WO2022262018A1 - Solution de nettoyage utilisée dans un procédé de nettoyage destiné à une tranche de semi-conducteur - Google Patents

Solution de nettoyage utilisée dans un procédé de nettoyage destiné à une tranche de semi-conducteur Download PDF

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Publication number
WO2022262018A1
WO2022262018A1 PCT/CN2021/104697 CN2021104697W WO2022262018A1 WO 2022262018 A1 WO2022262018 A1 WO 2022262018A1 CN 2021104697 W CN2021104697 W CN 2021104697W WO 2022262018 A1 WO2022262018 A1 WO 2022262018A1
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Prior art keywords
cleaning solution
cleaning
copper
guanidine
semiconductor wafer
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PCT/CN2021/104697
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English (en)
Chinese (zh)
Inventor
孙秀岩
王倩
郭磊
苏俊
金徽
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张家港安储科技有限公司
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Publication of WO2022262018A1 publication Critical patent/WO2022262018A1/fr

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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
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3272—Urea, guanidine or derivatives 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • 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
    • C11D7/265—Carboxylic acids or 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/267—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
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3218—Alkanolamines or alkanolimines
    • 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
    • C11D7/22—Organic compounds
    • C11D7/34—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
    • C23G1/18—Organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20—Other heavy metals
    • 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
    • H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

