US20010018407A1 - Cleaning agent - Google Patents

Cleaning agent Download PDF

Info

Publication number
US20010018407A1
US20010018407A1 US09/789,736 US78973601A US2001018407A1 US 20010018407 A1 US20010018407 A1 US 20010018407A1 US 78973601 A US78973601 A US 78973601A US 2001018407 A1 US2001018407 A1 US 2001018407A1
Authority
US
United States
Prior art keywords
acid
cleaning agent
cleaning
agent
substrate surface
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US09/789,736
Other versions
US6410494B2 (en
Inventor
Masahiko Kakizawa
Osamu Ichikawa
Ichiro Hayashida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Wako Pure Chemical Corp
Original Assignee
Wako Pure Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/868,891 external-priority patent/US6143705A/en
Application filed by Wako Pure Chemical Industries Ltd filed Critical Wako Pure Chemical Industries Ltd
Priority to US09/789,736 priority Critical patent/US6410494B2/en
Publication of US20010018407A1 publication Critical patent/US20010018407A1/en
Application granted granted Critical
Publication of US6410494B2 publication Critical patent/US6410494B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • 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
    • C11D7/264—Aldehydes; Ketones; Acetals or ketals
    • 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
    • C11D7/32—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
    • C11D7/3218—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
    • C11D7/3245—Aminoacids
    • C11D2111/22—

Definitions

  • the present invention relates to a cleaning agent for the semiconductor substrate surface used in production steps of semiconductors and LCDs (liquid crystal displays), and further relates to a method for cleaning the semiconductor substrate surface by using said cleaning agent.
  • Silicon wafers which are used for producing semiconductor devices mainly applied to production of LSIs, are prepared by cutting out from a single crystal of silicon ingot and being subjected to production steps of lapping and polishing. For these reasons, the surface of thus prepared silicon wafers are contaminated with a large amount of metallic impurities. Furthermore, in steps following to these production steps, the silicon wafers surface may have a number of risks of metallic contamination, because the wafers are subjected to production steps of semiconductor devices such as ion implantation step, metal terminal formation step and etc.
  • CMP chemical mechanical polishing
  • the cleaning step is conducted by a method of chemical cleaning, physical cleaning or combinations thereof.
  • RCA cleaning method which was developed in 1970's, is used widely in the art.
  • the solution of RCA cleaning is consisting of acid-type cleaning solutions and alkali-type cleaning solutions.
  • the acid-type cleaning solution such as HPM (hydrochloric acid-hydrogen peroxide mixed aqueous solution) and DHF (diluted hydrofluoric acid solution) is used for removing the metallic contaminants.
  • HPM hydroochloric acid-hydrogen peroxide mixed aqueous solution
  • DHF diluted hydrofluoric acid solution
  • the alkali type cleaning solution which is represented by APM (ammonia-hydrogen peroxide mixed aqueous solution)
  • APM ammonia-hydrogen peroxide mixed aqueous solution
  • the acid-type cleaning solution such as HPM and DHF may inevitably be used.
  • the metallized wirings being provided on the semiconductor substrate surface may be corroded with the cleaning solution, because such an acid-type cleaning solution possesses strong ability to dissolve the metals.
  • a physical (mechanical) cleaning method can be applied.
  • the physical cleaning method there can be exemplified by a brush-scrubbing method by using high speed rotating brush(s); an ice-scrubbing method by using jetted out fine particles of ice; a method of cleaning by high pressure jet stream of ultra-pure water; and a megasonic cleaning method by using ultrasonic wave and the like.
  • Each one of these physical cleaning methods is effective to avoid corrosion problem of the metallized wirings being provided on the semiconductor substrate surface.
  • the ability for removing metallic contaminants can hardly be expected only by use of these physical cleaning methods.
  • the problems to be solved by the invention is to provide a cleaning agent for the semiconductor substrate surface without corrosing the metallized wirings and without increasing micro-roughness on the semiconductor substrate surface, as well as to provide a cleaning method for the semiconductor substrate surface by use of said cleaning agent.
  • the present invention is established to solve the above-mentioned problems and the present invention relates to a cleaning agent for the semiconductor substrate surface which comprises an organic acid having at least one carboxyl group and a complexing agent having chelating ability.
  • the present invention further relates to a cleaning method for the semiconductor substrate surface, which comprises treating the semiconductor substrate surface with a cleaning agent comprising an organic acid having at least one carboxyl group and a complexing agent having chelating ability.
  • the inventors have found that the metallic contaminants being adsorbed and adhered on the semiconductor substrate surface can easily be removed by use of a cleaning agent containing an organic acid having at least one carboxyl group and a complexing agent having chelating ability, without corrosing metallized wirings being provided on the semiconductor substrate surface and without depreciating the planarization on the surface thereof which are occurred when a strong acid or strong alkali solution is used, and on the basis of these finding, the present invention has been established.
  • the organic acid to be used in the present invention is one having at least one carboxyl group, preferably one having 1 to 3 carboxyl groups and more preferably one having 2 to 3 carboxyl groups, and the organic acid may contain also 1 to 3 hydroxyl groups and/or 1 to 3 amino groups.
  • organic acids of the present invention include monocarboxylic acids such as formic acid, acetic acid and propionic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid and phthalic acid, tricarboxylic acids such as trimellitic acid and tricarballylic acid, oxycarboxylic acids exemplified by oxymonocarboxylic acids such as hydroxybutyric acid, lactic acid and salicylic acid, oxydicarboxylic acids such as malic acid and tartaric acid and oxytricarboxylic acids such as citric acid; aminocarboxylic acids such as aspartic acid and glutamic acid.
