Treatment liquid, substrate treatment method using the treatment liquid, and semiconductor substrate manufacturing method

Abstract

The present application provides a treatment liquid containing at least one corrosion inhibitor selected from the group consisting of a compound (1) represented by the following general formula (1), a hydrate of the compound (1), and a salt of the compound (1), an etching agent, and water, a substrate treatment method using the treatment liquid, and a semiconductor substrate manufacturing method. (In the formula, R 1 represents a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group, R 2 represents a hydrogen atom or an organic group containing a carbonyl group, R 1 and R 2 may be bonded to each other to form a ring structure.

Description

Technical Field

[0001] This invention relates to a processing liquid, a method for processing a substrate using the processing liquid, and a method for manufacturing a semiconductor substrate. Background Technology

[0002] In the wiring formation process, for example, a hard mask layer (HM layer) is formed on an interlayer insulating film that is sequentially stacked with a substrate, a metal wiring layer, an etch stop layer, and a silicon-based interlayer insulating film. The HM layer is then etched to form a model of the wiring pattern. The HM layer contains titanium nitride (TiN) and titanium oxide (TiO2). x ).

[0003] Next, the etched HM layer is used as a mask to dry etch the interlayer insulating film, creating a wiring pattern identical to the mask. Then, the HM layer is removed, and an interlayer insulating film is embedded in the wiring pattern shape by electrolytic plating, for example, embedding a copper metal film.

[0004] After dry etching, the components (substrate / metal wiring layer / etch stop layer / interlayer insulating film / HM layer) have Ti-containing residues and Si-containing residues originating from the HM layer and interlayer insulating film.

[0005] For example, Patent Document 1 describes a stripping composition comprising an organic solvent, a nucleophilic amine, and a reducing agent as a processing liquid for such a substrate.

[0006] Existing technical documents Patent documents Patent Document 1: Japanese Patent No. 2819392 Summary of the Invention

[0007] The problem that the invention aims to solve However, the aforementioned processing solution is required to balance damage suppression and cleaning performance on metal wiring layers, etch stop layers, etc., using various metals. From this perspective, there is still room for improvement in both suppressing damage to titanium-containing metal layers such as TiN, aluminum-containing metal layers such as alumina, or copper substrates and copper-containing metal layers, and in removing titanium-based residues (residues containing titanium or titanium alloys) and silicon-based residues (residues containing silicon atoms). Therefore, there is a need to develop a processing solution that can suppress damage to metal-containing layers containing titanium, aluminum, or copper atoms, and has excellent removal performance for residues containing titanium or silicon atoms.

[0008] The present invention was made in view of the following circumstances, and its object is to provide a processing liquid that can take into account both damage suppression and cleaning properties of metal-containing layers, a method for processing a substrate using the processing liquid, and a method for manufacturing a semiconductor substrate.

[0009] Methods for solving problems In order to achieve the above objectives, the inventors of this application conducted in-depth research and discovered a treatment liquid comprising at least one corrosion inhibitor, an etchant and water selected from the group consisting of a compound (1) having a specific structure, a hydrate of the compound (1) and a salt of the compound (1), thereby completing the present invention.

[0010] That is, the present invention is as follows.

[0011] [1] The processing solution comprises: at least one corrosion inhibitor selected from the group consisting of a compound (1) represented by the following general formula (1), a hydrate of the aforementioned compound (1), and a salt of the aforementioned compound (1); an etchant; and water.

[0012] [Chemical Formula 1] (where R) 1 R represents a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group. 2 R represents a hydrogen atom or an organic group containing a carbonyl group. 1 and R 2 They can bond together to form a ring structure. [2] The treatment liquid as described in [1], wherein R in the aforementioned general formula (1) 1 and R 2 At least one of them is an aliphatic hydrocarbon group with 1 to 15 carbon atoms, either substituted or unsubstituted.

[0013] [3] The treatment liquid as described in [1] or [2], wherein the aforementioned compound (1) is compound (1-1) represented by formula (1-1) or compound (1-2) represented by formula (1-2).

[0014] [Chemical Formula 2] (where R) 3 This refers to an aliphatic hydrocarbon group with 1 to 15 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group with 1 to 15 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group. [Chemical Formula 3] [4] The processing solution as described in [1] or [2], wherein the aforementioned etchant is at least one selected from the group consisting of hydrogen peroxide, hydrogen fluoride, hydroxylamine, hydroxylamine derivatives and alkanolamines.

[0015] [5] The treatment solution described in [1] or [2] also contains a pH adjuster.

[0016] [6] The treatment solution as described in [1] or [2], wherein the pH is 4 to 13.

[0017] [7] The processing solution described in [1] or [2] is a processing solution used to process an etched substrate having a layer containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms and copper atoms.

[0018] [8] A substrate processing method comprising a step of processing the etched substrate with the processing solution described in [1] or [2].

[0019] [9] The substrate processing method described in [8], wherein the substrate has a layer containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms and copper atoms.

[0020]

[10] A method for manufacturing a semiconductor substrate, comprising a step of treating an etched substrate with the processing solution described in [1] or [2].

[0021]

[11] The semiconductor substrate manufacturing method as described in

[10] , wherein the aforementioned substrate has a layer containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms and copper atoms.

[0022] Invention Effects According to the present invention, a processing liquid that can simultaneously achieve damage suppression and cleaning properties of metal-containing layers, a method for processing a substrate using the processing liquid, and a method for manufacturing a semiconductor substrate can be provided. Attached Figure Description

[0023] [ Figure 1 ] Figure 1 This is a simplified cross-sectional view showing an example of a substrate that is the object of processing by the processing liquid involved in this embodiment. Detailed Implementation

[0024] The following is a detailed description of a method for implementing the present invention (hereinafter referred to simply as "this embodiment"). This embodiment is provided to illustrate examples of the present invention and is not intended to limit the invention to the following. The present invention can be implemented with appropriate modifications within its scope. Furthermore, the various components and parameters disclosed in this specification can be used in any combination unless otherwise specified. Further, the upper and lower limits of the numerical values ​​disclosed in this specification can be used in any combination unless otherwise specified.

[0025] Furthermore, in the accompanying drawings, the same reference numerals are assigned to the same elements, and redundant descriptions are omitted. Additionally, unless otherwise specified, positional relationships such as top, bottom, left, and right are assumed to be based on the positional relationships shown in the accompanying drawings. Moreover, the scale of the dimensions in the accompanying drawings is not limited to the scale illustrated in the figures.

[0026] <Treatment Fluid> The processing liquid involved in this embodiment is a processing liquid comprising at least one corrosion inhibitor, an etchant, and water selected from the group consisting of a compound (1) represented by the following general formula (1), a hydrate of compound (1), and a salt of compound (1). It should be noted that the processing liquid involved in this embodiment is sometimes also referred to as a "cleaning liquid" or a "processing liquid for semiconductor devices".

