Composition, method for manufacturing semiconductor element

Abstract

The present application provides a composition, and a method for manufacturing a semiconductor element, which is excellent in removal performance of residue and corrosion resistance of a tungsten-containing film even when used after a prescribed period has passed since manufacture, and which can suppress deterioration of the electrical characteristics of the tungsten-containing film. The composition of the present application comprises: sorbic acid; citric acid; an amine-containing compound selected from at least one of ammonia, an organic amine, and a quaternary ammonium compound, and a salt thereof; a specific compound having at least one group selected from a phosphono group and a phosphoric acid group; and water, the pH of the composition being 4.0 to 9.0 at 25°C.

Description

TECHNICAL FIELD

[0001] The present application relates to a composition and a method for manufacturing a semiconductor device. BACKGROUND

[0002] A semiconductor device such as a CCD (Charge-Coupled Device) and a memory is manufactured by using a photolithography technique and forming a fine electronic circuit pattern on a substrate. Specifically, the semiconductor device is manufactured by forming a resist film on a substrate and on a laminate having a metal film to be a wiring material, an etching stopper layer, and an interlayer insulating layer, and performing a photolithography process and a dry etching process (e.g., a plasma etching treatment or the like).

[0003] In manufacturing a semiconductor device, a chemical mechanical polishing treatment is sometimes performed in which a polishing liquid containing polishing particles (e.g., silicon dioxide and aluminum oxide or the like) is used to planarize a surface of a semiconductor substrate having a metal wiring film, a barrier metal, and an insulating film or the like. In the chemical mechanical polishing treatment, residues of the polishing particles used in the chemical mechanical polishing treatment, metal components from the wiring metal film and / or the barrier metal being polished, and the like are easily left on the surface of the semiconductor substrate after the chemical mechanical polishing treatment.

[0004] Since these residues cause short-circuiting between wirings and adversely affect the electrical characteristics of the semiconductor, a cleaning process for removing these residues from the surface of the semiconductor substrate is generally performed.

[0005] For example, in Patent Literature 1, a cleaning agent containing at least one organic acid compound and a cleaning solution containing at least one preservative compound and at least one amine compound which substantially minimize or prevent the growth of microorganisms in the cleaning solution are disclosed.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

[0008] Patent Literature 1: Japanese Patent Application Laid-Open No. 2009-531512 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] With the miniaturization of semiconductor devices, compositions used in the manufacturing process of semiconductor devices such as a cleaning liquid for a semiconductor substrate are required to have more excellent residue (e.g., polishing particles, metal-containing substances, organic substances, substrate materials, and mixtures thereof) removal performance, to suppress damage to an object such as a substrate (e.g., corrosion of a metal-containing film or the like), and to suppress the influence on the electrical characteristics of a metal-containing film formed in a semiconductor substrate for the purpose of a wiring or the like.

[0011] On the other hand, since the kind of elements used in the manufacturing process of semiconductor elements has a tendency to increase, in order to cope with the new kind of elements, a composition including a wide range of pH ranging from strong acidity, strong alkalinity, and neutrality therebetween is required.

[0012] The present inventors and others have found, as a result of studying semiconductor substrate compositions in the vicinity of neutrality based on the technical content described in Patent Document 1, that there is room for improvement in terms of simultaneously solving the three problems of removal performance of metal-containing films (particularly, tungsten-containing films) on semiconductor substrates, corrosion resistance, and suppression of degradation of electrical characteristics when used after a prescribed period from manufacturing.

[0013] Therefore, an object of the present application is to provide a composition that is excellent in removal performance of residues and corrosion resistance of tungsten-containing films, and can suppress degradation of electrical characteristics of the tungsten-containing films even when used after a prescribed period from manufacturing. Also, an object of the present application is to provide a method for manufacturing semiconductor elements.

[0014] Means for solving the technical problem

[0015] As a result of intensive studies conducted by the present inventors and others in order to achieve the above-mentioned object, it has been found that the above-mentioned object can be solved by the following structure.

[0016] 〔1〕 A composition comprising: sorbic acid; citric acid; an amine-containing compound selected from at least one of ammonia, an organic amine, and a quaternary ammonium compound, and a salt thereof; a specific compound having at least one group selected from phosphono and phosphoric acid groups; and water, the composition having a pH of 4.0 to 9.0 at 25°C.

[0017] 〔2〕 The composition according to 〔1〕, wherein,

[0018] The content of the above-mentioned citric acid is in a ratio of 1 to 50 in terms of mass ratio to the content of the above-mentioned sorbic acid.

[0019] 〔3〕 The composition according to 〔1〕 or 〔2〕, wherein,

[0020] The content of the above-mentioned amine-containing compound is in a ratio of 10 to 500 in terms of mass ratio to the content of the above-mentioned sorbic acid.

[0021] 〔4〕 The composition according to any one of 〔1〕 to 〔3〕, wherein,

[0022] The above-mentioned specific compound includes a compound having a phosphono group.

[0023] 〔5〕 The composition according to any one of 〔1〕 to 〔4〕, wherein,

[0024] The specific compound includes a compound having at least two phosphono groups.

[0025] 〔6〕 The composition according to any one of 〔1〕 to 〔5〕, wherein the amine- containing compound includes at least one selected from the group consisting of ammonia, alkanolamine, and quaternary ammonium compound, and salts thereof.

[0026] 〔7〕 The composition according to any one of 〔1〕 to 〔6〕, wherein,

[0027] The amine-containing compound includes alkanolamine.

[0028] 〔8〕 The composition according to any one of 〔1〕 to 〔7〕, which substantially does not include abrasive grains.

[0029] 〔9〕 The composition according to any one of 〔1〕 to 〔8〕, which has an electrical conductivity of 0.01 to 30 mS / cm at 25°C.

[0030] 〔10〕 The composition according to any one of 〔1〕 to 〔9〕, wherein,

[0031] The content of the phosphate ion is 20 mass ppm or less with respect to the composition.

[0032] 〔11〕 The composition according to any one of 〔1〕 to 〔10〕, which is used as a cleaning solution for a semiconductor substrate on which a chemical mechanical polishing treatment is performed.

[0033] 〔12〕 The composition according to 〔11〕, wherein,

[0034] The semiconductor substrate includes tungsten.

[0035] 〔13〕 The composition according to 〔11〕 or 〔12〕, wherein,

[0036] The diluted solution obtained by diluting the composition with water by 50 times or more is used as the cleaning solution.

[0037] 〔14〕 A method for manufacturing a semiconductor element, which includes a step of cleaning a semiconductor substrate using the composition according to any one of 〔1〕 to 〔12〕.

[0038] 〔15〕 A method for manufacturing a semiconductor element, which includes a step of performing a chemical mechanical polishing treatment on a semiconductor substrate, and a step of cleaning the semiconductor substrate on which the chemical mechanical polishing treatment is performed using the composition according to any one of 〔1〕 to 〔12〕 or a diluted solution obtained by diluting the composition with water.

[0039] Effects of the Invention

[0040] According to the present application, it is possible to provide a composition in which the removal performance of residues and the corrosion resistance of a tungsten-containing film are excellent even when used after a prescribed period has elapsed from the time of manufacture, and in which the deterioration of the electrical characteristics of the tungsten-containing film is suppressed. Furthermore, the present application makes it possible to provide a method for manufacturing a semiconductor element. DETAILED DESCRIPTION

[0041] Hereinafter, one example of a mode for carrying out the present application will be described.

[0042] The present application is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.

[0043] In the present specification, a numerical range represented by "to" means a range including the lower limit value and the upper limit value recited before and after "to".

[0044] In the present specification, "preparation" means not only including the provision by treatment of raw materials or the like by synthesis or compounding, but also including the acquisition of a prescribed substance by purchase or the like.

[0045] In the present specification, in the case where two or more kinds of components are present, unless specifically specified, the "content" of the components means the total content of these two or more kinds of components.

[0046] In the compounds recited in the present specification, unless specifically specified, structural isomers, optical isomers and isotopes can be included. Furthermore, the structural isomers, optical isomers and isotopes can be included singly in one kind, or two or more kinds can be included.

[0047] In the present specification, psi represents pound-force per square inch and means 1 psi = 6894.76 Pa.

[0048] In the present specification, "ppm" represents "parts-per-million: one in 106", and "ppb" represents "parts-per-billion: one in 109". -9

[0049] In the present specification, (Angstrom) corresponds to 0.1 nm.

[0050] ​In the present specification, unless specifically specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values converted using tetrahydrofuran as an eluent, using a differential refractometer as a detector, using polystyrene as a standard substance, using the polystyrene of a standard substance measured by a gel permeation chromatography (GPC) analysis device, using TSKgel GMHXL, TSKgel G4000HXL, or TSKgel G2000HXL (all manufactured by TOSOH CORPORATION) as a column.

[0051] In the present specification, unless specifically specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight.

[0052] In the present specification, the "total solid content" indicates the total content of all components included in the composition other than solvents such as water and organic solvents.

[0053] [Composition]

[0054] The composition of the present application (hereinafter, also simply referred to as "composition") contains: sorbic acid; citric acid; an amine-containing compound selected from at least one of ammonia, an organic amine, and a quaternary ammonium compound, and a salt thereof; a specific compound having at least one group selected from phosphono and phosphoric acid groups; and water. And, the pH of the composition at 25°C is 4.0 to 9.0.

[0055] In the present specification, the sorbic acid, the citric acid, the above-mentioned amine-containing compound, and the above-mentioned specific compound are also respectively described as "component A", "component B", "component C", and "component D".

[0056] The present inventors found that, in the case where the composition contains the above-mentioned components A to D and the pH is 4.0 to 9.0, all of the three effects of the residue removal performance, the corrosion resistance of the tungsten-containing film, and the suppression of the deterioration of the electrical characteristics of the tungsten-containing film are excellent in balance, so that the present application was completed.

[0057] Although the detailed mechanism by which the effects of the present application are obtained by this composition is not clear, the present inventors speculate as follows.

[0058] It is speculated as follows: in the case where the pH of the composition used in the manufacturing process of the semiconductor element is adjusted to the region of 4 to 9, with the passage of time, extremely fine suspended matters in the air are dissolved or accumulated in the composition, as a result, not only the original residue removal performance and the corrosion resistance of the composition will be affected, but also these fine residues remain on the surface of the target after processing, so that the electrical characteristics will be affected.

[0059] On the other hand, it is presumed that since the present composition is inhibited from being mixed into the above-mentioned suspension or the like by containing the above-mentioned components A to D, the decrease in the residue removal property, the corrosion resistance, and the electrical characteristics is inhibited.

[0060] In the present specification, the effect that at least one of the residue removal performance, the corrosion resistance of the tungsten-containing film, and the inhibition of the deterioration of the electrical characteristics of the tungsten-containing film is excellent is also described as "the effect of the present invention is excellent".

[0061] Hereinafter, each component contained in the composition will be described in detail.

[0062] [Component A (Sorbic Acid)]

[0063] The composition contains sorbic acid (hexadienoic acid).

[0064] The sorbic acid can also be in the form of a salt. As the above-mentioned salt, for example, well-known salts such as sodium salt, potassium salt, and ammonium salt can be given.

[0065] The content of the sorbic acid is not particularly limited, and from the viewpoint that the effect of the present invention is more excellent, it is preferably 0.0001 to 0.1% by mass, more preferably 0.001 to 0.08% by mass, and further preferably 0.01 to 0.08% by mass, with respect to the total mass of the composition.

[0066] Also, the content of the sorbic acid is preferably 0.01 to 30.0% by mass, and more preferably 0.05 to 12.0% by mass, with respect to the total solid component in the composition.

[0067] [Component B (Citric Acid)]

[0068] The composition contains citric acid.

[0069] The citric acid can be in the form of a salt. As the above-mentioned salt, for example, well-known salts such as sodium salt, potassium salt, and ammonium salt can be given.

[0070] The content of the citric acid is preferably 0.001 to 1.0% by mass, and more preferably 0.01 to 0.5% by mass, with respect to the total mass of the composition.

[0071] The content of the citric acid is preferably 0.1 to 1.0% by mass, and more preferably 0.3 to 0.6% by mass, with respect to the total solid component in the composition.

[0072] From the viewpoint that the residue removal property is more excellent, the ratio B / A of the content of the citric acid to the content of the sorbic acid (the content of the citric acid B / the content of the sorbic acid B) is preferably 1 to 50, more preferably 3 to 30, and further preferably 4 to 10, in terms of mass ratio.

[0073] [Component C (Amine-Containing Compound)]

[0074] The composition contains, as component C, an amine-containing compound which is at least one selected from the group consisting of ammonia, an organic amine, and a quaternary ammonium compound, and salts thereof.

[0075] In addition, the compound contained in component D is not included in component C.

[0076] Component C can be in the form of a salt. As the above salt, for example, a salt of an inorganic acid which is bonded to hydrogen at least one selected from the group consisting of Cl, S, N, and P can be mentioned, and a hydrochloride, a sulfate, or a nitrate is preferable. Also, component C can form a salt with an acidic compound such as sorbic acid, citric acid, and an organic acid described later.