  • a dicarboxylic acid or an oxycarboxylic acid is preferable.
  • the organic acid relating to the present invention can be used singly or in combination suitably with 2 or more of them.
  • the complexing agent having chelating ability of the present invention is preferably those which can be able to form complex compounds with the metallic contaminants such as Fe and Al, and they are exemplified by aminopolycarboxylic acids such as ethylenediamine tetraacetic acid (EDTA), and trans-1,2-diaminocyclohexane tetraacetic acid (CyDTA), phosphonic acid derivatives such as ethylenediamine tetra(methylenephosphonic acid) (EDTPO), ethylenediamine di(methylenephosphonic acid) (EDDPO), nitrilotris(methylenephosphonic acid) (NTPO) and 1-hydroxyethylydene-1,1′-diphosphonic acid (HEDPO), condensed phosphoric acids such as tripolyphosphoric acid and hexamethaphosphoric acid, diketones such as acetylacetone and hexafluoroacetylacetone, amines such as ethylenedi
  • the complexing agents relating to the present invention may be used singly or used suitably combined with 2 or more of them.
  • the cleaning agent of the present invention are generally used in a solution, preferably in an aqueous solution.
  • the organic acid and the complexing agent contained thereof are dissolved in water to give the aqueous solution containing the organic acid and the complexing agent.
  • the complexing agent when used in the higher concentration, an adequate cleaning effect can be obtained.
  • the use of a large amount of complexing agent may bring harmful contamination with organic impurities on the semiconductor substrate surface, which results certain problems of electrical properties of the semiconductor. From the economical standpoint, it is preferable that the complexing agent may not be used in a large quantity.
  • the concentration of the organic acid in the solution is selected from a the range of 0.05 to 50% by weight, preferably 1 to 30% by weight.
  • the complexing agent is used in an amount within the range of 0.01 to 10% by weight, preferably 0.1 to 1.0% by weight in the solution.
  • the surface is treated with the cleaning agent of the present invention mentioned above.
  • the cleaning agent of the present invention for this purpose, generally, silicon wafers are dipped in the cleaning agent.
  • this purpose can also be achieved by taking a procedure to apply to spray or coat the cleaning agent on the semiconductor substrate surface or any other procedures so far as the semiconductor substrate surface is thoroughly allowed to contact with cleaning agent.
  • This treatment may be combined with any conventional physical cleaning method such as brush-scrubbing method and megasonic method.
  • the cleaning agent for the semiconductor substrate surface shows cleaning efficiency at ordinary temperature, and generally the cleaning agent is used at suitable temperature by heating, because the effect for removing contaminants of microfine particles is increased at higher temperature.
  • auxiliary ingredients such as surfactants, buffers and organic solvents may be contained in the cleaning agent of the present invention within the range which does not inhibit the cleaning efficiency according to the present invention.
  • the amount of metallic impurities on the surface of silicon wafers was measured by “diluted hydrofluoric acid/graphite furnace atomic absorption spectrometry”.
  • P-type (100) silicon wafers having 6 inches in diameter were dipped in an aqueous solution prepared by adding 100 ppb each of Fe, Al and Cu (each of which is a nitrate solution), then the silicon wafers contaminated with those metallic ions were dried by means of a spin-dryer.
  • Fe 5 ⁇ 10 13 atoms/cm 2 , Al 8 ⁇ 10 13 atoms/cm2 and Cu 2 ⁇ 10 13 atoms/cm 2 were adsorbed or adhered on the surface of silicon wafers.
  • each one of the above-mentioned silicon wafers was dipped in each one of the cleaning agent of the present invention nominated as Nos. 1 to 10, having the formations as shown in Table 1. Then the wafers were treated at 70° C. for 10 minutes. After that, the each one of thus obtained silicon wafers was washed with ultra-pure water and dried by means of a spin-dryer. The amount of those metallic ions on the surface were measured by the above-mentioned method. The results are shown in Table 1.
  • each one of the silicon wafers contaminated with Fe, Al and Cu was prepared by the procedures similar to those employed in Example 1.
  • each one of silicon wafers was treated by use of a rotation brush made of polyvinyl alcohol, and the cleaning agent of the present invention nominated as Nos. 14 to 23, having the formations as shown in Table 2.
  • Each one of the silicon wafers was treated at 25° C., for 1 minute. After the treatment, the silicon wafers was washed with ultra-pure water and dried by use of a spin-dryer. The amount of metallic ions on the surface of the wafers were measured by the procedures similar to those employed in Example 1. The results are shown in Table 2.
  • each one of silicon wafers provided with wirings of Al and Cu on the substrate surface thereof was dipped in the cleaning agent of the present invention, having the formations of Nos. 1 and 2 as shown in Table 1, respectively, relating to Example 1 as mentioned above, at 70° C. for 1 hour. After that, each one of thus obtained silicon wafers was washed with ultra-pure water and dried by use of a spin-dryer. The metallized wirings on the substrate surface was confirmed by a microscopic observation, and further confirmed by a circuit tester whether there is disconnection or not. As the result, there were confirmed that neither corrosion of the metallized wirings nor disconnection was observed on the surface of the silicon wafers which was dipped in the cleaning agent of the present invention.
  • DHF 1% hydrofluoric acid
  • the cleaning agent for the semiconductor substrate surface of the present invention and the cleaning method by using said cleaning agent, the metallic contaminants adsorbed and adhered on the semiconductor substrate surface can be removed efficiently without corrosing the metallized wirings and without giving adverse effect on the surface planarization as in the case by using a strong acid-type solution or a strong alkali-type solution being applied in the art.

