Cleaning composition and chemical mechanical polishing composition

Abstract

The present invention provides a detergent composition which enables thorough removal of a polishing agent, metal microparticles, and an anti-corrosion agent during washing of a semiconductor substrate as well as long-term maintaining of flatness of a metal wiring surface after washing, and which has excellent long-term quality stability, and a polishing composition capable of suppressing scratches on an object to be polished, such as a semiconductor substrate, and reducing filter clogging.　Provided are a detergent composition, which contains an alkanol hydroxylamine compound represented by formula (1) and has a pH of 10 to 13, and a chemical-mechanical polishing composition containing the detergent composition and a polishing agent. (In formula (1), Ra1 and Ra2 indicate alkyl groups which are the same or different, have a carbon number of 1 to 10, and have 1 to 3 hydrogen atoms or hydroxyl groups. Note, however, that Ra1 and Ra2 are not simultaneously hydrogen atoms, and the total number of the hydroxyl groups had by Ra1 and Ra2 is not zero.)

Description

[Technical Field]

[0001] This disclosure relates to a cleaning composition and a chemical mechanical polishing composition. This application claims priority from Japanese Patent Application No. 2020-083059, filed May 11, 2020, the contents of which are incorporated herein by reference. [Background technology]

[0002] 2. Description of the Related Art Semiconductor devices are becoming increasingly miniaturized and highly integrated, and market needs for semiconductor substrates having multilayer wiring structures including metal wiring are increasing. The manufacturing of such semiconductor substrates requires advanced planarization technology, for which chemical mechanical polishing (CMP) is used. CMP is a method of planarizing metal wiring and other surfaces by polishing them with a slurry containing abrasives, but this tends to leave behind abrasives and metal particles (polishing debris).

[0003] On the other hand, metal wiring is easily oxidized and corroded during polishing, so in CMP, anticorrosive agents (corrosion inhibitors) such as benzotriazole (BTA) and quinaldic acid (QCA) are added to prevent corrosion by forming a coating on the surface of the metal wiring that contains a complex with the surface metal of the metal wiring.

[0004] Known examples of cleaning agents used in post-CMP cleaning processes to remove abrasives, metal particulates, and anticorrosives include a cleaning agent for copper wiring semiconductors containing a specific amine and a specific polyphenol compound (Patent Document 1), a cleaning agent for copper wiring substrates containing a specific amino acid and an alkanol hydroxylamine (Patent Document 2), a cleaning agent for copper wiring semiconductors containing a specific cyclic amine and a polyphenol-based reducing agent containing 2 to 5 hydroxyl groups (Patent Document 3), a semiconductor workpiece cleaning composition containing an ammonium hydroxide compound, a chelating agent, and a corrosion inhibitor compound (Patent Document 4), a substrate cleaning agent containing an organic acid and / or complexing agent having at least one carboxyl group and a specific organic solvent (Patent Document 5), and a cleaning solution containing at least one organic alkali (Patent Document 6).

[0005] However, in recent years, there has been a demand for even higher levels of removal of abrasives, polishing debris, and anticorrosives, as well as the removal of anticorrosive-derived coatings, maintaining flatness after post-CMP cleaning processes (preventing uneven growth of oxide films), and maintaining the quality stability of cleaning chemicals. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-186470 [Patent Document 2] International Publication No. 2012 / 073909 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-235725 [Patent Document 4] Japanese Patent Application Laid-Open No. 2007-525836 [Patent Document 5] International Publication No. 2005 / 040324 [Patent Document 6] Japanese Patent Application Laid-Open No. 2002-359223 Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, an object of the present disclosure is to provide a cleaning composition that, when cleaning semiconductor substrates, enables sufficient removal of abrasives, metal fine particles, and anticorrosives, maintains the flatness of the metal wiring surface after cleaning for a long period of time, and has excellent long-term quality stability. Another object of the present disclosure is to provide a cleaning composition that, when cleaning semiconductor substrates, enables sufficient removal of abrasives, metal fine particles, and anticorrosives, sufficiently removes coatings containing anticorrosives, rapidly forms oxide films, and maintains the flatness of the metal wiring surface after cleaning for a long period of time, and has excellent long-term quality stability.

[0008] The inventors of the present disclosure also conducted research into polishing compositions for polishing semiconductor substrates and found that when polishing is performed using a polishing composition containing the above-mentioned detergent composition, abrasives and metal fine particles are easily removed in the post-polishing cleaning step, and the flatness of the metal wiring surface after cleaning is maintained even after a long waiting period. However, such polishing compositions have the problem of easily causing scratches on the workpiece to be polished and frequently clogging the filter during filtration when reused. That is, an object of the present disclosure is to provide a chemical mechanical polishing composition that can suppress scratches on the workpiece to be polished, such as a semiconductor substrate, and reduce filter clogging. [Means for solving the problem]

[0009] As a result of intensive research aimed at solving the above-mentioned problems, the inventors of the present disclosure have found that the above-mentioned problems can be solved by using a cleaning composition containing a specific alkanol hydroxylamine compound and adjusted to a specific pH, and a chemical mechanical polishing composition containing the cleaning composition. The present disclosure has been completed based on these findings.

[0010] That is, the present disclosure provides a compound represented by general formula (1) [ka] (In formula (1), R a1 and R a2 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have 1 to 3 hydroxyl groups. a1 and R a2 cannot be hydrogen atoms at the same time, and R a1 and R a2 The total number of hydroxyl groups in The present invention provides a cleaning composition containing an alkanol hydroxylamine compound represented by the following formula: and having a pH of 10 to 13.

[0011] Above R a1 and the above R a2is preferably an alkyl group having 1 to 10 carbon atoms and one hydroxyl group.

[0012] The content of the alkanol hydroxylamine compound in the detergent composition is preferably 0.05 to 25% by weight.

[0013] The above-mentioned detergent composition may further contain a basic compound other than the above-mentioned alkanol hydroxylamine compound.

[0014] The basic compound is represented by the general formula (2) [ka] (In formula (2), R b1 ~R b4 are the same or different and represent hydrocarbon groups which may have a substituent. It is preferable that the quaternary ammonium hydroxide is represented by the following formula:

[0015] The basic compound is preferably ammonia, tetramethylammonium hydroxide, or 2-hydroxyethyltrimethylammonium hydroxide.

[0016] The content of the basic compound in the detergent composition is preferably 0.01 to 5% by weight.

[0017] In the cleaning composition, the weight ratio of the alkanol hydroxylamine compound to the basic compound (alkanol hydroxylamine compound / basic compound) is preferably 1-10.

[0018] The cleaning composition further comprises a compound represented by the general formula (3) [ka] (In formula (3), R c represents a hydrogen atom or a hydrocarbon group which may have a hydroxyl group, and n is an integer of 2 to 40. It is preferable that the polyglycerin derivative is represented by the following formula:

[0019] The cleaning composition further comprises a compound represented by the general formula (4) [ka] (In formula (4), X represents a carboxyl group or a phosphonic acid group. R d and R e are the same or different and represent a hydrogen atom or an optionally substituted monovalent hydrocarbon group, R f R represents a divalent hydrocarbon group which may have a substituent. d ~R f Any two of may be bonded to each other to form a ring together with the adjacent nitrogen atom. The composition may contain a chelating agent represented by the formula:

[0020] The present disclosure also provides a chemical mechanical polishing composition containing the above-described cleaning composition and an abrasive. [Effects of the Invention]

[0021] The cleaning composition of the present disclosure is used to clean semiconductor substrates after a CMP process, and is capable of sufficiently removing abrasives, metal fine particles, and anticorrosives, maintaining the flatness of the substrate for a long period after cleaning, and exhibiting excellent long-term quality stability.

[0022] Furthermore, the chemical mechanical polishing composition of the present disclosure can suppress scratches on an object to be polished, such as a semiconductor substrate, and can reduce filter clogging during filtration when reused. DETAILED DESCRIPTION OF THE INVENTION

[0023] [Cleaning composition] The cleaning composition of the present disclosure contains an alkanol hydroxylamine compound and has a pH of 10-13.

