Compositions for semiconductor processing, methods for processing materials.

Abstract

The present invention provides a composition, for treating a semiconductor, in which etching of silicon germanium is suppressed and the ratio of the silicon etching rate to the silicon germanium etching rate is high. In addition, the present invention provides a method, for treating an object-to-be-treated, that uses the composition for treating a semiconductor. The composition for treating a semiconductor of the present invention includes: a quaternary ammonium salt having a hydroxyl group; a polar organic solvent; at least one kind of nitrogen-containing compound selected from the group consisting of compounds represented by formula (1), compounds represented by formula (2), and salts thereof; and water. The mass ratio of the nitrogen-containing compound to the quaternary ammonium salt is 0.00001 to 0.1.

Description

[Technical Field]

[0001] The present invention relates to a semiconductor processing composition and a method for processing an object to be processed. [Background technology]

[0002] When forming circuits and components, it is common to perform an etching process using chemical solutions. In this case, since multiple materials may be present on the substrate, it is desirable that the etching solution used is capable of selectively removing only specific materials.

[0003] For example, Patent Document 1 discloses a cleaning and removal composition and a cleaning and removal process that very efficiently clean and remove chemical mechanical polishing (CMP) residues and contaminants from the surface of a microelectronic device without damaging the low-k dielectric material or copper interconnect material. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2019-218548 [Overview of the project] [Problems that the invention aims to solve]

[0005] In recent years, semiconductor processing processes have been developed to selectively etch only Si from materials containing silicon (hereinafter also simply referred to as "Si") and silicon germanium (hereinafter also simply referred to as "SiGe"). In this process, there is a need for compositions and processing methods that further improve the ratio of the etching rate of Si to the etching rate of SiGe, thereby selectively etching only Si.

[0006] The present inventors used the composition disclosed in Patent Document 1 to etch Si from a workpiece containing Si and SiGe, but found that the etching rate of SiGe was high, and the ratio of the etching rate of Si to the etching rate of SiGe was low, making it difficult to selectively etch Si.

[0007] The object of the present invention is to provide a semiconductor processing composition in which the etching of SiGe is suppressed and the ratio of the etching rate of Si to the etching rate of SiGe is large. Furthermore, the present invention also aims to provide a method for processing an object using a semiconductor processing composition. [Means for solving the problem]

[0008] The inventors, after diligently conducting research to solve the above problems, found that the above problems could be solved by the following configuration.

[0009] [1] A semiconductor processing composition, Quaternary ammonium salts having a hydroxyl group, Polar organic solvents and A nitrogen-containing compound selected from the group consisting of the compound represented by formula (1) described later, the compound represented by formula (2) described later, and salts thereof, Water and, A semiconductor processing composition wherein the mass ratio of the nitrogen-containing compound to the quaternary ammonium salt is 0.00001 to 0.10. [2] The semiconductor processing composition according to [1], wherein the content of the nitrogen-containing compound is 0.0001 to 1.00% by mass of the total mass of the semiconductor processing composition. [3] The semiconductor processing composition according to [1] or [2], wherein the content of the polar organic solvent is 15 to 85% by mass relative to the total mass of the semiconductor processing composition. [4] A semiconductor processing composition according to any one of [1] to [3], comprising two or more of the above polar organic solvents. [5] The semiconductor processing composition according to any one of [1] to [4], wherein the polar organic solvent has a hydroxyl group. [6] The semiconductor processing composition according to any one of [1] to [5], wherein the above quaternary ammonium salt comprises an ammonium cation represented by formula (3) described later, or an ammonium cation represented by formula (4) described later. [7] The above quaternary ammonium salt is R in formula (3) above. 1 , R 3 , and, R 4 is a methyl group, and R 2 The semiconductor processing composition according to [6], which does not contain an ammonium cation in which the group is an ethylene group. [8] The semiconductor processing composition according to any one of [1] to [7], wherein the above quaternary ammonium salt comprises at least one selected from the group consisting of dimethylbis(2-hydroxyethyl)ammonium hydroxide, methyltris(2-hydroxyethyl)ammonium hydroxide, 4-methyl-4-(2-hydroxyethyl)morpholinium hydroxide, and oxydiethylenebis[dimethyl(2-hydroxyethyl)ammonium hydroxide]. [9] A semiconductor processing composition according to any one of [1] to [8], wherein the pH is 11.0 or higher.

[10] Further comprising a metallic component containing at least one metallic element selected from the group consisting of Cr, Fe, and Cu, The semiconductor processing composition according to any one of [1] to [9], wherein the content of the above metal element is 1 ppt to 1 ppm by mass with respect to the total mass of the semiconductor processing composition.

[11] The ratio of the content of the above metal element to the content of the above nitrogen-containing compound is 1 × 10 -7 A semiconductor processing composition as described in

[10] , wherein the value is ~1.

[12] The semiconductor processing composition according to any one of claims [1] to

[11] , further comprising a surfactant.

[13] The semiconductor processing composition according to

[12] , wherein the surfactant is a nonionic surfactant with an HLB value of 12.0 to 15.0.

[14] A semiconductor processing composition according to any one of [1] to

[13] , used for processing materials containing silicon and silicon germanium.

[15] A method for treating an object containing silicon and silicon germanium, comprising contacting the object with a semiconductor processing composition described in any one of [1] to

[14] to remove the silicon. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a semiconductor processing composition that suppresses the etching of SiGe and has a large ratio of the etching rate of Si to the etching rate of SiGe. Furthermore, according to the present invention, a method for processing an object to be processed using a semiconductor processing composition can be provided. [Modes for carrying out the invention]

[0011] The present invention will be described in detail below. The following description of the constituent elements represents a typical embodiment of the present invention, and the present invention is not limited to such embodiments.

[0012] The following definitions are used within this specification. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, "ppm" is an abbreviation for "parts per million," and 10 -6 It means that. Also, "ppb" is an abbreviation for "parts per billion," which means 10 -9 It means that. "ppt" is an abbreviation for "parts per trillion," and 10 -12 It means... In this specification, if two or more components are present, the "content" of those components means the total content of those two or more components.

[0013] In this specification, "silicon" means a material composed substantially of only the element Si. "Substantially" means that the Si content is 90% by mass or more of the total mass of the material. Therefore, other elements (except for the element Ge) may be present as long as the Si content is within the above range. Furthermore, in this specification, "silicon germanium" refers to a material composed substantially of only Si and Ge elements. "Substantially" means that the total content of Si and Ge elements is 90% by mass or more of the total mass of the material. Therefore, other elements may be present as long as the total content of Si and Ge elements is within the above range. In addition, in silicon germanium, the content ratio of Si to Ge elements is not particularly limited, and the mass ratio of the Ge element content to the total amount of Si and Ge elements is preferably 5 to 50% by mass.

[0014] Unless otherwise specified, "exposure" includes exposure using far-ultraviolet light such as mercury lamps and excimer lasers, X-rays, or EUV light, and drawing using particle beams such as electron beams or ion beams. "Preparation" includes not only preparing specific materials by synthesizing or mixing them, but also procuring the required items by purchasing them, etc.

[0015] Unless otherwise specified, the bonding direction of a divalent group (e.g., -COO-) is such that, when Y in a compound represented as "XYZ" is -COO-, the compound may be either "XO-CO-Z" or "X-CO-OZ".

[0016] {Composition for semiconductor processing} The semiconductor processing composition of the present invention (hereinafter also simply referred to as "the composition") comprises a quaternary ammonium salt having a hydroxyl group, a polar organic solvent, at least one nitrogen-containing compound selected from the group consisting of the compound represented by formula (1), the compound represented by formula (2), and their salts, and water, wherein the mass ratio of the nitrogen-containing compound to the quaternary ammonium salt is 0.00001 to 0.10. The mechanism by which the above-mentioned problems are solved by the composition having the above-mentioned structure is not necessarily clear, but the inventors believe it to be as follows. The composition, by containing a quaternary ammonium salt and water, exhibits etching ability for both Si and SiGe. However, it is presumed that the presence of a hydroxyl group in the quaternary ammonium salt suppresses only the etching of SiGe, thereby increasing the ratio of the etching rate of Si to the etching rate of SiGe. Furthermore, it is presumed that the inclusion of a nitrogen-containing compound in the composition in a mass ratio of 0.00001 to 0.10 relative to the quaternary ammonium salt containing a hydroxyl group, and the inclusion of a polar organic solvent in the composition, further suppresses the etching of SiGe, increasing the ratio of the etching rate of Si to the etching rate of SiGe, and thus meeting the required standards. Hereinafter, the effect of obtaining at least one of the following effects—that etching of SiGe can be further suppressed, and that the ratio of the etching rate of Si to the etching rate of SiGe can be made larger—is also referred to as "the effect of the present invention is superior."

