WO2023282287A1

WO2023282287A1 - Cleaning agent composition for post-cmp step

Info

Publication number: WO2023282287A1
Application number: PCT/JP2022/026835
Authority: WO
Inventors: 大輔殿谷; 千帆水島; 尊子張替; 裕大藤井; スリャデバラヴィ．バブ; ジフーンソ; スリシヴァラマクリシュナハヌップヴェギ; アリオスマン; ゴラハリーアルンクマールベンカタロナパ
Original assignee: 株式会社日本触媒; クラークソンユニバーシティ
Priority date: 2021-07-08
Filing date: 2022-07-06
Publication date: 2023-01-12
Also published as: TW202311514A

Abstract

The purpose of the present invention is to provide a cleaning agent composition that is for a post-CMP step and that exhibits excellent removal performance and attachment inhibition for metal residues or organic residues remaining on a polished surface obtained by flattening a substrate, and that has excellent corrosion inhibition. The present invention relates to: a cleaning agent composition for a post-CMP step in a semiconductor production process, the composition including (1A) at least one compound selected from the group consisting of N-vinyllactam-based polymers and nonionic surfactants including an alkylene oxide adduct of an alcohol having 6 or more carbon atoms, (1B) an aliphatic amine, and (1C) at least one corrosion inhibitor selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds; and a cleaning agent composition for a post-CMP step, the composition including (2A) at least one compound selected from the group consisting of N-vinyllactam-based polymers and nonionic surfactants having an alkylene oxide adduct structure of an aliphatic alcohol, (2B) an organic acid compound, and (2C) a pH conditioner.

Description

Post-cleaning composition for CMP process

The present invention relates to a cleaning composition after the CMP step in semiconductor manufacturing processes. More specifically, the present invention relates to a post-CMP cleaning composition that is excellent in removing metal residues and organic residues and suppressing their adhesion, as well as in corrosion suppression.

CMP (Chemical-Mechanical-Planarization/Polishing) is a type of wafer surface planarization technology in the semiconductor manufacturing process, using chemical abrasives and polishing pads, chemical action and mechanical polishing It is a polishing technology that grinds the unevenness of the wafer surface and flattens it by the combined action of Metal residues such as abrasive grains and polishing dust remain on the flattened wafer surface after polishing. In addition, since the wafer surface has high metal activity and is easily corroded (oxidized), a protective film is formed with an anticorrosive agent, and the components of the protective film may remain as organic residues after polishing. Since these residues adversely affect the electrical properties of semiconductors, etc., post-CMP cleaning is performed to remove the residues.

Post-CMP cleaning is usually performed by combining chemical cleaning using a cleaning agent and physical cleaning using a brush or the like. As the cleaning agent, a cleaning composition containing a main component, a chelating agent, a surfactant and the like is usually used.

Post-cleaning compositions for CMP processes have been extensively studied (Patent Documents 1 to 10).
For example, Patent Document 1 discloses a working liquid useful for modifying a wafer surface, which contains water, a pH buffering agent containing a basic pH adjuster and an acidic complexing agent, and a surfactant, and has a pH of 7 to 12. Patent Document 2 describes a cleaning agent for substrates having metal wiring, which contains an aqueous solution having a pH of 10 or more and containing a carboxylic acid having a nitrogen-containing heterocycle and an alkylhydroxylamine.

Further, in Patent Document 3, one or more kinds of basic compounds and one or more kinds of heterocyclic monocyclic aromatic compounds containing a nitrogen atom are included, and the hydrogen ion concentration (pH) is 8 to 11, and Patent Document 4 describes a semiconductor containing a compound having an amine group and a carboxyl group, adenine, purine, uric acid, derivatives thereof, etc., a pH adjuster, and water. A substrate cleaning solution for devices is described.

Further, for example, in Patent Document 5, a specific organic quaternary ammonium hydroxide, a surfactant, a chelating agent, an amino acid having a sulfur atom and/or a derivative thereof, benzotriazole, imidazole, triazole, A semiconductor device substrate cleaning liquid containing at least one selected from the group consisting of tetrazole and derivatives thereof and having a pH of 9 or more is disclosed.

In addition, Patent Document 6 describes a cleaning liquid that can reduce cerium compounds remaining on a substrate more safely and easily than the conventional technique, comprising water, sugars exhibiting reducing properties in an alkaline atmosphere, and an alkaline component. and has a pH of 7 or higher at 25°C. Patent Document 7 describes at least one selected from the group consisting of alkanolamine compounds and heterocyclic amine compounds, and a quaternary ammonium A cleaning solution for cleaning semiconductor wafers is described that includes hydroxide, citric acid, and ascorbic acid.

Japanese Patent Publication No. 2010-537404 WO2014/168166 JP 2014-212262 A JP 2016-86094 A JP 2014-154625 A JP 2014-225503 A JP 2020-96053 A JP 2012-216690 A JP 2018-107353 A WO2019/073931

However, conventional post-cleaning compositions for the CMP process remove metal residues such as abrasive grains or polishing shavings derived from abrasives and organic residues derived from anticorrosives existing on the wafer surface after the CMP process. It cannot be said that the preventive function is still sufficient, and there is room for improvement. In addition, semiconductor wafers have deposited layers such as metal films and insulating films that become wiring on the substrate, and various metal materials are used for these. You need to be able to perform.

In particular, in recent years, as semiconductor logic devices have become more and more highly integrated due to progress in miniaturization, it is expected that cobalt and ruthenium will be used for the metal deposit layer formed on the wafer surface as well as conventional aluminum and copper. Since a higher level of flatness is required in the CMP process, abrasive grains with a smaller grain size and a higher degree of sphericity than conventional ones are adopted, so that van der Waals forces and electrostatics on the polishing substrate are used. It becomes difficult to completely wash off the abrasive grains with conventional cleaning liquids. In addition, a new cleaning mechanism is required because the polishing residue generated after the CMP process becomes a complex of the organic antirust agent present as a protective layer on the outermost surface of the deposited metal layer and transition metal ions such as cobalt ions. In addition, with the adoption of new metal films, a new problem arises in that metal corrosion is caused when conventionally used post-CMP cleaning solutions are used at the interfaces of metal multilayer films.

In addition, when a polishing slurry containing ceria (cerium oxide: CeO ₂ ) particles is used to perform CMP on a SiO ₂ substrate, Si—O—Ce bonds are formed on the substrate, leaving ceria particles on the substrate. There was a problem that it became easier to Also, in order to remove these residues, it was necessary to use a component such as hydrogen peroxide that requires careful handling.
In addition, a semiconductor wafer has deposited layers such as a metal film and an insulating film that become wiring on a substrate, and various metal compound materials including copper, cobalt, tantalum, tungsten, titanium, etc. are used for these. Since these various metal compound materials are exposed on the wafer surface after CMP, the post-CMP cleaning composition can exhibit excellent cleaning function and corrosion inhibiting function for these metal compound materials as well. is desirable. Furthermore, in recent years, semiconductor devices have become increasingly faster and more highly integrated, and there is a demand for even more advanced CMP processing characteristics.
Thus, there has been a need for a post-cleaning composition for CMP processes that can simultaneously solve these problems as well as the CMP processing properties.

The present invention has been made in view of the above-mentioned current situation, and is a post-CMP cleaning composition that is excellent in removing and inhibiting adhesion of metal residues and organic residues remaining on a polished surface of a flattened substrate, and is also excellent in inhibiting corrosion. The purpose is to provide goods.

In order to solve the above problems, the present inventors have conducted various studies on post-cleaning compositions for the CMP process, and found that a specific nonionic surfactant and/or N-vinyllactam polymer and an aliphatic amine , and a specific corrosion inhibitor, the removal of metal residues and organic residues and the adhesion-inhibiting action are remarkably improved, and the corrosion-inhibiting action is also excellent. Further, by using a combination of a specific nonionic surfactant and/or N-vinyllactam polymer, an organic acid compound, and a pH adjuster, it is possible to perform the CMP process using ceria as polishing abrasive grains. It was found that the removal and adhesion suppression of metal residues and organic residues on the surface of the wafer that was carried out were remarkably improved, and the corrosion suppression was also excellent. Based on these findings, the inventors have made intensive studies and completed the present invention.

That is, the first present invention provides (1A) at least one selected from the group consisting of a nonionic surfactant containing an alkylene oxide adduct of an alcohol having 6 or more carbon atoms, and an N-vinyl lactam polymer. , (1B) aliphatic amines, and (1C) at least one corrosion inhibitor selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds. is a post-cleaning composition for the CMP process in.

The above aliphatic amines preferably have a molecular weight of 2000 or less.

The aliphatic amines preferably contain an amine compound represented by the following general formula (1) and/or a polyalkyleneimine.

(In Formula (1), R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom, an alkyl group, or —R ⁴ —(NH—R ⁵ ) _n —NH _2. R ⁴ and R ⁵ is the same or different and represents an alkylene group having 1 to 6 carbon atoms, and n represents an integer of 0 to 100.)

The nitrogen-containing heterocyclic compound preferably contains at least one selected from the group consisting of pyrrole, pyridine, triazole, triazine, purine, and derivatives thereof.

The carboxylate compound preferably contains a fatty acid salt.

The post-CMP cleaning composition is suitable for use on wafer surfaces where a compound containing at least one selected from the group consisting of cobalt, copper, aluminum, ruthenium, titanium nitride, silicon nitride, and silicon oxide is exposed. It is preferably used for washing.

The second aspect of the present invention provides (2A) at least one compound selected from the group consisting of a nonionic surfactant having an alkylene oxide adduct structure of an aliphatic alcohol, and an N-vinyllactam polymer. , (2B) an organic acid compound, and (2C) a pH adjuster.

The content of the oxidizing agent in the post-CMP cleaning composition is preferably 1.0% by mass or less with respect to 100% by mass of the post-CMP cleaning composition.

The aliphatic alcohol alkylene oxide adduct structure preferably has an alkylene oxide adduct structure of an aliphatic alcohol having 6 or more carbon atoms, and includes block polymer structures of two or more alkylene oxides.

The aliphatic alcohol is preferably a secondary or tertiary alkyl alcohol having 6 or more carbon atoms.

The pH adjuster is preferably a basic pH adjuster.

The basic pH adjuster preferably contains at least one compound selected from the group consisting of hydroxides, organic amines, organic amine salts, and ammonium salts.

The organic acid compound preferably contains at least one compound selected from the group consisting of carboxylic acid compounds and ascorbic acid.

The post-CMP cleaning composition is preferably a post-CMP cleaning composition using ceria as abrasive grains.

The post-CMP cleaning composition is preferably used for cleaning the surface of a film containing silicon oxide and/or silicon nitride in a semiconductor manufacturing process.

The post-cleaning composition for the CMP process of the present invention is excellent in removing and preventing adhesion of metal residues and organic residues on the wafer surface, and is also excellent in suppressing corrosion. The post-CMP cleaning composition of the present invention can be suitably used as a post-CMP cleaning composition in semiconductor manufacturing processes.

