Treatment method of treatment liquid and treated object

Abstract

This invention provides a treatment liquid with excellent removal and stability of organic residues. It also provides a method for treating a substance related to the above treatment liquid. The treatment liquid contains water, hydroxylamine, and one or more hydrazines selected from hydrazine, hydrazine salts, and hydrazine derivatives, wherein the total content of the hydrazines is less than 1 part by mass relative to 100 parts by mass of hydroxylamine.

Description

[0001] This application is a divisional application of application number 202080092116.6, entitled "Processing Liquid and Processing Method for Processed Objects". The parent application was filed on December 24, 2020, and has a priority date of January 28, 2020. Technical Field

[0002] This invention relates to a treatment liquid and a method for treating the substance being treated. Background Technology

[0003] With the miniaturization of semiconductor devices, there is an increasing demand for using processing solutions used in semiconductor device manufacturing to perform etching or cleaning processes efficiently and with good precision.

[0004] For example, Patent Document 1 discloses a cleaning agent composition, characterized in that it contains N-hydroxyformamide.

[0005] Previous technical documents

[0006] Patent documents

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

[0008] The technical problem to be solved by the invention

[0009] A technology is being researched for using a processing liquid to treat a substrate or similar material.

[0010] For the processing solution used to process such a workpiece, it is required, for example, to have excellent removal properties for organic residues generated due to prior processing of the workpiece (such as dry etching) (hereinafter referred to as "excellent organic residue removal properties"). Furthermore, the processing solution is also required to maintain certain performance even after a period of time, and to have excellent stability.

[0011] In view of the above, the objective of the present invention is to provide a treatment solution with excellent removal and stability of organic residues.

[0012] Furthermore, the objective of this invention is to provide a method for treating a substance related to the aforementioned treatment liquid.

[0013] means for solving technical problems

[0014] In order to solve the above-mentioned problems, the inventors conducted in-depth research and discovered that the above-mentioned problems can be solved by the following structure.

[0015] [1]

[0016] A treatment liquid comprising:

[0017] water;

[0018] Hydroxylamine; and

[0019] Selected from one or more hydrazines, hydrazine salts, and hydrazine derivatives.

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

[0021] [2]

[0022] According to the treatment solution described in [1], wherein,

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

[0024] [3]

[0025] According to the treatment solution described in [1] or [2], wherein,

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

[0027] [4]

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

[0029] The aforementioned hydrazine derivatives are selected from one or more of the compounds represented by general formula (A), the compounds represented by general formula (B), compounds having a pyrazole ring, and their salts.

[0030] H2N-NR N 2 (A)

[0031] H₂N-N=X (B)

[0032] In general formula (A), the two R N Each R represents a hydrogen atom or a substituent independently. N They can bond together to form a ring, in which two Rs N At least one of them is not a hydrogen atom.

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

[0034] [5]

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

[0036] The aforementioned hydrazine compounds contain hydrazine.

[0037] [6]

[0038] The treatment solution according to any one of [1] to [5] further contains a compound selected from Cl. - NO2 - and NO3 - One or more of the first anions.

[0039] [7]

[0040] According to the treatment solution described in [6], it contains Cl - NO2 - and NO3 - The three types of the first anion mentioned above constitute the composition.

[0041] [8]

[0042] According to the treatment solution described in [6] or [7], wherein,

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

[0044] [9]

[0045] The treatment solution according to any one of [6] to [8] further contains a component selected from SO4. 2- and PO4 3- One or more of the second anions,

[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 solution according to any one of [6] to [9], wherein,

[0049] NO2 - and NO3 - The total contains more than Cl by mass - It contains mass.

[0050]

[11]

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

[10] further contains a chelating agent.

[0052]

[12]

[0053] According to the treatment solution described in

[11] , wherein,

[0054] The chelating agents mentioned above contain functional groups selected from carboxylic acid groups, phosphonic acid groups, and sulfonic acid groups.

[0055]

[13]

[0056] According to the treatment solution described in

[11] or

[12] , wherein,

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

[0058]

[14]

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

[13] further contains a preservative.

[0060]

[15]

[0061] According to the treatment solution described in

[14] , wherein,

[0062] The above-mentioned preservatives are benzotriazoles.

[0063]

[16]

[0064] According to the treatment solution described in

[15] , wherein,

[0065] The above-mentioned benzotriazoles are benzotriazoles that can be substituted with one or more of the following: alkyl groups that may also contain substituents, aryl groups that may also contain substituents, halogen atoms, amino groups that may also contain substituents, nitro groups that may also contain substituents, alkoxy groups that may also contain substituents, and hydroxyl groups.

[0066]

[17]

[0067] According to the treatment solution described in

[14] , wherein,

[0068] The above-mentioned preservatives are selected from benzotriazole, 5-aminotetrazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthol triazole, 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-isobenzotriazole, 4-isobenzotriazole, 5-methylbenzotriazole, 4-isobenzotriazole, 5-methylbenzotriazole, 4-isobenzotriazole, 5-iso ... One or more of the following: 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 solution according to any one of [1] to

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

[0071]

[19]

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

[18] has a pH of 6 to 11.

[0073]

[20]

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

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

[0075] 〔twenty one〕

[0076] According to the treatment solution described in

[20] , wherein,

[0077] The cobalt-containing substances mentioned above are cobalt monomers, cobalt alloys, cobalt oxides, or cobalt nitrides.

[0078] 〔twenty two〕

[0079] A method for processing an object, wherein,

[0080] The cobalt-containing substance containing cobalt atoms is contacted with the treatment liquid described in any one of [1] to

[21] to dissolve the cobalt-containing substance.

[0081] 〔twenty three〕

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

[0083] Step A involves performing the following treatment on the workpiece containing the metal layer to oxidize the surface of the metal layer and form a metal oxide layer, the treatment including:

[0084] Liquid treatment involving contact with solutions selected from water, hydrogen peroxide solution, ammonia and hydrogen peroxide mixed aqueous solution, hydrofluoric acid and hydrogen peroxide solution mixed aqueous solution, sulfuric acid and hydrogen peroxide solution mixed aqueous solution, hydrochloric acid and hydrogen peroxide solution mixed aqueous solution, oxygen dissolved water, and ozone dissolved water.

[0085] Ozone treatment involving contact with ozone gas

[0086] Oxygen heating treatment performed under an oxygen atmosphere, or

[0087] Plasma treatment using oxygen; and

[0088] Step B involves contacting the workpiece obtained in step A with any one of the processing solutions [1] to

[19] to dissolve the metal oxide layer.

[0089] 〔twenty four〕

[0090] According to the treatment method for the object described in

[23] , wherein,

[0091] The above process A and process B are performed alternately and repeatedly.

[0092]

[25]

[0093] According to the treatment method for the object to be treated as described in

[23] or

[24] , wherein,

[0094] The aforementioned metal layer is composed of cobalt-containing substances, either as cobalt monomers or cobalt alloys.

[0095]

[26]

[0096] A method for processing an object, wherein,

[0097] After performing dry etching on the workpiece containing metallic materials...

[0098] The subject is brought into contact with the treatment solution described in any one of [1] to

[19] to remove dry etching residue.

[0099]

[27]

[0100] According to the treatment method for the object to be treated as described in

[26] , wherein,

[0101] The aforementioned metallic materials are cobalt-containing substances containing cobalt atoms.

[0102] Invention Effects

[0103] According to the present invention, a treatment solution with excellent removal properties and excellent stability for organic residues can be provided.

[0104] Furthermore, according to the present invention, a method for treating a substance related to the above-described treatment liquid can also be provided. Attached Figure Description

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

[0106] Figure 2 This is a cross-sectional view showing another embodiment of the object being processed.

[0107] Figure 3 This is a cross-sectional schematic diagram illustrating an example of a processing method for a processed object applicable to one embodiment of the present invention. Detailed Implementation

[0108] The present invention will now be described in detail.

[0109] The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0110] In addition, in this specification, the numerical range indicated by “~” refers to the range including the values ​​recorded before and after “~” as the lower and upper limits.

[0111] Furthermore, in this invention, "ppm" refers to "parts-per-million: parts per million (ppm)". -6 "ppb" refers to "parts-per-billion (10 ppb)". -9 "ppt" refers to "parts-per-trillion: one trillionth (10 -12 )".

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

[0113] [Treatment Fluid]

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

[0115] The mechanism by which the treatment fluid with this structure solves the above-mentioned problems is not necessarily clear, but the inventors believe it to be as follows.

[0116] That is, the treatment solution of the present invention contains both hydroxylamine and hydrazine in the water. Hydrazine has more nitrogen atoms than hydroxylamine, and the number of non-shared electron pairs on nitrogen atoms is greater than that of hydroxylamine. Thus, it is speculated that hydrazine has a suitable abundance of non-shared electron pairs on nitrogen atoms, so that when coexisting with hydroxylamine, hydrazine and / or hydroxylamine can appropriately interact with organic matter, thereby achieving excellent removal of organic residues from the treatment solution. Furthermore, it is speculated that since the content of hydrazine is below a specified amount, the decomposition of hydroxylamine that may occur during storage of the treatment solution is suppressed, contributing to the excellent stability of the treatment solution.

[0117] Furthermore, when the processing liquid of the present invention contains a specified type and amount of anions, the treated material can further exhibit excellent removal properties of residues containing metal as the main component (hereinafter referred to as "metal residue removal property of the processing liquid") and / or excellent surface smoothness of metal-containing substances (such as cobalt-containing substances) contained in the treated material after treatment (hereinafter referred to as "smoothness of the treated material").

[0118] Hereinafter, the treatment liquid of the present invention will be referred to as having "superior effect of treatment liquid" when it has better removal performance of organic residues, better stability, better removal performance of metal residues, and / or better smoothness of the treated object.

[0119] The components contained in the processing liquid of the present invention will be described in detail below.

[0120] <Water>

[0121] The treatment solution contains water.

[0122] There are no particular restrictions on water; examples include distilled water, ion-exchanged water, and pure water.

[0123] There is no particular limitation on the water content in the treatment solution, but it 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 solution. The upper limit is less than 100% by mass.

[0124] Hydroxylamine

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

[0126] Hydroxylamine can ionize in the treatment solution.

[0127] There is no particular limitation on the content of hydroxylamine compounds, but from the viewpoint of achieving better treatment results, it is preferably 0.001 to 25% by mass relative to the total mass of the treatment solution.

[0128] If the hydroxylamine content is 0.001% by mass or more relative to the total mass of the treatment solution, the cleaning properties of the treatment solution are superior; if it is 25% by mass or less, the smoothness of the treated material is superior.

[0129] From the viewpoint of achieving an excellent balance of performance of the treatment solution, the content of hydroxylamine relative to the total mass of the treatment solution is preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.5 to 8% by mass.