[0017] [Composition components] The following describes the components that may be included in the composition.

[0018] (Quaternary ammonium salts containing a hydroxyl group) The composition contains a quaternary ammonium salt having a hydroxyl group (hereinafter also simply referred to as "specific quaternary ammonium salt"). Although the details are not clear, it is thought that the composition contains a specific quaternary ammonium salt, which suppresses the etching of SiGe and allows for a higher ratio of the etching rate of Si to the etching rate of SiGe.

[0019] A specific quaternary ammonium salt contains both an ammonium cation and anion. In a specific quaternary ammonium salt, it is preferable that the ammonium cation has a hydroxyl group. The number of hydroxyl groups contained in the specific quaternary ammonium salt is not particularly limited and may be one or more. From the viewpoint of more excellent effects of the present invention, 1 to 6 is preferable, 1 to 4 is more preferable, and 1 to 3 is even more preferable. The ammonium cation contained in the specific quaternary ammonium salt may be an ammonium cation containing one quaternized nitrogen atom, or may be an ammonium cation containing a plurality (two or more) of quaternized nitrogen atoms.

[0020] From the viewpoint of more excellent effects of the present invention, the specific quaternary ammonium salt preferably contains an ammonium cation represented by the following formula (3) or an ammonium cation represented by the following formula (4).

[0021]

Chemical formula

[0022] In formula (3), R 1 [[ID=XX]]、R 3 、and R 4 each independently represents an alkyl group having 1 to 16 carbon atoms which may have a substituent, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and an -O- group as a substituent. R 1 、R<​​​​​​​​​​​​, R 3 , and, R 4 Examples of such groups include methyl group, hydroxymethyl group, ethyl group, 2-hydroxyethyl group, 2-ethoxyethanol group, propyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, butyl group, hexyl group, octyl group, decyl group, and dodecyl group.

[0023] R 2 This represents an alkylene group having 1 to 16 carbon atoms, which may have an -O- group. R 2 The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 6 is preferred, 1 to 4 is more preferred, and 1 or 2 is even more preferred in terms of achieving superior effects of the present invention. If the alkylene group has an -O- group, the -O- group may be located between carbon atoms of the alkylene group, or it may be located at the terminal end of the alkylene group. When the alkylene group has an -O- group, the number of -O- groups on the alkylene group is not particularly limited, but is preferably 1 to 3, and more preferably 1. R 2 Examples of such groups include methylene, ethylene, propylene, oxydimethylene, oxydiethylene, butylene, and hexylene groups.

[0024] R 1 and R 3 , R 3 and R 4 , and, R 1 and R 4 These elements may be independent of each other, or they may be bonded together to form a ring structure. The type of ring structure formed is not particularly limited and may be an aromatic ring or a non-aromatic ring. Furthermore, the formed ring structure may contain heteroatoms (for example, an oxygen atom, a sulfur atom, and a nitrogen atom). Examples of the ring structures formed include morpholine rings and piperidine rings.

[0025] In particular, the present invention has superior effects, R1 , R 3 , and, R 4 At least one of them represents an alkyl group having 1 to 16 carbon atoms and a hydroxyl group, or R 1 and R 3 , R 3 and R 4 , and, R 1 and R 4 It is preferable that one of them is bonded to each other to form a ring structure. Furthermore, in terms of the superior effects of the present invention, the specific quaternary ammonium salt is R in formula (3). 1 , R 3 , and, R 4 is a methyl group, and R 2 It is preferable that the ammonium cation, which is an ethylene group, is not included. In other words, it is preferable that the specific quaternary ammonium salt is not choline.

[0026] Examples of ammonium cations represented by formula (3) include trimethyl(2-hydroxyethyl)ammonium cation, triethyl(2-hydroxyethyl)ammonium cation, trimethyl(3-hydroxypropyl)ammonium cation, trimethyl(4-hydroxybutyl)ammonium cation, dimethylbis(2-hydroxyethyl)ammonium cation, diethylbis(2-hydroxyethyl)ammonium cation, methyltris(2-hydroxyethyl)ammonium cation, tetra(2-hydroxyethyl)ammonium cation, and 4-methyl-4-(2-hydroxyethyl)morpholinium cation.

[0027] Also, R 1 , R 2 -OH, R 3 , and, R 4 It is also preferable that not all of them are the same group. The above / R 1 , R 2 -OH, R 3 , and, R 4 "Not all of them are the same group" means R 1 , R 2 -OH, R3 , and, R 4 This means that the group consisting of these four groups contains at least two different types of groups. 1 , R 2 -OH, R 3 , and, R 4 The group consisting of these four groups may contain any of 2 to 4 different types of groups. For example, as mentioned above, R 1 and R 2 -OH groups are all 2-hydroxyethyl groups, R 3 and R 4 If R is a methyl group, 1 , R 2 -OH, R 3 , and, R 4 The group consisting of these four groups contains two types of groups. Furthermore, groups with different numbers of carbon atoms, such as methyl and ethyl groups, are considered different types of groups. Also, even if the number of carbon atoms is the same, groups with different bond positions, such as n-propyl and isopropyl groups; groups with different presence or absence of substituents, such as ethyl and 2-hydroxyethyl groups; and groups with different substituent positions, such as 2-hydroxypropyl and 3-hydroxypropyl groups, are all considered different groups. However, R 1 and R 3 , R 3 and R 4 , and, R 1 and R 4 If one of these groups is bonded to another to form a ring structure, the groups forming the ring structure are considered to be the same group.

[0028] [ka]

[0029] In formula (4), R 5 , R 6 , and, R 7 Each of these independently represents an alkylene group having 1 to 16 carbon atoms, which may have an -O- group. R 5 , R 6, and R 7 The number of carbon atoms in the alkylene group of 7 is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 or 2, in terms of more excellent effects of the present invention. When the alkylene group has an -O- group, the -O- group may be present between carbon atoms of the alkylene group or at the end of the alkylene group. When the alkylene group has an -O- group, the number of -O- groups in the alkylene group is not particularly limited, preferably 1 to 3, and more preferably 1. R 5 , R 6 , and R 7 Specific examples of 2 are the same as the groups exemplified in

[0030] R 8 , R 9 , R 10 , and R 11 each independently represents an alkyl group having 1 to 16 carbon atoms which may have a substituent, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and an -O- group as a substituent. R 8 , R 9 , R 10 , and R 11 The number of carbon atoms in the alkyl group of is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 or 2, in terms of more excellent effects of the present invention. When the alkyl group has an -O- group, the -O- group may be present between carbon atoms of the alkyl group or at the end of the alkyl group. When the alkyl group has an -O- group, the number of -O- groups in the alkyl group is not particularly limited, preferably 1 to 3, and more preferably 1. R 8 , R 9 , R 10 , and R 11 Specific examples of 1, R 3 , and, R 4 is the same as the group exemplified above.

[0031] Examples of the ammonium cation represented by formula (4) include, for example, oxyethylene bis[dimethyl(2-hydroxyethyl)ammonium] cation.

[0032] Also, it is also preferable that all of R 6 -OH, R 7 -OH, R 8 ~R 11 are not the same group. The above "all of R 6 -OH, R 7 -OH, R 8 ~R 11 are not the same group" means that at least two types of groups are included in the group consisting of the six groups of R 6 -OH, R 7 -OH, R 8 ~R 11 . The number of types of groups included in the group consisting of the six groups of R 6 -OH, R 7 -OH, R 8 ~R 11 may be any of 2 to 6 types. Note that specific examples of different groups are the same as those in the above "R 1 , R 2 -OH, R 3 , and, R 4 are not the same group".

[0033] The anion contained in the specific quaternary ammonium salt is not particularly limited, and examples include hydroxide ion, halide ion, cyanide ion, acetate ion, trifluoroacetate ion, hydrogen sulfate ion, sulfate ion, sulfite ion, sulfonate ion, thiosulfate ion, carbonate ion, oxalate ion, hydrogen phosphate ion, and phosphate ion. Among them, hydroxide ion or halide ion is preferable, hydroxide ion, chloride ion, fluoride ion, or bromide ion is more preferable, and hydroxide ion is even more preferable.