Abstract

Removing particles and metallic contaminants without corrosing the metallized wirings and without giving adverse effect of planarization on the semiconductor substrate surface can be effectively achieved by use of a cleaning agent which comprises an organic acid having at least one carboxyl group and a complexing agent having chelating ability.

Description

    BACKGROUND OF THE INVENTION
  • The present invention relates to a cleaning agent for the semiconductor substrate surface used in production steps of semiconductors and LCDs (liquid crystal displays), and further relates to a method for cleaning the semiconductor substrate surface by using said cleaning agent. [0001]
  • At present, according to the recent trend of high integration of LSI, various technologies have been introduced in production steps of semiconductors. Silicon wafers, which are used for producing semiconductor devices mainly applied to production of LSIs, are prepared by cutting out from a single crystal of silicon ingot and being subjected to production steps of lapping and polishing. For these reasons, the surface of thus prepared silicon wafers are contaminated with a large amount of metallic impurities. Furthermore, in steps following to these production steps, the silicon wafers surface may have a number of risks of metallic contamination, because the wafers are subjected to production steps of semiconductor devices such as ion implantation step, metal terminal formation step and etc. [0002]
  • In the recent years, there have been proposed to introduce chemical mechanical polishing (CMP) technologies for producing the semiconductor devices in accordance with the requirement of planarization of semiconductor substrate surface due to the recent trend of multi-level metallized wirings. The CMP technology is a method to make the surface of silicon wafers flatness by using slurry of silica or alumina. The objectives of polishing are silicon oxide film, wirings and plugs on the surface. In this case, the surface of silicon wafers is contaminated with silica or alumina slurry, metallic impurities containing in the slurries, and metallic impurities caused by polished plug or wiring metals. In such a case, a large amount of metallic contaminants are widely spreaded out on the whole surface of the silicon wafers. [0003]
  • When the semiconductor substrate surface is contaminated with metallic impurities as mentioned above, the electrical properties of semiconductor devices are affected for the worse, and as a result the reliability of semiconductor devices will be lowered. Further, the semiconductor device may possibly be destroyed for a large amount of metallic contamination. So that it is necessary to remove the metallic contaminants from the substrate surface by introducing cleaning step after the CMP process. [0004]
  • Nowadays, the cleaning step is conducted by a method of chemical cleaning, physical cleaning or combinations thereof. Among methods of chemical cleaning, RCA cleaning method which was developed in 1970's, is used widely in the art. The solution of RCA cleaning is consisting of acid-type cleaning solutions and alkali-type cleaning solutions. The acid-type cleaning solution, such as HPM (hydrochloric acid-hydrogen peroxide mixed aqueous solution) and DHF (diluted hydrofluoric acid solution) is used for removing the metallic contaminants. On the other hand, the alkali type cleaning solution, which is represented by APM (ammonia-hydrogen peroxide mixed aqueous solution), possesses an excellent ability to remove the particle contaminants, but it possesses insufficient ability to remove the metallic contaminants. [0005]
  • Under such circumstances, for the purpose to remove the metallic contaminants, the acid-type cleaning solution such as HPM and DHF may inevitably be used. [0006]
  • However, the metallized wirings being provided on the semiconductor substrate surface may be corroded with the cleaning solution, because such an acid-type cleaning solution possesses strong ability to dissolve the metals. [0007]
  • In order to avoid such corrosion problem of the metallized wirings being provided on the semiconductor substrate surface, a physical (mechanical) cleaning method can be applied. As to the physical cleaning method, there can be exemplified by a brush-scrubbing method by using high speed rotating brush(s); an ice-scrubbing method by using jetted out fine particles of ice; a method of cleaning by high pressure jet stream of ultra-pure water; and a megasonic cleaning method by using ultrasonic wave and the like. [0008]
  • Each one of these physical cleaning methods is effective to avoid corrosion problem of the metallized wirings being provided on the semiconductor substrate surface. However, the ability for removing metallic contaminants can hardly be expected only by use of these physical cleaning methods. For this reason, it is proposed to use the physical cleaning method in combination with chemical cleaning method by using an acid-type cleaning solution. [0009]
  • It should be noted that though the ability for removing metallic contaminants can be expected by conducting the RCA cleaning method using an inorganic acid, such the method has some problems exemplified that the metallized wirings being provided on the surface may be damaged, further the insulation film of silicon oxide being provided on the surface may be etched with the inorganic acid. [0010]
  • Therefore, it is necessary to dilute the concentration of the inorganic acid as lower as possible, and to reduce the cleaning time as shorter as possible. [0011]
  • However, as a result of such considerations, adequate effects for cleaning can not be expected. [0012]
  • In addition to the above, other method for cleaning the semiconductor substrate surface is available, in which an aqueous solution of a monocarboxylic acid in combination with a surfactant is used. However, this method is understood that though it is effective to improve the wettability between the aqueous solution and the semiconductor substrate surface by use of the surfactant, this method requires the longer time to remove the metallic contaminants, further an adequate cleaning efficiency can not be expected. [0013]
  • Additionally, other method for removing the metallic contaminants such as the one using of citric acid solution in combination with a brush-scrubbing cleaning was reported. However, the effect for removing the metallic contaminants was insufficient only by use of citric acid solution, so that an adequate cleaning effects was not obtained. [0014]
  • As explained above, there have not been found yet any effective means for removing particles and metallic contaminants without corrosing the metallized wirings and without giving adverse effect of planarization on the semiconductor substrate surface. [0015]
    • PROBLEMS TO BE SOLVED BY THE INVENTION
  • In consideration of these facts as mentioned above, the problems to be solved by the invention is to provide a cleaning agent for the semiconductor substrate surface without corrosing the metallized wirings and without increasing micro-roughness on the semiconductor substrate surface, as well as to provide a cleaning method for the semiconductor substrate surface by use of said cleaning agent. [0016]
    • MEANS FOR SOLVING THE PROBLEMS
