US20050022456A1 - Polishing slurry and method for chemical-mechanical polishing of copper - Google Patents

Polishing slurry and method for chemical-mechanical polishing of copper Download PDF

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Publication number
US20050022456A1
US20050022456A1 US10/631,698 US63169803A US2005022456A1 US 20050022456 A1 US20050022456 A1 US 20050022456A1 US 63169803 A US63169803 A US 63169803A US 2005022456 A1 US2005022456 A1 US 2005022456A1
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Prior art keywords
polishing slurry
slurry
moo
particles
salt
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US10/631,698
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S. Babu
Sharath Hegde
Sunil Jha
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Cyprus Amax Minerals Co
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Individual
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Priority to US10/631,698 priority Critical patent/US20050022456A1/en
Assigned to CLIMAX ENGINEERED MATERIALS, LLC reassignment CLIMAX ENGINEERED MATERIALS, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BABU, S.V., HEDGE, SHARATH, JHA, SUNIL CHANDRA
Priority to US10/846,718 priority patent/US20050026444A1/en
Priority to TW093120127A priority patent/TW200507097A/en
Priority to PCT/US2004/024143 priority patent/WO2005012451A2/en
Priority to EP10009005A priority patent/EP2256171A1/en
Priority to EP04779276A priority patent/EP1648974A4/en
Priority to SG200805239-1A priority patent/SG144929A1/en
Priority to CN200480021645.8A priority patent/CN100569882C/en
Priority to JP2006521994A priority patent/JP2007500943A/en
Priority to KR1020067000223A priority patent/KR20060118396A/en
Priority to US11/032,717 priority patent/US7186653B2/en
Publication of US20050022456A1 publication Critical patent/US20050022456A1/en
Priority to US11/527,429 priority patent/US20070043230A1/en
Priority to US11/540,297 priority patent/US7553430B2/en
Priority to US12/163,385 priority patent/US20080277378A1/en
Priority to US12/469,193 priority patent/US20090224200A1/en
Priority to JP2011234230A priority patent/JP2012084895A/en
Assigned to CYPRUS AMAX MINERALS COMPANY reassignment CYPRUS AMAX MINERALS COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CLIMAX ENGINEERED MATERIALS, LLC
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00—Brightening metals by chemical means
    • C23F3/04—Heavy metals
    • C23F3/06—Heavy metals with acidic solutions
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]

Definitions

  • This invention relates to chemical-mechanical polishing processes in general and more specifically to a molybdenum oxide slurry and method for the chemical-mechanical polishing of copper.
  • CMP Chemical-mechanical polishing
  • the CMP process is typically used in semiconductor processing to polish (e.g., planarize) the surface of the semiconductor wafer.
  • the CMP process is relatively new in that, until recently, conventional processes were sufficient with the comparatively low circuit densities involved.
  • increases in circuit densities e.g., the transition from wafers having 0.25 micron features to 0.18 micron features
  • CMP has become favored.
  • the more recent shift away from aluminum interconnect technology to copper interconnect technology has further favored the use of CMP to polish (e.g., planarize) semiconductor wafers.
  • the chemical-mechanical polishing (CMP) process involves scrubbing a semiconductor wafer with a pad in the presence of a chemically reactive slurry that contains abrasive particles.
  • CMP chemical-mechanical polishing
  • the polishing action of the chemical-mechanical polishing (CMP) process is both chemical and mechanical. Chemicals aid in material removal by modifying the surface film while abrasion between the surface particles, pad, and the modified film facilitates mechanical removal. It is believed that this synergistic interplay between the chemical and mechanical components in the process is the key to effective polishing of the CMP process.
  • the claimed invention involves a novel aqueous polishing slurry for chemical-mechanical polishing that is effective for polishing copper at high polish rates.
  • the aqueous slurry according to the present invention comprises particles of MoO 2 in an oxidizing agent.
  • Embodiments of slurries may contain MoO 2 in amounts ranging from about 0.5% to about 10% by weight particles of MoO 2 and the oxidizing agent may comprise ferric nitrate (Fe(NO 3 ) 3 ), nitric acid (HNO 3 ), potassium iodide (KI), potassium iodate (KIO 3 ) and mixtures thereof.
  • Additional oxidizing agents may include hydroxylamine hydrochloride ((NH 2 OH)Cl) and potassium permanganate (KMnO 4 ).
  • Embodiments of slurries according to the present invention may also be provided with an anionic surfactant comprising polyacrylic acid (PAA), a carboxylic acid or its salt, a sulfuric ester or its salt, a sulfonic acid or its salt, a phosphoric acid or its salt, a sulfosuccinic acid or its salt, and mixtures thereof.
  • PAA polyacrylic acid
  • Other embodiments of slurries according to the present invention may be provided with a cationic surfactant comprising any one or a mixture of a primary amine or its salt, a secondary amine or its salt, a tertiary amine or its salt, and a quaternary amine or its salt.
  • aqueous slurries may be provided with a copper passivating agent which may comprise any one or a mixture of heterocyclic organic compounds including benzotriazole (BTA), triazole, and benzimidazole. Further embodiments of slurries may contain any combination of these surfactants and passivating agents.
  • a copper passivating agent which may comprise any one or a mixture of heterocyclic organic compounds including benzotriazole (BTA), triazole, and benzimidazole.
  • Additional embodiments of slurries according to the present invention may also be provided with amounts of molybdenum sulfide (MoS 2 ) as a lubricant.
  • Aqueous slurries can optionally include acids or bases for adjusting the pH within an effective range of from about 1 to 14.
  • Yet additional embodiments of slurries according to the invention may also be provided with supplemental metal oxide particles.
  • Such supplemental metal oxide particles used in the aqueous slurry may comprise any one or a mixture of silica, ceria, aluminia, zirconia, titania, magnesia, iron oxide, tin oxide, and germania.
  • the present invention also includes a novel method of polishing copper by chemical-mechanical polishing.
  • the method of the present invention comprises polishing copper using a polishing pad and an aqueous slurry comprising MoO 2 particles and an oxidizing agent.
  • Embodiments of slurries may contain MoO 2 in amounts ranging from about 0.5% to about 10% by weight particles of MoO 2 and the oxidizing agent may comprise any one or a mixture of ferric nitrate (Fe(NO 3 ) 3 ), nitric acid (HNO 3 ), potassium iodide (KI), or potassium iodate (KIO 3 ).
  • Additional oxidizing agents may comprise any one or a mixture of hydroxylamine hydrochloride ((NH 2 OH)Cl) and potassium permanganate (KMnO 4 ).
  • Embodiments of slurries according to the present invention may also be provided with an anionic surfactant comprising polyacrylic acid (PAA), a carboxylic acid or its salt, a sulfuric ester or its salt, a sulfonic acid or its salt, a phosphoric acid or its salt, a sulfosuccinic acid or its salt, and mixtures thereof.
  • PAA polyacrylic acid
  • Other embodiments of slurries according to the present invention may be provided with a cationic surfactant comprising any one or a mixture of a primary amine or its salt, a secondary amine or its salt, a tertiary amine or its salt, and a quaternary amine or its salt.
