CN113430060B - Tungsten compatible cleaning solution for removing hard mask, preparation method and application thereof - Google Patents

Tungsten compatible cleaning solution for removing hard mask, preparation method and application thereof Download PDF

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CN113430060B
CN113430060B CN202010208618.2A CN202010208618A CN113430060B CN 113430060 B CN113430060 B CN 113430060B CN 202010208618 A CN202010208618 A CN 202010208618A CN 113430060 B CN113430060 B CN 113430060B
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cleaning
cleaning solution
hard mask
ammonium
raw materials
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CN113430060A (en
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王溯
蒋闯
徐锦波
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Shanghai Xinyang Semiconductor Material Co Ltd
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • 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
    • 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
    • H01L21/02082—Cleaning product to be cleaned
    • C11D2111/22—

Abstract

The invention discloses a tungsten compatible cleaning solution for removing a hard mask, a preparation method and application thereof. The invention provides a cleaning solution which is prepared from the following raw materials in parts by mass: 0.5% -20% of oxidant, 0.01% -30% of oxidant stabilizer, 0.1% -20% of fluoride, 0.1% -20% of organic base, 0.001% -10% of chelating agent, 0.001% -10% of corrosion inhibitor, 0.01% -15% of ammonium carboxylate, 0.001% -1.5% of surfactant, 0.001% -2.5% of passivating agent and the balance of water, wherein the mass fraction is the percentage of each component in the total mass of the raw materials; wherein the surfactant is EO-PO polymer L42. The cleaning liquid can selectively remove hard masks and other residues, has strong compatibility with tungsten and various metals and dielectrics, and has good cleaning effect.

