CN113430072B - Cobalt-compatible semi-aqueous cleaning solution for removing hard mask, preparation method and application thereof - Google Patents

Cobalt-compatible semi-aqueous cleaning solution for removing hard mask, preparation method and application thereof Download PDF

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CN113430072B
CN113430072B CN202010208598.9A CN202010208598A CN113430072B CN 113430072 B CN113430072 B CN 113430072B CN 202010208598 A CN202010208598 A CN 202010208598A CN 113430072 B CN113430072 B CN 113430072B
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water
semi
cleaning solution
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amino acid
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CN113430072A (en
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王溯
蒋闯
冯强强
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Shanghai Xinyang Semiconductor Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers

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  • General Physics & Mathematics (AREA)
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  • Computer Hardware Design (AREA)
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  • Power Engineering (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

The invention discloses a cobalt-compatible semi-aqueous cleaning solution for removing a hard mask, a preparation method and application thereof. The semi-water-based cleaning solution is prepared from the following raw materials in percentage by mass: 10% -45% of oxidant, 0-1.5% of D-amino acid oxidase, 0-2.5% of D-amino acid, 0.1% -15% of organic base, 0.001% -15% of chelating agent, 0.005% -15% of corrosion inhibitor, 0.05% -15% of ammonium carboxylate, 0.005% -1.5% of EO-PO polymer L42, 0.005% -2.5% of passivating agent, 20% -60% of water-soluble organic solvent and the balance of water, wherein the mass fraction is the mass percentage of each component in the total mass of each component. The semi-water-based cleaning solution has strong corrosion inhibition on various metals and dielectrics, particularly has strong compatibility on cobalt and good cleaning effect.

Description

Cobalt-compatible semi-aqueous cleaning solution for removing hard mask, preparation method and application thereof
Technical Field
The invention relates to a cobalt-compatible semi-aqueous cleaning solution for removing a hard mask, a preparation method and application thereof.
Background
In the chip manufacturing technology, the residual cleaning liquid after the plasma etching of the copper interconnection is mainly fluorine-containing cleaning liquid. With the continuous advancement of technology nodes, more and more materials are introduced, such as titanium, tungsten, titanium nitride and other metal materials, low-k dielectric materials and the like, so that the compatibility of the traditional fluorine-containing cleaning solution with various materials is challenging.
Plasma dry etching is commonly used to fabricate vertical sidewall trenches and anisotropic interconnect vias in copper (Cu)/low dielectric constant dual damascene manufacturing processes. As technology nodes evolve to 45nm and smaller (e.g., 28-14 nm), the shrinking dimensions of semiconductor devices makes achieving precise profile control of vias and trenches more challenging. Integrated circuit device companies are researching the use of various hard masks to improve etch selectivity to low dielectric constant materials for better profile control. The hard mask material (e.g., ti/TiN) is removed after the etch protection, and other metals and dielectric materials, particularly cobalt, are protected during the cleaning process to remove the hard mask material, thus challenging the compatibility of conventional fluorine-containing cleaning fluids with a variety of materials.
Developing a cobalt-compatible cleaning solution to selectively remove the hard mask is a problem in the art.
Disclosure of Invention
The invention aims to overcome the defects of poor compatibility and corrosion inhibition performance of the existing cleaning solution for removing the hard mask material on other metals and dielectric materials, poor cleaning effect and the like, and provides a cobalt-compatible semi-water-based cleaning solution for removing a hard mask, a preparation method and application thereof. The semi-water-based cleaning solution has strong corrosion inhibition on various metals and dielectrics and good cleaning effect.
The invention solves the technical problems through the following technical proposal.
The invention provides a semi-water-based cleaning solution which is prepared from the following raw materials in parts by mass:
10% -45% of oxidant, 0-1.5% of D-amino acid oxidase, 0-2.5% of D-amino acid, 0.1% -15% of organic base, 0.001% -15% of chelating agent, 0.005% -15% of corrosion inhibitor, 0.05% -15% of ammonium carboxylate, 0.005% -1.5% of EO-PO polymer L42, 0.005% -2.5% of passivating agent, 20% -60% of water-soluble organic solvent and the balance of water, wherein the mass fraction is the mass percentage of each component in the total mass of each component.