1 is an AFM observation image of the surface of a substrate for cleaning evaluation when cleaning performance evaluation of the cleaning compositions of Examples 1 to 3 and Comparative Examples 1 and 2 is performed. Using the cleaning compositions of Examples 11 to 12, 17 to 18, and Comparative Examples 4 and 5, cleaning treatment of SiO ₂ substrates A-1 and A-2 for cleaning performance evaluation and non-cleaning. 4 is an AFM image showing the surface condition of the substrate. FIG. 10 is an AFM image showing the surface state of the SiO ₂ substrates A-1 and A-2 for evaluating cleaning performance when the cleaning compositions of Examples 13 to 15 and Comparative Example 6 were used to clean the substrates. FIG. . An AFM showing the surface state of the SiN substrates B-1 and B-2 for cleaning performance evaluation with and without cleaning using the cleaning compositions of Examples 11, 13 and 16. It is an image.

The present invention will be described in detail below.
A combination of two or more of the individual preferred embodiments of the invention described below is also a preferred embodiment of the invention.

<Post-cleaning composition for CMP process>
A first aspect of the present invention provides (1A) at least one compound selected from the group consisting of a nonionic surfactant containing an alkylene oxide adduct of an alcohol having 6 or more carbon atoms, and an N-vinyllactam polymer. , (1B) aliphatic amines, and (1C) at least one corrosion inhibitor selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds in a semiconductor manufacturing process, A post-cleaning composition for a CMP process.
The second aspect of the present invention provides (2A) at least one compound selected from the group consisting of a nonionic surfactant having an alkylene oxide adduct structure of an aliphatic alcohol, and an N-vinyllactam polymer. , (2B) an organic acid compound, and (2C) a pH adjuster.
Each invention will be described below. In the present specification, the first invention is also referred to as the "first post-cleaning composition for the CMP process", and the second invention is also referred to as the "second post-CMP cleaning composition". called. In addition, these are also collectively referred to as "the post-cleaning composition for the CMP process of the present invention".

<First post-cleaning composition for CMP process>
The first post-CMP cleaning composition of the present invention contains the above-described three specific components (1A), (1B) and (1C) to remove and suppress adhesion of metal residues and organic residues. It is also excellent in corrosion control. The first post-cleaning composition for the CMP process of the present invention is excellent in removing and inhibiting the adhesion of metal residues and organic residues, and is also excellent in inhibiting corrosion. The nonionic surfactant or N-vinyllactam polymer contained in the surfactant permeates the surface of the substrate and the interface of the abrasive residue and dirt, causing it to float in the water, which is the main component of the cleaning liquid, while the aliphatic amines are highly distributed to the heavy metal ions. This is presumed to be due to the ability to reduce the adsorptive power of the polishing residue to the fresh metal surface exposed in the CMP process. In addition, the adsorption of the nitrogen-containing heterocyclic compound and the carboxylate compound on the surface of the deposited metal film allows the electrochemical interaction between the chemical components coexisting in the cleaning composition to be in an equilibrium state, thereby forming the deposited metal film. It is presumed that the corrosion potential and corrosion current value of the metal species constituting the can be reduced.

The components contained in the first post-CMP cleaning composition will be described.

(1A) Nonionic Surfactant and/or N-Vinyllactam Polymer The first post-cleaning composition for the CMP step is a nonionic surfactant containing an alkylene oxide adduct of an alcohol having 6 or more carbon atoms. , and at least one compound selected from the group consisting of N-vinyllactam polymers (hereinafter also referred to as “compound (1A)” or “component (1A)”). By including the above compound (1A), it can penetrate into the interface between the substrate surface and the abrasive residue and dirt, and stably maintain the state in which the residue and the like float in water, which is the main component of the cleaning liquid.
Ionic surfactants such as cationic or anionic surfactants are ionic, and are remarkably adsorbed due to electrostatic interaction with the cleaned substrate. It may become a contaminant when commercialized. On the other hand, nonionic surfactants and N-vinyllactam polymers have little electrostatic interaction due to their lack of ionicity, and are rinsed with pure water even when they are adsorbed on the cleaned substrate surface after the CMP process. can be easily removed by Therefore, in the present invention, nonionic surfactants and/or N-vinyllactam polymers are used.

(1A-1) Nonionic Surfactants As nonionic surfactants, there are polyhydric alcohol types in which polyhydric alcohols and fatty acids are ester-bonded, and compounds having hydroxyl groups such as higher alcohols, alkylphenols, and propylene glycol, and alkylene oxides. Known nonionic surfactants such as adduct ether type surfactants can be used, and in the present invention, at least nonionic surfactants containing alkylene oxide adducts of alcohols having 6 or more carbon atoms are included.

The alkylene oxide adduct of an alcohol having 6 or more carbon atoms is a compound obtained by adding an alkylene oxide to an alcohol having 6 or more carbon atoms.

Examples of alcohols having 6 or more carbon atoms include hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecanol, pentadecanol, hexadecanol, and heptadeca. alkyl alcohols such as nol, octadecanol, nonadecanol, eicosanol, 1,2-hexanediol, 1,6-hexanediol, 1,10-decanediol; cyclohexyl alcohol, cycloheptyl alcohol, 1,4-cyclohexanedimethanol, cycloalkyl alcohols such as 1,4-cyclohexanediol; allyl alcohol; alkylphenyl alcohols such as octylphenol and nonylphenol;
Of these, alkyl alcohols are preferable as the alcohol having 6 or more carbon atoms, from the viewpoints of relatively easy adjustment of the hydrophobicity depending on the structure and the addition position and environmental toxicity. The above alkyl alcohol may be linear or branched.

The carbon number of the alcohol is preferably 10 or more, preferably 20 or less, and more preferably 18 or less.
In addition, the alcohol having 6 or more carbon atoms is preferably a secondary or tertiary alcohol, more preferably a secondary alcohol, in that it can achieve both high penetrating power to the solid residue interface and metal corrosion inhibition performance. preferable.
The alcohol having 6 or more carbon atoms may be monovalent, divalent, or polyvalent, but monovalent alcohol is preferable from the viewpoint of ease of production and cost.

Examples of the alkylene oxide to be added to the alcohol having 6 or more carbon atoms include ethylene oxide, propylene oxide, butylene oxide, etc. Among them, at least one selected from the group consisting of ethylene oxide and propylene oxide is preferable, A mixed type of ethylene oxide and propylene oxide is more preferred.

Examples of the alkylene oxide adducts of alcohols having 6 or more carbon atoms include primary alcohol ethoxylate, secondary alcohol ethoxylate, tertiary alcohol ethoxylate, octylphenyl ethoxylate, nonylphenyl ethoxylate, benzylphenyl ethoxylate, and acetylene. Primary alcohol ethoxylate, acetylenic primary dialcohol ethoxylate, acetylenic secondary alcohol ethoxylate, acetylenic secondary dialcohol ethoxylate, acetylenic tertiary alcohol ethoxylate, acetylenic tertiary dialcohol ethoxylate, etc. be done.
The above ethoxylates are those to which at least ethylene oxide (EO) is added, and those to which ethylene oxide (EO) and other alkylene oxides (eg, propylene oxide (PO)) are added are also included.

The alkylene oxide adduct of the alcohol having 6 or more carbon atoms preferably has a clouding point of 25° C. or higher, and a clouding point of 40° C. or higher, because it can form a uniform solution without separating in the detergent composition. is more preferable. The above cloud point can be obtained by a method of lowering the temperature of a 1% aqueous solution of a nonionic surfactant while stirring and monitoring the temperature, and observing the temperature at which the solution becomes transparent visually.

Specific examples of the nonionic surfactant include, for example, a polyalkylene oxide alkyl ether surfactant, a block polymer system composed of polyethylene oxide and polypropylene oxide, a polyalkylene oxide alkylphenyl ether surfactant, polyoxy Alkylene distyrenated phenyl ether-based surfactants, polyalkylene tribenzylphenyl ether-based surfactants, acetylene polyalkylene oxide-based surfactants, and the like are included.
Among them, polyalkylene oxide alkyl ether-based surfactants and block polymer-based surfactants composed of polyethylene oxide and polypropylene oxide are preferable because they can suppress corrosion of the metal laminated film due to the detergent composition.

Specifically, the alkylene oxide adduct of alcohol having 6 or more carbon atoms is preferably a compound represented by the following general formula (2) or (3).

(In Formula (2), R ⁶ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or an alkyl group. R ⁹ and R ¹⁰ are the same or different and represent an alkylene group. x and y are the same or different and represent an integer of 0 to 50. (x+y) is an integer of 1 or more.
In formula (3), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and represent a hydrogen atom or an alkyl group. R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are the same or different and represent an alkylene group or an alkynylene group. x and y are the same or different and represent an integer of 0 to 50; (x+y) is an integer of 1 or more. )

In the general formula (2), the alkyl groups represented by R ⁶ , R ⁷ and R ⁸ may be linear or branched.
The number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-18, even more preferably 1-16.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, iso-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2 , 2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, octyl group, methylheptyl group, dimethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, trimethylpentyl group, 3-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2,2,3,3-tetramethylbutyl group, nonyl group, Examples include linear or branched alkyl groups such as decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups.

In general formula (2) above, two or more of R ⁶ , R ⁷ and R ⁸ are preferably alkyl groups in that the molecular structure is compact and high permeability can be exhibited.

In general formula (2) above, the total number of carbon atoms in R ⁶ , R ⁷ and R ⁸ is preferably 5 to 19, more preferably 7 to 17, even more preferably 9 to 15. Preferably, 11-13 is most preferred.

In general formula (2) above, the alkylene group represented by R ⁹ and R ¹⁰ may be linear or branched.
Examples of the alkylene group include methylene group, ethylene group, n-propylene group, 2-propylene group, n-butylene group, pentamethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group and nonamethylene group. , decamethylene group, methylmethylene group, methylethylene group, 1-methylpentylene group, 1,4-dimethylbutylene group and the like. Among them, an alkylene group having 2 or 3 carbon atoms is preferable in terms of ease of production and ability to control hydrophilicity and hydrophobicity.

In the above general formula (2), —(R ⁹ O) _x (R ¹⁰ O) _y H is —(CH ₂ CH ₂ O) _x H, -(CH ₂ CH ₂ O) _x (CH ₂ CH(CH ₃ )O) _y H, preferably -(CH ₂ CH ₂ O) _x (CH ₂ CH(CH ₃ ) O) _yH is more preferred.

In the general formula (2), x and y are the same or different and are an integer of 0 to 50, preferably an integer of 0 to 30, more preferably an integer of 0 to 24, 0 An integer of ˜16 is even more preferred.
x represents the average number of added moles of alkylene oxide (R ⁹ O), and y represents the average number of added moles of alkylene oxide (R ¹⁰ O). x and y may be the same or different in any alkylene oxide.
x is preferably an integer of 1-20, more preferably an integer of 3-18, even more preferably an integer of 5-16.
y is preferably an integer of 0-20, more preferably an integer of 0-15, even more preferably an integer of 1-10.
(x+y) is an integer of 1 or more. That is, at least one of x and y is an integer of 1 or more.
(x+y) is preferably an integer of 1-50, more preferably an integer of 3-30.

In the above general formula (3), the alkyl groups represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same as the alkyl groups represented by R ⁶ , R ⁷ and R ⁸ described above. be done.
Among them, the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a tert-butyl group in that the molecular structure becomes compact and high permeability can be expressed. , sec-butyl or iso-butyl groups are preferred.

In general formula (3) above, the total number of carbon atoms of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is preferably 5 to 20 from the viewpoint of the balance between hydrophilicity and hydrophobicity of the surfactant, It is more preferably 6-16, and even more preferably 8-12.