  • aqueous slurries may be provided with a copper passivating agent which may comprise any one or a mixture of heterocyclic organic compounds including benzotriazole (BTA), triazole, and benzimidazole. Further embodiments of slurries may contain any combination of these surfactants and passivating agents.
  • a copper passivating agent which may comprise any one or a mixture of heterocyclic organic compounds including benzotriazole (BTA), triazole, and benzimidazole.
  • Embodiments of slurries according to the present invention may also be provided with amounts of molybdenum sulfide (MoS 2 ) as a lubricant.
  • Aqueous slurries can optionally include acids or bases for adjusting the pH within an effective range of from about 1 to 14.
  • Yet additional embodiments of slurries according to the invention may also be provided with supplemental metal oxide particles.
  • Such supplemental metal oxide particles used in the aqueous slurry may comprise any one or a mixture of silica, ceria, aluminia, zirconia, titania, magnesia, iron oxide, tin oxide, and germania.
  • embodiments of aqueous polishing slurries according to the present invention may comprise a molybdenum oxide (MoO 2 ) polishing material and an oxidizing agent.
  • MoO 2 polishing material may be present in an amount of about 0.5 to about 10 wt. %, such as about 1 to about 3 wt. %, and more preferably in an amount of about 3 wt. %.
  • the molybdenum oxide polishing material may comprise fine particles of MoO 2 having a mean particle size in the range of about 25 nanometers (nm) to about 1 micron, such as about 25 nanometers to about 560 nm, and more preferably about 50 to 200 nm, as measured by a Horiba laser scattering analyzer.
  • the MoO 2 particles may be produced from a variety of molybdenum-containing precursor materials, such as, for example, ammonium molybdates and related compounds, as well as molybdenum oxides prepared from a variety of processes known in the art, wherein molybdenum precursors and products can be made in particles within the size ranges specified herein.
  • particles of MoO 2 may be reduced in size to the ranges specified herein by any of a variety of milling methods known in the art, such as attrition milling assisted by the use of appropriate reagents.
  • embodiments of slurries according to the present invention may utilize particles of MoO 2 produced from a precursor material comprising nano-particles of MoO 3 .
  • Nano-particles of MoO 3 are commercially available from the Climax Molybdenum Company of Ft. Madison, Iowa (US).
  • nano-particles of MoO 3 may be produced in accordance with the teachings provided in U.S. Pat. No. 6,468,497 B1, entitled “Method for Producing Nano-Particles of Molybdenum Oxide,” which is hereby incorporated herein by reference for all that it discloses.
  • the MoO 2 particles comprising the polishing material may be produced by heating nano-particles of MoO 3 for a time sufficient to convert substantially all of the MoO 3 to MoO 2 . More specifically, the nano-particles of MoO 3 may be heated in a reducing atmosphere (e.g., hydrogen) to a temperature in the range of about 400 to about 700° C. (550° C. preferred). Times may be in the range of about 30 to about 180 minutes, as may be required to reduce MoO 3 to MoO 2 in sufficient quantities.
  • a reducing atmosphere e.g., hydrogen
  • Heating may be accomplished in a rotary furnace, although other types of furnaces may be used. If necessary, the resulting MoO 2 product may then be ground to produce an MoO 2 polishing material having a mean particle diameter within the ranges specified herein. A particle classification step may optionally be used to ensure that the resulting MoO 2 polishing material lacks particles that may cause damage during polishing.
  • the oxidizing agent may comprise any one or a mixture of ferric nitrate (Fe(NO 3 ) 3 ), nitric acid (HNO 3 ), potassium iodide (KI), and potassium iodate (KIO 3 ).
  • Ferric nitrate oxidizing agent may be present in concentrations ranging from about 0.05 to about 0.2 molar (M) Fe(NO 3 ) 3 , such as about 0.1 to about 0.2M Fe(NO 3 ) 3 , and more preferably in a concentration of about 0.2 M Fe(NO 3 ) 3 .
  • Nitric acid oxidizing agent may be present in amounts ranging from about 0.5 to about 2 wt. % HNO 31 such as about 1 to about 2 wt.
  • Potassium iodide oxidizing agent may be present in amounts ranging from about 0.5 to about 5 wt. % KI, such as about 1 to about 5 wt. % KI, and more preferably in an amount of about 3 wt. % KI.
  • Potassium iodate oxidizing agent may be present in amounts ranging from about 1 to about 5 wt. % KIO 3 , such as about 1 to about 3 wt. % KIO 3 , and more preferably in an amount of about 3 wt. % KIO 3 .
  • Additional oxidizing agents may comprise any one or a mixture of hydroxylamine hydrochloride ((NH 2 OH)Cl) and potassium permanganate (KMnO 4 ).
  • Hydroxylamine hydrochloride oxidizing agent may be present in amounts ranging from about 1 to about 5 wt. % (NH 2 OH)Cl, such as about 2 to about 4 wt. % (NH 2 OH)Cl, and more preferably in an amount of about 3 wt. % (NH 2 OH)Cl.
  • Potassium permanganate oxidizing agent may be present in amounts ranging from about 1 to about 5 wt. % KMnO 4 , such as about 2 to about 4 wt.
  • polishing rates with slurries containing hydroxylamine hydrochloride and potassium permanganate are generally lower than with the other oxidizing agents identified herein.
  • Embodiments of slurries according to the present invention may also be provided with an anionic surfactant or a cationic surfactant.
  • the anionic surfactant used in the aqueous slurry may comprise any one or a mixture of polyacrylic acid (PAA), a carboxylic acid or its salt, a sulfuric ester or its salt, a sulfonic acid or its salt, a phosphoric acid or its salt, and a sulfosuccinic acid or its salt.
  • the cationic surfactant used in the aqueous slurry may comprise any one or a mixture of a primary amine or its salt, a secondary amine or its salt, a tertiary amine or its salt, and a quaternary amine or its salt.
  • the aqueous slurry may be provided with a copper passivating agent which may comprise any one or a mixture of heterocyclic organic compounds including benzotriazole (BTA), triazole, and benzimidazole.
  • BTA benzotriazole
  • the slurry may contain any combination of these surfactants and passivating agents.
  • a preferred anionic surfactant is polyacrylic acid (PAA).
  • a preferred cationic surfactant is cetyl pyridinium chloride (CPC)
  • a preferred copper passivating agent is benzotriazole (BTA).
  • PAA polyacrylic acid
  • BTA benzotriazole
  • PAA polyacrylic acid
  • PAA surfactant may be present in amounts ranging from about 0.1 to about 4 wt. % PAA, such as about 0.5 to about 1 wt. % PAA, and more preferably in an amount of about 1 wt. % PAA.
  • the cationic surfactant cetyl pyridinium chloride may be present in amounts ranging from about 0.01 to about 1 wt. % CPC, such as about 0.05 to about 0.5 wt. % CPC, and more preferably in an amount of about 0.1 wt. % CPC.
  • Benzotriazole (BTA) copper passivating agent may be present in concentrations ranging from about 0.5 to about 10 milli-molar (mM) BTA, such as about 1 to about 5 mM BTA, and more preferably in a concentration of about 1 mM BTA.
  • Embodiments of slurries according to the present invention may also be provided with amounts of molybdenum sulfide (MoS 2 ) as a lubricant.
  • Molybdenum sulfide particles may have mean diameters in the range of about 0.01 to about 1 micron.