In the semi-aqueous cleaning solution, the oxidizing agent may be an oxidizing agent conventionally used in the art, such as hydrogen peroxide (H 2O2), N-methylmorpholine oxide (NMMO or NMO), benzoyl peroxide, tetrabutylammonium peroxymonosulfate, ozone, ferric chloride, permanganate, perborate, perchlorate, persulfate, ammonium peroxodisulfate, peracetic acid, urea peroxide, nitric acid (HNO 3), ammonium chlorite (NH 4ClO2), ammonium chlorate (NH 4ClO3), ammonium iodate (NH 4IO3), ammonium perborate (NH 4BO3), ammonium perchlorate (NH 4ClO4), ammonium periodate (NH 4IO3), ammonium persulfate ((NH 4)2S2O8), tetramethylammonium chlorite ((N (CH 3)4)ClO2), tetramethylammonium chlorate ((N (CH 3)4)ClO3), tetramethylammonium iodate ((N (CH 3)4)IO3), tetramethylammonium perborate ((N (CH 3)4)BO3), tetramethylammonium perchlorate ((N (CH 3)4)ClO4), tetramethylammonium periodate ((N (CH 3)4)IO4)), tetramethylammonium persulfate ((CH) 35), urea peroxide (oo) and one or more of hydrogen peroxide (CO) and CO (CO) in water, CO or a plurality of acetic acid (CO) and CO (CO) peroxide, or a plurality of more of acetic acid and CO.
In the semi-aqueous cleaning solution, the mass fraction of the oxidizing agent may be 10% -35%, for example 10% -30% (e.g., 10%, 15%, 30%), and the mass fraction is the mass of the oxidizing agent in percentage of the total mass of the raw material.
In the semi-aqueous cleaning solution, the D-amino acid oxidase may be present in an amount of 0 to 0.5%, for example 0 to 0.01% (e.g., 0, 0.005%, 0.01%), and more for example 0.005% -0.5% (e.g., 0.005%, 0.01%), based on the total mass of the raw material.
In the semi-aqueous cleaning solution, the D-type amino acid may be one or more of D-glycine, D-alanine, D-valine, D-leucine, D-isoleucine, D-phenylalanine, D-proline, D-tryptophan, D-serine, D-tyrosine, D-cysteine, D-methionine, D-asparagine, D-glutamine, D-threonine, D-aspartic acid, D-glutamic acid, D-lysine, D-arginine and D-histidine, and further one or more of D-proline, D-arginine and D-histidine, which are conventionally used in the art.
In the semi-aqueous cleaning solution, the mass fraction of the D-type amino acid may be 0-1.5%, for example 0-0.5% (e.g. 0, 0.25%, 0.5%), and still more for example 0.1% -1.5% (e.g. 0.25%, 0.5%), and the mass fraction is the percentage of the mass of the D-type amino acid to the total mass of the raw material.
In the semi-aqueous cleaning solution, the organic base may be one or more of tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide (TEAH), benzyltrimethylammonium hydroxide (BTAH), choline, (2-hydroxyethyl) trimethylammonium hydroxide, tris (2-hydroxyethyl) methylammonium hydroxide, monoethanolamine (MEA), diglycolamine (DGA), triethanolamine (TEA), isobutolamine, isopropanolamine, tetrabutylphosphonium hydroxide (TBPH), and tetramethylguanidine, for example, tetramethylammonium hydroxide and/or choline, which are conventionally used in the art.
In the semi-aqueous cleaning solution, the mass fraction of the organic base may be 1% -10%, for example 3% -8% (e.g. 3%, 5%, 8%), and the mass fraction is the percentage of the mass of the organic base to the total mass of the raw materials.