In the general formula (3), examples of the alkylene group represented by R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ include the same alkylene groups represented by R ⁹ and R ¹⁰ described above. be done. Among them, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are preferably an alkylene group, more preferably an alkylene group having 2 or 2 carbon atoms.
In the general formula (3), examples of the alkynylene group represented by R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ include an ethynylene group (-C≡C-), a propynylene group (-C≡C —CH ₂ —), 1-butynylene group (—C≡C—CH ₂ —CH ₂ —), 2-butynylene group (—CH ₂ —C≡C—CH ₂ —), and the like. Among them, R ¹⁹ is preferably an alkynylene group, more preferably an ethynylene group, a propynylene group, a 1-butynylene group, or a 2-butynylene group, and an alkynylene group having 2 or 3 carbon atoms. is more preferred, and an alkylene group having 2 carbon atoms is most preferred.

In the general formula (3), —(R ¹⁵ O) _x (R ¹⁶ O) _y —H and —(R ¹⁷ O) _x (R ¹⁸ O) _y —H are the above-mentioned —(R ⁹ O ) _x (R ¹⁰ O) _y H and the same groups are preferably mentioned.

In the general formula (3), x and y are the same or different and are an integer of 0 to 50, preferably an integer of 0 to 30, more preferably an integer of 0 to 24, 0 An integer of 0 to 20 is more preferred, an integer of 0 to 16 is even more preferred, an integer of 0 to 15 is particularly preferred, and an integer of 0 to 10 is most preferred.
x represents the average number of added moles of alkylene oxide (R ¹⁵ O) and (R ¹⁷ O), and y represents the average number of added moles of alkylene oxide (R ¹⁶ O) and (R ¹⁸ O). x and y may be the same or different in any alkylene oxide.
x is preferably an integer of 1-20, more preferably an integer of 1-12, and even more preferably an integer of 2-8.
y is preferably an integer of 0 to 20, more preferably an integer of 0 to 10, still more preferably an integer of 0 to 8, and even more preferably an integer of 0 to 5 .
(x+y) is an integer of 1 or more. That is, at least one of x and y is an integer of 1 or more.
(x+y) is preferably an integer of 1-50, more preferably an integer of 2-30, and even more preferably an integer of 3-30.

(1A-2) N-Vinyllactam Polymer The N-vinyllactam polymer is obtained by polymerizing a monomer component containing an N-vinyllactam monomer which is a monomer having a lactam ring. It is a polymer that can be Specific examples of the N-vinyllactam monomers include N-vinylpyrrolidone, N-vinylcaprolactam, 3-methyl-N-vinylpyrrolidone, 4-methyl-N-vinylpyrrolidone, 5-methyl-N -vinylpyrrolidone, N-vinylpiperidone, 1-(2-propenyl)-2-pyrrolidone, N-vinyl-4-butylpyrrolidone, N-vinyl-4-propylpyrrolidone, N-vinyl-4-ethylpyrrolidone, N-vinyl -4-methylpyrrolidone, N-vinyl-4-methyl-5-ethylpyrrolidone, N-vinyl-4-methyl-5-propylpyrrolidone, N-vinyl-5-methyl-5-ethylpyrrolidone, N-vinyl-5 -propylpyrrolidone, N-vinyl-5-butylpyrrolidone, N-vinyl-4-methylcaprolactam, N-vinyl-6-methylcaprolactam, N-vinyl-6-propylcaprolactam, N-vinyl-7-butylcaprolactam and the like mentioned. Among them, polyvinylpyrrolidone obtained by polymerizing a monomer component containing N-vinylpyrrolidone is preferable as the N-vinyllactam polymer.

The weight average molecular weight of the N-vinyllactam polymer is preferably 500 to 50,000, more preferably 1,000 to 40,000, even more preferably 2,000 to 30,000.
The weight average molecular weight can be obtained by measuring by a gel permeation chromatography (GPC) method (in terms of PEO).

The above nonionic surfactant and N-vinyllactam polymer may be used alone or in combination of two or more.

The content of the compound (1A) (component (1A)) is preferably 0.5 to 65% by mass with respect to 100% by mass of the active ingredient in the first post-CMP step cleaning composition. , more preferably 1 to 60% by mass, even more preferably 2 to 55% by mass.
As used herein, the term “active ingredient” refers to all ingredients other than the solvent in the post-cleaning composition for the CMP process.

The content of the compound (1A) (component (1A)) is preferably 0.001 to 5% by mass with respect to 100% by mass of the first post-CMP step cleaning composition. 005 to 2% by mass, and even more preferably 0.01 to 1% by mass.

(1B) Aliphatic Amines The first post-cleaning composition for the CMP step contains aliphatic amines (hereinafter also referred to as "aliphatic amines (1B)" or "component (1B)"). . By including aliphatic amines, the ability of the aliphatic amines to coordinate heavy metal ions is high, so that the adsorption power of polishing residues to fresh metal surfaces exposed in the CMP process can be reduced.

Examples of the aliphatic amines (1B) include primary aliphatic amines, secondary aliphatic amines, and tertiary aliphatic amines.

The aliphatic amines (1B) preferably contain an amine compound represented by the following general formula (1) and/or a polyalkyleneimine.

In general formula (1) above, R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom, an alkyl group, or —R ⁴ —(NH—R ⁵ ) _n —NH ₂ .
The number of carbon atoms in the alkyl group represented by R ¹ , R ² and R ³ is preferably 1 to 6, more preferably 1 to 5, and 1 to 4, from the viewpoint of water solubility. is more preferred.

In --R ⁴ --(NH--R ⁵ ) _n --NH ₂ represented by R ¹ , R ² and R ³ , R ⁴ and R ⁵ are the same or different and represent an alkylene group having 1 to 6 carbon atoms. .
Also, n represents an integer of 0-100. n represents the number of repetitions of -(NH-R ⁵ )-, preferably an integer of 0 to 50, more preferably an integer of 0 to 30, still more preferably an integer of 0 to 20, particularly preferably Represents an integer from 0 to 10.

Specific examples of the compound represented by the general formula (1) include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, diethylenetriamine, N-ethylbutylamine, 1,2-bis-(3 -aminopropylamino)ethane, tributylamine, 3-(diethylamino)propylamine, triethylenetetramine, tetraethylenepentamine and the like. Among them, at least one selected from the group consisting of ethylenediamine, diethylenetriamine, N-ethylbutylamine, 3-(diethylamino)propylamine, and 1,2-bis-(3-aminopropylamino)ethane in terms of low toxicity. is preferred.

Examples of the polyalkyleneimine include polyethyleneimine, polypropyleneimine, polybutyleneimine, polypentyleneimine, and the like.
The above polyalkyleneimine may be linear or branched. Among them, a branched shape is preferable in terms of ease of production.

The molecular weight of the aliphatic amines (1B) is preferably 2000 or less. When the molecular weight is 2000 or less, the viscosity of the post-cleaning composition for the CMP process is favorable. The molecular weight of the aliphatic amines is more preferably 300 or less, still more preferably 250 or less, and even more preferably 220 or less.
The molecular weight of the above-mentioned aliphatic amine (1B) is preferably 50 or more because of its low boiling point.

The aliphatic amines (1B) may be used alone or in combination of two or more.

The content of the aliphatic amine (1B) (component (1B)) is 30 to 95% by mass with respect to 100% by mass of the active ingredients in the first post-CMP step cleaning composition. It is preferably from 35 to 93% by mass, and even more preferably from 40 to 90% by mass.

The content of the aliphatic amine (1B) (component (1B)) is preferably 0.01 to 5% by mass with respect to 100% by mass of the first post-cleaning composition for the CMP step. , more preferably 0.05 to 2% by mass, and even more preferably 0.1 to 1% by mass.

(1C) Corrosion inhibitor The post-cleaning composition for the first CMP step contains a corrosion inhibitor (hereinafter also referred to as "corrosion inhibitor (1C)" or "component (1C)"), As an inhibitor, at least one selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds is included.

(1C-1) Nitrogen-Containing Heterocyclic Compound The nitrogen-containing heterocyclic compound is not particularly limited as long as it is a compound having a heterocyclic ring having at least one nitrogen atom. It may contain atoms. The nitrogen-containing heterocyclic ring may be either saturated or unsaturated, but is preferably a nitrogen-containing unsaturated heterocyclic ring in terms of high adsorption performance with respect to the transition metal film.
In addition, the above nitrogen-containing heterocyclic compound may be a heteromonocyclic compound or a condensed heterocyclic compound.

Examples of the heteromonocyclic compounds include five-membered ring compounds such as pyrrole, pyrazoline, pyrazole, imidazole, triazole, imidazoline, oxazoline, oxazole, and isoxazole; piperidine, pyridine, pyrazine, piperazine, pyrimidine, pyridazine, triazine, morpholine 6-membered ring compounds such as; and derivatives thereof.
Examples of the derivative include compounds in which at least one atom in the nitrogen-containing heterocyclic ring is substituted with an alkyl group, an aryl group, an amino group, a carboxyl group, a hydroxy group, a ketone group, or a group combining these. be done.

Specific examples of the heteromonocyclic compounds include 1H-pyrrole, 1-pyrroline, 2-pyrroline, 3-pyrroline, pyrrolidine, pyrrolidone, γ-butyrolactam, γ-valerolactam, proline, prolyl, 1H-pyrazole, 1-pyrazoline, 2-pyrazoline, pyrazolidine, pyrarizolidone, 3-pyrazolone, 4-pyrazolone, 5-pyrazolone, 1H-pyrazole-4-carboxylic acid, ethyl pyrazole-4-carboxylate, 1-methyl-1H-pyrazole-5 -carboxylic acid, 5-methyl-1H-pyrazole-3-carboxylic acid, 3,5-pyrazoledicarboxylic acid, 3-amino-5-hydroxypyrazole, 1H-imidazole, 2-imidazoline, 3-imidazoline, 4-imidazoline, imidazolidine, imidazolidone, ethyleneurea, hydantoin, allantoin, histidine, histidyl, histamine, 1,2,3-triazole, 1,2,4-triazole, 1-hydroxybenzotriazole, 3-amino-1,2,4- triazole, 4-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, piperidine, piperidyl, piperidylidene, piperidylene, piperidone, pipecolic acid, pipecoloyl, pipecolamide, nipecotic acid, isonipecotoyl, isonipecotoamide, peretieline, isoperetieline, piperine, isopiperine, moldicine, isocavicin, pyridine, pyridyl, pyridylidene, pyridylene, pyridylene, 2-pyridone, 4-pyridone, picoline, α-collidine, β-collidine, γ-collidine, picoline , nicotinic acid, nicotinamide, isonicotinic acid, isonicotinoyl, citrazinic acid, quinolinic acid, rutidic acid, isocincomeronic acid, dipicolinic acid, cincomeronic acid, dinicotinic acid, berberic acid, fusaric acid, ethionamide, nicotine, cotinine, anabasine , Anatabine, Homarin, Aminohydroxypyrazole, Dihydroxypyridine, Pyrazine, Pyrazinoic acid, Pyrazinoyl, Pyrazinamide, Piperazine, Pyrimidine, Cytosine, Uracil, Thymine, Orotic acid, Uramyl, Thiamine, Pyritadin, Maleic hydrazide, Melamine, Cyanuric acid, etc. is mentioned.