  • Molybdenum sulfide particles may be present in amounts ranging from about 0.1 to about 10 wt. % MoS 2 , such as about 0.5 to about 5 wt. % MoS 2 , and more preferably in an amount of about 1 wt. % MoS 2 .
  • Molybdenum sulfide particles having the size ranges herein are commercially available from the Climax Molybdenum Company of Ft. Madison, Iowa (US).
  • the pH of embodiments of slurries according to the present invention may be in the range of about 1 to about 14, such as a pH in the range of about 3 to about 7, and preferably having a pH of 4.
  • the pH of embodiments of slurries according to the present invention may be adjusted by the addition of suitable acids (e.g., hydrochloric acid (HCl)) or bases (e.g., potassium hydroxide (KOH)), as would be known by persons having ordinary skill in the art.
  • suitable acids e.g., hydrochloric acid (HCl)
  • bases e.g., potassium hydroxide (KOH)
  • polishing slurries according to the invention may also be provided with supplemental metal oxide particles.
  • supplemental metal oxide particles used in the aqueous slurry may comprise any one or a mixture of silica, ceria, aluminia, zirconia, titania, magnesia, iron oxide, tin oxide, and germania.
  • Embodiments of slurries according to the present invention exhibit high polish rates for copper when used in the CMP process. More particularly, when potassium iodate (KIO 3 ) was used as an oxidizing agent in the molybdenum oxide slurries very high copper disk and copper film polish rates (e.g., up to ⁇ 1000 and 470 nm/min, respectively, were obtained, as detailed in the following examples. Addition of PAA enhanced the film polish rate to about 667 nm/min. Further, when molybdenum sulfide particles were added to slurries containing KIO 3 and PAA, copper film polish rates of about 750 nm/min were obtained.
  • KIO 3 potassium iodate
  • PAA copper film polish rates
  • polish rates with the KIO 3 -based slurries of the present invention are high for copper
  • the post-polish surface of the copper tended to be covered with a thick, uneven misty layer with roughness values as high as about 150 nm as measured by a non-contact optical profilometer.
  • the CMP polishing step may be followed by a buffing step.
  • the buffing step involved additionally polishing the copper surface with a dilute suspension of H 2 O 2 , glycine, BTA, and colloidal silica in de-ionized water at a pH of 4.
  • H 2 O 2 -based buffing step The advantage of using an H 2 O 2 -based buffing step is that H 2 O 2 reacts spontaneously with molybdenum oxide, thus removing residual amounts of molybdenum oxide that may remain on the surface. Very clean and smooth copper surfaces were obtained after subsequent buffing, some with roughness values as low as 0.35 nm as measured by a non-contact optical profilometer.
  • Polishing selectivity of one embodiment of a slurry of the present invention between Cu, Ta, and silicon oxide (SiO 2 ) was determined to be 235:1:1 for Cu:Ta:SiO 2 , as presented in Example 24.
  • Examples 25 and 26 involve the addition of ethylene diamine tetra acetic acid (EDTA) to test the complexing ability of EDTA with copper ions.
  • EDTA ethylene diamine tetra acetic acid
  • Examples 1-15 were used to polish a copper disk having a diameter of 1.25 inches.
  • the CMP polisher was a Struers DAP® with an IC-1400, k-groove polishing pad.
  • the carrier remained stationary (i.e., was not rotated).
  • the rotation rate of the platen was 90 revolutions per minute (rpm).
  • the down-force placed on the copper disk was 6.3 pounds per square inch (psi).
  • the slurry flow rate was 60 ml/min.
  • the amount of copper removed from the surface of the disk by CMP was determined by measuring the weight difference of the copper disk both before and after polishing, taking into consideration the density of the Cu meterial, the area of the disk that was polished, and the polishing time. This was then converted into the rate of removal in terms of nm of copper removed per minute.
  • examples 1-10 all contained 3 wt. % molybdenum oxide (MoO 2 ) in deionized water.
  • the mean particle size of molybdenum oxide for examples 1-10 was 1 micron (1000 nm).
  • the mean particle size of molybdenum oxide for examples 11-15 was 150 nm.
  • Various amounts and types of oxidizing agents were added, as identified in Table 1.
  • Example 11 contained 1.5 wt. % MoO 2 with 3 wt. % hydroxylamine hydrochloride ((NH 2 OH)Cl) as an oxidizing agent.
  • Example 12 contained 1.5 wt. % MoO 2 with 3 wt. % potassium permanganate (KMnO 4 ) as the oxidizing agent.
  • Examples 13-15 all contain 3 wt. % KIO 3 with varying amounts of MoO 2 , as noted.
  • the pH of slurries for examples 1-15 was adjusted to 4.0 by the addition of hydrochloric acid (HCl) or potassium hydroxide (KOH).
  • HCl hydrochloric acid
  • KOH potassium hydroxide
  • Examples 16-18 were used to polish a copper film deposited on a silicon substrate by sputter deposition.
  • the copper film had a diameter of 6 inches.
  • the CMP polisher was a Westech Model 372 with an IC-1400, k-groove polishing pad.
  • the carrier was rotated at a rate of 40 rpm.
  • the platen was rotated at 40 rpm.
  • the down-force placed on the copper film was 6 pounds per square inch (psi).
  • the slurry flow rate was set at 200 ml/min.
  • the amount of copper removed from the surface of the silicon substrate by CMP was determined by measuring the sheet resistance of the Cu film both before and after polishing at 17 points spread across the film utilizing a home-made paper mask and a 4-point probe. Sheet resistance was measured at the same points on the film before and after polishing. The measured sheet resistances both before and after polishing were then converted to respective film thicknesses before and after polishing based on the resistivity of the Cu material, the current applied, and the voltage across the 4-point probe. The difference between the starting and final thicknesses as 17 points were calculated, an average thickness loss was obtained which was then divided by the polish time to give the polish rate in nm/min.
  • the slurries all contained 3 wt. % molybdenum oxide (MoO 2 ) in deionized water and with a potassium iodate (KIO 3 ) oxidizing agent present in an amount of 3 wt. %.
  • the mean particle size of the molybdenum oxide for examples 16-18 was 1 micron (1000 nm).
  • Example 17 added 1 wt. % PAA to the slurry.
  • Example 18 added 1 wt. % PAA and 1 wt. % molybdenum sulfide (MoS 2 ) to the slurry.
  • Examples 19-23 Slurries of examples 19-23 were used to polish a copper film deposited on a silicon substrate by sputter deposition.
  • the copper film had a diameter of 6 inches.
  • the CMP polisher was a Westech Model 372 with an IC-1400, k-groove polishing pad.
  • the carrier was rotated at a rate of 75 rpm.
  • the platen was also rotated at 75 rpm.
  • the down-force placed on the copper film was 4 pounds per square inch (psi).
  • the slurry flow rate was set at 200 ml/min.
  • the amount of copper removed from the surface of the silicon substrate by CMP was determined by measuring the sheet resistance of the Cu film both before and after polishing at 17 points spread across the film utilizing a home-made paper mask and a 4-point probe. Sheet resistance was measured at the same points on the film before and after polishing. The measured sheet resistances both before and after polishing were then converted to respective film thicknesses before and after polishing based on the resistivity of the Cu material, the current applied, and the voltage across the 4-point probe. The difference between the starting and final thicknesses as 17 points were calculated, an average thickness loss was obtained which was then divided by the polish time to give the polish rate in nm/min.