[0077] <ammonia>

[0078] The composition can contain ammonia as component C. In the present specification, an ammonium cation (NH4 + ), and a salt of an ammonium cation and a counter anion (for example, ammonium hydroxide (NH4OH) and the like) correspond to ammonia.

[0079] <organic amine>

[0080] The composition can contain an organic amine as component C.

[0081] The organic amine is a compound or a salt thereof having at least one amino group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group in the molecule.

[0082] The organic amine can be any one of a chain (straight-chain or branched-chain) and a cyclic. The organic amine preferably does not include an aromatic ring. Also, the organic amine preferably does not have a carboxyl group.

[0083] As the organic amine, for example, an alkanolamine, an alicyclic amine, and an aliphatic amine other than the alkanolamine and the alicyclic amine can be mentioned.

[0084] The alkanolamine is a compound having at least one hydroxyalkyl group in the molecule in the organic amine. The alkanolamine can have any one of a primary to tertiary amino group, and preferably has a primary amino group.

[0085] The number of amino groups possessed by the alkanolamine is, for example, 1 to 5, and preferably 1 to 3. The number of hydroxyl groups possessed by the alkanolamine is, for example, 1 to 5, and more preferably 1 to 3.

[0086] Among them, the alkanolamine more preferably has only a primary amino group as the amino group.

[0087] As the alkanolamine, for example, monoethanolamine (MEA), 3-amino-1-propanol, 1-amino-2-propanol, tris(hydroxymethyl)aminomethane (Tris), 2-amino-2-methyl-1-propanol (AMP), 2-dimethylamino-2-methyl-1-propanol (DMAMP), 2-amino-2-methyl-1,3-propanediol (AMPDO), 2-amino-2-ethyl-1,3-propanediol (AEPDO), 2-amino-1,3-propanediol (2-APDO), 3-amino-1,2-propanediol (3-APDO), 3-methylamino-1,2-propanediol (MAPDO), 2-(methylamino)-2-methyl-1-propanediol (N-MAMP), 2-(2-aminoethoxy)ethanol (AEE), 2-(2-aminoethylamino)ethanol (AAE), diethanolamine (DEA), triethanolamine (TEA), N-methylethanolamine, N-butylethanolamine, N-cyclohexylethanolamine, 2-(ethylamino)ethanol, propylaminoethanol, diethyleneglycolamine (DEGA), N,N'-bis(2-hydroxyethyl)ethylenediamine, 1,2-bis(2-aminoethoxy)ethane, N-t-butyl diethanolamine, N-butyl diethanolamine, N-methyl diethanolamine, 1-piperidinoethanol, and 1-(2-hydroxyethyl)piperazine can be given.

[0088] Among them, MEA, Tris, DMAMP, AMP, AMPDO, AEPDO, 2-APDO, 3-APDO, or MAPDO is preferred, and MEA or Tris is more preferred.

[0089] As the alicyclic amine, for example, a cyclic amidine compound and a piperazine compound can be given. In addition, the compounds included in the alkanolamine are not included in the alicyclic amine.

[0090] The cyclic amidine compound is a compound having a heterocycle including an amidine structure (>N-C=N-) in a ring. The number of ring-forming atoms of the above-mentioned heterocycle possessed by the cyclic amidine compound is preferably 5 to 6, and more preferably 6.

[0091] As the cyclic amidine compound, for example, diazabicycloundecene (1,8-diazabicyclo[5.4.0]undec-7-ene: DBU), diazabicyclononene (1,5-diazabicyclo[4.3.0]non-5-ene: DBN), 3,4,6,7,8,9,10,11-octahydro-2H-pyrimido[1.2-a]azepine, 3,4,6,7,8,9-hexahydro-2H-pyrido[1.2-a]pyrimidine, 2,5,6,7-tetrahydro-3H-pyrrolo[1.2-a]imidazole, 3-ethyl-2,3,4,6,7,8,9,10-octahydropyrimido[1.2-a]azepine, and creatinine can be given.

[0092] The piperazine compound is a compound having a hetero 6-membered ring (piperazine ring) in which the opposite >CH- group of a cyclohexane ring is replaced with a tertiary amino group (>N-).

[0093] As the piperazine compound, for example, piperazine, 1-methylpiperazine, 2-methylpiperazine, 1-ethylpiperazine, 1-benzylpiperazine, 1-butylpiperazine, 1,4-dimethylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 1-phenylpiperazine, N-(2-aminoethyl)piperazine (AEP), 1,4-bis(2-aminoethyl)piperazine (BAEP), 1,4-bis(3-aminopropyl)piperazine (BAPP), and 1,4-diazabicyclo[2.2.2]octane (DABCO) can be given.

[0094] As the alicyclic amine other than the piperazine compound and the cyclic amidine compound, for example, a compound having a nitrogen-containing 5-membered ring or a nitrogen-containing 7-membered ring such as 1,3-dimethyl-2-imidazolidinone can be given.

[0095] As the alkanolamine and the alicyclic amine, for example, an aliphatic primary amine (aliphatic amine having a primary amino group), an aliphatic secondary amine (aliphatic amine having a secondary amino group), and an aliphatic tertiary amine (aliphatic amine having a tertiary amino group), and salts thereof can be given.

[0096] As the aliphatic primary amine, for example, methylamine, ethylamine, propylamine, dimethylamine, diethylamine, n-butylamine, 3-methoxypropylamine, t-butylamine, n-hexylamine, n-octylamine, and 2-ethylhexylamine can be given.

[0097] As the aliphatic secondary amine, for example, ethylenediamine (EDA), 1,3-propanediamine (PDA), 1,2-propanediamine, 1,3-butanediamine, 1,4-butanediamine, and the like alkylene diamine; and diethylenetriamine (DETA), triethylenetetramine (TETA), bis(amino-propyl)ethylenediamine (BAPEDA), tetraethylenepentamine, and the like polyalkyl polyamine can be given.

[0098] As the aliphatic tertiary amine, for example, trimethylamine, triethylamine, and the like tertiary alkyl amine; 1,3-bis(dimethylamino)butane and the like alkylene diamine; and N,N,N',N",N"-pentamethyldiethylenetriamine and the like polyalkyl polyamine can be given.

[0099] As the organic amine, an alkanolamine is preferred, and an alkanolamine of the above-mentioned preferable mode is more preferred.

[0100] <Quaternary Ammonium Compound>

[0101] The composition can contain, as the component C, a compound having at least one quaternary ammonium cation group in the molecule or a salt thereof, i.e., a quaternary ammonium compound.

[0102] The quaternary ammonium compound is not particularly limited as long as it is a compound having a quaternary ammonium cation group with at least one of the four hydrocarbon groups (preferably alkyl groups) substituted on the nitrogen atom or a salt thereof.

[0103] As the quaternary ammonium compound, for example, quaternary ammonium hydroxides, quaternary ammonium fluorides, quaternary ammonium bromides, quaternary ammonium iodides, quaternary ammonium acetates, and quaternary ammonium carbonates can be given.

[0104] As the quaternary ammonium compound, quaternary ammonium hydroxides are preferred, and more preferably a compound represented by the following formula (al).

[0105] [Chemical Formula 1]

[0106]

[0107] In the above formula (al), R a1 ~R a4 independently represent an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or a hydroxyalkyl group having 1 to 16 carbon atoms. At least two of Ralto R a4 may be bonded to each other to form a ring structure.

[0108] As the compound represented by the above formula (al), from the viewpoint of easy availability, a compound selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, tetrabutylammonium hydroxide (TBAH), methyltrispropylammonium hydroxide, methyltrisbutylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide (BzTMAH), hexadecyltrimethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide, and hydroxyspiro-(l,l') -bipyrrrolidine is preferred, and TMAH, more preferably TEAH or TBAH.

[0109] As the component C, a compound selected from the group consisting of ammonia, alkanolamines, and quaternary ammonium hydroxides, and salts thereof is preferred.

[0110] Among them, from the viewpoint of being able to further suppress the deterioration of the electrical properties of the wiring, a compound selected from the group consisting of alkanolamines and quaternary ammonium hydroxides, and salts thereof is more preferred.

[0111] Further, from the viewpoint of the corrosion resistance of the metal-containing film being more excellent, a compound selected from the group consisting of ammonia and alkanolamines, and salts thereof is more preferred.

[0112] As the component C, an alkanolamine or a salt thereof is further preferred, and Tris is particularly preferred.

[0113] The component C can be used alone as one kind, or two or more kinds can be used.

[0114] The content of component C is preferably 0.01 to 20 mass%, more preferably 0.1 to 10 mass%, relative to the total mass of the composition.

[0115] The content of component C is preferably 10 to 90 mass%, more preferably 30 to 70 mass%, relative to the total solid components in the composition.

[0116] From the viewpoint of more excellent corrosion resistance, the ratio C / A of the content of component C to the content of sorbic acid (content of component C / C / content of sorbic acid A) is preferably 10 to 500, more preferably 30 to 300, and further preferably 100 to 150, in terms of mass ratio.

[0117] Also, from the viewpoint of more excellent residue removal, the ratio B / C of the content of citric acid to the content of component C (content of citric acid B / content of component C C) is preferably 0.01 to 0.3, more preferably 0.03 to 0.2, and further preferably 0.04 to 0.1, in terms of mass ratio.

[0118] 〔Component D〕

[0119] The composition contains, as component D, a compound having at least one group selected from the group consisting of phosphono (-PO3H2) and phosphoric acid (-PO4H2) (hereinafter, also referred to as "specific group").

[0120] In addition, the phosphono group and the phosphoric acid group possessed by component D can form a salt with counter ions or other groups within the molecule.

[0121] The number of specific groups possessed by component D is not particularly limited, and is, for example, an integer of 1 to 6, preferably an integer of 2 to 5, and more preferably 2 or 3.

[0122] The number of carbon atoms of component D is preferably 15 or less, more preferably 12 or less, and further preferably 8 or less. The lower limit is not particularly limited, and is preferably 2 or more.

[0123] As component D, a phosphine compound having a phosphono group as a specific group and a phosphoric acid compound having a phosphoric acid group as a specific group can be given.

[0124] The phosphine compound has at least one phosphono group within the molecule. From the viewpoint of more excellent effects of the present application, the number of phosphono groups possessed by the phosphine compound is preferably 2 or more. The upper limit is not particularly limited, and is, for example, an integer of 6 or less, preferably an integer of 5 or less, and more preferably an integer of 4 or less.

[0125] The range of the number of carbon atoms of the phosphine compound is as described above.

[0126] As the phosphine compound, for example, 2-phosphonobutane-l,2,4-tricarboxylic acid (PBTCA), 4-phosphonobutanoic acid, nitrilotri(methylene phosphonic acid), ethylenediphosphonic acid, l-hydroxyethylidene-l,l'-diphosphonic acid (HEDPO), l-hydroxypropylidene-l,l'-diphosphonic acid, l-hydroxybutylidene-l,l'-diphosphonic acid, ethylaminobis(methylene phosphonic acid), dodecylaminobis(methylene phosphonic acid), nitrilotri(methylene phosphonic acid) (NTPO), ethylenediaminebis(methylene phosphonic acid) (EDDPO), 1,3-propanediaminebis(methylene phosphonic acid), ethylenediaminetetra(methylene phosphonic acid) (EDTPO), ethylenediaminetetra(ethylene phosphonic acid), 1,3-propanediaminetetra(methylene phosphonic acid) (PDTMP), 1,2-diaminopropanetetra(methylene phosphonic acid), 1,6-hexanediaminetetra(methylene phosphonic acid), diethylenetriaminepenta(methylene phosphonic acid) (DEPPO), diethylenetriaminepenta(ethylene phosphonic acid), triethylenetetraaminehexa(methylene phosphonic acid), and triethylenetetraaminehexa(ethylene phosphonic acid) can be given.

[0127] As the phosphine compound, HEDPO, NTPO, or EDTPO is preferred, and HEDPO is more preferred.

[0128] As the phosphoric acid compound, there is no particular limitation as long as it is a compound having at least one phosphoric acid group in the molecule, and, for example, condensed phosphoric acid and salts thereof, and organic compounds having a phosphoric acid group (phosphoric acid ester group) can be given.

[0129] As a more specific phosphoric acid compound, pyrrolinic acid, metaphosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid, and phytic acid, and salts thereof can be given.

[0130] As the component D, from the viewpoint of more excellent effects of the present application, a compound having a phosphonic acid group is preferred, a compound having at least two phosphonic acid groups is more preferred, a compound having two to four phosphonic acid groups is further preferred, and HEDPO or NTPO is particularly preferred.

[0131] The component D can be used alone in one kind, or two or more kinds can be used.

[0132] The content of the component D is preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass, with respect to the total mass of the composition.

[0133] The content of the component D is preferably 10 to 90% by mass, and more preferably 20 to 50% by mass, with respect to the total solid component in the composition.

[0134] [Water]

[0135] The composition contains water.

[0136] The kind of water is not particularly limited as long as it does not affect the semiconductor substrate, and distilled water, deionized water, and pure water (ultrapure water) can be used. From the viewpoint that impurities are hardly contained and the semiconductor substrate is less affected in the manufacturing process of the semiconductor substrate, pure water is preferred.

[0137] The content of water in the composition is not particularly limited and can be the remaining portion of components A to D and any component (described later) added as necessary.