In the semi-aqueous cleaning solution, the chelating agent may be a chelating agent conventionally used in the art, such as 1, 2-cyclohexanediamine-N, N ' -tetraacetic acid (CDTA), ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriamine pentaacetic acid, 1,4,7, 10-tetraazacyclododecane-1, 4,7, 10-tetraacetic acid, ethylene Glycol Tetraacetic Acid (EGTA), 1, 2-bis (o-aminophenoxy) ethane-N, one or more of N ', N ' -tetraacetic acid, N- {2- [ bis (carboxymethyl) amino ] ethyl } -N- (2-hydroxyethyl) glycine (HEDTA), ethylenediamine-N, N ' -bis (2-hydroxyphenylacetic acid) (EDDHA), dioxaoctamethylenediaza tetraacetic acid (DOCTA) and triethylenetetramine hexaacetic acid (TTHA), for example, ethylenediamine tetraacetic acid and/or 1, 2-cyclohexanediamine-N, N ' -tetraacetic acid.
The semi-aqueous cleaning solution may comprise 0.005% -5%, for example 0.01% -2% (e.g. 0.01%, 1%, 2%) of the chelating agent by mass of the total mass of the raw materials.
In the semi-water-based cleaning solution, the corrosion inhibitor can be a corrosion inhibitor conventionally used in the field, for example Benzotriazole (BTA), tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5-mercapto-1, 2, 4-triazole, 1-amino-1, 2, 4-benzotriazole, hydroxybenzotriazole, 2- (5-amino-pentyl) -benzotriazole, 1-amino-1, 2, 3-triazole, 1-amino-5-methyl-1, 2, 3-triazole, 3-amino-1, 2, 4-triazole, 3-mercapto-1, 2, 4-triazole, 3-isopropyl-1, 2, 4-triazole, 5-thiophen-benzotriazole, halo-benzotriazole (halogen is F, cl, br or I), naphthotriazole 2-Mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-aminotetrazole monohydrate, 5-amino-1, 3, 4-thiadiazole-2-thiol, 2, 4-diamino-6-methyl-1, 3, 5-triazine, thiazole, triazine, methyltetrazole, 1, 3-dimethyl-2-imidazolidinone, 1, 5-pentamethylene tetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, imidazolinethione, mercaptobenzimidazole, 4-methyl-4H-1, 2, 4-triazole-3-thiol, one or more of 5-amino-1, 3, 4-thiadiazole-2-thiol and benzothiazole, for example, benzotriazole and/or tolyltriazole.
In the semi-water-based cleaning solution, the mass fraction of the corrosion inhibitor can be 0.005% -5%, for example 0.01% -2% (for example 0.01%, 0.5%, 2%), and the mass fraction is the mass of the corrosion inhibitor accounting for the total mass of the raw materials.
In the semi-aqueous cleaning solution, the ammonium carboxylate may be one or more of ammonium carboxylates conventionally used in the art, such as ammonium oxalate, ammonium lactate, ammonium tartrate, ammonium tri-citrate, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium benzoate, ammonium ethylenediamine tetraacetate, diammonium ethylenediamine tetraacetate, triammonium ethylenediamine tetraacetate, tetraammonium ethylenediamine tetraacetate, ammonium succinate, ammonium formate and ammonium 1-H-pyrazole-3-carboxylate, for example, ammonium oxalate and/or triammonium citrate.
In the semi-aqueous cleaning solution, the mass fraction of the ammonium carboxylate may be 0.1% -6%, for example 0.5% -3% (e.g. 0.5%, 1%, 3%), the mass fraction being the mass of the ammonium carboxylate in percentage of the total mass of the raw material.
In the semi-aqueous cleaning solution, the mass fraction of the EO-PO polymer L42 may be 0.005% -1.2%, for example 0.01% -1% (e.g., 0.01%, 0.05%, 1%), and the mass fraction is the mass of the EO-PO polymer L42 in percentage of the total mass of the raw material.
In the invention, the EO-PO polymer is polyoxyethylene polyoxypropylene block polymer.
In the semi-aqueous cleaning solution, the passivating agent can be a passivating agent conventionally used in the field, for example, 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and the preparation method of the 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) is conventional in the field.