[0027] [Chemical Formula 4] (where R) 1 R represents a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group. 2 R represents a hydrogen atom or an organic group containing a carbonyl group. 1 and R 2 They can bond together to form a ring structure. By using the cleaning solution described in this embodiment, it is possible to achieve a high level of both damage suppression of titanium-containing metal layers such as TiN, aluminum-containing metal layers such as alumina, copper substrates, and copper-containing metal layers, and residue removal when removing titanium-based residues (residues containing titanium or titanium alloys) and silicon-based residues (residues containing silicon atoms). The reasons for this are not yet clear, but are speculated as follows. It is believed that compound (1) functions as an adsorbent, and the adsorption effect of compound (1) can achieve both damage suppression of metal layers and residue removal (however, the effects of this embodiment are not limited to this).

[0028] It should be noted that titanium-based residues refer to residues containing titanium or titanium-based alloys. Furthermore, titanium-based alloys refer to the state in which titanium, as a metallic element, is combined with other metallic or non-metallic elements. Details will be described later. For example, titanium oxide (TiO₂) can be cited as a titanium-based alloy.x (x represents quantity.) Titanium fluoride (TiF) x (x represents quantity.) Titanium oxynitride (TiON), titanium oxyfluoride (TiOF), etc. Additionally, silicon-based residues refer to residues containing silicon atoms. Examples include silicon (Si) and silicon oxide (SiO). x (x represents quantity.) ), silicon fluoride (SiF) x (x represents quantity.) Silicon bromide (SiBr) x (x represents quantity.) Silicon chloride (SiCl) x (x represents quantity.) etc.

[0029] Regarding the processing liquid involved in this embodiment, it is not limited to the aforementioned titanium-based and silicon-based residues, and can be suitably used as a cleaning liquid for removing etching residues containing organic or inorganic matter. In this case, it can be suitably used as a cleaning liquid for semiconductor (device) cleaning, etc. Etching residues refer to byproducts generated by etching such as dry etching, and include, for example, organic residues derived from photoresist, and other metal-containing residues other than titanium-based and silicon-based residues.

[0030] It should be noted that the aforementioned inorganic substances are compounds containing metals, such as metals, metal oxides, metal nitrides, metal chlorides, and metal fluorides. That is, the processing solution according to this embodiment can efficiently remove etching residues containing such inorganic substances.

[0031] More specifically, the processing solution of this embodiment can efficiently remove titanium-based and silicon-based residues originating from protective films and other layers such as hard mask layers (HM layers). Furthermore, the processing solution of this embodiment is also expected to efficiently remove inorganic residues originating from metal wiring layers comprising one of the metals selected below, and their metal oxides, metal nitrides, metal chlorides, and metal fluorides.

[0032] Examples of metals include at least one selected from the group consisting of tantalum (Ta), copper (Cu), cobalt (Co), ruthenium (Ru), aluminum (Al), tungsten (W), molybdenum (Mo), gold (Au), silver (Ag), iron (Fe), nickel (Ni), lead (Pb), zinc (Zn), tin (Sn), magnesium (Mg), bismuth (Bi), cadmium (Cd), titanium (Ti), zirconium (Zr), antimony (Sb), manganese (Mn), beryllium (Be), chromium (Cr), germanium (Ge), vanadium (V), gallium (Ga), hafnium (Hf), indium (In), niobium (Nb), rhenium (Re), and thallium (Tl), as well as their metal oxides, metal nitrides, metal chlorides, and metal fluorides.

[0033] Metal oxides can be exemplified by metal oxides containing the aforementioned metal atoms. A specific example of a metal oxide is TaO. x CuO x CoO x RuO x AlO x WO x MoO x AuO x AgO x FeO x NiO x (Unless otherwise specified, x represents quantity.) etc., but not limited to this.

[0034] Metal nitrides can be exemplified by metal nitrides containing the aforementioned metal atoms. A specific example of a metal nitride is TaN. x CuN x CoN x RuN x AlN x WN x MoN x AuN x AgN x FeN x NiN x And so on, but not limited to these.

[0035] Metal chlorides can be exemplified by metal chlorides containing the aforementioned metal atoms. A specific example of a metal chloride is TaCl. x CuCl x CoCl x 、RuCl x AlCl x WCl x MoCl x AuCl x AgCl x FeCl x NiCl x And so on, but not limited to these.

[0036] Metal fluorides can be exemplified by metal fluorides containing the aforementioned metal atoms. A specific example of a metal fluoride is TaF. x CuF x CoF x RuF x AlF x WF x MoF x AuF x AgFx ,FeF x NiF x And so on, but not limited to these.

[0037] As detailed below, the processing solution described in this embodiment is suitable for removing etching residues, and more particularly suitable for removing dry etching residues. Generally, from the viewpoint of improving semiconductor yield and preventing deterioration of electrical properties, dry etching residues need to be removed before the next process step. For example, the processing solution described in this embodiment is suitable for cleaning semiconductor substrates that have undergone dry etching via wiring processes.

[0038] For example, the processing solution according to this embodiment can effectively remove titanium-based residues containing titanium or titanium alloys originating from the HM layer, silicon-based compound residues originating from the HM layer, and etching residues containing inorganic matter originating from the metal wiring layer that adhere during the wiring process. In particular, titanium-based residues adhering to the semiconductor substrate after dry etching are highly moisture-resistant and difficult to remove by cleaning. The processing solution according to this embodiment can also efficiently clean such residues.

[0039] Hereinafter, exemplary descriptions will be provided of the components that can be incorporated into the processing liquid involved in this embodiment.

[0040] (Corrosion inhibitor) The processing liquid involved in this embodiment contains at least one corrosion inhibitor selected from the group consisting of compound (1) represented by the following general formula (1), hydrate of compound (1), and salt of compound (1).

[0041] [Chemical Formula 5] (where R) 1 R represents a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group. 2 R represents a hydrogen atom or an organic group containing a carbonyl group. 1 and R 2 They can bond together to form a ring structure. R in general formula (1) 1 and R 2 At least one of them is preferably an aliphatic hydrocarbon group with 1 to 15 carbon atoms, either substituted or unsubstituted.

[0042] Compound (1) is preferably compound (1-1) represented by formula (1-1) below or compound (1-2) represented by formula (1-2) below. By using such compounds, it is possible to achieve a higher level of balance between metal corrosion and cleaning performance.

[0043] [Chemical Formula 6] (where R) 3 This refers to an aliphatic hydrocarbon group with 1 to 15 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group with 1 to 15 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group. R 3 When the hydrocarbon group is aliphatic, the number of carbon atoms is preferably 1 to 13. The upper limit of this number of carbon atoms is more preferably 10 or less, and even more preferably 8 or less. Furthermore, the lower limit of this number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more. As an example of a preferred numerical range for the number of carbon atoms in this case, it is more preferably 1 to 10, even more preferably 1 to 8, even more preferably 3 to 8, and still even more preferably 5 to 8. Examples of aliphatic hydrocarbon groups include chain-type saturated hydrocarbon groups and chain-type unsaturated hydrocarbon groups, with chain-type saturated hydrocarbon groups being preferred.