[0138] The content of water is, for example, 60% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more, with respect to the total mass of the composition.

[0139] The upper limit is not particularly limited and can be, for example, 99.9% by mass or less, and preferably 99% by mass or less, with respect to the total mass of the composition.

[0140] [Arbitrary Component]

[0141] The composition can contain an arbitrary component in addition to components A to D and water described above. As the arbitrary component, for example, a preservative, a surfactant, a chelating agent, a pH adjuster, and various additives can be given.

[0142] Hereinafter, the arbitrary component will be described.

[0143] [Preservative]

[0144] The composition can contain a preservative.

[0145] The preservative refers to a compound having a function of preventing corrosion of an exposed surface of a metal film (particularly, a metal film containing tungsten) possessed by a semiconductor substrate, and for example, a water-soluble polymer can be given.

[0146] Further, the above component C can have the function of a preservative.

[0147] The water-soluble polymer is a water-soluble compound having a weight average molecular weight of 1000 or more. In the present specification, "water-soluble" means that the mass dissolved in 100 g of water at 20°C is 0.1 g or more. In addition, the water-soluble polymer does not contain a compound that functions as an organic acid and an anionic surfactant described later.

[0148] As the water-soluble polymer, for example, polyvinyl alcohol, hydroxyethyl cellulose, polyvinylpyrrolidone, poly(meth)acrylic acid, poly(meth)acrylamide, and polystyrene sulfonic acid, and the like can be given.

[0149] The weight average molecular weight of the water-soluble polymer is preferably 1000 to 100000, more preferably 2000 to 50000, and further preferably 5000 to 50000.

[0150] The composition can contain other preservatives in addition to the above-mentioned components.

[0151] As other preservatives, for example, ascorbic acid compounds, catechol compounds, hydrazine compounds, reducing sulfur compounds, sugar classes (fructose, glucose, and ribose, etc.), polyhydric alcohol classes (ethylene glycol, propylene glycol, and glycerin, etc.), polyvinylpyrrolidone, phenazine, flavonol and its derivatives, and anthocyanin and its derivatives can be mentioned.

[0152] The preservative can be used singly or in combination of two or more.

[0153] In the case where the composition contains a preservative, the content of the preservative is preferably 0.0001 to 10% by mass, more preferably 0.001 to 3% by mass, relative to the total mass of the composition.

[0154] In the case where the composition contains a preservative, the content of the preservative is preferably 0.001 to 30% by mass, more preferably 0.01 to 10% by mass, relative to the total solid content of the composition.

[0155] In addition, these preservatives can be used as commercially available products or preservatives synthesized by publicly known methods.

[0156] <Interface active agent>

[0157] The composition can contain an interface active agent.

[0158] The interface active agent is a compound having a hydrophilic group and a hydrophobic group (oleophilic group) in one molecule. As the interface active agent, for example, nonionic interface active agents, anionic interface active agents, and amphoteric interface active agents can be mentioned.

[0159] The composition preferably contains an interface active agent from the viewpoint of more excellent corrosion resistance of the metal film and removal of residues such as polishing grains.

[0160] The interface active agent generally has at least one hydrophobic group selected from aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups combining them.

[0161] In the case where the hydrophobic group contains an aromatic hydrocarbon group, the number of carbon atoms of the hydrophobic group possessed by the interface active agent is preferably 6 or more, more preferably 10 or more. In the case where the hydrophobic group does not contain an aromatic hydrocarbon group and consists of only an aliphatic hydrocarbon group, the number of carbon atoms of the hydrophobic group possessed by the interface active agent is preferably 9 or more, more preferably 13 or more, and further preferably 16 or more. As the upper limit of the number of carbon atoms of the hydrophobic group, it is preferably 20 or less, more preferably 18 or less.

[0162] The number of carbon atoms of the interface active agent as a whole is preferably 16 to 100.

[0163] As the nonionic surfactant, for example, an ester type nonionic surfactant, an ether type nonionic surfactant, an ester ether type nonionic surfactant, and an alkanolamine type nonionic surfactant can be mentioned, and an ether type nonionic surfactant is preferred.

[0164] As the nonionic surfactant, for example, polyethylene glycol, an alkyl polyglycoside (Triton BG-10 and Triton CG-110 surfactants manufactured by Dow Chemical Company), octylphenol ethoxylate (Triton X-114 manufactured by Dow Chemical Company), silane polyalkylene oxide (copolymer) (Y-17112-SGS sample manufactured by Momentive Performance Materials Inc.), nonylphenol ethoxylate (Tergitol NP-12 and Triton (registered trademark) X-102, X-100, X-45, X-15, BG-10, and CG-119 manufactured by Dow Chemical Company), Silwet (registered trademark) HS-312 manufactured by Momentive Performance Materials Inc., tristyrylphenol ethoxylate (MAKON TSP-20 manufactured by Stepan Company), polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, alkyl allyl formaldehyde condensation polyoxyethylene ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene ether of glycerol ester, polyoxyethylene ether of sorbitol ester, polyoxyethylene ether of sorbitol ester, polyethylene glycol fatty acid ester, glycerol ester, polyglycerol ester, sorbitol ester, propylene glycol ester, sucrose ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkyl amide, BRIJ (registered trademark) 56 (C 16 H 33 (OCH2CH2) 10 OH), BRIJ (registered trademark) 58 (C 16 H 33 (OCH2CH2) 20 OH), BRIJ (registered trademark) 35 (C 12 H 25 (OCH2CH2) 23alcohols (primary and secondary) ethoxylates, amine ethoxylates, glucosides, glucamides, polyethylene glycols, poly(ethylene glycol-co-propylene glycol), cetyl alcohol, stearyl alcohol, cetearyl alcohol (cetyl and stearyl alcohols), oleyl alcohol, octaethylene glycol monododecyl ether, pentaethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ether, decyl glucoside, lauryl glucoside, octyl glucoside, polyethylene glycol octyl phenol ether, nonoxynol-9, glycerol alkyl esters, glyceryl laurate, polyethylene glycol sorbitol alkyl esters, polysorbate esters, sorbitan alkyl esters, Span, cocamide MEA, cocamide DEA, dodecyl dimethyl amine oxide and block copolymers of polypropylene glycol, and mixtures thereof.

[0165] As anionic surfactants, for example, as hydrophilic groups (acid groups), phosphonic acid-based surfactants having a phosphono group, sulfonic acid-based surfactants having a sulfonic acid group, carboxylic acid-based surfactants having a carboxyl group, and sulfate-based surfactants having a sulfate group can be given.

[0166] As anionic surfactants, for example, the following can be given: alkylbenzenesulfonic acids such as dodecylbenzenesulfonic acid and ammonium dodecylbenzenesulfonate, and salts thereof; alkylnaphthalenesulfonic acids such as propylnaphthalenesulfonic acid and triisopropyl naphthalenesulfonic acid, and salts thereof; alkylphenyl ether disulfonic acids such as dodecylphenyl ether disulfonic acid and alkyl diphenyl ether sulfonic acid, and salts thereof; alkyl diphenyl ether disulfonic acids such as dodecyl diphenyl ether disulfonic acid and ammonium dodecyl diphenyl ether sulfonate, and salts thereof; phenol sulfonic acid-formalin concentrate and salts thereof; aryl phenol sulfonic acid-formalin concentrate and salts thereof; carboxylic acid salts such as decane carboxylic acid, N-acyl amino acid salt, and polyoxyethylene or polyoxypropylene alkyl ether carboxylic acid salt; acylated peptides; sulfonic acid salts; sulfuric acid ester salts such as sulfurized oil, alkyl sulfate, alkyl ether sulfate, polyoxyethylene or polyoxypropylene alkyl allyl ether sulfate, and alkyl amide sulfate; phosphate ester salts; alkyl phosphate; polyoxyethylene or polyoxypropylene alkyl allyl ether phosphate; ammonium lauryl sulfate; sodium lauryl sulfate (sodium dodecyl sulfate); sodium lauryl ether sulfate (SLES); sodium myreth sulfate; dioctyl sodium sulfosuccinate; octane sulfonate; perfluorooctane sulfonate (PFOS); perfluorobutane sulfonate; alkyl benzene sulfonate; alkyl aryl ether phosphoric acid ester; alkyl ether phosphoric acid ester; alkyl carboxylic acid ester; fatty acid salt (soap); sodium stearate; sodium lauroyl methyl amino acid; perfluorononanoate; perfluorooctanoate; and mixtures thereof.

[0167] As amphoteric surfactants, for example, the following can be given: carboxybetaine type amphoteric surfactants, sulfobetaine type amphoteric surfactants, amino carboxylate, imidazolinium betaine, lecithin, alkyl amine oxide, and mixtures thereof.

[0168] As the surfactant, for example, the compounds described in

[0092] to

[0096] of Japanese Patent Application Laid-Open No. 2015-158662,

[0045] to

[0046] of Japanese Patent Application Laid-Open No. 2012-151273, and

[0014] to

[0020] of Japanese Patent Application Laid-Open No. 2009-147389 can also be mentioned, and these are incorporated into the present specification.

[0169] The surfactant can be used alone or two or more kinds can be used.

[0170] In the case where the composition contains the surfactant, the content of the surfactant is preferably 0.001 to 8.0% by mass, more preferably 0.005 to 5.0% by mass, with respect to the total mass of the composition.

[0171] In the case where the composition contains the surfactant, the content of the surfactant is preferably 0.01 to 50.0% by mass, more preferably 0.1 to 45.0% by mass, with respect to the total solid content in the composition.

[0172] <Chelating agent>

[0173] The composition can contain a chelating agent.

[0174] The chelating agent is a compound having a function of chelating a metal contained in a residue such as a polishing particle in a semiconductor substrate. Among them, a compound having two or more functional groups (coordination bases) which coordinate and bond with a metal ion in one molecule is preferred.

[0175] Note that the compound contained in the citric acid and any one of the above-mentioned component C, the above-mentioned component D, and the later-described surfactant is not included in the chelating agent.

[0176] As the coordination base possessed by the chelating agent, for example, an acid group can be mentioned. As the acid group, for example, a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group can be mentioned.

[0177] The number of carbon atoms of the chelating agent is preferably 15 or less, more preferably 12 or less, and further preferably 8 or less. The lower limit is not particularly limited, and is preferably 2 or more.

[0178] The chelating agent can be used alone or two or more kinds can be used.

[0179] <pH adjuster>

[0180] The composition can contain a pH adjuster for adjusting and maintaining the pH of the composition. The composition can be adjusted to the range of the pH described later according to the pH adjuster.

[0181] As the pH adjuster, an alkaline compound and an acidic compound other than the above-mentioned components can be mentioned.

[0182] As the basic compound, a basic inorganic compound can be mentioned.

[0183] As the basic inorganic compound, for example, an alkali metal hydroxide and an alkaline earth metal hydroxide can be mentioned. In addition, the above-mentioned component C and preservative are not included in the basic inorganic compound.

[0184] As the alkali metal hydroxide, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide can be mentioned. As the alkaline earth metal hydroxide, for example, calcium hydroxide, strontium hydroxide, and barium hydroxide can be mentioned.

[0185] The composition can include, as the basic compound, at least one selected from a nitro group, a nitroso group, an oxime, a ketoxime, an aldoxime, a nitrone, a lactam, an isocyanide, a hydrazide such as carbohydrazide, and urea, in addition to the above-mentioned compound.

[0186] Further, the component C and the preservative included in the composition can function as a basic compound that adjusts the pH of the composition.

[0187] As the acidic compound, for example, an inorganic acid and an organic acid can be mentioned.

[0188] As the inorganic acid, for example, hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, boric acid, and hexafluorophosphoric acid can be mentioned.

[0189] As the inorganic acid, hydrochloric acid or sulfuric acid is preferable.

[0190] The organic acid is an organic compound having an acidic functional group and showing acidity (pH less than 7.0) in an aqueous solution. In addition, in the present specification, sorbic acid, citric acid, component D, the above-mentioned anionic surfactant, and the above-mentioned chelating agent are not included in the organic acid.

[0191] As the acidic functional group possessed by the organic acid, for example, a carboxyl group and a sulfonic acid group can be mentioned. As the organic acid, a carboxylic acid having at least one carboxyl group and a sulfonic acid having at least one sulfonic acid group can be mentioned.

[0192] As the carboxylic acid, for example, a lower (carbon number 1 to 4) aliphatic monobasic carboxylic acid such as formic acid, acetic acid, propionic acid, and butyric acid can be mentioned.

[0193] As the sulfonic acid, for example, a lower (carbon number 1 to 4) aliphatic monobasic sulfonic acid such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, 2-hydroxyethanesulfonic acid, and 3-hydroxypropanesulfonic acid can be mentioned.

[0194] Further, the acidic component included in the composition can function as an acidic compound that adjusts the pH of the composition.

[0195] The pH adjuster can be used singly or in combination of two or more.

[0196] When the composition contains a pH adjuster, the content thereof can be selected depending on the kind and amount of other ingredients and the pH of the composition targeted, but is preferably 0.03 to 10% by mass, more preferably 0.1 to 5% by mass, relative to the total mass of the composition.

[0197] <Additives>

[0198] The composition can contain other ingredients as additives.

