2) In the two RN Each independently represents a hydrogen atom or a substituent. N can be bonded to each other to form a ring, wherein two R N At least one of the R N At least one of them is a substituent or two R N bonded to each other to form a ring).

[0141] As R N The substituent represented by is preferably an alkyl group having a substituent (which may be linear or branched, and preferably has 1 to 5 carbon atoms) or -L N -NH2(L N represents a single bond or a divalent linking group. The divalent linking group is preferably -CO-, -CS-, -NH-, -C(=NH)-, or a group consisting of a combination of two or more thereof.

[0142] In the general formula (B) (H2N-N=X), X represents a divalent group. Among them, X is preferably =CR C 2. Two R's C Each independently represents a hydrogen atom or a substituent.

[0143] The total number of atoms other than hydrogen atoms in the hydrazine derivative is preferably 3 to 30, more preferably 3 to 15, and even more preferably 3 to 8.

[0144] Specific examples of the hydrazine derivative include pyrazole, carbohydrazine, semicarbohydrazine, thiosemicarbohydrazine, monomethylhydrazine, tert-butylhydrazine, dimethylhydrazine (1,1-dimethylhydrazine), and aminoguanidine.

[0145] Among them, the hydrazines preferably contain at least hydrazine.

[0146] The content of hydrazine is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the hydrazines.

[0147] In the treatment liquid, the total content of hydrazines (preferably hydrazine) is 1 part by mass or less relative to 100 parts by mass of hydroxylamine. From the perspective of further improving the stability of the treatment liquid, the total content is preferably 0.5 parts by mass or less. From the perspective of further improving the removal of organic residues in the treatment liquid, the total content is preferably 0.00001 parts by mass or more, more preferably 0.0001 parts by mass or more, further preferably 0.0005 parts by mass or more, and particularly preferably 0.005 parts by mass or more.

[0148] The total content of hydrazines (preferably hydrazine) in the treatment liquid is preferably 0.0001 to 3000 ppm by mass relative to the total mass of the treatment liquid. If the total content is 0.0001 ppm by mass or greater (preferably 0.0005 ppm by mass or greater, more preferably 0.005 ppm by mass or greater, and even more preferably 0.05 ppm by mass or greater), the treatment liquid exhibits even better organic residue removal performance. If the total content is 3000 ppm by mass or less (preferably 300 ppm by mass or less), the treatment liquid exhibits even better stability.

[0149] The type and content of hydrazines in the treatment liquid can be measured by ion chromatography (Dionex ICS-2100 manufactured by ThermoFisher Scientific KK, etc.).

[0150] Furthermore, when the components and blending of the raw materials used in the preparation of the treatment liquid are known, the value can be determined by calculation based on the blending amounts.

[0151] There are no particular limitations on the method for introducing hydrazines into the treatment liquid. For example, a substance containing hydrazines (hydrazines themselves or an aqueous solution thereof, etc.) can be added during the preparation of the treatment liquid. Alternatively, hydrazines can be introduced into the treatment liquid by using a substance containing hydrazines as a trace component (impurities, etc.) as a raw material during the preparation of the treatment liquid.

[0152] <First Anion>

[0153] The treatment liquid preferably contains a - 、NO2 - and NO3 - The first anion contains one or more kinds of first anions, more preferably contains two or more kinds of first anions, and further preferably contains three kinds of first anions.

[0154] That is, the treatment liquid preferably contains Cl - 、NO2 - and NO3 - of all kinds.

[0155] In the treatment solution, the total content of the first anion (Cl - 、NO2 - and NO3 - The total content of the hydroxylamine is preferably 0.00001 to 100 parts by mass relative to 100 parts by mass of hydroxylamine.

[0156] If the total content is 0.00001 parts by mass or more, the metal residue removal performance of the treatment liquid is further improved, and if it is 100 parts by mass or less, the smoothness of the treated object is further improved. From the perspective of excellent balance of the performance of the treatment liquid, the total content is preferably 0.0001 to 30 parts by mass, more preferably 0.1 to 25 parts by mass, and even more preferably 0.1 to 10 parts by mass.

[0157] As described above, the present inventors believe that the reason why the treatment liquid contains anions and thus has a more excellent effect is as follows.

[0158] Specifically, in the treatment solution of the present invention, the presence of the first anion in water allows the anion to react appropriately with metal residues after dry etching, increasing its solubility in water and thus improving cleaning performance. This effect becomes more pronounced when the total content of the first anions is greater than a specified amount relative to hydroxylamine. Furthermore, it is speculated that when the total content of the first anions is less than a specified amount relative to hydroxylamine, so-called pitting corrosion of the metal by the anions is suppressed, thereby improving the smoothness of the treated surface.

[0159] In the treatment liquid, the total content of the first anions is preferably 0.001 to 50,000 ppm by mass relative to the total mass of the treatment liquid.

[0160] If the total content is 0.001 ppm by mass or more relative to the total mass of the treatment liquid, the cleaning properties of the treatment liquid are further improved, and if it is 50,000 ppm by mass or less, the smoothness of the treated object is further improved. From the perspective of achieving an excellent balance of the properties of the treatment liquid, the total content is preferably 1 to 25,000 ppm by mass, and more preferably 2 to 15,000 ppm by mass relative to the total mass of the treatment liquid.

[0161] In the treatment solution, Cl - The content of α-HBr is preferably 0.001 to 5000 ppm by mass relative to the total mass of the treatment liquid.

[0162] If Cl - When the content is 0.05 ppm by mass or more relative to the total mass of the treatment liquid, the cleaning property of the treatment liquid is further improved, and when it is 5000 ppm by mass or less, the smoothness of the treated object is further improved.

[0163] From the perspective of excellent balance of the performance of the treatment liquid, Cl - The content of iodine is more preferably, for example, 0.05 to 2000 ppm by mass, and further preferably 0.1 to 500 ppm by mass, relative to the total mass of the treatment liquid.

[0164] In the treatment fluid, NO2 -The content of α-HBr is preferably 0.001 to 30,000 ppm by mass relative to the total mass of the treatment liquid.

[0165] If NO2 - When the content of NO2 is 0.001 ppm by mass or more relative to the total mass of the treatment liquid, the cleaning property of the treatment liquid is further improved, and when it is 30,000 ppm by mass or less, the smoothness of the treated object is further improved. - The content of the alkylene oxide is more preferably, for example, 0.5 to 20,000 ppm by mass, and further preferably 1 to 5,000 ppm by mass relative to the total mass of the treatment liquid.

[0166] In the treatment fluid, NO3 - The content of α-HBr is preferably 0.001 to 30,000 ppm by mass relative to the total mass of the treatment liquid.

[0167] If NO3 - When the content of NO3 is 0.001 ppm by mass or more relative to the total mass of the treatment liquid, the cleaning property of the treatment liquid is further improved, and when it is 30,000 ppm by mass or less, the smoothness of the treated object is further improved. - The content of the alkylene oxide is more preferably, for example, 0.5 to 20,000 ppm by mass, and further preferably 1 to 5,000 ppm by mass relative to the total mass of the treatment liquid.

[0168] The NO2 in the first anion - and NO3 - Also specifically called specific anions.

[0169] Including NO2 - and NO3 - The total content of the two specific anions is preferably 0.001 to 50,000 ppm by mass relative to the total mass of the treatment liquid.

[0170] From the viewpoint of excellent balance in the performance of the treatment liquid, the total content of the specific anions is preferably 1 to 50,000 ppm by mass, more preferably 2 to 10,000 ppm by mass, relative to the total mass of the treatment liquid.

[0171] In addition, the treatment liquid includes NO2 - and NO3 - The total mass of the two specific anions is preferably greater than Cl - In addition, at this time, the treatment liquid preferably contains more than 0 mass ppm of Cl relative to the total mass of the treatment liquid. - , more preferably containing 0.001 mass ppm or more.

[0172] For example, the total mass of specific anions is equal to that of Cl - The ratio of the total mass of specific anions to the mass of Cl - The content mass) is preferably 1.1 to 100, more preferably 1.5 to 30.

[0173] Furthermore, the content of the first anion in the treatment liquid preferably satisfies "Cl - Contains mass ≤ NO2 - The mass contained ≤ NO3 - The relationship of "the content mass" is more preferably satisfied with "0.001 mass ppm ≤ Cl - Contains mass ≤ NO2 - The mass contained ≤ NO3 - The relationship between the quality of the product and the quantity of the product is the same.

[0174] <Second Anion>

[0175] The treatment liquid may also contain SO4 2- and PO4 3- One or more second anions.

[0176] That is, the treatment liquid may contain only SO4 2- and PO4 3- It may contain one of them, or both of them, or neither of them.

[0177] When the treatment liquid contains one or more second anions, the total content of the first anion and the second anion (Cl - 、NO2 - 、NO3 - 、SO4 2- and PO4 3- The total content of the hydroxylamine is preferably 0.0001 to 30 parts by mass relative to 100 parts by mass of hydroxylamine.

[0178] If the total content is 0.0001 parts by mass or more, the cleaning properties of the treatment liquid are further improved, and if it is 30 parts by mass or less, the smoothness of the treated object is further improved. From the perspective of excellent balance of the performance of the treatment liquid, the total content is more preferably 0.1 to 25 parts by mass, and even more preferably 0.1 to 10 parts by mass.

[0179] When the treatment liquid contains the second anion, the total content of the second anion in the treatment liquid (SO4 2- and PO4 3- The total content of the above-mentioned substances is preferably more than 0 mass ppm and 1000 mass ppm or less, and more preferably more than 0 mass ppm and 50 mass ppm or less, relative to the total mass of the treatment liquid.

[0180] The treatment liquid contains SO4 2- In the case of SO4 2- The content of α-HBr is preferably more than 0 mass ppm and 500 mass ppm or less, and more preferably more than 0 mass ppm and 30 mass ppm or less, relative to the total mass of the treatment liquid.

[0181] The treatment fluid contains PO4 3- In the case of treatment fluid, PO4 3- The content of α-HBr is preferably more than 0 mass ppm and 500 mass ppm or less, and more preferably more than 0 mass ppm and 30 mass ppm or less, relative to the total mass of the treatment liquid.

[0182] The contents of the first anion and the second anion in the treatment liquid can be measured by ion chromatography (Dionex ICS-2100 manufactured by ThermoFisher Scientific KK, etc.).

[0183] Furthermore, when the components and blending of the raw materials used in the preparation of the treatment liquid are known, the value can be determined by calculation based on the blending amounts.

[0184] There is no particular limitation on the method of introducing the first anion and / or the second anion into the treatment liquid. For example, a substance containing the first anion and / or the second anion (such as nitric acid, nitrous acid, hydrochloric acid, sulfuric acid, phosphoric acid and their aqueous solutions) can be added as a supply source of the first anion and / or the second anion when preparing the treatment liquid.

[0185] Furthermore, a compound that generates a substance containing the first anion and / or the second anion by dissolving in water or undergoing a chemical reaction, etc., can be used as a supply source of the first anion and / or the second anion. As an example of this, nitrogen trioxide that reacts with water to generate nitrous acid can be cited.

[0186] Furthermore, by using a material containing the first anion and / or the second anion as an impurity (trace component) as a raw material when preparing the treatment liquid, the first anion and / or the second anion can be introduced into the treatment liquid.

[0187] <Chelating Agents>

[0188] The treatment liquid may contain a chelating agent. When the treatment liquid contains a chelating agent, the cleaning property of the treatment liquid is further improved. However, the chelating agent mentioned here does not include the above-mentioned hydrazines.