  • the slurries all contained 3 wt. % molybdenum oxide (MoO 2 ) in deionized water and with a potassium iodate (KIO 3 ) oxidizing agent present in an amount of 3 wt. %.
  • the mean particle diameter of the molybdenum oxide for examples 19-23 was 150 nm.
  • Example 20 added 1 mM benzotriazole (BTA) to the slurry.
  • Example 21 added 1 wt. % polyacrylic acid (PAA) to the slurry.
  • Example 22 added 0.1 wt. $ cetyl pyridinium chloride (CPC) to the slurry.
  • Example 23 added 2 wt. % PAA and 1 mM BTA to the slurry.
  • Silicon wafers (6 inch diameter) having a 0.3 micron Ta layer deposited by sputter deposition and wafers having a 1 micron SiO 2 layer applied by thermal oxidation were separately polished with a polishing slurry.
  • the amount of copper and Ta removed was determined using a four-point probe, and SiO 2 removed from the surface of the silicon wafer by CMP was measured using an optical interferometer, in order to determine the rate of removal in terms of nm of material removed per minute.
  • the slurry utilized comprised 3 wt % molybdenum oxide (MoO 2 ) in deionized water with potassium iodate (KIO 3 ) oxidizing agent present in an amount of 3 wt. %.
  • the mean particle size of the molybdenum oxide for example 24 was 1 micron (1000 nm).
  • the CMP polisher was a Westech Model 372 with an IC-1400, k-groove polishing pad.
  • the carrier was rotated at a rate of 40 rpm.
  • the platen was also rotated at 40 rpm.
  • the down-force placed on the copper film was 6 pounds per square inch (psi).
  • the slurry flow rate was 200 ml/min.
  • Examples 25 and 26 were used to polish a copper disk having a diameter of 1.25 inches.
  • the CMP polisher was a Struers DAP® with an IC-1400, k-groove polishing pad.
  • the carrier remained stationary (i.e., was not rotated).
  • the rotation rate of the platen was 90 revolutions per minute (rpm).
  • the down-force placed on the copper disk was 6.3 pounds per square inch (psi).
  • the slurry flow rate was 60 ml/min.
  • the amount of copper removed from the surface of the disk by CMP was determined by measuring the weight difference of the copper disk both before and after polishing, taking into consideration the density of the Cu meterial, the area of the disk that was polished, and the polishing time. This was then converted into the rate of removal in terms of nm of copper removed per minute.
  • examples 25 and 26 all contained 3 wt. % molybdenum oxide (MoO 2 ) in deionized water.
  • the mean particle size of molybdenum oxide for both examples 25 and 26 was 1 micron (1000 nm).
  • Various amounts and types of oxidizing agents were added, as identified in Table 5.
  • Slurries of both examples included the addition of 1 wt. % ethylene diamine tetra acetic acid (EDTA) to test the complexing ability of EDTA with copper ions.
  • EDTA ethylene diamine tetra acetic acid

Abstract

The claimed invention involves a novel aqueous polishing slurry for chemical-mechanical polishing that is effective for polishing copper at high polish rates. The aqueous slurry according to the present invention comprises particles of MoO2 in an oxidizing agent. A method for polishing copper by chemical-mechanical polishing includes contacting copper with a polishing pad and an aqueous slurry comprising particles of MoO2 in an oxidizing agent.

Description

    TECHNICAL FIELD
  • This invention relates to chemical-mechanical polishing processes in general and more specifically to a molybdenum oxide slurry and method for the chemical-mechanical polishing of copper.
    • BACKGROUND
  • Chemical-mechanical polishing (CMP) is the term used to refer to a process that are used in semiconductor manufacture. As its name implies, the CMP process is typically used in semiconductor processing to polish (e.g., planarize) the surface of the semiconductor wafer. The CMP process is relatively new in that, until recently, conventional processes were sufficient with the comparatively low circuit densities involved. However, increases in circuit densities (e.g., the transition from wafers having 0.25 micron features to 0.18 micron features) have forced the need to develop new processes for planarizing the wafer, of which CMP has become favored. Similarly, the more recent shift away from aluminum interconnect technology to copper interconnect technology has further favored the use of CMP to polish (e.g., planarize) semiconductor wafers.
  • Briefly, the chemical-mechanical polishing (CMP) process involves scrubbing a semiconductor wafer with a pad in the presence of a chemically reactive slurry that contains abrasive particles. As its name implies, the polishing action of the chemical-mechanical polishing (CMP) process is both chemical and mechanical. Chemicals aid in material removal by modifying the surface film while abrasion between the surface particles, pad, and the modified film facilitates mechanical removal. It is believed that this synergistic interplay between the chemical and mechanical components in the process is the key to effective polishing of the CMP process.
  • While the CMP process is being increasingly used in semiconductor manufacturing processes, the CMP process remains poorly understood, and the exact mechanisms though which the process works have not been determined. For example, while certain parameters for the CMP process have been developed that are satisfactory for wafers utilizing aluminum interconnect technology, those same process parameters have not proven to be particularly satisfactory for use with wafers utilizing copper interconnect technology. One important requirement of a successful CMP slurry for copper is a high polish rate. High polish rates lead to shorter copper overburden polishing times.
    • SUMMARY OF THE INVENTION
  • The following summary is provided as a brief overview of the claimed product and process. It shall not limit the invention in any respect, with a detailed and fully-enabling disclosure being set forth in the Detailed Description of Preferred Embodiments section. Likewise, the invention shall not be restricted to any numerical parameters, processing equipment, chemical reagents, operational conditions, and other variables unless otherwise stated herein.
  • The claimed invention involves a novel aqueous polishing slurry for chemical-mechanical polishing that is effective for polishing copper at high polish rates. The aqueous slurry according to the present invention comprises particles of MoO2 in an oxidizing agent.
  • Embodiments of slurries may contain MoO2 in amounts ranging from about 0.5% to about 10% by weight particles of MoO2 and the oxidizing agent may comprise ferric nitrate (Fe(NO3)3), nitric acid (HNO3), potassium iodide (KI), potassium iodate (KIO3) and mixtures thereof. Additional oxidizing agents may include hydroxylamine hydrochloride ((NH2OH)Cl) and potassium permanganate (KMnO4).
  • Embodiments of slurries according to the present invention may also be provided with an anionic surfactant comprising polyacrylic acid (PAA), a carboxylic acid or its salt, a sulfuric ester or its salt, a sulfonic acid or its salt, a phosphoric acid or its salt, a sulfosuccinic acid or its salt, and mixtures thereof. Other embodiments of slurries according to the present invention may be provided with a cationic surfactant comprising any one or a mixture of a primary amine or its salt, a secondary amine or its salt, a tertiary amine or its salt, and a quaternary amine or its salt.
  • Still yet other embodiments of aqueous slurries may be provided with a copper passivating agent which may comprise any one or a mixture of heterocyclic organic compounds including benzotriazole (BTA), triazole, and benzimidazole. Further embodiments of slurries may contain any combination of these surfactants and passivating agents.