  • the invention relates to the technical field of semiconductor manufacturing, in particular to a cleaning solution used in the semiconductor wafer cleaning process.
  • CMP chemical mechanical polishing
  • Metal chemical mechanical polishing fluids generally contain abrasive particles, complexing agents, metal corrosion inhibitors, oxidants, and the like.
  • the abrasive particles are mainly abrasive particles such as silicon dioxide, aluminum oxide, and cerium oxide according to the application.
  • a large number of fine abrasive particles and chemical additives in the polishing liquid, as well as debris peeled off by wafer abrasion may adhere to the wafer surface.
  • the common pollutants after wafer grinding are metal ions, organic compounds or abrasive particles. If there is no effective cleaning procedure to remove the above pollutants, it will affect the subsequent process progress and reduce the yield and reliability of components.
  • the cleaning process during or after the CMP process has become a key technology for the successful application of CMP to the semiconductor process. Therefore, after the metal CMP process, it is very necessary to remove the metal ions, metal corrosion inhibitors and abrasive particles remaining on the wafer surface, improve the hydrophilicity of the cleaned wafer surface, and reduce surface defects.
  • U.S. Patent No. 6,498,131 to Small et al. discloses a solution for removing surface residues after chemical mechanical polishing, which includes an aqueous solution with a pH value between 10 and 12.5, which includes at least one non- Ionic surfactant, at least one amine, at least one quaternary ammonium compound, and at least one surface retention agent selected from the group consisting of ethylene glycol, propylene glycol, polyethylene oxide, polypropylene oxide and mixtures thereof, the amine may be, for example, monoethanolamine etc.
  • U.S. Patent No. 6,492,308 of Naghshineh et al. discloses an alkaline cleaning solution for cleaning copper-containing integrated circuits, which is composed of tetraalkylammonium hydroxide, a polar organic amine and a corrosion inhibitor , the polar organic amine can be selected from monoethanolamine and the like.
  • the corrosion inhibitor is selected from ascorbic acid and gallic acid.
  • the Chinese patent CN101720352B of Zhang Peng et al discloses an alkaline cleaning solution for cleaning copper-containing integrated circuits.
  • the cleaning solution contains at least one quaternary base, a corrosion inhibitor, and at least one organic amine.
  • the corrosion inhibitor is selected from glucuronic acid, squaric acid, Adenosine and its derivatives, flavonols and their derivatives, anthocyanins and their derivatives, and quercetin and its derivatives.
  • the semiconductor technology node has been developed to below 10 nanometers, and there are still many problems to be overcome in the new planarization process due to the reduction of the line width.
  • the metal surface roughness may become worse, which will lead to poor electrical test (and reliability test results) of the copper wire wafer. Therefore, the copper wire wafer cleaning process still needs to be more effective than the previous technology.
  • metal cobalt has been used as a barrier layer in advanced copper manufacturing processes. From the perspective of standard electrode potential, compared with copper, cobalt has a lower electrode potential and is more prone to corrosion. Therefore, when cobalt is in contact with copper when cobalt is used as a barrier layer, cobalt will undergo galvanic corrosion in general cleaning solutions. Accelerate the corrosion of cobalt to destroy the barrier layer of cobalt. Therefore, in the advanced node copper wire wafer cleaning process, in addition to efficiently removing the pollutants remaining on the copper wire wafer surface and reducing the number of defects on the wafer surface, it is also necessary to completely protect the cobalt barrier layer.
  • quaternary ammonium bases such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, are often used in the cleaning solution after chemical mechanical polishing of copper. Due to its high toxicity, its use in semiconductor cleaning solutions is gradually banned. Therefore, a cleaning solution that does not contain highly toxic quaternary ammonium bases is required in the semiconductor cleaning process.
  • the problem to be solved in the present invention is to provide a method that does not contain quaternary ammonium base and can effectively clean the residue after chemical mechanical polishing on the copper surface. Furthermore, in addition to effectively cleaning the residues after chemical mechanical grinding on the copper surface, the cleaning solution At the same time, it can provide protection for the cobalt barrier layer in the copper advanced process.
  • the present invention relates to a cleaning solution used in the semiconductor wafer cleaning process, characterized in that the cleaning solution is made from the following raw materials in mass percentage:
  • the mass percentage of guanidine or guanidine derivatives is 1-20%, the mass percentage of alkanolamine is 1-20%, the mass percentage of antioxidant is 0.1-10%, and the mass of the optional nitrogen-containing heterocyclic metal corrosion inhibitor The percentage is 0.01 ⁇ 5%.
  • the beneficial effect of the present invention is that the cleaning liquid in the present invention reduces the toxicity of the cleaning liquid itself by removing the quaternary ammonium base.
  • metal corrosion inhibitors in addition to reducing the corrosion rate of copper, it increases the protection of the cobalt barrier layer, especially the galvanic corrosion protection, ensuring the accuracy of the product.
  • the guanidine or guanidine derivatives are selected from guanidine, 1,1,3,3-tetramethylguanidine, arginine, 2-tert-butyl-1,1,3,3-tetramethylguanidine , 2-(4-tolyl)-1,1,3,3-tetramethylguanidine, biguanide, metformin, phenformin, proguanil, butylbiguanide, 1-(o-tolyl) biguanide or more; the mass percentage of the derivative of guanidine or guanidine is selected from one of 1-20%, 1-10%, 5-15%, 5-10%; preferably 5-15%, more preferably 5% -10%.
  • the alkanolamine is selected from ethanolamine (MEA), diethanolamine (DEA), methylethanolamine, amine triethanolamine (TEA), isopropanolamine, isobutanolamine, diglycolamine, methyl One or more of diethanolamine, dimethylethanolamine and hydroxyethylethylenediamine; the mass percentage of the alkanolamine is selected from 1-20%, 1-10%, 5-15%, 3- One of 10%, 3-15%; preferably 1-20%, more preferably 3-10%.