[0130] The content of hydroxylamine in the treatment solution can be determined by ion chromatography (e.g., Thermo Fisher Scientific K.K.'s Dionex ICS-2100).

[0131] Furthermore, given the known composition and formulation of the raw materials used in the preparation of the treatment solution, the amount of raw materials can be calculated based on the formulation quantity.

[0132] <Hydrazine>

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

[0134] Hydrazine derivatives may or may not be salts.

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

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

[0137] H2N-NR N 2 (A)

[0138] H₂N-N=X (B)

[0139] In addition, hydrazine derivatives are preferably not azoles other than pyrazoles (such as benzotriazoles).

[0140] General formula (A)(H2N-NR) N In 2), there are two Rs.N Each R represents a hydrogen atom or a substituent independently. N They can bond together to form a ring, in which two Rs N At least one of them is not a hydrogen atom (in other words, both R atoms are not hydrogen atoms). N At least one of them is a substituent or both R N They bond together to form a ring.

[0141] As a result of R N The substituents indicated are preferably alkyl groups (which may also be straight-chain or branched. The number of carbon atoms is preferably 1 to 5) or -L N -NH2(L N This indicates a single bond or a divalent linking group. The divalent linking group is preferably -CO-, -CS-, -NH-, -C(=NH)-, or a combination of two or more of them.

[0142] In the general formula (B) (H₂N-N=X), X represents a divalent group. Preferably, X is =CR. C 2. Two Rs C Each can be used to represent a hydrogen atom or a substituent independently.

[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 hydrazine derivatives include pyrazole, carbazide, hemicarbazide, thiohemicarbazide, monomethylhydrazine, tert-butylhydrazine, dimethylhydrazine (1,1-dimethylhydrazine), and aminoguanidine.

[0145] Hydrazines preferably contain at least hydrazine.

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

[0147] In the treatment solution, the total content of hydrazine (preferably hydrazine) is 1 part by mass or less relative to 100 parts by mass of hydroxylamine. From the viewpoint of superior stability of the treatment solution, the aforementioned total content is preferably 0.5 parts by mass or less. From the viewpoint of superior removal of organic residues from the treatment solution, the aforementioned 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] In the treatment solution, the total content of hydrazine (preferably hydrazine) relative to the total mass of the treatment solution is preferably 0.0001 to 3000 ppm by mass. If the total content is 0.0001 ppm by mass or more (preferably 0.0005 ppm by mass or more, more preferably 0.005 ppm by mass or more, and even more preferably 0.05 ppm by mass or more), the removal performance of organic residues in the treatment solution is even better. If the total content is 3000 ppm by mass or less (preferably 300 ppm by mass or less), the stability of the treatment solution is even better.

[0149] The types and contents of hydrazine in the treatment solution can be determined by ion chromatography (such as the Dionex ICS-2100 from Thermo Fisher Scientific KK).

[0150] Furthermore, given the known composition and formulation of the raw materials used in the preparation of the treatment solution, the amount of raw materials can be calculated based on the formulation quantity.

[0151] There are no particular limitations on the method of introducing hydrazine into the treatment solution. For example, a substance containing hydrazine (hydrazine itself or its aqueous solution, etc.) can be added during the preparation of the treatment solution. Furthermore, hydrazine can be introduced into the treatment solution by using a substance containing hydrazine as a trace component (impurity, etc.) as a raw material during the preparation of the treatment solution.

[0152] <First Anion>

[0153] The treatment solution preferably contains Cl-. - NO2 - and NO3 - The first anion is one or more, more preferably two or more, and even more preferably three.

[0154] That is, the treatment solution preferably contains Cl. - NO2 - and NO3 - All kinds.

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

[0156] If the total content mentioned above is 0.00001 parts by mass or more, the removal performance of metal residues by the treatment solution is more excellent; if it is 100 parts by mass or less, the smoothness of the treated material is more excellent. From the viewpoint of achieving a good balance of performance of the treatment solution, the total content mentioned above 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 mentioned above, the treatment solution contains anions, and the inventors believe that the treatment solution has a superior effect for the following reasons.

[0158] That is, in the processing solution of the present invention, if a first anion is present in the water, the anion reacts appropriately with metal-containing residues after dry etching, thereby increasing its solubility in water and improving its cleaning properties. This effect becomes more pronounced if the total content of the first anion is above a predetermined amount relative to hydroxylamine. Furthermore, it is speculated that if the total content of the first anion is below a predetermined amount relative to hydroxylamine, the so-called pitting corrosion of the metal by the anion is suppressed, thereby improving the smoothness of the treated surface.

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

[0160] If the total content mentioned above is 0.001 ppm or more relative to the total mass of the treatment solution, the cleaning properties of the treatment solution are superior; if it is 50,000 ppm or less relative to the total mass of the treatment solution, the smoothness of the treated object is superior. From the viewpoint of achieving a good balance of performance of the treatment solution, the total content mentioned above relative to the total mass of the treatment solution is preferably 1 to 25,000 ppm, more preferably 2 to 15,000 ppm.

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

[0162] If Cl - If the content of [agent] is above 0.05 ppm by mass relative to the total mass of the treatment solution, the cleaning properties of the treatment solution will be better; if it is below 5000 ppm by mass, the smoothness of the treated object will be better.

[0163] From the perspective of achieving a good balance of performance in the treatment solution, Cl - The content of [the substance] relative to the total mass of the treatment liquid is more preferably 0.05 to 2000 ppm by mass, and even more preferably 0.1 to 500 ppm by mass.

[0164] In the treatment solution, NO2 -The content of [specific component] is preferably 0.001 to 30,000 ppm by mass relative to the total mass of the treatment solution.

[0165] If NO2 - When the NO2 content relative to the total mass of the treatment solution is 0.001 ppm or higher, the cleaning properties of the treatment solution are superior; if it is below 30,000 ppm, the smoothness of the treated material is superior. From the perspective of achieving a good balance of treatment solution performance, NO2... - The content of [the substance] relative to the total mass of the treatment liquid is more preferably 0.5 to 20,000 ppm by mass, and even more preferably 1 to 5,000 ppm by mass.

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

[0167] If NO3 - When the NO3 content relative to the total mass of the treatment solution is 0.001 ppm or higher, the cleaning properties of the treatment solution are superior; if it is below 30,000 ppm, the smoothness of the treated material is superior. From the perspective of achieving a good balance of treatment solution performance, NO3... - The content of [the substance] relative to the total mass of the treatment liquid is more preferably 0.5 to 20,000 ppm by mass, and even more preferably 1 to 5,000 ppm by mass.

[0168] NO2 in the first anion - and NO3 - It is also specifically referred to as a particular anion.

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

[0170] From the viewpoint of achieving a good balance of performance of the treatment solution, the total mass of the specific anions is preferably 1 to 50,000 ppm by mass relative to the total mass of the treatment solution, and more preferably 2 to 10,000 ppm by mass.

[0171] Furthermore, the treatment solution includes NO2. - and NO3 - The total mass of the two specific anions is preferably greater than that of Cl. - The mass content of the treatment solution. Furthermore, at this point, the treatment solution preferably contains more than 0 ppm of Cl relative to the total mass of the treatment solution. - More preferably, it contains 0.001 ppm or more by mass.

[0172] For example, the total mass of a specific anion contains the same as that of Cl. - The mass ratio of the total mass of a specific anion / Cl - The content of (by mass) is preferably 1.1 to 100, more preferably 1.5 to 30.

[0173] Furthermore, the content of the first anion in the treatment solution preferably satisfies the condition "Cl - The content of NO2 by mass ≤ - The content of NO3 is ≤ - The relationship between "containing mass" and "more preferably, satisfying "0.001 ppm mass ≤ Cl" is preferred. - The content of NO2 by mass ≤ - The content of NO3 is ≤ - The relationship between "containing quality" and "quality".

[0174] <Second anion>

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

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

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

[0178] If the total content is 0.0001 parts by mass or more, the cleaning properties of the treatment solution are superior; if it is 30 parts by mass or less, the smoothness of the treated object is superior. From the viewpoint of achieving a good balance of performance of the treatment solution, 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 solution contains a second anion, the total content of the second anion in the treatment solution (SO4) is... 2- and PO4 3- The total content of the solution is preferably more than 0 ppm and less than 1000 ppm, more preferably more than 0 ppm and less than 50 ppm, relative to the total mass of the treatment liquid.

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

[0181] The treatment solution contains PO4 3- In the case of PO4 in the treatment solution 3- The content of [agent] relative to the total mass of the treatment liquid is preferably more than 0 ppm by mass and less than 500 ppm by mass, more preferably more than 0 ppm by mass and less than 30 ppm by mass.

[0182] The contents of the first and second anions in the treatment solution can be determined by ion chromatography (e.g., ThermoFisher Scientific KK's Dionex ICS-2100).

[0183] Furthermore, given the known composition and formulation of the raw materials used in the preparation of the treatment solution, the amount of raw materials can be calculated based on the formulation quantity.

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

[0185] Furthermore, compounds that produce substances containing the first anion and / or the second anion through dissolution in water or chemical reactions can be used as a source of the first anion and / or the second anion. As an example, dinitrogen trioxide, which reacts with water to produce nitrous acid, can be cited.

[0186] Furthermore, by using a substance containing the first anion and / or the second anion as an impurity (trace component) as a raw material during the preparation of the treatment solution, the first anion and / or the second anion can be introduced into the treatment solution.

[0187] Chelating agents

[0188] The treatment solution may contain chelating agents. When the treatment solution contains chelating agents, its cleaning properties are superior. However, the chelating agents mentioned herein do not include the aforementioned hydrazine compounds.

[0189] Chelating agents are substances (preferably acids) that can function as chelating ligands, and are preferably compounds containing 1 or more (preferably 1 to 8) acid groups.

[0190] There are no particular limitations on the above-mentioned acid groups, but they are preferably selected from at least one functional group selected from carboxylic acid group, sulfonic acid group and phosphonic acid group.

[0191] Examples of chelating agents containing carboxylic acid groups include polyamino polycarboxylic acids, aliphatic dicarboxylic acids, aliphatic polycarboxylic acids containing hydroxyl groups, and ascorbic acid.

[0192] Polyaminopolycarboxylic acids are compounds containing multiple amino groups and multiple carboxylic acid groups. Examples include mono- or polyalkylene polyamine polycarboxylic acids, polyaminoalkane polycarboxylic acids, polyaminoalkol polycarboxylic acids, and hydroxyalkyl ether polyamine polycarboxylic acids.

