Composition for semiconductor cleaning and cleaning method

Abstract

To provide a composition for semiconductor cleaning that can reduce damage such as corrosion on a workpiece and efficiently remove contamination from the surface of the workpiece, and a cleaning method using the composition.SOLUTION: A composition for semiconductor cleaning according to the present invention contains a compound (A) having at least one group selected from the group consisting of amino groups and salts thereof, at least one group selected from the group consisting of sulfo groups and salts thereof, and a group having a ring structure with 4 to 12 carbon atoms, an alkanolamine (B), and a fluid medium, and the pH is equal or more than 3.0 and equal or less than 9.0.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a semiconductor cleaning composition and a cleaning method using the same. [Background technology]

[0002] The CMP slurry used in CMP (Chemical Mechanical Polishing) utilized in the manufacture of semiconductor devices contains chemicals such as etching agents and pH adjusters in addition to abrasive grains. Furthermore, polishing debris is generated by CMP, and if the components contained in the CMP slurry or the polishing debris remain on the object to be processed, it may cause fatal device defects. For this reason, a process of cleaning the object to be processed after CMP is essential.

[0003] On the surface of the workpiece after CMP, metal wiring materials such as copper and tungsten, insulating materials such as silicon oxide, barrier metal materials such as tantalum nitride, titanium nitride, silicon nitride, and gate electrode materials such as polysilicon are exposed. When such different materials coexist on the surface of the workpiece, it is necessary to remove only the contaminants from the surface of the workpiece and process it without causing damage such as corrosion. For example, Patent Document 1 and Patent Document 2 disclose a technology for reducing corrosion of the surface of the workpiece on which metal wiring materials and barrier metal materials are exposed, using an acidic semiconductor cleaning composition. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2010-258014 A [Patent Document 2] International Publication No. 2019 / 26478 Summary of the Invention [Problem to be solved by the invention]

[0005] With the recent trend toward finer circuit structures, there is a demand for processing techniques that can further reduce damage to objects to be processed and efficiently remove contamination from the surfaces of the objects to be processed.

[0006] For example, in the CMP of a workpiece provided with a wiring layer including a silicon nitride film or a polysilicon film, the silicon nitride film and the polysilicon film are materials with significantly different physical properties, so the workpiece is susceptible to damage such as corrosion, and contamination is likely to remain on its surface. Therefore, there is a demand for a processing technology that can reduce damage caused by corrosion of the workpiece as much as possible and efficiently remove contamination from the surface of the workpiece.

[0007] Some aspects of the present invention provide a semiconductor cleaning composition that can reduce damage such as corrosion on the surface of a workpiece and efficiently remove contamination from the surface of the workpiece, and a cleaning method using the same. [Means for solving the problem]

[0008] The present invention has been made to solve at least a part of the above-mentioned problems, and can be realized in any of the following aspects.

[0009] One aspect of the semiconductor cleaning composition according to the present invention is A compound (A) having at least one group selected from the group consisting of an amino group and a salt thereof, at least one group selected from the group consisting of a sulfo group and a salt thereof, and a group having a cyclic structure having 4 to 12 carbon atoms; Alkanolamine (B), A liquid medium; Contains The pH is between 3.0 and 9.0.

[0010] In one embodiment of the semiconductor cleaning composition, Furthermore, it may contain a water-soluble polymer (C).

[0011] In one embodiment of the semiconductor cleaning composition, Furthermore, a surfactant (D) may be contained.

[0012] In one embodiment of the semiconductor cleaning composition, The surfactant (D) may be a compound having a functional group represented by the following general formula (1) or (2) and an alkyl group having 8 to 18 carbon atoms. -SO 3 - M + ...(1) -COO - M + ...(2) (In the above formulas (1) and (2), M + represents a monovalent cation.)

[0013] One aspect of the cleaning method according to the present invention is to The method includes a step of treating a wiring layer having a silicon nitride film and a polysilicon film with the semiconductor cleaning composition according to any one of the above aspects. Effect of the Invention

[0014] By using the semiconductor cleaning composition according to the present invention, damage such as corrosion of the object to be treated can be reduced and contamination can be efficiently removed from the surface of the object to be treated. The semiconductor processing composition according to the present invention is particularly effective when processing a wiring layer having a silicon nitride film or a polysilicon film as the object to be treated. [Brief description of the drawings]

[0015] [Figure 1] 1A to 1C are cross-sectional views each showing a schematic process for producing a wiring substrate used in the cleaning method according to the embodiment; [Diagram 2] 1A to 1C are cross-sectional views each showing a schematic process for producing a wiring substrate used in the cleaning method according to the embodiment; [Diagram 3] 1A to 1C are cross-sectional views each showing a schematic process for producing a wiring substrate used in the cleaning method according to the embodiment; DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Preferred embodiments of the present invention will be described in detail below. Note that the present invention is not limited to the following embodiments, and includes various modified examples that are implemented within the scope of the present invention.

[0017] In this specification, a numerical range described using "X to Y" means that the range includes the numerical value X as the lower limit and the numerical value Y as the upper limit.

[0018] 1. Semiconductor cleaning composition A semiconductor cleaning composition according to one embodiment of the present invention contains a compound (A) having at least one group selected from the group consisting of amino groups and salts thereof, at least one group selected from the group consisting of sulfo groups and salts thereof, and a group having a cyclic structure having 4 to 12 carbon atoms, an alkanolamine (B), and a liquid medium, and has a pH of 3.0 or more and 9.0 or less.

[0019] The semiconductor cleaning composition according to this embodiment is used after diluting with a liquid medium such as pure water or an organic solvent. The composition may be of a concentrated type intended to be used without dilution, or of a non-diluted type intended to be used as is. In this specification, unless it is specified whether the composition is of a concentrated type or a non-diluted type, the term "semiconductor cleaning composition" is interpreted as a concept including both the concentrated type and the non-diluted type.

[0020] Such a semiconductor cleaning composition can be used as a cleaning agent for removing contaminants such as particles and organic residues present on the surface of a workpiece provided with a wiring layer having a silicon nitride film or a polysilicon film after CMP. Each component contained in the semiconductor cleaning composition according to this embodiment will be described in detail below.