  • Additional embodiments of slurries according to the present invention may also be provided with amounts of molybdenum sulfide (MoS2) as a lubricant. Aqueous slurries can optionally include acids or bases for adjusting the pH within an effective range of from about 1 to 14. Yet additional embodiments of slurries according to the invention may also be provided with supplemental metal oxide particles. Such supplemental metal oxide particles used in the aqueous slurry may comprise any one or a mixture of silica, ceria, aluminia, zirconia, titania, magnesia, iron oxide, tin oxide, and germania.
  • The present invention also includes a novel method of polishing copper by chemical-mechanical polishing. The method of the present invention comprises polishing copper using a polishing pad and an aqueous slurry comprising MoO2 particles and an oxidizing agent.
  • Embodiments of slurries may contain MoO2 in amounts ranging from about 0.5% to about 10% by weight particles of MoO2 and the oxidizing agent may comprise any one or a mixture of ferric nitrate (Fe(NO3)3), nitric acid (HNO3), potassium iodide (KI), or potassium iodate (KIO3). Additional oxidizing agents may comprise any one or a mixture of hydroxylamine hydrochloride ((NH2OH)Cl) and potassium permanganate (KMnO4).
  • Embodiments of slurries according to the present invention may also be provided with an anionic surfactant comprising polyacrylic acid (PAA), a carboxylic acid or its salt, a sulfuric ester or its salt, a sulfonic acid or its salt, a phosphoric acid or its salt, a sulfosuccinic acid or its salt, and mixtures thereof. Other embodiments of slurries according to the present invention may be provided with a cationic surfactant comprising any one or a mixture of a primary amine or its salt, a secondary amine or its salt, a tertiary amine or its salt, and a quaternary amine or its salt.
  • Still yet other embodiments of aqueous slurries may be provided with a copper passivating agent which may comprise any one or a mixture of heterocyclic organic compounds including benzotriazole (BTA), triazole, and benzimidazole. Further embodiments of slurries may contain any combination of these surfactants and passivating agents.
  • Embodiments of slurries according to the present invention may also be provided with amounts of molybdenum sulfide (MoS2) as a lubricant. Aqueous slurries can optionally include acids or bases for adjusting the pH within an effective range of from about 1 to 14. Yet additional embodiments of slurries according to the invention may also be provided with supplemental metal oxide particles. Such supplemental metal oxide particles used in the aqueous slurry may comprise any one or a mixture of silica, ceria, aluminia, zirconia, titania, magnesia, iron oxide, tin oxide, and germania.
    • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • Broadly described, embodiments of aqueous polishing slurries according to the present invention may comprise a molybdenum oxide (MoO2) polishing material and an oxidizing agent. The MoO2 polishing material may be present in an amount of about 0.5 to about 10 wt. %, such as about 1 to about 3 wt. %, and more preferably in an amount of about 3 wt. %. The molybdenum oxide polishing material may comprise fine particles of MoO2 having a mean particle size in the range of about 25 nanometers (nm) to about 1 micron, such as about 25 nanometers to about 560 nm, and more preferably about 50 to 200 nm, as measured by a Horiba laser scattering analyzer.
  • The MoO2 particles may be produced from a variety of molybdenum-containing precursor materials, such as, for example, ammonium molybdates and related compounds, as well as molybdenum oxides prepared from a variety of processes known in the art, wherein molybdenum precursors and products can be made in particles within the size ranges specified herein. Alternatively particles of MoO2 may be reduced in size to the ranges specified herein by any of a variety of milling methods known in the art, such as attrition milling assisted by the use of appropriate reagents.
  • By way of example, embodiments of slurries according to the present invention may utilize particles of MoO2 produced from a precursor material comprising nano-particles of MoO3. Nano-particles of MoO3 are commercially available from the Climax Molybdenum Company of Ft. Madison, Iowa (US). Alternatively, nano-particles of MoO3 may be produced in accordance with the teachings provided in U.S. Pat. No. 6,468,497 B1, entitled “Method for Producing Nano-Particles of Molybdenum Oxide,” which is hereby incorporated herein by reference for all that it discloses.
  • Regardless of whether the nano-particles of MoO3 are obtained commercially or manufactured in accordance with the teachings provided in U.S. Pat. No. 6,468,497 B1, identified above, the MoO2 particles comprising the polishing material may be produced by heating nano-particles of MoO3 for a time sufficient to convert substantially all of the MoO3 to MoO2. More specifically, the nano-particles of MoO3 may be heated in a reducing atmosphere (e.g., hydrogen) to a temperature in the range of about 400 to about 700° C. (550° C. preferred). Times may be in the range of about 30 to about 180 minutes, as may be required to reduce MoO3 to MoO2 in sufficient quantities. Heating may be accomplished in a rotary furnace, although other types of furnaces may be used. If necessary, the resulting MoO2 product may then be ground to produce an MoO2 polishing material having a mean particle diameter within the ranges specified herein. A particle classification step may optionally be used to ensure that the resulting MoO2 polishing material lacks particles that may cause damage during polishing.
  • The oxidizing agent may comprise any one or a mixture of ferric nitrate (Fe(NO3)3), nitric acid (HNO3), potassium iodide (KI), and potassium iodate (KIO3). Ferric nitrate oxidizing agent may be present in concentrations ranging from about 0.05 to about 0.2 molar (M) Fe(NO3)3, such as about 0.1 to about 0.2M Fe(NO3)3, and more preferably in a concentration of about 0.2 M Fe(NO3)3. Nitric acid oxidizing agent may be present in amounts ranging from about 0.5 to about 2 wt. % HNO31 such as about 1 to about 2 wt. % HNO3, and more preferably in an amount of about 2 wt. % HNO3. Potassium iodide oxidizing agent may be present in amounts ranging from about 0.5 to about 5 wt. % KI, such as about 1 to about 5 wt. % KI, and more preferably in an amount of about 3 wt. % KI. Potassium iodate oxidizing agent may be present in amounts ranging from about 1 to about 5 wt. % KIO3, such as about 1 to about 3 wt. % KIO3, and more preferably in an amount of about 3 wt. % KIO3.
  • Additional oxidizing agents may comprise any one or a mixture of hydroxylamine hydrochloride ((NH2OH)Cl) and potassium permanganate (KMnO4). Hydroxylamine hydrochloride oxidizing agent may be present in amounts ranging from about 1 to about 5 wt. % (NH2OH)Cl, such as about 2 to about 4 wt. % (NH2OH)Cl, and more preferably in an amount of about 3 wt. % (NH2OH)Cl. Potassium permanganate oxidizing agent may be present in amounts ranging from about 1 to about 5 wt. % KMnO4, such as about 2 to about 4 wt. % KMnO4, and more preferably in an amount of about 3 wt. % KMnO4. However, the polishing rates with slurries containing hydroxylamine hydrochloride and potassium permanganate are generally lower than with the other oxidizing agents identified herein.