[0044] R 3 When the hydrocarbon group is alicyclic, the number of carbon atoms is preferably 1 to 13. The upper limit of this number of carbon atoms is more preferably 10 or less, and even more preferably 8 or less. Furthermore, the lower limit of this number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more. As an example of a preferred numerical range for the number of carbon atoms in this case, it is more preferably 1 to 10, even more preferably 1 to 8, even more preferably 3 to 8, and still even more preferably 5 to 8. Examples of alicyclic hydrocarbon groups include cycloalkyl and cycloalkenyl groups, with cycloalkyl groups being preferred.

[0045] R 3 In the case of an aromatic hydrocarbon group, specific examples include phenyl and naphthyl groups, with phenyl being the preferred choice. Additionally, R... 3 When the aromatic hydrocarbon group is used, the preferred substituents are hydroxyl (OH), alkyl (methyl, etc.), etc., and more preferably hydroxyl. Suitable examples of aromatic hydrocarbon groups with substituents include aromatic hydrocarbon groups containing hydroxyl (phenolic group, etc.) and aromatic hydrocarbon groups containing alkyl (methyl, etc.).

[0046] [Chemical Formula 7] Furthermore, as specific and suitable examples of formula (1-1), examples include alkyl hydroxamic acids such as acetyl hydroxamic acid, butyryl hydroxamic acid, hexanoyl hydroxamic acid, caprylyl hydroxamic acid, decanoyl hydroxamic acid, benzoyl hydroxamic acid, and salicylic acid. Additionally, N-hydroxy-5-norbornene-2,3-dicarboximide represented by formula (1-2) is also suitable.

[0047] There are no particular limitations on the types of hydrates of the above compounds; known hydrates can be used.

[0048] The type of salt of the above-mentioned compounds is not particularly limited. Furthermore, the hydrate of the salt may also be used. Specific examples of salts are not particularly limited, for example, sodium salts, potassium salts, ammonium salts, alkylammonium salts (e.g., tetramethylammonium salt, etc.) may be mentioned. In addition, hydrates of these salts may also be used.

[0049] It should be noted that the processing liquid involved in this embodiment may further contain other corrosion inhibitors (second corrosion inhibitors) besides the aforementioned corrosion inhibitor (first corrosion inhibitor). Examples of other corrosion inhibitors include, for instance, compounds containing imidazole rings, triazole rings, pyridine rings, pyrimidine rings, tetrazolium rings, pyrazole rings, purine rings, phenanthroline rings, thiols, phosphonic acids, and hypophosphonic acids.

[0050] Corrosion inhibitors can be used alone or in combination with two or more.

[0051] The content of the corrosion inhibitor in the treatment solution involved in this embodiment is not particularly limited, but is preferably 0.00005 to 1.0% by mass. The upper limit of the content is more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less. Furthermore, the lower limit of the content is preferably 0.0005% by mass or more. By setting the content of the corrosion inhibitor within this range, a higher level of balance between metal corrosion and cleaning performance can be achieved.

[0052] (Etching agent) The etchant is not particularly limited, and a suitable type can be appropriately selected considering the type of metal layer to be treated. Suitable examples of etchants are preferably at least one selected from the group consisting of hydrogen peroxide, hydrogen fluoride, hydroxylamine, hydroxylamine derivatives, and alkanolamines. By using such an etchant, a higher level of balance between metal corrosion and cleaning performance can be achieved.

[0053] Specific examples of hydroxylamine derivatives include N-methylhydroxylamine, N-ethylhydroxylamine, N,N-diethylhydroxylamine, hydroxyurea, N,N-dibenzylhydroxylamine, 1,1'-(hydroxyimino)bis[2-propanol], and N-isopropylhydroxylamine.

[0054] Specific examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, aminoethylethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, diethanolisopropanolamine, N-methylethanolamine, and N-methyldiethanolamine.

[0055] Etching agents can be used alone or in combination with two or more.

[0056] The content of the etchant in the treatment solution involved in this embodiment is not particularly limited, but is preferably 0.1% to 30% by mass. The upper limit of the content is more preferably 20% by mass or less, further preferably 10% by mass or less, even more preferably 8% by mass or less, and still more preferably 6% by mass or less. Furthermore, the lower limit of the content is more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more. By setting the etchant content within this range, a higher level of balance between metal corrosion and cleaning performance can be achieved.

[0057] (water) The processing liquid involved in this embodiment contains water. From the viewpoint of manufacturing semiconductor devices, deionized water (DIW) or similar water can be used.

[0058] The water content in the treatment solution described in this embodiment is not particularly limited, but is preferably 60 to 99.99% by mass. A high water content allows it to be used appropriately as a so-called aqueous treatment solution, but the water content can also be selected based on the type of metal being cleaned and the intended use. It should be noted that, during preparation, other desired components besides water can be added, with water added as a remainder.

[0059] In addition to the components described above, the treatment liquid described in this embodiment may also contain other appropriate components. Examples of such components include pH adjusters, buffers, chelating agents, and surfactants.

[0060] (pH adjuster) The treatment solution described in this embodiment may also contain a pH adjuster to achieve a predetermined pH. Specific examples of pH adjusters are not particularly limited, and a suitable pH adjuster can be appropriately selected considering the intended use and the components contained therein. Examples of pH adjusters include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), ammonia (NH3), ethylenediamine, diethylenetriamine, methanesulfonic acid (MSA), acetic acid, sulfuric acid, phosphoric acid, and hydrochloric acid. It should be noted that ammonia (NH3) may be added, for example, in the form of ammonia water (e.g., NH3H2O, NH4OH).

[0061] A single pH adjuster may be used alone, or two or more may be used in combination. Alternatively, the treatment solution described in this embodiment may not contain a pH adjuster.

[0062] (Buffer) The treatment solution described in this embodiment may also contain a buffer. A buffer is a compound that inhibits pH changes in the treatment solution. By containing a buffer, the pH of the treatment solution can be efficiently controlled to a predetermined value. There are no particular limitations on the buffer, as long as it is a compound with pH buffering capacity. Specific examples of buffers include, for instance, Good's buffer.

[0063] A single buffer can be used, or two or more can be used in combination. Alternatively, the treatment solution described in this embodiment may not contain a buffer.

[0064] (chelating agent) The treatment solution described in this embodiment may also contain a chelating agent. A chelating agent is a compound capable of forming a complex with metal ions. By containing a chelating agent, improved cleaning performance and improved solution stability due to the inactivation of metal ions can be achieved. There are no particular limitations on the chelating agent as long as it is a compound with multiple coordination sites. Suitable examples of chelating agents include, for instance, at least one selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), citric acid, nitrotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), triethylenetetraaminehexaacetic acid (TTHA), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA-OH), hydroxyethyliminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), ethylene glycol ether diaminetetraacetic acid (GEDTA), dicarboxymethylglutamic acid (CMGA), ethylenediaminedisuccinic acid (EDDS), 1-hydroxyethyl-1,1-diphosphonic acid (HEDP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), ethylenediaminetetramethylenephosphonic acid (EDTMP), and nitrotriamethylenephosphonic acid (NTMP).