[0193] Examples of polyamino polycarboxylic acids include butanediaminetetraacetic acid (DTPA), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraaminehexaacetic acid (TTPA), 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid (PDTA), ethylenediaminetetraacetic acid (EDTA), trans-1,2-cyclohexanediaminetetraacetic acid (TTA), ethylenediaminediacetic acid (EDTA), ethylenediaminediacetic acid (EDTA), 1,6-hexamethylenediamine-N,N,N',N'-tetraacetic acid (HTA), N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid (DTA), diaminopropanetetraacetic acid (DTA), 1,4,7,10-tetraazacyclododecane-tetraacetic acid (DTA), diaminopropanoltetraacetic acid (DTA), and (hydroxyethyl)ethylenediaminetriacetic acid (DTA). Among these, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA), or trans-1,2-cyclohexanediaminetetraacetic acid (DTA) are preferred.

[0194] Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, and maleic acid, with oxalic acid, malonic acid, or succinic acid being preferred.

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

[0196] Examples of ascorbic acids include ascorbic acid, isoascorbic acid, ascorbic acid sulfate, ascorbic acid phosphate, ascorbic acid 2-glucoside, ascorbic acid palmitate, tetraisopalmitic acid ascorbate, and ascorbic acid isopalmitic acid and their salts, with ascorbic acid being preferred.

[0197] Examples of chelating agents containing sulfonic acid groups include methanesulfonic acid.

[0198] Examples of chelating agents containing phosphonic acid groups include methyl diphosphonic acid, aminotris(methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, nitrazinetrimethylenephosphonic 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), diol ether diaminetetra(methylenephosphonic acid), tetraethylenepentaminehexa(methylenephosphonic acid), and glycine-N,N-di(methylenephosphonic acid) (glyphosate).

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

[0200] The chelating agent is more preferably diethylenetriaminepentaacetic acid or citric acid.

[0201] When the treatment solution contains a chelating agent, from the viewpoint of achieving better treatment results, the content of the chelating agent relative to the total mass of the treatment solution is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.2 to 5% by mass.

[0202] A single chelating agent may be used, or two or more may be used. When using two or more chelating agents, it is preferable that their total amount is within the range described above.

[0203] <Preservatives>

[0204] The treatment solution may contain preservatives. Preservatives eliminate excessive etching of the treated material, thereby improving its smoothness. The preservatives mentioned herein do not include the aforementioned hydrazine compounds and chelating agents.

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

[0206] [Chemical Formula 1]

[0207]

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

[0209] In equation (1X), R 6a R 6b and R 6cEach can be used to represent a hydrogen atom or a substituent independently.

[0210] The substituents mentioned above are preferably, independently, a hydrocarbon group, a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom, etc.), an amino group, a nitro group, an alkoxy group (preferably with 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), or a hydroxyl group. If possible, their substituents may also contain substituents.

[0211] Substituents that may be contained in the above-mentioned hydrocarbon group and alkoxy group include, for example, hydroxyl, carboxyl, or substituted or unsubstituted amino groups (preferably alkyl groups with 1 to 6 carbon atoms, more preferably alkyl groups with 1 to 3 carbon atoms).

[0212] Substituents that may be present in the above-mentioned amino group include, for example, alkyl groups having 1 to 6 carbon atoms.

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

[0214] If possible, their hydrocarbon groups may also contain substituents, and examples of substituents that may be present are as described above.

[0215] Furthermore, when X is -CR 6a In the case of =, R 6a With R 6b They can bond together to form a ring.

[0216] As R 6a With R 6b Rings formed by bonding include, for example, benzene rings and naphthalene rings. In R 6a With R 6b When the ring is formed by bonding, the ring may also have substituents (e.g., hydrocarbon groups or carboxyl groups with 1 to 5 carbon atoms).

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

[0218] As azoles, benzotriazoles (compounds having a benzotriazole structure) are preferred. That is, benzotriazoles are also preferred as preservatives.

[0219] Regarding benzotriazoles, examples include benzotriazoles that can be substituted with one or more of the following: alkyl groups (which may also contain substituents), aryl groups (which may also contain substituents), halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms, etc.), amino groups (which may also contain substituents), nitro groups (which may also contain substituents), alkoxy groups (which may also contain substituents), and hydroxyl groups.

[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 mentioned above is a number that also takes into account the number of carbon atoms in the substituents that the alkyl group may contain.

[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 mentioned above is a number obtained by taking into account the number of carbon atoms in the substituents that the aryl group can contain.

[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 mentioned above is a number obtained by taking into account the number of carbon atoms in the substituents that the alkoxy group can contain.

[0223] Substituents that may be present in the above-mentioned alkyl, aryl, and alkoxy groups include, for example, hydroxyl, carboxyl, or substituted or unsubstituted amino groups (preferably alkyl groups with 1 to 6 carbon atoms, more preferably alkyl groups with 1 to 3 carbon atoms).

[0224] Substituents that may be present in the above-mentioned amino group include, for example, alkyl groups having 1 to 6 carbon atoms.

[0225] When the benzotriazole is a benzotriazole containing substituents, it is preferable that the substituents independently substitute for any one or more of the 1, 4, and 5 positions, and preferably that the substituents substitute for any one of the 1, 4, and 5 positions.

[0226] Substituents can replace positions other than 1, 4, and 5 of benzotriazole, or they can remain unsubstituted.

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

[0228] Preferably, it is an amino-substituted benzotriazole at the 1-position or an alkyl-substituted benzotriazole at the 5-position.

[0229] Benzotriazoles are also preferred to be unsubstituted benzotriazoles.

[0230] Examples of benzotriazoles include benzotriazole (BTA), 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthol triazole, 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-aminotetrazole (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-tetrazole-5-acetic acid, 2-mercaptobenzothiazole (2-MBT), and 1-phenyl-2-tetrazole. Phosphori-5-thione, 2-mercaptobenzimidazole (2-MBI), 4-methyl-2-phenylimidazolium, 2-mercaptothiazoline, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, imidazole, benzimidazole, triazine, methyltetrazole triazine, bismuth thiols I, 1,3-dimethyl-2-imidazolidineone, 1,5-pentamethylenetetrazolium, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, imidazoline thione, 4-methyl-4H-1,2,4-triazol-3-thiol, 5-amino-1,3,4-thiadiazol-2-thiol, benzothiazole, 2,3,5-trimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, quinoxaline, acetylpyrrole, pyrazines and pyrazines.

[0232] Preservatives are preferably selected from benzotriazole, 5-aminotetrazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthol triazole, 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-isobenzotriazole, etc. One or more of the following: 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] The preservative is more preferably benzotriazole, 1-amino-benzotriazole or 5-methyl-1H-benzotriazole, and even more preferably 5-methyl-1H-benzotriazole.

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

[0235] One preservative may be used, or two or more may be used. When using two or more preservatives, it is preferable that their total amount is within the range mentioned above.

[0236] <Organic solvents>

[0237] The processing solution of the present invention may contain organic solvents.

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

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

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

[0241] Their solvents can be water-soluble.

[0242] The treatment solution preferably contains one or more organic solvents selected from alcohol solvents, ketone solvents, ester solvents and ether solvents.

[0243] Examples of alcohol solvents include alkyl glycols (e.g., alkylene glycols), alkoxy alcohols (e.g., ethylene glycol monoethers), saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, and low molecular weight alcohols with cyclic structures.

[0244] The preferred alcohol solvent is ethylene glycol monoether or saturated aliphatic monohydric alcohol.

[0245] Examples of alkyl glycols include diols, 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 glycols.

[0246] Examples of alkylene glycols include ethylene glycol, propylene glycol, benzene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.

[0247] Examples of alkoxy alcohols include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and ethylene glycol monoethers.

[0248] Examples of 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 and diethylene glycol monobenzyl ether, 1-octanol, 2-octanol and 2-ethylhexanol, etc.

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

[0250] Examples of saturated aliphatic monohydric alcohols include methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 2-pentanol, tert-pentanol, and hexanol.

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

[0252] Examples of low molecular weight alcohols with cyclic structures include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

[0253] Examples of ketone solvents 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 ester solvents include ethyl acetate, butyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, and other glycol monoesters, as well 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 sulfonic acid solvents include sulfolane, 3-methylsulfolane, and 2,4-dimethylsulfolane.

[0256] Examples of sulfoxide solvents include dimethyl sulfoxide.

[0257] Examples of nitrile solvents include acetonitrile.

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

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

[0260] One or more organic solvents may be used. When using two or more organic solvents, it is preferable that their total amount is within the range described above.

[0261] <Reducing agents different from hydroxylamine>

[0262] The treatment solution may contain a reducing agent different from hydroxylamine. Additionally, hydrazines, chelating agents, and preservatives are not included among reducing agents different from hydroxylamine.

[0263] There are no particular limitations on the reducing agent, except that it is preferably a reducing substance containing an OH group or a CHO group, or a compound containing a sulfur atom. The reducing agent described above functions by reducing the OH group, which has oxidizing properties and is the cause of the decomposition of hydroxylamine. - Oxidation by ions or dissolved oxygen, etc.

[0264] Among reducing substances such as compounds containing OH or CHO groups or compounds containing sulfur atoms, the preferred choice is one of the compounds represented by formula (4) and compounds containing sulfur atoms.

[0265] [Chemical Formula 2]

[0266]

[0267] In equation (4), R 4a ~R 4e Each can independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group that may have heteroatoms. Additionally, in R... 4a ~R 4e In the case of a hydrocarbon group that may have heteroatoms, the aforementioned hydrocarbon group may have substituents.

[0268] In equation (4), R is... 4a ~R 4e The hydrocarbon group represented can have heteroatoms, and examples include hydrocarbon groups and hydrocarbon groups containing heteroatoms.

[0269] As mentioned above, R 4a ~R 4e Examples of hydrocarbon groups include alkyl (preferably 1 to 12 carbon atoms, more preferably 1 to 6), alkenyl (preferably 2 to 12 carbon atoms, more preferably 2 to 6), alkynyl (preferably 2 to 12 carbon atoms, more preferably 2 to 6), aryl (preferably 6 to 22 carbon atoms, more preferably 6 to 14, further preferably 6 to 10) and aralkyl (preferably 7 to 23 carbon atoms, more preferably 7 to 15, further preferably 7 to 11).

[0270] Furthermore, as mentioned above, R 4a ~R 4e The hydrocarbon groups containing heteroatoms mentioned above can be exemplified by -CH2- selected from, for example, -O-, -S-, -CO-, -SO2-, and -NR. a -A divalent group that replaces any one of the groups or a combination of multiple groups thereof. The above R a A hydrocarbon group representing 1 to 20 hydrogen atoms (preferably an alkyl group representing 1 to 5 carbon atoms).

[0271] Furthermore, examples of substituents include hydroxyl, carboxyl, or substituted or unsubstituted amino groups (preferably alkyl groups with 1 to 6 carbon atoms, more preferably alkyl groups with 1 to 3 carbon atoms).

[0272] Examples of compounds represented by formula (4) above 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 power, the compound represented by formula (4) preferably has two or more hydroxyl groups, more preferably three or more. There are no particular limitations on the substitution position of the hydroxyl groups, but from the viewpoint of adding reducing power, R is preferred. 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. Furthermore, examples of compounds represented by formula (4) having three or more hydroxyl groups include gallic acid.