[0021] 1.1. Compound (A) The semiconductor cleaning composition according to this embodiment contains a compound (A) (also referred to as "compound (A)" in this specification) having at least one group selected from the group consisting of amino groups and salts thereof, at least one group selected from the group consisting of sulfo groups and salts thereof, and a group having a cyclic structure with 4 to 12 carbon atoms.

[0022] In the present invention, the "amino group" is -NR 1 R 2 (However, R 1 , R 2 each independently represents any one selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, and an organic group having 1 to 20 carbon atoms and a heteroatom; R 1 and R 2 When R is a hydrocarbon group, 1 and R 2 may be bonded to form a cyclic structure.

[0023] Examples of the hydrocarbon group having 1 to 18 carbon atoms include saturated aliphatic hydrocarbon groups having 1 to 18 carbon atoms, unsaturated aliphatic hydrocarbon groups having 2 to 18 carbon atoms, hydrocarbon groups having 3 to 18 carbon atoms and having a cyclic saturated hydrocarbon group, and hydrocarbon groups having 6 to 18 carbon atoms and having an unsaturated cyclic hydrocarbon group.

[0024] Examples of the organic group having 1 to 20 carbon atoms and having a heteroatom include a hydrocarbon group having 1 to 20 carbon atoms and having a carboxy group, a hydrocarbon group having 1 to 20 carbon atoms and having a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms and having an amino group, a hydrocarbon group having 1 to 20 carbon atoms and having a sulfo group, and an organic group having 1 to 20 carbon atoms and having a heterocyclic group.

[0025] In the semiconductor cleaning composition according to this embodiment, the amino group of the compound (A) may form a salt represented by the following general formula (1). [ka] (In the above general formula (1), R 1 , R 2and R 3 Each independently represents any one selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, and an organic group having 1 to 20 carbon atoms and a hetero atom. - indicates an anion. 1 ~R 3 cannot be all hydrogen atoms. 1 ~R 3 Two or more of the above may be bonded to form a cyclic structure.)

[0026] In the above general formula (1), R 1 ~R 3 is a hydrocarbon group having 1 to 18 carbon atoms or an organic group having 1 to 20 carbon atoms and a hetero atom, the above-mentioned -NR 1 R 2 R in 1 , R 2 The term "C1-18 hydrocarbon group" and "C1-20 organic group having a hetero atom" are synonymous with each other. In the above general formula (1), M - Examples of anions represented by the formula include anions derived from acidic compounds, hydroxide ions (OH - ) etc.

[0027] The "sulfo group and its salts" of the present invention means -SO 3 - M + (M + represents a monovalent cation.) Here, M + Examples of monovalent cations represented by the formula (I) include, but are not limited to, H + , Li + , Na + , K + , N.H. 4 + Examples include:

[0028] The group having a cyclic structure with 4 to 12 carbon atoms is preferably a group having a steric hindrance, and is preferably, for example, an aromatic structure, a cyclic hydrocarbon structure, or a cyclic structure containing an N atom. Also, it is preferably a group having a 6-membered ring structure, and for example, a cyclohexyl group, a 6-membered ring structure containing two N atoms, a benzene ring structure, an adamantyl structure, or the like can be preferably used.

[0029] The compound (A) is preferably water-soluble. When the compound (A) is water-soluble, the compound (A) can be washed away completely without remaining on the surface by rinsing with ultrapure water or pure water after treating the surface of the object to be treated with the semiconductor cleaning composition according to this embodiment. In the present invention, "water-soluble" means that the mass dissolved in 100 g of neutral water at 20°C is 0.1 g or more.

[0030] Since the compound (A) has an amino group and a sulfo group, it is easily adsorbed to the surface of the object to be treated, and corrosion can be reduced. This can reduce damage caused by corrosion to the wiring layer including the silicon nitride film and the polysilicon film. In addition, since the compound (A) has a bulky structure, it is easy to adhere or adsorb contaminants such as particles and organic residues present on the surface to be treated. Therefore, when the surface of the object to be treated is treated using the semiconductor cleaning composition according to this embodiment and then rinsed with ultrapure water or pure water, the compound (A) that has adhered or adsorbed particles, organic residues, etc. to the surface is washed away without remaining, and a clean object to be treated without contamination can be obtained. Furthermore, the compound (A) functions as a pH adjuster for adjusting the pH of the semiconductor cleaning composition.

[0031] Examples of such compounds (A) include 2-cyclohexylaminoethanesulfonic acid (CHES), 3-cyclohexylaminopropanesulfonic acid (CAPS), 4-(cyclohexylamino)-1-butanesulfonic acid (CABS), 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid (HEPES), 3-anilino-1-propanesulfonic acid (APS), 1,4-piperazinediethanesulfonic acid (PIPES), 3-(1-naphthylamino)-1-propanesulfonic acid (NAPS), etc. These compounds (A) may be used alone or in combination of two or more.

[0032] The content of compound (A) in the semiconductor cleaning composition according to this embodiment can be appropriately changed depending on the materials of the metal wiring material such as tungsten, the insulating material such as silicon oxide or silicon nitride, the gate electrode material such as polysilicon or amorphous silicon, the barrier metal material such as tantalum nitride or titanium nitride, etc., exposed on the surface of the object to be treated after CMP, and the composition of the CMP slurry used.

[0033] Furthermore, the content of compound (A) can be appropriately changed depending on the dilution degree of the concentrated semiconductor cleaning composition according to this embodiment. The content of compound (A) is preferably 0.001 to 5 mass %, more preferably 0.01 to 1 mass %, and particularly preferably 0.02 to 0.1 mass %, based on 100 mass % of the cleaning agent prepared by diluting the concentrated semiconductor cleaning composition or the non-diluted semiconductor cleaning composition. When the content of compound (A) is within the above range, the surface of the wiring layer having a silicon nitride film or a polysilicon film can be easily formed. By adsorbing to the surface and protecting it, it is possible to reduce corrosion and damage to the wiring layer. Furthermore, when the surface is rinsed with ultrapure water or pure water, compound (A) is washed away without remaining, so that a clean, uncontaminated treated object can be obtained.

[0034] 1.2. Alkanolamines (B) The semiconductor cleaning composition according to this embodiment contains an alkanolamine (B). Examples of the alkanolamine (B) include primary alkanolamines, secondary alkanolamines, and tertiary alkanolamines.