[0065] A single chelating agent may be used alone, or two or more may be used in combination. Alternatively, the treatment solution described in this embodiment may not contain a chelating agent.

[0066] (surfactant) The processing solution described in this embodiment may contain a surfactant for purposes such as adjusting the wettability of the processing solution on the substrate. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

[0067] Examples of nonionic surfactants include, for example, polyepoxide alkyl phenyl ether surfactants, polyepoxide alkyl ether surfactants, block polymer surfactants containing polyethylene oxide and polypropylene oxide, polyoxyalkylene styrene phenyl ether surfactants, polyalkylene tribenzyl phenyl ether surfactants, and acetylene polyepoxide surfactants.

[0068] Examples of anionic surfactants include, for example, alkyl sulfonic acids, alkylbenzene sulfonic acids, alkylnaphthalene sulfonic acids, alkyl diphenyl ether sulfonic acids, fatty acid amide sulfonic acids, polyoxyethylene alkyl ether carboxylic acids, polyoxyethylene alkyl ether acetic acids, polyoxyethylene alkyl ether propionic acids, alkyl phosphonic acids, and salts of fatty acids. It should be noted that there are no particular limitations on these salts; for example, sodium salts, potassium salts, ammonium salts, and alkyl ammonium salts (e.g., tetramethylammonium salts) can be included.

[0069] Examples of cationic surfactants include alkylpyridinium surfactants and quaternary ammonium salt surfactants.

[0070] Examples of amphoteric surfactants include, for example, betaine-type surfactants, amino acid-type surfactants, imidazoline-type surfactants, and amine oxide-type surfactants.

[0071] These surfactants are usually available commercially. A single surfactant can be used alone, or in combination of two or more.

[0072] When the treatment liquid involved in this embodiment contains a surfactant, the content of the surfactant is not particularly limited. For example, it is preferably 0.0001 to 5% by mass relative to the total mass of the treatment liquid. The lower limit of the content is more preferably 0.0002% by mass or more, and even more preferably 0.002% by mass or more. In addition, the upper limit of the content is more preferably 3% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.2% by mass or less.

[0073] The treatment solution described in this embodiment may not contain one or more surfactants selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, nor may it contain one or more of the compounds exemplified as such surfactants. The treatment solution described in this embodiment may also not contain any surfactants.

[0074] (Organic solvent) Regarding the processing liquid involved in this embodiment, it may further contain organic solvents, provided that their effectiveness is not impaired. Water-soluble organic solvents are preferred. Examples of water-soluble organic solvents include alcohols (e.g., isopropanol, ethanol, ethylene glycol, propylene glycol, glycerol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, furfuryl alcohol, 2-methyl-2,4-pentanediol, 3-methoxy-3-methyl-1-butanol, etc.), dimethyl sulfoxide, ethers (e.g., ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether), and morpholine derivatives (e.g., N-methylmorpholine N-oxide).

[0075] Organic solvents can be used alone or in combination of two or more.

[0076] When the processing liquid according to this embodiment contains an organic solvent, the content of the organic solvent is preferably 0.05 to 50% by mass or less relative to the total content of water and organic solvent. This upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, and even more preferably 10% by mass or less. Alternatively, this lower limit may be 0.1% by mass or more.

[0077] It should be noted that, regarding the treatment liquid involved in this embodiment, from the viewpoints of component solubility, reducing environmental impact, and economy, an aqueous treatment liquid is preferred. An aqueous treatment liquid is a treatment liquid that does not contain organic solvents, or, in the case of containing water and organic solvents, the content of organic solvents is lower than the content of water. From this viewpoint, as a more suitable approach, the content of organic solvents in the treatment liquid involved in this embodiment is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 0% by mass or less (i.e., the solvent is only water).

[0078] (Impurities, etc.) The processing liquid involved in this embodiment may, for example, contain metal impurities comprising at least one metal atom selected from the group consisting of Fe atoms, Cr atoms, Ni atoms, Zn atoms, Ca atoms, and Pb atoms.

[0079] In this embodiment, the total content of metal atoms in the treatment liquid is preferably 100 ppt by mass or less relative to the total mass of the treatment liquid. A lower lower limit for the total content of metal atoms is preferred; for example, 0.001 ppt by mass or more is acceptable. Examples of total metal atom content range from 0.001 ppt by mass to 100 ppt by mass. It is believed that by setting the total content of metal atoms below the aforementioned preferred upper limit, the defect suppression and residue suppression properties of the treatment liquid are improved. It is also believed that by setting the total content of metal atoms above the aforementioned preferred lower limit, metal atoms are less likely to exist freely in the system and are less likely to adversely affect the overall manufacturing yield of the object being cleaned.

[0080] The content of metallic impurities can be adjusted, for example, through purification processes such as filtration. Filtration and other purification processes can be performed on part or all of the raw material before the preparation of the treatment solution, or they can be performed after the preparation of the treatment solution.

[0081] The treatment liquid involved in this embodiment may, for example, contain impurities derived from organic matter (organic impurities). The total content of the aforementioned organic impurities in the treatment liquid involved in this embodiment is preferably 5000 ppm by mass or less. The lower the lower limit of the organic impurity content, the more preferred; for example, 0.1 ppm by mass or more can be cited. Examples of the total content of organic impurities are, for example, 0.1 ppm by mass to 5000 ppm by mass.

[0082] The processing liquid involved in this embodiment may, for example, contain particles of a size that can be counted by a light-scattering liquid particle counter. The size of the particles is, for example, 0.04 μm or more. The number of particles in the processing liquid involved in this embodiment is, for example, 1000 or less per 1 mL of processing liquid, with a lower limit of, for example, 0.1 or more. It is believed that by keeping the number of particles in the processing liquid within the above range, the metal corrosion inhibition effect, defect inhibition effect, etc., provided by the processing liquid can be improved (however, the effects of this embodiment are not limited to this).

[0083] The aforementioned organic impurities and / or countable substances may be added to the treatment solution, or they may inevitably be introduced into the treatment solution during the manufacturing process. Examples of unavoidable introduction during the manufacturing process include, for example, the inclusion of organic impurities in the raw materials (e.g., organic solvents) used in the manufacturing of the treatment solution, and the introduction from the external environment (e.g., contamination) during the manufacturing process, but are not limited to the above-mentioned cases.

[0084] When adding the counted material to the treatment fluid, the presence ratio can be adjusted according to each specific size, taking into account factors such as the surface roughness of the object being cleaned.