  • the antioxidant is selected from one or more of ascorbic acid, 3,4,5-trihydroxybenzoic acid, catechol and derivatives thereof.
  • the mass percentage of the antioxidant is selected from one of 0.1-10%, 0.1-5%, 0.5-10%, 0.5-5%, 0.5-3.5%; preferably 0.1-5%, more preferably 0.5-3.5% .
  • the optional nitrogen-containing heterocyclic metal corrosion inhibitors are nitrogen-containing heterocyclic compounds, such as imidazole, phenyl azide, benzimidazole, benzothiazole, urea and derivatives of the above compounds.
  • the metal corrosion inhibitor of nitrogen-containing heterocyclic ring is selected from 1,2,4-triazole, 1,2,3-triazole, imidazole, phenyl azide, benzimidazole, benzothiazole, urea and the above compounds One or more of the derivatives; the mass percentage of the nitrogen-containing heterocyclic metal corrosion inhibitor is selected from 0.001-5%, 0.01-2%, One of 0.05-2%, 0.1-1.5%, preferably 0.01-2%, more preferably 0.1-1.5%
  • the pH value of the cleaning solution is greater than 8.
  • the pH value of the cleaning solution is generally at least 11, preferably pH>11, more preferably pH>13.
  • no oxidizing agents are contained in the cleaning solution, for example, hydrogen peroxide, abrasive particles, inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, inorganic alkalis, potassium hydroxide, sodium hydroxide, ammonia water, surfactants, halogenated Substances such as fluoride, chloride, bromide, sulfur-containing compounds, various organic solvents, metal-containing compounds.
  • inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, inorganic alkalis, potassium hydroxide, sodium hydroxide, ammonia water, surfactants, halogenated Substances such as fluoride, chloride, bromide, sulfur-containing compounds, various organic solvents, metal-containing compounds.
  • the cleaning solution is diluted with water before use, and the dilution ratio is 1:1 to 1:200, preferably 1:10 to 1:100, more preferably 1:20 to 1:60;
  • the cleaning solution It can be used for cleaning the surface of a copper semiconductor metal substrate containing a cobalt barrier layer;
  • the material of the metal substrate can be selected from one or more of copper, tantalum, tantalum nitride, titanium, and titanium nitride.
  • the cleaning temperature is 20 to 60 o C, preferably 20-30 o C.
  • the cleaning solution can be used to clean the wafer in a washing machine or on a polishing disc after polishing.
  • the invention can be used for cleaning the flattened wafer surface on a chemical mechanical flattening machine, and can also clean the flattened wafer surface on an independent cleaning machine.
  • Fig. 1 is a kind of change figure of copper surface roughness before and after cleaning that is used for cleaning liquid in semiconductor wafer cleaning process of the present invention
  • Fig. 2 is a kind of corrosion rate contrast figure of copper and cobalt of the cleaning solution containing quaternary ammonium alkali and the cleaning solution containing 1,1,3,3-tetramethylguanidine that is used for the cleaning solution in semiconductor wafer cleaning process of the present invention ;
  • Fig. 3 is a kind of copper and cobalt corrosion potential contrast figure in the cleaning solution containing quaternary ammonium alkali and containing 1,1,3,3-tetramethylguanidine used in the cleaning solution of the semiconductor wafer cleaning process of the present invention
  • Fig. 4 is a Tafel curve diagram of copper and cobalt in a cleaning solution SC01 and SC03 of the present invention used in the semiconductor wafer cleaning process;
  • Fig. 5 is a kind of electrochemical impedance spectroscopy of copper and cobalt in the cleaning liquid SC01 and SC03 that is used in semiconductor wafer cleaning process of the present invention
  • Fig. 6 is a kind of influence figure that is used for the corrosion rate of copper and cobalt in the cleaning solution of different alcohol amines in the semiconductor wafer cleaning process of the present invention
  • Figure 7 is a diagram of the influence of different alcohol amines on the corrosion potential of copper and cobalt in the cleaning solution used in the semiconductor wafer cleaning process of the present invention.
  • Fig. 8 is a diagram of the influence of different antioxidants and concentrations on the corrosion rate of copper and cobalt in the cleaning solution used in the semiconductor wafer cleaning process of the present invention.
  • Fig. 9 is a diagram of the influence of the concentration of ascorbic acid in the cleaning solution on the electrochemical impedance spectroscopy of copper and cobalt in the semiconductor wafer cleaning process of the present invention.
  • Fig. 10 is a kind of impact diagram of different dilution ratios of cleaning solution SC06 on the corrosion rate of copper and cobalt in semiconductor wafer cleaning process of the present invention
  • Fig. 11 is a diagram of the influence of adding a nitrogen-containing heterocyclic inhibitor to the corrosion rate of copper and cobalt in the cleaning solution used in the semiconductor wafer cleaning process of the present invention.
  • the problem to be solved by the present invention is to provide a cleaning solution for copper chemical mechanical polishing in the semiconductor wafer cleaning process.
  • the problem to be solved by the present invention is to provide a cleaning solution that does not contain quaternary ammonium alkali and reduces the copper corrosion rate and is used for the copper surface after chemical mechanical polishing in the semiconductor wafer cleaning process.
  • the problem to be solved by the present invention is to provide a cleaning solution for copper surface after chemical mechanical polishing in semiconductor wafer cleaning process, which does not contain quaternary ammonium alkali, reduces copper corrosion rate and can provide protection to cobalt barrier layer.
  • the invention relates to a cleaning solution used in the cleaning process of semiconductor wafers, which is characterized in That is, the cleaning solution is made according to the following raw materials in mass percentage:
  • the mass percentage of guanidine or guanidine derivatives is 1-20%, the mass percentage of alkanolamine is 1-20%, the mass percentage of antioxidant is 0.1-10%, and the mass of the optional nitrogen-containing heterocyclic metal corrosion inhibitor The percentage is 0.01 ⁇ 5%.
  • the beneficial effect of the present invention is that the cleaning liquid in the present invention does not contain quaternary ammonium base, thereby reducing the toxicity of the cleaning liquid itself. And through the selection and addition of metal corrosion inhibitors, not only the corrosion rate of copper is reduced, but also the cobalt barrier layer is protected, which significantly reduces the galvanic corrosion of cobalt and ensures the accuracy of the product.