[0035] Examples of primary alkanolamines include methanolamine, 2-aminoethanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-2-methyl-1-propanol, 2-(2-aminoethoxy)ethanol, and 4-amino-2-methyl-1-butanol.

[0036] Examples of secondary alkanolamines include N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, diisopropanolamine, 2-[(hydroxymethyl)amino]ethanol, 3-piperidinemethanol, 4-piperidinemethanol, 2-piperidineethanol, and 4-piperidineethanol.

[0037] Examples of tertiary alkanolamines include N,N-dimethylethanolamine, N,N-dimethylpropanolamine, N,N-diethylethanolamine, N-ethyldiethanolamine, N-methyldiethanolamine, triethanolamine, and triisopropanolamine.

[0038] These alkanolamines (B) may be used alone or in combination of two or more.

[0039] The content of alkanolamine (B) in the semiconductor cleaning composition according to this embodiment can be appropriately changed depending on the materials, such as metal wiring material such as tungsten, insulating material such as silicon oxide or silicon nitride, gate electrode material such as polysilicon or amorphous silicon, barrier metal material such as tantalum nitride or titanium nitride, etc., exposed on the surface of the object to be treated after CMP, and the composition of the CMP slurry used.

[0040] Furthermore, the content of alkanolamine (B) can be appropriately changed depending on the dilution degree of the concentrated semiconductor cleaning composition according to this embodiment. The content of alkanolamine (B) is preferably 0.001 to 5 mass%, more preferably 0.01 to 1 mass%, and particularly preferably 0.02 to 0.1 mass% relative to 100 mass% of the cleaning agent prepared by diluting the concentrated semiconductor cleaning composition or the non-diluted semiconductor cleaning composition. When the content of alkanolamine (B) is within the above range, it is possible to reduce corrosion by adsorbing to the surface of the wiring layer having polysilicon and protecting it, and to reduce damage to the wiring layer. In addition, after the treated object is rinsed with ultrapure water or pure water, the alkanolamine (B) is washed away without remaining on the surface of the wiring layer, so that a clean treated object without contamination can be obtained.

[0041] 1.3.Water-soluble polymer (C) The semiconductor cleaning composition according to this embodiment may contain a water-soluble polymer (C). The water-soluble polymer (C) is used for the purpose of acting on the surface of the object to be treated to remove abrasive grain residues and organic residues.

[0042] Examples of the water-soluble polymer (C) include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, polystyrenesulfonic acid, and salts thereof; copolymers of monomers such as styrene, α-methylstyrene, and 4-methylstyrene with acid monomers such as (meth)acrylic acid and maleic acid; polymers having repeating units with aromatic hydrocarbon groups obtained by condensing benzenesulfonic acid, naphthalenesulfonic acid, and the like with formalin, and salts thereof. These water-soluble polymers (C) may be used alone or in combination of two or more.

[0043] The weight average molecular weight (Mw) of the water-soluble polymer (C) is preferably from 1,000 to 1,500,000, more preferably from 3,000 to 100,000. In this specification, the term "weight average molecular weight (Mw)" refers to the weight average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography).

[0044] The viscosity of the semiconductor cleaning composition can be adjusted by containing the water-soluble polymer (C). The viscosity of the semiconductor cleaning composition according to this embodiment at 25°C is preferably less than 5 mPa·s, more preferably 4 mPa·s or less, even more preferably 2 mPa·s or less, even more preferably 1.2 mPa·s or less, and particularly preferably 1 mPa·s or less. When the viscosity of the semiconductor cleaning composition according to this embodiment at 25°C is within the above range, a sufficient filtration speed can be obtained when filtering and purifying the semiconductor cleaning composition, and a sufficient throughput for practical use can be obtained. In addition, when the viscosity of the semiconductor cleaning composition at 25°C is within the above range, even if the surface of the treated object is uneven in the treatment process using the semiconductor cleaning composition, the composition can penetrate the unevenness and come into contact with the uneven surface to treat it, so that the surface of the treated object can be treated more uniformly. When the viscosity of the semiconductor cleaning composition at 25°C exceeds the above range, the viscosity becomes too high, and the semiconductor cleaning composition may not be stably supplied to the treated object. The viscosity of the semiconductor cleaning composition is determined almost entirely by the weight-average molecular weight and content of the water-soluble polymer (C) to be added, and should therefore be adjusted while taking into consideration the balance between these factors.

[0045] In this specification, the "viscosity of the semiconductor cleaning composition" refers to the Ubbelohde viscosity measured in accordance with JIS K2283.

[0046] The content of the water-soluble polymer (C) in the semiconductor cleaning composition according to this embodiment can be appropriately changed depending on the surface condition after CMP of a processing target object provided with a wiring layer having a silicon nitride film or a polysilicon film, and the composition of the CMP slurry used.

[0047] The content of the water-soluble polymer (C) can be appropriately changed depending on the dilution degree of the concentrated semiconductor cleaning composition according to this embodiment. The content of the water-soluble polymer (C) is preferably 0.0001 to 5 mass %, more preferably 0.0005 to 1 mass %, and particularly preferably 0.001 to 0.1 mass %, based on 100 mass % of the cleaning agent prepared by diluting the concentrated semiconductor cleaning composition or the non-diluted semiconductor cleaning composition. When the content of the water-soluble polymer (C) is within the above range, the effect of removing contaminants such as particles and organic residues contained in the CMP slurry from the wiring layer is promoted, so that a cleaner treated surface is easily obtained.

[0048] 1.4. Surfactants (D) The semiconductor cleaning composition according to this embodiment may contain a surfactant (D). The surfactant (D) is used for the purpose of acting on the surface of the object to be treated to more effectively remove abrasive grain residues and organic residues. In the present invention, the surfactant (D) does not include the compound (A).