In the semi-aqueous cleaning solution, the mass fraction of the passivating agent may be 0.005% -2%, for example 0.01% -2% (e.g. 0.01%, 0.7%, 2%), and the mass fraction is the mass of the passivating agent in percentage of the total mass of the raw material.
In the semi-aqueous cleaning solution, the water-soluble organic solvent can be a water-soluble organic solvent conventionally used in the art, such as methanol, ethanol, isopropanol, butanol and higher alcohols (e.g., C2-C4 diols and C2-C4 triols), tetrahydrofurfuryl alcohol (THFA), halogenated alcohols (e.g., 3-chloro-1, 2-propanediol, 3-chloro-1-propanethiol, 1-chloro-2-propanol, 2-chloro-1-propanol, 3-bromo-1, 2-propanediol, 1-bromo-2-propanol, 3-bromo-1-propanol, 3-iodo-1-propanol, 4-chloro-1-butanol, 2-chloroethanol), acetic acid, propionic acid, trifluoroacetic acid, tetrahydrofuran (THF), N-methylpyrrolidone (NMP), cyclohexylpyrrolidone, N-octylpyrrolidone N-phenylpyrrolidone, methyldiethanolamine, methyl formate, dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetramethylene sulfone (sulfolane), diethyl ether, phenoxy-2-propanol (PPh), ethyl lactate, acetonitrile, acetone, ethylene glycol, propylene Glycol (PG), 1, 3-propanediol, 1, 4-propanediol, dioxane, dipropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (i.e., butyl carbitol), triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol N-propyl ether, dipropylene glycol N-propyl ether (DPGPE), tripropylene glycol N-propyl ether, propylene glycol N-butyl ether, dipropylene glycol N-butyl ether, tripropylene glycol N-butyl ether, propylene glycol phenyl ether, dipropylene glycol methyl ether acetate, tetraethylene glycol dimethyl ether (TEGDE), glycerol carbonate, N-formyl morpholine and triethyl phosphate, for example, dipropylene glycol methyl ether and/or diethylene glycol monomethyl ether.
In the semi-aqueous cleaning solution, the mass fraction of the water-soluble organic solvent may be 25% -55%, for example 30% -50% (e.g. 30%, 40%, 50%), and the mass fraction is the percentage of the mass of the water-soluble organic solvent to the total mass of the raw materials.
In the semi-aqueous cleaning solution, the water may be one or more of deionized water, pure water and ultrapure water, preferably ionized water.
In certain preferred embodiments of the present invention, the semi-aqueous cleaning solution is prepared from the following raw materials, wherein the raw materials comprise the following components in percentage by mass: 10% -35% of oxidant, 0-0.5% of D-amino acid oxidase, 0-1.5% of D-type amino acid, 1% -10% of organic base, 0.005% -5% of chelating agent, 0.005% -5% of corrosion inhibitor, 0.1% -6% of ammonium carboxylate, 0.005% -1.2% of EO-PO polymer L42, 0.005% -2% of passivating agent, 25% -55% of water-soluble organic solvent and the balance of water, wherein the mass fraction is the mass percentage of each component in the total mass of each component.
In certain preferred embodiments of the present invention, the semi-aqueous cleaning solution is prepared from the following raw materials, wherein the raw materials comprise the following components in percentage by mass: 10% -30% of oxidant, 0% -0.01% of D-amino acid oxidase, 0% -0.5% of D-type amino acid, 3% -8% of organic base, 0.01% -2% of chelating agent, 0.01% -2% of corrosion inhibitor, 0.5% -3% of ammonium carboxylate, 0.01% -1% of EO-PO polymer L42, 0.01% -2% of passivating agent, 30% -50% of water-soluble organic solvent and the balance of water, wherein the mass fraction is the mass percentage of each component in the total mass of each component.