[0024] The cleaning composition of the present disclosure can be preferably used as a cleaning agent for cleaning semiconductor substrates (silicon substrates, silicon carbide substrates, gallium arsenide substrates, gallium phosphide substrates, indium phosphide substrates, etc.), more preferably used as a post-CMP cleaning agent for cleaning semiconductor substrates having metal wiring (copper wiring, copper alloy wiring, tungsten wiring, aluminum wiring, etc.) in a cleaning step after the CMP step, and even more preferably used as a post-CMP cleaning agent for cleaning semiconductor substrates having copper wiring or copper alloy wiring.

[0025] The cleaning composition of the present disclosure can sufficiently remove surface films formed in the CMP process, which contain complexes of anticorrosives such as BTA and QCA with the surface metal of the metal wiring, thereby providing semiconductor substrates with metal wiring surfaces that maintain their flatness for a long period of time.

[0026] <Alkanol hydroxylamine compounds> The alkanol hydroxylamine compound according to the present disclosure is a compound represented by general formula (1) and functions as a reducing agent. a1 and R a2 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have 1 to 3 hydroxyl groups. a1 and R a2 cannot be hydrogen atoms at the same time, and R a1 and R a2 The total number of hydroxyl groups contained in the [ka]

[0027] The use of such alkanol hydroxylamine compounds can provide corrosion-inhibiting effects not only on cobalt but also on copper, tungsten, silicides such as SiGe, and other easily corrodible metals.

[0028] The above R a1 and R a2is a hydrogen atom, an alkyl group, or an alkanol group, and the hydroxyl group in the alkanol group may constitute a primary alcohol, a secondary alcohol, or a tertiary alcohol, but preferably constitutes a primary alcohol or a secondary alcohol, and more preferably constitutes a primary alcohol.

[0029] R a1 and R a2 The total number of hydroxyl groups in R is not 0. a1 and R a2 At least one of the groups is an alkanol group.

[0030] The above R a1 and the above R a2 is preferably an alkyl group having 1 to 10 carbon atoms and one hydroxyl group.

[0031] The above R a1 and R a2 The alkyl group having 1 to 10 carbon atoms in the formula (I) is a linear, branched, or cyclic alkyl group, and is preferably a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, a 2-methylbutyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a cyclopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a neohexyl group, a 2-methylpentyl group, a 1,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 1-ethylbutyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Of these, an ethyl group, an n-propyl group, and an isopropyl group are preferred.

[0032] The above R a1 and R a2Examples of the alkanol group according to the above include a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1,2-dihydroxyethyl group, a 2,2-dihydroxyethyl group, a 1-hydroxy-n-propyl group, a 2-hydroxy-n-propyl group, a 3-hydroxy-n-propyl group, a 1,2-dihydroxy-n-propyl group, a 1,3-dihydroxy-n-propyl group, a 2,2-dihydroxy-n-propyl group, a 2,3-dihydroxy-n-propyl group, a 3,3-dihydroxy-n-propyl group, a 1,2,3-trihydroxy-n-propyl group, a 2,2,3-tri ... hydroxy-n-propyl group, 2,3,3-trihydroxy-n-propyl group, 1-hydroxyisopropyl group, 2-hydroxyisopropyl group, 1,1-dihydroxyisopropyl group, 1,2-dihydroxyisopropyl group, 1,3-dihydroxyisopropyl group, 1,2,3-trihydroxyisopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group, 1,2-dihydroxy-n-butyl group, 1,3-dihydroxy-n-butyl group, 1,4-dihydroxy- n-butyl group, 2,2-dihydroxy-n-butyl group, 2,3-dihydroxy-n-butyl group, 2,4-dihydroxy-n-butyl group, 3,3-dihydroxy-n-butyl group, 3,4-dihydroxy-n-butyl group, 4,4-dihydroxy-n-butyl group, 1,2,3-trihydroxy-n-butyl group, 1,2,4-trihydroxy-n-butyl group, 1,3,4-trihydroxy-n-butyl group, 2,2,3-trihydroxy-n-butyl group, 2,2,4-trihydroxy-n-butyl group, 2,3,3-trihydroxy-n-butyl group, 3,3,4- Trihydroxy-n-butyl, 2,4,4-trihydroxy-n-butyl, 3,4,4-trihydroxy-n-butyl, 2,3,4-trihydroxy-n-butyl, 1-hydroxy-sec-butyl, 2-hydroxy-sec-butyl, 3-hydroxy-sec-butyl, 4-hydroxy-sec-butyl, 1,1-dihydroxy-sec-butyl, 1,2-dihydroxy-sec-butyl, 1,3-dihydroxy-sec-butyl, 1,4-dihydroxy-sec-butyl, 2,3-dihydroxy-sec-butyl, 2,4-dihydroxy-sec-butyl, 3,3-dihydroxy-sec-butyl, 3,4-dihydroxy-sec-butyl, 4,4-dihydroxy-sec-butyl, 1-hydroxy-2-methyl-n-propyl, 2-hydroxy-2-methyl-n-propyl, 3-hydroxy-2-methyl-n-propyl, 1,2-dihydroxy-2-methyl-n-propyl, 1,3-dihydroxy-2-methyl-n-propyl, 2,3-dihydroxy-2-methyl-n-propyl, 3,3-dihydroxy-2-methyl-n-propyl, 3-hydroxy-2-hydroxymethyl-n-propyl, 1, Examples include a 2,3-trihydroxy-2-methyl-n-propyl group, a 1,3,3-trihydroxy-2-methyl-n-propyl group, a 2,3,3-trihydroxy-2-methyl-n-propyl group, a 1,3-dihydroxy-2-hydroxymethyl-n-propyl group, a 2,3-dihydroxy-2-hydroxymethyl-n-propyl group, a 1-hydroxy-2-methylisopropyl group, a 1,3-dihydroxy-2-methylisopropyl group, and a 1,3-dihydroxy-2-hydroxymethylisopropyl group, and among these, a 2-hydroxyethyl group, a 2-hydroxy-n-propyl group, and a 2-hydroxyisopropyl group are preferred.

[0033] The alkanol hydroxylamine compounds of the present disclosure are monoalkanol hydroxylamines (hydroxyl group, hydrogen atom, and alkanol group bonded to the nitrogen atom), alkylalkanol hydroxylamines (hydroxyl group, alkyl group, and alkanol group bonded to the nitrogen atom), or dialkanol hydroxylamines (hydroxyl group and two alkanol groups bonded to the nitrogen atom), preferably dialkanol hydroxylamines, such as N-(2-hydroxyethyl)-N-hydroxylamine, ... Examples thereof include -(1,3-dihydroxy-n-propyl)-N-hydroxylamine, N-ethyl-N-hydroxymethyl-N-hydroxylamine, N-ethyl-N-(2-hydroxyethyl)-N-hydroxylamine, N-ethyl-N-(1,2-dihydroxyethyl)-N-hydroxylamine, N,N-bis(1,2-dihydroxyethyl)-N-hydroxylamine, N,N-bis(2-hydroxyethyl)-N-hydroxylamine, and N,N-bis(2-hydroxypropyl)-N-hydroxylamine. Among these, N,N-bis(2-hydroxyethyl)-N-hydroxylamine is more preferred.

[0034] These alkanol hydroxylamine compounds effectively remove abrasives, polishing debris, anticorrosives, and anticorrosive-containing coatings, and also effectively inhibit uneven corrosion and oxidation of metal interconnect surfaces, thereby maintaining the flatness of substrates left after post-CMP cleaning processes.

[0035] These alkanolhydroxylamine compounds may be obtained by a known method, for example, by oxidizing the corresponding alkanolamine with an oxidizing agent such as hydrogen peroxide, or commercially available compounds may be used.