[0199] As the other ingredients, for example, an oxidizing agent, a fluorine compound, and an organic solvent can be mentioned.

[0200] As the oxidizing agent, for example, a peroxide, a persulfide (e.g., monopersulfide and dipersulfide), and percarbonate, an acid thereof, and a salt thereof can be mentioned.

[0201] As the oxidizing agent, for example, a halogen oxide (iodic acid, metaperiodic acid, and orthoperiodic acid, and a salt thereof), perboric acid, perborate, cerium compound, and ferricyanide (potassium ferricyanide, etc.) can be mentioned.

[0202] When the composition contains an oxidizing agent, the content of the oxidizing agent is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, relative to the total mass of the composition.

[0203] When the composition contains an oxidizing agent, the content of the oxidizing agent is preferably 0.1 to 50.0% by mass, more preferably 1.0 to 30.0% by mass, relative to the total solid content in the composition.

[0204] As the fluorine compound, for example, the compounds described in

[0013] to

[0015] of Japanese Patent Application Publication No. 2005-150236 can be mentioned, which are incorporated into the present specification.

[0205] As the organic solvent, a publicly known organic solvent can be used, and for example, a hydrophilic organic solvent such as an alcohol and a ketone can be mentioned. The organic solvent can be used singly or in combination of two or more.

[0206] The amounts of the fluorine compound and the organic solvent used can be appropriately set within a range not impairing the effects of the present application.

[0207] The content of each component in the composition described above can be measured by a known method such as a gas chromatography-mass spectrometry (GC-MS) method, a liquid chromatography-mass spectrometry (LC-MS) method, and an ion-exchange chromatography (IC) method.

[0208] 〔Physical properties of the composition〕

[0209] <ph>

[0210] The pH of the composition of the present application is 4.0 to 9.0 at 25°C.

[0211] The pH of the composition is preferably 5.0 to 7.0, more preferably 5.5 to 6.5.

[0212] The pH of the composition can be measured using a well-known pH meter (e.g., "WM-32EP" manufactured by DKK-TOA CORPORATION, etc.) according to the method of JIS Z8802-1984. The measurement temperature of the pH is 25°C.

[0213] The pH of the composition can be adjusted by the content of sorbic acid, citric acid, component C, component D, a preservative, a surfactant, a chelating agent, and the like having a pH adjusting agent function, and the above-mentioned pH adjusting agent.

[0214] <Conductivity>

[0215] The conductivity of the composition is not particularly limited, and is preferably 0.01 to 30 mS / cm, more preferably 0.1 to 20 mS / cm, and further preferably 5 to 17 mS / cm.

[0216] The conductivity of the composition is the conductivity (mS / cm) at 25°C measured using a conductivity meter (e.g., "WM-32EP" manufactured by DKK-TOA CORPORATION, etc.).

[0217] The conductivity of the composition can be adjusted by the content of the above-mentioned sorbic acid, citric acid, and component C, and the like which can be ionized in the composition.

[0218] <Metal Content>

[0219] In the composition, the content (measured as ion concentration) of each metal (metal elements of Fe, Co, Na, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag) contained as an impurity in the liquid is preferably 5 mass ppm or less, more preferably 1 mass ppm or less, with respect to the total mass of the composition. In the production of the most advanced semiconductor elements, since it can be assumed that a composition with higher purity is required, the metal content is further preferably a value lower than 1 mass ppm, i.e., in the mass ppb order or less, and is particularly preferably 100 mass ppb or less, and most preferably less than 10 mass ppb. As a lower limit, 0 is preferable.

[0220] As a method of reducing the metal content, for example, purification treatment such as distillation and filtration using an ion exchange resin or a filter can be performed at the stage of the raw material used when the composition is produced or at the stage after the production of the composition.

[0221] As another method for reducing the metal content, a container that will be described later, which has a small amount of impurities eluted, can be used as a container for storing the raw material or the manufactured composition. Also, in manufacturing the composition, lining the inner wall of a pipe with a fluororesin can be mentioned as a method for reducing the elution of metal components from the pipe and the like.

[0222] <Content of Phosphate Ion>

[0223] In the composition, the content of the phosphate ion is preferably 200 mass ppm or less, more preferably 50 mass ppm or less, and further preferably 20 mass ppm or less, relative to the total mass of the composition, from the viewpoint of balancing the residue removal property, the corrosion resistance, and the wiring electrical property. As a lower limit, it can be 0 mass ppm, and more preferably 0.1 mass ppm or more, relative to the total mass of the composition.

[0224] In addition, the content of the above-described phosphate ion indicates the total content of dihydrogen phosphate ion (H2PO4 - ), hydrogen phosphate ion (HPO4 2- ), phosphate ion (PO4 3- ), hydrogen phosphite ion (H2PO3 - ), and phosphite ion (HPO3 2- ).

[0225] As a method for reducing the metal content, for example, purification treatment such as distillation and filtration using an ion exchange resin can be performed at the stage of the raw material used in manufacturing the composition or at the stage after the manufacturing of the composition.

[0226] <Coarse Particles>

[0227] The composition can contain coarse particles, but the content thereof is preferably low.

[0228] The coarse particles refer to particles having a diameter (particle size) of 0.1 μm or more when the shape of the particles is regarded as a sphere.

[0229] As the content of the coarse particles in the composition, the content of the particles having a particle size of 0.1 μm or more is preferably 10,000 or less, and more preferably 5,000 or less, per 1 mL of the composition. The lower limit is preferably 0 or more, and more preferably 0.01 or more, per 1 mL of the composition.

[0230] The coarse particles contained in the composition are particles such as dust, dirt, organic solid substances, and inorganic solid substances contained as impurities in the raw material, and particles such as dust, dirt, organic solid substances, and inorganic solid substances brought in as contaminants in the preparation of the composition, and correspond to substances that are not dissolved in the composition and exist as particles in the end.

[0231] The content of the coarse particles present in the composition can be measured in liquid phase using a commercially available measuring device used in a light scattering type particle measuring method using laser light as a light source.

[0232] As a method for removing the coarse particles, for example, purification treatment such as sieving described later can be mentioned.

[0233] The preferred composition does not substantially contain abrasive particles depending on the use thereof.

[0234] The abrasive particle refers to a fine particle composed of a material such as silica and alumina, which is contained in a polishing liquid used in a chemical mechanical polishing treatment described later.

[0235] In the present specification, as the abrasive particle, for example, a particle having a diameter (particle size) of 10 nm or more when the shape of the abrasive particle is regarded as a sphere can be mentioned, and the composition does not substantially contain the abrasive particle means that the content of the abrasive particle having a particle size of 10 nm or more contained in the composition is 1 mass% or less per composition.

[0236] The measurement of the content of the abrasive particle present in the composition and the removal of the abrasive particle can be performed according to the measurement method of the content of the coarse particle and the removal method of the coarse particle, respectively.

[0237] [Manufacture of the composition]

[0238] The composition can be manufactured by a known method. Hereinafter, the manufacturing method of the composition will be described in detail.

[0239] <Preparation step>

[0240] As the preparation method of the composition, for example, the composition can be manufactured by mixing the above-described components.

[0241] The order and / or timing of mixing the above-described components are not particularly limited, and for example, a method in which components A to D and optional components are sequentially added to a container in which purified pure water is charged and mixed by stirring can be mentioned. In particular, from the viewpoint of easily preparing a composition having a desired composition, it is preferred that, under stirring conditions, component B, component D, and optional components are sequentially added to a container in which purified pure water is charged, and then, after component C and a pH adjuster are added as necessary to adjust the pH of the mixed solution, component A is added and mixed. In addition, when water and the components are added to the container, they can be added at once or in multiple times.

[0242] As the stirring device and stirring method used for the preparation of the composition, a publicly known device can be used as a stirrer or a disperser. As the stirrer, for example, an industrial mixer, a portable stirrer, a mechanical stirrer, and an electromagnetic stirrer can be given. As the disperser, for example, an industrial disperser, a homogenizer, an ultrasonic disperser, and a bead mill can be given.

[0243] As for the mixing of the components in the preparation process of the composition and the purification treatment described later, and the storage of the manufactured composition, it is preferable to be performed at 40°C or lower, and more preferably at 30°C or lower. Also, as a lower limit, it is preferable to be 5°C or higher, and more preferably 10°C or higher. By performing the preparation, treatment, and / or storage of the composition in the above temperature range, the performance can be maintained stably for a long period of time.

[0244] < Purification Treatment >

[0245] It is preferable to perform the purification treatment in advance on one or more of the raw materials used for the preparation of the composition. As the purification treatment, for example, publicly known methods such as distillation, ion exchange, and filtration (sifting) can be given.

[0246] As for the degree of purification, it is preferable to purify to a purity of 99 mass% or more of the raw material, and more preferably to a purity of 99.9 mass% or more of the raw material. As an upper limit, it is preferable to be 99.9999 mass% or less.

[0247] As the method of the purification treatment, for example, a method of passing the raw material through an ion exchange resin or a RO membrane (Reverse Osmosis Membrane), distillation of the raw material, and sifting described later can be given.

[0248] As the purification treatment, a plurality of the above-mentioned purification methods can be combined and performed. For example, after one purification of passing the raw material through a RO membrane, two purifications of passing through a purification device composed of a cation exchange resin, an anion exchange resin, or a mixed bed type ion exchange resin can be performed.

[0249] Also, the purification treatment can be performed a plurality of times.

[0250] (Sifting)

[0251] As the filter used for the sifting, a publicly known filter for filtration can be given. For example, a filter composed of a fluororesin such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), a polyamide-based resin such as nylon, and a polyolefin resin (including high density or ultrahigh molecular weight) such as polyethylene and polypropylene (PP) can be given.

[0252] Among these materials, filters of a material selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesin (including PTFE and PFA), and polyamide-based resin (including nylon) are preferable, and filters of fluororesin are more preferable. By using a filter formed of these materials for the filtration of the raw material, polar foreign matter that is likely to be a cause of defects can be effectively removed.

[0253] The critical surface tension of the filter is preferably 70 to 95 mN / m, and more preferably 75 to 85 mN / m. In addition, the value of the critical surface tension of the filter is a nominal value of the manufacturer. By using a filter having a critical surface tension in the above range, polar foreign matter that is likely to be a cause of defects can be effectively removed.

[0254] The pore diameter of the filter is preferably 2 to 20 nm, and more preferably 2 to 15 nm. By being in this range, clogging of the filter can be suppressed, and fine foreign matter such as impurities and agglomerates contained in the raw material can be reliably removed. The pore diameter herein can be referred to the nominal value of the filter manufacturer.

[0255] The screening can be performed only once, or two or more times. In the case where the screening is performed two or more times, the filters used can be the same or different.

[0256] In addition, the temperature of the screening is preferably room temperature (25°C) or lower, more preferably 23°C or lower, and further preferably 20°C or lower. In addition, it is preferably 0°C or higher, more preferably 5°C or higher, and further preferably 10°C or higher. By performing the screening in the above temperature range, the amount of particulate foreign matter and impurities dissolved in the raw material can be reduced, and the foreign matter and impurities can be effectively removed.

[0257] <Container>

[0258] As long as problems such as corrosion do not occur, the composition (including the manner of diluting the liquid described later) can be stored, transported, and used by being filled in an arbitrary container.

[0259] As a container for a semiconductor, a container in which the cleanliness inside the container is high and the elution of impurities from the inner wall of the accommodation portion of the container into each liquid is suppressed is preferable. As such a container, various containers commercially available as containers for semiconductor compositions can be given, and for example, "Clean Bottle" series manufactured by AICELLO CORPORATION and "Pure Bottle" manufactured by KODAMA PLASTICS Co., Ltd. can be given, and are not limited to these.

[0260] Also, as the container that houses the composition, it is preferable that the inner wall or the like of the housing portion thereof, which is in contact with each liquid, be a container formed of a fluororesin (perfluororesin) or a metal subjected to rust-preventive and metal elution-preventive treatment.

[0261] The inner wall of the container is preferably formed of a resin selected from one or more of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a different resin therefrom or a metal such as stainless steel, Hastelloy, Inconel, and Monel, which is subjected to rust-preventive and metal elution-preventive treatment.

[0262] As the different resin, a fluororesin (perfluororesin) is preferable. In this way, by using a container having a fluororesin inner wall, as compared with a container having a polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin inner wall, it is possible to suppress the occurrence of adverse conditions such as elution of oligomers of ethylene or propylene.

[0263] As such a container having a fluororesin inner wall, for example, there can be mentioned FluoroPure PFA Composite Cartridge manufactured by Entegris Inc. Also, it is possible to use the container described in the fourth page of Japanese Patent Application Laid-Open No. 3-502677, the third page of International Publication No. 2004 / 016526, and the ninth and sixteenth pages of International Publication No. 99 / 046309, and the like.

[0264] Also, the inner wall of the container can preferably use, in addition to the fluororesin described above, quartz and a metal material subjected to electrolytic polishing (i.e., a metal material subjected to electrolytic polishing).

[0265] The metal material used in the production of the metal material subjected to electrolytic polishing described above contains at least one selected from chromium and nickel, and preferably has a total content of chromium and nickel of more than 25% by mass with respect to the total mass of the metal material, and for example, there can be mentioned stainless steel and nickel-chromium alloy.