  • Embodiments of slurries according to the present invention may also be provided with an anionic surfactant or a cationic surfactant. The anionic surfactant used in the aqueous slurry may comprise any one or a mixture of polyacrylic acid (PAA), a carboxylic acid or its salt, a sulfuric ester or its salt, a sulfonic acid or its salt, a phosphoric acid or its salt, and a sulfosuccinic acid or its salt. The cationic surfactant used in the aqueous slurry may comprise any one or a mixture of a primary amine or its salt, a secondary amine or its salt, a tertiary amine or its salt, and a quaternary amine or its salt. Optionally, the aqueous slurry may be provided with a copper passivating agent which may comprise any one or a mixture of heterocyclic organic compounds including benzotriazole (BTA), triazole, and benzimidazole. Further, the slurry may contain any combination of these surfactants and passivating agents.
  • A preferred anionic surfactant is polyacrylic acid (PAA). A preferred cationic surfactant is cetyl pyridinium chloride (CPC) A preferred copper passivating agent is benzotriazole (BTA). The addition of PAA improved slurry dispersability and surface quality. It is believed that the addition of PAA modifies the surface charge of the molybdenum oxide particles such that interaction between the molybdenum oxide particles and copper is favorable, leading to an increase in the polish rate. Polyacrylic acid (PAA) surfactant may be present in amounts ranging from about 0.1 to about 4 wt. % PAA, such as about 0.5 to about 1 wt. % PAA, and more preferably in an amount of about 1 wt. % PAA. The cationic surfactant cetyl pyridinium chloride (CPC) may be present in amounts ranging from about 0.01 to about 1 wt. % CPC, such as about 0.05 to about 0.5 wt. % CPC, and more preferably in an amount of about 0.1 wt. % CPC. Benzotriazole (BTA) copper passivating agent may be present in concentrations ranging from about 0.5 to about 10 milli-molar (mM) BTA, such as about 1 to about 5 mM BTA, and more preferably in a concentration of about 1 mM BTA.
  • Embodiments of slurries according to the present invention may also be provided with amounts of molybdenum sulfide (MoS2) as a lubricant. It has been found that the addition of molybdenum sulfide particles increases the polish rate of copper for slurries containing KIO3 and PAA. Molybdenum sulfide particles may have mean diameters in the range of about 0.01 to about 1 micron. Molybdenum sulfide particles may be present in amounts ranging from about 0.1 to about 10 wt. % MoS2, such as about 0.5 to about 5 wt. % MoS2, and more preferably in an amount of about 1 wt. % MoS2. Molybdenum sulfide particles having the size ranges herein are commercially available from the Climax Molybdenum Company of Ft. Madison, Iowa (US).
  • The pH of embodiments of slurries according to the present invention may be in the range of about 1 to about 14, such as a pH in the range of about 3 to about 7, and preferably having a pH of 4. The pH of embodiments of slurries according to the present invention may be adjusted by the addition of suitable acids (e.g., hydrochloric acid (HCl)) or bases (e.g., potassium hydroxide (KOH)), as would be known by persons having ordinary skill in the art.
  • Yet additional embodiments of polishing slurries according to the invention may also be provided with supplemental metal oxide particles. Such supplemental metal oxide particles used in the aqueous slurry may comprise any one or a mixture of silica, ceria, aluminia, zirconia, titania, magnesia, iron oxide, tin oxide, and germania.
  • Embodiments of slurries according to the present invention exhibit high polish rates for copper when used in the CMP process. More particularly, when potassium iodate (KIO3) was used as an oxidizing agent in the molybdenum oxide slurries very high copper disk and copper film polish rates (e.g., up to ˜1000 and 470 nm/min, respectively, were obtained, as detailed in the following examples. Addition of PAA enhanced the film polish rate to about 667 nm/min. Further, when molybdenum sulfide particles were added to slurries containing KIO3 and PAA, copper film polish rates of about 750 nm/min were obtained.
  • While polish rates with the KIO3-based slurries of the present invention are high for copper, the post-polish surface of the copper tended to be covered with a thick, uneven misty layer with roughness values as high as about 150 nm as measured by a non-contact optical profilometer. If the post-polish surface quality is desired to be higher, the CMP polishing step may be followed by a buffing step. In one embodiment, the buffing step involved additionally polishing the copper surface with a dilute suspension of H2O2, glycine, BTA, and colloidal silica in de-ionized water at a pH of 4. The advantage of using an H2O2-based buffing step is that H2O2 reacts spontaneously with molybdenum oxide, thus removing residual amounts of molybdenum oxide that may remain on the surface. Very clean and smooth copper surfaces were obtained after subsequent buffing, some with roughness values as low as 0.35 nm as measured by a non-contact optical profilometer.
  • Polishing selectivity of one embodiment of a slurry of the present invention between Cu, Ta, and silicon oxide (SiO2) was determined to be 235:1:1 for Cu:Ta:SiO2, as presented in Example 24.
  • Examples 25 and 26 involve the addition of ethylene diamine tetra acetic acid (EDTA) to test the complexing ability of EDTA with copper ions. The polish rates for the two specified slurry compositions are presented in Table 5.
  • In order to provide further information regarding the invention, the following examples are provided. The examples present below are representative only and are not intended to limit the invention in any respect.
    • EXAMPLES 1-15
  • Slurries of examples 1-15 were used to polish a copper disk having a diameter of 1.25 inches. The CMP polisher was a Struers DAP® with an IC-1400, k-groove polishing pad. The carrier remained stationary (i.e., was not rotated). The rotation rate of the platen was 90 revolutions per minute (rpm). The down-force placed on the copper disk was 6.3 pounds per square inch (psi). The slurry flow rate was 60 ml/min. The amount of copper removed from the surface of the disk by CMP was determined by measuring the weight difference of the copper disk both before and after polishing, taking into consideration the density of the Cu meterial, the area of the disk that was polished, and the polishing time. This was then converted into the rate of removal in terms of nm of copper removed per minute.
  • The slurries of examples 1-10 all contained 3 wt. % molybdenum oxide (MoO2) in deionized water. The mean particle size of molybdenum oxide for examples 1-10 was 1 micron (1000 nm). The mean particle size of molybdenum oxide for examples 11-15 was 150 nm. Various amounts and types of oxidizing agents were added, as identified in Table 1. Example 11 contained 1.5 wt. % MoO2 with 3 wt. % hydroxylamine hydrochloride ((NH2OH)Cl) as an oxidizing agent. Example 12 contained 1.5 wt. % MoO2 with 3 wt. % potassium permanganate (KMnO4) as the oxidizing agent. Examples 13-15 all contain 3 wt. % KIO3 with varying amounts of MoO2, as noted. The pH of slurries for examples 1-15 was adjusted to 4.0 by the addition of hydrochloric acid (HCl) or potassium hydroxide (KOH). The slurry compositions and polishing rates for the copper disk are presented in Table 1.