[0049] The surfactant (D) preferably contains a compound having a functional group represented by the following general formula (2) or (3) and an alkyl group having 8 to 12 carbon atoms. -SO 3 - M + ...(2) -COO - M + ...(3) (In the above formulas (2) and (3), M + represents a monovalent cation.) The surfactant (D) has a function of adsorbing to the surface of the treated object and reducing damage caused by corrosion. Therefore, when the semiconductor cleaning composition according to this embodiment contains the surfactant (D), the damage caused by corrosion on the wiring layer of the treated object may be reduced. In addition, when the treated object is treated with the semiconductor cleaning composition according to this embodiment and then rinsed with ultrapure water or pure water, the surfactant (D) is washed away without remaining on the wiring layer, so that a clean, uncontaminated treated surface may be obtained. Furthermore, the surfactant (D) functions as a pH adjuster for adjusting the pH of the semiconductor cleaning composition.

[0050] In the above general formulas (2) and (3), M + Examples of monovalent cations represented by the formula (I) include, but are not limited to, H + , Li + , Na + , K + Among these, cations represented by the following general formula (4) are preferred. + The monovalent cation represented by the following formula (4) is preferable because it can reduce metal contamination of the object to be treated.

[0051] [ka] (In the above formula (4), R 4 Or R 7 each independently represents a hydrogen atom or an organic group.

[0052] In the above general formula (4), R 4 Or R 7 Examples of the organic group represented by the formula (I) include an alkyl group, a cycloalkyl group, an alkenyl group, a hydroxyalkyl group, an aralkyl group, and an aryl group.

[0053] The alkyl group is preferably a lower alkyl group having 1 to 6 carbon atoms, more preferably a lower alkyl group having 1 to 4 carbon atoms. The alkyl group may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, and the like.

[0054] The cycloalkyl group preferably has a carbon number of 3 to 6. Specific examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

[0055] The alkenyl group preferably has 2 to 6 carbon atoms. The alkenyl group may be linear or branched. Specific examples of the alkenyl group include vinyl, n-propenyl, iso-propenyl, n-butenyl, iso-butenyl, sec-butenyl, and tert-butenyl.

[0056] The hydroxyalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. The hydroxyalkyl group may be linear or branched. The substitution position of the hydroxy group contained in the hydroxyalkyl group is not particularly limited. Specific examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a dihydroxybutyl group, a hydroxypentyl group, a dihydroxypentyl group, a hydroxyhexyl group, and a dihydroxyhexyl group.

[0057] The aralkyl group preferably has a carbon number of 7 to 12. Specific examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylhexyl group, a methylbenzyl group, a methylphenethyl group, and an ethylbenzyl group.

[0058] The aryl group preferably has a carbon number of 6 to 14. Specific examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6-xylyl group, a 3,5-xylyl group, a naphthyl group, and an anthryl group.

[0059] The aromatic ring of the aralkyl group or aryl group may have, as a substituent, for example, a lower alkyl group such as a methyl group or an ethyl group, a halogen atom, a nitro group, an amino group, a hydroxyl group, or the like.

[0060] Specific examples of the surfactant (D) include alkyl (C8-C12) triethanolamine sulfate, alkyl (C8-C12) diethanolamine sulfate, alkyl (C8-C12) monoethanolamine sulfate, alkyl (C8-C12) triethanolamine benzenesulfonate, sodium alkyl (C8-C12) benzenesulfonate, polyoxyethylene alkyl (C8-C12) ether triethanolamine acetate, polyoxyethylene alkyl (C8-C12) ether sodium acetate, polyoxyethylene alkyl (C8-C12) ether triethanolamine sulfate, polyoxyethylene alkyl (C8-C12) ether sodium sulfate, etc. These surfactants (D) may be used alone or in combination of two or more. Here, "alkyl (C8-C12)" refers to a straight or branched alkyl group having 8 to 12 carbon atoms.

[0061] The content of the surfactant (D) in the semiconductor cleaning composition according to this embodiment can be appropriately changed depending on the materials, such as metal wiring materials such as copper and tungsten, insulating materials such as silicon oxide and silicon nitride, and barrier metal materials such as tantalum nitride and titanium nitride, exposed on the surface of the object to be treated after CMP, and the composition of the CMP slurry used.

[0062] Furthermore, the content of the surfactant (D) can be appropriately changed depending on the dilution degree of the concentrated type semiconductor cleaning composition according to this embodiment. The content of the surfactant (D) is preferably 0.0001 to 1 mass%, more preferably 0.001 to 0.1 mass%, and particularly preferably 0.005 to 0.05 mass%, when the total mass of the non-diluted type semiconductor cleaning composition is taken as 100 mass%. When the content of the surfactant (D) is within the above range, the surfactant (D) adsorbs to the wiring layer surface of the treated object to protect it, thereby reducing corrosion and reducing damage to the wiring layer. In addition, after the treated object is rinsed with ultrapure water or pure water, the surfactant (D) is washed away without remaining on the wiring layer surface, so that a cleaner and uncontaminated treated object may be obtained.

[0063] 1.5. Liquid Media The semiconductor cleaning composition according to this embodiment is a liquid containing a liquid medium as a main component. As the liquid medium, an aqueous medium containing water as a main component is preferable. Examples of such an aqueous medium include water, Examples of the medium include a mixed medium of water and an alcohol, a mixed medium containing water and an organic solvent compatible with water, etc. Among these, it is preferable to use water, or a mixed medium of water and an alcohol, and it is more preferable to use water.

[0064] 1.6. Other Additives The semiconductor cleaning composition according to this embodiment may contain an organic acid or an inorganic acid, and a pH adjuster, if necessary.

[0065] <Organic or inorganic acid> Specific examples of organic acids include citric acid, maleic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glycolic acid, ethylenediaminetetraacetic acid, acrylic acid, methacrylic acid, benzoic acid, naphthalenesulfonic acid, and salts thereof. These organic acids may be used alone or in combination of two or more.

[0066] The organic acid may be an amino acid, such as a compound represented by the following general formula (5):

[0067] [ka] (In the above general formula (5), R 8 , R 9 and R 10 each independently represents any one selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an organic group having 1 to 20 carbon atoms and a hetero atom.

[0068] R in the above general formula (5) 8 , R 9 and R 10 Examples of the hydrocarbon group having 1 to 10 carbon atoms include saturated aliphatic hydrocarbon groups having 1 to 10 carbon atoms, cyclic saturated hydrocarbon groups having 1 to 10 carbon atoms, and aromatic hydrocarbon groups having 6 to 10 carbon atoms. Among these, saturated aliphatic hydrocarbon groups having 1 to 10 carbon atoms are preferred.