Description

Tungsten compatible cleaning solution for removing hard mask, preparation method and application thereof
Technical Field
The invention relates to a tungsten compatible 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 cobalt, 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 develop 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 manufacturers 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) needs to be removed after the etching protection, and other metals and dielectric materials need to be protected during the cleaning process to remove the hard mask material, thus making compatibility of conventional fluorine-containing cleaning fluids with a variety of materials challenging.
Developing a 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 tungsten compatible cleaning solution for removing a hard mask, a preparation method and application thereof. The cleaning fluids of the present invention are useful for selectively removing hard masks and other residues from Integrated Circuit (IC) wet process cleaning processes, and in particular, compositions and methods for selectively removing TiN, taN, tiN xOy, ti hard masks, and hard masks comprising alloys of the foregoing, as well as other residues, from such chips or wafers comprising low-k dielectric materials, TEOS, copper, cobalt, and other low-k dielectric materials. In addition, the cleaning liquid has strong compatibility to tungsten, various metals and dielectrics and good cleaning effect.
The invention solves the technical problems through the following technical proposal.
The invention provides a cleaning solution which is prepared from the following raw materials in parts by mass: 0.5% -20% of oxidant, 0.01% -30% of oxidant stabilizer, 0.1% -20% of fluoride, 0.1% -20% of organic base, 0.001% -10% of chelating agent, 0.001% -10% of corrosion inhibitor, 0.01% -15% of ammonium carboxylate, 0.001% -1.5% of surfactant, 0.001% -2.5% of passivating agent and the balance of water, wherein the mass fraction is the percentage of each component in the total mass of the raw materials;
Wherein the surfactant is EO-PO polymer L42.
Among the cleaning solutions, the oxidizing agent may be an oxidizing agent conventionally used in the art, preferably hydrogen peroxide (H 2O2), benzoyl peroxide, tetrabutylammonium peroxymonosulfate, ozone, ferric chloride, permanganate, perborate, perchlorate, persulfate, ammonium peroxydisulfate, peracetic acid, carbamide 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 [ (N (CH 3)4)S2O8]、[(CO(NH2)2)H2O2) ] and peracetic acid [ CH 3 (c=o ]) preferably one or more of hydrogen peroxide and/or acetic acid.
In the cleaning solution, the mass fraction of the oxidizing agent may be 0.5% -10%, preferably 1% -5% (e.g. 1%, 2.5%, 5%), and the mass fraction is the mass of the oxidizing agent in percentage of the total mass of the raw material.
In the cleaning solution, the oxidant stabilizer may be an oxidant stabilizer conventionally used in the art, preferably one or more of N-methylmorpholine oxide (NMMO or NMO), pyrimidine N-oxide, pyridine N-oxide, pyridazine N-oxide, quinoline N-oxide and trimethylamine N-oxide, more preferably one or more of N-methylmorpholine oxide, pyridine N-oxide and trimethylamine N-oxide.
In the cleaning solution, the mass fraction of the oxidant stabilizer may be 0.5% -20%, preferably 1% -10% (e.g. 1%, 5%, 10%), and the mass fraction is the mass of the oxidant stabilizer in percentage of the total mass of the raw materials.
In the cleaning liquid, the fluoride may be fluoride conventionally used in the art, preferably one or more of hydrogen fluoride, ammonium fluoride, potassium fluoride, alkali metal fluoride, tetraalkylammonium fluoride, fluoroboric acid, ammonium tetrafluoroborate, alkali metal tetrafluoroborate, tetraalkylammonium tetrafluoroborate and trimethyloxonium tetrafluoroborate, more preferably hydrogen fluoride and/or fluoroboric acid.
The mass fraction of fluoride in the cleaning liquid may be 0.5% -10%, preferably 1% -5% (e.g. 1%, 2.5%, 5%), the mass fraction being the mass of fluoride in the total mass of raw materials.
Among the cleaning solutions, the organic base may be one or more of tetramethyl ammonium hydroxide (TMAH), tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetraethyl ammonium hydroxide (TEAH), benzyl Trimethyl Ammonium Hydroxide (BTAH), choline, (2-hydroxyethyl) trimethyl ammonium hydroxide, tris (2-hydroxyethyl) methyl ammonium hydroxide, monoethanolamine (MEA), diglycolamine (DGA), triethanolamine (TEA), isobutolamine, isopropanolamine, tetrabutyl phosphonium hydroxide (TBPH) and tetramethyl guanidine, more preferably tetramethyl ammonium hydroxide and/or choline, which are conventionally used in the art.
In the cleaning solution, the mass fraction of the organic base may be 0.5% -10%, preferably 1% -5% (e.g. 1%, 2.5%, 5%), and the mass fraction is the mass of the organic base in percentage of the total mass of the raw materials.
Among the cleaning solutions, the chelating agent may be one or more of 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, N' -tetraacetic acid, N- {2- [ bis (carboxymethyl) amino ] ethyl } -N- (2-hydroxyethyl) glycine (HEDTA), ethylenediamine-N, N '-bis (2-hydroxyphenylacetic acid) (EDDHA), dioxaoctamethylenediazotetraacetic acid (DOCTA) and triethylenetetramine hexaacetic acid (TTHA), more preferably ethylenediamine tetraacetic acid and/or 1, 2-cyclohexanediamine-N, N' -tetraacetic acid.
In the cleaning solution, the mass fraction of the chelating agent may be 0.005% -5%, preferably 0.01% -2% (e.g. 0.01%, 1%, 2%), and the mass fraction is the percentage of the chelating agent mass to the total mass of the raw materials.
In the cleaning solution, the corrosion inhibitor can be a corrosion inhibitor conventionally used in the field, preferably 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=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, more preferably benzotriazole and/or tolyltriazole.
In the cleaning solution, the mass fraction of the corrosion inhibitor may be 0.005% -5%, preferably 0.01% -2% (e.g. 0.01%, 0.5%, 2%), and the mass fraction is the mass of the corrosion inhibitor in percentage of the total mass of the raw materials.
In the cleaning solution, the ammonium carboxylate may be one or more of ammonium carboxylate, preferably ammonium oxalate, ammonium lactate, ammonium tartrate, ammonium citrate, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium benzoate, ammonium ethylenediamine tetraacetate, ammonium succinate, ammonium formate and ammonium 1-H-pyrazole-3-carboxylate, more preferably ammonium oxalate and/or ammonium citrate, which are conventionally used in the art.
In the cleaning solution, the mass fraction of the ammonium carboxylate may be 0.1% -5%, preferably 0.5% -3% (e.g. 0.5%, 1%, 3%), and the mass fraction is the mass of the ammonium carboxylate in percentage of the total mass of the raw material.
In the cleaning solution, the mass fraction of the surfactant may be 0.01% -1.5%, preferably 0.01% -1% (e.g. 0.01%, 0.05%, 1%), and the mass fraction is the mass of the surfactant in percentage of the total mass of the raw materials.
In the cleaning solution, the passivating agent can be a passivating agent conventionally used in the field, preferably 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole). The preparation method of the 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) is conventional in the art, and refers to patent application CN106188103A.
In the cleaning solution, the mass fraction of the passivating agent may be 0.01% -2.5%, preferably 0.01% -2% (e.g. 0.01%, 0.7%, 1%, 1.5%, 2%), and the mass fraction is the mass of the passivating agent in percentage of the total mass of the raw material.
In the cleaning liquid, the water is preferably one or more of deionized water, pure water and ultrapure water, and more preferably deionized water.
In certain preferred embodiments of the present invention, the cleaning solution is prepared from the following raw materials, wherein the raw materials comprise the following components in percentage by mass: 0.5% -10% of oxidant, 0.5% -20% of oxidant stabilizer, 0.5% -10% of fluoride, 0.5% -10% of organic base, 0.005% -5% of chelating agent, 0.005% -5% of corrosion inhibitor, 0.1% -5% of ammonium carboxylate, 0.01% -1.5% of surfactant, 0.01% -2.5% of passivating agent and the balance of water, wherein the mass fraction is the percentage of each component in the total mass of the raw materials.