[0189] The chelating agent refers to a substance (preferably an acid) capable of functioning as a chelating ligand, and is preferably a compound containing 1 or more (preferably 1 to 8) acid groups.

[0190] The acid group is not particularly limited, but is preferably at least one functional group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphonic acid group.

[0191] Examples of the carboxylic acid group-containing chelating agent include polyaminopolycarboxylic acids, aliphatic dicarboxylic acids, hydroxyl group-containing aliphatic polycarboxylic acids, and ascorbic acids.

[0192] The polyaminopolycarboxylic acid is a compound containing a plurality of amino groups and a plurality of carboxylic acid groups, and examples thereof include mono- or polyalkylenepolyaminepolycarboxylic acids, polyaminoalkanepolycarboxylic acids, polyaminoalkanolpolycarboxylic acids, and hydroxyalkyletherpolyaminepolycarboxylic acids.

[0193] 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-cyclohexanediaminetetraacetic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6-hexamethylenediamine-N,N,N',N'-tetraacetic acid, N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclododecanetetraacetic acid, diaminopropanoltetraacetic acid, and (hydroxyethyl)ethylenediaminetriacetic acid. Among these, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA), or trans-1,2-cyclohexanediaminetetraacetic acid is preferred.

[0194] Examples of the aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, and maleic acid, and oxalic acid, malonic acid, and succinic acid are preferred.

[0195] Examples of the hydroxyl group-containing aliphatic polycarboxylic acids include malic acid, tartaric acid, and citric acid, with citric acid being preferred.

[0196] Examples of the ascorbic acid include ascorbic acid, erythorbic acid, ascorbic acid sulfate, ascorbic acid phosphate, ascorbic acid 2-glucoside, ascorbic acid palmitate, ascorbyl tetraisopalmitate, ascorbic acid isopalmitate, and salts thereof, and ascorbic acid is preferred.

[0197] Examples of the chelating agent containing a sulfonic acid group include methanesulfonic acid.

[0198] Examples of the phosphonic acid group-containing chelating agent include methyldiphosphonic acid, aminotri(methylenephosphonic acid), 1-hydroxyethylene-1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid (NTMP), ethylenediaminetetra(methylenephosphonic acid) (EDTPO), hexamethylenediaminetetra(methylenephosphonic acid), propylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), triethylenetetraaminehexa(methylenephosphonic acid), triaminotriethylaminehexa(methylenephosphonic acid), trans-1,2-cyclohexanediaminetetra(methylenephosphonic acid), glycol ether diaminetetra(methylenephosphonic acid), tetraethylenepentaminehepta(methylenephosphonic acid), and glycine-N,N-di(methylenephosphonic acid) (glyphosphine).

[0199] From the viewpoint of achieving a more excellent effect of the treatment liquid, the chelating agent is preferably one or more selected from diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, oxalic acid, malonic acid, succinic acid, citric acid, methanesulfonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and nitrilotrimethylenephosphonic acid.

[0200] Among them, the chelating agent is more preferably diethylenetriaminepentaacetic acid or citric acid.

[0201] When the treatment liquid contains a chelating agent, the content of the chelating agent is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and even more preferably 0.2 to 5 mass % relative to the total mass of the treatment liquid from the viewpoint of further improving the effect of the treatment liquid.

[0202] The chelating agent may be used alone or in combination of two or more. When two or more chelating agents are used, the total amount thereof is preferably within the above range.

[0203] <Preservatives>

[0204] The treatment liquid may contain an antiseptic. The antiseptic has the function of eliminating excessive etching of the treated object and further improving the smoothness of the treated object. The antiseptic mentioned here does not include the above-mentioned hydrazines and chelating agents.

[0205] As the preservative, for example, a compound represented by the following formula (1X) is preferable.

[0206] [Chemical Formula 1]

[0207]

[0208] In formula (1X), X represents -CR 6a = or -N =.

[0209] In formula (1X), R 6a 、R 6b and R 6cEach independently represents a hydrogen atom or a substituent.

[0210] The above-mentioned substituents are preferably each independently a hydrocarbon group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an amino group, a nitro group, an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms), or a hydroxyl group. These substituents may further contain substituents if possible.

[0211] Examples of substituents that the hydrocarbon group and the alkoxy group may further contain include, independently, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amino group (the substituent is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms).

[0212] Examples of the substituent that the amino group may have include an alkyl group having 1 to 6 carbon atoms.

[0213] In the above formula (1X), R 6a and R 6b The hydrocarbon groups represented can be independently exemplified by alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), alkynyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 14, and further preferably 6 to 10), and aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 15, and further preferably 7 to 11).

[0214] If possible, their hydrocarbon groups may further contain a substituent, and examples of the substituent that may further contain are as described above.

[0215] And, in X is -CR 6a =, R 6a With R 6b They may be bonded to form a ring.

[0216] As R 6a With R 6b Examples of the ring formed by the bonding include a benzene ring and a naphthalene ring. 6a With R 6b When they are bonded to form a ring, the ring may further have a substituent (for example, a hydrocarbon group having 1 to 5 carbon atoms or a carboxyl group).

[0217] The antiseptic is preferably an azole (a compound having a heterocyclic five-membered ring structure containing one or more nitrogen atoms). However, the azole as the antiseptic is not a pyrazole.

[0218] As the azole, benzotriazoles (compounds having a benzotriazole structure) are also preferred. That is, the preservative is also preferably a benzotriazole.

[0219] Examples of benzotriazoles include benzotriazoles which may be substituted with one or more substituents selected from an alkyl group which may optionally contain a substituent, an aryl group which may optionally contain a substituent, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an amino group which may optionally contain a substituent, a nitro group, an alkoxy group which may optionally contain a substituent, and a hydroxyl group.

[0220] The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The preferred number of carbon atoms is a number including the number of carbon atoms in substituents that the alkyl group may have.

[0221] The number of carbon atoms in the aryl group is preferably 6 to 22, more preferably 6 to 14, and even more preferably 6 to 10. The preferred number of carbon atoms is a number including the number of carbon atoms in the substituents that the aryl group may have.

[0222] The number of carbon atoms in the alkoxy group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The preferred number of carbon atoms is a number including the number of carbon atoms in the substituents that the alkoxy group may have.

[0223] Examples of substituents that may be contained in the alkyl group, the aryl group, and the alkoxy group include, independently, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amino group (the substituent is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms).

[0224] Examples of the substituent that may be contained in the amino group include an alkyl group having 1 to 6 carbon atoms.

[0225] When the benzotriazole is a benzotriazole having a substituent, the substituent is preferably independently substituted at one or more of the 1-position, 4-position, and 5-position, and preferably at any one of the 1-position, 4-position, and 5-position.

[0226] The substituent may be substituted at positions other than the 1-position, 4-position, and 5-position of benzotriazole, or may be unsubstituted.

[0227] Preferred examples of the substituent contained in benzotriazole are as described above.

[0228] Among them, benzotriazole in which the 1-position is substituted by an amino group or benzotriazole in which the 5-position is substituted by an alkyl group is preferred.

[0229] The benzotriazoles are also preferably unsubstituted benzotriazoles.

[0230] Examples of the benzotriazoles include benzotriazole (BTA), 1-hydroxybenzotriazole, 5-phenylmercaptobenzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphtholtriazole, 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, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole, and 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.

[0231] Examples of preservatives other than benzotriazoles 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, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 1H-tetrazolyl-5-acetic acid, 2-mercaptobenzothiazole (2-MBT), and 1-phenyl-2-tetrazolyl. phenoxy-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, methyltetrazolyltriazine, bismuthiolate 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, benzothiazole, 2,3,5-trimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, quinoxaline, acetylpyrrole, pyridazine and pyrazine.

[0232] The preservative is preferably selected from benzotriazole, 5-aminotetrazolyl, 1-hydroxybenzotriazole, 5-phenylmercapto-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphtholtriazole, 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, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole, One or more of propylbenzotriazole, 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.

[0233] Among them, the preservative is more preferably benzotriazole, 1-amino-benzotriazole or 5-methyl-1H-benzotriazole, and further preferably 5-methyl-1H-benzotriazole.

[0234] When the treatment liquid contains an antiseptic (preferably an azole), the content of the antiseptic is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, relative to the total mass of the treatment liquid.

[0235] The preservative may be used alone or in combination of two or more. When two or more preservatives are used, the total amount thereof is preferably within the above range.

[0236] <Organic Solvents>

[0237] The treatment liquid of the present invention may contain an organic solvent.

[0238] The organic solvent may be a water-soluble organic solvent.

[0239] The organic solvent being water-soluble means that water at 25° C. and the organic solvent can be mixed (dissolved) in any proportion.

[0240] Examples of the organic solvent include alcohol solvents, ketone solvents, ester solvents, ether solvents (for example, glycol diethers), sulfonic acid solvents, sulfoxide solvents, nitrile solvents, and amide solvents.

[0241] Their solvents may be water-soluble.

[0242] Among them, the treatment liquid preferably contains one or more organic solvents selected from alcohol solvents, ketone solvents, ester solvents, and ether solvents.

[0243] Examples of the alcohol solvent include alkanediols (including, for example, alkylene glycols), alkoxy alcohols (including, for example, ethylene glycol monoethers), saturated aliphatic monoalcohols, unsaturated non-aromatic monoalcohols, and low-molecular-weight alcohols having a ring structure.

[0244] Among them, the alcohol solvent is preferably ethylene glycol monoether or saturated aliphatic monohydric alcohol.

[0245] 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.

[0246] Examples of the alkylene glycol include ethylene glycol, propylene glycol, benzyl alcohol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.

[0247] Examples of the alkoxy alcohol include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and ethylene glycol monoether.

[0248] Examples of the ethylene glycol monoethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl 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, diethylene glycol monobenzyl ether, 1-octanol, 2-octanol, and 2-ethylhexanol.

[0249] Among these, ethylene glycol monobutyl ether is preferred.

[0250] 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.

[0251] Examples of the unsaturated non-aromatic monohydric alcohol include allyl alcohol, propargyl alcohol, 2-butenol, 3-butenol, and 4-penten-2-ol.

[0252] Examples of the low-molecular-weight alcohol having a ring structure include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

[0253] 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.

[0254] 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 ethylene 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.

[0255] Examples of the sulfonic acid solvent include sulfolane, 3-methylsulfolane, and 2,4-dimethylsulfolane.

[0256] Examples of the sulfoxide-based solvent include dimethyl sulfoxide.

[0257] Examples of the nitrile solvent include acetonitrile and the like.

[0258] Examples of amide solvents include N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and hexamethylphosphoric acid triamide.

[0259] When the treatment liquid contains an organic solvent, the content of the organic solvent is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, relative to the total mass of the treatment liquid.

[0260] The organic solvent may be used alone or in combination of two or more. When two or more organic solvents are used, the total amount thereof is preferably within the above range.

[0261] <Reducing Agents Different from Hydroxylamine>

[0262] The treatment liquid may contain a reducing agent different from hydroxylamine. In addition, hydrazines, chelating agents, and preservatives are not included in the reducing agent different from hydroxylamine.

[0263] The reducing agent other than hydroxylamine is not particularly limited, but is preferably a reducing substance such as a compound containing an OH group or a CHO group or a compound containing a sulfur atom. The reducing agent has the function of reducing OH, which has an oxidizing effect and is the cause of decomposition of hydroxylamine. - Oxidation by ions or dissolved oxygen.