Examples of the condensed heterocyclic compound include indole, isoindole, benzimidazole, benzotriazole, triazine, quinoline, isoquinoline, quinazoline, purine, cinnoline, phthalazine, quinoxaline, acridine, phenanthridine, and derivatives thereof. be done.

Specific examples of the condensed heterocyclic compound include benzotriazole and uric acid.

Among them, the nitrogen-containing heterocyclic compound may contain at least one selected from the group consisting of pyrrole, pyridine, triazole, triazine, purine, and derivatives thereof, because of its high adsorption performance to transition metal films. Uric acid, nicotinic acid, triazole, or melamine is more preferred, and uric acid is even more preferred.
The above nitrogen-containing heterocyclic compounds may be used alone or in combination of two or more.

(1C-2) Carboxylate Compound The carboxylate compound is not particularly limited as long as it is a salt of a compound having a carboxy group, but fatty acid salts are preferred.
The fatty acid salt may be either a saturated fatty acid salt or an unsaturated fatty acid salt.
The number of carbon atoms in the fatty acid salt is preferably 6 to 50, more preferably 8 to 40, even more preferably 10 to 30, from the viewpoint of improving the corrosion resistance of the adsorbed metal film. , 14-24.

Specific examples of the fatty acid salts include saturated butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, and arachidic acid. Salts of fatty acids; salts of unsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, eicosenoic acid, linoleic acid and linolenic acid. Among them, the fatty acid salts improve the corrosion resistance of the adsorbed metal film, and include capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, arachidic acid, myristoleic acid, It is preferably a salt of at least one fatty acid selected from the group consisting of palmitoleic acid, oleic acid, eicosenoic acid, linoleic acid and linolenic acid.

Examples of the above salts include alkali metal salts such as potassium salts and cesium salts; alkaline earth metal salts such as magnesium salts, calcium salts, strontium salts and barium salts; ammonium salts; quaternary ammonium salts; Examples include organic amine salts such as salts. Among these salts, alkali metal salts, ammonium salts, quaternary ammonium salts and organic amine salts are preferred, alkali metal salts and ammonium salts are more preferred, and potassium salts and ammonium salts are even more preferred.

Among them, the carboxylate compound is palmitate, stearate, arachidate, palmitoleate, oleate, or eicosenoic acid from the viewpoint of improving corrosion resistance due to the balance of polar groups and hydrophobic groups. It is preferably a salt, more preferably an alkali metal salt or ammonium salt of palmitic acid, stearic acid, arachidic acid, palmitoleic acid, oleic acid or eicosenoic acid, and even more preferably an alkali metal salt of oleic acid. , and potassium oleate.

The above carboxylate compounds may be used alone or in combination of two or more.

The post-cleaning composition for the first CMP step may further contain other corrosion inhibitors in addition to the nitrogen-containing heterocyclic compound and the carboxylate compound.
Other corrosion inhibitors include known corrosion inhibitors such as rust inhibitors and anticorrosive agents.
Specific examples of the corrosion inhibitor include oxide-coated corrosion inhibitors such as chromates, molybdates, tungstates, and nitrites; precipitation of polymerized phosphates, zinc salts, sulfur-containing organic compounds, and the like; Coating type corrosion inhibitors, adsorption coating type corrosion inhibitors such as alkanolamines, alkyleneamine ethylene oxide adducts, alkyl phosphate ester salts, various surfactants, and the like can be mentioned.

The total content of (1C-1) nitrogen-containing heterocyclic compound and (1C-2) carboxylate compound in the corrosion inhibitor is 50% by mass or more with respect to 100% by mass of the total amount of corrosion inhibitor. It is preferably 55% by mass or more, more preferably 60% by mass or more, and particularly preferably 100% by mass.

In addition, the content ratio [(1C-1)/(1C-2)] of (1C-1) nitrogen-containing heterocyclic compound and (1C-2) carboxylate compound is 0/100 to 100 in mass ratio. /0 is preferable, and either compound may be used alone or may be used by mixing at any ratio.

The content of the corrosion inhibitor (1C) (component (1C)) is 0.2 to 35% by mass with respect to 100% by mass of the active ingredients in the first post-CMP step cleaning composition. is preferred, 0.5 to 30 mass % is more preferred, and 1 to 25 mass % is even more preferred.

The content of the corrosion inhibitor (1C) (component (1C)) is preferably 0.001 to 3% by mass with respect to 100% by mass of the first post-CMP step cleaning composition. It is more preferably 0.003 to 2% by mass, even more preferably 0.005 to 1% by mass.

(1D) Other Components The first post-cleaning composition for the CMP process of the present invention may include other optional components (1D) in addition to the components (1A), (1B), and (1C) described above. may contain
Examples of the component (1D) include pH adjusters, chelating agents, solvents, surfactants, and the like.

The pH adjuster is not particularly limited as long as it is a component capable of adjusting the pH to a target, and examples thereof include acid compounds and alkali compounds.
Examples of the acid compound include inorganic acids such as sulfuric acid and nitric acid and salts thereof, and organic acids such as acetic acid and lactic acid and salts thereof.
Examples of the alkali compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and cesium hydroxide; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and monoisopropanolamine; tetramethylammonium hydroxide. , tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethyl-2-hydroxyethylammonium hydroxide (choline), triethyl(hydroxyethyl)ammonium hydroxide and the like; quaternary ammonium salts;
The above pH adjusters may be used alone or in combination of two or more.

Examples of the chelating agent include oxalic acid, citric acid, tartaric acid, malic acid, picolinic acid, glycine and the like. Phosphonic acid chelating agents such as N,N,N',N'-ethylenediaminetetrakis (methylene phosphonic acid), glycine-N,N-bis (methylene phosphonic acid), nitrilotris (methylene phosphonic acid) and the like can also be mentioned. . Moreover, sulfur-containing amino acids such as cysteine and methionine are preferably used as the chelating agent.
The above chelating agents may be used alone or in combination of two or more.

Examples of the solvent include water, aprotic polar organic solvents such as water, N-methyl-2-pyrrolidinone, N,N-dimethylacetamide and dimethylsulfoxide, protic organic solvents such as lower alcohols, aromatic alcohols and glycols. is mentioned. Especially, it is preferable that the said solvent contains water. The solvent may be a mixed liquid containing two or more kinds.

Examples of the surfactant include anionic surfactants and cationic surfactants other than the nonionic surfactants described above.
Examples of the anionic surfactant include aliphatic monocarboxylates, polyoxyethylene alkyl ether carboxylates, N-acylsarcosine salts, N-acylglutamate carboxylate anionic surfactants; dialkyl sulfosuccinates; sulfonate type anions such as acid salts, alkanesulfonates, alpha-olefinsulfonates, alkylbenzenesulfonates, naphthalenesulfonates-formaldehyde condensates, alkylnaphthalenesulfonates, N-methyl-N-acyl taurates, etc. Surfactants; sulfuric acid ester type anionic surfactants such as alkyl sulfates, polyoxyethylene alkyl ether sulfates, oil sulfates; and alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene Phosphate ester type anionic surfactants of alkylphenyl ether phosphates can be mentioned.

Examples of the cationic surfactant include alkylamine salt-type cationic surfactants such as monoalkylamine salts, dialkylamine salts, and trialkylamine salts; and dialkyldimethylammonium chloride, dialkyldimethylammonium bromide, dialkyldimethyl Quaternary ammonium salt type cationic surfactants such as ammonium iodide, alkyltrimethylammonium chloride, alkyltrimethylammonium bromide, alkyltrimethylammonium iodide, alkylbenzyldimethylammonium chloride and the like.

The first post-CMP cleaning composition is preferably an aqueous solution having a pH (hydrogen ion concentration) of 7.5 or higher at 25°C. When the pH of the first post-CMP cleaning composition is within the above range, the corrosion rate of the metal film can be suppressed even if the cleaning solution does not contain a predetermined amount of the active ingredient.
The pH (25°C) of the first post-CMP cleaning composition is preferably 8.0 or higher, still more preferably 8.5 or higher, and even more preferably 10.0 or higher. .
The pH of the first post-CMP cleaning composition can be adjusted by adjusting the content of the alkali compound described above.
The above pH can be determined using a pH meter (eg, F71S, manufactured by Horiba Ltd.).

The first post-CMP cleaning composition preferably has a corrosion current value of 10 μA/cm ² or less and a corrosion potential difference at the interface of dissimilar metals of 60 mV or less. When the corrosion current value and the corrosion potential difference are within the above ranges, corrosion of the substrate to be cleaned can be suppressed.
More preferably, the first post-CMP cleaning composition has a corrosion current value of 5 μA/cm ² or less and a corrosion potential difference at the interface of different metals of 30 mV or less. More preferably, the corrosion potential difference at the dissimilar metal interface is ² or less and the corrosion potential difference at the dissimilar metal interface is 25 mV or less, and it is particularly preferable that the corrosion current value is 1 μA/cm ² or less and the dissimilar metal interface corrosion potential difference is 20 mV or less. .
In the present specification, the corrosion current value and the corrosion potential difference can be obtained by measuring by the method described in Examples below.

<Second post-cleaning composition for CMP process>
The second post-CMP cleaning composition of the present invention contains the three specific components (2A), (2B), and (2C) described above, thereby removing metal residue and organic residue from the wafer surface. Excellent removal and adhesion prevention, and excellent corrosion control. In particular, when ceria is used as abrasive grains to clean the surface of a wafer subjected to a CMP process, the effect is further exhibited. In addition, the second post-CMP cleaning composition of the present invention exhibits the above effects even more when used for cleaning the surface of a film containing silicon oxide and/or silicon nitride in a semiconductor manufacturing process. .

The second post-CMP cleaning composition is excellent in removing and preventing adhesion of metal residue, ceria abrasive residue and organic residue, and is also excellent in corrosion inhibition, because of the second post-CMP step cleaning composition. The nonionic surfactant and/or N-vinyllactam polymer contained in the cleaning composition permeate the substrate surface and the interface between the abrasive residue and dirt, and float in water, which is the main component of the cleaning liquid, while the organic acid compound It is presumed that the contaminants can be removed from the substrate surface by cutting the covalent bond formed at the interface between the contaminants and the substrate by the pH adjuster, the oxidizing agent, or the like. In addition, the adsorption of organic acid compounds, nonionic surfactants, and/or N-vinyllactam polymers on the surface of the deposited metal film that appears after the CMP process causes an electrochemical reaction between chemical components coexisting in the cleaning solution. It is presumed that the corrosion potential and the corrosion current value of the metal species constituting the deposited metal film can be reduced by setting the interaction to an equilibrium state.

Each component contained in the second post-CMP cleaning composition will be described.
(2A) Nonionic Surfactant and/or N-Vinyllactam Polymer The post-cleaning composition for the second CMP step comprises a nonionic surfactant having an aliphatic alcohol alkylene oxide adduct structure, and , and N-vinyllactam polymers (hereinafter also referred to as "compound (2A)" or "component (2A)"). By including such a specific compound, it is possible to stably maintain the state of being suspended in water, which is the main component of the cleaning composition, by penetrating into the interface between the substrate surface and the abrasive residue and dirt.

(2A-1) Nonionic Surfactant The alkylene oxide adduct structure of the fatty alcohol is a structure in which an alkylene oxide is added to the fatty alcohol.