[0085] The processing liquid described in this embodiment can be used for various purposes. From the viewpoint of effectively utilizing the effects and advantages of this embodiment, it is suitable as a processing liquid for a semiconductor substrate comprising a substrate and a film formed on the substrate, wherein the film contains at least one atom selected from the group consisting of silicon atoms, titanium atoms, aluminum atoms, and copper atoms. Further, it is suitable for cleaning semiconductor substrates having a film containing titanium atoms, specifically, for cleaning semiconductor substrates having a film containing at least one atom selected from the group consisting of titanium and titanium alloys. More specifically, a suitable example of this embodiment is a processing liquid for a semiconductor substrate. For such a semiconductor substrate, an example is a semiconductor substrate comprising a substrate and a film formed on the substrate, wherein the film contains at least one atom selected from the group consisting of titanium and titanium alloys. As a more suitable example, a semiconductor substrate is configured to include: a substrate; a film containing at least one atom selected from the group consisting of titanium and titanium alloys; and a film (semiconductor substrate) containing at least one atom selected from the group consisting of silicon atoms, aluminum atoms, and copper atoms. As such a semiconductor substrate, this embodiment can exert the effects and advantages of excellent removal of titanium residues and excellent protection of the metal layer to be protected.

[0086] The pH of the treatment solution involved in this embodiment is not particularly limited, but is preferably 4 to 13. The lower limit of pH is more preferably 5 or higher, further preferably 6 or higher, even more preferably 7 or higher, and still more preferably 8 or higher. Furthermore, the upper limit of pH is more preferably 12 or lower, and even more preferably 11 or lower. By setting the pH within this range, the balance between damage suppression of the metal-containing layer and residue removal can be improved at a higher level.

[0087] The processing liquid described in this embodiment can be suitably used as a processing liquid for treating etched substrates. Specifically, the processing liquid for treating etched substrates is more suitable when the substrate has a layer containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms, and copper atoms.

[0088] Here, refer to Figure 1 The substrate that can be used as the processing liquid involved in this embodiment will be described.

[0089] Figure 1 This is a simplified cross-sectional view showing an example of a substrate that is the object of processing by the processing liquid involved in this embodiment.

[0090] Figure 1In the pre-processing substrate 100 (substrate stack) shown, a substrate 10, a metal wiring layer 20, an etch stop layer 30, and an interlayer insulating film 40 are sequentially stacked. A hard mask layer (HM layer) 50 is formed on the interlayer insulating film 40 (substrate 10 / metal wiring layer 20 / etch stop layer 30 / interlayer insulating film 40 / HM layer 50). That is, the pre-processing substrate 100 is a substrate having a metal wiring layer 20 and an etch stop layer 30 as metal-containing layers.

[0091] The substrate 100 before processing is a substrate that has undergone dry etching using a wiring process. Specifically, it is a substrate in the state after dry etching of the interlayer insulating film 40, using the HM layer 50, which has a wiring pattern formed by dry etching, as a mask. Dry etching residue 60 is attached to the sides of the HM layer 50 and the interlayer insulating film 40. It should be noted that this description uses the case of etching by dry etching as an example, but if etching is performed by wet etching, the resulting residue is wet etching residue.

[0092] In the gaps between the interlayer insulating films 40 of the wiring pattern shape, the metal wiring layer 20 and the etch stop layer 30 are exposed, and dry etching residue 60 is also attached.

[0093] As substrate 10, for example, a substrate made of materials such as silicon, amorphous silicon, or glass can be used.

[0094] The metal wiring layer 20 is a wiring layer containing one of the following metals: molybdenum (Mo), tungsten (W), ruthenium (Ru), copper (Cu), gold (Au), silver (Ag), iron (Fe), nickel (Ni), silicon (Si), aluminum (Al), lead (Pb), zinc (Zn), tin (Sn), tantalum (Ta), magnesium (Mg), cobalt (Co), bismuth (Bi), cadmium (Cd), titanium (Ti), zirconium (Zr), antimony (Sb), manganese (Mn), beryllium (Be), chromium (Cr), germanium (Ge), vanadium (V), gallium (Ga), hafnium (Hf), indium (In), niobium (Nb), rhenium (Re), and thallium (Tl), as well as their metal oxides, metal nitrides, metal chlorides, and metal fluorides.

[0095] It should be noted that the metal wiring layer 20 is not limited to wiring, but broadly includes materials that function as functional layers such as electrodes, insulating layers, low-dielectric layers, and various conductor layers. This includes layers formed using the aforementioned metals, as well as their metal oxides, metal nitrides, metal chlorides, and metal fluorides. For example, in silicon-based systems, examples include layers such as SiN, SiO2, Low-k films (SiOC films, SiCOH films, etc.), and ILDs.

[0096] The material of the etch stop layer 30 is not particularly limited. For example, aluminum oxide (Al₂O₃) can be used as the etch stop layer 30. x Materials based on SiN, SiON, and SiOCN.

[0097] Regarding the material of the interlayer insulating film 40, any material with insulating properties is acceptable; there are no particular limitations on the material, and a suitable material can be selected appropriately considering manufacturing conditions, etc. As the interlayer insulating film 40, for example, a layer containing silicon-based materials such as SiO2, SiN, SiOC, or SiOCN can be used.

[0098] The material of the HM layer 50 can be any material that functions as a protective film against etching; there are no particular limitations on the material, and a suitable material can be appropriately selected considering manufacturing conditions, etc. For example, a layer containing titanium or a titanium-based alloy can be suitable as the HM layer 50. The processing solution involved in this embodiment has excellent removal properties for titanium-based residues, thus efficiently removing residues generated from the HM layer 50 using such a material (see dry etching residue 60). It should be noted that titanium nitride (TiN) and titanium oxide (TiO2) can be used as titanium-based alloys. x (x represents quantity.) Titanium-based materials such as titanium oxynitride (TiON) and titanium oxyfluoride (TiOF).

[0099] The dry etching residue 60 mainly originates from Ti-containing residues containing titanium-based materials in the HM layer 50, but is not limited to such residues. The dry etching residue 60 may contain, for example, etching residues containing inorganic substances as described above. The processing solution according to this embodiment is suitable for removing the aforementioned titanium-based residues.

[0100] <Handling Method> The processing liquid described in this embodiment can be suitably used as a semiconductor substrate processing method. As a suitable example of the substrate processing method described in this embodiment, a substrate processing method including a step of processing an etched substrate using the aforementioned processing liquid can be given. Furthermore, from the viewpoint of fully utilizing the effects of this embodiment, the substrate is preferably a substrate having a layer containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms, and copper atoms. In this case, the object of processing is a substrate laminate comprising a substrate and a metal layer formed on the substrate; examples of metal layers include those containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms, and copper atoms.

[0101] Here, refer to Figure 1The processing method described in this embodiment is illustrated. The cleaning method described in this embodiment is a process of cleaning the substrate 100 before processing, which has undergone dry etching by the wiring process, using the above-described processing solution. The cleaning method is not particularly limited, and known cleaning methods can be used.

[0102] As a cleaning operation, examples include a method of continuously coating a processing liquid onto a substrate 100 rotating at a certain speed (spin coating method), a method of immersing the substrate 100 in a processing liquid for a certain time (immersion method), and a method of spraying a processing liquid onto the surface of the substrate 100 (spraying method).