[0264] Among reducing substances such as compounds containing an OH group or a CHO group or compounds containing a sulfur atom, one selected from the group consisting of compounds represented by formula (4) and compounds containing a sulfur atom is preferred.

[0265] [Chemical Formula 2]

[0266]

[0267] In formula (4), R 4a ~R 4e Each independently represents a hydrogen atom, a hydroxyl group or a hydrocarbon group which may have a hetero atom. 4a ~R 4e When containing a hydrocarbon group which may have a heteroatom, the hydrocarbon group may have a substituent.

[0268] In formula (4), as R 4a ~R 4e Examples of the hydrocarbon group which may have a hetero atom include a hydrocarbon group and a hydrocarbon group containing a hetero atom.

[0269] As the above R 4a ~R 4e Examples of the hydrocarbon groups represented include alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), alkynyl groups (preferably having 2 to 12 carbon atoms, more 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).

[0270] And, as the above R 4a ~R 4e The heteroatom-containing hydrocarbon group represented by may be -CH2- in the above hydrocarbon groups, for example, selected from -O-, -S-, -CO-, -SO2- and -NR a - or a group substituted with a divalent group formed by combining a plurality of them. a represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 5 carbon atoms).

[0271] Examples of the substituent include a hydroxyl group, a carboxyl group, and a substituted or unsubstituted amino group (the substituent is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms).

[0272] Examples of the compound represented by the above formula (4) include gallic acid, resorcinol, ascorbic acid, tert-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, and 2,6-di-tert-butyl-p-cresol.

[0273] From the viewpoint of adding reducing properties, the compound represented by formula (4) preferably has two or more hydroxyl groups, more preferably three or more. The substitution position of the hydroxyl group is not particularly limited, but from the viewpoint of adding reducing properties, R 4a and / or R 4b .

[0274] Examples of compounds represented by formula (4) having two or more hydroxyl groups include catechol, resorcinol, tert-butylcatechol, and 4,4'-dihydroxyphenyl-2,2-propane. Examples of compounds represented by formula (4) having three or more hydroxyl groups include gallic acid.

[0275] Examples of the sulfur atom-containing compound include mercaptosuccinic acid, dithiodiglycerol [S(CH2CH(OH)CH2(OH))2], bis(2,3-dihydroxypropylthio)ethylene [CH2CH2(SCH2CH(OH)CH2(OH))2], sodium 3-(2,3-dihydroxypropylthio)-2-methyl-propanesulfonate [CH2(OH)CH(OH)CH2SCH2CH(CH3)CH2SO3Na], 1-thioglycerol [HSCH2CH(OH)CH2(OH)], sodium 3-mercapto-1-propanesulfonate [HSCH2CH2CH2SO3Na], 2-mercaptoethanol [HSCH2CH2(OH)], thioacetic acid [HSCH2CO2H], and 3-mercapto-1-propanol [HSCH2CH2CH2OH]. Among these, compounds containing an SH group (mercapto compounds) are preferred, 1-thioglycerol, sodium 3-mercapto-1-propanesulfonate, 2-mercaptoethanol, 3-mercapto-1-propanol, or thioacetic acid are more preferred, and 1-thioglycerol or thioacetic acid is even more preferred.

[0276] Furthermore, a reducing agent other than hydroxylamine may be used alone or in combination of two or more.

[0277] <Fluoride>

[0278] The treatment liquid may contain fluoride, which promotes the decomposition and solubilization of the residue.

[0279] The fluoride is not particularly limited, and examples thereof include hydrofluoric acid (HF), fluorosilicic acid (H2SiF6), fluoroboric acid, ammonium fluorosilicate salt ((NH4)2SiF6), tetramethylammonium hexafluorophosphate, ammonium fluoride, ammonium fluoride salt, ammonium difluoride salt, quaternary ammonium tetrafluoroborate and quaternary phosphonium tetrafluoroborate represented by the formulas NR4BF4 and PR4BF4, respectively, and tetrabutylammonium tetrafluoroborate (TBA-BF4).

[0280] In addition, in the quaternary ammonium tetrafluoroborate (e.g., tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate) and quaternary phosphonium tetrafluoroborate represented by the above formulas NR4BF4 and PR4BF4, R can be the same or different, and R is hydrogen, a linear, branched or cyclic C1-C6 alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), and a linear or branched C6-C10 aryl group (e.g., benzyl). The fluoride can be used alone or in combination of two or more types.

[0281] When the treatment liquid contains a fluoride, the content of the fluoride is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, based on the total mass of the treatment liquid.

[0282] <Metal component>

[0283] The treatment liquid may contain a metal component.

[0284] Examples of the metal component include metal particles and metal ions. For example, when referring to the content of the metal component, the total content of the metal particles and the metal ions is indicated.

[0285] The treatment liquid may contain either or both of metal particles and metal ions. The treatment liquid preferably contains both metal particles and metal ions.

[0286] 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.

[0287] The metal component may contain one type of metal atom or two or more types of metal atoms.

[0288] The metal particles may be in the form of a single substance, an alloy, or a combination of metal and organic matter.

[0289] The metal component can be a metal component inevitably contained in each component (raw material) contained in the treatment liquid, can also be a metal component inevitably contained during the manufacture, storage, and / or transfer of the treatment liquid, or can be intentionally added.

[0290] When the treatment liquid contains a metal component, the content of the metal component is more often more than 0 mass ppt and 10 mass ppm or less relative to the total mass of the treatment liquid. From the viewpoint of more excellent effects of the treatment liquid, it is preferably more than 0 mass ppm and 1 mass ppm or less, and more preferably more than 0 mass ppb and 100 mass ppb or less.

[0291] In addition, regarding the type and content of the metal component in the treatment liquid, it can be measured by the SP-ICP-MS method (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry).

[0292] <pH regulator>

[0293] The treatment liquid can contain a pH regulator in addition to the above components. Examples of the pH regulator include acid compounds and base compounds.

[0294] (Acid compound)

[0295] Examples of the acid compound include acetic acid, perchloric acid, hypochlorous acid, and periodic acid. <00007(

[0296] (Base compound)

[0297] Examples of the base compound include ammonia water, amine compounds different from hydroxylamine and hydrazine compounds, and quaternary ammonium hydroxides.

[0298] In addition, as an amine compound different from hydroxylamine and hydrazine compounds, a cyclic compound (a compound having a cyclic structure) can be cited. Examples of the cyclic compound include an amine compound having a cyclic structure described later.

[0299] In addition, quaternary ammonium hydroxides are not included in amine compounds different from hydroxylamine and hydrazine compounds.

[0300] As an amine compound different from hydroxylamine and hydrazine compounds, a cyclic amine compound is preferred.

[0301] In the cyclic amine compound, the amino group can exist only in either the above cyclic structure or outside the above cyclic structure, or can exist in both.

[0302] Examples of the amine compound having a cyclic structure include tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2]octane, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, 2-piperidinol, cyclohexylamine, and 1,5-diazabicyclo[4,3,0]-5-nonene.

[0303] Among them, the amine compound is preferably tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine, 1,8-diazabicyclo[5.4.0]-7-undecene, or 1,4-diazabicyclo[2.2.2]octane.

[0304] When the treatment liquid contains an amine compound other than hydroxylamine and hydrazines, the content thereof is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, based on the total mass of the treatment liquid.

[0305] Examples of the quaternary ammonium hydroxide salt include compounds represented by the following formula (5).

[0306] [Chemical Formula 3]

[0307]

[0308] In the above formula (5), R 5a ~R 5d 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. 5a ~R 5d At least two of the R 5a With R 5b Combination of R 5c With R 5d At least one of the combinations may be bonded to each other to form a ring structure.

[0309] The compound represented by the above formula (5) is preferably tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide.

[0310] When the treatment liquid contains a quaternary ammonium hydroxide salt, the content of the quaternary ammonium hydroxide salt is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, relative to the total mass of the treatment liquid.

[0311] As the base compound, water-soluble amines other than those mentioned above can also be used.

[0312] The pKa of the water-soluble amine is preferably 7.5 to 13.0 at room temperature. In this specification, a water-soluble amine means an amine that can dissolve 50 g or more in 1 L of water at room temperature. Water-soluble amines do not include ammonia water.

[0313] Examples of water-soluble amines having a pKa of 7.5 to 13 include diglycolamine (DGA) (pKa = 9.80), methylamine (pKa = 10.6), ethylamine (pKa = 10.6), propylamine (pKa = 10.6), butylamine (pKa = 10.6), pentylamine (pKa = 10.0), ethanolamine (pKa = 9.3), propanolamine (pKa = 9.3), butanolamine (pKa = 9.3), methoxyethylamine (pKa = 10.0), methoxypropylamine (pKa = 10.0), dimethylamine (pKa = 10.8), diethylamine (pKa = 10.9), dipropylamine (pKa = 10.8), trimethylamine (pKa = 9.80), and triethylamine (pKa = 10.72).

[0314] Furthermore, as the water-soluble amine, unsubstituted hydroxylamine and hydroxylamine derivatives can also be used.

[0315] In addition, the pka of a water-soluble amine in this specification is the acid dissociation constant in water. The acid dissociation constant in water can be measured by combining a spectrometer and potentiometric measurement.

[0316] Among them, the pH adjuster is preferably one or more compounds selected from acetic acid, perchloric acid, hypochlorous acid, periodic acid, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, ammonia water, and water-soluble amines.

[0317] The pH of the treatment liquid is preferably 1 to 13, more preferably 6 to 11, from the viewpoint of achieving a more excellent effect of the treatment liquid.

[0318] In this specification, the pH of the treatment liquid is a value measured at room temperature (25° C.) using F-51 (product name) manufactured by HORIBA, Ltd.

[0319] The content of the pH adjuster may be appropriately set so that the treatment liquid can reach the target pH.

[0320] <Method for producing treatment liquid>

[0321] The method for producing the treatment liquid is not particularly limited, and known methods can be used. For example, a method of mixing water, hydroxylamine, and hydrazines (or their aqueous solutions, etc.) can be used. In addition, when mixing the above components, other optional components (such as substances containing the first anion and / or the second anion) can be further mixed as needed.

[0322] Furthermore, when the treatment liquid is produced, the treatment liquid may be filtered using a filter to be purified as needed.

[0323] The treatment liquid of the present invention is preferably used for a treatment object containing a metallic material as a material containing metal, and more preferably for a treatment object containing a cobalt-containing substance containing cobalt atoms (abbreviated as "cobalt-containing substance").

[0324] Furthermore, the treatment liquid is preferably used for a treatment object containing a cobalt-containing substance containing cobalt atoms and a metal-containing substance containing metal atoms other than cobalt atoms.

[0325] <Processing Liquid Storage Body>

[0326] The treatment liquid can be contained in a container and stored until use.

[0327] The container and the treatment liquid contained therein are collectively referred to as a treatment liquid container. The treatment liquid is taken out of the stored treatment liquid container and used. Furthermore, the treatment liquid can be transported as a treatment liquid container.

[0328] As a container, preferably for semiconductor applications, the cleanliness inside the container is high and the elution of impurities is small. Examples of containers that can be used include the "Clean Bottle" series manufactured by AICELLO CHEMICAL CO., LID. and the "Pure Bottle" manufactured by KODAMA PLASTICS CO., LTD.