[0266] The total content of chromium and nickel in the metal material is more preferably 30% by mass or more with respect to the total mass of the metal material. As an upper limit, it is preferably 90% by mass or less.

[0267] As the method of electrolytically polishing the metal material, it is possible to use a publicly known method. For example, it is possible to use the method described in the paragraphs

[0011] to

[0014] of Japanese Patent Application Laid-Open No. 2015-227501 and the paragraphs

[0036] to

[0042] of Japanese Patent Application Laid-Open No. 2008-264929, and the like.

[0268] These containers are preferably washed inside before filling with the composition. As the liquid used for the washing, it is preferable that the amount of metal impurities in the liquid be reduced. The composition can also be filled into a container such as a gallon bottle or a coating bottle after production and transported and stored.

[0269] It is also possible to replace the inside of the container with a non-reactive gas (nitrogen or argon, etc.) having a purity of 99.99995% or more for the purpose of preventing changes in the components of the composition in storage. In particular, a gas having a low water content is preferred. Also, the temperature during transportation and storage can be room temperature, but the temperature can also be controlled to be in the range of -20°C to 20°C in order to prevent deterioration.

[0270] (clean room)

[0271] The operations, including the production of the composition, the opening of the container, and the filling of the composition, the analysis, and the measurement are all preferably performed in a clean room. The clean room preferably satisfies the 14644-1 clean room standard. Of these, more preferably, any one of ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, ISO Class 4, ISO Class 5, and ISO Class 6 is satisfied, further preferably, any one of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4 is satisfied, particularly preferably, ISO Class 1 or ISO Class 2 is satisfied, most preferably, ISO Class 1 is satisfied.

[0272] <concentration step>

[0273] The above composition can be provided in the cleaning of a semiconductor substrate as a diluted composition (dilution) after a dilution step in which it is diluted with a diluent such as water.

[0274] In addition, as long as the requirements of the present application are satisfied, the dilution is also one of the compositions of the present application.

[0275] As for the dilution rate of the composition in the dilution step, as long as it is appropriately adjusted according to the kind and content of each component, and the applicable object such as a semiconductor substrate, the ratio of the dilution liquid to the composition before dilution (dilution ratio) is, for example, 10 to 1000 times, preferably 30 to 400 times, more preferably 50 to 300 times, in terms of mass ratio or volume ratio (volume ratio at 25°C).

[0276] In particular, in the case of being used as various cleaning liquids, it is preferred that the composition be diluted by 30 times or more, more preferably 50 times or more, further preferably 100 times or more.

[0277] Also, the preferred content of each component (excluding water) with respect to the total mass of the dilution liquid is, for example, an amount obtained by dividing the amount described as the preferred content of each component with respect to the total mass of the composition (composition before dilution) by the dilution ratio (for example, 100) in the above range.

[0278] The preferred range of the pH of the dilution liquid is the same as the preferred range of the pH of the above composition, respectively.

[0279] The conductivity of the diluent is not particularly limited, and is preferably 0.1 to 1.0 mS / cm, more preferably 0.2 to 0.6 mS / cm.

[0280] The method of measuring and adjusting the conductivity of the diluent is the same as the method of measuring and adjusting the composition. The conductivity of the diluent can also be adjusted according to the dilution rate.

[0281] The specific method of the dilution process of the dilution composition is the same as the method of preparing the composition described above. The stirring device and method used in the dilution process can also be the same as the known stirring devices listed in the method of preparing the composition described above.

[0282] It is preferable to purify the water used in the dilution process in advance. Furthermore, it is preferable to purify the diluent obtained by the dilution process.

[0283] As the purification process, the ion component reduction process using ion exchange resin or RO membrane, and the removal of foreign matter using sieving, which are described above as the purification process for the composition, can be cited, and it is preferable to perform any one of these processes.

[0284] [USES OF THE COMPOSITION]

[0285] Next, the uses of the composition will be described.

[0286] The composition can be used as a composition used in the manufacturing process of a semiconductor element. That is, the composition can also be used in any process for manufacturing a semiconductor element.

[0287] As the uses of the composition, for example, a cleaning solution for cleaning a semiconductor substrate (semiconductor substrate cleaning solution), a cleaning solution used in the cleaning of a member used in the manufacturing of a semiconductor substrate (member cleaning solution), and a treatment solution used for removing a target object such as a metal-containing substance on a semiconductor substrate (semiconductor substrate treatment solution) can be cited.

[0288] As the semiconductor substrate cleaning solution described above, there is no particular limitation as long as it is a cleaning solution suitable for a semiconductor substrate and used with the purpose of removing metal impurities or fine particles and the like adhering to a semiconductor substrate, and for example, a semiconductor substrate cleaning solution for which a chemical mechanical polishing (CMP: Chemical Mechanical Polishing) process is performed (pCMP cleaning solution), a cleaning solution for polishing cleaning of a semiconductor substrate for which a CMP process is performed (polishing cleaning cleaning solution), a cleaning solution for cleaning of a semiconductor substrate for which backside grinding is performed, a semiconductor substrate cleaning solution for which an etching process is performed (post-etching residue cleaning solution), and a cleaning solution for a semiconductor substrate to which a solder is used to solder an electronic part or a semiconductor substrate on which a solder bump is formed.

[0289] As the cleaning solution for the above-mentioned components, for example, a cleaning solution for cleaning an object such as a component which contacts a semiconductor substrate in a manufacturing process of a semiconductor element and a component which contacts a processing solution before being applied to a semiconductor substrate can be mentioned. More specifically, a cleaning solution for cleaning a brush for cleaning a semiconductor substrate subjected to CMP processing (a brush cleaning solution), a cleaning solution for a polishing pad for CMP processing of a semiconductor substrate (a pad cleaning solution), a cleaning solution for cleaning a resin product such as a container for storing a semiconductor substrate, a cleaning solution for cleaning a glass substrate, and a cleaning solution for mechanical cleaning can be mentioned.

[0290] As the processing solution for a semiconductor substrate, an etching solution for dissolving and removing a metal-containing substance on a semiconductor substrate, a pre-wetting solution for improving the coatability of a photosensitive or radiation-sensitive composition before a process of forming a resist film using the photosensitive or radiation-sensitive composition, a rinsing solution for rinsing a substance adhered to a semiconductor substrate, and the like can be mentioned.

[0291] As to the composition, for example, in the case where the composition is applied to an object such as a semiconductor substrate, a cleaning brush, and a polishing pad mentioned in the above-mentioned examples of the uses after a prescribed period from the manufacture, the effect of excellent removal performance of residues is exerted.

[0292] In the above-mentioned uses, the composition can be used for only one use, or can be used for two or more uses.

[0293] As a method of using the composition for the above-mentioned uses, for example, a method of contacting an object of the above-mentioned uses with the composition can be mentioned. Thereby, one or more of cleaning the object (removal of residues on the object, and the like) or removing a metal-containing substance contained in the object can be performed.

[0294] More specifically, a cleaning method using the composition to remove residues adhered to an object (for example, a method of cleaning a semiconductor substrate subjected to CMP) can be mentioned. Further, an etching processing method using the composition to dissolve a metal-containing substance on an object for removal, a pre-wetting processing method of applying the composition to a semiconductor substrate before a process of forming a resist film using a photosensitive or radiation-sensitive composition, and a rinsing processing method of rinsing a semiconductor substrate using the composition can be mentioned.

[0295] [Semiconductor Substrate]

[0296] Hereinafter, a semiconductor substrate will be described.

[0297] In the following description, the structure of the semiconductor substrate is described typically by citing an example in which the composition is used in contact with the semiconductor substrate, but the manner in which the composition is applied is not limited to the following description, and as described above, the semiconductor substrate to which the member cleaned by the composition or the treatment liquid in contact with the member cleaned by the composition is applied can be the semiconductor substrate described in the following description.

[0298] As one of the objects to which the composition is applied, the semiconductor substrate can be cited, for example, a semiconductor substrate having a metal-containing substance on the semiconductor substrate.

[0299] In the present description, "on the semiconductor substrate" includes, for example, the front surface and the back surface, the side surface, and the inside of the groove, and the like of the semiconductor substrate. Also, the metal-containing substance on the semiconductor substrate includes not only a case where the metal-containing substance is present directly on the surface of the semiconductor substrate, but also a case where the metal-containing substance is present on the semiconductor substrate through another layer.

[0300] The semiconductor substrate can have two or more metal-containing substances.

[0301] The metal-containing substance can be a substance containing metal (metal atom).

[0302] As the metal contained in the metal-containing substance, for example, at least one metal M selected from Cu (copper), Al (aluminum), Ru (ruthenium), Co (cobalt), W (tungsten), Ti (titanium), Ta (tantalum), Cr (chromium), Hf (hafnium), Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium) can be cited.

[0303] As the metal-containing substance, for example, a single body of the metal M, an alloy containing the metal M, an oxide of the metal M, a nitride of the metal M, and an oxynitride of the metal M can be cited. The metal-containing substance can be a mixture containing two or more of these compounds. Also, the oxide, the nitride, and the oxynitride described above can be any one of a composite oxide, a composite nitride, and a composite oxynitride containing metal.

[0304] The content of the metal atom in the metal-containing substance is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more, with respect to the total mass of the metal-containing substance. As an upper limit, it is preferably 100% by mass or less.

[0305] The semiconductor substrate preferably has a metal M-containing substance containing the metal M, more preferably has a metal-containing substance of at least one metal selected from Cu, Al, W, Co, Ti, Ta, Ru, and Mo, further preferably has a metal-containing substance containing at least one metal selected from W, Co, Cu, Al, Ti, Ta, and Ru, and particularly preferably has a W-containing substance containing W.

[0306] As the semiconductor substrate, for example, a semiconductor substrate having a metal wiring film, a barrier metal, and an insulating film on the surface of a wafer constituting a substrate can be given.

[0307] As the wafer constituting a substrate, for example, a silicon (Si) wafer, a silicon carbide (SiC) wafer, a resin-based wafer containing silicon (glass epoxy resin wafer), and the like composed of a silicon-based material, a gallium phosphide (GaP) wafer, a gallium arsenide (GaAs) wafer, and an indium phosphide (InP) wafer can be given.

[0308] As the silicon wafer, for example, an n-type silicon wafer in which a 5-valent atom (for example, phosphorus (P), arsenic (As), antimony (Sb), and the like) is doped in a silicon wafer, and a p-type silicon wafer in which a 3-valent atom (for example, boron (B) and gallium (Ga), and the like) is doped in a silicon wafer can be given. As the silicon of the silicon wafer, for example, amorphous silicon, single-crystal silicon, polycrystalline silicon, and poly-crystalline silicon can be given.

[0309] Among them, a wafer composed of a silicon wafer, a silicon carbide wafer, and a resin-based wafer containing silicon (glass epoxy resin wafer), and the like composed of a silicon-based material is preferable.

[0310] The semiconductor substrate can have an insulating film on the above-described wafer.

[0311] As the insulating film, for example, a silicon oxide film (for example, a silicon dioxide (SiO2) film, a tetraethyl orthosilicate (Si(OC2H5)4) film (TEOS film), and the like), a silicon nitride film (for example, silicon nitride (Si3N4) and silicon carbon nitride (SiNC), and the like), and a low dielectric constant (Low-k) film (for example, a carbon-doped silicon oxide (SiOC) film and a silicon carbide (SiC) film, and the like) can be given, and a low dielectric constant (Low-k) film is preferable.

[0312] The semiconductor substrate generally has a metal film containing a metal as a metal wiring film, a barrier metal, or another film.

[0313] As the metal film possessed by the semiconductor substrate, a metal film containing a metal M is preferable, a metal film containing at least one metal selected from Cu, Al, W, Co, Ti, Ta, Ru, and Mo is more preferable, and a metal film containing at least one metal selected from W, Co, Cu, and Ru is further preferable.

[0314] As the metal film containing at least one metal selected from W, Co, Cu, and Ru, for example, a film in which tungsten is the main component (W-containing film), a film in which cobalt is the main component (Co-containing film), a film in which copper is the main component (Cu-containing film), and a film in which ruthenium is the main component (Ru-containing film) can be given.

[0315] As the object of the composition, a semiconductor substrate having a W-containing film is preferable.

[0316] As the W-containing film, for example, a metal film composed of only tungsten (W metal film) and a metal film composed of tungsten and another metal (W alloy metal film) can be given. As the W alloy metal film, for example, a tungsten-titanium alloy metal film (WTi alloy metal film) and a tungsten-cobalt alloy metal film (WCo alloy metal film) can be given. The W-containing film is used, for example, for a barrier metal or a connecting portion between a via and a wiring.

[0317] As the Cu-containing film, for example, a wiring film composed of only copper (Cu wiring film) and a wiring film composed of copper and another metal (Cu alloy wiring film) can be given.

[0318] As the Co-containing film, for example, a metal film composed of only cobalt (Co metal film) and a metal film composed of cobalt and another metal (Co alloy metal film) can be given.

[0319] As the Ru-containing film, for example, a metal film composed of only ruthenium (Ru metal film) and a metal film composed of ruthenium and another metal (Ru alloy metal film) can be given. The Ru-containing film is generally used as a barrier metal.