In certain preferred embodiments of the present invention, the cleaning solution is prepared from the following raw materials, wherein the raw materials comprise the following components in percentage by mass: 1% -5% of oxidant, 1% -10% of oxidant stabilizer, 1% -5% of fluoride, 1% -5% 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 surfactant, 0.01% -2% of passivating agent and the balance of water, wherein the mass fraction of each component accounts for the total mass of the raw materials.
In certain preferred embodiments of the present invention, the cleaning solution is prepared from the following raw materials, wherein the raw materials comprise the following components in percentage by mass: 0.5% -20% of oxidant, 0.01% -30% of oxidant stabilizer, 0.1% -20% of fluoride, 0.1% -20% of organic base, 0.001% -10% of chelating agent, 0.001% -10% of corrosion inhibitor, 0.01% -15% of ammonium carboxylate, 0.001% -1.5% of surfactant, 0.001% -2.5% of passivating agent and the balance of water, wherein the mass fraction is the percentage of each component in the total mass of the raw materials.
In certain preferred embodiments of the present invention, the cleaning solution is prepared from the following raw materials, wherein the raw materials comprise the following components in percentage by mass: 0.5% -10% of oxidant, 0.5% -20% of oxidant stabilizer, 0.5% -10% of fluoride, 0.5% -10% of organic base, 0.005% -5% of chelating agent, 0.005% -5% of corrosion inhibitor, 0.1% -5% of ammonium carboxylate, 0.01% -1.5% of surfactant, 0.01% -2.5% of passivating agent and the balance of water, wherein the mass fraction is the percentage of each component in the total mass of the raw materials.
In certain preferred embodiments of the present invention, the cleaning solution is prepared from the following raw materials, wherein the raw materials comprise the following components in percentage by mass: 1% -5% of oxidant, 1% -10% of oxidant stabilizer, 1% -5% of fluoride, 1% -5% 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 surfactant, 0.01% -2% of passivating agent and the balance of water, wherein the mass fraction of each component accounts for the total mass of the raw materials.
The invention also provides a preparation method of the cleaning liquid, which comprises the following steps: mixing the raw materials to obtain the 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 cleaning solution in cleaning a semiconductor device with a hard mask and/or after plasma etching.
Wherein the material of the hard mask can be titanium-containing or tantalum-containing material; the titanium-containing material can be one or more of titanium, titanium nitride and titanium oxynitride; the tantalum-containing material may be tantalum nitride.
The plasma etched substrate may be a copper interconnect substrate.
Wherein the temperature of the washing may be room temperature, preferably 35 ℃ -50 ℃ (e.g. 40 ℃). The washing time may be 5min-30min (e.g., 20 min).
In the present invention, unless otherwise specified, "room temperature" means 10 to 40 ℃.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: the cleaning fluids of the present invention are useful for selectively removing hard masks and other residues from Integrated Circuit (IC) wet process cleaning processes, and in particular, compositions and methods for selectively removing TiN, taN, tiN xOy, ti hard masks, and hard masks comprising alloys of the foregoing, as well as other residues, from such chips or wafers comprising low-k dielectric materials, TEOS, copper, cobalt, and other low-k dielectric materials. In addition, the cleaning liquid has strong compatibility to tungsten, various metals and dielectrics and good cleaning effect.
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; NMO: n-methylmorpholine oxide; CDTA:1, 2-cyclohexanediamine-N, N' -tetraacetic acid;
AlN xOy: aluminum oxynitride; alN: aluminum nitride; w: tungsten; cu: copper; LP-TEOS: depositing ethyl orthosilicate at low pressure; co: cobalt; BD2: a low-k dielectric material commonly used in the art under the trade name BLACK DIAMOND; siCN: silicon carbon nitrogen; ti: titanium; tiN: the TiN is PVD TiN, wherein PVD refers to (Physical Vapor Deposition) physical vapor deposition; taN-tantalum nitride; tiN xOy -titanium oxynitride.
The preparation of 1- (benzotriazol-1-methyl) -1- (2-methylbenzimidazole) is described with reference to CN106188103A, which is denoted by D in the following table.
The EO-PO products of the examples were all purchased from Nantong Jinlai chemical Co., ltd.
Examples 1 to 13
The cleaning solution comprises the following raw materials: the types and amounts of oxidizing agents, oxidizing agent stabilizers, fluorides, organic bases, chelating agents, corrosion inhibitors, ammonium carboxylates, surfactants, passivating agents are listed in tables 1 and 2; the water in the cleaning liquid is deionized water, and the balance is the deionized water.
In the following examples, the cleaning liquid is prepared by adding the solid component of the raw material components in the examples to the liquid component and stirring the mixture uniformly.
In the following examples, the specific operating temperatures are not limited, and all refer to being conducted under room temperature conditions.
TABLE 1 kinds of raw material components of cleaning liquid
TABLE 2 mass fractions of raw material components of cleaning liquid
Application examples 1 to 13
(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 cleaning solution for 30min at 40 ℃, and then cleaning with deionized water and drying with nitrogen.
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).
The corrosion effects are rated in 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 cleaning solution for 20min at 40 ℃, 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 rate (A/min), etching effect and cleaning effect of the cleaning solutions of examples 1 to 13 are shown in Table 3.
As can be seen from Table 3, the cleaning solution of the invention has lower etching rates to AlN xOy, alN, W, cu, LP-TEOS, co, BD, siCN and the like, which shows that the cleaning solution has better corrosion inhibition performance to the materials; the high etch rate of Ti, tiN, taN, tiN xOy indicates that it is preferable to remove such materials as the hard mask. And after the patterned wafer with the through hole feature and the patterned wafer with the metal line feature are cleaned by the cleaning solution, the undercut phenomenon is hardly observed, which shows that the cleaning solution has good compatibility with various metals and dielectrics.
In addition, after the patterned wafer with the through hole feature and the patterned wafer with the metal line feature are cleaned by the cleaning solution of the present invention, almost no residue is observed, indicating that the cleaning effect is good.
Comparative examples 1 to 11
The preparation method is described in examples 1-13.
TABLE 4 kinds of raw material components of cleaning liquid
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TABLE 5 mass fractions of raw material components of cleaning solution
The cleaning solutions of comparative examples 1 to 11 were subjected to etching rate (A/min), etching effect and cleaning effect, and the test methods were the same as those of application examples 1 to 13, and the results are shown in Table 6.
As can be seen from Table 6, the cleaning solutions of comparative examples 1 to 11 significantly increased the etching rate of AlN xOy, alN, W, cu, LP-TEOS, co, BD2, siCN, etc., and had poor corrosion inhibition performance, as compared with examples 1 to 13. The reduced etch rate for Ti, tiN, taN, tiN xOy indicates poor removal of such materials, e.g., hard masks.
Also, after the patterned wafer having the via feature and the patterned wafer having the metal line feature were cleaned with the cleaning solution of comparative examples 1 to 11, a more serious undercut phenomenon occurred, with more residues.