  • The present invention is established to solve the above-mentioned problems and the present invention relates to a cleaning agent for the semiconductor substrate surface which comprises an organic acid having at least one carboxyl group and a complexing agent having chelating ability. [0017]
  • The present invention further relates to a cleaning method for the semiconductor substrate surface, which comprises treating the semiconductor substrate surface with a cleaning agent comprising an organic acid having at least one carboxyl group and a complexing agent having chelating ability. [0018]
  • The present inventors have made an extensive research work for achieving the above-mentioned object. [0019]
  • As a result, the inventors have found that the metallic contaminants being adsorbed and adhered on the semiconductor substrate surface can easily be removed by use of a cleaning agent containing an organic acid having at least one carboxyl group and a complexing agent having chelating ability, without corrosing metallized wirings being provided on the semiconductor substrate surface and without depreciating the planarization on the surface thereof which are occurred when a strong acid or strong alkali solution is used, and on the basis of these finding, the present invention has been established. [0020]
  • The reason why the above-mentioned object can be achieved by conducting a method of the present invention is presumed as follows. That is, when the organic acid dissolves metal oxides and metal hydroxides, such as Fe and Al, even though they are in quite small amounts, said dissolved metallic ions may form metal complexes with the complexing agent. As the result, an equilibrium in the reaction system of the cleaning agent may be transferred to the direction toward to dissolve the metals, which improves the metal dissolving power of the organic acid, thus removal of the metallic contaminants being adsorbed and adhered on the semiconductor substrate surface can be achieved. [0021]
  • The organic acid to be used in the present invention is one having at least one carboxyl group, preferably one having 1 to 3 carboxyl groups and more preferably one having 2 to 3 carboxyl groups, and the organic acid may contain also 1 to 3 hydroxyl groups and/or 1 to 3 amino groups. [0022]
  • The examples of said organic acids of the present invention include monocarboxylic acids such as formic acid, acetic acid and propionic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid and phthalic acid, tricarboxylic acids such as trimellitic acid and tricarballylic acid, oxycarboxylic acids exemplified by oxymonocarboxylic acids such as hydroxybutyric acid, lactic acid and salicylic acid, oxydicarboxylic acids such as malic acid and tartaric acid and oxytricarboxylic acids such as citric acid; aminocarboxylic acids such as aspartic acid and glutamic acid. Among them, a dicarboxylic acid or an oxycarboxylic acid is preferable. The organic acid relating to the present invention can be used singly or in combination suitably with 2 or more of them. [0023]
  • The complexing agent having chelating ability of the present invention is preferably those which can be able to form complex compounds with the metallic contaminants such as Fe and Al, and they are exemplified by aminopolycarboxylic acids such as ethylenediamine tetraacetic acid (EDTA), and trans-1,2-diaminocyclohexane tetraacetic acid (CyDTA), phosphonic acid derivatives such as ethylenediamine tetra(methylenephosphonic acid) (EDTPO), ethylenediamine di(methylenephosphonic acid) (EDDPO), nitrilotris(methylenephosphonic acid) (NTPO) and 1-hydroxyethylydene-1,1′-diphosphonic acid (HEDPO), condensed phosphoric acids such as tripolyphosphoric acid and hexamethaphosphoric acid, diketones such as acetylacetone and hexafluoroacetylacetone, amines such as ethylenediamine and triethanolamine, an inorganic ion such as a halide ion (for example F[0024] −, Cl−, Br−, I−), a cyanide ion, a thiocyanate ion, a thiosulfate ion and an ammonium ion. Among them, a phosphonic acid derivative is preferable.
  • The complexing agents relating to the present invention may be used singly or used suitably combined with 2 or more of them. [0025]
  • The cleaning agent of the present invention are generally used in a solution, preferably in an aqueous solution. The organic acid and the complexing agent contained thereof are dissolved in water to give the aqueous solution containing the organic acid and the complexing agent. [0026]
  • When the concentration of the organic acid and the complexing agent in the aqueous solution is too low, an adequate cleaning effect can not be obtained and additionally, in case of the semiconductor substrate surface being unexpectedly contaminated severely, the cleaning effect may be decreased. On the other hand when the concentration of the organic acid in the solution is too high, adequate cleaning effect can be obtained, but is not preferable from the cost-performance standpoint. [0027]
  • On the other hand, when the complexing agent is used in the higher concentration, an adequate cleaning effect can be obtained. However, the use of a large amount of complexing agent may bring harmful contamination with organic impurities on the semiconductor substrate surface, which results certain problems of electrical properties of the semiconductor. From the economical standpoint, it is preferable that the complexing agent may not be used in a large quantity. [0028]
  • Generally, the concentration of the organic acid in the solution is selected from a the range of 0.05 to 50% by weight, preferably 1 to 30% by weight. [0029]
  • Generally the complexing agent is used in an amount within the range of 0.01 to 10% by weight, preferably 0.1 to 1.0% by weight in the solution. [0030]
  • In order to clean the semiconductor substrate surface, the surface is treated with the cleaning agent of the present invention mentioned above. For this purpose, generally, silicon wafers are dipped in the cleaning agent. In addition, this purpose can also be achieved by taking a procedure to apply to spray or coat the cleaning agent on the semiconductor substrate surface or any other procedures so far as the semiconductor substrate surface is thoroughly allowed to contact with cleaning agent. [0031]
  • This treatment may be combined with any conventional physical cleaning method such as brush-scrubbing method and megasonic method. [0032]
  • In the present invention, the cleaning agent for the semiconductor substrate surface shows cleaning efficiency at ordinary temperature, and generally the cleaning agent is used at suitable temperature by heating, because the effect for removing contaminants of microfine particles is increased at higher temperature. [0033]
  • In addition to the constitutional ingredients as mentioned above, various auxiliary ingredients such as surfactants, buffers and organic solvents may be contained in the cleaning agent of the present invention within the range which does not inhibit the cleaning efficiency according to the present invention. [0034]
  • The present invention is explained in more detail by referring to the following Examples and Reference Examples, but the present invention is not limited by them. [0035]
  • In the present invention, the amount of metallic impurities on the surface of silicon wafers was measured by “diluted hydrofluoric acid/graphite furnace atomic absorption spectrometry”. [0036]
  • In case of preparing reagents and carrying out of analytical operations, ultra-pure water was used, and also hydrofluoric acid of ultra-pure reagent grade was used for the analysis. [0037]