[0069] R in the above general formula (5) 8 , R 9 and R 10 Examples of the organic group having 1 to 20 carbon atoms and having a hetero atom in the formula (I) include a hydrocarbon group having 1 to 20 carbon atoms and having a carboxy group, a hydrocarbon group having 1 to 20 carbon atoms and having a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms and having an amino group, a hydrocarbon group having 1 to 20 carbon atoms and having a mercapto group, and an organic group having 1 to 20 carbon atoms and having a heterocycle, and these groups may further contain hetero atoms such as oxygen, sulfur, halogen, etc., and a part of them may be substituted with other substituents.

[0070] Examples of the compound represented by the above general formula (5) include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, isoleucine, leucine, lysine, methionine, phenylalanine, serine, threonine, tyrosine, valine, tryptophan, histidine, 2-amino-3-aminopropanoic acid, dodecylaminoethylaminoethylglycine, etc. These amino acids may be used alone or in combination of two or more.

[0071] As the organic acid, it is also preferable to use a compound represented by the following general formula (6).

[0072] [ka] (In the above general formula (6), R 11 represents an organic group having 1 to 20 carbon atoms.

[0073] R in the above general formula (6) 11 In the above, examples of the organic group having 1 to 20 carbon atoms include saturated aliphatic hydrocarbon groups having 6 to 20 carbon atoms, unsaturated aliphatic hydrocarbon groups having 6 to 20 carbon atoms, organic groups having 6 to 20 carbon atoms and containing a cyclic saturated hydrocarbon group, organic groups having 6 to 20 carbon atoms and containing an unsaturated cyclic hydrocarbon group, hydrocarbon groups having 1 to 20 carbon atoms and containing a carboxy group, hydrocarbon groups having 1 to 20 carbon atoms and containing a hydroxy group, hydrocarbon groups having 1 to 20 carbon atoms and containing an amino group, organic groups having 1 to 20 carbon atoms and containing a heterocyclic group, etc. Among these, organic groups having 6 to 20 carbon atoms and containing an unsaturated cyclic hydrocarbon group, and hydrocarbon groups having 1 to 20 carbon atoms and containing a carboxy group are preferred, and organic groups having 6 to 20 carbon atoms and containing an aryl group, and a carboxymethyl group are particularly preferred.

[0074] Specific examples of the compound represented by the above general formula (6) include hydroxyphenyl lactic acid, hydroxymalonic acid, etc., and among these, hydroxyphenyl lactic acid is preferable. The above-exemplified compounds may be used alone or in combination of two or more.

[0075] Examples of the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, and the like.

[0076] The content of the organic acid or inorganic acid can be appropriately changed according to the materials such as metal wiring materials such as copper and tungsten exposed on the surface of the object to be processed after CMP, insulating materials such as silicon oxide and silicon nitride, and barrier metal materials such as tantalum nitride and titanium nitride, and the composition of the CMP slurry used.

[0077] Furthermore, the content of the organic acid or inorganic acid can also be appropriately changed according to the dilution degree of the concentrated type semiconductor cleaning composition according to the present embodiment. When the total mass of the cleaning agent prepared by diluting the concentrated type semiconductor cleaning composition or the non-diluted type semiconductor cleaning composition is 100% by mass, the content of the organic acid or inorganic acid is preferably 0.0001 to 1% by mass, more preferably 0.0005 to 0.5% by mass. When the content of the organic acid or inorganic acid is within the above range, impurities attached to the wiring layer may be effectively removed. In addition, the progress of excessive etching may be more effectively reduced, and a good object to be processed may be obtained.

[0078] <pH adjuster> The lower limit of the pH of the semiconductor cleaning composition according to the present embodiment is 3.0 or more, preferably 3.5 or more, more preferably 4.0 or more. The upper limit of the pH of the semiconductor cleaning composition according to the present embodiment is 9.0 or less, preferably 8.5 or less, more preferably 8.0 or less. When the pH of the semiconductor cleaning composition is less than the lower limit value, contamination tends to remain in the wiring layer including the silicon nitride film, and defects tend to occur. On the other hand, when the pH of the semiconductor cleaning composition exceeds the upper limit value, the object to be processed tends to be easily damaged such as corrosion.

[0079] In the semiconductor cleaning composition according to the present embodiment, if the desired pH cannot be obtained even by adding the above-mentioned components, a pH adjuster may be added separately to adjust the pH to within the above range. Examples of the pH adjuster include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, organic ammonium salts such as tetramethylammonium hydroxide, and basic compounds such as ammonium hydroxide and ammonia. These pH adjusters may be used alone or in combination of two or more.

[0080] 1.7. Method for preparing semiconductor cleaning composition The semiconductor cleaning composition according to the present embodiment is not particularly limited and can be prepared by using a known method. Specifically, it can be prepared by dissolving each of the above-mentioned components in a liquid medium such as water or an organic solvent, and filtering the mixture. The mixing order and mixing method of each of the above-mentioned components are not particularly limited.

[0081] In the method for preparing the semiconductor cleaning composition according to the present embodiment, it is preferable to control the amount of particles by filtering with a depth type or pleat type filter as necessary. Here, the depth type filter is a high-precision filtration filter also called a deep layer filtration or volume filtration type filter. Such depth type filters include those having a laminated structure in which filtration membranes having a large number of holes are laminated, and those having rolled up fiber bundles. Specific examples of depth type filters include Profile II, Nexis NXA, Nexis NXT, Polyfine XLD, Ulti Pleats Profile, etc. (all manufactured by Nippon Pall Co., Ltd.), depth cartridge filter, wind cartridge filter, etc. (all manufactured by Advantech Co., Ltd.), CP filter, BM filter, etc. (all manufactured by Chisso Corporation), Slope Pure, Dia, Microsilia, etc. (all manufactured by Roki Techno Co., Ltd.), etc.

[0082] Examples of pleated type filters include cylindrical high precision filtration filters obtained by pleating a precision filtration membrane sheet made of nonwoven fabric, filter paper, metal mesh, etc., and then forming it into a cylindrical shape, sealing the seams of the pleats of the sheet liquid-tight, and sealing both ends of the cylinder liquid-tight.Specific examples include HDCII, Polyfine II, etc. (all manufactured by Nippon Pall Corporation), PP pleated cartridge filter (manufactured by Advantec Co., Ltd.), Porousfine (manufactured by Chisso Corporation), Sartonpore, Micropure, etc. (all manufactured by Roki Techno Co., Ltd.).