Claims (9)

1. The cleaning fluid is characterized by being prepared from the following raw materials in parts by mass: 1% -5% of an oxidant, 1% -10% of an oxidant stabilizer, 1% -5% of fluoride, 1% -5% of 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 a surfactant, 0.01% -2% of a passivating agent and the balance of water, wherein the mass fraction of each component accounts for the total mass of the raw materials;
Wherein the surfactant is EO-PO polymer L42;
the passivating agent is 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole);
the oxidant is hydrogen peroxide and/or peracetic acid;
The oxidant stabilizer is one or more of N-methylmorpholine oxide, pyridine N-oxide and trimethylamine N-oxide;
the fluoride is hydrogen fluoride and/or fluoboric acid;
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.
2. The cleaning solution of claim 1,
The water is one or more of deionized water, pure water and ultrapure water.
3. The cleaning solution of claim 2,
The water is deionized water.
4. A method of preparing a cleaning solution as claimed in any one of claims 1 to 3, comprising the steps of: mixing the raw materials to obtain the cleaning solution.
5. A method for preparing a cleaning liquid according to claim 4,
The mixing is that solid components in the raw material components are added into liquid components and stirred uniformly;
And/or, the temperature of the mixing is room temperature.
6. Use of a cleaning solution according to any of claims 1-3 for cleaning semiconductor devices after hard mask and/or plasma etching.
7. A method for cleaning a semiconductor device having a hard mask and/or a plasma etched semiconductor device, comprising applying the cleaning solution of claim 6,
The hard mask is made of titanium-containing or tantalum-containing materials;
And/or, the substrate subjected to plasma etching is a copper interconnection substrate;
and/or, the cleaning temperature is room temperature;
and/or the cleaning time is 5min-30min.
8. A method for cleaning a semiconductor device having a hard mask and/or a plasma etched semiconductor device, as claimed in claim 7,
The titanium-containing material is one or more of titanium, titanium nitride and titanium oxynitride;
And/or the tantalum-containing material is tantalum nitride.
9. Use of a cleaning solution according to claim 6 for cleaning semiconductor devices after hard mask and/or plasma etching, wherein the cleaning temperature is between 35 ℃ and 50 ℃.
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CN110643434A (en) * 2018-06-26 2020-01-03 弗萨姆材料美国有限责任公司 Post Chemical Mechanical Planarization (CMP) clean

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WO2001042408A2 (en) * 1999-12-08 2001-06-14 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
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