  • Use the cleaning solution of the present invention to clean the metal-containing wafer after polishing which can remove residues such as abrasive particles and metal ions on the wafer surface after polishing, reduce the roughness of the metal surface, reduce surface defects after cleaning, and prevent the wafer from Metal corrosion that may occur while waiting for the next step.
  • the concentration in the cleaning solution of the present invention is generally to save production, transportation and storage costs.
  • a higher concentration cleaning solution is prepared and then diluted with ultrapure water at the end of use to about 1:1-1: Use after 200 times.
  • the stock solution of the cleaning composition with a higher concentration can also be directly used to clean the wafer.
  • the guanidine or guanidine derivatives are selected from guanidine, 1,1,3,3-tetramethylguanidine, arginine, 2-tert-butyl-1,1,3,3-tetramethylguanidine , 2-(4-tolyl)-1,1,3,3-tetramethylguanidine, biguanide, metformin, phenformin, proguanil, butylbiguanide, 1-(o-tolyl) biguanide or more; the mass percentage of the derivative of guanidine or guanidine is selected from one of 1-20%, 1-10%, 5-15%, 5-10%; preferably 5-15%, more preferably 5% -10%.
  • the alkanolamine is selected from ethanolamine (MEA), diethanolamine (DEA), methylethanolamine, amine triethanolamine (TEA), isopropanolamine, isobutanolamine, diglycolamine, methyl One or more of diethanolamine, dimethylethanolamine and hydroxyethylethylenediamine; the mass percentage of the alkanolamine is selected from 1-20%, 1-10%, 5-15%, 3- One of 10%, 3-15%; preferably 1-20%, more preferably 3-10%.
  • the antioxidant is selected from one or more of ascorbic acid, 3,4,5-trihydroxybenzoic acid, catechol and derivatives thereof.
  • the mass percentage of the antioxidant is selected from one of 0.1-10%, 0.1-5%, 0.5-10%, 0.5-5%, 0.5-3.5%; preferably 0.1-5%, more preferably 0.5-3.5% .
  • the optional nitrogen-containing heterocyclic metal corrosion inhibitor is a nitrogen-containing ring compound, such as imidazole, phenyl azide, benzimidazole, benzothiazole, urea, and derivatives of the above compounds.
  • the metal corrosion inhibitor of nitrogen-containing heterocyclic ring is selected from 1,2,4-triazole, 1,2,3-triazole, imidazole, phenyl azide, benzimidazole, benzothiazole, urea and the above compounds One or more of the derivatives; the mass percentage of the nitrogen-containing heterocyclic metal corrosion inhibitor is selected from 0.001-5%, 0.01-2%, One of 0.05-2%, 0.1-1.5%.
  • the pH value of the cleaning solution is greater than 8.
  • the pH value of the cleaning solution is generally at least 11, preferably pH>11, more preferably pH>13.
  • the cleaning solution is diluted with water before use, and the dilution ratio is 1:1 to 1:200, preferably 1:10 to 1:100, more preferably 1:20 to 1:60;
  • the cleaning solution It can be used for cleaning the surface of a copper semiconductor metal substrate containing a cobalt barrier layer;
  • the material of the metal substrate can be selected from one or more of copper, tantalum, tantalum nitride, titanium, and titanium nitride.
  • the cleaning solution can be used to clean the wafer in a washing machine or on a polishing disc after polishing.
  • the invention can be used for cleaning the flattened wafer surface on a chemical mechanical flattening machine, and can also clean the flattened wafer surface on an independent cleaning machine.
  • the cleaning solution of the present invention can be used at normal temperature, and the cleaning composition is in contact with the metal-containing semiconductor wafer for an effective period of time, which can effectively remove the pollutants remaining on the surface of the wafer while maintaining the copper wire Better surface roughness.
  • a longer contact time eg, 1-3 minutes
  • a shorter contact time eg, less than 1 minute
  • the user can find the concentration of the cleaning solution and the contact time according to the needs to achieve the optimum process.
  • the raw materials of each component are firstly mixed, and during the mixing process, the mixing temperature is room temperature. After mixing, shake and filter to make it more evenly mixed.
  • the cleaning solution the sum of the mass fractions of each component is 100%, and the amount of water used is to make up the sum of the mass fractions of each component to 100%.
  • the dilution ratio of cleaning solution and water was 1:60. All measurements are at room temperature, ie 25°C. Copper and cobalt blank wafers of 100 nm thickness were used in all measurements.
  • the measurement is carried out by RST5000 electrochemical workstation, the scanning rate is 0.002v/s, and the sampling interval is 0.001V.
  • the reference electrode used is an Ag/AgCl reference electrode, the counter electrode used is a carbon rod, and copper and cobalt electrodes are used as working electrodes.
  • the copper and cobalt wafers were cleaned in 500 ml cleaning solution at 400 rpm for 5-20 minutes using magnetic stirring. Corrosion rates were obtained from the change in copper and cobalt thickness before and after cleaning. The thickness of copper and cobalt is measured by the instrument RTS-9 dual electric four-probe tester.
  • Copper surface roughness was measured using atomic force microscope FM-Nanoview1000AFM.
  • the cleaning solution SC01 containing 1,1,3,3-tetramethylguanidine has similar corrosion rates of copper and cobalt. At the same time, the surface roughness of copper did not change significantly.
  • Figure 1 shows the AFM images of copper surface roughness before and after cleaning. From top to bottom, Ra is 1.82 before cleaning, Ra is 2.02 after cleaning with cleaning solution SC01, Ra is 1.99 after cleaning with cleaning solution SC02, and Ra is 1.99 after cleaning with cleaning solution SC03. Ra was 2.07 after washing.
  • Figure 2 shows the corrosion rate of copper and cobalt in the cleaning solution containing 1,1,3,3-tetramethylguanidine.
  • the cleaning solution SC01 containing 1,1,3,3-tetramethylguanidine showed a higher cobalt corrosion potential, so that The corrosion potential difference Ecorr(Co)-Ecorr(Cu) of copper and cobalt is positive. Comparing SC01, SC02 and SC03 without quaternary ammonium alkali formula shows that the corrosion potential difference Ecorr(Co)-Ecorr(Cu) of copper and cobalt is negative. Therefore, in the cleaning solution SC01 containing 1,1,3,3-tetramethylguanidine, copper is galvanically corroded and cobalt is protected. Fig.