[0275] Examples of compounds containing sulfur atoms 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-methylpropanesulfonate [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 (thiol compounds) are preferred, more preferably 1-thioglycerol, sodium 3-mercapto-1-propanesulfonate, 2-mercaptoethanol, 3-mercapto-1-propanol or thioacetic acid, and even more preferably 1-thioglycerol or thioacetic acid.

[0276] In addition, reducing agents different from hydroxylamine can be used alone or in combination with two or more.

[0277] <Fluorides>

[0278] The treatment solution may contain fluorides. Fluorides promote the decomposition and solubilization of residues.

[0279] There are no particular limitations on fluorides, and examples include hydrofluoric acid (HF), fluorosilicic acid (H2SiF6), fluoroboric acid, ammonium fluorosilicate ((NH4)2SiF6), tetramethylammonium hexafluorophosphate, ammonium fluoride, ammonium fluoride salt, ammonium difluoride salt, quaternary ammonium tetrafluoroborate and quaternary phosphorus tetrafluoroborate represented by the formulas NR4BF4 and PR4BF4, respectively, and tetrabutylammonium tetrafluoroborate (TBA-BF4).

[0280] Furthermore, in the tetrafluoroborate quaternary ammonium compounds (e.g., tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate) and tetrafluoroborate quaternary phosphorus compounds represented by the above formulas NR4BF4 and PR4BF4 respectively, R can be of the same or different types, and R is hydrogen, a straight-chain, branched, or cyclic C1-C6 alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl) and a straight-chain or branched C6-C10 aryl group (e.g., benzyl). Fluorides can be used alone or in appropriate combinations of two or more types.

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

[0282] <Metal component>

[0283] The treatment solution may contain metallic components.

[0284] As a metallic component, examples include metal particles and metal ions. For instance, when referring to the content of a metallic component, it can be expressed as the total content of metal particles and metal ions.

[0285] The treatment solution may contain either metal particles or metal ions, or both. Preferably, the treatment solution contains both metal particles and metal ions.

[0286] Metal atoms contained in a metallic composition can be, for example, 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] Metallic components can contain one type of metal atom or two or more types.

[0288] Metal particles can be monomers, alloys, or exist in the form of metal-organic combinations.

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

[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 the 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 may exist only in either the above cyclic structure or outside the above cyclic structure, or may exist in both.

[0302] Examples of amine compounds with cyclic structures 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-piperidinemethanol, cyclohexylamine, and 1,5-diazabicyclo[4,3,0]-5-nonene.

[0303] Among them, the preferred amine compounds are 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 solution contains amine compounds different from hydroxylamine and hydrazine, the content of such compounds relative to the total mass of the treatment solution is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass.

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

[0306] [Chemical Formula 3]

[0307]

[0308] In equation (5) above, R 5a ~R 5d Each of the following can be independently represented: alkyl (1-16 carbon atoms), aryl (6-16 carbon atoms), aralkyl (7-16 carbon atoms), or hydroxyalkyl (1-16 carbon atoms). R 5a ~R 5d At least two of them can bond to each other to form a ring structure, especially R 5a With R 5b Combinations and R 5c With R 5d At least one of the combinations can bond with each other to form a ring structure.

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

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

[0311] As an alkaline compound, other water-soluble amines besides those mentioned above can also be used.

[0312] The pKa of water-soluble amines is preferably 7.5 to 13.0 at room temperature. Furthermore, in this specification, "water-soluble amine" refers to an amine that can dissolve more than 50 g in 1 L of water at room temperature. Also, as a water-soluble amine, it does not contain ammonia.

[0313] Examples of water-soluble amines with pKa values ​​of 7.5 to 13 include diethylene glycolamine (DGA) (pKa = 9.80), methylamine (pKa = 10.6), ethylamine (pKa = 10.6), propylamine (pKa = 10.6), butylamine (pKa = 10.6), pentanamine (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, unsubstituted hydroxylamine and hydroxylamine derivatives can also be used as water-soluble amines.

[0315] Furthermore, the pKa of water-soluble amines in this specification refers to the acid dissociation constant in water. The acid dissociation constant in water can be determined using a combination of spectrophotometry and potentiometric measurement.

[0316] The pH adjuster is preferably a compound selected from one or more of acetic acid, perchloric acid, hypochlorous acid, periodic acid, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, and water-soluble amines.

[0317] From the viewpoint of achieving better treatment results, the pH of the treatment solution is preferably 1 to 13, and more preferably 6 to 11.

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

[0319] The solution can be treated by adjusting the pH level appropriately to achieve the target pH.

[0320] <Method for manufacturing treatment fluid>

[0321] There are no particular limitations on the manufacturing method of the above-mentioned treatment solution, and well-known manufacturing methods can be used. For example, a method of mixing water, hydroxylamine, and hydrazine (or aqueous solutions thereof) can be cited. In addition, when mixing the above components, other arbitrary components (substances containing a first anion and / or a second anion, etc.) can be further mixed as needed.

[0322] Furthermore, during the manufacturing of the treatment solution, a filter can be used to purify it as needed.

[0323] The processing liquid of the present invention is preferably used for a workpiece containing a metal-based material as a metal-containing material, and more preferably for a workpiece containing a cobalt-containing substance (hereinafter referred to as "cobalt-containing substance") containing cobalt atoms.

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

[0325] <Processing Fluid Containment>

[0326] The treatment fluid can be contained in a container and stored until it is used.

[0327] This container and the processing liquid contained within it are collectively referred to as a processing liquid container. The processing liquid is retrieved from the stored processing liquid container for use. Furthermore, the processing liquid can be transported using the processing liquid container.

[0328] As a container, it is preferable to have a high degree of cleanliness and minimal leaching of impurities for semiconductor applications. Examples of usable containers 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 different resin. Furthermore, the inner wall of the container is also preferably formed of a metal treated with rust prevention and metal leaching prevention measures, such as stainless steel, Herstal alloy, Ingalls alloy, and Monel alloy.

[0330] Of the aforementioned different resins, fluorinated resins (perfluorinated resins) are preferred. By using a container with an inner wall made of fluorinated resin, compared to a container with an inner wall made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin, it is possible to suppress undesirable conditions such as the leaching of oligomers of ethylene or propylene.

[0331] Examples of containers with fluorinated resin inner walls include the Fluoro Pure PFA composite container manufactured by Entegris. Furthermore, containers described in Japanese Patent Publication No. 3-502677 (page 4), International Publication No. 2004 / 016526 (page 3), and International Publication No. 99 / 46309 (pages 9 and 16) can also be used.

[0332] Furthermore, in addition to the aforementioned fluorinated resins, the inner wall of the container can preferably be made of quartz and electrolytically polished metal materials (i.e., metal materials that have undergone electrolytic polishing).

[0333] The metal material used in the manufacture of the aforementioned electrolytically ground metal material is preferably a metal material containing at least one selected from chromium and nickel, wherein the total content of chromium and nickel is more than 25% by mass relative to the total mass of the metal material, such as stainless steel and nickel-chromium alloys.

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

[0335] Furthermore, there is no particular limit to the total content of chromium and nickel in the metallic material, but it is preferably 90% by mass or less relative to the total mass of the metallic material.

[0336] There are no particular restrictions on the type of stainless steel used; any known type of stainless steel can be used. Among these, an alloy containing 8% by mass or more of nickel is preferred, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferred.

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

[0338] There are no particular restrictions on the nickel-chromium alloy used; any known nickel-chromium alloy can be used. Among these, a nickel-chromium alloy with 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, for example, Hoechst alloys (product name, hereinafter the same), Monel alloys (product name, hereinafter the same), and Ingonane alloys (product name, hereinafter the same). More specifically, examples include Hoechst alloy C-276 (Ni content 63% by mass, Cr content 16% by mass), Hoechst alloy-C (Ni content 60% by mass, Cr content 17% by mass), and Hoechst alloy C-22 (Ni content 61% by mass, Cr content 22% by mass).

[0340] In addition to the alloys mentioned above, nickel-chromium alloys may also contain boron, silicon, tungsten, molybdenum, copper, or cobalt, depending on the requirements.

[0341] There are no particular limitations on the method for electrolytic polishing of metallic materials, and known methods can be used. For example, the methods described in paragraphs

[0011] -

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

[0036] -

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

[0342] Furthermore, the metal material is preferably polished. There are no particular limitations on the polishing method; known methods can be used. There are no particular limitations on the size of the abrasive grains used in fine polishing, but from the viewpoint that the surface roughness of the metal material is more easily reduced, a size of #400 or less is preferred.

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

[0344] Furthermore, the metal material can be a metal material that has been treated by combining one or more of the following processes: polishing, pickling, and magnetic fluid grinding, which involve changing the size of the abrasive grains and other specifications.

[0345] These containers are preferably cleaned inside before being filled with the treatment liquid. Preferably, the liquid used for cleaning has a reduced amount of metallic impurities.

[0346] The treatment fluid can be transported or stored after manufacturing in containers such as gallon bottles or coated bottles.

[0347] To prevent changes in the composition of the processing liquid during storage, the container can be purged with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher. A gas with low water content is particularly preferred. Furthermore, transportation and storage can be carried out at room temperature, but to prevent deterioration, the temperature can be controlled within the range of -20°C to 20°C.

[0348] In addition, the above-mentioned treatment solution can be used as a kit to divide its raw materials into multiple parts.

[0349] Furthermore, the treatment solution can be prepared as a concentrate. When the treatment solution is prepared as a concentrate, its concentration ratio can be appropriately determined according to the composition, preferably 5 to 2000 times. That is, the concentrate can be diluted 5 to 2000 times for use.

[0350] [Methods for processing the object]

[0351] In the treatment method for a workpiece using the treatment liquid of the present invention (hereinafter, simply referred to as "the treatment method"), the treatment liquid is generally capable of contacting the workpiece containing a metallic material as a metal-containing material. At this time, the workpiece may contain multiple types of metallic materials. Furthermore, it is preferable that the treatment liquid dissolves at least one of the multiple types of metallic materials.

[0352] Metallic materials only need to have metal atoms (such as cobalt (Co), ruthenium (Ru), tungsten (W), molybdenum (Mo), aluminum (Al), copper (Cu), titanium (Ti) and / or tantalum (Ta), etc.). Examples include single metals, alloys, metal oxides (which can be composite oxides) and metal nitrides (which can be composite nitrides).

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

[0354] Examples of metallic materials include cobalt-containing substances and other metallic substances. Details about cobalt-containing and metallic substances will be discussed later.

[0355] For example, it is also preferable that the workpiece may contain at least one of a variety of metallic materials that is cobalt-containing, and it is also preferable to use the treatment solution to contact the workpiece containing the cobalt-containing material and dissolve (etch) the cobalt-containing material.