[0329] The inner wall of the container is preferably formed of one or more resins selected from polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a combination thereof. Furthermore, the inner wall of the container is preferably formed of a metal treated to prevent rust and metal elution, such as stainless steel, Hoechst alloy, Inconel, or Monel.

[0330] As the above-mentioned different resins, fluorine-based resins (perfluorinated resins) are preferably used. By using a container whose inner wall is a fluorine-based resin, compared with a container whose inner wall is a polyethylene resin, a polypropylene resin or a polyethylene-polypropylene resin, the generation of adverse conditions such as the dissolution of oligomers of ethylene or propylene can be suppressed.

[0331] Examples of containers with fluorine-based resin inner walls include Fluoro Pure PFA composite barrels manufactured by Entegris. Furthermore, 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 / 46309, pages 9 and 16, etc., can also be used.

[0332] Furthermore, in addition to the above-mentioned fluorine-based resin, quartz and electrolytically polished metal materials (ie, metal materials that have been electrolytically polished) can also be preferably used for the inner wall of the container.

[0333] The metal material used in the manufacture of the above-mentioned electrolytically polished metal material is preferably a metal material containing at least one selected from chromium and nickel, and the total content of chromium and nickel exceeds 25% by mass relative to the total mass of the metal material. Examples thereof include stainless steel and nickel-chromium alloy.

[0334] The total content of chromium and nickel in the metal material is preferably 30% by mass or more relative to the total mass of the metal material.

[0335] The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is preferably 90% by mass or less based on the total mass of the metal material.

[0336] The stainless steel is not particularly limited, and known stainless steels can be used. Among them, alloys containing 8% by mass or more of nickel are preferred, and austenitic stainless steel containing 8% by mass or more of nickel is more preferred.

[0337] Examples of austenitic stainless steel include SUS (Steel Use Stainless Steel) 304 (Ni content: 8 mass%, Cr content: 18 mass%), SUS304L (Ni content: 9 mass%, Cr content: 18 mass%), SUS316 (Ni content: 10 mass%, Cr content: 16 mass%), and SUS316L (Ni content: 12 mass%, Cr content: 16 mass%).

[0338] 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.

[0339] Examples of nickel-chromium alloys include Herschel alloy (product name, hereinafter the same), Monel alloy (product name, hereinafter the same), and Inconel alloy (product name, hereinafter the same). More specifically, Herschel alloy C-276 (Ni content: 63 mass %, Cr content: 16 mass %), Herschel alloy-C (Ni content: 60 mass %, Cr content: 17 mass %), and Herschel alloy C-22 (Ni content: 61 mass %, Cr content: 22 mass %) can be mentioned.

[0340] Furthermore, the nickel-chromium alloy may contain boron, silicon, tungsten, molybdenum, copper, or cobalt in addition to the above alloys as needed.

[0341] The method for electrolytic polishing the metal material is not particularly limited, 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.

[0342] The metal material is preferably polished. The polishing method is not particularly limited, and known methods can be used. The size of the abrasive grains used in the fine polishing is not particularly limited, but is preferably less than #400 from the perspective of making the surface unevenness of the metal material smaller.

[0343] In addition, polishing is preferably performed before electrolytic polishing.

[0344] 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 specifications such as the size of the abrasive grains.

[0345] These containers are preferably cleaned before being filled with the treatment liquid. It is preferable that the liquid used for cleaning has a reduced amount of metallic impurities in the liquid.

[0346] After production, the treatment liquid can be transported or stored in containers such as gallon bottles or coating bottles.

[0347] To prevent changes in the composition of the treatment liquid during storage, the container can be replaced with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher. Gases with low water content are particularly preferred. While transport and storage can be performed at room temperature, to prevent deterioration, the temperature can be controlled within a range of -20°C to 20°C.

[0348] Furthermore, the above-mentioned treatment solution may be provided as a kit in which the raw material thereof is divided into a plurality of parts.

[0349] Furthermore, the treatment liquid can be prepared as a concentrated liquid. In the case of using the treatment liquid as a concentrated liquid, the concentration ratio can be appropriately determined according to the composition, and is preferably 5 to 2000 times. That is, the concentrated liquid can be diluted 5 to 2000 times before use.

[0350] [Processing method of the object to be processed]

[0351] In the method for treating an object to be treated using the treatment solution of the present invention (hereinafter referred to as the "present treatment method"), the treatment solution is generally used in contact with an object to be treated containing a metal-based material as a material containing metal. In this case, the object to be treated may contain multiple types of metal-based materials. Furthermore, it is also preferred that the treatment solution dissolve at least one of the multiple types of metal-based materials.

[0352] The metal-based material only needs to have metal atoms (cobalt (Co), ruthenium (Ru), tungsten (W), molybdenum (Mo), aluminum (Al), copper (Cu), titanium (Ti) and / or tantalum (Ta), etc.), for example, single metals, alloys, metal oxides (which may be composite oxides) and metal nitrides (which may be composite nitrides).

[0353] The content of metal atoms in the metal-based material is preferably 30 to 100 mass %, more preferably 40 to 100 mass %, and even more preferably 52 to 100 mass % relative to the total mass of the metal-based material.

[0354] Examples of the metal-based material include cobalt-containing substances and metal-containing substances, etc. The details of the cobalt-containing substances and the metal-containing substances will be described later.

[0355] For example, the workpiece may preferably contain at least one cobalt-containing substance among a plurality of metal-based materials, and the treatment liquid may be brought into contact with the workpiece containing the cobalt-containing substance to dissolve (etch) the cobalt-containing substance.

[0356] That is, the processing liquid may be, for example, an etching processing liquid.

[0357] The object to be treated is preferably a metal-containing substance (hereinafter simply referred to as "metal-containing substance") containing a cobalt-containing substance and other metal atoms (hereinafter simply referred to as "other metal atoms") other than cobalt atoms.

[0358] In this case, the treatment liquid may be used for etching only the cobalt-containing substance or for etching both the cobalt-containing substance and the metal-containing substance.

[0359] The form of the processed object is not particularly limited, for example Figure 1As shown, the object to be processed 10 may include a substrate 12, an insulating film 14 having a hole portion arranged on the substrate 12, a metal-containing substance portion 16 arranged in a layer along the inner wall of the hole portion of the insulating film 14, and a cobalt-containing substance portion 18 filled in the hole portion. Figure 1 In the embodiment, the metal-containing substance portion can function as a barrier metal layer.

[0360] Figure 1 The method in which the object to be processed contains one cobalt-containing substance portion is described in, but is not limited to this method. For example, Figure 2 As shown, a treatment object 20 may include a substrate 12, an insulating film 14 having a plurality of pores disposed on the substrate 12, a metal-containing substance portion 16 disposed in a layer along the inner wall of each pore of the insulating film 14, and a cobalt-containing substance portion 18 filled in each pore. In other words, the treatment object may have a cobalt-containing substance at multiple locations and a metal-containing substance at multiple locations.

[0361] There is no particular limitation on the type of substrate that can be included in the object to be processed, and examples thereof include semiconductor wafers, glass substrates for photomasks, glass substrates for liquid crystal displays, glass substrates for plasma displays, substrates for FEDs (Field Emission Displays), substrates for optical disks, substrates for magnetic disks, and substrates for magneto-optical disks.

[0362] Examples of materials constituting the semiconductor substrate include silicon, silicon germanium, and Group III-V compounds such as GaAs, or any combination thereof.

[0363] The size, thickness, shape, layer structure, etc. of the substrate are not particularly limited and can be appropriately selected as needed.

[0364] As the insulating film, a known insulating film can be used.

[0365] exist Figure 1 and Figure 2 In the embodiment, the insulating film has a hole portion, but the present invention is not limited to this embodiment, and the insulating film may have a groove portion.

[0366] The cobalt-containing substance only needs to contain a cobalt atom, and examples thereof include cobalt element (metallic cobalt), cobalt alloys (preferably alloys containing cobalt as the largest metal component by mass), cobalt oxides, and cobalt nitrides.

[0367] The content of cobalt atoms in the cobalt-containing substance is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 99 to 100% by mass relative to the total mass of the cobalt-containing substance.

[0368] Furthermore, the type of other metal atoms in the metal-containing substance is not particularly limited, and examples thereof include titanium and tantalum. Among them, the other metal atoms are preferably metal atoms that are more noble than cobalt.

[0369] The metal-containing substance may contain any other metal atom as described above, and examples thereof include simple metals, alloys, oxides, and nitrides.

[0370] As the metal-containing substance, from the viewpoint of further improving the effect of the treatment liquid, titanium alone, titanium alloy, titanium oxide, titanium nitride, tantalum alone, tantalum alloy, tantalum oxide, or tantalum nitride is preferred.

[0371] When the object to be treated contains a metal-containing substance, the cobalt-containing substance and the metal-containing substance may be in contact with each other in the object to be treated, or may be arranged via another member.

[0372] The form of the cobalt-containing substance and the metal-containing substance is not particularly limited, and may be, for example, a film-like form, a wiring-like form, or a particle-like form.

[0373] When the cobalt-containing substance and the metal-containing substance are in the form of a film, the thickness thereof is not particularly limited and may be appropriately selected according to the intended use. For example, it is preferably 50 nm or less, more preferably 20 nm or less, and even more preferably 10 nm or less.

[0374] The cobalt-containing substance and the metal-containing substance may be disposed on only one main surface of the substrate or on both main surfaces. Furthermore, the cobalt-containing substance and 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.

[0375] Furthermore, the object to be treated may contain two or more cobalt-containing substances, or may contain two or more metal-containing substances.

[0376] While the description of the treated object above primarily focuses on a cobalt-containing substance, such a cobalt-containing substance may also contain a different metal-based material in place of the cobalt-containing substance. For example, such a treated object may contain a ruthenium-containing substance, a tungsten-containing substance, a molybdenum-containing substance, an aluminum-containing substance, or a copper-containing substance in place of the cobalt-containing substance. The details of the ruthenium-containing substance, tungsten-containing substance, molybdenum-containing substance, aluminum-containing substance, and copper-containing substance are similar to, for example, replacing the cobalt in the cobalt-containing substance described in the previous paragraph with ruthenium, tungsten, molybdenum, aluminum, and copper, respectively.

[0377] Furthermore, when the object to be processed contains a ruthenium-containing substance, a tungsten-containing substance, a molybdenum-containing substance, an aluminum-containing substance, or a copper-containing substance in place of the cobalt-containing substance, the "other metal atoms" in the metal-containing substance may also be metal atoms other than ruthenium atoms, metal atoms other than tungsten atoms, metal atoms other than molybdenum atoms, metal atoms other than aluminum atoms, and metal atoms other than copper atoms, respectively. In this case, the metal-containing substance may preferably be titanium alone, a titanium alloy, titanium oxide, titanium nitride, tantalum alone, a tantalum alloy, tantalum oxide, or tantalum nitride.

[0378] The above-mentioned object to be processed may contain various layers and / or structures as needed in addition to the above. For example, the substrate may have metal wiring, a gate electrode, a source electrode, a drain electrode, an insulating layer, a ferromagnetic layer and / or a non-magnetic layer.

[0379] The substrate may have 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 also have layers of silicon oxide, silicon nitride, silicon carbide, and / or carbon-doped silicon oxide.