[0320] As a method of forming the above-described metal wiring film, barrier metal, and insulating film on a wafer constituting a semiconductor substrate, there is no particular limitation as long as it is a method commonly used in the field.

[0321] As a method of forming the insulating film, for example, a method of forming a silicon oxide film by heat treating a wafer constituting a semiconductor substrate in the presence of oxygen, and then flowing a gas of silane and ammonia to form a silicon nitride film by a chemical vapor deposition (CVD) method can be given.

[0322] As a method of forming the W-containing film, Cu-containing film, Ru-containing film, and Co-containing film, for example, a method of forming a circuit on a wafer having the above-described insulating film by a known method using a resist or the like, and then forming a W-containing film, Cu-containing film, Ru-containing film, or Co-containing film by a method such as plating or a CVD method can be given.

[0323] <CMP processing>

[0324] The semiconductor substrate can be a semiconductor substrate on which a planarization treatment such as CMP processing is performed after the insulating film, barrier metal, and metal film are provided on the wafer.

[0325] The CMP treatment generally refers to a treatment of planarizing the surface of a semiconductor substrate by adhering a polishing pad to a circular polishing table (table), impregnating the surface of the adhered polishing pad with a polishing liquid containing polishing particles (polishing grains), pressing the surface of the semiconductor substrate having a metal film, a barrier metal, and an insulating film against the surface of the adhered polishing pad, rotating both the polishing table and the base in a state where a prescribed pressure (polishing pressure) is applied from the back surface thereof, and planarizing the surface of the semiconductor substrate based on the combined action of chemical action and mechanical friction of the components contained in the polishing liquid.

[0326] On the surface of the semiconductor substrate on which the CMP treatment is performed, there are sometimes impurities such as polishing grains (for example, silicon dioxide and aluminum oxide, etc.) used in the CMP treatment, the metal film being polished, and / or metal impurities (metal residues) from the barrier metal. Also, there are sometimes organic impurities from the polishing liquid used at the time of the CMP treatment. Since these impurities cause, for example, short-circuiting between wirings and deterioration of the electrical characteristics of the semiconductor substrate, the semiconductor substrate on which the CMP treatment is performed is provided to a cleaning treatment for removing these impurities from the surface.

[0327] As the semiconductor substrate on which the CMP treatment is performed, the substrate on which the CMP treatment is performed described in Precision Engineering Journal Vol. 84, No. 3, 2018 can be cited, but is not limited thereto.

[0328] A polishing liquid is used in the CMP treatment.

[0329] As the polishing liquid used in the CMP treatment, a known polishing liquid can be appropriately used depending on the kind of the semiconductor substrate, the composition of the polishing liquid, and the kind of the residue to be removed as an object.

[0330] As the polishing liquid, a polishing liquid containing iron ions and hydrogen peroxide or a polishing liquid containing chemically modified colloidal silica (for example, cationically modified and anionically modified, etc.) can be cited. Also, as the polishing liquid, a polishing liquid containing an iron complex described in Japanese Patent Application Publication No. 2020-068378, Japanese Patent Application Publication No. 2020-015899, and U.S. Patent No. 11043151 and a polishing liquid containing chemically modified colloidal silica described in Japanese Patent Application Publication No. 2021-082645 can be cited, and these contents are incorporated into the present specification.

[0331] The polishing pad that can be used in the CMP treatment is not particularly limited.

[0332] As a material constituting the polishing pad, for example, a thermoplastic resin or an elastomer and a polyurethane resin (more preferably, a foamed polyurethane resin) can be given. Also, a polishing pad including a nonwoven fabric impregnated with a polyurethane resin and a polishing pad having a suede-like surface can be used. From the viewpoint of higher hydrophilicity and easy impregnation of the polishing liquid, a polishing pad including a polyurethane resin is preferred.

[0333] As commercially available products, for example, a thermoplastic resin or an elastomer polishing pad is available from JSR Corporation, and a polyurethane resin polishing pad is available from NITTA DuPont Incorporated.

[0334] <Polishing cleaning>

[0335] The semiconductor substrate can be a semiconductor substrate subjected to polishing cleaning after the CMP treatment.

[0336] The polishing cleaning is a treatment for reducing impurities on the surface of the semiconductor substrate using a polishing pad. Specifically, the polishing surface of the semiconductor substrate subjected to the CMP treatment is pressed against the surface of the polishing pad adhered to a circular platform to bring the polishing pad into contact with the semiconductor substrate, while a cleaning liquid for polishing cleaning is supplied to the contact portion thereof, and the semiconductor substrate is slid against the polishing pad. By this treatment, the impurities on the surface of the semiconductor substrate subjected to the CMP treatment are removed by the frictional force based on the polishing pad and the chemical action based on the cleaning liquid.

[0337] As the cleaning liquid for polishing cleaning, a known cleaning liquid for polishing cleaning can be appropriately used depending on the kind of the semiconductor substrate and the kind and amount of the impurities to be removed. As the components included in the cleaning liquid for polishing cleaning, for example, a water-soluble polymer such as polyvinyl alcohol, water as a dispersion medium, and an acid such as nitric acid can be given.

[0338] As described later, the composition can be used as a cleaning liquid for polishing cleaning to perform polishing cleaning on a semiconductor substrate.

[0339] As for the polishing device and the polishing conditions and the like used in the polishing cleaning, a known device and conditions can be appropriately selected depending on the kind of the semiconductor substrate and the object to be removed and the like. As the polishing cleaning, for example, the treatment described in

[0085] to

[0088] of International Publication No. 2017 / 169539 can be given, which is incorporated into the present specification.

[0340] The following describes each use of the cleaning solution for a semiconductor substrate (preferably, a semiconductor substrate subjected to CMP treatment), the cleaning solution for cleaning a semiconductor substrate subjected to CMP treatment, the cleaning solution for a brush used in cleaning a semiconductor substrate subjected to CMP treatment, the cleaning solution for a polishing pad used in CMP treatment of a semiconductor substrate, and the cleaning solution for polishing cleaning of a semiconductor substrate subjected to CMP treatment.

[0341] The semiconductor substrate subjected to CMP treatment used in the above uses is not particularly limited as long as it is the above-described semiconductor substrate, and is preferably a semiconductor substrate containing tungsten, and more preferably a semiconductor substrate having a W-containing film.

[0342] [1st Use: Cleaning of Semiconductor Substrate Subjected to CMP Treatment]

[0343] The composition can be used as a cleaning solution for a semiconductor substrate in a cleaning method for a semiconductor substrate including a step of cleaning a semiconductor substrate subjected to CMP treatment (hereinafter, also referred to as "1st use"). That is, in a manufacturing method for a semiconductor element including a step of subjecting a semiconductor substrate to CMP treatment and a step of cleaning a semiconductor substrate subjected to CMP treatment, the composition can be used as a cleaning solution used in cleaning a semiconductor substrate subjected to CMP treatment.

[0344] The composition can be applied to a publicly known method for cleaning a semiconductor substrate subjected to CMP treatment.

[0345] The composition used in the 1st use can be a diluted solution obtained in the above-described dilution step, and preferably includes a step of applying the diluted solution to cleaning of a semiconductor substrate subjected to CMP treatment.

[0346] As the cleaning step of cleaning a semiconductor substrate subjected to CMP treatment, there is no particular limitation as long as it is a method of cleaning a semiconductor substrate by bringing the composition into contact with the semiconductor substrate, and a publicly known method in the field of manufacturing semiconductor elements, such as immersion in a scrub composition for removing residues and the like by physically contacting a cleaning member such as a brush with the surface of a semiconductor substrate while supplying the composition to the semiconductor substrate, rotation (dripping) for dripping the composition while rotating a semiconductor substrate, and spraying (spraying) for spraying the composition, can be appropriately employed.

[0347] In the cleaning of the semiconductor substrate, in order to further reduce the impurities remaining on the surface of the semiconductor substrate, and further enhance the cleaning ability of the composition, a mechanical agitation method can be used. As the mechanical agitation method, for example, a method in which the composition is circulated on the semiconductor substrate, a method in which the composition is flowed or sprayed on the semiconductor substrate, and a method in which the composition is agitated by ultrasonic waves or megasonic waves can be given.

[0348] The above cleaning process can be performed only once, or can be performed two or more times. In the case of cleaning two or more times, the same method can be repeated, or different methods can be combined.

[0349] As the cleaning method of the semiconductor substrate, either of a single wafer method and a batch method can be used.

[0350] The single wafer method generally refers to a method in which one semiconductor substrate is processed at a time, and the batch method generally refers to a method in which a plurality of semiconductor substrates are processed at a time.

[0351] The temperature of the composition used for cleaning the semiconductor substrate is not particularly limited as long as it is a temperature generally used in the field. The cleaning is generally performed at room temperature (about 25°C), but the temperature can be arbitrarily selected in order to improve the cleaning property and suppress damage to the components. As the temperature of the composition, it is preferably 10 to 60°C, more preferably 15 to 50°C.

[0352] The cleaning time in the cleaning of the semiconductor substrate can be appropriately changed depending on the kind and content of the components contained in the composition, and the like. In actual use, it is preferably 10 to 120 seconds, more preferably 20 to 90 seconds, and further preferably 30 to 60 seconds.

[0353] The supply amount (supply rate) of the composition in the cleaning process of the semiconductor substrate is preferably 50 to 5000 mL / minute, and more preferably 500 to 2000 mL / minute.

[0354] The preferred mode of the composition used in the first use is as described below.

[0355] The pH of the composition is 4.0 to 9.0, and is preferably within the preferred range of the pH of the above composition.

[0356] The composition used in the first use can be a diluted solution obtained in the above dilution process. The dilution ratio when the diluted solution is used is preferably 10 times or more, more preferably 30 times or more, further preferably 50 times or more, and particularly preferably 100 times or more, in terms of mass ratio. The upper limit is not particularly limited, and is preferably 1000 times or less, more preferably 400 times or less, and further preferably 300 times or less. The pH of the diluted solution is 4.0 to 9.0, and is preferably within the preferred range of the pH of the above diluted solution.

[0357] The ratio B / A of the content of citric acid to the content A of sorbic acid in the composition is preferably 1 to 50, preferably within the above-mentioned preferable range of the ratio B / A. Also, the ratio C / A of the content of component C to the content A of sorbic acid in the composition is preferably 10 to 500, preferably within the above-mentioned preferable range of the ratio C / A.

[0358] The electric conductivity of the composition at 25°C is preferably 0.05 mS / cm or more, more preferably 0.1 to 20 mS / cm.

[0359] A rinsing process for rinsing the semiconductor substrate with a solvent can be performed after the above-mentioned cleaning of the semiconductor substrate (hereinafter, also referred to as "rinsing process").

[0360] The rinsing process is preferably a process performed continuously after the cleaning process of the semiconductor substrate and performed for 5 to 300 seconds using a rinsing liquid. The rinsing process can be performed using the above-mentioned mechanical agitation method.

[0361] As the rinsing liquid, for example, water (preferably deionized (DI) water), methanol, ethanol, isopropanol, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate can be given. Also, an aqueous rinsing liquid having a pH of 8.0 or more (diluted aqueous ammonia or the like) can be used.

[0362] As the method of contacting the rinsing liquid with the semiconductor substrate, the method of contacting the above-mentioned composition with the semiconductor substrate can be similarly applied.

[0363] Also, a drying process for drying the semiconductor substrate can be performed after the above-mentioned rinsing process.

[0364] As the drying method, for example, a spin-drying method, a method of flowing a drying gas over the semiconductor substrate, a method of heating the substrate by a heating mechanism such as a hot plate and an infrared lamp, a Marangoni drying method, a Noguchi drying method, an IPA (isopropyl alcohol) drying method, and a method of arbitrarily combining them can be given.

[0365] [2nd use: cleaning of a cleaning brush]

[0366] The composition can be used as a cleaning liquid for a brush (hereinafter, also referred to as "2nd use") in a cleaning method of a cleaning brush including a process of cleaning a cleaning brush used for cleaning a semiconductor substrate subjected to CMP treatment.

[0367] As the cleaning object of the 2nd use, a cleaning brush, a publicly known brush used in a scrub cleaning that removes a residue or the like by physically contacting a surface on a semiconductor substrate can be given.

[0368] The shape of the cleaning brush is not particularly limited, and for example, a cylindrical roll-type brush, a pencil-type brush, or the like can be mentioned, with a roll-type brush being preferred. Also, the cleaning brush generally has a plurality of cylindrical protrusions protruding radially from the surface.

[0369] As the material constituting the cleaning brush, for example, a polymer resin having a hydroxyl group such as a polyvinyl alcohol (PVA) resin, a polyurethane resin, and a polyolefin resin can be mentioned. As the cleaning brush, a cleaning brush composed of a sponge-like material of the above polymer resin is preferred, and a cleaning brush composed of a sponge-like material of a PVA resin is more preferred.

[0370] As a commercially available product of the cleaning brush, for example, a brush manufactured by Entegris, Inc. (for example, model "PVP1ARXR1") and a brush (Bell Eater (registered trademark) A series) manufactured by AION Co., Ltd. can be mentioned.

[0371] As the cleaning method of the cleaning brush using the composition, an immersion type, a spray type, or the like described as the cleaning step of the semiconductor substrate in the above-mentioned first use, or a publicly known method performed in the field of semiconductor device manufacturing can be appropriately employed.