[0356] That is, the processing solution can be, for example, an etching processing solution.

[0357] The material to be treated is preferably a metal-containing material (hereinafter referred to as "metal-containing material") that contains cobalt-containing substances and contains other metal atoms besides cobalt atoms (hereinafter referred to as "other metal atoms").

[0358] At this point, the processing solution can be used for etching only cobalt-containing materials, or for etching both cobalt-containing and metal-containing materials.

[0359] There are no particular restrictions on the shape of the object being processed, for example, Figure 1As shown, the workpiece 10 may include a substrate 12, an insulating film 14 having holes disposed on the substrate 12, a layered metal-containing material portion 16 disposed along the inner wall of the holes in the insulating film 14, and a cobalt-containing material portion 18 filled into the holes. Figure 1 In this process, the metal-containing material can function as a barrier metal layer.

[0360] Figure 1 The method of treating an object containing a cobalt-containing component is described, but it is not limited to this method. For example, Figure 2 As shown, the workpiece 20 may include a substrate 12, an insulating film 14 having multiple holes disposed on the substrate 12, a metal-containing material portion 16 disposed in layers along the inner wall of each hole of the insulating film 14, and a cobalt-containing material portion 18 filled into each hole. That is, the workpiece may have a cobalt-containing material in multiple locations and a metal-containing material in multiple locations.

[0361] There are no particular restrictions on the types of substrates that can be contained in the processed material. Examples include semiconductor wafers, glass substrates for photomasks, glass substrates for liquid crystal displays, glass substrates for plasma displays, substrates for FED (Field Emission Display), substrates for optical discs, substrates for magnetic disks, and substrates for optical discs.

[0362] Materials constituting semiconductor substrates include, for example, group III-V compounds such as silicon, silicon germanium, and GaAs, or any combination thereof.

[0363] There are no particular restrictions on the size, thickness, shape, and layer structure of the substrate; it can be selected appropriately according to the needs.

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

[0365] exist Figure 1 and Figure 2 In this context, the insulating film has pores, but it is not limited to this method; it can also be an insulating film with grooves.

[0366] Cobalt-containing substances only need to have cobalt atoms, such as cobalt monomers (metallic cobalt), cobalt alloys (preferably alloys in which cobalt is the most abundant metal component), cobalt oxides, and cobalt nitrides.

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

[0368] Furthermore, there are no particular restrictions on the types of other metal atoms in the metallic substance; for example, titanium and tantalum can be cited. Among these, metal atoms that are more expensive than cobalt are preferred as other metal atoms.

[0369] Metallic substances only need to contain the other metal atoms mentioned above, such as metal monomers, alloys, oxides, and nitrides.

[0370] From the viewpoint of achieving better treatment effect, titanium monomers, titanium alloys, titanium oxides, titanium nitrides, tantalum monomers, tantalum alloys, tantalum oxides, or tantalum nitrides are preferred as metallic substances.

[0371] When the material being processed contains metallic substances, the cobalt-containing substances and the metallic substances can come into contact within the material being processed or can be disposed of via other components.

[0372] There are no particular restrictions on the form of cobalt-containing and metal-containing substances; for example, they can be any of the following forms: film-like, wire-like, or particle-like.

[0373] When the cobalt-containing and metal-containing substances are in the form of a film, there is no particular limitation on its thickness. It can be selected appropriately according to the application. For example, it is preferred to be less than 50 nm, more preferably less than 20 nm, and even more preferably less than 10 nm.

[0374] The cobalt-containing material and the metal-containing material can be disposed on only one side of the main surface of the substrate, or on both sides of the main surface. Furthermore, the cobalt-containing material and the metal-containing material can be disposed on the entire main surface of the substrate, or on a portion of the main surface of the substrate.

[0375] In addition, the treated material may contain two or more cobalt-containing substances or two or more metal-containing substances.

[0376] The description of the processed materials above primarily focuses on those containing cobalt-containing substances. However, processed materials containing cobalt-containing substances can also contain different metallic materials to replace the cobalt-containing substances. For example, these processed materials can contain ruthenium-containing substances, tungsten-containing substances, molybdenum-containing substances, aluminum-containing substances, or copper-containing substances to replace the cobalt-containing substances. Details regarding ruthenium-containing substances, tungsten-containing substances, molybdenum-containing substances, aluminum-containing substances, and copper-containing substances are, for example, the same as those described in the previous paragraph where cobalt in the cobalt-containing substances is replaced with ruthenium, tungsten, molybdenum, aluminum, and copper, respectively.

[0377] Furthermore, when the processed material contains ruthenium-containing, tungsten-containing, molybdenum-containing, aluminum-containing, or copper-containing substances instead of cobalt-containing substances, the "other metal atoms" in the aforementioned metal-containing substances also become 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, titanium monomers, titanium alloys, titanium oxides, titanium nitrides, tantalum monomers, tantalum alloys, tantalum oxides, or tantalum nitrides are preferred as the metal-containing substances.

[0378] In addition to the above, the processed material may contain various layers and / or structures as needed. For example, the substrate may have metal wiring, gate electrode, source electrode, drain electrode, insulating layer, strong magnetic layer and / or non-magnetic layer, etc.

[0379] The substrate may have exposed integrated circuit structures, such as interconnects including metal wiring and dielectric materials. Examples of metals and alloys used for the interconnects include aluminum, aluminum-copper alloys, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. The substrate may have layers of silicon oxide, silicon nitride, silicon carbide, and / or carbon-doped silicon oxide.

[0380] There are no particular limitations on the manufacturing method of the processed object. For example, an insulating film is formed on a substrate, and holes or grooves are formed on the insulating film. After sequentially depositing a metal-containing layer and a cobalt-containing layer on the insulating film using methods such as sputtering, chemical vapor deposition (CVD), and molecular beam epitaxy (MBE), planarization treatment such as CMP is performed, thereby manufacturing the processed object. Figure 1 The object being processed is shown.

[0381] As a method for processing the workpiece according to the present invention, an example is a method of contacting the workpiece containing at least one metallic material with the aforementioned processing liquid. By employing this method, one or more metallic materials contained in the workpiece can be dissolved or the workpiece can be cleaned (such as cleaning dry etching residue contained in the workpiece).

[0382] <Method 1>

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

[0384] There are no particular limitations on the method of bringing the object to be treated into contact with the treatment liquid. Examples include immersing the object in the treatment liquid placed in a tank, spraying the treatment liquid onto the object, allowing the treatment liquid to flow over the object, and any combination thereof. Among these, the method of immersing the object in the treatment liquid is preferred.

[0385] Furthermore, in order to further enhance the cleaning ability of the treatment solution, mechanical stirring can be used.

[0386] Examples of mechanical stirring methods include circulating the treatment liquid over the workpiece, flowing or spraying the treatment liquid over or onto the workpiece, and stirring the treatment liquid using ultrasound or megason.

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

[0388] There is no particular limitation on the treatment time (the contact time between the treatment liquid and the treated object), but it is preferably 0.25 to 10 minutes, and more preferably 0.5 to 2 minutes.

[0389] There are no particular limitations on the temperature of the treatment solution during the process, but it is preferably 20 to 75°C, and more preferably 20 to 65°C.

[0390] This treatment primarily dissolves cobalt-containing substances in the treated material.

[0391] When the material being treated contains metallic substances in addition to cobalt-containing substances, this treatment may or may not dissolve the metallic substances along with the cobalt-containing substances. If the metallic substances are dissolved, this dissolution may be intentional or unavoidable.

[0392] In cases where there is no intentional dissolution of the metal-containing substance, it is preferable that the amount of the metal-containing substance that is inevitably dissolved is small. The situation where the amount of the metal-containing substance that is inevitably dissolved is also referred to as the case where the treatment solution exhibits excellent resistance to the component containing the metal-containing substance.

[0393] In addition, in the first method, the material being treated may contain ruthenium, tungsten, molybdenum, aluminum, or copper, in addition to cobalt.

[0394] <Method 2>

[0395] Furthermore, as another method for processing the object to be processed according to the present invention, the following second method can be cited.

[0396] That is, the treatment method for the workpiece includes: step A, performing an oxidation treatment on the workpiece including a metal layer to oxidize the surface of the metal layer to form a metal oxide layer; and step B, contacting the workpiece obtained in step A with a treatment liquid to dissolve the metal oxide layer.

[0397] Method 2 can be a form of method 1.

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

[0399] The aforementioned metal oxide layer is a layer formed by oxidizing the surface of the aforementioned metal layer, also known as a form of metallic material. A portion of the surface of the metal layer can be a metal oxide layer, or the entire surface of the metal layer can be a metal oxide layer.

[0400] The metal oxide layer is an oxide of a metal monomer or alloy, and preferably includes a layer of 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 including cobalt oxide or cobalt alloy oxide, and even more preferably a layer including cobalt oxide.

[0401] The thickness of the metal oxide layer is, for example, 1 to 10 atomic layers. Furthermore, the thickness of 1 atomic layer of the metal and the metal oxide is less than 1 nm (e.g., 0.3 nm to 0.4 nm). That is, the oxidation process is a process that oxidizes the surface layer of the metal layer to, for example, 1 to 10 atomic layers to form a metal oxide layer.

[0402] In many cases, the metal oxide layer is more soluble in the processing solution than the metal layer (making it easier to etch).

[0403] That is, in the second method, in step A, the surface of the metal layer is formed into a thin metal oxide layer, and in step B, the processing liquid is used to remove only the aforementioned metal oxide layer (and the portion of the metal layer below the metal oxide layer that can inevitably be dissolved), thereby removing (dissolving) only the very thin surface of the metal layer included in the processed object.

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

[0405] When alternating between process A and process B, it is preferable to perform process A and process B 1 to 20 times each.

[0406] The workpiece to be processed in the second method may consist of a single metal layer or two or more metal layers. Furthermore, the workpiece to be processed in the second method may contain metallic materials other than metal layers or metal oxide layers, and may also have some or all of such metallic materials intentionally or unavoidably removed through steps A and B.

[0407] Process A is as follows: an oxidation treatment is performed on the workpiece including the metal layer to oxidize the surface of the metal layer and form a metal oxide layer.

[0408] There are no limitations on the oxidation treatment method used to oxidize the surface of a metal layer to form a metal oxide layer. For example, it can be carried out by treating the workpiece by liquid treatment that brings the workpiece into contact with an oxidizing solution, gas treatment that brings the workpiece into contact with an oxidizing gas (such as ozone treatment that brings the workpiece into contact with ozone gas or oxygen heating treatment that heats the workpiece in an oxygen atmosphere, etc.), or plasma treatment that uses oxygen on the workpiece.

[0409] Oxidation treatment can be performed in one or more ways.

[0410] As an oxidation treatment, it is preferable to at least perform a liquid treatment in which a specified solution comes into contact with the substance to be treated.