[0380] The method for manufacturing the object to be processed is not particularly limited. For example, an insulating film is formed on a substrate, and holes or grooves are formed in the insulating film. A metal-containing material layer and a cobalt-containing material layer are sequentially arranged on the insulating film by sputtering, chemical vapor deposition (CVD) or molecular beam epitaxy (MBE), and then a planarization process such as CMP is performed to produce the object to be processed. Figure 1 The treated object shown.

[0381] As a method for treating a workpiece according to the present invention, for example, a method of contacting a workpiece containing at least one metal-based material with the above-mentioned treatment solution can be cited. By adopting this method, one or more metal-based materials contained in the workpiece can be dissolved or the workpiece can be cleaned (e.g., cleaning dry etching residues contained in the workpiece).

[0382] <First Method>

[0383] As a more specific example of the method for treating a treated object of the present invention, a method in which a treated object containing at least a cobalt-containing substance is brought into contact with the treatment solution to dissolve the cobalt-containing substance can be cited. This method for treating a treated object is also referred to as the first embodiment of the method for treating a treated object of the present invention.

[0384] The method for contacting the treated object with the treatment liquid 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 the treated object, a method of flowing the treatment liquid on the treated object, and any combination thereof. Among them, the method of immersing the treated object in the treatment liquid is preferred.

[0385] Furthermore, in order to further enhance the cleaning ability of the treatment liquid, a mechanical stirring method may be utilized.

[0386] Examples of mechanical stirring methods include a method of circulating the treatment liquid on the treatment object, a method of flowing or spraying the treatment liquid on the treatment object, and a method of stirring the treatment liquid using ultrasonic waves or megasonic waves.

[0387] The contact time between the object to be treated and the treatment liquid can be adjusted appropriately.

[0388] 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.

[0389] The temperature of the treatment liquid during the treatment is not particularly limited, but is preferably 20 to 75°C, more preferably 20 to 65°C.

[0390] By carrying out this treatment, the cobalt-containing substances in the treated object are mainly dissolved.

[0391] When the treated object contains a metal-containing substance in addition to the cobalt-containing substance, the metal-containing substance may or may not be dissolved together with the cobalt-containing substance by this treatment. When the metal-containing substance is dissolved, the metal-containing substance may be dissolved intentionally or inevitably.

[0392] When the metal-containing substance is not intentionally dissolved, it is preferable that the amount of the metal-containing substance that is inevitably dissolved is small. When the metal-containing substance is not intentionally dissolved, the fact that the metal-containing substance is inevitably dissolved is small is also referred to as having excellent resistance of the treatment liquid to the component containing the metal-containing substance.

[0393] In the first embodiment, the object to be processed may contain a ruthenium-containing substance, a tungsten-containing substance, a molybdenum-containing substance, an aluminum-containing substance, or a copper-containing substance instead of or in addition to the cobalt-containing substance.

[0394] <Method 2>

[0395] Furthermore, as another embodiment of the method for treating the object to be treated of the present invention, the following second embodiment can be cited.

[0396] That is, the method for treating the object to be treated includes: step A, performing oxidation treatment on the object to be treated including a metal layer to oxidize the surface layer of the above-mentioned metal layer to form a metal oxide layer; and step B, bringing the object to be treated obtained in the above-mentioned step A into contact with a treatment liquid to dissolve the above-mentioned metal oxide layer.

[0397] The second aspect may be a form of the first aspect.

[0398] The metal layer is a form of a metal-based material and is a layer composed of a metal-based material that can be oxidized. The metal layer is preferably, for example, a metal monomer or alloy. Furthermore, the metal layer is preferably a cobalt-containing substance (cobalt monomer or cobalt alloy, etc.), a ruthenium-containing substance (ruthenium monomer or ruthenium alloy, etc.), a tungsten-containing substance (tungsten monomer or tungsten alloy, etc.), a molybdenum-containing substance (molybdenum monomer or molybdenum alloy, etc.), an aluminum-containing substance (aluminum monomer or aluminum alloy, etc.) or a copper-containing substance (copper monomer or copper alloy, etc.), more preferably a cobalt-containing substance (cobalt monomer or cobalt alloy, etc.).

[0399] The metal oxide layer is formed by oxidizing the surface of the metal layer, and is also referred to as a form of a metal-based material. A portion of the surface of the metal layer may be the metal oxide layer, or the entire surface of the metal layer may be the metal oxide layer.

[0400] The metal oxide layer is an oxide of a metal monomer or alloy and is preferably a layer comprising cobalt oxide, cobalt alloy oxide, ruthenium oxide, ruthenium alloy oxide, tungsten oxide, tungsten alloy oxide, molybdenum oxide, molybdenum alloy oxide, aluminum oxide, aluminum alloy oxide, copper oxide or copper alloy oxide, more preferably a layer comprising cobalt oxide or cobalt alloy oxide, and even more preferably a layer comprising cobalt oxide.

[0401] The thickness of the metal oxide layer is, for example, about 1 to 10 atomic layers. Furthermore, the thickness of one atomic layer of the metal and the metal oxide is less than 1 nm (for example, 0.3 nm to 0.4 nm). In other words, the oxidation treatment is a treatment that oxidizes, for example, about 1 to 10 atomic layers of the surface layer of the metal layer to form the metal oxide layer.

[0402] The metal oxide layer often has higher solubility in the treatment solution than the metal layer (is easily etched).

[0403] That is, in the second method, in process A, the surface of the metal layer is formed into a thin metal oxide layer, and in process B, a treatment liquid is used to remove only the above-mentioned metal oxide layer (and the portion of the metal layer present in the lower layer of the metal oxide layer that can inevitably be dissolved), thereby being able to remove (dissolve) only the very thin surface of the metal layer included in the treated object.

[0404] Furthermore, by alternately and repeatedly performing step A and step B, the etching amount can be controlled with high precision.

[0405] When step A and step B are performed alternately, it is preferred that step A and step B be performed 1 to 20 times each.

[0406] The object to be treated in the second embodiment may include a single metal layer or two or more metal layers. Furthermore, the object to be treated in the second embodiment may include a metal material other than the metal layer or metal oxide layer, and some or all of the metal material may be removed intentionally or unavoidably through steps A and B.

[0407] Step A is a step of performing an oxidation treatment on the workpiece including the metal layer to oxidize the surface of the metal layer to form a metal oxide layer.

[0408] The method of oxidation treatment for oxidizing the surface layer of the metal layer to form a metal oxide layer is not limited. For example, it can be implemented by subjecting the above-mentioned object to the following treatment, namely, liquid treatment in which the above-mentioned object is brought into contact with an oxidizing solution, gas treatment in which the above-mentioned object is brought into contact with an oxidizing gas (ozone treatment in which the above-mentioned object is brought into contact with ozone gas or oxygen heating treatment in which the above-mentioned object is heated in an oxygen atmosphere, etc., as described later), or plasma treatment using oxygen gas on the above-mentioned object.

[0409] The oxidation treatment may be performed alone or in combination of two or more.

[0410] Among these, as the oxidation treatment, it is preferable to perform at least a liquid treatment in which a predetermined solution is brought into contact with the above-mentioned object to be treated.

[0411] The oxidizing solution may be any solution that can oxidize the surface layer of the metal layer.

[0412] The above-mentioned oxidizing solution is preferably a solution selected from water, hydrogen peroxide solution, a mixed aqueous solution of ammonia and hydrogen peroxide (APM), a mixed aqueous solution of hydrofluoric 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), oxygen-dissolved water, ozone-dissolved water, perchloric acid, and nitric acid (hereinafter also referred to as "specific solution").

[0413] Among the above-mentioned specific solutions, a solution selected from water, hydrogen peroxide solution, APM, FPM, SPM, HPM, oxygen-dissolved water, and ozone-dissolved water is preferred.

[0414] 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.

[0415] 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).

[0416] The composition of FPM is preferably within the range of, for example, "hydrofluoric acid:hydrogen peroxide solution:water=1:1:1" to "hydrofluoric acid:hydrogen peroxide solution:water=1:1:200" (mass ratio).

[0417] 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).

[0418] 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).

[0419] The description of the preferred composition ratios thereof indicates a composition ratio when ammonia water is 28 mass %, hydrofluoric acid is 49 mass %, sulfuric acid is 98 mass %, hydrochloric acid is 37 mass %, and hydrogen peroxide water is 30 mass %.

[0420] In addition, the volume ratio is based on the volume at room temperature.

[0421] The description of ["A:B:C=x:y:z" to "A:B:C=X:Y:Z"] as a preferred range indicates that at least one (preferably two, more preferably all) of the ranges ["A:B=x:y" to "A:B=X:Y"], ["B:C=y:z" to "B:C=Y:Z"] and ["A:C=x:z" to "A:C=X:Z"] is preferably satisfied.

[0422] The composition of the oxygen-dissolved water is, for example, an aqueous solution in which the content of O 2 is 1 to 200 ppm by mass relative to the total mass of the oxygen-dissolved water.

[0423] The composition of the ozone-dissolved water is, for example, an aqueous solution having an O 3 content of 1 to 200 ppm by mass relative to the total mass of the ozone-dissolved water.

[0424] 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.

[0425] 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.

[0426] In liquid treatment, there is no particular limitation on the method of bringing the object to be treated into contact with the oxidizing solution (preferably a specific solution). Examples include a method of immersing the object to be treated in the oxidizing solution placed in a tank, a method of spraying the oxidizing solution onto the object to be treated, a method of allowing the oxidizing solution to flow over the object to be treated, and any combination thereof.

[0427] The contact time between the treatment object and the oxidizing solution is, for example, preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes.

[0428] The temperature of the oxidation solution is preferably 20 to 75°C, more preferably 20 to 60°C.

[0429] Examples of the oxidizing gas that comes into contact with the workpiece during the gas treatment include dry air, oxygen (O 2 ), ozone (O 3 ) gas, and mixed gases thereof. The oxidizing gas may contain gases other than the above gases.

[0430] Among the oxidizing gases that come into contact with the object during gas treatment, oxygen or ozone gas is preferred. When oxygen or ozone gas is brought into contact with the object, it is also preferred that the gas be brought into contact under an oxygen atmosphere, an ozone atmosphere, or a mixed gas atmosphere of oxygen and ozone.

[0431] In the gas treatment, it is also preferable to heat the object to be treated (for example, to heat it at 40 to 200° C.) while bringing oxygen gas into contact with the object to be treated.

[0432] Among these, 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.

[0433] In the above-mentioned ozone treatment, ozone gas can be brought into contact with the object under an ozone atmosphere, or can be brought into contact with the object under a mixed gas atmosphere of ozone gas and other gases (e.g., oxygen). Furthermore, the ozone treatment can be a treatment in which the object is heated while the ozone gas is brought into contact with the object.

[0434] In process A (especially in the case of liquid treatment), the object to be treated may contain metal materials other than the metal layer that is oxidized by oxidation treatment and the surface layer becomes a metal oxide layer, and part or all of this metal material may be intentionally or inevitably removed by process A (especially liquid treatment).

[0435] Furthermore, in step A (particularly when liquid treatment is performed), a portion of the metal layer of the object to be treated may be removed intentionally or unavoidably.

[0436] Step B is a step of bringing the object to be treated obtained in step A into contact with a treatment liquid to dissolve the metal oxide layer.

[0437] In step B, the method for bringing the object to be treated into contact with the treatment liquid is not limited, and examples thereof include the same method as that for bringing the object to be treated into contact with the oxidizing solution.

[0438] 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.

[0439] The temperature of the treatment liquid is preferably 20 to 75°C, more preferably 20 to 60°C.