[0083] The filter used preferably has a rated filtration accuracy of 0.001 to 20 μm. By using a filter with a rated filtration accuracy within the above range, a filtrate in which the number of particles with a particle diameter of 20 μm or more per 1 mL is zero when measured with a particle counter can be efficiently obtained. In addition, the number of coarse particles captured by the filter is minimized, thereby extending the usable period of the filter.

[0084] 2. Cleaning agents The "cleaning agent" in the present invention refers to a liquid agent prepared by diluting the above-mentioned concentrated type semiconductor cleaning composition with a liquid medium or the above-mentioned non-diluted type semiconductor cleaning composition itself, which is actually used to clean the object to be treated. The above-mentioned concentrated type semiconductor cleaning composition is usually present in a state in which each component is concentrated. Therefore, each user can prepare a cleaning agent by appropriately diluting the above-mentioned concentrated type semiconductor cleaning composition with a liquid medium, or can use the non-diluted type semiconductor cleaning composition as it is as a cleaning agent.

[0085] The liquid medium used for dilution here is the same as the liquid medium contained in the above-mentioned semiconductor cleaning composition, and can be appropriately selected from the liquid media exemplified above.

[0086] A method of diluting a concentrated semiconductor cleaning composition by adding a liquid medium includes a method of merging a pipe for supplying a concentrated semiconductor cleaning composition and a pipe for supplying a liquid medium in the middle, mixing them, and supplying the mixed cleaning agent to the object to be treated. This mixing can be performed by a commonly used method such as a method of causing the liquids to collide and mix with each other through a narrow passage under pressure, a method of repeatedly dividing and separating the liquid flow by filling the pipe with a filler such as a glass tube, and a method of providing a blade that rotates by power in the pipe.

[0087] Another method for diluting a concentrated semiconductor cleaning composition by adding a liquid medium is to provide a pipe for supplying the concentrated semiconductor cleaning composition and a pipe for supplying the liquid medium separately, supply a predetermined amount of liquid from each pipe to the object to be treated, and mix them on the surface of the object to be treated. Another method for diluting a concentrated semiconductor cleaning composition by adding a liquid medium is to put a predetermined amount of the concentrated semiconductor cleaning composition and a predetermined amount of the liquid medium in one container, mix them, and then supply the mixed cleaning agent to the surface of the object to be treated.

[0088] The dilution ratio when adding a liquid medium to the concentrated type semiconductor cleaning composition is preferably 1 to 500 parts by mass (1 to 500 times) by adding a liquid medium to 1 part by mass of the concentrated type semiconductor cleaning composition, more preferably 20 to 500 parts by mass (20 to 500 times), and particularly preferably 30 to 300 parts by mass (30 to 300 times). It is preferable to dilute with the same liquid medium as the liquid medium contained in the concentrated type semiconductor cleaning composition described above. By making the semiconductor cleaning composition in a concentrated state in this way, it becomes possible to transport and store the cleaning agent in a smaller container than when the cleaning agent is transported and stored as it is. As a result, the cost of transportation and storage can be reduced. In addition, since a smaller amount of cleaning agent is purified than when the cleaning agent is purified by filtering or the like as it is, the purification time can be shortened, which makes it possible to mass-produce it.

[0089] 3. Cleaning method The cleaning method according to one embodiment of the present invention includes a step of treating a wiring layer including a silicon nitride film and a polysilicon film with the above-mentioned semiconductor cleaning composition (cleaning agent). Hereinafter, an example of the cleaning method according to this embodiment will be described in detail with reference to the drawings.

[0090] <Preparation of wiring board> 1 is a cross-sectional view showing a typical process for producing a wiring board used in the cleaning method according to the present embodiment. Such a wiring board is formed through the following process.

[0091] Fig. 1 is a cross-sectional view showing a schematic diagram of a target object before CMP processing. As shown in Fig. 1, the target object 100 has a base body 10. The base body 10 may be composed of, for example, a silicon substrate and a silicon oxide film formed thereon. Furthermore, although not shown, functional devices such as transistors may be formed on the base body 10.

[0092] The workpiece 100 is constructed by sequentially laminating a gate oxide film 12 formed on a substrate 10, a gate electrode 14 formed on the gate oxide film 12, and a silicon nitride film 16 formed to cover the periphery of the gate electrode 14.

[0093] The material of the gate oxide film 12 may be, for example, a silicon oxide film formed by a vacuum process (e.g., a PETEOS film (Plasma Enhanced-TEOS film), a HDP film (High Density Plasma Enhanced-TEOS film), a silicon oxide film obtained by a thermal chemical vapor deposition method, etc.), FSG (Fluorine-doped Examples of such insulating films include an insulating film called silicate glass, a boron phosphorus silicate film (BPSG film), an insulating film called SiON (silicon oxynitride), and silicon nitride.

[0094] Examples of the material of the gate electrode 14 include a polysilicon film and an amorphous silicon film. The gate electrode 14 is formed by etching a gate electrode film formed on the gate oxide film 12 by a CVD method using a gate resist pattern as a mask, and etching the gate electrode film and the gate oxide film 12. After etching, the resist pattern is removed.

[0095] 1, a silicon nitride film 16 is formed so as to completely cover the periphery of the gate electrode 14. Typically, the silicon nitride film 16 is deposited to a thickness of 100 to 10,000 Å by chemical vapor deposition, physical vapor deposition, or atomic layer deposition.

[0096] Next, the silicon nitride film 16 of the processing target 100 in Fig. 1 is polished at high speed by CMP until the gate electrode 14 is exposed, to obtain the state shown in Fig. 2 (first polishing step). Furthermore, the gate electrode 14 exposed on the surface is polished by CMP (second polishing step). In this manner, the wiring substrate 200 shown in Fig. 3 is obtained.

[0097] <Processing of wiring board> Next, the surface (wiring layer) of the wiring substrate 200 shown in Fig. 3 is treated with the above-mentioned cleaning agent. According to the cleaning method of this embodiment, it is possible to reduce corrosion of the wiring material and the gate electrode material, and to efficiently remove the oxide film and organic residues on the wiring substrate.