Examples of the aliphatic alcohol include methanol, ethanol, propanol, isopropanol, butanol, isobutyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetra decanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, methanediol, ethylene glycol, 1,4-butanediol, 1,2-hexanediol, 1,6-hexanediol, Alkyl alcohols such as 1,10-decanediol; cycloalkyl alcohols such as cyclopentyl alcohol, cyclohexyl alcohol, cycloheptyl alcohol, 1,4-cyclohexanedimethanol and 1,4-cyclohexanediol; and allyl alcohol.
Of these, alkyl alcohols are preferred because the hydrophobicity can be adjusted relatively easily by adjusting the structure or the position of addition. The above alkyl alcohol may be linear or branched.

The number of carbon atoms in the aliphatic alcohol is preferably 6 or more, more preferably 10 or more. The number of carbon atoms in the alcohol is preferably 18 or less, more preferably 16 or less.

The above-mentioned aliphatic alcohol is preferably a secondary or tertiary alcohol, more preferably a secondary alcohol, in terms of high penetrating power to the solid residue interface and excellent suppression of metal corrosion.
The aliphatic alcohol is preferably a secondary or tertiary alkyl alcohol having 6 or more carbon atoms.
The aliphatic alcohol may be monohydric, dihydric, or polyhydric, but monohydric alcohols are preferred in terms of ease of production and cost.

Examples of the alkylene oxide added to the aliphatic alcohol include ethylene oxide, propylene oxide and butylene oxide. Among them, at least one selected from the group consisting of ethylene oxide and propylene oxide is preferable, and a mixed type of ethylene oxide and propylene oxide is more preferable.

The alkylene oxide adduct structure of the fatty alcohol preferably contains two or more alkylene oxides. The alkylene oxide adduct structure of the aliphatic alcohol has an alkylene oxide adduct structure of an alcohol having 6 or more carbon atoms, and preferably includes block polymer structures of two or more alkylene oxides.

Examples of the alkylene oxide adduct structure of the aliphatic alcohol include primary alcohol ethoxylate, secondary alcohol ethoxylate, tertiary alcohol ethoxylate, acetylenic primary alcohol ethoxylate, acetylenic primary dialcohol ethoxylate, acetylenic di-alcohol ethoxylate, Examples include primary alcohol ethoxylates, acetylenic secondary dialcohol ethoxylates, acetylenic tertiary alcohol ethoxylates, acetylenic tertiary dialcohol ethoxylates, and the like.
The above ethoxylates are those to which at least ethylene oxide (EO) is added, and those to which ethylene oxide (EO) and other alkylene oxides (eg, propylene oxide (PO)) are added are also included.

The alkylene oxide adduct structure of the above-mentioned aliphatic alcohol preferably has a clouding point of 25° C. or higher, more preferably 40° C. or higher, in that a uniform solution can be formed without separating in the detergent composition. is more preferable. The above cloud point can be obtained by a method of lowering the temperature of a 1% aqueous solution of a nonionic surfactant while stirring and monitoring the temperature, and observing the temperature at which the solution becomes transparent visually.

Specific examples of the nonionic surfactant (2A-1) include, for example, a polyalkylene oxide alkyl ether surfactant, a block polymer system composed of polyethylene oxide and polypropylene oxide, and an acetylene polyalkylene oxide surfactant. agents and the like. Among them, polyalkylene oxide alkyl ether-based surfactants and block polymer-based surfactants composed of polyethylene oxide and polypropylene oxide are preferable because they can suppress corrosion of the metal laminated film due to the detergent composition.

The nonionic surfactant (2A-1) is represented by general formula (2) or (3) described in the section “Compound (1A)” of the first post-cleaning composition for the CMP step. Compounds similar to the represented compounds are more preferred.

(2A-2) N-Vinyllactam Polymer As the N-vinyllactam polymer (2A-2), the same compounds as the above N-vinyllactam polymer (1A-2) can be mentioned. Among them, polyvinylpyrrolidone obtained by polymerizing a monomer component containing N-vinylpyrrolidone is preferable as the N-vinyllactam polymer (2A-2).

The weight average molecular weight of the N-vinyllactam polymer (2A-2) is preferably 500 to 50,000, more preferably 1,000 to 40,000, even more preferably 2,000 to 30,000.
The weight average molecular weight can be obtained by measuring by a gel permeation chromatography (GPC) method (in terms of PEO).

The content of the compound (2A) (component (2A)) is preferably 0.005 to 3% by mass with respect to 100% by mass of the second post-CMP step cleaning composition. It is more preferably from 01 to 1% by mass, and even more preferably from 0.1 to 0.5% by mass.

(2B) Organic Acid Compound The second post-CMP cleaning composition preferably contains an organic acid compound (hereinafter also referred to as “organic acid compound (2B)” or “component (2B)”). . By further including the organic acid compound, it is believed that the organic acid compound can break the covalent bond formed at the interface between the contaminant and the substrate and remove the contaminant from the substrate surface. In addition, the adsorption of the organic acid compound on the surface of the deposited metal film that appears after the CMP process brings the electrochemical interaction between the chemical components coexisting in the cleaning solution into an equilibrium state, and the metal species that compose the deposited metal film are eliminated. It is thought that the corrosion potential and corrosion current value can be reduced.

Preferred examples of the organic acid compound (2B) include carboxylic acid compounds, ascorbic acid, phenol compounds, phosphonic acids, boronic acids, and the like. Among them, carboxylic acid compounds and ascorbic acid are preferable in that organic acid compound residues can be easily removed by rinsing with pure water or alcohol after the process, and the adverse effect on the next process can be minimized. more preferred.

Examples of the carboxylic acid compound include organic acid compounds having a carboxyl group. , monocarboxylic acid compounds such as stearic acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, gluconic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, 5-norbornene dicarboxylic acid acid compounds; tricarboxylic acid compounds such as citric acid; aspartic acid, glutamic acid, glycine, alanine, phenylalanine, leucine, isoleucine, cysteine, methionine, tyrosine, valine, threonine, serine, proline, tryptophan, asparagine, glutamine, lysine, arginine, amino acids such as histidine; aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and propylenediaminetetraacetic acid; and the like. Moreover, these derivatives may also be included.

Among them, the carboxylic acid compound is preferably a dicarboxylic acid compound, a tricarboxylic acid compound, an aminopolycarboxylic acid, more preferably citric acid, oxalic acid, 5-norbornene dicarboxylic acid, ethylenediaminetetraacetic acid, citric acid, Acids, oxalic acid, 5-norbornenedicarboxylic acid, and ethylenediaminetetraacetic acid are more preferred.

The above organic acid compounds may be used alone or in combination of two or more.

The content of the organic acid compound (2B) (component (2B)) is preferably 0.05 to 10% by mass with respect to 100% by mass of the second post-CMP step cleaning composition. It is more preferably 0.1 to 7% by mass, even more preferably 0.5 to 4% by mass.

(2C) pH adjuster The post-cleaning composition for the second CMP step contains a pH adjuster (hereinafter also referred to as “pH adjuster (2C)” or “component (2C)”), It can improve the stability of chemical species in the unoxidized state in water.
The pH adjuster (2C) used in the second aspect of the present invention is not particularly limited as long as it is a compound capable of adjusting the pH to a desired value, and examples thereof include known acidic compounds and basic compounds. Among them, the pH adjuster (2C) is preferably a basic pH adjuster because it can suppress the generation of oxygen due to the decomposition of water and the generation of hydrogen due to dissolution of the metal component in the cleaning liquid. By adjusting the second post-CMP cleaning composition to be basic, the effect of suppressing corrosion on the wafer surface can be further enhanced.

Examples of the acidic compound include nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, and boric acid.

Examples of the basic compound include inorganic hydroxides such as sodium hydroxide and potassium hydroxide; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and monoisopropanolamine; methylamine, dimethylamine, trimethylamine; Alkylamines such as ethylamine, diethylamine, triethylamine, ethylenediamine, N,N-diisopropylethylamine, tetramethylethylenediamine, and hexamethylenediamine; aromatic amines such as aniline and toluidine; and nitrogen-containing complexes such as pyrrole, pyridine, picoline, and lutidine. organic amines such as cyclic compounds; salts of the above-mentioned organic amines (organic amine salts); tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethyl-2-hydroxyethylammonium hydroxide (choline), quaternary ammonium salts such as triethyl(hydroxyethyl)ammonium hydroxide and dimethylbis(2-hydroxyethyl)ammonium hydroxide; ammonium salts such as ammonium carbonate, ammonium hydrogencarbonate and ammonium carbamate; and ammonia. Among them, hydroxides, organic amines, organic amine salts, quaternary ammonium salts, and ammonium salts are preferable because etching of the film surface containing silicon oxide and/or silicon nitride can be suppressed, and hydroxides, organic amines, Quaternary ammonium salts and ammonium salts are more preferred.

The pH adjuster (2C) may be used alone or in combination of two or more.

The content of the pH adjuster (2C) (component (2C)) is preferably 0.01 to 15% by mass with respect to 100% by mass of the second post-CMP step cleaning composition. It is more preferably 0.1 to 10% by mass, even more preferably 0.5 to 5% by mass.

(2D) Oxidizing Agent The second post-CMP cleaning composition may further contain an oxidizing agent, but preferably does not contain an oxidizing agent from the viewpoint of suppressing metal corrosion.
Examples of the oxidizing agent (2D) include hydrogen peroxide, ozone, nitric acid, nitrous acid, persulfuric acid, dichromic acid, permanganic acid, and salts thereof. Among them, hydrogen peroxide is preferable from the viewpoint of easy availability of high-purity products required in the field of semiconductors and ease of disposal.

The content of the oxidizing agent (2D) (component (2D)) is preferably 1.0% by mass or less with respect to 100% by mass of the second post-CMP step cleaning composition. The content of the oxidizing agent is more preferably 0.5% by mass or less with respect to 100% by mass of the second post-CMP cleaning composition, from the viewpoint of causing corrosion of the metal film. It is preferably 0.1% by mass or less, even more preferably 0.05% by mass or less, particularly preferably 0.03% by mass or less, and most preferably 0% by mass. preferable.

(2E) Other components The post-cleaning composition for the second CMP process may optionally contain other components in addition to the components (2A), (2B), (2C) and (2D) described above. Component (2E) may also be included. Examples of the other component (2E) include solvents, chelating agents, anionic surfactants, cationic surfactants, corrosion inhibitors, and the like. These contents can be set appropriately.

Examples of solvents used in the second post-CMP cleaning composition include water, aprotic polar organic solvents such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, and dimethylsulfoxide; Examples include protic organic solvents such as lower alcohols, aromatic alcohols and glycols. Especially, it is preferable that the said solvent contains water. The solvent may be a mixed liquid or the like containing water and another solvent such as alcohol.
One of the above solvents may be used alone, or two or more thereof may be used in combination.

Examples of the chelating agent used in the second post-cleaning composition for the CMP step include N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid), glycine-N,N-bis(methylene phosphonic acid), phosphonic acid-based chelating agents such as nitrilotris (methylene phosphonic acid), thiol-based chelating agents such as methanethiol, thiophenol, glutathione, triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, etc. mentioned. The above chelating agents may be used alone or in combination of two or more.

The anionic surfactant and the cationic surfactant used in the second post-cleaning composition for the CMP process are described in the section on the post-cleaning composition for the first CMP process. An anionic surfactant similar to the cationic surfactant, an anionic surfactant similar to the cationic surfactant, and a cationic surfactant.