[0411] The oxidation solution described above can be any solution that can oxidize the surface of the metal layer. Furthermore, the oxidation solution is preferably a solution other than the processing solution of the present invention.

[0412] The preferred oxidizing solution is a solution selected from water, hydrogen peroxide solution, a mixture of ammonia and hydrogen peroxide (APM), a mixture of hydrofluoric acid and hydrogen peroxide solution (FPM), a mixture of sulfuric acid and hydrogen peroxide solution (SPM), a mixture 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] Of the aforementioned specific solutions, solutions selected from water, hydrogen peroxide water, APM, FPM, SPM, HPM, oxygen-dissolved water, and ozone-dissolved water are preferred.

[0414] Regarding the composition of hydrogen peroxide water, for example, the content of H2O2 relative to the total mass of hydrogen peroxide water is 0.5 to 31% by mass, more preferably 3 to 15% by mass.

[0415] The composition of APM is preferably in the range of "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 in the range of "hydrofluoric acid: hydrogen peroxide water: water = 1:1:1" to "hydrofluoric acid: hydrogen peroxide water: water = 1:1:200" (mass ratio).

[0417] The composition of SPM is preferably in the range of "sulfuric acid: hydrogen peroxide water: water = 3:1:0" to "sulfuric acid: hydrogen peroxide water: water = 1:1:10" (mass ratio).

[0418] The composition of HPM is preferably in the range of "hydrochloric acid: hydrogen peroxide water: water = 1:1:1" to "hydrochloric acid: hydrogen peroxide water: water = 1:1:30" (mass ratio).

[0419] Furthermore, the preferred composition ratios described herein represent the composition ratios in the case of 28% by mass of ammonia, 49% by mass of hydrofluoric acid, 98% by mass of sulfuric acid, 37% by mass of hydrochloric acid, and 30% by mass of hydrogen peroxide.

[0420] Furthermore, 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"] are preferably satisfied.

[0422] Oxygen-dissolved water is, for example, an aqueous solution with an O2 content of 1 to 200 ppm by mass relative to the total mass of oxygen-dissolved water.

[0423] Ozone-dissolved water is, for example, an aqueous solution with an O3 content of 1 to 200 ppm by mass relative to the total mass of the ozone-dissolved water.

[0424] Perchloric acid, for example, is an aqueous solution containing 0.001 to 60% by mass of HClO4 relative to the total mass of the solution.

[0425] Nitric acid, for example, is an aqueous solution containing HNO3 at a concentration of 0.001 to 60% by mass relative to the total mass of the solution.

[0426] In liquid processing, there are no particular limitations on the method of contacting the work to be treated with an oxidizing solution (preferably a specific solution). Examples include immersing the work to be treated in an oxidizing solution placed in a tank, spraying an oxidizing solution onto the work to be treated, allowing the oxidizing solution to flow over the work to be treated, and any combination thereof.

[0427] The contact time between the treated material and the oxidizing solution is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes.

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

[0429] Examples of oxidizing gases that come into contact with the treated material during gas processing include dry air, oxygen (O2), ozone (O3), and mixtures thereof. Oxidizing gases may also include gases other than those mentioned above.

[0430] In gas treatment, oxygen or ozone gas is preferred among the oxidizing gases that come into contact with the workpiece. When oxygen or ozone gas comes into contact with the workpiece, it is also preferable to contact it in an oxygen atmosphere, an ozone atmosphere, or a mixed atmosphere of oxygen and ozone.

[0431] In gas processing, it is also preferable to heat the workpiece while contacting it with oxygen (for example, heating at 40 to 200°C).

[0432] Among them, the gas treatment is preferably ozone treatment in which ozone gas is brought into contact with the object to be treated, or oxygen heating treatment in which the object to be treated is heated in an oxygen atmosphere.

[0433] In the above-described ozone treatment, ozone gas can be brought into contact with the object being treated in an ozone atmosphere, or in a mixed atmosphere of ozone gas and other gases (such as oxygen). Furthermore, ozone treatment can involve heating the object while bringing it into contact with ozone gas.

[0434] In step A (especially in the case of liquid treatment), the workpiece may contain metallic materials other than a metallic layer that has been oxidized by oxidation treatment to form a metallic oxide layer on the surface. Alternatively, step A (especially liquid treatment) may intentionally or unavoidably remove some or all of such metallic materials.

[0435] Furthermore, in process A (especially in the case of liquid treatment), a portion of the metal layer of the workpiece may be intentionally or unavoidably removed.

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

[0437] In process B, the method of bringing the workpiece into contact with the treatment liquid is not limited, and examples can be given that are the same as the method of bringing the workpiece into contact with the oxidizing solution.

[0438] The contact time between the object being treated and the treatment liquid is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes.

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

[0440] In process B, the removal of the metal oxide layer can be carried out locally or as a whole.

[0441] In process B, part or all of the metal layer (e.g., removing the metal oxide layer covering the surface and exposing the surface metal layer) may be intentionally or unavoidably removed.

[0442] In step B, the workpiece may contain other metallic materials besides the metal oxide layer and the metal layer on the surface where the metal oxide layer is formed, or some or all of such metallic materials may be intentionally or unavoidably removed.

[0443] Furthermore, where there is no intentional dissolution of the aforementioned metal layer and / or other metal-based materials, it is preferable that the amount of the aforementioned metal layer and / or other metal-based materials inevitably dissolved is small.

[0444] For the processing solution used in process B, pre-degassing treatment can be performed to reduce the amount of dissolved oxygen. The metal layer exposed by removing the metal oxide layer through the processing solution is oxidized by dissolved oxygen in the processing solution to become a new metal oxide layer. This metal oxide layer is further removed by the processing solution. As a result, excessive removal of the metal layer can be suppressed by reducing the amount of dissolved oxygen in the processing solution.

[0445] <Third Method>

[0446] As another aspect (third aspect) of the processing method for the object to be processed according to the present invention, an example is to remove dry etching residue by contacting the object to be processed with a processing liquid after performing dry etching on the object containing a metallic material.

[0447] The metal-based material contained in the processed material in the above-described method can be a single type or two or more types. At least one of the single type or two or more metal-based materials is preferably a cobalt-containing material, a ruthenium-containing material, a molybdenum-containing material, an aluminum-containing material, or a copper-containing material, and more preferably a cobalt-containing material.

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

[0449] In this method, the workpiece in contact with the processing solution contains a metallic material. Furthermore, in this method, the workpiece is brought into contact with the processing solution after undergoing dry etching. Therefore, the workpiece in contact with the processing solution contains dry etching residue on its surface. In this method, the dry etching residue present on the surface of the workpiece is removed.

[0450] This method of processing the object being processed is also referred to as the third method of processing the object being processed according to the present invention.

[0451] In addition, the third method can be a form that specifically defines the structure of the object to be treated and the purpose of the treatment in the first method described above.

[0452] The treatment solution of the present invention can also be suitably used for cleaning purposes (residue removal purposes) of such treated objects.

[0453] Figure 3 A schematic diagram is shown illustrating an example of the workpiece (the workpiece after dry etching) in the third method described above.

[0454] Figure 3 The workpiece 30 shown has, sequentially on a substrate 32, a metal film 34, an etch stop layer 36, an interlayer insulating film 38, and a metal hard mask 40. Holes 42 exposing the metal film 34 are formed at predetermined locations through a dry etching process or similar procedure. That is, Figure 3 The workpiece shown is a laminate comprising, in sequence, 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 opening of the metal hard mask 40, extending from its surface 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, and is coated with dry etching residue 46.

[0455] Furthermore, the metal hard mask in the workpiece can become a barrier metal after further processing of the workpiece. In other words, the layer that becomes a barrier metal in the later process can be used as a metal hard mask in the dry etching process. That is, the barrier metal can be used as a metal hard mask.

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

[0457] Preferably, the metal-containing film 34 is a cobalt-containing material and the metal hard mask 40 is a metal-containing material.

[0458] The interlayer insulating film can be made of known materials.

[0459] Dry etching residue can be organic residue containing organic matter as the main component. Organic residue is residue with an organic matter content of 50% by mass or more. Organic residue can also be residue that substantially does not contain metallic substances and / or cobalt-containing substances.

[0460] Furthermore, dry etching residue can contain metallic components as the main component, or it can be metallic residue containing metallic substances and / or cobalt-containing substances. Metallic residue is residue with a metallic content exceeding 50% by mass. Metallic residue can also be residue that substantially does not contain organic matter.

[0461] As a specific method of the third approach, one example is a method of bringing the treatment liquid into contact with the aforementioned material to be treated.

[0462] The method of contact between the treatment liquid and the treated object is the same as that described in Method 1.

[0463] Dry etching residue on the workpiece is removed by contacting the processing solution with the workpiece. During this process, a metallic material (e.g., a cobalt-containing substance, preferably a cobalt-containing substance as the metal film 34) can be dissolved simultaneously. The amount of metallic material (cobalt-containing substance, etc.) dissolved is not particularly limited. The dissolution of the metallic material (cobalt-containing substance, etc.) can be an intentional dissolution of part or all of the metal film 34 (cobalt-containing substance, etc.) in the bottom wall 44b of the hole 42, or it can be an unavoidable dissolution caused by contact between the processing solution and the metallic material (cobalt-containing substance, etc.).

[0464] This treatment method may include a rinsing step, which involves rinsing the object being treated with a rinsing solution, as needed.

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

[0466] Furthermore, the aforementioned rinsing process can be included between process A and process B in the second method.

[0467] As rinsing solutions, preferably, are water, hydrofluoric acid (preferably 0.001-1% by mass), hydrochloric acid (preferably 0.001-1% by mass), hydrogen peroxide solution (preferably 0.5-31% by mass, more preferably 3-15% by mass), a mixture of hydrofluoric acid and hydrogen peroxide solution (FPM), a mixture of sulfuric acid and hydrogen peroxide solution (SPM), a mixture of ammonia and hydrogen peroxide solution (APM), a mixture of hydrochloric acid and hydrogen peroxide solution (HPM), carbon dioxide solution (preferably 10-60 ppm by mass), ozone solution (preferably 10-60 ppm by mass), hydrogen water (preferably 10-20 ppm by mass), citric acid aqueous solution (preferably 0.01-10% by mass), sulfuric acid (preferably...). The following are the ingredients: 1-10% sulfuric acid aqueous solution, ammonia (preferably 0.01-10% ammonia), isopropanol (IPA), hypochlorous acid aqueous solution (preferably 1-10% hypochlorous acid aqueous solution), aqua regia (preferably aqua regia in a volume ratio of 37% hydrochloric acid to 60% nitric acid equivalent to 2.6:1.4 to 3.4:0.6), ultrapure water, nitric acid (preferably 0.001-1% nitric acid), perchloric acid (preferably 0.001-1% perchloric acid), oxalic acid aqueous solution (preferably 0.01-10% oxalic acid aqueous solution), acetic acid (preferably 0.01-10% acetic acid aqueous solution or acetic acid stock solution), or periodic acid aqueous solution (preferably 0.5-10% periodic acid aqueous solution. Examples of periodic acid include o-periodic acid and metaperiodic acid).