[0036] The content of the alkanolhydroxylamine compound in the cleaning composition of the present disclosure is preferably 0.05 to 25 wt%, more preferably 0.1 to 15 wt%, and even more preferably 0.2 to 0.5 wt%. If the content of the alkanolhydroxylamine compound is less than 0.05 wt%, oxidation or corrosion of metal wiring may not be sufficiently prevented, while if it exceeds 25 wt%, the alkanolhydroxylamine compound may not dissolve in water and may cause phase separation.

[0037] The water used in the aqueous solution according to the present disclosure may be any water that does not adversely affect the substrate in the manufacturing process of the semiconductor device, and examples thereof include purified water such as distilled water and deionized water, and ultrapure water, among which ultrapure water is preferred.

[0038] <Basic compounds> The pH of the cleaning composition according to the present disclosure may be adjusted by adding a basic compound other than the alkanol hydroxylamine compound.

[0039] The basic compound may be an inorganic basic compound or an organic basic compound.

[0040] Examples of inorganic basic compounds include alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxides (Mg(OH)2, etc.), ammonia, etc. Among these, ammonia is preferred because it does not contain metal ions.

[0041] Examples of organic basic compounds include primary to tertiary amines, alkanolamines, quaternary ammonium hydroxides, etc. Among these, quaternary ammonium hydroxides are preferred.

[0042] Examples of primary to tertiary amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, 1,3-propanediamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, piperidine, piperazine, trimethylamine, and triethylamine.

[0043] Examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyl-N,N-diethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-(β-aminoethyl)ethanolamine, N-ethylethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, tris(hydroxymethyl)aminomethane, and 2-morpholinomethanol.

[0044] Quaternary ammonium hydroxide is a compound represented by general formula (2). In formula (2), R b1 ~R b4 are the same or different and represent hydrocarbon groups which may have a substituent, and OH - represents a hydroxide ion. [ka]

[0045] Above R b1 ~R b4 Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

[0046] Above R b1 ~R b4The aliphatic hydrocarbon group in the above is a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and preferably a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, a 2-methylbutyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a cyclopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a neohexyl group, a 2-methylpentyl group, a 1,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 1-ethylbutyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Of these, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferred.

[0047] Above R b1 ~R b4 The aromatic hydrocarbon group in the above is an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

[0048] Above R b1 ~R b4Examples of the substituent that may be possessed by the alkyl group include a hydroxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, an isobutyloxy group, etc.), an aryl group (a phenyl group, a naphthyl group, etc.), an aryloxy group (a phenoxy group, a tolyloxy group, a naphthyloxy group, etc.), an aralkyloxy group (a benzyloxy group, a phenethyloxy group, etc.), an acyloxy group (an acetyloxy group, a propionyloxy group, a benzoyloxy group, etc.), a carboxyl group, an alkoxycarbonyl group (a methoxycarbonyl group, etc.), an aryloxy group (a phenyl group, a naphthyloxy ... Examples of the alkyl group include an aryl group (e.g., ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group), an aryloxycarbonyl group (e.g., phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group), an aralkyloxycarbonyl group (e.g., benzyloxycarbonyl group), an amino group, a primary or secondary amino group (e.g., methylamino group, ethylamino group, dimethylamino group, diethylamino group), an acylamino group (e.g., acetylamino group, propionylamino group, benzoylamino group), an acyl group (e.g., acetyl group, propionyl group, benzoyl group), and an oxo group.

[0049] Examples of ammonium cations related to the above-mentioned quaternary ammonium hydroxides include tetramethylammonium, trimethylethylammonium, dimethyldiethylammonium, triethylmethylammonium, tripropylmethylammonium, tributylmethylammonium, trioctylmethylammonium, tetraethylammonium, trimethylpropylammonium, trimethylphenylammonium, benzyltrimethylammonium, benzyltriethylammonium, diallyldimethylammonium, n-octyltrimethylammonium, tetrapropylammonium, tetra-n-butylammonium, 2-hydroxyethyltrimethylammonium, 2-hydroxypropyltrimethylammonium, and phenyltrimethylammonium.

[0050] Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, trimethylethylammonium hydroxide, dimethyldiethylammonium hydroxide, triethylmethylammonium hydroxide, tripropylmethylammonium hydroxide, tributylmethylammonium hydroxide, trioctylmethylammonium hydroxide, tetraethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, diallyldimethylammonium hydroxide, n-octyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetra-n-butylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxypropyltrimethylammonium (β-methylcholine), and phenyltrimethylammonium hydroxide. Among these, tetramethylammonium hydroxide and 2-hydroxyethyltrimethylammonium hydroxide (choline) are preferred.

[0051] The basic compounds may be used alone or in combination of two or more kinds.

[0052] The content of the basic compound in the cleaning composition of the present disclosure is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, and even more preferably 0.1 to 1% by weight.

[0053] <Polyglycerin derivatives> The polyglycerin derivative according to the present disclosure is represented by the following formula (3): c represents a hydrogen atom or a hydrocarbon group which may have a hydroxyl group, and n is the average degree of polymerization of glycerin units and is an integer of 2 to 40. [ka]

[0054] Rc Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkapolyenyl group, and an acyl group.

[0055] Above R c is preferably an alkyl group, an acyl group or a hydrogen atom.

[0056] The alkyl group is preferably a linear alkyl group having 1 to 18 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 12 to 18 carbon atoms, or a branched alkyl group having preferably 3 to 18 carbon atoms, more preferably 3 to 18 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, an isooctyl group, a decyl group, an isodecyl group, a dodecyl group (lauryl group), a tetradecyl group, an oleyl group, an isododecyl group, a myristyl group, an isomyristyl group, a cetyl group, an isocetyl group, a stearyl group, an isostearyl group, etc. Among these, a linear alkyl group is preferred, a dodecyl group (lauryl group) or a stearyl group is more preferred, and a dodecyl group (lauryl group) is even more preferred.

[0057] The alkenyl group is preferably a linear alkenyl group having 2 to 18 carbon atoms, more preferably 8 to 18 carbon atoms, or a branched alkenyl group having 3 to 18 carbon atoms, more preferably 8 to 18 carbon atoms, and examples thereof include a vinyl group, a propenyl group, an allyl group, a hexenyl group, a 2-ethylhexenyl group, an oleyl group, etc. Of these, a hexenyl group and an oleyl group are more preferred.

[0058] The alkapolyenyl group is preferably an alkapolyenyl group having 2 to 18 carbon atoms, and examples thereof include an alkadienyl group, an alkatrienyl group, an alkatetraenyl group, a linoleyl group, and a linolenyl group.

[0059] The acyl group is an aliphatic acyl group or aromatic acyl group having 2 to 24 carbon atoms, and examples of the aliphatic acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a stearoyl group, and an oleoyl group, while examples of the aromatic acyl group include a benzoyl group, a toluoyl group, and a naphthoyl group. Among these, an aliphatic acyl group is preferred, an acetyl group, a butyryl group, a stearoyl group, and an oleoyl group are more preferred, and an acetyl group and an oleoyl group are even more preferred.

[0060] The above n is 2 to 40, preferably 4 to 30, and more preferably 4 to 20. If n is less than 2, water solubility tends to be low and cleaning properties tend to be reduced. On the other hand, if n is more than 40, water solubility tends to be too high and water dispersibility tends to be reduced, and foaming properties and workability tend to be reduced.

[0061] The -C3H6O2- in the parentheses in the above formula (3) may be either of the structures -CH2-CHOH-CH2O- and -CH(CH2OH)CH2O-.

[0062] The weight-average molecular weight of the polyglycerol derivative according to the present disclosure is preferably from 200 to 3000, more preferably from 400 to 1500, and even more preferably from 400 to 800. When the weight-average molecular weight is within the above range, surface activity and workability tend to be improved. In the present disclosure, the weight average molecular weight can be measured by gel permeation chromatography (GPC).