[0034] Examples of specific quaternary ammonium salts include trimethyl(2-hydroxyethyl)ammonium hydroxide (also known as choline), trimethyl(2-hydroxyethyl)ammonium chloride, triethyl(2-hydroxyethyl)ammonium hydroxide, trimethyl(3-hydroxypropyl)ammonium hydroxide, trimethyl(4-hydroxybutyl)ammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium chloride, diethylbis(2-hydroxyethyl)ammonium hydroxide, methyltris(2-hydroxyethyl)ammonium hydroxide, tetra(2-hydroxyethyl)ammonium hydroxide, 4-methyl-4-(2-hydroxyethyl)morpholinium hydroxide, and oxydiethylenebis[dimethyl(2-hydroxyethyl)ammonium hydroxide]. Among these, dimethylbis(2-hydroxyethyl)ammonium hydroxide, methyltris(2-hydroxyethyl)ammonium hydroxide, 4-methyl-4-(2-hydroxyethyl)morpholinium hydroxide, or oxydiethylenebis[dimethyl(2-hydroxyethyl)ammonium hydroxide] is preferred in terms of exhibiting superior effects of the present invention.

[0035] A specific quaternary ammonium salt may be used alone or in combination of two or more types.

[0036] The content of the specific quaternary ammonium salt is not particularly limited, but in terms of achieving superior effects of the present invention, it is preferably 1.0 to 15.0% by mass, more preferably 3.0 to 12.0% by mass, and even more preferably 4.0 to 10.0% by mass, relative to the total mass of the composition. When two or more specific quaternary ammonium salts are used, it is preferable that the total content of the two or more specific quaternary ammonium salts is within the above range.

[0037] (Polar organic solvents) The composition contains a polar organic solvent. In this specification, a polar organic solvent means an organic solvent that dissolves in 100g of water at a temperature of 25°C in an amount of 0.1g or more. Polar organic solvents are typically liquid at a temperature of 25°C. Polar organic solvents that are miscible with water in any ratio are preferred.

[0038] Examples of polar organic solvents include glycol-based solvents, glycol ether-based solvents, alcohol-based solvents, ketone-based solvents, amide-based solvents, and sulfur-containing solvents.

[0039] Examples of glycol-based solvents include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.

[0040] Examples of glycol ether-based solvents include glycol monoethers. Examples of glycol monoethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl 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.

[0041] Examples of alcohol-based solvents include alkanediols, alkoxy alcohols, saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, alcohols containing a cyclic structure, and alcohols having an amino group (-NH2). Examples of alkanediols include glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, and pinacol. Examples of alkoxy alcohols include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, and 1-methoxy-2-butanol. Examples of saturated aliphatic monohydric alcohols include methanol, ethanol, n-propyl alcohol, isopropanol (isopropyl alcohol), 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, and 1-hexanol. Examples of unsaturated non-aromatic monohydric alcohols include allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol. Examples of alcohols containing a ring structure include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol. Examples of alcohols containing an amino group include methanolamine, monoethanolamine, and 1-amino-2-propanol.

[0042] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0043] Examples of amide solvents include N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide.

[0044] Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.

[0045] Among the polar organic solvents listed above, alcohol-based solvents or sulfur-containing solvents are preferred in terms of exhibiting superior effects of the present invention, and monoethanolamine or dimethyl sulfoxide are more preferred.

[0046] A single polar organic solvent may be used, or two or more may be used in combination. In particular, the composition preferably contains two or more polar organic solvents in order to achieve the best effects of the present invention. When the composition contains two or more polar organic solvents, the number of polar organic solvents is preferably 2 to 4, and more preferably 2.

[0047] In particular, in terms of achieving superior effects of the present invention, it is preferable that the composition contains a polar organic solvent having a hydroxyl group (for example, the alcohol-based solvent described above). For example, if the composition contains two or more polar organic solvents, it is preferable that at least one of them is a polar organic solvent having a hydroxyl group. Furthermore, it is more preferable that the composition contains a polar organic solvent without a hydroxyl group and a polar organic solvent having a hydroxyl group.

[0048] The content of the polar organic solvent is not particularly limited, but in terms of achieving superior effects of the present invention, it is preferably 10 to 90% by mass, more preferably 15 to 85% by mass, and even more preferably 25 to 45% by mass, based on the total mass of the composition. When two or more polar organic solvents are used, it is preferable that the total content of the two or more polar organic solvents is within the above range.

[0049] When two types of polar organic solvents are used in combination, the mixing ratio of the two polar organic solvents is not particularly limited. In particular, in terms of achieving superior effects of the present invention, when the composition contains two types of polar organic solvents, a first polar organic solvent and a second polar organic solvent, the mass ratio of the second polar organic solvent to the first polar organic solvent is preferably 0.1 to 10, more preferably 0.3 to 3.3, and even more preferably 0.4 to 2.5.

[0050] (nitrogen-containing compounds) The composition comprises at least one nitrogen-containing compound selected from the group consisting of the compound represented by formula (1), the compound represented by formula (2), and salts thereof.

[0051] [ka]

[0052] In formula (1), R 12 represents an amino group (-NH2) or an alkyl group having 1 to 16 carbon atoms, which may have substituents. R 12 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2, in terms of achieving superior effects of the present invention. R 12 Examples of alkyl groups represented by include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, and dodecyl groups.

[0053] R 13 , and, R 14 Each of these independently represents a hydrogen atom or an alkyl group which may have substituents having 1 to 16 carbon atoms, and the alkyl group may have one or more substituents selected from the group consisting of a hydroxyl group and an -O- group. R 13 , and, R 14The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2, in terms of achieving superior effects of the present invention. When the alkyl group has hydroxyl groups, the number of hydroxyl groups in the alkyl group is not particularly limited, but is preferably 1 to 3, and more preferably 1. If the alkyl group has an -O- group, the -O- group may be located between carbon atoms of the alkyl group, or it may be located at the terminal end of the alkyl group. When the alkyl group has an -O- group, the number of -O- groups in the alkyl group is not particularly limited, but 1 to 3 is preferred, and 1 is more preferred. R 13 , and, R 14 A concrete example is R 1 , R 3 , and, R 4 This is similar to the basis mentioned earlier.

[0054] R 12 and R 13 , R 13 and R 14 , and, R 12 and R 14 These elements may be independent of each other, or they may be bonded together to form a ring structure. The type of ring structure formed is not particularly limited and may be an aromatic ring or a non-aromatic ring. Furthermore, the formed ring structure may contain heteroatoms (for example, an oxygen atom, a sulfur atom, and a nitrogen atom). Examples of the ring structures formed include morpholine rings and piperidine rings.

[0055] Examples of compounds represented by formula (1) include hydrazine, monomethylhydrazine, 1,1-dimethylhydrazine, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine, N-methylmorpholine, and N-ethylmorpholine. Among these, hydrazine, trimethylamine, N-methyldiethanolamine, N,N-dimethylethanolamine, or N-methylmorpholine are preferred in terms of exhibiting superior effects of the present invention.

[0056] Examples of salts of the compound represented by formula (1) include salts of the compound represented by formula (1) with an inorganic acid, and salts of the compound represented by formula (1) with an organic acid. Examples of salts of inorganic acids with compounds represented by formula (1) include salts of inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, hydroiodic acid, and perchloric acid with compounds represented by formula (1). Examples of salts of organic acids with compounds represented by formula (1) include salts of organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, oxalic acid, maleic acid, citric acid, fumaric acid, lactic acid, malic acid, succinic acid, tartaric acid, gluconic acid, ascorbic acid, and methanesulfonic acid with compounds represented by formula (1). The salt of the compound represented by formula (1) may be separated into cations and anions in the composition.

[0057] The molecular weight of the compound represented by formula (1) is preferably 30 to 1000, more preferably 30 to 500, and even more preferably 30 to 300.

[0058] [ka]

[0059] In formula (2), R 15 This represents an alkylene group that may have an -O- group. R 15 The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 6 is preferred, and 1 to 4 is more preferred, in terms of achieving superior effects of the present invention. If the alkylene group has an -O- group, the -O- group may be located between carbon atoms of the alkylene group, or it may be located at the terminal end of the alkylene group. When the alkylene group has an -O- group, the number of -O- groups on the alkylene group is not particularly limited, but is preferably 1 to 3, and more preferably 1. R 15 A concrete example is R 2 This is similar to the basis mentioned earlier.