[0440] In step B, the metal oxide layer can be removed locally or entirely.

[0441] In step B, a part or all of the metal layer (for example, the metal oxide layer covering the surface is removed to expose the metal layer at the surface layer) may be removed intentionally or unavoidably.

[0442] In step B, the object to be treated may contain other metallic materials in addition to the metal oxide layer and the metal layer having the metal oxide layer formed on the surface, and part or all of such metallic materials may be removed intentionally or unavoidably.

[0443] Furthermore, when the metal layer and / or the other metal-based materials are not intentionally dissolved, it is preferable that the amount of the metal layer and / or the other metal-based materials that are inevitably dissolved is small.

[0444] The treatment liquid used in step B may be pre-degassed to reduce the amount of dissolved oxygen. The metal layer exposed by the treatment liquid after the metal oxide layer is removed is oxidized by the dissolved oxygen in the treatment liquid to form a new metal oxide layer. This metal oxide layer is further removed by the treatment liquid. As a result, the excessive removal of the metal layer can be suppressed by reducing the amount of dissolved oxygen in the treatment liquid.

[0445] <Third Method>

[0446] Another embodiment (third embodiment) of the method for treating an object of the present invention includes subjecting an object containing a metal material to dry etching and then contacting the object with a treatment liquid to remove dry etching residue.

[0447] The metal-based material contained in the object to be treated in the present embodiment may be a single metal or two or more metal-based materials. At least one of the single metal or two or more metal-based materials is preferably a cobalt-containing substance, a ruthenium-containing substance, a molybdenum-containing substance, an aluminum-containing substance, or a copper-containing substance, and more preferably a cobalt-containing substance.

[0448] That is, as the third aspect of the method for treating an object of the present invention, it is preferable to perform dry etching on an object containing a cobalt-containing substance containing cobalt atoms and then contact the object with a treatment liquid to remove dry etching residue.

[0449] In this method, the object to be processed, which comes into contact with the processing liquid, contains a metal-based material. Furthermore, in this method, the object is subjected to dry etching and then brought into contact with the processing liquid. Therefore, the object, when in contact with the processing liquid, contains dry etching residue on its surface. In this method, the dry etching residue present on the surface of the object is removed.

[0450] This method of treating an object to be treated is also referred to as a third embodiment of the method of treating an object to be treated of the present invention.

[0451] In addition, the third aspect may be a form in which the structure of the object to be processed and the purpose of the processing in the first aspect are particularly limited.

[0452] The treatment liquid of the present invention can also be suitably used for cleaning such an object to be treated (for removing residues).

[0453] Figure 3 A schematic diagram showing an example of an object to be processed (object to be processed after dry etching) in the third embodiment is shown.

[0454] Figure 3 The workpiece 30 shown has a metal-containing film 34, an etching stopper layer 36, an interlayer insulating film 38, and a metal hard mask 40 in this order on a substrate 32. A hole 42 exposing the metal-containing film 34 is formed at a predetermined position by a dry etching process or the like. Figure 3 The object to be processed is shown as a stacked structure including, in this order, a substrate 32, a metal-containing film 34, an etch stop layer 36, an interlayer insulating film 38, and a metal hard mask 40. A hole 42 is provided at the position of the opening of the metal hard mask 40, penetrating from the surface of the metal hard mask 40 to the surface of the metal-containing film 34. The inner wall 44 of the hole 42 is composed of a cross-sectional wall 44a including the etch stop layer 36, the interlayer insulating film 38, and the metal hard mask 40, and a bottom wall 44b including the exposed metal-containing film 34. Dry etching residue 46 is adhered to the inner wall 44 of the hole 42.

[0455] Furthermore, the metal hard mask in the object can become a barrier metal after further processing. In other words, the layer that becomes the barrier metal in the subsequent steps can be used as a metal hard mask in the dry etching step. In other words, the barrier metal can be used as a metal hard mask.

[0456] For example, it is preferred that at least one of the metal-containing film 34 and the metal hard mask 40 is a cobalt-containing material. It is preferred that the metal-containing film 34 is a cobalt-containing material and the metal hard mask 40 is a metal-containing material, or that the metal-containing film 34 is a metal-containing material and the metal hard mask 40 is a cobalt-containing material.

[0457] It is preferred that the metal-containing film 34 is made of a cobalt-containing material and the metal hard mask 40 is made of a metal-containing material.

[0458] A known material can be used for the interlayer insulating film.

[0459] The dry etching residue may be an organic residue containing an organic substance as a main component. The organic residue may be a residue containing an organic substance of 50% by mass or more. The organic residue may be a residue substantially free of metal-containing substances and / or cobalt-containing substances.

[0460] Furthermore, the dry etching residue may contain a metal component as a main component, or may be a metal residue containing a metal-containing substance and / or a cobalt-containing substance. A metal residue is a residue containing a metal component exceeding 50% by mass. The metal residue may be a residue containing substantially no organic matter.

[0461] As a specific method of the third aspect, there is a method of bringing the treatment liquid into contact with the above-mentioned treatment object.

[0462] The method of contacting the treatment liquid with the object to be treated is the same as that described in the first embodiment.

[0463] The dry etching residue on the object to be processed is removed by bringing the treatment liquid into contact with the object to be processed. At this time, the metal-based material (for example, a cobalt-containing substance, etc., preferably a cobalt-containing substance as the metal-containing film 34) can be dissolved at the same time. At this time, the amount of the metal-based material (cobalt-containing substance, etc.) dissolved is not particularly limited. The dissolution of the metal-based material (cobalt-containing substance, etc.) can be an intentional dissolution for removing part or all of the metal-containing film 34 (cobalt-containing substance, etc.) in the bottom wall 44b of the hole 42, or it can be an inevitable dissolution caused by the contact between the treatment liquid and the metal-based material (cobalt-containing substance, etc.).

[0464] This treatment method may include a rinsing step of rinsing the object to be treated using a rinsing liquid, if necessary.

[0465] For example, the method for treating the object to be treated in the first aspect, the second aspect, or the third aspect may further include a rinsing step after the steps described in the description of each aspect.

[0466] Furthermore, the rinsing step may be included between step A and step B in the second embodiment.

[0467] Preferred rinse liquids include, for example, water, hydrofluoric acid (preferably 0.001 to 1 mass% hydrofluoric acid), hydrochloric acid (preferably 0.001 to 1 mass% hydrochloric acid), hydrogen peroxide solution (preferably 0.5 to 31 mass% hydrogen peroxide solution, more preferably 3 to 15 mass% hydrogen peroxide solution), a mixture of hydrofluoric acid and hydrogen peroxide solution (FPM), a mixture of sulfuric acid and hydrogen peroxide solution (SPM), a mixture of ammonia water and hydrogen peroxide solution (APM), a mixture of hydrochloric acid and hydrogen peroxide solution (HPM), carbon dioxide water (preferably 10 to 60 mass ppm carbon dioxide water), ozone water (preferably 10 to 60 mass ppm ozone water), hydrogen water (preferably 10 to 20 mass ppm hydrogen water), citric acid aqueous solution (preferably 0.01 to 10 mass% citric acid aqueous solution), sulfuric acid (preferably 1-10 mass% sulfuric acid aqueous solution), ammonia water (preferably 0.01-10 mass% ammonia water), isopropyl alcohol (IPA), hypochlorous acid aqueous solution (preferably 1-10 mass% hypochlorous acid aqueous solution), aqua regia (preferably a aqua regia with a volume ratio of "37 mass% hydrochloric acid:60 mass% nitric acid" corresponding to "2.6:1.4" to "3.4:0.6"), ultrapure water, nitric acid (preferably 0.001-1 mass% nitric acid), perchloric acid (preferably 0.001-1 mass% perchloric acid), oxalic acid aqueous solution (preferably 0.01-10 mass% oxalic acid aqueous solution), acetic acid (preferably 0.01-10 mass% acetic acid aqueous solution or acetic acid stock solution) or periodic acid aqueous solution (preferably 0.5-10 mass% periodic acid aqueous solution. Examples of periodic acid include o-periodic acid and meta-periodic acid).

[0468] Preferred conditions for FPM, SPM, APM, and HPM are, for example, the same as the preferred conditions for FPM, SPM, APM, and HPM used as the above-mentioned specific solution.

[0469] In addition, hydrofluoric acid, nitric acid, perchloric acid, and hydrochloric acid respectively represent aqueous solutions obtained by dissolving HF, HNO 3 , HClO 4 , and HCl in water.

[0470] Ozone water, carbon dioxide water, and hydrogen water refer to aqueous solutions obtained by dissolving O3, CO2, and H2 in water, respectively.

[0471] These rinsing liquids may be mixed and used within a range that does not impair the purpose of the rinsing step. Furthermore, the rinsing liquid may contain an organic solvent.

[0472] As a specific method of the rinsing step, there is a method of bringing a rinsing liquid into contact with the object to be treated.

[0473] The contacting method may be a method of immersing the substrate in a rinse liquid placed in a tank, a method of spraying the rinse liquid on the substrate, a method of flowing the rinse liquid on the substrate, or a method of any combination thereof.

[0474] The treatment time (the contact time between the rinse liquid and the treated object) is not particularly limited, and is, for example, 5 seconds to 5 minutes.

[0475] The temperature of the rinse liquid during the treatment is not particularly limited, but is generally preferably 16 to 60° C., more preferably 18 to 40° C. When SPM is used as the rinse liquid, the temperature is preferably 90 to 250° C.

[0476] Furthermore, the present treatment method may optionally include a drying step after the rinsing step. The drying method is not particularly limited, and examples thereof include spin drying, flow of a dry gas over the substrate, heating of the substrate by a heating mechanism such as a hot plate or infrared lamp, IPA (isopropyl alcohol) vapor drying, Marangoni drying, Notagnoni drying, or a combination thereof.

[0477] Drying time varies depending on the specific method used, but is generally about 30 seconds to several minutes.

[0478] The present processing method can be combined and implemented before or after other steps in the semiconductor device manufacturing method. The present processing method can be incorporated into other steps when the present processing method is implemented, or the present processing method can be incorporated into other steps and implemented.

[0479] Other processes include, for example, the formation process of various 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, modification, etc.), the formation process of the resist, the exposure process and removal process, the heat treatment process, the cleaning process and the inspection process.

[0480] This processing method can be performed in either the back-end of the line (BEOL) or the front-end of the line (FEOL).

[0481] In addition, the processing liquid can be applied to objects such as NAND, DRAM (Dynamic Random Access Memory), SRAM (Static Random Access Memory), ReRAM (Resistive Random Access Memory), FRAM (registered trademark) (Ferroelectric Random Access Memory), MRAM (Magnetoresistive Random Access Memory) or PRAM (Phasechange Random Access Memory), etc., or it can be a logic circuit or a processor, etc.

[0482] Example

[0483] The present invention will be described in further detail below with reference to the following examples. The materials, amounts used, ratios, treatment contents, and treatment steps shown in the following examples may be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed in a limiting sense by the following examples.

[0484] In the examples, "%" refers to "mass %" unless otherwise specified, and "ppm" refers to "mass ppm" unless otherwise specified.

[0485] [Preparation of treatment solution]

[0486] The components shown below were mixed at a predetermined ratio to prepare treatment liquids suitable for each test.

[0487] Each raw material used in each treatment liquid shown below is of high purity grade and is further purified in advance by distillation, ion exchange, filtration, or a combination thereof.