In certain preferred embodiments of the present invention, the semi-aqueous cleaning solution is prepared from the following raw materials, wherein the raw materials comprise the following components in percentage by mass: 10% -30% of an oxidizing agent, 0.005% -0.5% (e.g., 0.005% -0.01%) of a D-amino acid oxidase, 0.1% -1.5% (e.g., 0.25% -0.5%) of a D-amino acid, 3% -8% of an organic base, 0.01% -2% of a chelating agent, 0.01% -2% of a corrosion inhibitor, 0.5% -3% of ammonium carboxylate, 0.01% -1% of an EO-PO polymer L42, 0.01% -2% of a passivating agent, 30% -50% of a water-soluble organic solvent, and the balance of water, wherein the mass percentages are percentages of the mass of each component by mass of the total mass of each component.
In certain preferred embodiments of the present invention, the semi-aqueous cleaning solution is prepared from the following raw materials, wherein the raw materials comprise the following components in percentage by mass: 10% -35% of oxidant, 0-0.5% of D-amino acid oxidase, 0-1.5% of D-type amino acid, 1% -10% of organic base, 0.005% -5% of chelating agent, 0.005% -5% of corrosion inhibitor, 0.1% -6% of ammonium carboxylate, 0.005% -1.2% of EO-PO polymer L42, 0.005% -2% of passivating agent, 25% -55% of water-soluble organic solvent and the balance of water, wherein the mass fraction is the mass percentage of each component in the total mass of each component.
In certain preferred embodiments of the present invention, the semi-aqueous cleaning solution is prepared from the following raw materials, wherein the raw materials comprise the following components in percentage by mass: the chemical composition comprises, by mass, 0-0.5% of a base acid oxidase, 3-8% of an organic base, 0.01-2% of a chelating agent, 0.01-2% of a corrosion inhibitor, 0.5-3% of ammonium carboxylate, 0.01-1% of an EO-PO polymer L42, 0.01-2% of a passivating agent, 30-50% of a water-soluble organic solvent and the balance of water, wherein the mass percentages of the components are the total mass of the components.
In certain preferred embodiments of the present invention, the semi-aqueous cleaning solution is prepared from the following raw materials, wherein the raw materials comprise the following components in percentage by mass: 10% -30% of an oxidizing agent, 0.005% -0.5% (e.g., 0.005% -0.01%) of a D-amino acid oxidase, 0.1% -1.5% (e.g., 0.25% -0.5%) of a D-amino acid, 3% -8% of an organic base, 0.01% -2% of a chelating agent, 0.01% -2% of a corrosion inhibitor, 0.5% -3% of ammonium carboxylate, 0.01% -1% of an EO-PO polymer L42, 0.01% -2% of a passivating agent, 30% -50% of a water-soluble organic solvent, and the balance of water, wherein the mass percentages are percentages of the mass of each component by mass of the total mass of each component.
The invention also provides a preparation method of the semi-water-based cleaning liquid, which comprises the following steps: mixing the raw materials to obtain the semi-water-based cleaning solution.
Wherein, the mixing is preferably to add the solid component in the raw material components into the liquid component and stir the mixture uniformly.
Wherein the temperature of the mixing may be room temperature.
The invention also provides application of the semi-water-based cleaning solution in a cleaning process of a semiconductor device.
The semiconductor device is etched by plasma, and for example, the semiconductor device contains a hard mask material, wherein the hard mask material can be one or more of titanium nitride (TiN), tantalum nitride (TaN), titanium oxynitride (TiN xOy) and titanium (Ti).
The temperature of the cleaning in the cleaning process may be, for example, 40-60 c (e.g., 50 c) which is conventionally used in the art. The cleaning time in the cleaning process can be 5min-30min (e.g. 20 min).
In the present invention, unless otherwise specified, "room temperature" means 10 to 40 ℃.