[0060] R 16 , R 17 , R 18 , and, R 19 Each of these independently represents an alkyl group having 1 to 16 carbon atoms, which may have substituents, and the alkyl group may have one or more substituents selected from the group consisting of a hydroxyl group and an -O- group. R 16 , R 17 , R 18 , and, R 19 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2. When the alkyl group has hydroxyl groups, the number of hydroxyl groups in the alkyl group is not particularly limited, but is preferably 1 to 3, and more preferably 1. If the alkyl group has an -O- group, the -O- group may be located between carbon atoms of the alkyl group, or it may be located at the terminal end of the alkyl group. When the alkyl group has an -O- group, the number of -O- groups in the alkyl group is not particularly limited, but 1 to 3 is preferred, and 1 is more preferred. R 16 , R 17 , R 18 , and, R 19 A concrete example is R 1 , R 3 , and, R 4 This is similar to the basis mentioned earlier.

[0061] Examples of compounds represented by formula (2) include N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, bis(2-dimethylaminoethyl) ether, and N-(2-hydroxyethyl)-N,N',N'-trimethylbis(2-aminoethyl) ether. Among these, bis(2-dimethylaminoethyl) ether is preferred because it offers superior effects for the invention.

[0062] Examples of salts of the compound represented by formula (2) include salts of the compound represented by formula (2) with an inorganic acid, and salts of the compound represented by formula (1) with an organic acid. Examples of salts of inorganic acids with compounds represented by formula (2) include salts of inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, hydroiodic acid, and perchloric acid with compounds represented by formula (1). Examples of salts of organic acids with compounds represented by formula (2) include salts of organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, oxalic acid, maleic acid, citric acid, fumaric acid, lactic acid, malic acid, succinic acid, tartaric acid, gluconic acid, ascorbic acid, and methanesulfonic acid with compounds represented by formula (2). The salt of the compound represented by formula (2) may be separated into cations and anions in the composition.

[0063] The molecular weight of the compound represented by formula (2) is preferably 90 to 1000, more preferably 90 to 500, and even more preferably 90 to 300.

[0064] The mass ratio of the nitrogen-containing compound to the specific quaternary ammonium salt is 0.00001 to 0.10, and is preferably 0.0001 to 0.10, and more preferably 0.001 to 0.10, in that the effects of the present invention are more superior.

[0065] The nitrogen-containing compound content is not particularly limited, but in terms of achieving superior effects of the present invention, it is preferably 0.00001 to 2.00% by mass, more preferably 0.0001 to 1.00% by mass, and even more preferably 0.01 to 0.50% by mass, based on the total mass of the composition.

[0066] (water) The composition includes water. The water used is preferably distilled water, ion-exchanged water, or water that has undergone purification treatment such as ultrapure water, with ultrapure water used in semiconductor manufacturing being more preferable. The water contained in the composition may contain unavoidable trace amounts of mixed components. The water content is not particularly limited, but in terms of achieving superior effects of the present invention, it is preferably 4 to 85% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 50% by mass, based on the total mass of the composition.

[0067] (optional ingredient) The composition may contain any components other than those listed above. Optional components include, for example, metal components, basic compounds, acidic compounds, surfactants, and corrosion inhibitors. The following details the optional components that the composition may contain.

[0068] <Metal components> The composition may contain a metallic component (hereinafter also simply referred to as "specific metallic component") which includes at least one metallic element selected from the group consisting of Cr, Fe, and Cu. The specific metal component is selected from the group consisting of metal particles and metal ions. The metal particles may be in their elemental form or as an alloy.

[0069] The specific metal component may be any of the following: a metal component that is inevitably present in each component (raw material) contained in the composition; a metal component that is inevitably present in one or more processes selected from the group consisting of the manufacturing, storage, and transport of the composition; or a metal component that is intentionally added.

[0070] Examples of metal elements included in specific metal components include metal elements selected from the group consisting of Cr, Fe, and Cu.

[0071] While there are no particular limitations on the content of metal elements in the specific metal component, it is preferable that the content be 1 ppt to 1 ppm by mass relative to the total mass of the composition, as this provides superior effects for the present invention.

[0072] The ratio of the content of the metal element contained in the specific metal component to the content of the nitrogen-containing compound is not particularly limited, but in terms of superior effects of the present invention, 1 × 10 -7 ~1 is preferable.

[0073] <Basic compounds> The composition may contain basic compounds. Basic compounds are compounds that exhibit alkalinity (pH greater than 7.0) in aqueous solutions. Examples of basic compounds include organic bases, inorganic bases, and their salts. However, basic compounds do not include the specified quaternary ammonium salts and the nitrogen-containing compounds mentioned above.

[0074] Examples of organic bases include quaternary ammonium salts, alkylamine compounds or their salts, amine oxide compounds, nitro compounds, nitroso compounds, oxime compounds, ketoxime compounds, aldoxime compounds, lactam compounds, and isocyanide compounds. However, the quaternary ammonium salt as an optional component is a different compound from the specified quaternary ammonium salt mentioned above. Furthermore, the alkylamine compound as an optional component is a different compound from the nitrogen-containing compound mentioned above.

[0075] Examples of inorganic bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, and ammonia or its salts.

[0076] The content of the basic compound is not particularly limited, but it is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, relative to the total mass of the composition. There is no particular upper limit, but it is preferably 20.0% by mass or less, relative to the total mass of the composition. It is also preferable to adjust the basic compound within the preferred range described above so that it falls within the preferred pH range of the composition described later.

[0077] <Acidic compounds> The composition may contain acidic compounds. Acidic compounds are compounds that exhibit acidity (pH less than 7.0) in aqueous solutions. Examples of acidic compounds include inorganic acids, organic acids, and their salts.

[0078] Examples of inorganic acids include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, hydrofluoric acid, perchloric acid, hypochlorous acid, and their salts.

[0079] Examples of organic acids include carboxylic acids, sulfonic acids, and their salts. Examples of carboxylic acids include lower (1-4 carbon atoms) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid, as well as their salts. Examples of sulfonic acids include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (tosylic acid), and their salts.

[0080] The content of the acidic compound is not particularly limited, but it is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, relative to the total mass of the composition. There is no particular upper limit, but it is preferably 20.0% by mass or less, relative to the total mass of the composition. It is also preferable to adjust the acidic compound to a pH range suitable for the composition described later, within the preferred range described above.

[0081] <Surfactants> The composition may contain a surfactant. The surfactant is not particularly limited as long as it is a compound having both a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule. Examples include anionic surfactants, cationic surfactants, and nonionic surfactants.

[0082] Examples of hydrophobic groups found in surfactants include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. When the hydrophobic group includes an aromatic hydrocarbon group, the number of carbon atoms in the hydrophobic group is preferably 6 or more, and more preferably 10 or more. When the hydrophobic group does not contain an aromatic hydrocarbon group and consists only of aliphatic hydrocarbon groups, the number of carbon atoms in the hydrophobic group is preferably 8 or more, and more preferably 10 or more. There is no particular upper limit to the number of carbon atoms in the hydrophobic group, but it is preferably 24 or less, and more preferably 20 or less.

[0083] As a surfactant, nonionic surfactants with an HLB (Hydrophilic-Lipophilic Balance) value of 12.0 to 15.0, as described in paragraph

[0029] and subsequent paragraphs of Japanese Patent Application Publication No. 2021-009885, are also preferred. In that case, an HLB value of 12.5 to 14.0 is preferred, and 12.5 to 13.5 is more preferred. The HLB value is a value that represents the degree of affinity of a surfactant for water and water-insoluble organic compounds. Typically, it is defined by the following formula (G). Formula G: HLB value = 20 × formula weight of hydrophilic portion of surfactant / molecular weight of surfactant

[0084] Examples of the surfactants mentioned above include polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, and oleic acid triethanolamine.

[0085] The surfactant content is not particularly limited, but is preferably 10 ppm by mass or more, and more preferably 30 ppm by mass or more, relative to the total mass of the composition. There is no particular upper limit, but in order to suppress foaming of the composition, it is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the composition.