    TABLE 1
    Mean
    Particle Polish
    Size Rate
    Example Slurry Composition (nm) pH (nm/min)
    1 3% MoO2 + 0.05 M 1000 4 69
    Fe (NO3)3
    2 3% MoO2 + 0.1 M Fe (NO3)3 1000 4 88
    3 3% MoO2 + 0.2 M Fe (NO3)3 1000 4 230
    4 3% MoO2 + 0.5% HNO3 1000 4 348
    5 3% MoO2 + 1% HNO3 1000 4 221
    6 3% MoO2 + 2% HNO3 1000 4 353
    7 3% MoO2 + 3% KI 1000 4 157
    8 3% MoO2 + 1% KIO3 1000 4 123
    9 3% MoO2 + 2% KIO3 1000 4 345
    10 3% MoO2 + 3% KIO3 1000 4 1014
    11 1.5% MoO2 + 3% (NH2OH) Cl 150 4 68
    12 1.5% MoO2 + 3% KMnO4 150 4 31
    13 1% MoO2 + 3% KIO3 150 4 169
    14 2% MoO2 + 3% KIO3 150 4 524
    15 3% MoO2 + 3% KIO3 150 4 862
    • EXAMPLES 16-18
  • Slurries of examples 16-18 were used to polish a copper film deposited on a silicon substrate by sputter deposition. The copper film had a diameter of 6 inches. The CMP polisher was a Westech Model 372 with an IC-1400, k-groove polishing pad. The carrier was rotated at a rate of 40 rpm. The platen was rotated at 40 rpm. The down-force placed on the copper film was 6 pounds per square inch (psi). The slurry flow rate was set at 200 ml/min.
  • The amount of copper removed from the surface of the silicon substrate by CMP was determined by measuring the sheet resistance of the Cu film both before and after polishing at 17 points spread across the film utilizing a home-made paper mask and a 4-point probe. Sheet resistance was measured at the same points on the film before and after polishing. The measured sheet resistances both before and after polishing were then converted to respective film thicknesses before and after polishing based on the resistivity of the Cu material, the current applied, and the voltage across the 4-point probe. The difference between the starting and final thicknesses as 17 points were calculated, an average thickness loss was obtained which was then divided by the polish time to give the polish rate in nm/min.
  • The slurries all contained 3 wt. % molybdenum oxide (MoO2) in deionized water and with a potassium iodate (KIO3) oxidizing agent present in an amount of 3 wt. %. The mean particle size of the molybdenum oxide for examples 16-18 was 1 micron (1000 nm). Example 17 added 1 wt. % PAA to the slurry. Example 18 added 1 wt. % PAA and 1 wt. % molybdenum sulfide (MoS2) to the slurry. The pH of the slurries of examples 16-18 was adjusted to 4.0 by the addition of hydrochloric acid (HCl) or potassium hydroxide (KOH). The slurry compositions and polishing rates for the copper film are presented in Table 2.
    TABLE 2
    Mean
    Particle Polish
    Size Rate
    Example Slurry Composition (nm) pH (nm/min)
    16 3% MoO2 + 3% KIO3 1000 4 471
    17 3% MoO2 + 3% KIO3 + 1% PAA 1000 4 667
    18 3% MoO2 + 3% KIO3 + 1% 1000 4 750
    PAA + 1% MoS2
    • EXAMPLES 19-23
  • Slurries of examples 19-23 were used to polish a copper film deposited on a silicon substrate by sputter deposition. The copper film had a diameter of 6 inches. The CMP polisher was a Westech Model 372 with an IC-1400, k-groove polishing pad. The carrier was rotated at a rate of 75 rpm. The platen was also rotated at 75 rpm. The down-force placed on the copper film was 4 pounds per square inch (psi). The slurry flow rate was set at 200 ml/min.
  • The amount of copper removed from the surface of the silicon substrate by CMP was determined by measuring the sheet resistance of the Cu film both before and after polishing at 17 points spread across the film utilizing a home-made paper mask and a 4-point probe. Sheet resistance was measured at the same points on the film before and after polishing. The measured sheet resistances both before and after polishing were then converted to respective film thicknesses before and after polishing based on the resistivity of the Cu material, the current applied, and the voltage across the 4-point probe. The difference between the starting and final thicknesses as 17 points were calculated, an average thickness loss was obtained which was then divided by the polish time to give the polish rate in nm/min.
  • The slurries all contained 3 wt. % molybdenum oxide (MoO2) in deionized water and with a potassium iodate (KIO3) oxidizing agent present in an amount of 3 wt. %. The mean particle diameter of the molybdenum oxide for examples 19-23 was 150 nm. Example 20 added 1 mM benzotriazole (BTA) to the slurry. Example 21 added 1 wt. % polyacrylic acid (PAA) to the slurry. Example 22 added 0.1 wt. $ cetyl pyridinium chloride (CPC) to the slurry. Example 23 added 2 wt. % PAA and 1 mM BTA to the slurry. The pH of the slurries of examples 19-23 was adjusted to 4.0 by the addition of hydrochloric acid (HCl) or potassium hydroxide (KOH). The slurry compositions and polishing rates for the copper film are presented in Table 3.
    TABLE 3
    Mean
    Particle
    Size Polish Rate
    Example Slurry Composition (nm) pH (nm/min)
    19 3% MoO2 + 3% KIO3 150 4 695
    20 3% MoO2 + 3% KIO3 + 1 mM 150 4 471
    BTA
    21 3% MoO2 + 3% KIO3 + 150 4 997
    1% PAA
    22 3% MoO2 + 3% KIO3 + 0.1% 150 4 913
    CPC
    23 3% MoO2 + 3% 150 4 660
    KIO3 + 2% PAA +
    1 mM BTA
    • EXAMPLE 24
  • Silicon wafers (6 inch diameter) having a 0.3 micron Ta layer deposited by sputter deposition and wafers having a 1 micron SiO2 layer applied by thermal oxidation were separately polished with a polishing slurry. The amount of copper and Ta removed was determined using a four-point probe, and SiO2 removed from the surface of the silicon wafer by CMP was measured using an optical interferometer, in order to determine the rate of removal in terms of nm of material removed per minute.
  • The slurry utilized comprised 3 wt % molybdenum oxide (MoO2) in deionized water with potassium iodate (KIO3) oxidizing agent present in an amount of 3 wt. %. The mean particle size of the molybdenum oxide for example 24 was 1 micron (1000 nm). The CMP polisher was a Westech Model 372 with an IC-1400, k-groove polishing pad. The carrier was rotated at a rate of 40 rpm. The platen was also rotated at 40 rpm. The down-force placed on the copper film was 6 pounds per square inch (psi). The slurry flow rate was 200 ml/min. The slurry composition and polishing rates for Cu, Ta, and SiO2 are presented in Table 4.
    TABLE 4
    Cu Polish Ta Polish SiO2
    Slurry Rate Rate Polish Rate
    Example Composition (nm/min) (nm/min) (nm/min)
    24 3% MoO2 + 3% KIO3 471 2 2
    • EXAMPLES 25 and 26
  • Slurries of examples 25 and 26 were used to polish a copper disk having a diameter of 1.25 inches. The CMP polisher was a Struers DAP® with an IC-1400, k-groove polishing pad. The carrier remained stationary (i.e., was not rotated). The rotation rate of the platen was 90 revolutions per minute (rpm). The down-force placed on the copper disk was 6.3 pounds per square inch (psi). The slurry flow rate was 60 ml/min. The amount of copper removed from the surface of the disk by CMP was determined by measuring the weight difference of the copper disk both before and after polishing, taking into consideration the density of the Cu meterial, the area of the disk that was polished, and the polishing time. This was then converted into the rate of removal in terms of nm of copper removed per minute.