[0468] The preferred conditions for FPM, SPM, APM and HPM are, for example, the same as the preferred conditions for FPM, SPM, APM and HPM used in the specific solutions described above.

[0469] In addition, hydrofluoric acid, nitric acid, perchloric acid and hydrochloric acid refer to aqueous solutions obtained by dissolving HF, HNO3, HClO4 and HCl in water, respectively.

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

[0471] The rinsing solutions can be mixed and used without compromising the purpose of the rinsing process. Furthermore, the rinsing solutions may contain organic solvents.

[0472] As a specific method for the rinsing process, one example is the method of bringing the rinsing solution into contact with the object being treated.

[0473] As a method of making contact, it can be carried out by immersing the substrate in a rinsing liquid placed in a tank, spraying the rinsing liquid onto the substrate, making the rinsing liquid flow onto the substrate, or any combination thereof.

[0474] There is no particular limitation on the treatment time (the contact time between the rinsing solution and the treated object), for example, it is 5 seconds to 5 minutes.

[0475] There are no particular limitations on the temperature of the rinsing solution used in the treatment; for example, it is generally preferred to be 16–60°C, and more preferably 18–40°C. When SPM is used as the rinsing solution, its temperature is preferably 90–250°C.

[0476] Furthermore, this processing method may include a drying process after the rinsing process, if necessary. The drying method is not particularly limited and may include rotary drying, flow of drying gas on the substrate, heating via a heating mechanism of the substrate such as a heating plate or infrared lamp, IPA (isopropyl alcohol) vapor drying, marangoni drying, notagononi drying, or combinations thereof.

[0477] The drying time varies depending on the specific method used, but it is usually around 30 seconds to a few minutes.

[0478] This processing method can be combined and implemented before or after other processes in the manufacturing process of semiconductor devices. It can be incorporated into other processes during the implementation of this processing method, or it can be incorporated into other processes and implemented thereafter.

[0479] Other processes include, for example, the formation processes of various structures such as metal wiring, gate structure, source structure, drain structure, insulating layer, strong magnetic layer and / or non-magnetic layer (layer formation, etching, chemical mechanical polishing, modification, etc.), resist formation process, exposure process and removal process, heat treatment process, cleaning process and inspection process, etc.

[0480] In this processing method, it can be performed in the back end of the line (BEOL) or in the front end of the line (FEOL).

[0481] In addition, the processing fluid can be applied to devices such as NAND, DRAM (Dynamic Random Access Memory), SRAM (Static Random Access Memory), ReRAM (Resistive Random Access Memory), FRAM (Ferroelectric Random Access Memory), MRAM (Magnetoresistive Random Access Memory), or PRAM (Phase Change Random Access Memory), as well as logic circuits or processors.

[0482] Example

[0483] The present invention will now be described in further detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0484] Additionally, in the embodiments, unless otherwise stated, “%” refers to “mass %”, and unless otherwise stated, “ppm” refers to “mass ppm”.

[0485] [Preparation of the treatment solution]

[0486] The components shown below were mixed in the prescribed proportions to prepare treatment solutions suitable for each test.

[0487] The raw materials used in the various treatment solutions shown below are of high purity and are further purified by pre-distillation, ion exchange, filtration, or combination.

[0488] Hydroxylamine

[0489] ·HA: Hydroxylamine

[0490] <Hydrazine>

[0491] ·hydrazine

[0492] ·pyrazole

[0493] ·Carbazine

[0494] · Semicarbazide

[0495] ·Thiosemicarbazide

[0496] Monomethylhydrazine

[0497] ·tert-butylhydrazine

[0498] · Dimethylhydrazine (1,1-dimethylhydrazine)

[0499] Aminoguanidine

[0500] <Organic solvents>

[0501] Methanol

[0502] Isopropanol

[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-Phenylenzotriazole

[0529] ·1-Aminobenzotriazole

[0530] 5-Methyl-1H-benzotriazole

[0531] ·benzotriazole-5-carboxylic acid

[0532] 4-Methylbenzotriazole

[0533] Chelating agents

[0534] Diethylenetriaminepentaacetic acid

[0535] · ethylenediaminetetraacetic acid

[0536] trans-1,2-cyclohexanediaminetetraacetic acid

[0537] ·oxalic acid

[0538] ·Malondiic acid

[0539] Citric acid

[0540] Methanesulfonic acid

[0541] ·1-Hydroxyethylidene-1,1-Diphosphonic acid

[0542] ·trimethylphosphonic acid

[0543] <The source of the first or second anion>

[0544] The specified amounts of the first anion and / or the second anion are supplied to the treatment solution 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] · Aqueous phosphoric acid solution (H3PO4aq: a 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 with 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 processing such as removing a part of the water from the sample to be detected to concentrate the target substance, the measurement was carried out.

[0556] <pH regulator>

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

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

[0559] In order to make the treatment liquid reach a specified pH, the required 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] [Test]

[0562] The following tests were carried out using the treatment liquids of the prepared examples or comparative examples.

[0563] <Evaluation of the removal of organic residues>

[0564] A multilayer substrate having a photoresist film, a metal hard mask (TiN layer), an etch stop layer (Al₂O₃ layer), a Co layer, and an interlayer dielectric (ILD) sequentially laminated on the surface of a substrate was prepared. Patterning treatment based on lithography, etching treatment using a metal plasma etching device, and removal treatment of the photoresist film based on oxygen plasma ashing were performed on this multilayer substrate to produce a multilayer substrate for evaluation test (hereinafter also referred to as "test piece").

[0565] The obtained test pieces were cleaned (treated) using the treatment solutions of each embodiment and each comparative example.

[0566] Specifically, first, 200 mL of the treatment solution was filled into a 500 mL glass beaker. While stirring, the temperature of the treatment solution was raised to 40°C. Next, while stirring, the prepared test piece was immersed in the 40°C treatment solution for 5 minutes to clean it. While immersing the test piece in the treatment solution, 4-inch plastic locking tweezers were used to hold the test piece so that the side of the test piece with the light-obscured surface facing the stir bar.

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

[0568] Next, the test piece was exposed to a nitrogen stream to blow away the droplets adhering to its surface, thus drying the surface of the test piece.

[0569] After the nitrogen drying process, the test piece was removed from the holding part of the plastic tweezers and placed in a covered plastic storage box with the component side facing up for storage.

[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 (UlvaC-PHI, product name Quantera SXM). The carbon atom content in the organic residue of 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. Organic residue removal rate is over 95%.

[0572] 2: The removal rate of organic residues is above 80% and less than 95%.

[0573] 3: The removal rate of organic residues is above 75% and less than 80%.

[0574] 4. The removal rate of organic residues is above 50% and less than 75%.

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

[0576] <Stability Evaluation>

[0577] Next, storage tests were conducted using the treatment solutions from each embodiment and each comparative example, and the long-term stability of the removal performance of each treatment solution was evaluated.

[0578] Specifically, firstly, 200 mL of each treatment solution was filled into 250 mL high-density polyethylene containers and sealed. The containers filled with the treatment solutions were then stored at 60°C for 24 hours (storage treatment).

[0579] Using the treated solution after storage treatment, an evaluation test on the removal of organic residues was conducted according to the aforementioned evaluation method. The maintenance rate of the organic residue removal rate obtained using the treated solution after storage treatment (=[organic residue removal rate obtained using the treated solution after storage treatment] ÷ [organic residue removal rate obtained using the treated solution before storage treatment] × 100) was calculated, with the organic residue removal rate calculated using the treated solution before storage treatment set at 100%. The obtained maintenance rates were classified according to the following evaluation criteria, and the stability of each treated solution was evaluated.

[0580] Furthermore, even when using any treatment solution, the retention rate did not exceed 100%.

[0581] 1: Maintenance rate above 99%

[0582] 2: The maintenance rate is above 95% but less than 99%.

[0583] 3: The maintenance rate is above 85% but less than 95%.

[0584] 4: The maintenance rate is above 75% but less than 85%.

[0585] 5: Maintenance rate less than 75%

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

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

[0588] One cycle was defined as immersing the obtained substrate in water at 40°C for 1 minute, followed by immersion in the respective processing solutions listed in the table at 40°C for 30 seconds. This cycle was repeated until the metallic cobalt dissolved to a depth of 10 nm, and the process was then completed.

[0589] Then, the surface of the treated cobalt layer was observed using a scanning electron microscope, and the smoothness of the treated part was evaluated in 10 stages from 1 to 10.

[0590] Regarding smoothness, "1" is the best rating, and the higher the number, the worse the rating. Specifically, as observed, the smoothness of the workpiece in the treatment solution is rated as "1" when the surface of the cobalt layer is smooth and no roughness is observed. Beyond that, roughness is observed as the rating approaches "10," and the surface of the cobalt layer is rated as becoming rough. Ratings of "1-8" represent a practically usable level, "9" represents a practically usable level, and "10" represents a practically problematic level.

[0591] <Evaluation of Metal Residue Removal Performance>

[0592] A workpiece (pre-processing laminate) was formed on a substrate (Si) having a cobalt layer, a SiN film, a SiO2 film, and a barrier metal (TaN) including defined openings in sequence. Using the obtained workpiece, plasma etching (dry etching) was performed using the barrier metal as a mask until the cobalt layer was exposed, and the SiN film and SiO2 film were etched to form vias, thereby manufacturing sample 1 (reference). Figure 3 If the cross-section of the laminate is confirmed using SEM / EDX (scanning electron microscope with energy dispersive X-ray analysis device), plasma etching residues (metal residues) with cobalt or other metals as the main components are confirmed on the hole wall.

[0593] Then, the removal of metal residues was evaluated through the following procedures. First, the prepared sample 1 slice (approximately 2.0 cm × 2.0 cm) was immersed (treated) in each treatment solution at a temperature of 40°C for 1 minute. After a specified time, the sample 1 slice was removed, immediately washed with ultrapure water, and dried with N2.

[0594] Subsequently, the surface of the sliced ​​sample 1 after impregnation was observed using SEM / EDX, and the removal performance of the above-mentioned metal residue was evaluated in 10 stages from 1 to 10.

[0595] Regarding cleanability, "1" represents a good rating, with higher numbers indicating worse performance. Specifically, as an observation, if the aforementioned metal residue is completely removed, the rating is "1," and if the aforementioned metal residue is hardly removed, the rating is "10." Ratings of "1-6" indicate a practically usable level, "7-9" indicate a practically usable level, and "10" indicates a practically problematic level.