[0086] <Corrosion inhibitor> The composition may contain a corrosion inhibitor. Corrosion inhibitors are added to the composition to prevent etching of other materials present on the workpiece. The type of corrosion inhibitor is selected appropriately depending on the material properties of other materials present in the object being treated. Examples of corrosion inhibitors include amine compounds, imine compounds, thiol compounds, and thioether compounds. Among these, imine compounds are preferred, and unsaturated heterocyclic compounds containing nitrogen are more preferred. Examples of nitrogen-containing unsaturated heterocyclic compounds include pyridine, triazine, imidazole, benzimidazole, purine, and xanthine, as well as their derivatives.

[0087] The content of the corrosion inhibitor is not particularly limited, but it is preferably 0.1% by mass or more, and more preferably 1% by mass or more, relative to the total mass of the composition. There is no particular upper limit, but it is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the composition.

[0088] [Properties of the composition] The following describes the chemical and physical properties of the composition.

[0089] (pH) The pH of the composition is not particularly limited, but is preferably 11 or higher. The preferred pH range for the composition is preferably 11.0 to 15.0, more preferably 12.0 to 15.0, and even more preferably 13.0 to 14.5, in terms of achieving superior effects of the present invention. In this specification, the pH of the composition is obtained by measuring it at 25°C using a pH meter (F-51 (product name) manufactured by Horiba, Ltd.).

[0090] (Coarse particles) The composition preferably contains substantially no coarse particles. "Coarse particles" refers to particles with a diameter of 0.2 μm or larger, assuming the particle shape is spherical. "Substantially free of coarse particles" means that, when the composition is measured using a commercially available measuring device in a light scattering liquid particle measurement method, there are 10 or fewer particles of 0.2 μm or larger per 1 mL of the composition. The lower limit is preferably 0 or more. Coarse particles contained in the composition include particles such as dust, dirt, organic solids, and inorganic solids that are present as impurities in the raw materials, as well as particles such as dust, dirt, organic solids, and inorganic solids that are introduced as contaminants during the preparation of the composition, and which ultimately remain as particles in the composition without dissolving. One method for measuring the content of coarse particles is to use a commercially available measuring device that employs a light scattering type liquid particle measurement method with a laser as the light source, and measure the particle content in the liquid phase. One method for removing coarse particles is filtering.

[0091] [Method for producing the composition] As a method for producing the composition, for example, a known production method can be used. The method for producing the composition may include one or more steps selected from the group of steps consisting of a composition preparation step, a filtration step, and an electrostatic discharge step. The following details the processes that may be included in the manufacturing process of the composition. The containers used to house the composition are also described in detail.

[0092] It is preferable that each step in the method for producing the composition be carried out in a cleanroom. The cleanroom preferably meets the 14644-1 cleanroom standard. It is also preferable that it meets one of the ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, and ISO Class 4 standards, more preferably ISO Class 1 or ISO Class 2, and even more preferably ISO Class 1.

[0093] (Composition preparation process) For example, a composition preparation step involves preparing a specific quaternary ammonium salt, a polar organic solvent, a nitrogen-containing compound, water, and an optional component, and then mixing the components to prepare the composition. The order in which the components are mixed in the composition preparation step is not particularly limited.

[0094] Alternatively, a concentrate may be prepared with a lower content of one or more solvents selected from the group consisting of polar organic solvents and water, etc., than the concentration used at the time of use, and the composition may be prepared by diluting it with a diluent (polar organic solvent, water, or both) at the time of use to adjust the content of each component to a predetermined level. Alternatively, the composition may be prepared by diluting the concentrate with a diluent and then adjusting the pH to a set level using a basic compound or an acidic compound. When diluting the concentrate, a predetermined amount of the diluent may be added to the concentrate, or a predetermined amount of the concentrate may be added to the diluent.

[0095] (Filtration process) The method for producing the composition may include a filtration step to filter the composition in order to remove foreign matter, coarse particles, etc. from the composition. Examples of filtration methods include known filtration methods, and filtering using a filter is preferred.

[0096] Examples of filters used in filtering include filters used in publicly known filtering methods. Examples of materials that make up the filter include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight resins), with polyamide resins, PTFE, or polypropylene (including high-density polypropylene) being preferred. By using a filter made of the above materials, highly polar foreign substances that are prone to causing defects can be more effectively removed from the composition.

[0097] The critical surface tension of the filter is preferably 70 mN / m or higher. The upper limit is preferably 95 mN / m or lower. Of these, 75 to 85 mN / m is more preferable. The critical surface tension value is the manufacturer's nominal value. By using a filter with a critical surface tension within the above range, highly polar foreign substances that are prone to causing defects can be more effectively removed from the composition.

[0098] The pore size of the filter is preferably 0.001 to 1.0 μm, more preferably 0.02 to 0.5 μm, and even more preferably 0.01 to 0.1 μm. When the pore size of the filter is within the above range, fine foreign matter can be removed from the composition while suppressing clogging during filtration.

[0099] Filters may be a combination of two or more types. Filtering using the first filter may be performed once or more times. When filtering is performed two or more times using a first filter and a second filter different from the first filter, each filter may be the same or different, but it is preferable that they be different. It is preferable that the first filter and the second filter differ in at least one of their pore size and constituent material. It is preferable that the pore size of the second and subsequent filters is the same as or smaller than the pore size of the first filter. Alternatively, a combination of first filters with different pore sizes may be used within the range of the above-mentioned filter pore sizes. The pore size can be determined by referring to the nominal value provided by the filter manufacturer. Examples of filters include those manufactured by Nippon Pall Corporation, Advantech Toyo Corporation, Nippon Integris Corporation, and Kitz Microfilter Corporation. Specifically, these include polyamide P-nylon filters (pore size 0.02 μm, critical surface tension 77 mN / m, manufactured by Nippon Pall Co., Ltd.), high-density polyethylene PE-clean filters (pore size 0.02 μm, manufactured by Nippon Pall Co., Ltd.), and high-density polyethylene PE-clean filters (pore size 0.01 μm, manufactured by Nippon Pall Co., Ltd.).

[0100] A second filter could be, for example, a filter made of the same material as the first filter. The pore size of the second filter may be the same as that of the first filter. When the pore size of the second filter is smaller than that of the first filter, the ratio of the pore size of the second filter to that of the first filter (pore size of the second filter / pore size of the first filter) is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and even more preferably 0.3 to 0.9. When the pore size of the second filter is within the above range, fine foreign matter mixed in the composition can be removed more effectively.

[0101] Filtering using the first filter may be performed, for example, with a mixture containing some of the components of the composition, and after the remaining components are mixed in to prepare the composition, filtering may be performed using the second filter.

[0102] It is preferable to wash the filter used before filtering the composition. The cleaning process is preferably a cleaning process using a liquid, and more preferably a cleaning process using a liquid containing the composition and components contained in the composition.

[0103] The temperature of the composition during filtering is preferably room temperature (25°C) or lower, more preferably 23°C or lower, and even more preferably 20°C or lower. The lower limit is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher. At the above temperature, the amount of particulate matter and impurities in the composition is reduced, allowing for more efficient filtering.

[0104] (static elimination process) The method for producing the composition may further include a static elimination step for removing static electricity from the composition.

[0105] (container) For example, a known container can be used as the container for housing the composition. The container should preferably be one that is clean inside and has low impurity leaching, suitable for semiconductor applications. Examples of suitable containers include the "Clean Bottle" series (manufactured by Aicello Chemical Co., Ltd.) and the "Pure Bottle" (manufactured by Kodama Resin Industry Co., Ltd.). Furthermore, in terms of preventing contamination of raw materials and compositions, it is also preferable to use a multilayer container with a six-layer structure made of six types of resins for the inner wall, or a multilayer container with a seven-layer structure made of seven types of resins. Examples of multilayer containers include those described in Japanese Patent Publication No. 2015-123351, the contents of which are incorporated herein by reference. Examples of materials for the inner wall of the container include, for example, at least one first resin selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, a second resin different from the first resin, and metals such as stainless steel, Hastelloy, Inconel, and Monel. Furthermore, it is preferable that the inner wall of the container be formed or coated using the above materials.

[0106] As the second resin, fluororesin (perfluororesin) is preferred. When using fluororesin, the elution of ethylene or propylene oligomers can be suppressed. Examples of the above-mentioned containers include the FluoroPurePFA composite drum (manufactured by Entegris), the containers described on page 4 of Japanese Patent Publication No. 3-502677, page 3 of International Publication No. 2004 / 016526, and pages 9 and 16 of International Publication No. 99 / 046309.