[0098] The cleaning method according to this embodiment may include a metal film such as tungsten as the wiring material of the wiring board, titanium nitride or tantalum nitride as a barrier metal, or a hafnium oxide film as a high-k material.

[0099] The cleaning method is not particularly limited, but is performed by a method in which the above-mentioned cleaning agent is directly brought into contact with the surface of the wiring board 200. Examples of the method of directly bringing the cleaning agent into contact with the wiring board 200 include a dip type in which a cleaning tank is filled with the cleaning agent and the wiring board is immersed in the cleaning agent; a spin type in which the wiring board is rotated at high speed while the cleaning agent is flowed down from a nozzle onto the wiring board; and a spray type in which the cleaning agent is sprayed onto the wiring board for cleaning. Examples of devices for performing such methods include a batch type processing device that simultaneously processes multiple wiring boards stored in a cassette, and a single-wafer processing device that processes one wiring board by mounting it on a holder.

[0100] In the cleaning method according to this embodiment, the temperature of the cleaning agent is usually room temperature, but it may be higher or lower as long as the performance is not impaired. For example, it can be heated to about 40 to 70°C or cooled to 5 to 15°C.

[0101] In addition to the method of directly contacting the cleaning agent with the surface of the wiring board 200, it is also preferable to use a cleaning method using physical force in combination. This improves the removability of contamination caused by particles attached to the wiring board 200 and shortens the processing time. Examples of cleaning methods using physical force include scrubbing using a cleaning brush and ultrasonic cleaning.

[0102] Furthermore, it is preferable to perform cleaning with ultrapure water or pure water before and / or after cleaning by the cleaning method according to this embodiment.

[0103] 4. Working Example The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the examples, "parts" and "%" are based on mass unless otherwise specified.

[0104] 4.1. Preparation of semiconductor cleaning composition Each component was added to a polyethylene container so as to obtain the content shown in Tables 1 and 2 below, and an appropriate amount of ion-exchanged water was added and stirred for 15 minutes. Ion-exchanged water was added to this mixture so that the total amount of all components became 100 mass %, and ammonium hydroxide was used to adjust the pH to the values ​​shown in Tables 1 and 2 below. The mixture was then filtered through a filter with a pore size of 0.02 μm to obtain each semiconductor cleaning composition shown in Tables 1 and 2 below. The pH was measured using a pH meter "F52" manufactured by Horiba, Ltd.

[0105] 4.2. Defect Assessment 4.2.1. Preparation of Chemical Mechanical Polishing Composition 5 kg of high-purity colloidal silica (manufactured by Fuso Chemical Co., Ltd., product number: PL-3; silica concentration 20%) and 6 g of 3-mercaptopropyltrimethoxysilane (manufactured by Alfa Aesar, product name "(3-mercaptopropyl)trimethoxysilane") were mixed and heated under reflux for 2 hours to obtain a thiolated silica sol. Hydrogen peroxide was added to the silica sol and heated under reflux for 8 hours to oxidize the surface of the silica particles and fix the sulfonic acid group. In this way, a silica particle dispersion with a silica concentration of 20%, a primary particle diameter of 45 nm, and a secondary particle diameter of 68 nm was obtained. Next, 14,043 g of pure water, 3,940 g of 20% silica particle water dispersion, 43 g of phosphoric acid (manufactured by Fujifilm Wako Pure Chemical Industries, product name "phosphoric acid"), and 2 g of polyvinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd., product name "Polyvinylpyrrolidone") were added to a polyethylene bottle with a capacity of 20 L, and the mixture was stirred at room temperature for 1 hour to prepare a chemical mechanical polishing composition A.

[0106] 4.2.2. Evaluation Test Using chemical mechanical polishing composition A, a 12-inch wafer with a 250 nm silicon nitride film and a 12-inch wafer with a 500 nm polysilicon film were polished under the following conditions, and then the semiconductor cleaning composition prepared above was used as a cleaning agent to perform a cleaning under the following conditions. Finally, brush scrubbing was performed under the following conditions to obtain the cleaned objects.

[0107] The number of defects on the entire surface of the cleaned object was measured using a defect inspection device (KLA Tencor, model "Surfscan SP2"). If the number of defects in both the silicon nitride film and the polysilicon film was less than 100, it was judged to be good, and if the number of defects in at least either the silicon nitride film or the polysilicon film was 100 or more, it was judged to be defective because it was not suitable for practical use. The results are shown in Tables 1 and 2 below.

[0108] <Polishing treatment conditions> Polishing equipment: Applied Materials, model "Reflexion-LK" Polishing pad: Fujibo Co., Ltd., "Porous polyurethane pad; H800-type1(3-1S)775" Chemical mechanical polishing composition: Chemical mechanical polishing composition A prepared as above ·Chemical mechanical polishing composition supply rate: 300mL / min Platen rotation speed: 90 rpm Head rotation speed: 91 rpm Head pressure: 2.0psi Processing time: 60 seconds

[0109] <Cleaning treatment conditions> Polishing equipment: Applied Materials, model "Reflexion-LK" Polishing pad: Fujibo Co., Ltd., "Porous polyurethane pad; H800-type1(3-1S)775" Cleaning agent: the semiconductor cleaning composition prepared above Cleaning agent supply rate: 300mL / min Platen rotation speed: 50 rpm Head rotation speed: 51 rpm Head pressure: 1.0 psi Processing time: 60 seconds

[0110] <Brush scrub cleaning conditions> Treatment agent: Pure water Upper brush rotation speed: 400 rpm Lower brush rotation speed: 400 rpm Substrate rotation speed: 50 rpm Treatment agent supply rate: 1200mL / min Processing time: 40 seconds

[0111] 4.3.Corrosion assessment The corrosiveness can be judged by comparing and evaluating the etching rate when a wafer with a polysilicon film is immersed in a semiconductor cleaning composition. It can be judged that the lower the etching rate, the less corrosive the wiring including the polysilicon film is. Specifically, the evaluation was performed as follows.