[0063] The polyglycerin derivatives according to the present disclosure include: C 12 H 25 O-(C3H6O2)4-H, C 12 H 25 O-(C3H6O2) 10 -H, C 12 H 25 O-(C3H6O2) 20 -H, HO-(C3H6O2) 10 -H, HO-(C3H6O2) 20 -H, CH2=CH-CH2-O-(C3H6O2)6-H, CH2=CH-CH2-O-(C3H6O2)6-H, CH3-(CH2)7-CH=CH-(CH2)8-O-(C3H6O2)4-H, CH3-(CH2)7-CH=CH-(CH2)8-O-(C3H6O2) 10 -H, etc.

[0064] The polyglycerol derivative according to the present disclosure can be prepared, for example, by reacting R c It can be produced by adding 2,3-epoxy-1-propanol to the corresponding aliphatic alcohol.

[0065] The content of the polyglycerol derivative represented by the above formula (3) in the cleansing composition of the present disclosure is preferably 0.01 to 15 wt %, more preferably 0.05 to 10 wt %, and even more preferably 0.1 to 5 wt %.

[0066] The cleansing composition of the present disclosure may contain two or more types of polyglycerin derivatives represented by the above formula (3). The cleansing composition of the present disclosure may also contain a polyglycerol derivative other than the polyglycerol derivative represented by the above formula (3), such as a polyglycerol diether or polyglycerol diester.

[0067] The content of the polyglycerol derivative of the formula (3) relative to the total amount of the polyglycerol derivative of the formula (3) and other polyglycerol derivatives is preferably 75% or more, more preferably 90% or more. If it is less than 75%, the polyglycerol derivative as a whole tends to be difficult to dissolve. The content of the polyglycerol derivative can be determined by calculating the peak area ratio when the product is eluted by high performance liquid chromatography and the peak area is calculated using a differential refractive index detector.

[0068] <Chelating agent> The cleaning composition of the present disclosure may contain a chelating agent to enhance the effect of removing abrasives, polishing debris, anticorrosives, and anticorrosive coatings. The chelating agent used in the present disclosure may be a nitrogen-containing compound represented by the following formula (4). In formula (4), X represents a carboxyl group or a phosphonic acid group. R d and R e are the same or different and represent a hydrogen atom or an optionally substituted monovalent hydrocarbon group, R f R represents a divalent hydrocarbon group which may have a substituent. d ~R f Any two of may be bonded to each other to form a ring together with the adjacent nitrogen atom. [ka]

[0069] R d and R e Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group.

[0070] R d and R e Examples of the monovalent aliphatic hydrocarbon group include a linear or branched alkyl group, a linear or branched alkenyl group, and a linear or branched alkynyl group.

[0071] R d and R e The linear or branched alkyl group in the above is preferably a linear alkyl group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 2 to 4 carbon atoms, or a branched alkyl group having 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a 2-ethylhexyl group.

[0072] Rd and R e The linear or branched alkenyl group in the above is preferably a linear alkenyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 4 carbon atoms, or a branched alkenyl group having 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms, and examples thereof include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, and a 2-butenyl group. , 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 1-octenyl group, 1-nonenyl group, 1-decenyl group, isopropenyl group, 2-methyl-1-propenyl group, methallyl group, 3-methyl-2-butenyl group, 4-methyl-3-pentenyl group, and the like.

[0073] R d and R e The linear or branched alkynyl group according to the above is preferably a linear alkynyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 4 carbon atoms, or a branched alkynyl group having 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms. Examples of the linear or branched alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-pentynyl group, a 2-pentynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group, a 2-hexynyl group, a 3-hexynyl group, a 4-hexynyl group, a 5-hexynyl group, a 1-heptynyl group, a 1-octynyl group, a 1-nonynyl group, a 1-decynyl group, a trimethylsilylethynyl group, and a triethylsilylethynyl group.

[0074] R d and R e Examples of the alicyclic hydrocarbon group include a cycloalkyl group and a cycloalkenyl group.

[0075] R d and R eThe cycloalkyl group in the above is a cycloalkyl group having preferably 3 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 5 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.

[0076] R d and R e The cycloalkenyl group in the above is preferably a cycloalkenyl group having 3 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 5 to 8 carbon atoms, and examples thereof include a cyclopentenyl group and a cyclohexenyl group.

[0077] R d and R e The monovalent aromatic hydrocarbon group in the above is preferably an aryl group having 6 to 18 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

[0078] R d and R e The monovalent aliphatic hydrocarbon group, the monovalent alicyclic hydrocarbon group, or the monovalent aromatic hydrocarbon group in the above formula (1) may have each other as a substituent, or may be linked to each other via an oxygen atom or a sulfur atom.

[0079] R f The divalent hydrocarbon group according to the above R d and R e In the monovalent hydrocarbon group represented by the formula (I), one hydrogen atom is replaced with a single bond.

[0080] R d ~R fmay have, the same or different, at least one group selected from a carboxyl group, a phosphonic acid group, an amido group, an N-substituted amido group, a hydroxyl group, a thiol group, an amino group, an N-substituted amino group, an N,N-substituted amino group, an imino group, an N-substituted imino group, an alkylidene group, a heterocyclic group having one or more nitrogen atoms as heteroatoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an oxo group, a substituted oxy group (an alkoxy group having 1 to 4 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyloxy group having 7 to 16 carbon atoms, an acyloxy group having 1 to 4 carbon atoms, etc.), a carboxyl group, a substituted oxycarbonyl group (an alkoxycarbonyl group having 1 to 4 carbon atoms, an aryloxycarbonyl group having 6 to 10 carbon atoms, an aralkyloxycarbonyl group having 7 to 16 carbon atoms, etc.), a cyano group, a nitro group, a sulfo group, etc. Among these, a carboxyl group, a phosphonic acid group, an amide group, an N-substituted amide group, a hydroxyl group, a thiol group, an amino group, an N-substituted amino group, an N,N-substituted amino group, an imino group, an N-substituted imino group, an alkylidene group, and a heterocyclic group having one or more nitrogen atoms as a heteroatom are preferred.

[0081] R d ~R f The linear or branched alkylidene group that may be contained in is preferably a linear alkylidene group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 2 to 4 carbon atoms, or a branched alkylidene group having preferably 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms, and examples thereof include a methylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a sec-butylidene group, a pentylidene group, an isopentylidene group, an octylidene group, and an isooctylidene group.

[0082] R d ~R f Examples of the heterocyclic group having one or more nitrogen atoms as heteroatoms that may be contained in the ring include a pyrrolidine ring, a pyrroline ring, a piperidine ring, a pyrrole ring, an imidazolidine ring, an imidazole ring, a piperazine ring, a pyridine ring, a diazine ring, a triazine ring, and an indole ring.

[0083] R d ~R f The total number of carboxyl groups and phosphonic acid groups that the may have is preferably 0 to 4, and more preferably 1 or 2.

[0084] R d ~R f The total number of amide groups, N-substituted amide groups, and thiol groups that may be contained in the alkyl group is preferably 0 to 4, and more preferably 1 or 2.

[0085] R d ~R f The total number of amino groups, N-substituted amino groups and N,N-substituted amino groups that may be contained in the alkyl group is preferably 0 to 6, more preferably 1 to 4, and even more preferably 1 or 2.

[0086] R d ~R f The total number of imino groups and N-substituted imino groups that may be contained is preferably 0 to 4, and more preferably 1 or 2.

[0087] R d ~R f The total number of hydroxyl groups that may be possessed by is preferably 0 to 4, and more preferably 1 or 2.

[0088] The substituents of the N-substituted amino group, N,N-substituted amino group, and N-substituted imino group are the same as those of the R d ~R f The hydrocarbon group is the same as the hydrocarbon group that may be contained in

[0089] R d ~R f Any two of may be bonded to each other to form a ring together with the adjacent nitrogen atom. Examples of the ring formed include a pyrrolidine ring, a pyrroline ring, a piperidine ring, a pyrrole ring, an imidazolidine ring, an imidazole ring, a piperazine ring, an imidazolidine ring, a pyridine ring, a diazine ring, a triazine ring, and an indole ring.