[0107] In addition to fluororesin, other materials such as quartz and electropolished metal materials (electropolished metal materials) are also preferred for the inner wall of the container. The metal material used for electropolished metal materials preferably contains at least one selected from the group consisting of chromium (Cr) and nickel (Ni), and the total content of Cr and Ni is more than 25% by mass of the total mass of the metal material. Examples include stainless steel and Ni-Cr alloys. The total content of Cr and Ni in the metallic material is preferably 25% by mass or more, and more preferably 30% by mass or more, relative to the total mass of the metallic material. The upper limit is preferably 90% by mass or less, relative to the total mass of the metallic material.

[0108] Examples of stainless steel include well-known stainless steels. Among these, stainless steel containing 8% by mass or more of Ni is preferred, and austenitic stainless steel containing 8% by mass or more of Ni is more preferred. Examples of austenitic stainless steels include SUS (Steel Use Stainless) 304 (Ni content: 8 mass%, Cr content: 18 mass%), SUS304L (Ni content: 9 mass%, Cr content: 18 mass%), SUS316 (Ni content: 10 mass%, Cr content: 16 mass%), and SUS316L (Ni content: 12 mass%, Cr content: 16 mass%).

[0109] Examples of Ni-Cr alloys include well-known Ni-Cr alloys. Among these, Ni-Cr alloys having a Ni content of 40-75% by mass and a Cr content of 1-30% by mass are preferred. Examples of Ni-Cr alloys include Hastelloy, Monel, and Inconel. Specifically, these include Hastelloy C-276 (Ni content: 63% by mass, Cr content: 16% by mass), Hastelloy-C (Ni content: 60% by mass, Cr content: 17% by mass), and Hastelloy C-22 (Ni content: 61% by mass, Cr content: 22% by mass). The Ni-Cr alloy may, if necessary, also contain boron, silicon, tungsten, molybdenum, copper, or cobalt in addition to the alloys mentioned above.

[0110] Examples of methods for electropolishing metal materials include known methods. Specifically, examples include the methods described in paragraphs

[0011] to

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

[0036] to

[0042] of Japanese Patent Publication No. 2008-264929, the contents of which are incorporated herein by reference.

[0111] It is preferable that the metal material be buffed. Examples of buff polishing methods include well-known methods. For the finishing of buff polishing, the size of the abrasive grains used is preferably #400 or smaller, as this makes it easier to reduce the surface irregularities of the metal material. Buff polishing is preferably performed before electrolytic polishing. The metal material may be treated by combining one or more of the following processes: buffing in multiple stages with varying grit sizes of abrasive particles, acid cleaning, and magnetic fluid polishing.

[0112] It is preferable to clean the inside of the container before filling it with the composition. The liquid used for cleaning can be appropriately selected depending on the application, and a liquid containing at least one of the composition or components added to the composition is preferred.

[0113] To prevent changes in the components of the composition during storage, the container may be purged with an inert gas (e.g., nitrogen and argon) with a purity of 99.99995% by volume or higher. Gases with a particularly low water content are preferred. Furthermore, during the transport and storage of the container containing the composition, either room temperature or temperature control may be used. Among these, temperature control within the range of -20 to 20°C is preferred in order to prevent deterioration.

[0114] {Use} The composition is used in semiconductor processing. More specifically, it is preferred for use in semiconductor devices. "For semiconductor devices" means that it is used in the manufacturing of semiconductor devices. The composition can also be used in processes for manufacturing semiconductor devices, for example, for processing silicon-based materials, insulating films, resist films, anti-reflective films, etching residues, and ashing residues (hereinafter also simply referred to as "residues") present on a substrate. The composition may also be used for processing substrates after chemical mechanical polishing. In particular, the composition is preferably used for processing workpieces containing Si and SiGe (hereinafter also simply referred to as "workpieces").

[0115] {object to be processed} The material to be treated contains Si and SiGe. The material to be processed is not particularly limited as long as it contains Si and SiGe, but typically Si and SiGe are arranged on a substrate. Here, "on the substrate" includes the front and back surfaces, sides, and inside the grooves of the substrate. Furthermore, "Si and SiGe are arranged on the substrate" includes cases where Si and SiGe are directly on the surface of the substrate, as well as cases where Si and SiGe are on the substrate via other layers. Furthermore, "Si and SiGe are arranged on the substrate" means that as long as Si and SiGe are present on the substrate at the same time, the form of their existence is irrelevant. For example, Si and SiGe may be in contact with each other, or they may be in contact with each other through other layers or materials. Alternatively, they may be present on the same substrate but not in contact with each other.

[0116] The substrate is not particularly limited, but examples include metal substrates, semiconductor substrates, non-metallic conductive substrates, metal oxide substrates, glass substrates, and resin substrates. Among these, semiconductor substrates are preferred. Examples of semiconductor substrates include semiconductor wafers, photomask glass substrates, liquid crystal display glass substrates, plasma display glass substrates, FED (Field Emission Display) substrates, optical disk substrates, magnetic disk substrates, and magneto-optical disk substrates. Examples of materials that make up a semiconductor substrate include silicon, group III-V compounds such as GaAs, and combinations thereof.

[0117] Examples of applications for the processed materials include DRAM (Dynamic Random Access Memory), FRAM (Registered Trademark) (Ferroelectric Random Access Memory), MRAM (Magnetoresistive Random Access Memory), PRAM (Phase Change Random Access Memory), logic circuits, and processors.

[0118] The form of Si or SiGe on the substrate may be in the form of a film, wiring, plate, columnar, or particulate arrangement.

[0119] The material to be treated may contain, in addition to Si and SiGe, a desired layer or structure, or both. For example, one or more components selected from the group consisting of metal wiring, gate electrodes, source electrodes, drain electrodes, insulating layers, ferromagnetic layers, and non-magnetic layers may be arranged on the substrate. The substrate may contain exposed integrated circuit structures. Examples of integrated circuit structures include interconnection mechanisms such as metal wiring and dielectric materials. Examples of metals and alloys used in the interconnection mechanisms include aluminum, copper-aluminum alloy, copper, nickel, nickel silicide, cobalt, cobalt silicide, ruthenium, platinum, gold, titanium, tantalum, tungsten, silicon, titanium nitride, and tantalum nitride. The substrate may contain one or more layers of material selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide.

[0120] {Processing method for the object to be processed} The present invention relates to a method for treating a workpiece (hereinafter also referred to as "this treatment method"), which comprises step A of contacting a workpiece containing Si and SiGe with the composition described above. By carrying out this treatment method, Si in the workpiece is selectively etched. The materials to be processed using this processing method are as described above.

[0121] Methods of contact include, for example, immersing the object to be treated in a composition placed in a tank, spraying the composition onto the object to be treated, flowing the composition over the object to be treated, and methods combining these, with the method of immersing the object to be treated in the composition being preferred.

[0122] Furthermore, a mechanical stirring method may be used to further enhance the cleaning ability of the composition. Examples of mechanical stirring methods include circulating the composition over the workpiece, flowing or spraying the composition over the workpiece, and stirring the composition using ultrasound or megasonic waves.

[0123] The processing time for process A can be adjusted as needed. The processing time (contact time between the composition and the object to be processed) is preferably 0.25 to 10 minutes, and more preferably 0.5 to 2 minutes. The temperature of the composition during processing is preferably 20 to 100°C, and more preferably 40 to 80°C.

[0124] <Other processes> This processing method may include other steps besides step A described above. Other processes include, for example, the formation of one or more structures selected from the group consisting of metal wiring, gate structures, source structures, drain structures, insulating layers, ferromagnetic layers, and non-magnetic layers (e.g., layer formation, etching, chemical mechanical polishing, and modification), as well as resist formation, exposure, removal, heat treatment, cleaning, and inspection processes. This processing method may be performed at any stage of the backend process (BEOL), middle process (MOL), or frontend process (FEOL), but it is preferable to perform it in the frontend or middle process. [Examples]

[0125] The present invention will be described in more detail below based on examples. The materials, quantities, proportions, processing details, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted restrictively by the following examples.