[0488] <Hydroxyamine>

[0489] HA: Hydroxylamine

[0490] <Hydrazines>

[0491] Hydrazine

[0492] Pyrazole

[0493] ·Carboxyhydrazine

[0494] · Semicarbazide

[0495] ·Semicarbazide

[0496] Monomethylhydrazine

[0497] tert-Butylhydrazine

[0498] Dimethylhydrazine (1,1-dimethylhydrazine)

[0499] Aminoguanidine

[0500] <Organic Solvents>

[0501] Methanol

[0502] Isopropyl alcohol

[0503] 1-Butanol

[0504] 1,3-Propanediol

[0505] Ethylene glycol

[0506] Propylene glycol

[0507] Diethylene glycol

[0508] Dipropylene glycol

[0509] 3-Methoxy-3-methyl-1-butanol

[0510] 3-Methoxy-1-butanol

[0511] 1-Methoxy-2-butanol

[0512] Ethylene glycol monomethyl ether

[0513] Ethylene glycol monoethyl ether

[0514] Ethylene glycol monobutyl ether

[0515] Diethylene glycol monomethyl ether

[0516] Diethylene glycol monobutyl ether

[0517] Triethylene glycol monomethyl ether

[0518] 1-Methoxy-2-propanol

[0519] ·acetone

[0520] Cyclohexanone

[0521] 2-Butanone

[0522] Ethyl acetate

[0523] Butyl acetate

[0524] Propylene glycol monomethyl ether acetate

[0525] <Preservatives>

[0526] Benzotriazole

[0527] 5-aminotetrazole

[0528] 5-phenylbenzotriazole

[0529] 1-Aminobenzotriazole

[0530] 5-Methyl-1H-benzotriazole

[0531] ·Benzotriazole-5-carboxylic acid

[0532] 4-Methylbenzotriazole

[0533] <Chelating Agents>

[0534] Diethylenetriaminepentaacetic acid

[0535] ·EDTA

[0536] · trans-1,2-cyclohexanediaminetetraacetic acid

[0537] ·oxalic acid

[0538] Malonic acid

[0539] Citric acid

[0540] Methanesulfonic acid

[0541] 1-Hydroxyethylidene-1,1-diphosphonic acid

[0542] Nitrilotrimethylenephosphonic acid

[0543] <Supply Source of First Anion or Second Anion>

[0544] A predetermined amount of the first anion and / or the second anion is supplied to the treatment liquid by adding appropriate amounts of the following raw materials.

[0545] Hydrochloric acid aqueous solution (HClaq: Cl - supply source)

[0546] Nitrous acid / nitric acid aqueous solution (HNO2 / HNO3aq: NO2 - and NO3 - supply source)

[0547] Nitrogen trioxide (N2O3: NO2 - supply source)

[0548] Nitric acid aqueous solution (HNO3aq: NO3 - supply source)

[0549] ·Sulfuric acid aqueous solution (H2SO4aq: SO4 2- supply source)

[0550] · Phosphoric acid aqueous solution (H3PO4aq: source of PO4 3- )

[0551] The above-mentioned nitrous acid / nitric acid aqueous solution is an aqueous solution containing nitric acid and nitrous acid produced by reacting H2O with NO2 in pure water.

[0552] The above-mentioned dinitrogen trioxide dissolves in H2O to produce nitrous acid and becomes a source of NO2 - .

[0553] <Water>

[0554] · Water: Water purified by repeatedly distilling, filtering through a filter, and performing ion exchange on ultrapure water until the first anion and the second anion become less than the detection limit.

[0555] In addition, the above-mentioned detection limit is less than 0.001 mass ppm. When performing detection, as needed, after performing a treatment such as removing a part of the water from the sample to be detected to concentrate the target substance, the measurement was performed.

[0556] <pH regulator>

[0557] · Acetic acid (pH regulator for adjusting to the acidic side)

[0558] · 1,8-Diazabicyclo[5.4.0]-7-undecene (pH regulator for adjusting to the alkaline side)

[0559] In order to make the treatment liquid reach a specified pH, an appropriate amount of either acetic acid or 1,8-diazabicyclo[5.4.0]-7-undecene was added as a pH regulator.

[0560] In addition, in any treatment liquid, the addition amount of the pH regulator is 3.0 mass% or less with respect to the total mass of the treatment liquid.

[0561] [Experiment]

[0562] The following experiment was performed using the treatment liquid of the prepared example or comparative example.

[0563] <Evaluation of organic residue removal performance>

[0564] A multi-layer substrate in which a photoresist film, a metal hard mask (TiN layer), an etch stop layer (Al2O3 layer), a Co layer, and an interlayer dielectric (ILD) were sequentially stacked on the surface of a substrate was prepared. The multi-layer substrate was subjected to lithography-based patterning treatment, etching treatment using a metal plasma etching device, and removal treatment of the photoresist film based on oxygen plasma ashing to produce a multi-layer substrate for evaluation test (hereinafter also referred to as "test piece"). "

[0565] The obtained test pieces were cleaned (treated) using the treatment liquids of the respective Examples and Comparative Examples.

[0566] Specifically, first, fill 200 mL of the treatment liquid into a 500 mL glass beaker. While stirring with a stirrer, raise the temperature of the treatment liquid to 40°C. Next, immerse the test piece prepared above in the treatment liquid at a liquid temperature of 40°C for 5 minutes while stirring, thereby cleaning the test piece. While immersing the test piece in the treatment liquid, use 4-inch long plastic locking tweezers to hold the test piece so that the surface of the test piece on the side where the photoresist is removed faces the stirrer.

[0567] After the cleaning time, the test piece was immediately removed from the treatment solution and placed in 400 mL of ion-exchanged water (17°C) filled in a 500 mL plastic beaker and stirred gently. After immersing the test piece in the ion-exchanged water for 30 seconds, the test piece was immediately removed and rinsed under a stream of 17°C ion-exchanged water for 30 seconds.

[0568] Next, the test piece was exposed to a nitrogen gas flow to blow off the liquid droplets adhering to the surface of the test piece, thereby drying the surface of the test piece.

[0569] After the nitrogen drying step, the test piece was removed from the holding portion of the plastic tweezers and stored in a plastic storage box with a lid with the component surface facing upward.

[0570] The surface composition of the obtained test pieces was analyzed using X-ray photoelectron spectroscopy (XPS). The surface of the obtained test pieces was measured using an XPS apparatus (Quantera SXM, manufactured by UlvaC-PHI). The carbon atom content of the organic residue in the test pieces measured before and after treatment was compared, and the reduction rate due to treatment was calculated and defined as the organic residue removal rate. The organic residue removal performance of each treatment solution was evaluated according to the following evaluation criteria.

[0571] 1: The removal rate of organic residue is more than 95%

[0572] 2: The organic residue removal rate is more than 80% and less than 95%

[0573] 3: The organic residue removal rate is more than 75% and less than 80%

[0574] 4: The organic residue removal rate is more than 50% and less than 75%

[0575] 5: Organic residue removal rate is less than 50%

[0576] <Evaluation of Stability>

[0577] Next, a storage test was performed using the treatment liquids of each example and each comparative example, and the temporal stability of the removal performance of each treatment liquid was evaluated.

[0578] Specifically, first, 200 mL of each treatment liquid was filled into a 250 mL high-density polyethylene container and sealed, and the container filled with the treatment liquid was stored in an environment of 60° C. for 24 hours (storage treatment).

[0579] Using the treatment liquid after the storage treatment, an organic residue removal evaluation test was conducted according to the above-mentioned method for evaluating organic residue removal. The maintenance rate of the organic residue removal rate obtained using the treatment liquid after the storage treatment was calculated (= [Organic residue removal rate obtained using the treatment liquid after the storage treatment] ÷ [Organic residue removal rate obtained using the treatment liquid before the storage treatment] × 100), with the organic residue removal rate obtained using the treatment liquid before the storage treatment being set as 100%. The obtained maintenance rates were classified according to the following evaluation criteria, and the stability of each treatment liquid was evaluated.

[0580] In addition, even when any of the treatment liquids was used, the maintenance rate did not exceed 100%.

[0581] 1: Maintenance rate is above 99%

[0582] 2: Maintenance rate is 95% or more and less than 99%

[0583] 3: Maintenance rate is 85% or more and less than 95%

[0584] 4: Maintenance rate is 75% or more and less than 85%

[0585] 5: Maintenance rate is less than 75%

[0586] <Smoothness (Smoothness of the Treated Object) Evaluation>

[0587] A substrate was prepared by forming a metal cobalt layer on one surface of a commercially available silicon wafer (diameter: 12 inches) by CVD (Chemical Vapor Deposition). The thickness of the metal cobalt layer was set to 20 nm.

[0588] The obtained substrate was immersed in water at 40° C. for 1 minute and then immersed in each treatment liquid listed in the table at 40° C. for 30 seconds as one cycle. This cycle was repeated until the metal cobalt was dissolved to a thickness of 10 nm.

[0589] Then, the surface of the treated metal cobalt layer was observed using a scanning electron microscope, and the smoothness of the treated portion treated with the treatment liquid was evaluated on a 10-point scale of 1 to 10.

[0590] Regarding smoothness, "1" is the best rating, and higher numbers indicate worse ratings. Specifically, if the surface of the metal cobalt layer is smooth and no roughness is observed, the smoothness of the treated object in the treatment solution is rated "1." Otherwise, as the rating approaches "10," roughness is observed, and the surface of the metal cobalt layer is rated as rough. Ratings of "1-8" indicate levels that are practically usable, "9" indicates a practically usable level, and "10" indicates a practically problematic level.

[0591] <Evaluation of Metal Residue Removability>

[0592] A workpiece (pre-processed laminate) was formed, which had a metal cobalt layer, a SiN film, a SiO2 film, and a barrier metal (TaN) including a predetermined opening in this order on a substrate (Si). Using the obtained workpiece, plasma etching (dry etching) was performed using the barrier metal as a mask, and the SiN film and the SiO2 film were etched until the metal cobalt layer was exposed to form a through hole, thereby manufacturing Sample 1 (reference Figure 3 When a cross section of the laminate is examined using SEM / EDX (scanning electron microscope with energy dispersive X-ray analyzer), plasma etching residues (metal residues) containing a metal such as cobalt as a main component are observed on the hole wall surfaces.

[0593] The metal residue removal performance was then evaluated using the following process: First, a slice (approximately 2.0 cm × 2.0 cm) of the prepared Sample 1 was immersed (treated) in each treatment solution at a temperature of 40°C for 1 minute. After the prescribed time, the slice of Sample 1 was removed, immediately rinsed with ultrapure water, and dried with N2.

[0594] Thereafter, the surface of the slice of the sample 1 after immersion was observed using SEM / EDX, and the removability of the metal residue was evaluated on a 10-step scale of 1 to 10.

[0595] Regarding cleaning performance, "1" represents a good rating, and higher numbers indicate a poorer rating. Specifically, as a result of observation, if the metal residue is completely removed, the rating is "1," and if the metal residue is barely removed, the rating is "10." Ratings of "1-6" indicate a level that is practically usable, "7-9" indicates a level that is practically usable, and "10" indicates a level that is practically problematic.

[0596] Among them, from the viewpoint of performance balance, it is preferable that the evaluation of the metal residue removability is 1 to 6 and the evaluation of the smoothness is 1 to 8.

[0597] [result]

[0598] The formulations of the treatment liquids used in a series of Test X and the results are shown in Tables 1a-1 to 1n-1 and Tables 1a-2 to 1n-2.