    • EXAMPLE 1
  • P-type (100) silicon wafers having 6 inches in diameter were dipped in an aqueous solution prepared by adding 100 ppb each of Fe, Al and Cu (each of which is a nitrate solution), then the silicon wafers contaminated with those metallic ions were dried by means of a spin-dryer. [0038]
  • Fe 5×10[0039] 13 atoms/cm2, Al 8×1013 atoms/cm2 and Cu 2×1013 atoms/cm2 were adsorbed or adhered on the surface of silicon wafers.
  • Each one of the above-mentioned silicon wafers was dipped in each one of the cleaning agent of the present invention nominated as Nos. 1 to 10, having the formations as shown in Table 1. Then the wafers were treated at 70° C. for 10 minutes. After that, the each one of thus obtained silicon wafers was washed with ultra-pure water and dried by means of a spin-dryer. The amount of those metallic ions on the surface were measured by the above-mentioned method. The results are shown in Table 1. [0040]
    • Reference Example 1
  • The silicon wafers contaminated with Fe, Al and Cu prepared in Example 1 were dipped in each one of the solutions nominated as Nos. 11 and 12, having the formations shown in Table 1, and in ultra-pure water (No. 13), then the silicon wafers were treated similarly as in Example 1. The results are also shown in Table 1. [0041]
    TABLE 1
    Formation of the cleaning agent Amount of metallic ions on
    Concentration Complexing Concentration the surface of wafers (Atoms/cm2)
    No. Organic acid (W/W %) agent (W/W%) Fe Al Cu
    1 Citric acid 5 EDTPO 0.1 1 × 1010 6 × 1011 8 × 1010
    2 Oxalic acid 5 Hexamethaphosphoric 0.1 3 × 1010 6 × 1012 7 × 1011
    acid
    3 Malonic acid 5 Acetylacetone 0.05 8 × 1012 1 × 1012 4 × 1012
    4 Tartaric acid 5 CyDTA 0.1 8 × 1011 6 × 1010 5 × 1011
    5 Citric acid 5 EDTA.2NH4 1 6 × 1010 8 × 1011 8 × 1010
    6 Citric acid 0.5 Ammonium fluoride 1 4 × 1011 1 × 1010 3 × 1011
    7 Citric acid 10 Ammonium fluoride 0.1 6 × 1012 3 × 1010 5 × 1012
    8 Citric acid 50 Ammonium fluoride 0.1 2 × 1012 2 × 1010 1 × 1012
    9 Oxalic acid 5 HEDPO 0.1 1 × 1010 4 × 1011 1 × 1011
    10  Fumaric acid 1 Sodium cyanide 0.1 4 × 1011 7 × 1012 1 × 1012
    11  — — EDTA 0.1 3 × 1013 5 × 1013 2 × 1013
    12  Malic acid 10 — — 9 × 1012 1 × 1013 8 × 1012
    13  — — — — 5 × 1013 8 × 1013 2 × 1013
  • As can be seen from the data shown in Table 1, the amount of the metallic ions on the surface of silicon wafers can be reduced remarkably by treating with the cleaning agent of the present invention. [0042]
    • EXAMPLE 2
  • Each one of the silicon wafers contaminated with Fe, Al and Cu was prepared by the procedures similar to those employed in Example 1. In case of carrying out a brush-scrubbing cleaning method, each one of silicon wafers was treated by use of a rotation brush made of polyvinyl alcohol, and the cleaning agent of the present invention nominated as Nos. 14 to 23, having the formations as shown in Table 2. Each one of the silicon wafers was treated at 25° C., for 1 minute. After the treatment, the silicon wafers was washed with ultra-pure water and dried by use of a spin-dryer. The amount of metallic ions on the surface of the wafers were measured by the procedures similar to those employed in Example 1. The results are shown in Table 2. [0043]
    • Reference Example 2
  • In case of cleaning the silicon wafers being contaminated with Fe, Al and Cu used in Example 1, by use of a rotation type brush made of polyvinyl alcohol, each one of the cleaning agents nominated as Nos. 24 and 25, having the formations shown in Table 2 and ultra-pure water (No. 26) was used. The silicon wafers were treated similarly as in Example 2, and the amount of those metallic ions remained on the surface of the silicon wafers were measured. The results are also shown in Table 2. [0044]
    TABLE 2
    Formation of the cleaning agent Amount of metallic ions on
    Concentration Complexing Concentration the surface of wafers (Atoms/cm2)
    No. Organic acid (W/W %) agent (W/W%) Fe Al Cu
    14 Oxalic acid 5 NTPO 0.5 2 × 1011 1 × 1010 2 × 1011
    15 Citric acid 5 NTPO 0.5 1 × 1011 2 × 1010 4 × 1011
    16 Malonic acid 5 NTPO 0.5 4 × 1011 4 × 1011 7 × 1011
    17 Succinic acid 5 NTPO 0.5 5 × 1011 5 × 1011 7 × 1011
    18 Acetic acid 5 NTPO 0.5 6 × 1011 9 × 1011 1 × 1012
    19 Glutaric acid 1 Potassium 5 2 × 1011 5 × 1011 4 × 1010
    thiocyanate
    20 Citric acid 20 EDDPO 1 4 × 1010 2 × 1011 1 × 1012
    21 Adipic acid 1 Ammonium 10 8 × 1011 3 × 1010 2 × 1011
    fluoride
    22 Citric acid 10 EDTA 0.1 2 × 1011 5 × 1011 2 × 1011
    Oxalic acid 1
    23 Oxalic acid 1 Ammonium fluoride 0.1 8 × 1010 4 × 1010 8 × 1010
    Hexamethaphosphoric 0.1
    acid
    24 Succinic acid 1 — — 6 × 1012 7 × 1012 5 × 1012
    25 — — Ethylenediamine 1 1 × 1012 5 × 1012 7 × 1012
    26 — — — — 6 × 1012 8 × 1012 9 × 1012
  • As can be seen from the data shown in Table 2, in case of conducting physical cleaning in combination with use of the cleaning agent of the present invention, it is understood that the amount of metallic contaminants remained on the surface of silicon wafers were remarkably reduced. Further, as shown from the results performed by the cleaning agents of the present invention nominated as Nos. 14 to 18, the organic acids having 2 or more of carboxyl group, such as oxalic acid, citric acid, malonic acid and succinic acid, show cleaning efficiency higher than that of shown by acetic acid which is an organic acid having only one carboxyl group. [0045]
    • EXAMPLE 3
  • Each one of silicon wafers provided with wirings of Al and Cu on the substrate surface thereof was dipped in the cleaning agent of the present invention, having the formations of Nos. 1 and 2 as shown in Table 1, respectively, relating to Example 1 as mentioned above, at 70° C. for 1 hour. After that, each one of thus obtained silicon wafers was washed with ultra-pure water and dried by use of a spin-dryer. The metallized wirings on the substrate surface was confirmed by a microscopic observation, and further confirmed by a circuit tester whether there is disconnection or not. As the result, there were confirmed that neither corrosion of the metallized wirings nor disconnection was observed on the surface of the silicon wafers which was dipped in the cleaning agent of the present invention. [0046]
    • Reference Example 3
  • By the procedures similar to those employed in Example 3, each one of the silicon wafers were treated by use of HPM (HCl:H[0047] 2O2:H2O= 1:1:5) and DHF (1% hydrofluoric acid), and confirmed whether or not there were any corrosion and disconnection on the surface of the silicon wafers. As the result, there were confirmed that Al and Cu wirings were corroded, and some disconnection were observed.
  • As clearly understood from the description in the specification, by using the cleaning agent for the semiconductor substrate surface of the present invention and the cleaning method by using said cleaning agent, the metallic contaminants adsorbed and adhered on the semiconductor substrate surface can be removed efficiently without corrosing the metallized wirings and without giving adverse effect on the surface planarization as in the case by using a strong acid-type solution or a strong alkali-type solution being applied in the art. [0048]
  • Thus, the present invention will contribute greatly in the art. [0049]