Examples of corrosion inhibitors used in the second post-CMP process cleaning composition include nitrogen-containing organic compounds such as benzotriazole, 3-aminotriazole, trialkylamine, ammonia, uric acid, melamine, urea and thiourea. compounds, polyethylene glycol, water-soluble polymers such as polyvinyl alcohol, alkyl alcohol compounds with 4 or less carbon atoms, oxide film type rust inhibitors such as chromates, molybdates, tungstates, nitrites, polymerized phosphates , zinc salts, sulfur-containing organic compounds, and other precipitation film-type rust inhibitors; However, nitrogen-containing organic compounds are preferred, azole compounds are more preferred, and diazole compounds, imidazole compounds, triazole compounds, tetrazole compounds, thiazole compounds, benzotriazole compounds, and derivatives thereof are more preferred.
The above corrosion inhibitors may be used alone or in combination of two or more. Among them, the corrosion inhibitor is preferably a benzotriazole-based compound, and particularly preferably benzotriazole.

The second post-CMP cleaning composition is preferably an aqueous solution having a pH (hydrogen ion concentration) of 7.5 or higher at 25°C. When the pH of the second post-CMP cleaning composition is within the above range, corrosion of the metal film can be suppressed.
The pH (25° C.) of the second post-CMP cleaning composition is more preferably 8.0 or higher, and even more preferably 8.5 or higher.
The adjustment of the pH of the second post-CMP cleaning composition can be carried out by appropriately adjusting the content of the pH adjusting agent described above.
The above pH can be determined using a pH meter (eg, F71S, manufactured by Horiba Ltd.).

<Preparation method>
The first post-cleaning composition for the CMP process of the present invention is prepared by mixing the component (1A), component (1B), component (1C), and optionally component (1D) described above. be able to. Further, the second post-CMP cleaning composition of the present invention contains the components (2A), (2B), (2C) and, if necessary, components (2D) and (2E). It can be prepared by mixing.
The above-mentioned mixing is not particularly limited, and can be performed by mixing/dispersing means using a known stirrer, mixer, disperser, or the like.

<How to use>
The post-CMP cleaning composition of the present invention is used in the post-CMP cleaning step in the semiconductor manufacturing process. More specifically, the post-CMP cleaning composition of the present invention is preferably used in a step of cleaning a semiconductor substrate (wafer) after a CMP step in a semiconductor manufacturing process.
The post-CMP cleaning method using the post-CMP cleaning composition of the present invention preferably includes the step of cleaning the surface of the semiconductor substrate after CMP using the post-CMP cleaning composition.

Examples of the semiconductor substrate include substrates made of silicon, silicon carbide, silicon nitride, gallium arsenide, gallium nitride, gallium phosphide, or indium phosphide.

The semiconductor substrate may have metal wiring, and the metal wiring includes, for example, copper wiring, tungsten wiring, aluminum wiring, cobalt wiring, ruthenium wiring, or alloy wiring of these metals and other metals. etc. Other metals include metals such as tungsten, titanium, tantalum, and chromium.

The semiconductor substrate may include a barrier metal layer. For example, when the semiconductor substrate includes copper wiring, a barrier metal layer is formed to prevent diffusion of copper. Examples of the barrier metal layer include layers made of tantalum, cobalt, titanium, ruthenium, and compounds containing these metals.

Further, the semiconductor substrate may be anticorrosion treated. The anticorrosive treatment includes a method of treating the surface of the semiconductor substrate with an anticorrosive agent. The anticorrosive agent is not particularly limited, and includes compounds known as anticorrosive agents such as benzotriazoles, imidazoles, quinaldines, and quinolines. In particular, in the second post-CMP cleaning composition, an azole anticorrosive agent is preferably used because of its high anticorrosion effect. Examples of the azole-based anticorrosive agents include azole-based, triazole-based, tetrazole-based, oxazole-based, isoxazole-based, oxadiazole-based, thiazole-based, isothiazole-based, and thiadiazole-based anticorrosives.
The treatment method is not particularly limited, and includes known methods such as coating the surface of the semiconductor substrate with an anticorrosive agent and drying or heating to form a coating (protective film).

The semiconductor substrate may include an insulating film. Examples of the insulating film include p-TEOS thermal oxide film, silicon nitride (SiN), silicon nitride carbide (SiCN), low dielectric constant film Low-k (SiOC, SiC), cobalt silicide (CoSi ₂ ), and the like. be done.

After the CMP process, polishing dust and organic residues such as the metal wiring, protective film, and insulating film described above remain on the surface of the semiconductor substrate.

Furthermore, the chemical polishing agent used in the CMP process may remain on the semiconductor substrate after the CMP process. The chemical polishing agent is a slurry of abrasive grains, and metal oxides such as CeO ₂ , Fe ₂ O ₃ , SnO ₂ , MnO and SiO ₂ are used as the abrasive grains. Therefore, residues of these metal oxides may exist on the surface of the semiconductor substrate after the CMP process.
Further, on the surface of the semiconductor substrate, organic residues such as organometallic complexes resulting from the reaction between the metal in the slurry and the anticorrosive agent may remain on the surface of the semiconductor substrate.
The CMP process can be performed by a known method.

The post-CMP cleaning composition of the present invention is suitably used for cleaning the surface of a semiconductor substrate (wafer) after a CMP process on which the metal residue or organic residue described above is present. The residue can be removed by cleaning the surface of the semiconductor substrate on which such residue is present using the post-CMP cleaning composition of the present invention. In addition, it is possible to prevent the residue from redepositing on the surface of the semiconductor substrate. Furthermore, corrosion of the surface of the semiconductor substrate can be suppressed.

Thus, the post-CMP cleaning composition of the present invention can be suitably used for cleaning semiconductor substrates after the CMP process on which the above-mentioned metal residue and organic residue are present. In particular, the first post-CMP cleaning composition of the present invention is a compound containing at least one selected from the group consisting of cobalt, copper, aluminum, ruthenium, titanium nitride, silicon nitride, and silicon oxide. can be suitably used for cleaning the exposed wafer surface, and is more suitable for cleaning the wafer surface exposed to the compound containing at least one selected from the group consisting of cobalt, copper, and titanium nitride. It can be used more preferably for cleaning the wafer surface where the cobalt compound is exposed.

In particular, there is a problem that Si--O--Ce bonds are formed on a wafer surface that has undergone a CMP process using ceria as abrasive grains, and as a result, ceria (CeO ₂ ) particles tend to remain. . Therefore, there has been used a method of suppressing residual ceria particles by oxidizing with a component such as a hydrogen peroxide solution that requires careful handling. However, when the second post-CMP cleaning composition of the present invention is used, the ceria particles can be satisfactorily removed without containing hydrogen peroxide. Thus, the second post-CMP cleaning composition is preferably a post-CMP cleaning composition using ceria as abrasive grains.

Moreover, the second post-CMP cleaning composition is preferably used for cleaning the surface of a film containing silicon oxide and/or silicon nitride in a semiconductor manufacturing process. The post-CMP cleaning composition is particularly effective in removing the above-mentioned residues and preventing redeposition when used to clean a film surface (substrate surface) containing silicon oxide and/or silicon nitride. It can be done suitably. Furthermore, corrosion of the surface of the semiconductor substrate can be suppressed.

The method for cleaning the substrate (wafer) surface after CMP using the post-CMP cleaning composition of the present invention is not particularly limited, and may be performed by a known method. Wafers) may be cleaned by immersing them in the post-CMP cleaning composition, or may be cleaned by spinning, spraying, brush cleaning, or ultrasonic cleaning. Also, a batch type in which a plurality of substrates are processed at once, or a single substrate type in which substrates are processed one by one may be used.

In the method of cleaning a substrate (wafer) surface using the post-CMP cleaning composition of the present invention, the cleaning time is not particularly limited, and a conventional method may be used. 10 to 300 seconds, preferably 15 to 250 seconds. The cleaning time means the contact time between the post-CMP cleaning composition and the substrate surface.
The temperature for the above washing is not particularly limited, and is, for example, 5 to 80.degree. C., preferably 10 to 70.degree. C., more preferably 10 to 65.degree. The atmosphere is preferably an inert atmosphere in which nitrogen gas, argon gas, or the like is circulated in order to reduce dissolved oxygen in the cleaning composition.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited only to these examples. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

<Preparation of detergent composition>
Example 1
A nonionic surfactant, an aliphatic amine, and a carboxylate compound are mixed with water so as to have the formulation shown in Table 1, and then potassium hydroxide is added so that the pH (25 ° C.) becomes 11. was added to prepare the cleaning composition of Example 1. The "ratio" in the table indicates the mass ratio of each component in the active ingredients (all components other than water). The obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation, which will be described later. In the electrochemical evaluation, corrosion potential of Co film (Co E _CORR ): -640 mV, corrosion current value of Co film (Co I _CORR ): 1 μA/cm ² , corrosion potential of TiN film (TiN E _CORR ): -620 mV, Corrosion current value of TiN film (TiN I _CORR ): ND (current value is below the lower limit of measurement), corrosion potential difference (ΔE _CORR ) of Co/TiN interface: 20 mV.

Example 2
A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation. In the electrochemical evaluation, Co E _CORR : -640 mV, Co I _CORR : 8 μA/cm ² , TiN E _CORR : -650 mV, TiN I _CORR : ND, and ΔE _CORR at the Co/TiN interface: 10 mV.

Example 3
A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation. In electrochemical evaluation, Co E _CORR : -660 mV, Co I _CORR : 3 μA/cm ² , TiN E _CORR : -690 mV, TiN I _CORR : ND, and ΔE _CORR at the Co/TiN interface: 30 mV.

Example 4
A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation. In the electrochemical evaluation, Co E _CORR : -490 mV, Co I _CORR : ND, TiN E _CORR : -470 mV, TiN I _CORR : ND, and ΔE _CORR at the Co/TiN interface: 20 mV.

Example 5
A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation. In electrochemical evaluation, Co E _CORR : -600 mV, Co I _CORR : 4 μA/cm ² , TiN E _CORR : -640 mV, TiN I _CORR : ND, and ΔE _CORR at the Co/TiN interface: 40 mV.

Example 6
Nonionic surfactants, aliphatic amines, nitrogen-containing heterocyclic compounds, and other additives are mixed with water so as to have the formulation shown in Table 1, and then the pH (25 ° C.) is 11. A detergent composition was prepared by adding trimethyl-2-hydroxyethylammonium hydroxide (“choline”, 46% aqueous solution) so that Detergency performance evaluation and electrochemical evaluation were performed on the obtained detergent composition. In electrochemical evaluation, corrosion potential of Co film (Co E _CORR ): -500 mV, corrosion current value of Co film (Co I _CORR ): 2 μA/cm ² , corrosion potential of Cu film (Cu E _CORR ): -440 mV, Corrosion current value of Cu film (Cu I _CORR ): 10 μA/cm ² Corrosion potential difference (ΔE _CORR ) of Co/Cu interface: 60 mV.