[0112] A 12-inch wafer with a polysilicon film manufactured by Advantech was cut into a 3 cm square to prepare a test piece. This test piece was immersed in the semiconductor cleaning composition prepared above at 60°C for 0.5 hours, then washed with water and dried. The weight of the test piece before and after immersion was measured, and the polysilicon density was found to be 2.3 g / cm. 3 The thickness of the etched polysilicon film was calculated from the area of ​​the polysilicon film wafer (3 cm x 3 cm) and the etching rate of the polysilicon film was evaluated. When the etching rate was less than 1 Å / min, it was judged to be very good because the corrosiveness was extremely low. When the etching rate was 1 Å / min or more, it was judged to be poor because the corrosiveness was too high to be put to practical use. The results are shown in Tables 1 and 2 below.

[0113] 4.4.Evaluation Results Tables 1 and 2 below show the compositions and evaluation results of the semiconductor cleaning compositions used in each of the Examples and Comparative Examples.

[0114] [Table 1]

[0115] [Table 2]

[0116] In Tables 1 and 2 above, the numerical values ​​of each component represent mass %. In the above, the total amount of each component is 100% by mass, and the remainder is ion-exchanged water. The following provides additional information about the components listed in Tables 1 and 2 above.

[0117] <Compound (A)> CAPS: Tokyo Chemical Industry Co., Ltd., 3-cyclohexylaminopropanesulfonic acid HEPES: Tokyo Chemical Industry Co., Ltd., 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid APS: Sigma-Aldrich, 3-anilino-1-propanesulfonic acid PIPES: Sigma-Aldrich, 1,4-piperazinediethanesulfonic acid NAPS: Sigma-Aldrich, 3-(1-naphthylamino)-1-propanesulfonic acid <Alkanolamine (B)> Monoethanolamine: Tokyo Chemical Industry Co., Ltd., 2-Aminoethanol Triethanolamine: Tokyo Chemical Industry Co., Ltd. Tris(hydroxymethyl)aminomethane: Tokyo Chemical Industry Co., Ltd. <Water-soluble polymer (C)> Polystyrene sulfonic acid: Alfa Aesar, product name "Poly(styrene sulfonic acid), sodium salt, MW 70,000" Polyacrylic acid: Toagosei Co., Ltd., product name "Jurimer AC-10L", Mw = 20,000 to 30,000 <Surfactant (D)> Triethanolamine dodecylbenzenesulfonate: Toho Chemical Industry Co., Ltd., product name "Lunox S-40TD, 38% aqueous solution" Triethanolamine dodecyl sulfate: Kao Corporation, product name "EMAL TD, 40% aqueous solution" Polyoxyethylene dodecyl ether triethanolamine sulfate: Toho Chemical Co., Ltd., product name "Alscope N-335T, 35.5% aqueous solution" Sodium polyoxyethylene dodecyl ether acetate: Sanyo Chemical Industries, product name "Viewlight LCA" <Other additives> Citric acid: Fujifilm Wako Pure Chemical Industries, Ltd. Acetic acid: Fujifilm Wako Pure Chemical Industries, Ltd. Malonic acid: Fujifilm Wako Pure Chemical Industries, Ltd. Maleic acid: Fujifilm Wako Pure Chemical Industries, Ltd. Glycolic Acid: Tokyo Chemical Industry Co., Ltd. Nitric acid: Tokyo Chemical Industry Co., Ltd., product name "Nitric Acid" (67% aqueous solution) Sulfuric acid: Fujifilm Wako Pure Chemical Industries, trade name "sulfuric acid" (10% aqueous solution) Phosphoric acid: Fujifilm Wako Pure Chemical Industries, product name "phosphoric acid"

[0118] As shown in Examples 1 to 11, a semiconductor cleaning composition containing a compound (A), an alkanolamine (B), and a liquid medium and having a pH of 3.0 to 9.0 can reduce damage caused by corrosion to a polysilicon film, and the composition also showed good results in defect evaluation of a polysilicon film and a silicon nitride film after a CMP process.

[0119] On the other hand, the semiconductor cleaning compositions of Comparative Examples 1 to 4, which do not contain the compound (A) or the alkanolamine (B), showed poor results in the defect evaluation after the CMP process using the compositions. The semiconductor cleaning composition of Comparative Example 5, which has a pH of 10.0, caused corrosion of the polysilicon film, resulting in poor results. The semiconductor cleaning composition of Comparative Example 6, which has a pH of 2.0, showed many defects on the silicon nitride film, resulting in poor results.

[0120] The present invention is not limited to the above-described embodiments, and various modifications are possible. For example, the present invention includes a configuration that is substantially the same as the configuration described in the embodiments (for example, a configuration having the same functions, methods, and results, or a configuration having the same objectives and effects). In addition, the present invention includes a configuration in which a non-essential part of the configuration described in the embodiments is replaced. Further, the present invention includes a configuration that exhibits the same operational effects as the configuration described in the embodiments or a configuration that can achieve the same objective. Moreover, the present invention includes a configuration in which known techniques are added to the configuration described in the embodiments.

Explanation of Reference Numerals

[0121] 10... Substrate, 12... Gate oxide film, 14... Gate electrode, 16... Silicon nitride film, 100... Object to be processed, 200... Wiring board

Claims

1. A compound (A) having at least one group selected from the group consisting of an amino group and a salt thereof, at least one group selected from the group consisting of a sulfo group and a salt thereof, and a group having a cyclic structure having 4 to 12 carbon atoms; An alkanolamine (B), A liquid medium; Contains A semiconductor cleaning composition having a pH of 3.0 or more and 9.0 or less.

2. The semiconductor cleaning composition according to claim 1 , further comprising a water-soluble polymer (C).

3. The semiconductor cleaning composition according to claim 1 , further comprising a surfactant (D).

4. 4. The semiconductor cleaning composition according to claim 3, wherein the surfactant (D) is a compound having a functional group represented by the following general formula (1) or (2) and an alkyl group having 8 to 18 carbon atoms: -SO ３ － M ＋ ・・・・・(1) -COO － M ＋ ・・・・・(2) (In the above formulas (1) and (2), M ＋ represents a monovalent cation.)

5. A cleaning method comprising the step of treating a wiring layer having a silicon nitride film and a polysilicon film with the semiconductor cleaning composition according to any one of claims 1 to 4.

Images