Claims (16)

What is claimed:
1. A cleaning agent for the semiconductor substrate surface, which comprises an organic acid having at least one carboxyl group and a complexing agent having chelating ability.
2. The cleaning agent as claimed in
claim 1
, wherein the cleaning agent is an aqueous solution.
3. The cleaning agent as claimed in
claim 1
, wherein the organic acid is one having 1 to 3 carboxyl groups.
4. The cleaning agent as claimed in
claim 1
, wherein the organic acid is one having 2 to 3 carboxyl groups.
5. The cleaning agent as claimed in
claim 1
, wherein the organic acid is one selected from the group consisting of a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, an oxycarboxylic acid and an aminocarboxylic acid.
6. The cleaning agent as claimed in
claim 1
, wherein the organic acid is a dicarboxylic acid or an oxycarboxylic acid.
7. The cleaning agent as claimed in
claim 6
, wherein the oxycarboxylic acid is an oxydicarboxylic acid or an oxytricarboxylic acid.
8. The cleaning agent as claimed in
claim 6
, wherein the dicarboxylic acid is one selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, maleic acid and phtalic acid.
9. The cleaning agent as claimed in
claim 6
, wherein the oxycarboxylic acid is one selected from the group consisting of malic acid, tartaric acid and citric acid.
10. The cleaning agent as claimed in
claim 1
, wherein the complexing agent is one having chelating ability to form complex compounds with metallic contaminants on the semiconductor substrate surface.
11. The cleaning agent as claimed in
claim 1
, wherein the complexing agent is one selected from the group consisting of an aminopolycarboxylic acid, a phosphonic acid derivative, a condensed phosphoric acid, a diketone, an amine, and an inorganic ion selected from the group consisting of a halide ion, a cyanide ion, a thiocyanate ion, a thiosulfate ion and an ammonium ion.
12. The cleaning agent as claimed in
claim 1
, wherein the complexing agent is a phosphonic acid derivative.
13. The cleaning agent as claimed in
claim 12
, wherein the phosphonic acid derivative is one selected from the group consisting of ethylenediamine tetra(methylenephosphonic acid), ethylenediamine di(methylenephosphonic acid), nitrilotris(methylenephosphonic acid) and 1-hydroxyethylydene-1,1′-diphosphonic acid.
14. The cleaning agent as claimed in
claim 1
, wherein the organic acid is a dicarboxylic acid or an oxycarboxylic acid and the complexing agent is a phosphonic acid derivative.
15. A cleaning method for the semiconductor substrate surface, which comprises treating the semiconductor substrate surface with a cleaning agent comprising an organic acid having at least one carboxyl group and a complexing agent having chelating ability.
16. The method as claimed in
claim 15
, wherein the treatment of the semiconductor substrate surface is to dip the semiconductor in the cleaning agent.
US09/789,736 1996-06-05 2001-02-22 Cleaning agent Expired - Lifetime US6410494B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US09/789,736 US6410494B2 (en) 1996-06-05 2001-02-22 Cleaning agent

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP16535396 1996-06-05
JP8-165353 1996-06-05
JPJP8-165353 1996-06-05
US08/868,891 US6143705A (en) 1996-06-05 1997-06-04 Cleaning agent
US09/658,926 US6514921B1 (en) 1996-06-05 2000-09-11 Cleaning agent
US09/789,736 US6410494B2 (en) 1996-06-05 2001-02-22 Cleaning agent

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US09/658,926 Division US6514921B1 (en) 1996-06-05 2000-09-11 Cleaning agent

Publications (2)

Publication Number Publication Date
US20010018407A1 true US20010018407A1 (en) 2001-08-30
US6410494B2 US6410494B2 (en) 2002-06-25

Family

ID=26490119

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/789,736 Expired - Lifetime US6410494B2 (en) 1996-06-05 2001-02-22 Cleaning agent

Country Status (1)

Country Link
US (1) US6410494B2 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1577934A1 (en) * 2004-03-19 2005-09-21 Air Products And Chemicals, Inc. Alkaline post-chemical mechanical planarization cleaning compositions
US20050258139A1 (en) * 2004-05-19 2005-11-24 Haruki Nojo Polishing method to reduce dishing of tungsten on a dielectric
US20060124026A1 (en) * 2004-12-10 2006-06-15 3M Innovative Properties Company Polishing solutions
US20060154838A1 (en) * 2002-11-08 2006-07-13 Wako Pure Chemical Industries Cleaning composition and method of cleaning therewith
US20070235061A1 (en) * 2003-10-27 2007-10-11 Wako Pure Chemical Industries, Ltd. Cleaning Agent for Substrate and Cleaning Method
US20080254625A1 (en) * 2005-10-21 2008-10-16 Freescale Semiconductor, Inc. Method for Cleaning a Semiconductor Structure and Chemistry Thereof
WO2009032460A1 (en) * 2007-08-02 2009-03-12 Advanced Technology Materials, Inc. Non-fluoride containing composition for the removal of residue from a microelectronic device
WO2009071333A3 (en) * 2007-12-06 2009-07-23 Fraunhofer Ges Forschung Texturing and cleaning medium for the surface treatment of wafers and use thereof
WO2013028662A3 (en) * 2011-08-22 2013-06-27 Ekc Technology, Inc. Composition for cleaning substrates post-chemical mechanical polishing
CN103230894A (en) * 2013-04-11 2013-08-07 中国科学院上海硅酸盐研究所 Cleaning process of bismuth germanate wafer
US20180158670A1 (en) * 2016-12-05 2018-06-07 The Regents Of The University Of California High-k gate dielectrics on 2d substrates, inert surfaces, and 3d materials
US10113141B2 (en) 2012-02-17 2018-10-30 Mitsubishi Chemical Corporation Cleaning liquid for semiconductor device and method for cleaning substrate for semiconductor device