[0103] The cleaning temperature is not particularly limited, but it is preferably performed between 10 and 80°C. The lower limit of the cleaning temperature (temperature of the cleaning solution) is more preferably 15°C or higher, and even more preferably 20°C or higher. Furthermore, the upper limit of the cleaning temperature (temperature of the cleaning solution) is more preferably 75°C or lower, even more preferably 70°C or lower, and even more preferably 50°C or lower. By setting the lower limit of the cleaning temperature within the above range, the removal of etching residues can be further improved. Additionally, by setting the upper limit of the cleaning temperature within the above range, unintended compositional changes in the cleaning solution can be further effectively suppressed, and cleaning can be performed more efficiently from the viewpoints of workability, safety, and cost.

[0104] The cleaning time can be appropriately selected to remove etching residues, impurities, etc., adhering to the surface of the substrate 100 before processing. For example, a cleaning time of 10 seconds to 30 minutes is preferred. A lower limit of 20 seconds or more is more preferred, and a further preferred value is 30 seconds or more. Furthermore, an upper limit of 15 minutes or less is more preferred, and a further preferred value is 10 minutes or less. Additionally, depending on the method of use, even a time of 5 minutes or less can be expected to achieve the desired effect.

[0105] Because the cleaning solution according to this embodiment is used, damage to the metal wiring layer 20, etch stop layer 30, interlayer insulating film 40, and HM layer 50 can be suppressed in the substrate 100 before processing where dry etching residue 60 is attached, and the dry etching residue 60 originating from the HM layer 50, which serves as a protective film, can be effectively cleaned and removed. In particular, in the case of an HM layer containing titanium and / or titanium alloys, the cleaning solution according to this embodiment is especially suitable because of its excellent removal properties for titanium-based residues.

[0106] Furthermore, by using the processing liquid involved in this embodiment, damage to protective films such as the HM layer 50 is suppressed, as well as damage to various functional layers (metal wiring layer 20, etch stop layer 30, interlayer insulating film 40, etc.) is also suppressed.

[0107] Semiconductor Manufacturing Methods The processing liquid and processing method using the processing liquid described in this embodiment can be suitably used as a method for manufacturing a semiconductor substrate. As a suitable example of a method for manufacturing a semiconductor substrate according to this embodiment, a method for manufacturing a semiconductor substrate that includes a step of processing an etched substrate using the aforementioned processing liquid can be cited. Furthermore, from the viewpoint of fully realizing the effects of this embodiment, it is preferable that the substrate has a layer containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms, and copper atoms.

[0108] As a specific example of the semiconductor manufacturing method according to this embodiment, a semiconductor manufacturing method including the following steps can be cited: (1) a step of preparing a substrate having a layer containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms, and copper atoms; (2) a step of etching the substrate; and (3) a step of removing impurities from the substrate by contacting the aforementioned processing liquid with the substrate after etching. Hereinafter, [the following will be described in the context of semiconductor manufacturing methods]. Figure 1 The case of cleaning the substrate 100 before processing is shown as an example for illustration.

[0109] (1) A process for preparing a substrate having a layer containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms and copper atoms. In step (1), a substrate is prepared having a layer containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms, and copper atoms. Although not illustrated, Figure 1 In the case of preparing for etching, a stack consisting of a substrate 10, a metal wiring layer 20, an etch stop layer 30, an interlayer insulating film 40, and a hard mask layer (HM layer) 50 that is equivalent to a protective film is prepared.

[0110] There is no particular limitation on the method of sequentially stacking the metal wiring layer 20, the etch stop layer 30, the interlayer insulating film 40 and the hard mask layer (HM layer) 50, which is equivalent to a protective film, on the substrate 10, and known methods can be used.

[0111] (2) The process of etching the substrate Next, the substrate is etched. Through etching, a desired result can be obtained. Figure 1The substrate 100 before processing is shown. The etching method is not particularly limited; it can be wet etching or dry etching, but dry etching is preferred. Dry etching is advantageous from the viewpoint that it allows for nanoscale metal wiring and control of the gas used. Furthermore, while there is concern about greater damage to the substrate in dry etching, it is still preferred from the viewpoint that such damage can be effectively suppressed by using the processing liquid according to this embodiment, thus more effectively reflecting the advantages of this embodiment.

[0112] In the case of dry etching, plasma can be used. Generally, in the case of plasma etching, there are problems such as the substrate being easily damaged and the need to clean it with a processing solution due to the generation of plasma etching residue. However, if the processing solution involved in this embodiment is used, it is preferable that such problems can be effectively suppressed.

[0113] (3) After etching, the process of removing impurities from the substrate by bringing the above-mentioned treatment solution into contact with the substrate. As step (3), the processing method described in this embodiment can be used. This allows for the obtaining of a semiconductor substrate from which residues have been removed. Furthermore, known post-processing can be performed after cleaning, as needed.

[0114] As described above, the processing solution according to this embodiment can be used, for example, as a processing solution for removing residues generated in semiconductor etching processes, and is particularly suitable for removing residues generated by dry etching. The processing solution according to this embodiment has advantages such as excellent damage suppression of titanium-containing metal layers (e.g., TiN), aluminum-containing metal layers (e.g., alumina), copper substrates, and copper-containing metal layers, as well as excellent residue removal performance when removing titanium-based residues (residues containing titanium or titanium alloys) and silicon-based residues (residues containing silicon atoms). Therefore, as a processing solution for etching substrates having hard mask layers (HM layers) containing titanium, titanium alloys, or silicon atoms, it can achieve higher performance compared to conventional processing solutions.

[0115] Example The present invention will be further described in detail through the following embodiments and comparative examples, but the present invention is not limited to the following embodiments in any way.

[0116] 1. Experiment 1 (Comparative Example 1-1) First, as a reference, the treatment solution for Comparative Example 1-1 was prepared according to the proportions shown in Table 1. The treatment solution for Comparative Example 1-1 was an aqueous treatment solution containing 1.0% by mass hydrogen peroxide as an etchant, no corrosion inhibitor, 0.02% by mass tetramethylammonium hydroxide (TMAH) as a pH adjuster, and deionized water (DIW) as the remainder. Furthermore, the pH of the treatment solution was 9.5.

[0117] (Comparative Examples 1-2 to 1-4, Examples 1-1 to 1-12) Except for the preparation of the treatment solution with the composition shown in Table 1, the treatment solution was prepared in the same manner as in Comparative Example 1-1.

[0118] (Methods for pH measurement) The pH of the treatment solution was measured using a pH·ORP meter (portable pH meter "ORION STARA324", manufactured by Thermo Scientific) at a temperature of 22°C. Unless otherwise specified, the methods for pH measurement are the same for other experiments (examples and comparative examples).