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: the semi-aqueous cleaning solution of the present invention is useful for selectively removing hard masks and other residues from Integrated Circuit (IC) wet process cleaning processes, and more particularly for selectively removing TiN, taN, tiNxOy, ti hard masks, and hard masks comprising alloys of the above, and other residues from such chips or wafers comprising low-k dielectric materials, TEOS, copper, cobalt, and other low-k dielectric materials, and is highly corrosion-inhibiting for a variety of metals and dielectrics, particularly cobalt-compatible, and has good cleaning results.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Abbreviations involved in the examples are as follows:
TMAH: tetramethyl ammonium hydroxide;
BTA: benzotriazole;
CDTA:1, 2-cyclohexanediamine-N, N' -tetraacetic acid;
F:1- (benzotriazol-1-methyl) -1- (2-methylbenzimidazole), said 1- (benzotriazol-1-methyl) -1- (2-methylbenzimidazole);
DPGME: dipropylene glycol methyl ether;
AlN xOy: aluminum oxynitride;
AlN: aluminum nitride;
W: tungsten;
cu: copper;
LP-TEOS: depositing ethyl orthosilicate at low pressure;
BD2: a low-k dielectric material commonly used in the art under the trade name BLACK DIAMOND (BD 2);
SiCN: silicon carbon nitrogen;
co: cobalt;
Ti: titanium;
TiN: the TiN is PVD TiN, wherein PVD refers to (Physical Vapor Deposition) physical vapor deposition;
TaN: tantalum nitride;
TiNxOy: titanium oxynitride.
The EO-PO products of the examples were all purchased from Nantong Jinlai chemical Co., ltd.
The D-amino acid oxidases in the examples were all purchased from Shanghai Ala Biotechnology Co., ltd.
1- (Benzotriazol-1-methyl) -1- (2-methylbenzimidazole) in the examples, the preparation method of the 1- (benzotriazol-1-methyl) -1- (2-methylbenzimidazole) is described with reference to CN106188103B, which is denoted by F in the following examples.
Examples 1 to 14
The raw material components of the semi-water-based cleaning liquid are as follows: the types and contents of the oxidizing agent, D-amino acid oxidase, D-amino acid, organic base, chelating agent, corrosion inhibitor, ammonium carboxylate, EO-PO polymer L42, passivating agent, and water-soluble organic solvent are listed in Table 1, the balance is made up with water, and the water in the cleaning composition is deionized water.
In the following examples, the semi-aqueous cleaning solution is prepared by adding the solid components of the raw material components in the examples to the liquid components and stirring them uniformly.
In the following examples, the specific operating temperatures are not limited, and all refer to being conducted under room temperature conditions.
TABLE 1 types and mass fractions of the raw material components of the semi-aqueous cleaning solution
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Application example 1
(1) Etch rate determination
Etching rate sample to be detected: a dummy wafer (dummy wafer) of a single material such as aluminum, copper, titanium nitride, tungsten, cobalt, dielectric material (low-k or high-k), etc. is deposited on the silicon wafer.
Etching experiment: and (3) statically soaking the sample to be detected in a semi-water-based cleaning solution for 30min at 50 ℃, and then drying by nitrogen after deionized water cleaning.
Method of measuring etch rate (a/min): the thickness of the sample before and after etching was measured separately, wherein the metal sample was measured for thickness using a four-point probe apparatus (CRESTEST-e of Japanese Napson), and the nonmetal sample was measured for thickness using an optical film thickness measuring apparatus (U.S. FILMETRICS F).
Etching effects are classified into four classes: a-compatibility is good, and undercut is avoided; b-very slight undercut; c-having a small undercut; d-undercut is more pronounced and severe.
(2) Cleaning effect measurement
Cleaning effect sample to be detected: patterned wafers with post plasma etch residues and post ash residues with patterned features (metal lines, holes via, metal pad or trench, etc.).
The cleaning effect experimental method comprises the following steps: the sample is statically immersed in a semi-water-based cleaning solution for 20min at 50 ℃, and then is cleaned by deionized water and then dried by nitrogen. The cleaning and corrosion effects were observed with an electron microscope SEM.
The cleaning effect is classified into four grades: a-no residue was observed; b-very little residue was observed; c-small residues were observed; d-significantly more residue was observed.
The etching rates of the semi-aqueous cleaning solutions of examples 1 to 14 and comparative examples 1 to 10 are shown in Table 2, and the etching effects and cleaning effects are shown in Table 3.