[0372] Also, as to the cleaning conditions including the temperature of the cleaning liquid and the cleaning time, they can be appropriately selected based on the material constituting the cleaning brush or the like, with reference to the cleaning conditions in the cleaning step of the semiconductor substrate and the publicly known cleaning method described above.

[0373] The preferred mode of the composition used in the second use is as described below.

[0374] The pH of the composition is preferably in the range of 4.0 to 9.0.

[0375] The composition used in the second use can be the diluted liquid obtained in the above-mentioned dilution step. The dilution ratio when the diluted liquid is used is preferably 10 to 100 times, more preferably 30 to 100 times, in terms of mass ratio. The pH of the diluted liquid is preferably in the range of 4.0 to 9.0.

[0376] The ratio B / A of the content of citric acid to the content A of sorbic acid in the composition is preferably 1 to 50, preferably in the range of the above-mentioned ratio B / A. Also, the ratio C / A of the content of the component C to the content A of sorbic acid in the composition is preferably 10 to 500, preferably in the range of the above-mentioned ratio C / A.

[0377] The electric conductivity of the composition at 25°C is preferably 0.05 mS / cm or more, more preferably 0.1 to 10 mS / cm.

[0378] 〔3rd Use: Cleaning of Polishing Pad〕

[0379] The composition can be used as a cleaning solution for a polishing pad (hereinafter, also referred to as "the third use") in a cleaning method of a polishing pad including a process of cleaning a polishing pad used for CMP processing of a semiconductor substrate.

[0380] The polishing pad as the object to be cleaned in the third use is not particularly limited as long as it is a known polishing pad used in CMP processing of a semiconductor substrate, and the polishing pad described in the above-mentioned <CMP processing> can be given. Among them, a polishing pad containing a polyurethane resin is preferred.

[0381] As the cleaning method of the polishing pad, a known method performed in the field of semiconductor device manufacturing, such as immersion and spraying, described in the cleaning process of the semiconductor substrate in the above-mentioned first use can be appropriately adopted.

[0382] Also, the cleaning conditions including the temperature of the cleaning solution and the cleaning time can be appropriately selected based on the constituent material of the polishing pad and the like, and by referring to the cleaning conditions in the cleaning process of the semiconductor substrate and the known cleaning method described above.

[0383] The preferred mode of the composition used in the third use is as described below.

[0384] The pH of the composition is 4.0 to 9.0, preferably in the preferred range of the pH of the above-mentioned composition.

[0385] The composition used in the third use can be a diluted solution obtained in the above-mentioned dilution process. The dilution ratio when the diluted solution is used is preferably 10 to 100 times, more preferably 30 to 100 times, and further preferably 50 to 100 times, in terms of mass ratio. The pH of the diluted solution is 4.0 to 9.0, preferably in the preferred range of the pH of the above-mentioned diluted solution.

[0386] The ratio B / A of the content of citric acid to the content A of sorbic acid in the composition is preferably 1 to 50, preferably in the preferred range of the ratio B / A described above. Also, the ratio C / A of the content of component C to the content A of sorbic acid in the composition is preferably 10 to 500, preferably in the preferred range of the ratio C / A described above.

[0387] The electric conductivity of the composition at 25°C is preferably 0.05 mS / cm or more, and more preferably 0.1 to 10 mS / cm.

[0388] 〔Fourth use: polishing cleaning〕

[0389] In a cleaning method of a semiconductor substrate including a polishing cleaning step of bringing a polishing pad into contact with a surface of a semiconductor substrate subjected to CMP treatment to clean the surface of the semiconductor substrate, the composition can be used as a cleaning solution for polishing cleaning (hereinafter, also referred to as "4th use").

[0390] The specific method of polishing cleaning for the 4th use is as described above in <Polishing Cleaning>. Also, the polishing pad used in polishing cleaning for the 4th use is as described above in <CMP Treatment>.

[0391] The preferred mode of the composition used in the 4th use is as described below.

[0392] The pH of the composition is preferably in the range of 4.0 to 9.0.

[0393] The composition used in the 4th use can be the diluted solution obtained in the dilution step described above. The dilution factor when the diluted solution is used is preferably 10 to 100 times, more preferably 30 to 100 times, and further more preferably 50 to 100 times, in terms of mass ratio. The pH of the diluted solution is preferably in the range of 4.0 to 9.0.

[0394] The ratio B / A of the content of citric acid to the content A of sorbic acid in the composition is preferably 1 to 50, and preferably in the range of the preferred ratio B / A described above. Also, the ratio C / A of the content of component C to the content A of sorbic acid in the composition is preferably 10 to 500, and preferably in the range of the preferred ratio C / A described above.

[0395] The electric conductivity of the composition at 25°C is preferably 0.05 mS / cm or more, and more preferably 0.2 to 20 mS / cm.

[0396] The composition used in the 4th use preferably substantially does not contain abrasive grains.

[0397] [Other uses]

[0398] The composition can also be used in any of the uses other than cleaning of a semiconductor substrate subjected to CMP treatment, cleaning of a cleaning brush used in cleaning of a semiconductor substrate subjected to CMP treatment, cleaning of a polishing pad used in CMP treatment of a semiconductor substrate, and polishing cleaning of a semiconductor substrate subjected to CMP treatment.

[0399] [Cleaning of a semiconductor substrate subjected to backgrinding]

[0400] It is known that a technique of reducing the thickness of a wafer by grinding the surface opposite to the circuit formation surface of a semiconductor substrate (backgrinding) is used for the purpose of miniaturization and thinning of semiconductor elements.

[0401] The composition can be used as a cleaning solution for cleaning a semiconductor substrate subjected to backgrinding. By using the composition, the residue generated by the backgrinding and the etching treatment accompanying the backgrinding can be removed.

[0402] <Cleaning of a semiconductor substrate subjected to etching treatment>

[0403] In a manufacturing process of a semiconductor element, when a resist pattern is used as a mask and a metal layer and / or an insulating layer of a semiconductor substrate are etched by plasma etching, residue from the resist, the metal layer and the insulating layer is generated on the semiconductor substrate. Also, when an unnecessary resist pattern is removed by plasma ashing, residue from the ashed resist is generated on the semiconductor substrate.

[0404] The composition can be used as a cleaning solution for cleaning a semiconductor substrate subjected to etching treatment. By using the composition, the above-mentioned etching residue and / or ashing residue generated on the semiconductor substrate subjected to the etching treatment can be removed.

[0405] <Cleaning of solder residue on a semiconductor substrate>

[0406] When an electronic component is mounted on a semiconductor substrate by soldering, an oxide that hinders the connection of a metal such as an electrode or a wiring with a solder metal is removed, and a soldering flux (accelerator) that promotes the connection is used. Thus, in a substrate on which an electronic component is soldered using a soldering flux and / or a substrate on which a solder bump for soldering an electronic component is formed using a soldering flux, etc., residue from the soldering flux is sometimes left.

[0407] The composition can be used as a cleaning solution for cleaning a semiconductor substrate on which an electronic component is soldered using a soldering flux or a semiconductor substrate on which a solder bump is formed using a soldering flux. By using the composition, residue from the soldering flux left on the above-mentioned semiconductor substrate can be removed.

[0408] <Cleaning of a semiconductor substrate subjected to etching treatment>

[0409] In a manufacturing process of a semiconductor element, when a resist pattern is used as a mask and a metal layer and / or an insulating layer of a semiconductor substrate are etched by plasma etching, residue from the resist, the metal layer and the insulating layer is generated on the semiconductor substrate. Also, when an unnecessary resist pattern is removed by plasma ashing, residue from the ashed resist is generated on the semiconductor substrate.

[0410] The composition can be used as a cleaning liquid in a cleaning step of cleaning a semiconductor substrate subjected to an etching treatment. By using the composition, the above-described etching residue and / or incineration residue generated on a semiconductor substrate subjected to an etching treatment can be removed.

[0411] <Cleaning of Semiconductor Substrate Subjected to Bonding Treatment>

[0412] In a manufacturing process of a semiconductor element, a semiconductor wafer manufactured by dicing (cutting) a wafer into a prescribed size is individually picked up while holding a cut film and is sent to a next bonding step. In the dicing, a cutting chip of the wafer and a cutting chip of the cut film and the like foreign matter adhere to the surface of the semiconductor wafer. In particular, in a bonding step such as flip chip bonding in which a terminal provided on the surface of the semiconductor wafer is connected to a substrate or direct bonding in which another semiconductor wafer is directly bonded to the semiconductor wafer, it is known that the bonding quality is sometimes deteriorated by a fine foreign matter of several μm or less, and a process of removing the foreign matter from the semiconductor wafer supplied to the bonding step is performed at the time of cleaning.

[0413] The present composition can be used as a cleaning liquid in a cleaning step of cleaning a semiconductor wafer before being supplied to a bonding step. By using the present composition, a cutting chip and the like foreign matter generated in a dicing step before the bonding step can be removed from the semiconductor wafer.

[0414] <Cleaning of Resin Product>

[0415] The composition can be used for cleaning a resin product, particularly a resin container used for housing and transporting a semiconductor substrate and the like in a manufacturing process of a semiconductor element.

[0416] In order to prevent invasion of a fine particle and prevent chemical contamination when a semiconductor substrate is housed and transported, a container for housing a semiconductor substrate is used. As such a container, for example, a FOSB (Front Opening Shipping Box) used when a wafer is shipped to a semiconductor element manufacturer and a FOUP (Front Opening Unified Pod) and a SMIF (Standard Mechanical Interface) in which a wafer is accommodated to be transported between steps of wafer processing can be cited. Here, when an operation of housing and taking out a semiconductor substrate in the container is repeatedly performed a plurality of times, a metal impurity is sometimes generated by contact of the semiconductor substrate with the inside of the container. Also, the inside of the container is sometimes contaminated by a residue generated in a manufacturing process of a semiconductor element and remaining on the semiconductor substrate. In order to prevent the metal impurity and the residue from adhering to the semiconductor substrate, the inside of the container is cleaned.

[0417] By using the composition to clean the above-mentioned container, the above-mentioned etching residue and / or incineration residue generated on a semiconductor substrate on which etching treatment is performed can be removed.

[0418] <Cleaning of glass substrate>

[0419] The composition can be used as a cleaning solution for cleaning a glass substrate, particularly, a glass substrate for a liquid crystal display, a plasma display, an organic electroluminescence (EL) display, a touch panel, and the like, a flat panel display, and a glass substrate for a hard disk. By using the composition, a residue such as a metal impurity remaining on the glass substrate can be removed.

[0420] <Etching treatment>

[0421] The composition can be used for etching treatment for removing a metal film on a semiconductor substrate. As the etching treatment, for example, a method of dissolving and removing a metal-containing substance on an object by bringing the composition into contact with the semiconductor substrate can be mentioned. The method of bringing the composition into contact with the semiconductor substrate is not particularly limited, and the method described in the first use can be applied.

[0422] As a specific manner of the etching treatment, the description of

[0049] to

[0069] of International Publication No. 2019 / 138814 can be cited, and these contents are incorporated into the present specification.

[0423] The treatment performed using the composition according to the above-mentioned uses can be performed in combination before or after other processes performed in the production of a semiconductor element. During the performance of the above-mentioned treatment, the treatment can be combined with other processes, or the treatment can be combined between other processes.

[0424] As the other processes, for example, a formation process (layer formation, etching, CMP treatment, modification, and the like) of each structure such as a metal wiring, a gate structure, a source structure, a drain structure, an insulating layer, a ferromagnetic layer, and / or a non-magnetic layer, a formation process of a resist, an exposure process and a removal process, a heat treatment process, a cleaning process, and an inspection process, and the like can be mentioned.

[0425] The above-mentioned treatment can be performed at any stage in a back end of the line (BEOL), a middle of the line (MOL), and a front end of the line (FEOL).

[0426] Examples

[0427] The present application will be further described in detail based on examples below. The materials, amounts and ratios, etc. shown in the following examples can be appropriately changed as long as the purpose of the present application is not deviated. Therefore, the scope of the present application is not limited by the following examples.

[0428] In the following examples, the pH and conductivity of the compositions were measured using a portable conductivity / pH meter (manufactured by DKK-TOA CORPORATION, "WM-32EP"). The pH measurement was performed at 25°C according to JIS Z8802-1984.

[0429] In the production of the compositions of the examples and comparative examples, the operation of the container, preparation, filling, storage and analysis measurement of the composition were performed in a dust-free room satisfying a level of ISO Class 6 or less.

[0430] [Raw materials of the composition]

[0431] In order to produce the compositions, the following compounds were used. In addition, the various components used in the examples were components classified as semiconductor grade or high purity grade components equivalent thereto.

[0432] • Sorbic acid

[0433] • Citric acid

[0434] [Component C]

[0435] • Tris (tris(hydroxymethyl)aminomethane)

[0436] • MEA (monoethanolamine)

[0437] • Ammonia

[0438] • TMAH (tetramethylammonium hydroxide)

[0439] [Component D]

[0440] • HEDPO (1-hydroxyethylidene-1,1'-diphosphonic acid)

[0441] • NTPO (nitrilotri(methylene phosphonic acid))

[0442] • EDTPO (ethylenediaminetetra phosphonic acid)

[0443] • PBTCA (2-phosphonobutane-1,2,4-tricarboxylic acid)

[0444] • Phytic acid

[0445] As the pH adjuster, the above-described ingredient C was used, and as the water, commercially available ultrapure water (manufactured by FUJIFILM Wako Pure Chemical Corporation) was used in the production of the composition in this example.