[0126] {Preparation of composition} For Example 1, dimethylbis(2-hydroxyethyl)ammonium hydroxide as a specific quaternary ammonium, dimethyl sulfoxide and monoethanolamine as polar organic solvents, and hydrazine as a nitrogen-containing compound were added to ultrapure water in the amounts shown in Table 1 to form a mixture. The mixture was then thoroughly stirred with a stirrer to adjust the pH and obtain the composition of Example 1. The compositions of Examples 2-27 and Comparative Examples 1-4 were prepared using the same procedure as in Example 1, except that the type and amount of each component were changed according to Table 1 or 2. The "-" symbol in the table indicates that the component was not added. Furthermore, if multiple compounds are listed in the same column, it indicates that both compounds were added. In this case, the percentages are listed in order to the right of the column. The content of each component in each composition is as shown in the table. However, the water content is the remainder of each composition. The pH of each composition is also as shown in the table. Furthermore, all of the components listed in the table are classified as semiconductor grade or equivalent high-purity grade. Furthermore, the concentrations of the metal elements Cr, Fe, and Cu in the composition were adjusted as appropriate by adding these components to the composition or by performing a filtration treatment on the composition, so that they matched the values ​​shown in the table.

[0127] [component] The following describes the individual components used in the preparation of each composition.

[0128] (Quaternary ammonium salts containing a hydroxyl group) • Dimethylbis(2-hydroxyethyl)ammonium hydroxide Methyltris(2-hydroxyethyl)ammonium hydroxide · 4-Methyl-4-(2-hydroxyethyl)morpholinium hydroxide • Oxydiethylenebis[dimethyl(2-hydroxyethyl)ammonium hydroxide] • Choline: Trimethyl(2-hydroxyethyl)ammonium hydroxide (Comparative example) TMAH: Tetramethylammonium hydroxide

[0129] (Polar organic solvents) • DMSO: Dimethyl sulfoxide MEA: Monoethanolamine ·Sulfolane

[0130] (nitrogen-containing compounds) • Hydrazine Trimethylamine • N,N-dimethylethanolamine N-methyldiethanolamine • N-methylmorpholine • Bis(2-dimethylaminoethyl) ether

[0131] (water) ·Ultra pure water

[0132] (Additives) • Corrosion inhibitor: xanthine • Surfactant 1: "TDK9" (product name) manufactured by Oriental Union Chemical Co., Ltd., HLB value: 13.3 • Surfactant 2: "TDK12" (product name) manufactured by Oriental Union Chemical Co., Ltd., HLB value: 14.5 • Surfactant 3: Dow Chemical Company's "Triton (trademark) CF10" (product name), HLB value: 12.6 • Surfactant 4: "TDK40" (product name) manufactured by Oriental Union Chemical Co., Ltd., HLB value: 18.0 • Surfactant 5: Dow Chemical Company's "Triton (trademark) CF12" (product name), HLB value: 10.6 • Surfactant 6: Benzylldodecyldimethylammonium chloride • Surfactant 7: "Paionin MA-1600" (product name) manufactured by Takemoto Oil Co., Ltd.

[0133] {evaluation} The various evaluation methods are described in detail below.

[0134] [pH] The pH of the composition was obtained by measuring it at 25°C using a pH meter (Horiba, Ltd., F-51 (product name)).

[0135] [Cr, Fe, and Cu content] The amounts of the metallic elements Cr, Fe, and Cu contained in the composition were measured under the following measurement conditions. The compositions of each example and comparative example were measured using an Agilent 8800 triple quadrupole ICP-MS (for semiconductor analysis, option #200).

[0136] (Measurement conditions) The sample introduction system used a quartz torch, a coaxial PFA (perfluoroalkoxyalkane) nebulizer (for self-priming), and a platinum interface cone. The measurement parameters for the cool plasma conditions are as follows: • RF (Radio Frequency) output (W): 600 Carrier gas flow rate (L / min): 0.7 Makeup gas flow rate (L / min): 1 • Sampling depth (mm): 18

[0137] [Etching rate] The etching rate of SiGe (ER(SiGe)) and the ratio of the etching rate of Si to SiGe (ERR(Si / SiGe)) were evaluated using the following procedure. A SiGe layer (mass ratio: Si / Ge=4 / 1) was formed on a commercially available 12-inch silicon wafer by heteroepitaxy, and a 2cm square chip was cut from the wafer to obtain a test specimen. The thickness of the SiGe layer on the obtained specimens was measured using a spectroscopic ellipsometer (Vace, manufactured by J.A. Woolam Japan). Test specimens were placed in containers filled with the composition of each example or comparative example, and the compositions were stirred and etched for 20 minutes. The temperature of the compositions was 40°C. After etching, the specimens were dried by nitrogen blowing, and the thickness of the SiGe layer was measured using a spectroscopic ellipsometer. The ER(SiGe) (Å / min) was calculated from the change in SiGe layer thickness before and after etching. The same tests were conducted using a Si layer instead of a SiGe layer and a silicon germanium wafer instead of a silicon wafer, and ER(Si)(Å / min) and ERR(Si / SiGe) were calculated. Furthermore, ER(SiGe) and ERR(Si / SiGe) were evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1 or 2. Furthermore, it is preferable that ER(SiGe) has a small value, and that ERR(Si / SiGe) has a large value. (ER(SiGe) evaluation criteria) A: Less than 10 Å / min B: 10 Å / min or more, less than 20 Å / min C: 20 Å / min or more, less than 30 Å / min D: 30Å / min or more (ERR (Si / SiGe) evaluation criteria) A: 30 or more B: 20 ​​or more, less than 30 C: 10 or more, less than 20 D: Less than 10

[0138] [Defect prevention] The defect suppression performance when the composition was used for treatment was evaluated by the following method. While rotating the silicon wafer, 0.5 mL of each composition was spin-dispensed onto the surface of the silicon wafer. After spin-drying the silicon wafers, the number of defects present on the silicon wafers was measured using a surface inspection device (SP-5, manufactured by KLA-Tencor). Furthermore, defect suppression performance was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1 or 2. (Evaluation criteria for defect prevention) A: The number of defects on the silicon wafer is less than 1000. B: More than 1000 defects on the silicon wafer In addition, although some of the examples described later had more than 1000 defects on the wafer, the defect suppression performance of the composition was at a practically acceptable level.

[0139] In the table, each entry represents the following: The "content" of each component represents the percentage (mass) of each component relative to the total mass of the composition. "B / A" in the nitrogen-containing compound column represents the ratio of the mass of the nitrogen-containing compound to the mass of the specific quaternary ammonium salt. "C / B" in the metal component column indicates the ratio of the mass of the metal component to the mass of the nitrogen-containing compound. In the numerical values in the "B / A" and "C / B" columns, the notation "E-n" means "×10 -n ", and the notation "E+n" means "×10 n ". n represents an integer. For the additive column, the notation "Surfactant 1 (13.3)" in Table 2, for example, indicates that Surfactant 1 is added and the HLB value of the surfactant is 13.3. "<0.001" means less than 0.001. In the columns where numerical values are described, the "-" notation indicates that the compound, etc. is not added or the value cannot be calculated. ER(SiGe), ERR(Si / SiGe), and A to D, or A or B described in the defect suppression column represent those evaluated according to the above criteria.

[0140]

Table 1

[0141]

Table 2

[0142] [[ID=3�]]From the results of Tables 1 and 2, it was confirmed that from the examples and comparative examples, the etching of SiGe was suppressed and the ratio of the etching rate of Si to the etching rate of SiGe was large for the composition. From the comparison between Example 17 and Example 18, it was confirmed that when the content of the nitrogen-containing compound was 0.0001 to 1.00% by mass based on the total mass of the composition, the effects of the present invention were more excellent. From the comparison between Examples 4 and 6 and Examples 3 and 5, it was confirmed that when the content of the polar organic solvent was 15 to 85% by mass based on the total mass of the composition, the effects of the present invention were more excellent. A comparison of Examples 2, 3, and 7 confirmed that the effects of the present invention are superior when the composition contains two or more polar organic solvents. A comparison of Examples 1 and 2 confirmed that the effects of the present invention are superior when the polar organic solvent has a hydroxyl group. From a comparison of Examples 1 and 14, R in formula (3) 1 , R 3 , and, R 4 is a methyl group, R 2 It was confirmed that the etching of SiGe is further suppressed when the ammonium cation, which is an ethylene group, is not included. From a comparison of Examples 16 and 19 with other examples, the ratio of the content of metal components to the content of nitrogen-containing compounds was 1 × 10⁻⁶. -7 It was confirmed that the effects of the present invention are superior when the ratio is ~1. Specifically, in Example 19, the ERR (Si / SiGe) evaluation is "B" because it is below the lower limit of the above ratio, and in Example 16, the defect suppression performance is "B" because it is above the upper limit of the above ratio. Note that the ER (SiGe) evaluation in Example 16 is "B" because it is mainly due to the use of choline. A comparison of Examples 21-23 and 24-27 confirmed that when a surfactant is included as an additive in the composition, the effects of the present invention are superior when the surfactant is a nonionic surfactant with an HLB value of 12.0-15.0.