[0090] Specific examples of the nitrogen-containing compound represented by formula (4) include compounds in which X in formula (4) is a carboxyl group and R d , R e an amino acid in which at least one of the following is a hydrogen atom; an amino acid in which X in formula (4) is a carboxyl group and R d and R e is a linear or branched alkyl group having a carboxyl group via an N,N-substituted amino group; X in formula (4) is a phosphonic acid group, and R d and R e However, examples thereof include aminophosphonic acids, which are linear or branched alkyl groups having a phosphonic acid group via an N,N-substituted amino group.

[0091] Examples of the amino acids include glycine, serine, proline, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan, valine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, ornithine, picolinic acid, nicotinic acid, 4-imidazolecarboxylic acid, selenocysteine, tyrosine, sarcosine, tricine, 3-amino-1,2,4-triazole-5-carboxylic acid, and 4,6-dimorpholin-4-yl-[1,3,5]triazine-2-carboxylic acid.

[0092] Examples of the aminocarboxylic acid include ethylenediaminetetracarboxylic acid, nitrilotricarboxylic acid, diethylenetriaminepentacarboxylic acid, hydroxyethylethylenediaminetricarboxylic acid, triethylenetetraaminehexacarboxylic acid, 1,3-propanediaminetetracarboxylic acid, 1,3-diamino-2-hydroxypropanetetracarboxylic acid, hydroxyethyliminodicarboxylic acid, dihydroxyethylglycine, glycol ether diaminetetracarboxylic acid, and phosphonobutanetricarboxylic acid.

[0093] Examples of the aminophosphonic acid include hydroxyethylidene diphosphonic acid, nitrilotrismethylene phosphonic acid, and ethylenediaminetetramethylene phosphonic acid.

[0094] These may be used alone or in combination of two or more.

[0095] The carboxyl group or phosphonic group of the chelating agent may form a salt with a counter ion (such as a Na ion, a Ca ion, an Mg ion, a Cu ion, or an Mn ion).

[0096] The content of the chelating agent in the cleaning composition of the present disclosure is preferably 0.05 to 25% by weight, more preferably 0.2 to 15% by weight, and even more preferably 0.2 to 0.5% by weight.

[0097] The cleaning composition of the present disclosure may contain components other than the above-mentioned alkanol hydroxylamine compound, basic compound, polyglycerin derivative, and chelating agent, as long as they do not adversely affect cleaning of metal wiring on a substrate. The content of such components in the composition is preferably 0.01 to 2.0 wt %, more preferably 0.05 to 1.5 wt %.

[0098] The pH of the cleaning composition of the present disclosure is 10 to 13, preferably 11.5 to 12.5. By adjusting the pH within this range, the alkanol hydroxylamine compound can more effectively remove abrasives, polishing debris, anticorrosives, and coatings containing anticorrosives, and can more effectively inhibit corrosion and oxidation of the metal wiring surface.

[0099] In the detergent composition of the present disclosure, the weight ratio of the alkanolhydroxylamine compound to the basic compound (alkanolhydroxylamine compound / basic compound) is preferably 1 to 10, more preferably 1.2 to 7, and even more preferably 1.4 to 5, in order to adjust the pH of the detergent composition within the above range.

[0100] The cleaning composition of the present disclosure can be obtained, for example, by adding an alkanolhydroxylamine compound or the like to ultrapure water from which dissolved oxygen has been removed by bubbling with an inert gas (such as nitrogen gas), and stirring the mixture to homogeneity.

[0101] <Semiconductor substrate cleaning method> Cleaning of semiconductor substrates using the cleaning composition of the present disclosure can be carried out by a known cleaning method such as an immersion method in which a substrate having metal wiring is immersed in the cleaning composition, a spin (drop) method, a spray method, etc. Also, either a batch method in which multiple substrates are treated at once, or a single-wafer method in which substrates are treated one by one, can be employed.

[0102] The cleaning temperature during cleaning is, for example, 15 to 30° C., and the cleaning time is, for example, 15 to 120 seconds.

[0103] [Chemical mechanical polishing composition] The chemical mechanical polishing composition of the present disclosure contains an abrasive and a composition containing the alkanol hydroxylamine compound, the basic compound, the polyglycerin derivative, and the optional chelating agent.

[0104] The chemical mechanical polishing composition of the present disclosure has the effect of easily removing the abrasive, polishing debris, anticorrosive, and anticorrosive-containing coating during post-polishing cleaning, thereby facilitating the inhibition of corrosion and oxidation of the metal wiring surface. In addition, the interaction between the alkanol hydroxylamine compound and the polyglycerin derivative effectively reduces the aggregation of the abrasive and inhibits the generation of secondary particles, thereby significantly reducing scratches on the object to be polished (device wafers, semiconductor substrates such as liquid crystal display substrates).

[0105] The content of the alkanol hydroxylamine compound in the chemical mechanical polishing composition of the present disclosure is preferably 0.05 to 25 wt %, more preferably 0.1 to 15 wt %, and even more preferably 0.2 to 0.5 wt %. If the content of the alkanol hydroxylamine compound is less than 0.05 wt %, oxidation or corrosion of the metal wiring may not be sufficiently suppressed during post-polishing cleaning, while if it exceeds 25 wt %, the compound may not dissolve in water and may undergo phase separation.

[0106] The content of the polyglycerin derivative in the chemical mechanical polishing composition of the present disclosure is preferably 0.01 to 15 wt %, more preferably 0.05 to 10 wt %, and even more preferably 0.1 to 5 wt %. If the content of the polyglycerin derivative is less than 0.01%, the aggregation of the abrasive cannot be alleviated, the secondary particles become large, and scratches tend to occur on the surface of the object to be polished. If the content of the polyglycerin derivative is more than 20 wt %, the viscosity of the chemical mechanical polishing composition tends to be too high, making the polishing operation difficult.

[0107] In the chemical mechanical polishing composition of the present disclosure, the weight ratio of the alkanol hydroxylamine compound to the polyglycerin derivative (alkanol hydroxylamine compound / polyglycerin derivative) is preferably 0.003 to 10, more preferably 0.01 to 5, and even more preferably 0.05 to 3, in order to suppress the generation of secondary particles due to aggregation of the abrasive described below and thereby reduce scratches on the polished object.

[0108] <Abrasives> As the abrasive according to the present disclosure, known and commonly used abrasives can be used, and among them, silicon dioxide, aluminum oxide, cerium oxide, silicon nitride, or zirconium oxide can be preferably used. These can be used alone or in combination of two or more.

[0109] The average particle size of the abrasive as measured by the BET method is preferably 0.005 to 10 μm. If the average particle size of the abrasive is less than 0.005 μm, the polishing rate will be extremely slow, and if the average particle size of the abrasive is more than 10 μm, scratches will be more likely to occur.

[0110] The content of the abrasive in the chemical mechanical polishing composition of the present disclosure is preferably 0.1 to 50 wt %, more preferably 0.5 to 40 wt %, and even more preferably 1 to 35 wt %. By setting the content of the abrasive within this range, the viscosity of the polishing composition can be adjusted to a range suitable for polishing, and the removal rate can be improved.

[0111] In the chemical mechanical polishing composition of the present disclosure, the weight ratio of the alkanol hydroxylamine compound to the abrasive (alkanol hydroxylamine compound / abrasive) is preferably 0.001 to 0.5, more preferably 0.01 to 0.4, and even more preferably 0.05 to 0.3, in order to suppress the generation of secondary particles due to aggregation of the abrasive and reduce scratches on the object to be polished.

[0112] Examples of water used in the chemical mechanical polishing composition of the present disclosure include ultrapure water, ion-exchanged water, distilled water, and tap water. The water content in the chemical mechanical polishing composition is, for example, 40 to 99 wt %, preferably 45 to 95 wt %, and more preferably 55 to 90 wt %. By adjusting the water content within the above range, the viscosity of the chemical mechanical polishing composition can be adjusted to a range suitable for polishing, and the polishing rate can be improved.