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6486108B1 (en) * 2000-05-31 2002-11-26 Micron Technology, Inc. Cleaning composition useful in semiconductor integrated circuit fabrication
EP1335016A1 (en) * 2002-02-06 2003-08-13 Shipley Company LLC Cleaning composition
TWI339680B (en) * 2002-02-19 2011-04-01 Kanto Kagaku Washing liquid composition for semiconductor substrate
DE60328014D1 (en) * 2002-04-25 2009-07-30 Fujifilm Electronic Materials NON-CORROSIVE CLEANING AGENTS FOR REMOVING DETERGENT RESIDUES
JP4221191B2 (en) * 2002-05-16 2009-02-12 関東化学株式会社 Cleaning liquid composition after CMP
JP4375991B2 (en) * 2003-04-09 2009-12-02 関東化学株式会社 Semiconductor substrate cleaning liquid composition
JP5600376B2 (en) * 2005-01-27 2014-10-01 アドバンスド テクノロジー マテリアルズ，インコーポレイテッド Composition for the treatment of semiconductor substrates
US7923423B2 (en) * 2005-01-27 2011-04-12 Advanced Technology Materials, Inc. Compositions for processing of semiconductor substrates
TW200734448A (en) * 2006-02-03 2007-09-16 Advanced Tech Materials Low pH post-CMP residue removal composition and method of use
US8685909B2 (en) 2006-09-21 2014-04-01 Advanced Technology Materials, Inc. Antioxidants for post-CMP cleaning formulations
US20080076688A1 (en) * 2006-09-21 2008-03-27 Barnes Jeffrey A Copper passivating post-chemical mechanical polishing cleaning composition and method of use
EP2082024A4 (en) * 2006-09-25 2010-11-17 Advanced Tech Materials Compositions and methods for the removal of photoresist for a wafer rework application
US9074170B2 (en) 2008-10-21 2015-07-07 Advanced Technology Materials, Inc. Copper cleaning and protection formulations
US8148310B2 (en) 2009-10-24 2012-04-03 Wai Mun Lee Composition and method for cleaning semiconductor substrates comprising an alkyl diphosphonic acid
US7947130B2 (en) * 2009-10-24 2011-05-24 Wai Mun Lee Troika acid semiconductor cleaning compositions and methods of use
US8431516B2 (en) 2009-10-24 2013-04-30 Wai Mun Lee Composition and method for cleaning semiconductor substrates comprising an alkyl diphosphonic acid
US8148311B2 (en) 2009-10-24 2012-04-03 Wai Mun Lee Composition and method for cleaning semiconductor substrates comprising an alkyl diphosphonic acid
KR101966635B1 (en) 2012-04-27 2019-08-27 후지 필름 일렉트로닉 머트리얼즈 가부시키가이샤 Cleaning agent for semiconductor substrates and method for processing semiconductor substrate surface
KR101799946B1 (en) 2014-11-18 2017-11-22 삼성에스디아이 주식회사 Cleaning composition after chemical mechanical polishing of organic film and cleaning method using the same

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2970044A (en) 1957-12-30 1961-01-31 Ibm Solution and process for etching indium dots
US3290174A (en) 1961-10-09 1966-12-06 Rohr Corp Two-stage process for derusting and protecting the surfaces of ferrous materials
NL149551B (en) 1964-08-04 1976-05-17 Dow Chemical Co METHOD FOR CLEANING AND PASSIVING IRON-CONTAINING METAL SURFACES ON WHICH METALLIC COPPER HAS BEEN DEPOSITED.
FR1603558A (en) 1968-12-18 1971-05-03 Cleaning heating surfaces with complexing agent soln
GB1571438A (en) 1977-03-15 1980-07-16 Colgate Palmolive Co Cleaning compositions
US4264418A (en) 1978-09-19 1981-04-28 Kilene Corp. Method for detersifying and oxide coating removal
US4239567A (en) 1978-10-16 1980-12-16 Western Electric Company, Inc. Removably holding planar articles for polishing operations
SU1070210A1 (en) 1981-09-17 1984-01-30 Предприятие П/Я А-3562 Solution for etching iron
US4395304A (en) 1982-05-11 1983-07-26 Rca Corporation Selective etching of phosphosilicate glass
US4610728A (en) 1982-10-19 1986-09-09 Ram Natesh Method and composition for dissolving deposits of magnetite
US4452643A (en) 1983-01-12 1984-06-05 Halliburton Company Method of removing copper and copper oxide from a ferrous metal surface
US4529450A (en) 1983-10-18 1985-07-16 The United States Of America As Represented By The Secretary Of The Navy Metal oxide remover and method of using
US4626324A (en) 1984-04-30 1986-12-02 Allied Corporation Baths for the electrolytic deposition of nickel-indium alloys on printed circuit boards
US4623399A (en) 1985-02-04 1986-11-18 Dowell Schlumberger Incorporated Solvent for removing iron oxide deposits
JPS61231188A (en) 1985-04-04 1986-10-15 Nippon Paint Co Ltd Method for controlling aluminum surface cleaning agent
JP2504978B2 (en) 1987-01-27 1996-06-05 株式会社リコー Toner carrier
US4802990A (en) 1987-07-30 1989-02-07 Inskeep Jr Eugene L Solution and method for dissolving minerals
DE69231971T2 (en) * 1991-01-24 2002-04-04 Wako Pure Chem Ind Ltd Solutions for surface treatment of semiconductors
JP3075290B2 (en) * 1991-02-28 2000-08-14 三菱瓦斯化学株式会社 Cleaning liquid for semiconductor substrates
TW263531B (en) 1992-03-11 1995-11-21 Mitsubishi Gas Chemical Co
NZ248582A (en) 1992-09-24 1995-02-24 Colgate Palmolive Co Acidic, thickened cleaner containing dicarboxylic acids and aminoalkylene phosphonic acid for cleaning lime scale from acid-resistant or zirconium white enamel hard surfaces
US5288332A (en) 1993-02-05 1994-02-22 Honeywell Inc. A process for removing corrosive by-products from a circuit assembly
US5389194A (en) 1993-02-05 1995-02-14 Lsi Logic Corporation Methods of cleaning semiconductor substrates after polishing
US5635104A (en) 1993-06-24 1997-06-03 The Procter & Gamble Company Bleaching solutions and method utilizing selected bleach activators effective at low perhydroxyl concentrations
US5466389A (en) 1994-04-20 1995-11-14 J. T. Baker Inc. PH adjusted nonionic surfactant-containing alkaline cleaner composition for cleaning microelectronics substrates
JPH07286172A (en) 1994-04-20 1995-10-31 Asahi Glass Co Ltd Etching liquid and etching method
US5498293A (en) 1994-06-23 1996-03-12 Mallinckrodt Baker, Inc. Cleaning wafer substrates of metal contamination while maintaining wafer smoothness
US5637151A (en) 1994-06-27 1997-06-10 Siemens Components, Inc. Method for reducing metal contamination of silicon wafers during semiconductor manufacturing
US5460802A (en) 1994-07-18 1995-10-24 Minnesota Mining And Manufacturing Company Oral disinfectant for companion animals
US5662769A (en) * 1995-02-21 1997-09-02 Advanced Micro Devices, Inc. Chemical solutions for removing metal-compound contaminants from wafers after CMP and the method of wafer cleaning
KR100429440B1 (en) 1995-07-27 2004-07-15 미쓰비시 가가꾸 가부시키가이샤 Method of surface treatment of gas and surface treatment composition used therefor
EP0784336A3 (en) 1995-12-15 1998-05-13 Texas Instruments Incorporated Improvements in or relating to the fabrication and processing of semiconductor devices