Example 7
Nonionic surfactants, aliphatic amines, nitrogen-containing heterocyclic compounds, and other additives are mixed with water so as to have the formulation shown in Table 1, and then the pH (25 ° C.) is 11. Ammonia (28% aqueous solution) was added to prepare a cleaning composition. Detergency performance evaluation and electrochemical evaluation were performed on the obtained detergent composition. In the electrochemical evaluation, Co E _CORR : −500 mV, Co I _CORR : 2 μA/cm ² , Cu E _CORR : −440 mV, Cu I _CORR : 10 μA/cm ² , and ΔE _CORR at the Co/Cu interface: 60 mV.

Example 8
The N-vinyllactam polymer, aliphatic amines, nitrogen-containing heterocyclic compound, and other additives were mixed with water so as to obtain the formulation shown in Table 1, and then the pH (25°C) was adjusted. A detergent composition was prepared by adding potassium hydroxide so as to obtain 11. Detergency performance evaluation and electrochemical evaluation were performed on the obtained detergent composition. Electrochemical evaluation showed Co E _CORR : −440 mV, Co I _CORR : <1 μA/cm ² , Cu E _CORR : −460 mV, Cu I _CORR : 5 μA/cm ² , and ΔE _CORR at the Co/Cu interface: 20 mV. .

Example 9
The N-vinyllactam polymer, aliphatic amines, nitrogen-containing heterocyclic compound, and other additives were mixed with water so as to obtain the formulation shown in Table 1, and then the pH (25°C) was adjusted. A detergent composition was prepared by adding trimethyl-2-hydroxyethylammonium hydroxide (“choline”, 46% aqueous solution) to 11. Detergency performance evaluation and electrochemical evaluation were performed on the obtained detergent composition. In the electrochemical evaluation, Co E _CORR : −490 mV, Co I _CORR : 10 μA/cm ² , Cu E _CORR : −460 mV, Cu I _CORR : 5 μA/cm ² , and ΔE _CORR at the Co/Cu interface: 30 mV.

Example 10
The N-vinyllactam polymer, aliphatic amines, nitrogen-containing heterocyclic compound, and other additives were mixed with water so as to obtain the formulation shown in Table 1, and then the pH (25°C) was adjusted. Ammonia (28% aqueous solution) was added to give a detergent composition of 11. Detergency performance evaluation and electrochemical evaluation were performed on the obtained detergent composition. Electrochemical evaluation showed Co E _CORR : −440 mV, Co I _CORR : <1 μA/cm ² , Cu E _CORR : −460 mV, Cu I _CORR : 5 μA/cm ² , and ΔE _CORR at the Co/Cu interface: 20 mV. .

Comparative example 1
A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation. In the electrochemical evaluation, Co E _CORR : −800 mV, Co I _CORR : 306 μA/cm ² , TiN E _CORR : −670 mV, TiN I _CORR : 0.9 μA/cm ² , and ΔE _CORR at the Co/TiN interface: 130 mV. rice field.

Comparative example 2
A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation. In the electrochemical evaluation, Co E _CORR : −65 mV, Co I _CORR : 54 μA/cm ² , TiN E _CORR : −415 mV, TiN I _CORR : 0.55 μA/cm ² , and ΔE _CORR at the Co/TiN interface: 320 mV. rice field.

Comparative example 3
A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation. In the electrochemical evaluation, Co E _CORR : -700 mV, Co I _CORR : 15 μA/cm ² , TiN E _CORR : -720 mV, TiN I _CORR : ND, and ΔE _CORR at the Co/TiN interface: 20 mV.

In addition, the compounds in Table 1 are specifically as follows.
DEAP: 3-(diethylamino)propylamine EN: ethylenediamine TEP: tetraethylenepentamine PO: potassium oleate EDTA: ethylenediaminetetraacetic acid nonionic surfactant A-1:

(In the formula, R ⁶ is H. Both R ⁷ and R ⁸ are linear alkyl groups having 1 to 12 carbon atoms, and the total number of carbon atoms of R ⁷ and R ⁸ is 11 to 13. R ⁹ represents —C ₂ H ₄ —, R ¹⁰ represents —CH ₂ CH(CH ₃ )—, x=12, y=3, and x and y represent the average number of added moles. A mixture of compounds.

Nonionic surfactant A-2:

(wherein R ¹¹ and R ¹² represent a methyl group, R ¹³ and R ¹⁴ represent an isobutyl group, R ¹⁹ represents -C≡C-, R ¹⁵ and R ¹⁷ represent -C ₂ H ₄ - where x=4 and y=0.)

Nonionic surfactant A-3:

(Wherein, R ²⁰ represents —C ₂ H ₄ —, R ²¹ represents —CH ₂ CH(CH ₃ )—, x=23, y=0, n=11.)

N-vinyllactam polymer A-4: polyvinylpyrrolidone (weight average molecular weight 7200)
N-vinyllactam polymer A-5: polyvinylpyrrolidone (weight average molecular weight 22000)
N-vinyl lactam polymer A-6: polyvinylpyrrolidone (weight average molecular weight 3000)

<Washing performance evaluation>
(Preparation of Co-BTA particle dispersion)
Prepare 1 L of a solution of 200 μmol/L cobalt (II) nitrate in a 0.01 mol/L pure nitric acid aqueous solution and 1 L of a solution of 200 μmol/L benzotriazole in a 0.01 mol/L nitric acid pure aqueous solution. Then, the two were mixed at room temperature to obtain 2 L of an aqueous solution in which insoluble aggregates of cobalt (II) ions and benzotriazole (hereinafter referred to as "Co-BTA particles") were dispersed. Potassium hydroxide powder was added to the resulting aqueous solution to adjust the pH of the aqueous solution to 8.0 to obtain a Co-BTA particle dispersion.

(Preparation of cleaning evaluation substrate)
A 1 cm square test piece was prepared by depositing Co, TiN, SiN, or SiO ₂ to a thickness of about 5 to 200 nm, respectively, on a silicon wafer. 100 mL of the Co-BTA particle dispersion obtained above was placed in a beaker, and the test piece was immersed in the dispersion for 1 minute while stirring at 300 rpm using a magnetic rotor. After the immersion, the test piece taken out was rinsed with pure water and air-dried to remove moisture, thereby obtaining a substrate for cleaning evaluation.

(Microscopic observation)
The surface state of the cleaning evaluation substrate obtained above was observed using an atomic force microscope (AFM). XE-300P (manufactured by Park Systems) was used as the equipment, and observation was performed in a non-contact mode (observation conditions: scan rate 0.5 Hz, observation area 5 μm×5 μm) using a PPP-NCHR AFM probe.

(washing treatment)
The substrate for cleaning evaluation was immersed in 100 mL of the cleaning composition of the example or comparative example obtained above, and subjected to ultrasonic waves for 1 minute using an ultrasonic cleaner (8895, manufactured by Cole-Parmer). A cleaning treatment was performed by irradiation (treatment conditions: output 115 W, 40 KHz, beaker internal temperature: 25°C). After ultrasonic irradiation, the substrate for cleaning evaluation was taken out and rinsed with pure water, and the surface state of the substrate for cleaning evaluation was observed in the same manner as described above. FIG. 1 shows an AFM observation image of the obtained substrate surface for cleaning evaluation.

From FIG. 1, in the AFM observation before the cleaning treatment, white foreign matter adhered to all of the Co film, TiN film, SiN film, and SiO ₂ film, and contamination with Co-BTA particles of various particle sizes occurred. I was able to confirm that. When the cleaning compositions of Examples 1 to 3 were used for cleaning, the Co—BTA particles could be completely removed from any of the Co film, TiN film, SiN film, and SiO ₂ film, and the cleaning power was excellent. I understood it. On the other hand, when the cleaning compositions of Comparative Examples 1 and 2 were used, significant white foreign matter remained on the Co film, indicating insufficient cleaning power.

<Electrochemical evaluation>
A 1 cm square test piece was prepared by depositing Co, Cu, TiN, SiN, or SiO ₂ with a thickness of about 5 to 1500 nm on a silicon wafer. The prepared test piece was placed in a beaker containing 100 mL of a 10 mmol/L pure aqueous solution of benzotriazole adjusted to pH=10.0, and the test piece was left for 1 minute while stirring at 300 rpm with a magnetic rotor. After that, it was taken out and washed with pure water to obtain a test piece for electrochemical evaluation.
After attaching the above test piece for electrochemical evaluation as a working electrode in a three-electrode glass cell equipped with a platinum counter electrode and an SCE standard electrode and connecting it to a potentiostat, the glass cell was treated with the detergent composition of the example or comparative example. Dynamic polarization curves were acquired over a voltage range with an open circuit potential of ±0.5 V by filling and sweeping at a scan rate of 5 mV/s. Furthermore, the corrosion potential and corrosion current values were calculated by the Tafel extrapolation method. Also, based on the obtained values, electrochemical evaluation was performed according to the following criteria. Table 2 shows the results.
Corrosion current value (I _CORR )
○: 10 μA/cm ² or less ×: 10 μA/cm ² super corrosion potential difference (ΔE _CORR )
○: 60 mV or less ×: over 60 mV

A detergent composition that does not corrode must simultaneously satisfy a corrosion current value of 10 μA/cm ² or less and a corrosion potential difference of 60 mV or less at the interface of dissimilar metals. When the detergent compositions of Examples 1 to 10 were used, this evaluation criterion was satisfied at the same time, and it can be judged that the occurrence of corrosion can be suppressed extremely well. On the other hand, when the detergent compositions of Comparative Examples 1 to 3 were used, at least one of the evaluation criteria was not satisfied.

Examples 11-18, Comparative Examples 4-6
<Preparation of detergent composition>
Nonionic surfactant, N-vinyllactam polymer, organic acid compound, ammonium carbamate, After mixing ammonium carbonate and an oxidizing agent, potassium hydroxide was added to adjust the pH to 12 (25° C.) to prepare detergent compositions of Examples and Comparative Examples.

In addition, the compounds in Table 3 are specifically as follows.
Nonionic surfactant A: The same compound as the nonionic surfactant A-1 used in Example 1 above.
Nonionic surfactant B:

(Wherein, n represents the average number of added moles of ethylene oxide, n=9.5.)

N-vinyllactam polymer: polyvinylpyrrolidone (weight average molecular weight 7200)
EDTA: ethylenediaminetetraacetic acid

The following cleaning performance evaluation was performed on the obtained cleaning compositions of Examples and Comparative Examples.
<Washing performance evaluation>
(Preparation Example 1) Preparation of positively charged ceria nanoparticle dispersion A-1 Colloidal ceria (product name: HC90, manufactured by Solvay) having an average particle diameter of 90 nm was dispersed in ultrapure water at a concentration of 0.05% by mass. , Proline (manufactured by Sigma-Aldrich) was added to a concentration of 0.025% by mass, stirred, and finally adjusted to pH = 4.0 with nitric acid to prepare a positively charged ceria nanoparticle dispersion liquid A-1. got

(Preparation Example 2) Preparation of Positively Charged Ceria Nanoparticle Dispersion Liquid A-2 Colloidal ceria (product name: HC30, manufactured by Solvay) having an average particle diameter of 30 nm was dispersed in ultrapure water at a concentration of 0.05% by mass. , Proline (manufactured by Sigma-Aldrich) was added to a concentration of 0.025% by mass, stirred, and finally adjusted to pH = 4.0 with nitric acid to obtain a positively charged ceria nanoparticle dispersion liquid A-2. got

(Preparation Example 3) Preparation of Negatively Charged Ceria Nanoparticle Dispersion B-1 Colloidal ceria (product name: HC90, manufactured by Solvay) having an average particle diameter of 90 nm was dispersed in ultrapure water at a concentration of 0.05% by mass. , citric acid (manufactured by Sigma-Aldrich) was added to a concentration of 0.025% by mass, stirred, and finally adjusted to pH = 5.0 with nitric acid to prepare a negatively charged ceria nanoparticle dispersion liquid B-. got 1.