[0113] The chemical mechanical polishing composition of the present disclosure may contain, if necessary, additives such as rust inhibitors, viscosity adjusters, surfactants, pH adjusters, preservatives, and antifoaming agents in addition to the above-mentioned basic compounds, polyglycerin derivatives, and chelating agents.

[0114] The content of the additive in the chemical mechanical polishing composition of the present disclosure is preferably 0.001 to 10 wt %, more preferably 0.05 to 5 wt %, and even more preferably 0.01 to 2 wt %.

[0115] The pH of the chemical mechanical polishing composition of the present disclosure is preferably 10 to 13, and more preferably 11.5 to 12.5.

[0116] The chemical mechanical polishing composition of the present disclosure can be produced by mixing the cleaning composition of the present disclosure with the above-mentioned raw materials such as an abrasive using a conventional mixer. Also, the chemical mechanical polishing composition of the present disclosure can be produced by mixing the above-mentioned raw materials such as the alkanol hydroxylamine compound, the basic compound, the polyglycerin derivative, the chelating agent, the abrasive, and water using a conventional mixer. Such a chemical mechanical polishing composition is in the form of a slurry, and the particle size distribution can be measured using, for example, a laser scattering particle size distribution analyzer.

[0117] The configurations and combinations thereof in the above-described embodiments are merely examples, and additions, omissions, substitutions, and other modifications of the configurations are possible as appropriate within the scope of the gist of the present disclosure. The invention according to the present disclosure is not limited to the embodiments, but is limited only by the claims.

[0118] Additionally, each feature disclosed herein can be combined with any other feature disclosed herein. [Example]

[0119] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples. (Examples 1 to 5 are referred to as Reference Examples 1 to 5) .

[0120] [Cleaning composition]

[0121] <Examples 1 to 5 and Comparative Examples 1 and 2> The components shown in Table 1 were blended to give the contents (wt %) shown in Table 1 to prepare detergent compositions.

[0122] The cleaning compositions were evaluated for maintenance of flatness, removal of abrasives and the like, quality stability, corrosion prevention, removal of complex-containing coatings, and formation of copper oxide coatings as follows. The results are shown in Table 1.

[0123] (Maintaining flatness) A semiconductor wafer (Sematec 845 (copper interconnect, TaN barrier metal, TEOS oxide film), 8-inch diameter, manufactured by Sematec Corporation) was immersed in a 1% benzotriazole (BTA) solution for 1 hour to form a copper(I)-benzotriazole film on the copper interconnect surface. The wafer was then rinsed with pure water, dried, and cut into 2 cm x 2 cm strip samples. The samples were then immersed in 10 mL of the cleaning composition of each example or comparative example for 1 hour, rinsed with pure water, dried under a nitrogen gas stream, and stored at 75% humidity and 40°C for 1 or 3 days. The changes in the roughness of the interconnect surface were measured using a scanning probe microscope (SII NanoTechnology, NanoNavi-S-image, Dynamic Force Mode). The higher the value, the more uneven the interconnect surface. A larger difference in roughness between the 1-day and 3-day samples indicates poorer maintenance of flatness.

[0124] (Removal of abrasives, etc.) 10 mL of the cleaning composition of each of the examples and comparative examples was placed in a centrifuge tube, and 100 μL of a silicon dioxide dispersion (0.2 g of silicon dioxide particles (manufactured by Wako Pure Chemical Industries, Ltd., particle size: 70 nm) dispersed in 10 mL of ultrapure water) was added to prepare Sample 1. 100 μL of an aqueous solution of copper sulfate (CuSO4) was further added to Sample 1 to prepare Sample 2. The zeta potential of Samples 1 and 2 was measured to evaluate the removability of silicon dioxide (abrasive) itself and the removability when silicon dioxide (abrasive) and copper ions (polishing debris) coexist. A smaller zeta potential indicates better removability by the cleaning composition.

[0125] (Quality stability) 50 mL of the cleaning composition of each of the Examples and Comparative Examples was sealed in a 100 mL polyethylene container and stored in a thermostatic chamber at 40°C for one week. The cleaning composition (colorless and clear) immediately after sealing was visually observed for coloration. Coloration indicates poor quality stability of the cleaning composition.

[0126] ○ (Excellent): The composition was not colored. × (bad): The composition was colored

[0127] (corrosion prevention) The samples were obtained in the same manner as in the evaluation of flatness maintenance, and after one day of storage, and the degree of corrosion on the copper wiring surface was observed using a field emission scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation). The evaluation criteria were as follows:

[0128] ○ (Excellent): The wiring surface was not corroded at all. × (bad): At least a part of the wiring surface is corroded

[0129] (Removal of complex-containing coating) (1) A copper-plated silicon substrate (copper plating film thickness 1.5 μm, 8 inches diameter, manufactured by Sematech) was immersed in a 1% benzotriazole (BTA) aqueous solution for 1 hour to form a copper(I)-BTA film on the copper wiring surface, then rinsed with pure water, dried, and cut into 2 cm × 2 cm strip samples. The above samples were immersed in 10 mL of the compositions of the examples and comparative examples for 1 hour, rinsed with pure water, dried under a nitrogen gas stream, and stored at 75% humidity and 40°C for 1 day. (2) A copper-plated silicon substrate (copper plating film thickness: 1.5 μm, 4-inch diameter, manufactured by Sematech) was washed sequentially with methanol and isopropanol and then immersed in a 1% quinaldic acid (QCA) solution containing 0.07% hydrogen peroxide for 30 seconds to form a copper(II)-QCA coating on the copper wiring surface. The substrate was then rinsed with pure water, dried, and cut into 2 cm × 2 cm strip samples. The samples (1) and (2) above were immersed in 10 mL of the compositions of the examples and comparative examples for 1 hour, rinsed with pure water, dried under a nitrogen gas stream, and stored at 75% humidity and 40°C for 1 day. The N1s of each sample stored for 1 day was measured using an X-ray photoelectron spectrometer (XPS) (Kratos, AXIS-His) to confirm whether the copper(I)-BTA coating and copper(II)-QCA coating had been removed. That is, if the N1s spectrum intensity was the same as that of a copper-plated substrate (purchased product) without a coating, it was determined that the copper(I)-BTA coating or copper(II)-QCA coating had been removed.

[0130] (Formation of copper oxide film) In the evaluation of the removal of the complex-containing coating, it was determined that the copper(I)-BTA coating or copper(II)-QCA coating had been removed in all cases of the examples and comparative examples (except Comparative Example 1). For the samples from which these coatings had been removed, the copper LMM analytical lines were measured using an X-ray photoelectron spectrometer (XPS) (Kratos; AXIS-His). The abundance ratio of copper(I) oxide to metallic copper was calculated from the intensities of the analytical lines of copper(I) oxide and metallic copper formed on the copper plating surface. The results are shown in Table 1. Furthermore, using an argon sputtering device built into the X-ray photoelectron spectrometer (XPS), the surface of each sample was etched for 35 seconds (3.5 nm of silicon dioxide equivalent), and the abundance ratio of copper(I) oxide formed inside the copper plating to metallic copper after etching was calculated using the same method as above. The larger the abundance ratio of copper(I) oxide to metallic copper before and after etching, the thicker the copper(I) oxide coating.

[0131] The cleaning compositions of Examples 1 to 5 were excellent in maintaining the flatness of semiconductor wafer surfaces, with small roughness (unevenness) values ​​and differences between samples stored for one and three days (1.5 to 1.7, 1.5 to 1.9, and 0 to 0.2, respectively), and were also found to be excellent in removing abrasives, etc., maintaining quality stability, preventing corrosion, removing complex-containing coatings, and preventing the formation of copper oxide coatings. In contrast, the cleaning composition of Comparative Example 1 had very large roughness values ​​and differences between samples stored for one and three days (6.3, 9.1, and 2.8, respectively), and the cleaning composition of Comparative Example 2 had very large roughness values ​​and differences between samples stored for three days (5.8 and 4.7, respectively).