[0119] (Methods for evaluating metal corrosion) First, substrates with copper (500 nm thick), titanium nitride (50 nm thick), or aluminum oxide (5 nm thick) films deposited on a 12-inch silicon substrate using PVD were prepared. These substrates were then cut into 2 cm × 2 cm pieces from a top view to create test samples (wafer specimens).

[0120] Next, the copper and titanium nitride samples were immersed in a diluted hydrogen fluoride aqueous solution (HF / H2O) at room temperature for 1 minute for DHF cleaning. After DHF cleaning, they were rinsed with water at room temperature for 30 seconds and dried by nitrogen purging, serving as the untreated samples. On the other hand, the alumina sample was not subjected to the above DHF cleaning and served as the untreated sample. These untreated samples were then placed in a 100mL beaker containing 80mL of the prepared treatment solution and immersed in the treatment solution at 25°C. After the specified immersion time, the wafer samples were removed from the cleaning solution, rinsed with water at room temperature for 30 seconds, and dried by nitrogen purging. It should be noted that the immersion time for the copper sample was 10 minutes, the immersion time for the titanium nitride sample was 30 minutes, and the immersion time for the alumina sample was 10 minutes.

[0121] Then, the film thickness of the samples (wafer specimens) before and after immersion in the cleaning solution was measured. The film thicknesses of copper, titanium nitride, and aluminum oxide were measured using X-ray electron spectrometry (Rigaku Corporation, "PrimusIV") via X-ray fluorescence X-ray analysis (XRF). The etching rate ("ER") was then calculated based on the change in film thickness before and after the cleaning process. / min). The evaluation of metal corrosion is based on the etching rate of the corresponding comparative example (Ref.), i.e., Comparative Example 1-1. The proportions of each embodiment and each comparative example relative to this reference value are determined, and the evaluation is judged according to the following criteria. It should be noted that the best evaluation results among the copper sample, titanium nitride sample, and alumina sample are recorded in the table. For example, the treatment solution recorded as "A" in the table means that the treatment solution has one or more evaluation results of copper sample, titanium nitride sample, and alumina sample that are "A".

[0122] A: The etching rate was reduced by more than 20% compared to the corresponding Comparative Example 1-1.

[0123] B: The etching rate is reduced by less than 20% or increased by less than 20% compared to the corresponding Comparative Example 1-1.

[0124] C: The etching rate is increased by more than 20% compared to the corresponding Comparative Example 1-1.

[0125] (Evaluation method for cleanability) First, substrates with titanium-based metal films (titanium oxide: 250 nm thick) or amorphous silicon films (100 nm thick) deposited on a 12-inch silicon substrate were prepared using the PVD method. These substrates were then cut into 2 cm × 2 cm pieces from a top view to create test samples.

[0126] Next, the sample was immersed in a diluted hydrogen fluoride aqueous solution (HF / H2O) at room temperature for 1 minute for DHF cleaning. Afterward, it was washed with water at room temperature for 30 seconds and dried by nitrogen purging to obtain the untreated sample. Then, the untreated sample was placed in a 100 mL beaker containing 80 mL of the prepared treatment solution and immersed in the treatment solution at 25°C. After immersion for 30 minutes, the wafer sample was removed from the cleaning solution, washed with water at room temperature for 30 seconds, and dried by nitrogen purging.

[0127] Then, the film thickness of the wafer samples before and after immersion in the cleaning solution was measured. The titanium oxide film thickness was measured using X-ray fluorescence X-ray analysis (XRF) with an X-ray electron spectrometer (Rigaku, "PrimusIV"). The amorphous silicon film thickness was measured using an ellipsometry (M-2000, JAWoolam). The etching rate was calculated based on the change in film thickness of the titanium oxide or amorphous silicon film before and after the cleaning treatment.

[0128] The cleaning performance was evaluated using the etching rate of the corresponding comparative example (Ref.), i.e., Comparative Example 1-1, as the baseline value. The proportions of each embodiment and each comparative example relative to this baseline value were determined, and the results were judged according to the following criteria. It should be noted that the best evaluation results for the titanium-based metal film and the amorphous silicon film are recorded in the table. For example, a processing solution marked "A" in the table refers to a processing solution for which at least one of the titanium-based metal film and amorphous silicon film evaluation results is "A".

[0129] A: The etching rate increased by more than 10% compared to the corresponding Comparative Example 1-1.

[0130] B: The etch rate increases by less than 10% or decreases by less than 10% compared to the corresponding Comparative Example 1-1.

[0131] C: The etching rate is reduced by more than 10% compared to the corresponding Comparative Example 1-1.

[0132] Table 1 shows the composition and evaluation results for each embodiment and comparative example of Experiment 1. It should be noted that "[ ]" in the table indicates content (mass %). Additionally, "-" for an ingredient indicates that the ingredient was not added.

[0133] [Table 1] 2. Experiment 2 (Comparative Example 2-1) First, as a reference, the treatment solution of Comparative Example 2-1 was prepared according to the proportions shown in Table 2. The treatment solution of Comparative Example 2-1 was an aqueous treatment solution containing 1.0% by mass hydrogen peroxide as an etchant, no corrosion inhibitor, 0.05% by mass tetramethylammonium hydroxide (TMAH) as a pH adjuster, 0.05% by mass ethylenediaminetetraacetic acid (EDTA) as an additive, and deionized water (DIW) as the remainder. Furthermore, the pH of the treatment solution was 9.5.

[0134] (Examples 2-1 to 2-5) Except for the preparation of the treatment solution with the composition shown in Table 2, the treatment solution was prepared in the same manner as in Comparative Example 2-1.

[0135] (Methods for evaluating metal corrosion) Except for the fact that Comparative Example 2-1 was used as the reference, the metal corrosion was evaluated according to the evaluation method of Experiment 1. That is, the evaluation of the metal corrosion in Experiment 2 was based on the etching rate of Comparative Example 2-1, the proportions of each embodiment and each comparative example relative to this reference value were determined, and the judgment was made according to the following criteria.

[0136] A: The etching rate is reduced by more than 20% compared to the corresponding Comparative Example 2-1.

[0137] B: The etching rate is reduced by less than 20% or increased by less than 20% compared to the corresponding Comparative Example 2-1.

[0138] C: The etching rate is increased by more than 20% compared to the corresponding Comparative Example 2-1.

[0139] (Evaluation method for cleanability) Except for the fact that Comparative Example 2-1 was used as the reference, the cleaning performance was evaluated according to the evaluation method of Experiment 1. That is, the evaluation of the cleaning performance of Experiment 2 was based on the etching rate of Comparative Example 2-1, the proportions of each embodiment and each comparative example relative to this reference value were calculated, and the results were judged according to the following criteria.

[0140] A: The etching rate increased by more than 10% compared to the corresponding Comparative Example 2-1.

[0141] B: The etching rate increases by less than 10% or decreases by less than 10% compared to the corresponding Comparative Example 2-1.

[0142] C: The etching rate is reduced by more than 10% compared to the corresponding Comparative Example 2-1.