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Abstract

La présente invention concerne une solution de nettoyage utilisée dans un procédé de nettoyage destiné à une tranche de semi-conducteur, la solution de nettoyage étant constituée des matières premières suivantes en pourcentage en masse : le pourcentage en masse de guanidine ou d'un dérivé de guanidine est de 1 à 20 %, le pourcentage en masse d'alcanolamine est de 1 à 20 %, le pourcentage en masse d'un antioxydant est de 0,1 à 10 %, et le pourcentage en masse d'un inhibiteur de corrosion de métal hétérocyclique contenant de l'azote facultatif est de 0,01 à 5 %. La solution de nettoyage de la présente invention ne contient pas de base d'ammonium quaternaire. La solution de nettoyage décrite permet d'éliminer efficacement des particules abrasives, des ions métalliques et d'autres résidus restant sur la surface d'une tranche de cuivre après polissage, et ne corrode pas de manière significative une surface de cuivre. De plus, la solution de nettoyage décrite permet d'avoir des propriétés protectrices pour une couche barrière de cobalt utilisée dans des nœuds avancés semi-conducteurs.
PCT/CN2021/104697 2021-06-16 2021-07-06 Solution de nettoyage utilisée dans un procédé de nettoyage destiné à une tranche de semi-conducteur WO2022262018A1 (fr)

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CN202110663474.4A CN113444590A (zh) 2021-06-16 2021-06-16 一种用于在半导体晶圆清洗过程中的清洗液
CN202110663474.4 2021-06-16

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WO2022262018A1 true WO2022262018A1 (fr) 2022-12-22

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Citations (4)

* Cited by examiner, † Cited by third party
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