[0132] [Table 1]

[0133] [Chemical mechanical polishing composition]

[0134] <Examples 6 and 7 and Comparative Examples 3 to 6> The components listed in Table 2 were blended to the content (weight %) shown in Table 2 and mixed using a mixer (product name "TK Homomixer", manufactured by Primix Corporation) to prepare a chemical mechanical polishing composition.

[0135] The chemical mechanical polishing composition was evaluated for polishing properties and filterability as follows. The results are shown in Table 2.

[0136] (abrasive) The workpiece was an 8-inch silicon wafer with a 1 μm thick silicon oxide film formed on its surface by thermal oxidation. The polishing machine used was a single-sided polisher (trade name "EPO113" manufactured by Ebara Corporation), and the polishing pad used was an "IC1000" (manufactured by Rodel).

[0137] Polishing conditions Processing pressure: 5psi Plate rotation speed: 60 rpm Wafer rotation speed: 50 rpm CMP polishing composition supply amount: 150ml / min Polishing time: 2 minutes

[0138] The silicon wafer was polished under the above polishing conditions, and after polishing, the silicon wafer was washed with pure water and dried. Scratches of 0.2 μm or more in length on the silicon wafer surface due to polishing were observed and evaluated according to the following criteria. Note that a Surfscan SP-1 (manufactured by KLA Kencol Co., Ltd.) was used to observe the scratches.

[0139] Evaluation criteria ◎ (Excellent): 0 scratches ○ (Acceptable): 1 or more scratches but less than 5 △ (slightly poor): Number of scratches: 5 or more, but less than 10 × (Poor): 10 or more scratches

[0140] (Filterability test) The CMP polishing compositions 1 to 10 used in the polishing were each collected, and 1 liter of each CMP polishing composition was filtered through a membrane filter (diameter 47 mm) with a pore size of 1 μm at a primary pressure (raw solution side of the filter: p1) of 2 kg / cm 2 Filtration was carried out as set, the secondary pressure (filtrate side of the filter: p2) was measured, the pressure loss was calculated using the following formula, and the filterability was evaluated according to the following criteria. Note that a "Manostar Gauge WO81FN100" (manufactured by Yamamoto Electric Works Co., Ltd.) was used for the pressure measurement. Pressure loss (%) = {(p1-p2) / p1}·100

[0141] Evaluation criteria ◎ (Excellent): Less than 5% ○ (Acceptable): 5% or more, less than 30% △ (slightly poor): 30% or more, less than 50% × (Poor): 50% or more, or filtration impossible due to clogging midway

[0142] The materials used in the examples and comparative examples are as follows. (Polyglycerin derivatives) C1: 1 mol of lauryl alcohol plus 20 mol of 2,3-epoxy-1-propanol (trade name "Glycidol", manufactured by Daicel Corporation) C2: 1 mol of glycerin is added to 19 mol of 2,3-epoxy-1-propanol (trade name "Glycidol", manufactured by Daicel Corporation).

[0143] (Polyoxyalkylene derivatives) A1: 1 mol of ethylene glycol is mixed with 48 mol of ethylene oxide, and then 38 mol of propylene oxide is added. A2: 1 mol of lauryl alcohol to 20 mol of ethylene oxide

[0144] (abrasive) Contains colloidal silica (average primary particle size: 0.035 μm) and cerium oxide (average primary particle size: 0.2 μm)

[0145] The chemical mechanical polishing compositions of Examples 6 and 7 were rated as excellent in polishing ability and excellent in filterability, and were able to suppress the generation of scratches on the silicon wafer surface and also suppress the pressure loss caused by passing through a membrane filter. In contrast, the chemical mechanical polishing compositions of Comparative Examples 3 and 4 were rated as excellent in polishing ability but fair in filterability. Furthermore, the chemical mechanical polishing compositions of Comparative Examples 5 and 6, which used a polyoxyalkylene derivative, were rated as excellent in polishing ability or poor in filterability and poor in filterability.

[0146] [Table 2]