TABLE 2
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TABLE 3 Table 3
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From tables 2 and 3, the semi-water-based cleaning solution of the invention has lower etching rate to AlN xOy、AlN、W、Cu、LP-TEOS、BD2、SiCN、Co、Ti、TiN、TaN、TiNxOy and the like, which shows that the corrosion inhibition performance is better and the cobalt compatibility is good; and after the patterned wafer with the through hole feature and the patterned wafer with the metal line feature are cleaned by the semi-water-based cleaning solution, the undercut phenomenon is hardly observed, which shows that the semi-water-based cleaning solution has good compatibility with various metals and dielectrics. In addition, after the patterned wafer with through hole features and the patterned wafer with metal line features are cleaned by the semi-aqueous cleaning solution of the invention, almost no residues are observed, which indicates that the cleaning effect is good.
Compared with examples 1-14, the semi-aqueous cleaning solutions of comparative examples 1-10 have significantly higher etching rates for AlN xOy, alN, W, cu, LP-TEOS, BD2, siCN, etc., have poor corrosion inhibition performance, or have significantly lower etching rates for Ti, tiN, taN, tiN xOy, etc., and cannot effectively remove the hard mask material, and have significantly higher etching rates for Co, and poor cobalt compatibility. It can be seen that the semi-aqueous cleaning solutions of comparative examples 1-10 do not allow for selective removal of the hard mask material, and have poor compatibility with other metals (especially Co) and dielectric materials. Also, after cleaning the patterned wafer with via features and the patterned wafer with metal line features with the semi-aqueous cleaning solutions of comparative examples 1-10, a more severe undercut phenomenon occurred with more residues.

Claims (5)

1. The semi-water-based cleaning solution is characterized by being prepared from the following raw materials in percentage by mass: 10% -30% of an oxidant, 0% -0.01% of D-amino acid oxidase, 0% -0.5% of D-amino acid, 3% -8% of organic base, 0.01% -2% of chelating agent, 0.01% -2% of corrosion inhibitor, 0.5% -3% of ammonium carboxylate, 0.01% -1% of EO-PO polymer L42, 0.01% -2% of passivating agent, 30% -50% of water-soluble organic solvent and the balance of water, wherein the mass fraction is the mass percentage of each component in the total mass of each component;
wherein the oxidant is one or more of hydrogen peroxide, carbamide peroxide and peracetic acid;
the D-type amino acid is one or more of D-proline, D-arginine and D-histidine;
The organic base is tetramethyl ammonium hydroxide and/or choline;
the chelating agent is ethylenediamine tetraacetic acid and/or 1, 2-cyclohexanediamine-N, N, N ', N' -tetraacetic acid;
The corrosion inhibitor is benzotriazole and/or tolyltriazole;
the ammonium carboxylate is ammonium oxalate and/or ammonium citrate;
the passivating agent is 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole);
The water-soluble organic solvent is dipropylene glycol methyl ether and/or diethylene glycol monomethyl ether;
the water is one or more of deionized water, pure water and ultrapure water.
2. The semi-aqueous cleaning solution of claim 1,
The mass fraction of the D-amino acid oxidase is 0.005% -0.01%;
and/or the mass fraction of the D-type amino acid is 0.25% -0.5%;
And/or, the water is deionized water.
3. A method of preparing a semi-aqueous cleaning solution as claimed in claim 1 or 2, comprising the steps of: mixing the raw materials to obtain the semi-water-based cleaning solution.
4. Use of the semi-aqueous cleaning solution according to claim 1 or 2 in a cleaning process for semiconductor devices.
5. The use of the semi-aqueous cleaning solution as claimed in claim 4 in a cleaning process for semiconductor devices, wherein the semiconductor devices are plasma etched;
And/or the semiconductor device contains a hard mask material, wherein the hard mask material is one or more of titanium nitride, tantalum nitride, titanium oxynitride and titanium;
and/or, the cleaning temperature in the cleaning process is 40-60 ℃;
and/or the cleaning time in the cleaning process is 5 min-30 min.
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