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7700532B2 (en) 2002-11-08 2010-04-20 Wako Pure Chemical Industries, Ltd. Cleaning composition and method of cleaning therewith
US20060154838A1 (en) * 2002-11-08 2006-07-13 Wako Pure Chemical Industries Cleaning composition and method of cleaning therewith
US8900371B2 (en) 2003-10-27 2014-12-02 Wako Pure Chemical Industries, Ltd. Cleaning agent for substrate and cleaning method
US20070235061A1 (en) * 2003-10-27 2007-10-11 Wako Pure Chemical Industries, Ltd. Cleaning Agent for Substrate and Cleaning Method
EP1577934A1 (en) * 2004-03-19 2005-09-21 Air Products And Chemicals, Inc. Alkaline post-chemical mechanical planarization cleaning compositions
US7316976B2 (en) * 2004-05-19 2008-01-08 Dupont Air Products Nanomaterials Llc Polishing method to reduce dishing of tungsten on a dielectric
US20050258139A1 (en) * 2004-05-19 2005-11-24 Haruki Nojo Polishing method to reduce dishing of tungsten on a dielectric
WO2006065347A2 (en) * 2004-12-10 2006-06-22 3M Innovative Properties Company Polishing solutions
WO2006065347A3 (en) * 2004-12-10 2007-02-01 3M Innovative Properties Co Polishing solutions
US20060124026A1 (en) * 2004-12-10 2006-06-15 3M Innovative Properties Company Polishing solutions
US20080254625A1 (en) * 2005-10-21 2008-10-16 Freescale Semiconductor, Inc. Method for Cleaning a Semiconductor Structure and Chemistry Thereof
US8211844B2 (en) * 2005-10-21 2012-07-03 Freescale Semiconductor, Inc. Method for cleaning a semiconductor structure and chemistry thereof
WO2009032460A1 (en) * 2007-08-02 2009-03-12 Advanced Technology Materials, Inc. Non-fluoride containing composition for the removal of residue from a microelectronic device
US20100261632A1 (en) * 2007-08-02 2010-10-14 Advanced Technology Materials, Inc. Non-fluoride containing composition for the removal of residue from a microelectronic device
WO2009071333A3 (en) * 2007-12-06 2009-07-23 Fraunhofer Ges Forschung Texturing and cleaning medium for the surface treatment of wafers and use thereof
US8900472B2 (en) 2007-12-06 2014-12-02 Fraunhofer-Gesellschaft zur Föerderung der Angewandten Forschung E.V. Texturing and cleaning agent for the surface treatment of wafers and use thereof
US20110092074A1 (en) * 2007-12-06 2011-04-21 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Texturing and cleaning agent for the surface treatment of wafers and use thereof
WO2013028662A3 (en) * 2011-08-22 2013-06-27 Ekc Technology, Inc. Composition for cleaning substrates post-chemical mechanical polishing
US10113141B2 (en) 2012-02-17 2018-10-30 Mitsubishi Chemical Corporation Cleaning liquid for semiconductor device and method for cleaning substrate for semiconductor device
CN103230894A (en) * 2013-04-11 2013-08-07 中国科学院上海硅酸盐研究所 Cleaning process of bismuth germanate wafer
US20180158670A1 (en) * 2016-12-05 2018-06-07 The Regents Of The University Of California High-k gate dielectrics on 2d substrates, inert surfaces, and 3d materials
US11127590B2 (en) * 2016-12-05 2021-09-21 The Regents Of The University Of California Method for ALD deposition on inert surfaces via Al2O3 nanoparticles

Also Published As

Publication number Publication date
US6410494B2 (en) 2002-06-25

Similar Documents

Publication Publication Date Title
US6514921B1 (en) Cleaning agent
US6410494B2 (en) Cleaning agent
JP3219020B2 (en) Cleaning agent
KR100355212B1 (en) Post-washing method
EP0897975B1 (en) Cleaning solution
KR100748410B1 (en) Substrate surface cleaning liquid mediums and cleaning method
JP4516176B2 (en) Substrate cleaning solution for electronic materials
CN1918698B (en) Cleaning liquid for substrate for semiconductor device and cleaning method
EP1888735B1 (en) Copper passivating post-chemical mechanical polishing cleaning composition and method of use
KR101331747B1 (en) Compositions for processing of semiconductor substrates
US6546939B1 (en) Post clean treatment
KR100913557B1 (en) Liquid detergent for semiconductor device substrate and method of cleaning
CN100437922C (en) Cleaning composition and method of cleaning therewith
US7396806B2 (en) Semiconductor cleaner comprising a reducing agent, dispersant, and phosphonic acid-based chelant
JP2002069495A (en) Detergent composition
EP1363321A2 (en) Post-CMP washing liquid composition
JP2004307725A (en) Semiconductor-substrate washing liquid composition
JPH11131093A (en) Cleaning liquid
JP2002020787A (en) Detergent for copper wiring semiconductor substrate
KR20000029749A (en) Aqueous cleaning solution for a semiconductor substrate
JP3198878B2 (en) Surface treatment composition and substrate surface treatment method using the same
TW424002B (en) A cleaning method after finishing polishing process of Cu interconnection
CN101432412A (en) Cleaning solutions including preservative compounds for post CMP cleaning processes

Legal Events

Date Code Title Description
STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12