[0147] Variations of the invention according to the present disclosure are described below. [Appendix 1] General formula (1) [ka] (In formula (1), R a1 and R a2 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have 1 to 3 hydroxyl groups. a1 and R a2 cannot be hydrogen atoms at the same time, and R a1 and R a2 The total number of hydroxyl groups in and a pH of 10 to 13. [Appendix 2] R a1 and the R a2 is an alkyl group having 1 to 10 carbon atoms and one hydroxyl group. [Appendix 3] The cleaning composition according to Appendices 1 or 2, wherein the content of the alkanol hydroxylamine compound is 0.05 to 25% by weight. [Appendix 4] The cleaning composition according to any one of Appendices 1 to 3, wherein the content of the alkanol hydroxylamine compound is 0.2 to 0.5% by weight. [Appendix 5] The cleaning composition according to any one of Appendices 1 to 4, wherein the alkanol hydroxylamine compound is a dialkanol hydroxylamine. [Appendix 6] The cleaning composition according to any one of Appendices 1 to 5, wherein the alkanol hydroxylamine compound is N,N-bis(2-hydroxyethyl)-N-hydroxylamine. [Appendix 7] The cleaning composition according to any one of Appendices 1 to 6, further comprising a basic compound other than the alkanol hydroxylamine compound. [Appendix 8] The basic compound is represented by the general formula (2) [ka] (In formula (2), R b1 ~R b4 are the same or different and represent hydrocarbon groups which may have a substituent. 8. The cleaning composition according to claim 7, wherein the quaternary ammonium hydroxide is represented by the formula: [Appendix 9] R b1 ~R b4 9. The cleaning composition according to claim 8, wherein the hydrocarbon group is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. [Appendix 10] R b1 ~R b4 9. The cleaning composition according to claim 8, wherein the hydrocarbon group is a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms. [Appendix 11] R b1 ~R b4 The cleaning composition according to Appendix 8, wherein the hydrocarbon group according to the formula (I) is a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. [Appendix 12] The cleaning composition according to Appendix 7, wherein the basic compound is ammonia, tetramethylammonium hydroxide, or 2-hydroxyethyltrimethylammonium hydroxide. [Appendix 13] The cleaning composition according to any one of Appendices 7 to 12, wherein the content of the basic compound is 0.01 to 5% by weight. [Appendix 14] The cleaning composition according to any one of Appendices 7 to 12, wherein the content of the basic compound is 0.1 to 1% by weight. [Appendix 15] The cleaning composition according to any one of Appendices 7 to 14, wherein the weight ratio of the alkanol hydroxylamine compound to the basic compound (alkanol hydroxylamine compound / basic compound) is 1 to 10. [Appendix 16] The cleaning composition according to any one of Appendices 7 to 14, wherein the weight ratio of the alkanol hydroxylamine compound to the basic compound (alkanol hydroxylamine compound / basic compound) is 1.4 to 5. [Appendix 17] Furthermore, the general formula (3) [ka] (In formula (3), R c represents a hydrogen atom or a hydrocarbon group which may have a hydroxyl group, and n is an integer of 2 to 40. 17. The cleansing composition according to any one of claims 1 to 16, comprising a polyglycerol derivative represented by the following formula: [Appendix 18] R c 18. The cleaning composition according to claim 17, wherein the hydrocarbon group is a linear alkyl group having 12 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or an aliphatic acyl group having 2 to 24 carbon atoms. [Appendix 19] R c 18. The cleaning composition according to claim 17, wherein the hydrocarbon group is a dodecyl group, a stearyl group, an acetyl group, or an oleoyl group. [Appendix 20] The cleaning composition according to any one of Appendices 17 to 19, wherein n is 2 to 40. [Appendix 21] The cleaning composition according to any one of Appendices 17 to 19, wherein n is 4 to 20. [Appendix 22] The cleansing composition according to any one of Appendices 17 to 21, wherein the polyglycerin derivative has a weight-average molecular weight of 200 to 3,000. [Appendix 23] The cleansing composition according to any one of Appendices 17 to 21, wherein the polyglycerin derivative has a weight-average molecular weight of 400 to 800. [Appendix 24] The cleansing composition according to any one of Appendices 17 to 23, wherein the content of the polyglycerin derivative is 0.01 to 15% by weight. [Appendix 25] The cleansing composition according to any one of Appendices 17 to 23, wherein the content of the polyglycerin derivative is 0.1 to 5% by weight. [Appendix 26] Furthermore, the general formula (4) [ka] (In formula (4), X represents a carboxyl group or a phosphonic acid group. R d and R e are the same or different and represent a hydrogen atom or an optionally substituted monovalent hydrocarbon group, R f R represents a divalent hydrocarbon group which may have a substituent. d ~R f Any two of may be bonded to each other to form a ring together with the adjacent nitrogen atom. 26. The cleaning composition according to any one of claims 1 to 25, comprising a chelating agent represented by the formula: [Appendix 27] The cleaning composition according to Appendix 26, wherein the chelating agent is an amino acid, an aminocarboxylic acid, or an aminophosphonic acid. [Appendix 28] The cleaning composition according to Appendix 26, wherein the chelating agent is histidine or 4-imidazolecarboxylic acid. [Appendix 29] The cleaning composition according to any one of Appendices 26 to 28, wherein the content of the chelating agent is 0.05 to 25% by weight. [Appendix 30] The cleaning composition according to any one of Appendices 26 to 30, wherein the content of the chelating agent is 0.2 to 0.5% by weight. [Appendix 31] The cleaning composition according to any one of Appendices 1 to 30, which has a pH of 10 to 13. [Appendix 32] The cleaning composition according to any one of Appendices 1 to 30, which has a pH of 11.5 to 12.5. [Appendix 33] A method for cleaning a semiconductor substrate, comprising cleaning the semiconductor substrate by a dipping, spin or spray cleaning method using the cleaning composition according to any one of Appendices 1 to 32. [Appendix 34] A chemical mechanical polishing composition containing the cleaning composition according to any one of Appendices 1 to 32 and an abrasive. [Appendix 35] The chemical mechanical polishing composition according to Appendix 34, wherein the content of the alkanol hydroxylamine compound is 0.05 to 25 wt %. [Appendix 36] The chemical mechanical polishing composition according to Appendix 34, wherein the content of the alkanol hydroxylamine compound is 0.2 to 0.5 wt %. [Appendix 37] The chemical mechanical polishing composition according to any one of Appendices 34 to 36, wherein the content of the polyglycerin derivative is 0.01 to 15 wt %. [Appendix 38] The chemical mechanical polishing composition according to any one of Appendices 34 to 36, wherein the content of the polyglycerin derivative is 0.1 to 5 wt %. [Appendix 39] The chemical mechanical polishing composition according to any one of Appendices 34 to 38, wherein the weight ratio of the alkanol hydroxylamine compound to the polyglycerin derivative (alkanol hydroxylamine compound / polyglycerin derivative) is 0.003 to 10. [Appendix 40] The chemical mechanical polishing composition according to any one of Appendices 34 to 38, wherein the weight ratio of the alkanol hydroxylamine compound to the polyglycerin derivative (alkanol hydroxylamine compound / polyglycerin derivative) is 0.05 to 3. [Appendix 41] The chemical mechanical polishing composition according to any one of Appendices 34 to 40, wherein the abrasive has an average particle size of 0.005 to 10 μm. [Appendix 42] The chemical mechanical polishing composition according to any one of Appendices 34 to 41, wherein the content of the abrasive is 0.1 to 50 wt %. [Appendix 43] The chemical mechanical polishing composition according to any one of Appendices 34 to 41, wherein the content of the abrasive is 1 to 35 wt %. [Appendix 44] The chemical mechanical polishing composition according to any one of Appendices 34 to 43, wherein the weight ratio of the alkanolhydroxylamine compound to the abrasive (alkanolhydroxylamine compound / abrasive) is 0.001 to 0.5. [Appendix 45] The chemical mechanical polishing composition according to any one of Appendices 34 to 43, wherein the weight ratio of the alkanolhydroxylamine compound to the abrasive (alkanolhydroxylamine compound / abrasive) is 0.05 to 0.3. [Appendix 46] The chemical mechanical polishing composition according to any one of Appendices 34 to 45, wherein the water content is 40 to 99 wt %. [Appendix 47] The chemical mechanical polishing composition according to any one of Appendices 34 to 45, wherein the water content is 55 to 90 wt %. [Appendix 48] The chemical mechanical polishing composition according to any one of Appendices 34 to 47, which has a pH of 10 to 13. [Appendix 49] The chemical mechanical polishing composition according to any one of Appendices 34 to 47, which has a pH of 11.5 to 12.5. [Appendix 50] Use of a composition containing the cleaning composition according to any one of Appendices 1 to 32 and an abrasive as a chemical mechanical polishing composition. [Appendix 51] A method for producing a composition for chemical mechanical polishing, comprising mixing the cleaning composition according to any one of Appendices 1 to 32 with an abrasive. [Industrial Applicability]

[0148] The cleaning composition of the present disclosure is used to clean semiconductor substrates after a CMP process, and is capable of sufficiently removing abrasives, metal fine particles, and anticorrosives, maintaining the flatness of the substrate for a long period after cleaning, and exhibiting excellent long-term quality stability. Furthermore, the chemical mechanical polishing composition of the present disclosure can suppress scratches on polished objects such as semiconductor substrates and reduce filter clogging during filtration during reuse. Therefore, the present disclosure has industrial applicability.

Claims

1. General formula (1) 【Chemistry 1】 (In formula (1), R ａ１ and R ａ２ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have 1 to 3 hydroxyl groups. ａ１ and R ａ２ cannot be a hydrogen atom at the same time, and R ａ１ and R ａ２ The total of the hydroxyl groups in an alkanol hydroxylamine compound represented by the formula: General formula (3) 【Transformation 3】 (In formula (3), R c represents a hydrogen atom or a hydrocarbon group which may have a hydroxyl group, and n represents an integer of 2 to 40.) and a basic compound other than the alkanol hydroxylamine compound, a weight ratio of the alkanol hydroxylamine compound to the basic compound (alkanol hydroxylamine compound / basic compound) is 1 to 10; A cleaning composition having a pH of 10 to 13.

2. The R ａ１ and the R ａ２ The cleaning composition according to claim 1, wherein is an alkyl group having 1 to 10 carbon atoms and one hydroxyl group.

3. 3. The cleaning composition according to claim 1, wherein the content of the alkanol hydroxylamine compound is 0.05 to 25% by weight.

4. The basic compound is represented by the general formula (2): 【Chemistry 2】 (In formula (2), R ｂ１ ~R ｂ４ are the same or different and represent hydrocarbon groups which may have a substituent. The cleaning composition according to any one of claims 1 to 3, wherein the quaternary ammonium hydroxide is represented by the formula:

5. The cleaning composition according to any one of claims 1 to 4, wherein the basic compound is ammonia, tetramethylammonium hydroxide, or 2-hydroxyethyltrimethylammonium hydroxide.

6. The cleaning composition according to any one of claims 1 to 5, wherein the content of the basic compound is 0.01 to 5% by weight.

7. Furthermore, general formula (4) 【Chemistry 4】 (In formula (4), X represents a carboxyl group or a phosphonic acid group. R ｄ and R ｅ are the same or different and represent a hydrogen atom or an optionally substituted monovalent hydrocarbon group, R ｆ represents a divalent hydrocarbon group which may have a substituent. ｄ ~R ｆ Any two of may be bonded to each other to form a ring together with the adjacent nitrogen atom. The cleaning composition according to any one of claims 1 to 6, comprising a chelating agent represented by the formula:

8. A chemical mechanical polishing composition comprising the cleaning composition according to any one of claims 1 to 7 and an abrasive.

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