Claims

1. A semiconductor processing composition, Quaternary ammonium salts having a hydroxyl group, Polar organic solvents and A nitrogen-containing compound selected from the group consisting of the compound represented by formula (1), the compound represented by formula (2), and salts thereof, Water and, A semiconductor processing composition wherein the mass ratio of the nitrogen-containing compound to the quaternary ammonium salt is 0.00001 to 0.

10. 【Chemistry 1】 In formula (1), R １２ represents an amino group or an alkyl group having 1 to 16 carbon atoms. R １３ , and R １４ each independently represent a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and a -O- group. R １２ and R １３ , R １３ and R １４ , and R １２ and R １４ each independently may be bonded to each other to form a ring structure. 【Chemistry 2】 In formula (2), R １５ R represents an alkylene group having 1 to 16 carbon atoms, which may have an -O- group. １６ , R １７ , R １８ , and, R １９ Each of these independently represents an alkyl group having 1 to 16 carbon atoms, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and an -O- group.

2. A semiconductor processing composition, Quaternary ammonium salts having a hydroxyl group, Polar organic solvents and A nitrogen-containing compound selected from the group consisting of the compound represented by formula (1), the compound represented by formula (2), and salts thereof, Water and, A semiconductor processing composition wherein the mass ratio of the nitrogen-containing compound to the quaternary ammonium salt is 0.00001 to 0.

10. 【Transformation 3】 In formula (1), R １２ R represents an amino group or an alkyl group having 1 to 16 carbon atoms. １３ , and, R １４ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms. １２ and R １３ , R １３ and R １４ , and, R １２ and R １４ These elements may be independent of each other, or they may be bonded together to form a ring structure. 【Chemistry 4】 In formula (2), R １５ R represents an alkylene group having 1 to 16 carbon atoms, which may have an -O- group. １６ , R １７ , R １８ , and, R １９ Each of these independently represents an alkyl group having 1 to 16 carbon atoms, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and an -O- group.

3. It further comprises a metallic component containing at least one metallic element selected from the group consisting of Cr, Fe, and Cu, The semiconductor processing composition according to claim 1 or 2, wherein the content of the metal element is 1 ppt to 1 ppm by mass with respect to the total mass of the semiconductor processing composition.

4. The ratio of the content of the metal element to the content of the nitrogen-containing compound is 1 × 10 －７ The semiconductor processing composition according to claim 3, wherein the value is 1.

5. A semiconductor processing composition, Quaternary ammonium salts having a hydroxyl group, Polar organic solvents and A nitrogen-containing compound selected from the group consisting of the compound represented by formula (1), the compound represented by formula (2), and salts thereof, Water and, It includes a metallic component containing at least one metallic element selected from the group consisting of Cr, Fe, and Cu, The ratio of the content of the metal element to the content of the nitrogen-containing compound is 1 × 10 －７ It is 1, A semiconductor processing composition wherein the mass ratio of the nitrogen-containing compound to the quaternary ammonium salt is 0.00001 to 0.

10. 【Transformation 5】 In formula (1), R １２ R represents an amino group or an alkyl group having 1 to 16 carbon atoms. １３ , and, R １４ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and an -O- group. １２ and R １３ , R １３ and R １４ , and, R １２ and R １４ These elements may be independent of each other, or they may be bonded together to form a ring structure. 【Transformation 6】 In formula (2), R １５ R represents an alkylene group having 1 to 16 carbon atoms, which may have an -O- group. １６ , R １７ , R １８ , and, R １９ Each of these independently represents an alkyl group having 1 to 16 carbon atoms, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and an -O- group.

6. The semiconductor processing composition according to any one of claims 1 to 5, wherein the quaternary ammonium salt comprises an ammonium cation represented by formula (3) or an ammonium cation represented by formula (4). 【Transformation 7】 In formula (3), R １ , R ３ , and, R ４ Each of these independently represents an alkyl group having 1 to 16 carbon atoms, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and an -O- group. ２ R represents an alkylene group having 1 to 16 carbon atoms, which may have an -O- group. １ and R ３ , R ３ and R ４ , and, R １ and R ４ These elements may be independent of each other, or they may be bonded together to form a ring structure. 【Transformation 8】 In formula (4), R ５ , R ６ , and, R ７ Each of these independently represents an alkylene group having 1 to 16 carbon atoms, which may have an -O- group. ８ , R ９ , R １０ , and, R １１ Each of these independently represents an alkyl group having 1 to 16 carbon atoms, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and an -O- group.

7. The quaternary ammonium salt is R in formula (3). １ , R ３ , and, R ４ is a methyl group, and R ２ The semiconductor processing composition according to claim 6, wherein the ammonium cation is an ethylene group.

8. The semiconductor processing composition according to any one of claims 1 to 7, wherein the quaternary ammonium salt comprises at least one selected from the group consisting of dimethylbis(2-hydroxyethyl)ammonium hydroxide, methyltris(2-hydroxyethyl)ammonium hydroxide, 4-methyl-4-(2-hydroxyethyl)morpholinium hydroxide, and oxydiethylenebis[dimethyl(2-hydroxyethyl)ammonium hydroxide].

9. A semiconductor processing composition, Quaternary ammonium salts having a hydroxyl group, Polar organic solvents and A nitrogen-containing compound selected from the group consisting of the compound represented by formula (1), the compound represented by formula (2), and salts thereof, Water and, The mass ratio of the nitrogen-containing compound to the quaternary ammonium salt is 0.00001 to 0.

10. A semiconductor processing composition wherein the quaternary ammonium salt comprises an ammonium cation represented by formula (3) or an ammonium cation represented by formula (4). 【Chemistry 9】 In formula (1), R １２ R represents an amino group or an alkyl group having 1 to 16 carbon atoms. １３ , and, R １４ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and an -O- group. １２ and R １３ , R １３ and R １４ , and, R １２ and R １４ These elements may be independent of each other, or they may be bonded together to form a ring structure. 【Chemistry 10】 In formula (2), R １５ R represents an alkylene group having 1 to 16 carbon atoms, which may have an -O- group. １６ , R １７ , R １８ , and, R １９ Each of these independently represents an alkyl group having 1 to 16 carbon atoms, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and an -O- group. 【Chemistry 11】 In formula (3), R １ , R ３ , and, R ４ Each of these independently represents an alkyl group having 1 to 16 carbon atoms, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and an -O- group. ２ R represents an alkylene group having 1 to 16 carbon atoms, which may have an -O- group. １ and R ３ , R ３ and R ４ , and, R １ and R ４ One of them combines with another to form a ring structure. 【Chemistry 12】 In formula (4), R ５ , R ６ , and R ７ each independently represents an alkylene group having 1 to 16 carbon atoms which may have an -O- group. R ８ , R ９ , R １０ , and R １１ each independently represents an alkyl group having 1 to 16 carbon atoms, and the alkyl group may have one or more groups selected from the group consisting of a hydroxyl group and an -O- group.

10. The semiconductor processing composition according to any one of claims 1 to 9, wherein the content of the nitrogen-containing compound is 0.0001 to 1.00% by mass with respect to the total mass of the semiconductor processing composition.

11. The semiconductor processing composition according to any one of claims 1 to 10, wherein the content of the polar organic solvent is 15 to 85% by mass with respect to the total mass of the semiconductor processing composition.

12. A semiconductor processing composition according to any one of claims 1 to 11, comprising two or more of the aforementioned polar organic solvents.

13. The semiconductor processing composition according to any one of claims 1 to 12, wherein the polar organic solvent has a hydroxyl group.

14. A semiconductor processing composition according to any one of claims 1 to 13, wherein the pH is 11.0 or higher.

15. A semiconductor processing composition according to any one of claims 1 to 14, further comprising a surfactant.

16. The semiconductor processing composition according to claim 15, wherein the surfactant is a nonionic surfactant having an HLB value of 12.0 to 15.

0.

17. A semiconductor processing composition according to any one of claims 1 to 16, used for processing materials containing silicon and silicon germanium.

18. A method for treating an object containing silicon and silicon germanium, comprising contacting the object with a semiconductor processing composition according to any one of claims 1 to 17 to remove the silicon.

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