[0599] In the tables, “%” means “mass %”, and “ppm” means “mass ppm”.

[0600] The column "HA (%)" shows the content (mass %) of hydroxylamine in each treatment liquid relative to the total mass of the treatment liquid.

[0601] The upper part of the columns "Chelating agent / content", "Benzotriazole compound / content", and "Organic solvent / content" indicates the type of each component added, and the lower part indicates the amount of each component added (mass %).

[0602] The column "Hydrazines (per 100 parts of HA)" shows the total content (parts by mass) of hydrazines in each treatment liquid relative to 100 parts by mass of hydroxylamine. When two hydrazines were used, the respective contents were adjusted to be equal.

[0603] The column "Anions (ppm)" shows the content (mass ppm) of each anion in each treatment liquid relative to the total mass of the treatment liquid.

[0604] The column "First anion content (relative to 100 parts of HA)" shows the total content (parts by mass) of the first anions in each treatment liquid relative to 100 parts by mass of hydroxylamine.

[0605] The column "First anion content and second anion content (relative to 100 parts of HA)" shows the total content (parts by mass) of the first anion and the second anion in each treatment liquid relative to 100 parts by mass of hydroxylamine.

[0606] The "pH" column shows the pH of each treatment liquid.

[0607] Components not explicitly described in the table (the remainder) in each treatment liquid include a pH adjuster and water added to achieve a predetermined pH.

[0608] Table 1a-1 and Table 1a-2 respectively show the formulations of the treatment liquids in Examples 001 to 049 and the test results.

[0609] For example, the treatment liquid of Example 001 contained 0.1% by mass of hydroxylamine relative to the total mass of the treatment liquid, and 0.001 ppm by mass of hydrazine (0.0001 parts by mass relative to 100 parts by mass of hydroxylamine) of hydrazine relative to the total mass of the treatment liquid. It contained no first anion, no second anion, no chelating agent, no preservative, and no organic solvent. The remainder consisted of a pH adjuster added to achieve a pH of 9 and water. The test results of the treatment liquid of Example 001 showed an organic residue removability rating of 3, a stability rating of 3, a metal residue removability rating of 9, and a smoothness rating of 3.

[0610] The same relationships apply to Tables 1b-1 and 1b-2 and subsequent tables.

[0611] [Table 1]

[0612]

[0613] [Table 2]

[0614]

[0615] [Table 3]

[0616]

[0617] [Table 4]

[0618]

[0619] [Table 5]

[0620]

[0621] [Table 6]

[0622]

[0623] [Table 7]

[0624]

[0625] [Table 8]

[0626]

[0627] [Table 9]

[0628]

[0629] [Table 10]

[0630]

[0631] [Table 11]

[0632]

[0633] [Table 12]

[0634]

[0635] [Table 13]

[0636]

[0637] [Table 14]

[0638]

[0639] [Table 15]

[0640]

[0641] [Table 16]

[0642]

[0643] [Table 17]

[0644]

[0645] [Table 18]

[0646]

[0647] [Table 19]

[0648]

[0649] [Table 20]

[0650]

[0651] [Table 21]

[0652]

[0653] [Table 22]

[0654]

[0655] [Table 23]

[0656]

[0657] [Table 24]

[0658]

[0659] [Table 25]

[0660]

[0661] [Table 26]

[0662]

[0663] [Table 27]

[0664]

[0665] [Table 28]

[0666]

[0667] From the results shown in the table, it was confirmed that the problems of the present invention can be solved by using the processing liquid of the present invention.

[0668] Furthermore, it was confirmed that when the content of hydrazines was 0.0001 parts by mass or more (preferably 0.005 to 0.5 parts by mass) relative to 100 parts by mass of hydroxylamine, the effect of the treatment liquid was further improved (see comparison of the results of Examples 001 to 005, comparison of the results of Example 001 and Example 011, etc.).

[0669] It was confirmed that when the hydrazines contained hydrazine, the effect of the treatment liquid was more excellent (see comparison of the results of Example 014 and Examples 020 to 027, etc.).

[0670] It was confirmed that when the treatment liquid contained the first anion, the effect of the treatment liquid was more excellent (see comparison of the results of Example 009 and Examples 036 to 045, etc.).

[0671] Furthermore, it was confirmed that the effect of the treatment liquid was more excellent when the total content of the first anion and the second anion was 0.0001 to 30 parts by mass relative to 100 parts by mass of hydroxylamine (see comparison of the results of Example 009 and Examples 036 to 045, etc.).

[0672] Confirmed that NO2 - and NO3 - When the total content mass of the two specific anions constituting is greater than the content mass of C1, the effect of the treatment liquid is more excellent (see the comparison of the results of Example 056 and Example 057, etc.).

[0673] It was confirmed that when the treatment liquid contains a chelating agent (more preferably diethylenetriaminepentaacetic acid or citric acid), the effect of the treatment liquid is more excellent (see comparison of the results of Examples 093 to 155 with Examples 055, 056, 063, 064, 070, 071, and 072, etc.).

[0674] It was confirmed that when the treatment liquid contains a preservative (more preferably benzotriazole, 1-amino-benzotriazole or 5-methyl-1H-benzotriazole, and even more preferably 5-methyl-1H-benzotriazole), the effect of the treatment liquid is more excellent (see comparison of the results of Examples 156 to 204 with Examples 055, 056, 063, 064, 070, 071, and 072, etc.).

[0675] It was confirmed that when the treatment liquid contains one or more organic solvents selected from alcohol solvents, ketone solvents, ester solvents and ether solvents (more preferably ethylene glycol monobutyl ether), the effect of the treatment liquid is more excellent (refer to the comparison of the results of Examples 205 to 372 with Examples 055, 056, 063, 064, 070, 071 and 072, etc.).

[0676] Explanation of symbols

[0677] 20-processed object, 12-substrate, 14-insulating film, 16-metal-containing material portion, 18-cobalt-containing material portion, 30-processed object, 32-substrate, 34-metal-containing film, 36-etching stop layer, 38-interlayer insulating film, 40-metal hard mask, 42-hole, 46-dry etching residue, 44-inner wall, 44a-cross-section wall, 44b-bottom wall.

Claims

1. A treatment liquid comprising: water; Hydroxylamine; and One or more hydrazines selected from hydrazine, hydrazine salts and hydrazine derivatives, The total content of the hydrazines is 1 part by mass or less relative to 100 parts by mass of the hydroxylamine.

2. The treatment liquid according to claim 1, wherein The total content of the hydrazines is 0.0001 parts by mass or more relative to 100 parts by mass of the hydroxylamine.

3. The treatment liquid according to claim 1 or 2, wherein The total content of the hydrazines is 0.005 to 0.5 parts by mass relative to 100 parts by mass of the hydroxylamine.

4. The treatment liquid according to claim 1 or 2, wherein The hydrazine derivative is one or more selected from the group consisting of a compound represented by the general formula (A), a compound represented by the general formula (B), a compound having a pyrazole ring, and salts thereof. H2N-N-R N 2 (A) H2N-N=X (B) In the general formula (A), two R N Each independently represents a hydrogen atom or a substituent, and the two R N are optionally bonded to each other to form a ring, wherein two R N At least one of them is not a hydrogen atom, In the general formula (B), X represents a divalent group.

5. The treatment liquid according to claim 1 or 2, wherein The hydrazines contain hydrazine.

6. The treatment liquid according to claim 1 or 2, further comprising a compound selected from Cl - 、NO2 - and NO3 - One or more first anions.

7. The treatment liquid according to claim 6, comprising Cl - 、NO2 - and NO3 - The three types of the first anions are constituted.

8. The treatment liquid according to claim 6, wherein The total content of the first anion is 0.0001 to 30 parts by mass relative to 100 parts by mass of the hydroxylamine.

9. The treatment liquid according to claim 6, further comprising SO4 2- and PO4 3- One or more second anions in The total content of the first anion and the second anion is 0.0001 parts by mass to 30 parts by mass based on 100 parts by mass of the hydroxylamine.

10. The treatment liquid according to claim 6, wherein NO2 - and NO3 - The total mass of Cl - Contains quality. The treatment liquid according to claim 1 or 2, further comprising a chelating agent.

12. The treatment liquid according to claim 11, wherein The chelating agent contains a functional group selected from carboxylic acid, phosphonic acid and sulfonic acid groups.

13. The treatment liquid according to claim 11, wherein The chelating agent is one or more selected from diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, oxalic acid, malonic acid, succinic acid, citric acid, methanesulfonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and nitrilotrimethylenephosphonic acid. The treatment liquid according to claim 1 or 2, further comprising an antiseptic.

15. The treatment liquid according to claim 14, wherein The preservative is a benzotriazole.

16. The treatment liquid according to claim 15, wherein The benzotriazoles are benzotriazoles optionally substituted with one or more substituents selected from an alkyl group optionally containing a substituent, an aryl group optionally containing a substituent, a halogen atom, an amino group optionally containing a substituent, a nitro group, an alkoxy group optionally containing a substituent, and a hydroxyl group.

17. The treatment liquid according to claim 14, wherein The preservative is selected from benzotriazole, 5-aminotetrazolyl, 1-hydroxybenzotriazole, 5-phenylmercapto-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphtholtriazole, 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, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole, 4-isopropylbenzotriazole, 5 ... One or more of propylbenzotriazole, 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.

18. The treatment liquid according to claim 1 or 2, further comprising at least one organic solvent selected from the group consisting of alcohol solvents, ketone solvents, ester solvents, and ether solvents. The treatment liquid according to claim 1 or 2, which has a pH of 6 to 11.

20. The treatment liquid according to claim 1 or 2, which is used for a treatment object containing a cobalt-containing substance containing cobalt atoms and a metal-containing substance containing metal atoms other than cobalt atoms.

21. The treatment liquid according to claim 20, wherein The cobalt-containing substance is cobalt monomer, cobalt alloy, cobalt oxide or cobalt nitride.

22. A method for treating an object, wherein: An object to be treated containing a cobalt-containing substance containing cobalt atoms is brought into contact with the treatment liquid according to any one of claims 1 to 21 to dissolve the cobalt-containing substance.

23. A method for treating an object, comprising: Step A, subjecting a workpiece containing a metal layer to a treatment to oxidize a surface of the metal layer to form a metal oxide layer, the treatment comprising: Liquid treatment in contact with a solution selected from water, hydrogen peroxide solution, a mixed aqueous solution of ammonia and hydrogen peroxide solution, a mixed aqueous solution of hydrofluoric 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, oxygen-dissolved water, and ozone-dissolved water, Ozone treatment in contact with ozone gas, Heat treatment in oxygen atmosphere, or Plasma treatment using oxygen; and In step B, the object to be treated obtained in step A is brought into contact with the treatment liquid according to any one of claims 1 to 19 to dissolve the metal oxide layer.

24. The method for treating an object according to claim 23, wherein: The step A and the step B are repeated alternately.

25. The method for treating an object according to claim 23, wherein: The metal layer is composed of a cobalt-containing substance as a single substance or a cobalt alloy.

26. A method for treating an object, wherein: After dry etching is performed on the workpiece containing metal materials, The object to be processed is brought into contact with the processing liquid according to any one of claims 1 to 19 to remove dry etching residues.

27. The method for treating an object according to claim 26, wherein: The metal-based material is a cobalt-containing substance containing cobalt atoms.

Images