[0596] From the perspective of performance balance, the preferred evaluation values ​​are 1 to 6 for metal residue removal and 1 to 8 for smoothness.

[0597] [result]

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

[0599] In the table, "%" refers to "mass %" and "ppm" refers to "mass ppm".

[0600] The “HA(%)” column indicates the content (mass%) of hydroxylamine in each treatment solution relative to the total mass of the treatment solution.

[0601] The "chelating agent / content", "benzotriazole compound / content", and "organic solvent / content" columns are listed in the first paragraph, indicating the types of each added component, and the second paragraph indicates the amount of each component added (mass %).

[0602] The "Hydrazine (relative to 100 parts HA)" column indicates the total content (parts by mass) of hydrazine in each treatment solution relative to 100 parts by mass of hydroxylamine. Additionally, when using two types of hydrazine, the mass content of each type is adjusted to be equal.

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

[0604] The "First Anion Content (relative to HA 100 parts)" column indicates the total content (parts by mass) of the first anion in each treatment solution relative to 100 parts by mass of hydroxylamine.

[0605] The column “Content of the first anion and the second anion (relative to 100 parts of HA)” indicates the total content (parts by mass) of the first and second anions in each treatment solution relative to 100 parts by mass of hydroxylamine.

[0606] The “pH” column indicates the pH of each treatment solution.

[0607] The remaining components in each treatment solution not explicitly listed in the table include pH adjusters and water added to achieve the specified pH.

[0608] Tables 1a-1 and 1a-2 respectively show the formulation and test results of the treatment solutions in Examples 001 to 049.

[0609] For example, the treatment solution of Example 001 contains 0.1% by mass of hydroxylamine relative to the total mass of the treatment solution, and 0.001 ppm by mass of hydrazine (0.0001 parts by mass relative to 100 parts by mass of hydroxylamine) of hydrazine as a hydrazine derivative. It does not contain a first anion, a second anion, a chelating agent, a preservative, or an organic solvent. The remainder consists of a pH adjuster and water added to achieve a pH of 9. Regarding the test results of the treatment solution of Example 001, the evaluation for organic residue removal was 3, the evaluation for stability was 3, the evaluation for metal residue removal was 9, and the evaluation for smoothness was 3.

[0610] The relationships are the same from Table 1b-1 onwards and from Table 1b-2 onwards.

[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] Based on the results shown in the table, it is confirmed that the problem of the present invention can be solved simply by using the treatment solution of the present invention.

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

[0669] It was confirmed that the treatment solution was more effective when hydrazine was present (see the comparison of results from Examples 014, 020 to 027, etc.).

[0670] It was confirmed that the treatment solution was more effective when it contained the first anion (see the comparison of results from Examples 009, 036 to 045, etc.).

[0671] Furthermore, it was confirmed that 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, the effect of the treatment solution was even better (see the comparison of the results of Examples 009, 036 to 045, etc.).

[0672] Confirmed by NO2 - and NO3 - When the total mass of the two specific anions in the composition is greater than the mass of C1, the treatment solution performs better (see the comparison of results between Example 056 and Example 057, etc.).

[0673] It was confirmed that the treatment solution contained a chelating agent (more preferably diethylenetriaminepentaacetic acid or citric acid), and the effect of the treatment solution was even better (see the 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 the treatment solution contained a preservative (more preferably benzotriazole, 1-amino-benzotriazole or 5-methyl-1H-benzotriazole, and even more preferably 5-methyl-1H-benzotriazole), and the effect of the treatment solution was even better (see the 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 solution 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 solution is even better (see the comparison of the results of Examples 205 to 372 with Examples 055, 056, 063, 064, 070, 071 and 072, etc.).

[0676] Symbol Explanation

[0677] 20 - Subject to be processed, 12 - Substrate, 14 - Insulating film, 16 - Metal-containing part, 18 - Cobalt-containing part, 30 - Subject to be processed, 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 - Section wall, 44b - Bottom wall.

Claims

1. A processing liquid for manufacturing semiconductor devices, comprising: water; Hydroxylamine; and Selected from one or more hydrazines, hydrazine salts, and hydrazine derivatives. The total content of the hydrazine compounds is between 0.0001 and 1 part by weight relative to 100 parts by weight of the hydroxylamine. The processing solution for semiconductor device manufacturing further contains one or more organic solvents selected from alcohol-based solvents, ketone-based solvents, ester-based solvents, and ether-based solvents, wherein the organic solvent includes ethylene glycol monobutyl ether. The hydrazine derivative is selected from one or more compounds represented by general formula (A), compounds represented by general formula (B), compounds having a pyrazole ring, and their salts. H2N-N-R N 2 (A) H2N-N=X (B) In general formula (A), the two R N Each R represents a hydrogen atom or a substituent independently. N They can be optionally bonded together to form a ring, wherein, Two Rs N At least one of them is not a hydrogen atom. In general formula (B), X represents a divalent group.

2. The processing liquid for semiconductor device manufacturing according to claim 1, 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.

3. The processing liquid for semiconductor device manufacturing according to claim 1 or 2, wherein, The hydrazine compounds contain hydrazine.

4. The processing solution for semiconductor device manufacturing according to claim 1 or 2, further comprising a compound selected from Cl. - NO2 - and NO3 - One or more of the first anions.

5. The processing solution for semiconductor device manufacturing according to claim 4, wherein it contains Cl - NO2 - and NO3 - The three types of the first anion constituted.

6. The processing solution for semiconductor device manufacturing according to claim 4, wherein the solution is selected from Cl... - NO2 - and NO3 - Among one or more of the first anions, there is one composed of NO2. - and NO3 - The two types of the first anion constituted.

7. The processing liquid for semiconductor device manufacturing according to claim 4, 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.

8. The processing liquid for semiconductor device manufacturing according to claim 4, further comprising a component selected from SO4. 2- and PO4 3- One or more of the second anions, 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.

9. The processing liquid for semiconductor device manufacturing according to claim 4, wherein, NO2 - and NO3 - The total contains more than Cl by mass - It contains mass.

10. The processing liquid for semiconductor device manufacturing according to claim 1 or 2, further comprising a chelating agent.

11. The processing liquid for semiconductor device manufacturing according to claim 10, wherein, The chelating agent contains functional groups selected from carboxylic acid groups, phosphonic acid groups, and sulfonic acid groups.

12. The processing liquid for semiconductor device manufacturing according to claim 10, wherein, The chelating agent is selected from one or more of diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, oxalic acid, malonic acid, succinic acid, citric acid, methanesulfonic acid, 1-hydroxyethylene-1,1-diphosphonic acid, and triazinetrimethylenephosphonic acid.

13. The processing liquid for semiconductor device manufacturing according to claim 1 or 2, further comprising a preservative.

14. The processing liquid for semiconductor device manufacturing according to claim 13, wherein, The preservative is a benzotriazole.

15. The processing liquid for semiconductor device manufacturing according to claim 14, wherein, The benzotriazoles are optionally substituted benzotriazoles, wherein the substituents are selected from one or more of the following: alkyl groups optionally containing substituents, aryl groups optionally containing substituents, halogen atoms, amino groups optionally containing substituents, nitro groups, alkoxy groups optionally containing substituents, and hydroxyl groups.

16. The processing liquid for semiconductor device manufacturing according to claim 13, wherein, The preservative is selected from benzotriazole, 5-aminotetrazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthol triazole, toluenetriazole, 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-isobenzotriazole, etc. One or more of the following: 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.

17. The processing solution for semiconductor device manufacturing according to claim 1 or 2, wherein the pH is 6 to 11.

18. The processing solution for semiconductor device manufacturing according to claim 1 or 2, wherein the pH is 6 to 9.

19. The processing liquid for semiconductor device manufacturing according to claim 1 or 2, used for a processed material containing a cobalt-containing substance containing cobalt atoms and a metal-containing substance containing other metal atoms besides cobalt atoms.

20. The processing liquid for semiconductor device manufacturing according to claim 19, wherein, The cobalt-containing substance is a cobalt monomer, cobalt alloy, cobalt oxide, or cobalt nitride.

21. The processing liquid for semiconductor device manufacturing according to claim 13, wherein, The content of the preservative is 0.01% to 0.5% by mass relative to the total mass of the treatment liquid.

22. The processing liquid for semiconductor device manufacturing according to claim 13, wherein, The preservative is 5-methyl-1H-benzotriazole.

23. The processing liquid for semiconductor device manufacturing according to claim 1 or 2, wherein, The hydroxylamine content is 5% to 15% by mass relative to the total mass of the treatment solution.

24. The processing liquid for semiconductor device manufacturing according to claim 1 or 2, wherein, The content of hydroxylamine is 1% to 10% by mass relative to the total mass of the treatment solution.

25. The processing liquid for semiconductor device manufacturing according to claim 1, wherein, The content of the organic solvent is 0.5% to 10% by mass relative to the total mass of the treatment liquid.

26. The processing liquid for semiconductor device manufacturing according to claim 10, wherein, The content of the chelating agent is 0.2% to 1.0% by mass relative to the total mass of the treatment solution.

27. The processing solution for semiconductor device manufacturing according to claim 1 or 2, further comprising a pH adjuster, and including a water-soluble amine as the pH adjuster.

28. A method for treating an object, wherein, The cobalt-containing material containing cobalt atoms is contacted with the processing liquid for semiconductor device manufacturing according to any one of claims 1 to 27 to dissolve the cobalt-containing material.

29. A method for treating an object, comprising: Step A involves performing the following treatment on the workpiece containing the metal layer to oxidize the surface of the metal layer and form a metal oxide layer, the treatment including: Liquid treatment involving contact with solutions selected from water, hydrogen peroxide solution, ammonia and hydrogen peroxide mixed aqueous solution, hydrofluoric acid and hydrogen peroxide solution mixed aqueous solution, sulfuric acid and hydrogen peroxide solution mixed aqueous solution, hydrochloric acid and hydrogen peroxide solution mixed aqueous solution, oxygen dissolved water, and ozone dissolved water. Ozone treatment involving contact with ozone gas Oxygen heating treatment performed under an oxygen atmosphere, or Plasma treatment using oxygen; and Step B involves contacting the workpiece obtained in step A with a processing solution for semiconductor device manufacturing according to any one of claims 1 to 18, 21 to 27 to dissolve the metal oxide layer.

30. The method for processing the object according to claim 29, wherein, The process A and process B are performed alternately and repeatedly.

31. The method for processing the object according to claim 29, wherein, The metal layer is composed of cobalt-containing substances as cobalt monomers or cobalt alloys.

32. A method for treating an object, wherein, After performing dry etching on the workpiece containing metallic materials... Dry etching residue is removed by contacting the workpiece with a processing solution for semiconductor device manufacturing as described in any one of claims 1 to 18, 21 to 27.

33. The method for processing the object according to claim 32, wherein, The metallic material is a cobalt-containing substance containing cobalt atoms.

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