[0446] [Example 1]

[0447] [Preparation Example]

[0448] The composition 101 was produced according to the following method.

[0449] After the addition of citric acid and 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO) to ultrapure water with stirring, respectively, trimethylolaminomethane (Tris) was added, followed by the addition of citric acid. In addition, each ingredient was added so as to become the blending amount described in Table 1. The mixture liquid obtained by sufficiently stirring was subjected to filtration, and the composition 101 was obtained.

[0450] The compositions 102 to 116 and comparative compositions 1 to 5 having the compositions shown in Table 1 were each produced according to the production method of the composition 101.

[0451] A sample 800 mL of each of the compositions produced by the above-described method was transferred to a "Clean Barrier Bottle" (manufactured by Aicello Corporation, capacity 1 L) under atmospheric pressure, a space under atmospheric pressure was left in the upper portion of the container, and the container was closed. The container containing the sample was stored in a dark environment at 25°C for 14 days.

[0452] The sample obtained in this manner after storage was used in the following performance evaluation test.

[0453] [Evaluation of Corrosion Resistance]

[0454] A wafer (diameter 12 inches) having a metal film composed of tungsten (W) on the surface was cut, and a wafer piece sample having a 2 cm port was prepared. The thickness of the metal film (W film) was approximately 100 nm. The wafer piece sample was immersed in 200 mL of the above-described sample (25°C) while being stirred at a stirring speed of 250 rpm, and immersion treatment was performed for 30 minutes.

[0455] The film thickness of the metal film dissolved by the immersion treatment was calculated from the difference in the thickness of the metal film measured before and after the immersion treatment, and the corrosion rate of the metal film per unit time (unit: A / minute) was calculated.

[0456] From the obtained corrosion rate of the metal film, the corrosion resistance of each sample to tungsten was evaluated by the following evaluation criteria. The evaluation results are shown in Table 1.

[0457] In addition, the lower the etching rate of the W film, the more excellent the corrosion inhibiting performance of the composition against tungsten. In fact, it is desirable to evaluate "4" or more.

[0458] (Evaluation Criteria for Corrosion Resistance)

[0459] 8: Etching rate is / minute or less

[0460] 7: Etching rate is more than / minute and / minute or less

[0461] 6: Etching rate is more than / minute and / minute or less

[0462] 5: Etching rate is more than / minute and / minute or less

[0463] 4: Etching rate is more than / minute and / minute or less

[0464] 3: Etching rate is more than / minute and / minute or less

[0465] 2: Etching rate is more than / minute and less than / minute

[0466] 1: Etching rate is / minute or more

[0467] (Evaluation of Residue Removability)

[0468] A silicon wafer (12 inches in diameter) having a CVD-W film (tungsten film) with a film thickness of 1000 A on the surface was subjected to CMP processing using a polishing device ("FREX300II" manufactured by EBARA CORPORATION) under the following conditions.

[0469] • Polishing liquid: Polishing liquid obtained by adding 2 mass% of hydrogen peroxide with respect to the total mass of the slurry to CMP slurry (product name "W2000", manufactured by Cabot Corporation)

[0470] • Worktable rotation speed: 80 rpm

[0471] • Head rotation speed: 78 rpm

[0472] • Polishing pressure: 120 hPa

[0473] ​• Polishing pad: "IC 1400" manufactured by Nitta Corporation

[0474] • Polishing liquid supply rate: 250 mL / min

[0475] • Polishing time: 60 seconds

[0476] Each sample adjusted to room temperature (25°C) was used as a cleaning liquid, and the polished surface of the wafer on which the above CMP treatment was performed was scrubbed and cleaned for 30 seconds. Then, the cleaned wafer was rinsed with water and dried (thoroughly dried).

[0477] Using a defect detection device (manufactured by Applied Materials, Inc., Complus-II), defects present on the polished surface of the wafer were detected, and the type of each defect was determined by SEM (scanning electron microscope)-based observation and EDAX (energy dispersive X-ray analysis device)-based constituent element analysis. Thus, the number of defects based on residues of the CMP treatment was obtained. Using an atomic force microscope (AFM) for surface roughness measurement, defects in a square observation area of 10 μm on one side present at the center portion and at two end portions sandwiching the center portion were measured, and the number of defects based on residues of the CMP treatment having a length of 0.1 μm or more was counted.

[0478] From the average number of defects obtained by averaging the number of defects of each observation area, the residue removal performance of each sample with respect to the semiconductor substrate was evaluated based on the following criteria. In fact, evaluation of "4" or more is desired.

[0479] (Residue removal performance evaluation criteria)

[0480] 8: The average number of defects per observation area is less than 20.

[0481] 7: The average number of defects per observation area is 20 or more and less than 30.

[0482] 6: The average number of defects per observation area is 30 or more and less than 40.

[0483] 5: The average number of defects per observation area is 40 or more and less than 50.

[0484] 4: The average number of defects per observation area is 50 or more and less than 60.

[0485] 3: The average number of defects per observation area is 60 or more and less than 80.

[0486] 2: The average number of defects per observation area is 80 or more and less than 100.

[0487] 1: The average number of defects per observation area is 100 or more.

[0488] (Evaluation of electrical characteristics of the wiring)

[0489] The silicon wafer having the W film on the surface was subjected to a series of processes consisting of a CMP treatment, a scrub cleaning using each sample, rinsing, and drying, according to the method described in the evaluation test of the residue removal.

[0490] The surface resistance (sheet resistance value) of the W film of the silicon wafer was measured using a sheet resistance meter ("VR-120" manufactured by Kokusai Electric Semiconductor Service Inc.) before and after the series of processes described above. The rate of change of the sheet resistance value (Ω / D) after the processes described above with respect to the sheet resistance value (Ω / D) before the processes described above ({(sheet resistance value of the W film after the processes) - (sheet resistance value of the W film before the processes)} / (sheet resistance value of the W film before the processes) x 100) was calculated, and the influence on the electrical characteristics of the W wiring was evaluated based on the following criteria. In fact, evaluation of "4" or more is desired.

[0491] (Evaluation criteria of electrical characteristics)

[0492] 8: The rate of change of the sheet resistance value is less than 1%.

[0493] 7: The rate of change of the sheet resistance value is 1% or more and less than 1.2%.

[0494] 6: The rate of change of the sheet resistance value is 1.2% or more and less than 1.5%.

[0495] 5: The rate of change of the sheet resistance value is 1.5% or more and less than 1.7%.

[0496] 4: The rate of change of the sheet resistance value is 1.7% or more and less than 2.0%.

[0497] 3: The rate of change of the sheet resistance value is 2.0% or more and less than 2.5%.

[0498] 2: The rate of change of the sheet resistance value is 2.5% or more and less than 3%.

[0499] 1: The rate of change of the sheet resistance value is 3% or more.

[0500] In Table 1 below, the composition and physical properties of each composition and the evaluation results based on the evaluation described above are shown.

[0501] In the table, the column of "Amount (%) " indicates the content of each component with respect to the total mass of the composition (unit: mass %). In addition, the content of each component in the table indicates the content of each component as a compound. Also, water is the remainder of the components other than water, and in the table, the value rounded off to three decimal places is described as the content of water.

[0502] The value in the column of "Ratio B / A" indicates the mass ratio of the content of citric acid with respect to the content of sorbic acid (content of citric acid / content of sorbic acid), the value in the column of "Ratio C / A" indicates the mass ratio of the content of component C with respect to the content of sorbic acid (content of component C / content of sorbic acid), and the value in the column of "Ratio B / C" indicates the mass ratio of the content of citric acid with respect to the content of component C (content of citric acid / content of component C).

[0503] The column of "Phosphate ion (ppm)" indicates the content of phosphate ion in each composition (unit: mass ppm).

[0504] The value in the column of "pH" indicates the pH of the composition at 25°C measured by the pH meter described above.

[0505] The value in the column of "Conductivity (mS / cm)" indicates the conductivity of the composition measured by the conductivity meter described above (unit: mS / cm). In addition, "*1" in the column of "Conductivity (mS / cm)" indicates that the pH of the composition is low and the conductivity cannot be measured.

[0506] In the table, the mark of "-" indicates that the component corresponding to the column is not contained in the composition.

[0507]

[0508] It was confirmed from the results shown in the above table that, when the composition of the present application was compared with Comparative Compositions 1 to 4 not containing any of sorbic acid, citric acid, component C, and component D, and Comparative Composition 5 having a pH of less than 4.0, the use of the composition over time when cleaning a semiconductor substrate resulted in a balanced excellent effect on residue removal, corrosion resistance, and wiring electrical characteristics.

[0509] It was confirmed that the wiring electrical characteristics were more excellent when the content of sorbic acid was 0.001 mass % or more with respect to the total mass of the composition, and the residue removal and the wiring electrical characteristics were further excellent when the content of sorbic acid was 0.01 mass % or more with respect to the total mass of the composition (comparison of Compositions 107 to 109).

[0510] Further, it was confirmed that the corrosion resistance to W film was more excellent when Component D had phosphono groups (comparisons of compositions 107 and 113 to 116). Further, it was confirmed that the corrosion resistance to W film was further excellent when Component D had at least 2 phosphono groups (comparisons of compositions 107 and 113 to 115).

[0511] [Example 2]

[0512] Compositions 101 to 106 and 110 to 115 were prepared according to the method described in the production example of Example 1. Each of the prepared compositions was diluted 100 times by mass with ultrapure water, and compositions 201 to 212 were prepared, respectively.

[0513] A sample 800 mL of each of the compositions prepared by the above method was transferred to a "Clean Barrier Bottle" (manufactured by Aicello Corporation, capacity 1 L) under atmospheric pressure, a space under atmospheric pressure was left in the upper portion of the container and was closed. The container containing the sample was stored in a dark environment at 25°C for 14 days.

[0514] Using each of the obtained samples after storage, the corrosion resistance, the residue removal property and the wiring electrical characteristics were evaluated according to the test method described in Example 1, respectively.

[0515] The pH and the conductivity of compositions 201 to 212, and the evaluation results based on the above evaluation are shown in the following Table 2.

[0516] In addition, the content of each component other than water included in compositions 201 to 212 was 1 / 100 of the content of each component of compositions 101 to 106 and 110 to 115, and the content of water was the remaining portion from the total content of each component other than water. Further, the ratios B / A, C / A and B / C of compositions 201 to 212 were the same as the ratios B / A, C / A and B / C of compositions 101 to 106 and 110 to 115.

[0517] [Table 2]

[0518]

[0519] From the results shown in the above table, it was confirmed that compositions 201 to 212 were equally to compositions 101 to 106 and 110 to 115, and that the residue removal property, the corrosion resistance and the wiring electrical characteristics when using the composition after the elapse of time to clean a semiconductor substrate were all excellent in balance.< / ph>

Claims

1. A composition comprising: Sorbic acid; Citric acid; An amine-containing compound selected from at least one of ammonia, organic amines and quaternary ammonium compounds, and their salts; A specific compound having at least one group selected from phosphonoyl and phosphate groups; and water, The composition has a pH of 4.0–7.0 at 25°C. The ratio of the citric acid content to the sorbic acid content is 1 to 50 by mass.

2. The composition according to claim 1, wherein, The ratio of the content of the amine compound to the content of the sorbic acid is 10 to 500 by mass.

3. The composition according to claim 1 or 2, wherein, The specific compound includes compounds having a phosphonoyl group.

4. The composition according to claim 1 or 2, wherein, The specific compound comprises a compound having at least two phosphono groups.

5. The composition according to claim 1 or 2, wherein, The amine-containing compound comprises at least one selected from ammonia, alkanolamines, quaternary ammonium compounds, and their salts.

6. The composition according to claim 1 or 2, wherein, The amine-containing compound includes alkanolamines.

7. The composition according to claim 1 or 2, substantially does not contain abrasive particles.

8. The composition according to claim 1 or 2, wherein the conductivity at 25°C is 0.01 mS / cm to 30 mS / cm.

9. The composition according to claim 1 or 2, wherein, The phosphate ion content is less than 20 ppm by mass relative to the composition.

10. The composition according to claim 1 or 2, used as a cleaning solution for semiconductor substrates subjected to chemical mechanical polishing.

11. The composition according to claim 10, wherein, The semiconductor substrate contains tungsten.

12. The composition according to claim 10, wherein, A diluted solution made by diluting water more than 50 times is used as a cleaning solution.

13. A method for manufacturing a semiconductor element, comprising a step of cleaning a semiconductor substrate using the composition of any one of claims 1 to 11.

14. A method for manufacturing a semiconductor device, comprising: The process of performing chemical mechanical polishing on a semiconductor substrate; and The process of cleaning a semiconductor substrate subjected to the chemical mechanical polishing treatment using the composition of any one of claims 1 to 11 or a diluted solution of the composition prepared by diluting the composition with water.

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