(Preparation Example 4) Preparation of Negatively Charged Ceria Nanoparticle Dispersion B-2 Colloidal ceria (product name: HC30, manufactured by Solvay) having an average particle diameter of 30 nm was dispersed in ultrapure water at a concentration of 0.05% by mass. , citric acid (manufactured by Sigma-Aldrich) was added to a concentration of 0.025% by mass, stirred, and finally adjusted to pH = 5.0 with nitric acid to prepare a negatively charged ceria nanoparticle dispersion liquid B-. got 2.

(Preparation Example 5) Preparation of SiO ₂ substrate for cleaning performance evaluation A 1 cm square test piece was prepared by depositing SiO ₂ to a thickness of about 10 to 50 nm on a silicon wafer, and 100 mL of the positively charged ceria nanoparticle dispersion was prepared. A-1 or A-2 was placed in a beaker, and the test piece was immersed for 1 minute while stirring at 300 rpm with a magnetic rotor. The removed test pieces were rinsed with pure water and dried at room temperature to obtain cleaning performance evaluation substrates A-1 and A-2. The surface state of the substrate was observed using an atomic force microscope (AFM). The equipment used was XE-300P (manufactured by Park Systems), and a PPP-NCHR AFM probe was used in non-contact mode (observation conditions: scan rate 0.5 Hz, observation area 5 μm×5 μm).

(Preparation Example 6) Preparation of SiN substrate for cleaning performance evaluation A 1 cm square test piece was prepared by depositing SiN to a thickness of about 10 to 50 nm on a silicon wafer, and 100 mL of the negatively charged ceria nanoparticle dispersion B- was prepared. 1 or B-2 was placed in a beaker and the test piece was immersed for 1 minute while stirring at 300 rpm with a magnetic rotor. The removed test pieces were rinsed with pure water and dried at room temperature to obtain cleaning performance evaluation substrates B-1 and B-2. The surface state of the substrate was observed using an atomic force microscope (AFM). The equipment used was XE-300P (manufactured by Park Systems), and a PPP-NCHR AFM probe was used in non-contact mode (observation conditions: scan rate 0.5 Hz, observation area 5 μm×5 μm).

(washing treatment)
100 mL of the cleaning composition of the above example or comparative example was weighed into a beaker, the cleaning performance evaluation board was immersed in the cleaning composition, and an ultrasonic cleaner (8895, manufactured by Cole-Parmer) was used. Then, cleaning treatment was performed by ultrasonic irradiation for 1 minute (treatment conditions: output 115 W, 40 kHz, temperature in beaker: 25°C). After the ultrasonic wave irradiation, the cleaning performance evaluation substrate taken out was rinsed with pure water, and the surface state of the cleaning performance evaluation substrate was observed in the same manner as described above.

FIG. 2 shows cleaning treatment of SiO ₂ substrates for cleaning performance evaluation (evaluation substrates A-1 and A-2) using the cleaning compositions of Examples 11-12, 17-18 and Comparative Examples 4-5. 2 shows AFM images showing the surface condition of the substrate with and without cleaning. These cleaning compositions do not contain hydrogen peroxide.
From the surface state of the unwashed cleaning performance evaluation substrate, when contaminated with 90 nm colloidal ceria (ceria nanoparticle dispersion liquid A-1), white foreign matter was confirmed, and 30 nm colloidal ceria (ceria nanoparticle dispersion liquid A It can be seen that in the case of contamination in -2), the size of the foreign matter is reduced and the density is increased.
Washing using the detergent compositions of Examples 11 to 12 and 17 to 18 containing all three types of nonionic surfactant A or N-vinyllactam polymer, organic acid compound, and pH adjuster. It was confirmed that even if the colloidal ceria had a fine particle size of 30 nm, it could be removed cleanly when the treatment was performed. When using the detergent compositions of Comparative Examples 4 and 5 lacking one or more of the nonionic surfactant A, the N-vinyllactam polymer, the organic acid compound, and the pH adjuster, the particle size of the colloidal ceria was 90 nm, cleaning residues were observed.

FIG. 3 shows the results of cleaning the cleaning performance evaluation SiO ₂ substrates (evaluation substrates A-1 and A-2) using the cleaning compositions of Examples 13 to 15 and Comparative Example 6. 2 shows an AFM image representing the surface state. These cleaning compositions contain hydrogen peroxide. When the cleaning compositions of Examples 13 to 15 were used, good cleaning performance was confirmed, and even when the colloidal ceria had a fine particle size of 30 nm, it was possible to cleanly remove the particles, demonstrating excellent cleaning performance. confirmed.
On the other hand, when the cleaning composition of Comparative Example 6 containing the nonionic surfactant B was used, cleaning residues were observed even when the colloidal ceria had a particle size of 90 nm.

FIG. 4 shows the case where the cleaning performance evaluation SiN substrates (evaluation substrates B-1 and B-2) were cleaned using the cleaning compositions of Examples 11, 13, and 16, and when they were not cleaned. 4 shows an AFM image showing the surface condition of the substrate.
The cleaning compositions of Examples exhibited excellent cleaning performance when compared with uncleaned substrates, both when the particle size of colloidal ceria was 90 nm and when the particle size of colloidal ceria was 30 nm. It was confirmed to have

From the above, it contains component (2A) a nonionic surfactant or N-vinyllactam polymer having an alkylene oxide adduct structure of an aliphatic alcohol, (2B) an organic acid compound, and (2C) a pH adjuster. The high cleaning performance of the cleaning composition for cleaning was shown. Cleaner compositions containing an oxidizing agent such as hydrogen peroxide also showed excellent cleaning performance, but the performance levels were comparable to those without. It was determined that the use of oxidizing agents was not necessary due to concerns about corrosion of metal parts and health hazards to the human body.

Examples 19-21
After mixing a nonionic surfactant, an organic acid compound, and ammonium carbamate with water so that the mass % of each component in 100 mass % of the cleaning composition as shown in Table 4, the pH is 12 (25 ° C.), tetramethylammonium hydroxide (25% aqueous solution), trimethyl-2-hydroxyethylammonium hydroxide (“choline”, 50% aqueous solution), or dimethylbis(2-hydroxyethyl)ammonium hydroxide (50% aqueous solution) was added to prepare a detergent composition.

Examples 22-23
After mixing the nonionic surfactant and the organic acid compound with water so that the mass % of each component in 100 mass % of the cleaning composition as shown in Table 4, the pH becomes 12 (25 ° C.). A detergent composition was prepared by adding dimethylbis(2-hydroxyethyl)ammonium hydroxide (50% aqueous solution) as follows.

Comparative example 7
Hydrogen peroxide (30% aqueous solution) and ammonia (29% aqueous solution) were mixed with water so that the mass % of each component in 100% by mass of the cleaning composition as shown in Table 4 was mixed to obtain a cleaning composition. prepared the product.

The obtained cleaning composition and the cleaning composition of Example 11 were evaluated for etching rate by the following method. Table 4 shows the results.
<Evaluation of etching grade>
5 mL of each cleaning composition was placed in a bottle, and a 1.5 cm ² silicon oxide (SiO ₂ ) film-coated wafer was immersed therein and left at room temperature for 6 days. Thereafter, the treated body was taken out from the cleaning agent composition, washed with water, and then the cross section was observed with an SEM to measure the film thickness of the silicon oxide film. The etching rate was calculated from the silicon oxide film thickness before and after the treatment.

From Table 4, component (2A) a nonionic surfactant and / or N-vinyl lactam polymer having an alkylene oxide adduct structure of an aliphatic alcohol, (2B) an organic acid compound, and (2C) a pH adjuster It was confirmed that the cleaning composition containing and is excellent in the etching rate for silicon oxide films.

Claims

(1A) at least one compound selected from the group consisting of a nonionic surfactant containing an alkylene oxide adduct of an alcohol having 6 or more carbon atoms, and an N-vinyl lactam polymer;
(1B) aliphatic amines;
(1C) A post-CMP cleaning composition for a semiconductor manufacturing process, comprising at least one corrosion inhibitor selected from the group consisting of a nitrogen-containing heterocyclic compound and a carboxylate compound.
2. The post-CMP cleaning composition according to claim 1, wherein the aliphatic amine has a molecular weight of 2000 or less.
3. The post-CMP cleaning composition according to claim 1, wherein the aliphatic amines comprise an amine compound represented by the following general formula (1) and/or a polyalkyleneimine. .

(In Formula (1), R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, an alkyl group, or —R 4 —(NH—R 5 ) n —NH 2. R 4 and R 5 is the same or different and represents an alkylene group having 1 to 6 carbon atoms, and n represents an integer of 0 to 100.)
4. The nitrogen-containing heterocyclic compound according to any one of claims 1 to 3, characterized in that it contains at least one selected from the group consisting of pyrrole, pyridine, triazole, triazine, purine, and derivatives thereof. A post-cleaning composition for a CMP process.
The post-CMP cleaning composition according to any one of claims 1 to 4, wherein the carboxylate compound contains a fatty acid salt.
The post-CMP cleaning composition is applied to the wafer surface where a compound containing at least one selected from the group consisting of cobalt, copper, aluminum, ruthenium, titanium nitride, silicon nitride, and silicon oxide is exposed. The post-cleaning composition for a CMP process according to any one of claims 1 to 5, which is used for cleaning.
(2A) at least one compound selected from the group consisting of a nonionic surfactant having an alkylene oxide adduct structure of an aliphatic alcohol, and an N-vinyl lactam polymer;
(2B) an organic acid compound;
(2C) A post-cleaning composition for a CMP process, comprising a pH adjuster.
8. The post-CMP cleaning composition according to claim 7, wherein the content of the oxidizing agent is 1.0% by mass or less with respect to 100% by mass of the post-CMP cleaning composition. .
8. The alkylene oxide adduct structure of the aliphatic alcohol has an alkylene oxide adduct structure of an aliphatic alcohol having 6 or more carbon atoms and includes block polymer structures of two or more alkylene oxides. 9. or the post-cleaning composition for CMP process according to 8.
The post-CMP cleaning composition according to any one of claims 7 to 9, wherein the aliphatic alcohol is a secondary or tertiary alkyl alcohol having 6 or more carbon atoms.
The post-CMP cleaning composition according to any one of claims 7 to 10, wherein the pH adjuster is a basic pH adjuster.
12. The CMP process according to claim 11, wherein the basic pH adjuster comprises at least one compound selected from the group consisting of hydroxides, organic amines, organic amine salts, and ammonium salts. Post cleanser composition.
The post-CMP cleaning composition according to any one of claims 7 to 12, wherein the organic acid compound contains at least one compound selected from the group consisting of a carboxylic acid compound and ascorbic acid. thing.
14. The post-CMP cleaning composition according to any one of claims 7 to 13, which is a post-CMP cleaning composition using ceria as abrasive grains.
15. The post-CMP cleaning composition according to any one of claims 7 to 14, which is used for cleaning the surface of a film containing silicon oxide and/or silicon nitride in a semiconductor manufacturing process.