[0143] 3. Experiments 3-18 In Experiments 3-18, the corresponding comparative examples (Ref.) were used as the baseline values, and the proportions of each embodiment (and each comparative example) relative to the baseline values ​​were determined in the same manner as in Experiments 1 and 2. The metal corrosion and cleanability were evaluated according to the following criteria.

[0144] In Experiment 3 (Comparative Example 3-1, Example 3-1), Comparative Example 3-1 is used as the corresponding comparative example (Ref.).

[0145] In the case of Experiment 4 (Comparative Example 4-1, Example 4-1), Comparative Example 4-1 is used as the corresponding comparative example (Ref.).

[0146] In the case of Experiment 5 (Comparative Example 5-1, Example 5-1), Comparative Example 5-1 is used as the corresponding comparative example (Ref.).

[0147] In the case of Experiment 6 (Comparative Example 6-1, Example 6-1), Comparative Example 6-1 is used as the corresponding comparative example (Ref.).

[0148] In the case of Experiment 7 (Comparative Example 7-1, Example 7-1), Comparative Example 7-1 is used as the corresponding comparative example (Ref.).

[0149] In the case of Experiment 8 (Comparative Example 8-1, Example 8-1), Comparative Example 8-1 is used as the corresponding comparative example (Ref.).

[0150] In the case of Experiment 9 (Comparative Example 9-1, Example 9-1), Comparative Example 9-1 is used as the corresponding comparative example (Ref.).

[0151] In the case of Experiment 10 (Comparative Example 10-1, Example 10-1), Comparative Example 10-1 is used as the corresponding comparative example (Ref.).

[0152] In the case of Experiment 11 (Comparative Example 11-1, Example 11-1), Comparative Example 11-1 is used as the corresponding comparative example (Ref.).

[0153] In the case of Experiment 12 (Comparative Example 12-1, Example 12-1), Comparative Example 12-1 is used as the corresponding comparative example (Ref.).

[0154] In the case of Experiment 13 (Comparative Example 13-1, Example 13-1), Comparative Example 13-1 is used as the corresponding comparative example (Ref.).

[0155] In the case of Experiment 14 (Comparative Example 14-1, Example 14-1), Comparative Example 14-1 is used as the corresponding comparative example (Ref.).

[0156] In the case of Experiment 15 (Comparative Example 15-1, Example 15-1), Comparative Example 15-1 is used as the corresponding comparative example (Ref.).

[0157] In the case of Experiment 16 (Comparative Example 16-1, Example 16-1), Comparative Example 16-1 is used as the corresponding comparative example (Ref.).

[0158] In the case of Experiment 17 (Comparative Example 17-1, Example 17-1), Comparative Example 17-1 is used as the corresponding comparative example (Ref.).

[0159] In the case of Experiment 18 (Comparative Example 18-1, Example 18-1), Comparative Example 18-1 is used as the corresponding comparative example (Ref.).

[0160] Furthermore, the treatment solutions of each comparative example and embodiment were prepared in a manner that resulted in the compositions described in Tables 2 to 4.

[0161] (Methods for evaluating metal corrosion) A: The etching rate is reduced by more than 20% compared to the corresponding comparative example.

[0162] B: The etching rate is reduced by less than 20% or increased by less than 20% compared to the corresponding comparative example.

[0163] C: The etching rate is increased by more than 20% compared to the corresponding comparative example.

[0164] (Evaluation method for cleanability) A: The etching rate is increased by more than 10% compared to the corresponding comparative example.

[0165] B: The etch rate increases by less than 10% or decreases by less than 10% compared to the corresponding comparative example.

[0166] C: The etching rate is reduced by more than 10% compared to the corresponding comparative example.

[0167] Tables 2-4 show the composition and evaluation results for each embodiment and comparative example in Experiments 2-18. It should be noted that "[ ]" in the tables indicates content (mass %). Additionally, "-" for an ingredient indicates that the ingredient was not added.

[0168] [Table 2] [Table 3] [Table 4] HF: Hydrogen fluoride TMAH: Tetramethylammonium hydroxide NH4OH: Ammonium hydroxide EDTA: Ethylenediaminetetraacetic acid NTMP: Triammonium phosphonate HEDTA: Hydroxyethylethylenediaminetriacetic acid In summary, it has been confirmed that the treatment solution described in this embodiment has excellent effects in inhibiting metal corrosion and cleaning.

[0169] This application is based on patent application (Japanese Patent Application No. 2024-052719) filed with the Japan Patent Office on March 28, 2024, the contents of which are incorporated herein by reference.

[0170] Explanation of reference numerals in the attached figures 10: Substrate 20: Metal wiring layer 30: Etching Stop Layer 40: Interlayer insulating film 50: Hard mask layer 60: Dry etching residue 100: Substrate before processing (substrate laminate)

Claims

1. A treatment fluid, comprising: At least one corrosion inhibitor is selected from the group consisting of a compound (1) represented by the following general formula (1), a hydrate of said compound (1), and a salt of said compound (1); Etching agent; and water, [Chemical Formula 1] In equation (1), R 1 R represents a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group. 2 R represents a hydrogen atom or an organic group containing a carbonyl group. 1 and R 2 They can bond together to form a ring structure.

2. The treatment solution as described in claim 1, wherein, In the general formula (1) R 1 and R 2 At least one of them is an aliphatic hydrocarbon group with 1 to 15 carbon atoms, either substituted or unsubstituted.

3. The treatment liquid as described in claim 1 or 2, wherein, The compound (1) is either compound (1-1) represented by formula (1-1) or compound (1-2) represented by formula (1-2). [Chemical Formula 2] In equation (1-1), R 3 This indicates an aliphatic hydrocarbon group with 1 to 15 carbon atoms that is substituted or unsubstituted, an alicyclic hydrocarbon group with 1 to 15 carbon atoms that is substituted or unsubstituted, or an aromatic hydrocarbon group that is substituted or unsubstituted. [Chemical Formula 3] 。 4. The treatment liquid as described in claim 1 or 2, wherein, The etchant is selected from at least one of the following groups: hydrogen peroxide, hydrogen fluoride, hydroxylamine, hydroxylamine derivatives, and alkanolamines.

5. The treatment solution as described in claim 1 or 2, further comprising a pH adjuster.

6. The treatment solution as described in claim 1 or 2, wherein the pH is 4 to 13.

7. The processing solution as described in claim 1 or 2, wherein it is a processing solution for treating the etched substrate. The substrate has a layer containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms and copper atoms.

8. A method for processing a substrate, comprising a step of processing the etched substrate using the processing solution described in claim 1 or 2.

9. The substrate processing method as described in claim 8, wherein, The substrate has a layer containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms and copper atoms.

10. A method for manufacturing a semiconductor substrate, comprising a step of treating an etched substrate with the processing solution described in claim 1 or 2.

11. The method for manufacturing a semiconductor substrate as claimed in claim 10, wherein, The substrate has a layer containing at least one metal selected from the group consisting of titanium atoms, aluminum atoms and copper atoms.

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