  • The slurries of examples 25 and 26 all contained 3 wt. % molybdenum oxide (MoO2) in deionized water. The mean particle size of molybdenum oxide for both examples 25 and 26 was 1 micron (1000 nm). Various amounts and types of oxidizing agents were added, as identified in Table 5. Slurries of both examples included the addition of 1 wt. % ethylene diamine tetra acetic acid (EDTA) to test the complexing ability of EDTA with copper ions. The slurry compositions and polishing rates for the copper disk are presented in Table 5.
    TABLE 5
    Mean Particle Polish
    Size Rate
    Example Slurry Composition (nm) pH (nm/min)
    25 3% MoO2 + 3% KI + 1% 1000 4 146
    EDTA
    26 3% MoO2 + 3% KI + 1% 1000 4 259
    KMnO4 + 1% EDTA
  • In conclusion, the claimed product and process collectively represent an important development in CMP technology. The product and process discussed above are novel, distinctive, and highly beneficial from a technical and utilitarian standpoint. Having herein set forth preferred embodiments of the present invention, it is anticipated that suitable modifications can be made thereto which will nonetheless remain within the scope of the invention. The invention shall therefore only be construed in accordance with the following claims:

Claims (60)

1. An aqueous polishing slurry for chemical-mechanical polishing, comprising particles of MoO2 and an oxidizing agent.
2. The aqueous polishing slurry of claim 1, wherein said polishing slurry comprises about 0.5% to about 10% by weight particles of MoO2.
3. The aqueous polishing slurry of claim 1, wherein said polishing slurry comprises about 1% to about 3% by weight particles of MoO2.
4. The aqueous polishing slurry of claim 1, wherein said polishing slurry comprises about 3% by weight particles of MoO2.
5. The aqueous polishing slurry of claim 1, wherein the particles of MoO2 have a mean particle size in the range of about 25 nanometers to about 1 micron.
6. The aqueous polishing slurry of claim 1, wherein the particles of MoO2 have a mean particle size in the range of about 25 nanometers to about 560 nanometers.
7. The aqueous polishing slurry of claim 1, wherein the particles of MoO2 have a mean particle size in the range of about 50 nanometers to about 200 nanometers.
8. The aqueous polishing slurry of claim 1, wherein said oxidizing agent comprises one or more selected from the group consisting of ferric nitrate, nitric acid, potassium iodide, and potassium iodate.
9. The aqueous polishing slurry of claim 1, wherein said oxidizing agent comprises one or more selected from the group consisting of hydroxylamine hydrochloride and potassium permanganate.
10. The aqueous polishing slurry of claim 1, wherein said oxidizing agent is potassium iodate.
11. The aqueous polishing slurry of claim 1, further comprising an acid or a base for adjusting the pH of said polishing slurry within the range of from about 1 to about 14.
12. The aqueous polishing slurry of claim 1, further comprising an acid or a base for adjusting the pH of said polishing slurry within the range of from about 3 to about 7.
13. The aqueous polishing slurry of claim 1, further comprising an acid or a base for adjusting the pH of said polishing slurry to about 4.
14. The aqueous polishing slurry of claim 1, wherein said polishing slurry further comprises an anionic surfactant.
15. The aqueous polishing slurry of claim 14, wherein said anionic surfactant comprises one or more selected from the group consisting of polyacrylic acid, a carbolic acid or its salt, a sulfuric ester or its salt, a sulfonic acid or its salt, a phosphoric acid or its salt, and a sulfosuccinic acid or its salt.
16. The aqueous polishing slurry of claim 14, wherein said anionic surfactant is polyacrylic acid.
17. The aqueous polishing slurry of claim 1, wherein said polishing slurry further comprises a cationic surfactant.
18. The aqueous polishing slurry of claim 17, wherein said cationic surfactant comprises one or more selected from the group consisting of a primary amine or its salt, a secondary amine or its salt, a tertiary amine or its salt, and a quaternary amine or its salt.
19. The aqueous polishing slurry of claim 17, wherein said cationic surfactant is cetyl pyridinium chloride.
20. The aqueous polishing slurry of claim 1, further comprising a copper passivating agent.
21. The aqueous polishing slurry of claim 20, wherein said copper passivating agent comprises a heterocyclic organic compound.
22. The aqueous polishing slurry of claim 20, wherein the copper passivating agent comprises one or more selected from the group consisting of benzotriazole, triazole, and benzimidazole.
23. The aqueous polishing slurry of claim 1 further comprising supplemental metal oxide particles.
24. The aqueous polishing slurry of claim 23, wherein said supplemental metal oxide particles comprise one or more selected from the group consisting of silica, ceria, aluminia, zirconia, titania, magnesia, iron oxide, tin oxide, and germania.
25. The aqueous polishing slurry of claim 1, wherein said polishing slurry further comprises molybdenum sulfide particles.
26. The aqueous polishing slurry of claim 1, wherein said polishing slurry further comprises about 0.1% to about 10% by weight molybdenum sulfide particles.
27. The aqueous polishing slurry of claim 1, wherein said polishing slurry further comprises about 0.5% to about 5% by weight molybdenum sulfide particles.
28. The aqueous polishing slurry of claim 1, wherein said polishing slurry further comprises about 1% by weight molybdenum sulfide particles.
29. The aqueous polishing slurry of claim 1, wherein said slurry further comprises ethylene diamine tetra acetic acid.
30. A method for producing MoO2, comprising:
providing a supply of MoO3;
heating said supply of MoO3 in a reducing atmosphere to a temperature in the range of about 400° C. to about 700° C. for a time in the range of about 30 minutes to about 180 minutes.
31. The method of claim 30, wherein said reducing atmosphere comprises hydrogen.
32. A method for polishing copper by chemical-mechanical polishing comprising polishing copper using a polishing pad and an aqueous slurry comprising MoO2 and an oxidizing agent.
33. The method of claim 32, wherein said slurry comprises about 0.5% to about 10% by weight particles of MoO2.
34. The method of claim 32, wherein said slurry comprises about 1% to about 3% by weight particles of MoO2.
35. The method of claim 32, wherein said slurry comprises about 3% by weight particles of MoO2.
36. The method of claim 32, wherein the particles of MoO2 have a mean particle size in the range of about 25 nanometers to about 1 micron.
37. The method of claim 32, wherein the particles of MoO2 have a mean particle size in the range of about 25 nanometers to about 560 nanometers.
38. The method of claim 32, wherein the particles of MoO2 have a mean particle size in the range of about 50 nanometers to about 200 nanometers.
39. The method of claim 32, wherein said oxidizing agent comprises one or more selected from the group consisting of ferric nitrate, nitric acid, potassium iodide, and potassium iodate.
40. The method of claim 32, wherein said oxidizing agent comprises one or more selected from the group consisting of hydroxylamine hydrochloride and potassium permanganate.
41. The method of claim 32, wherein said oxidizing agent is potassium iodate.
42. The method of claim 32, further comprising an acid or a base for adjusting the pH of said slurry within the range of from about 1 to about 14.
43. The method of claim 32, further comprising an acid or a base for adjusting the pH of said slurry within the range of from about 3 to about 7.
44. The method of claim 32, further comprising an acid or a base for adjusting the pH of said slurry to about 4.
45. The method of claim 32, wherein said slurry further comprises an anionic surfactant.
46. The method of claim 45, wherein said anionic surfactant comprises one or more selected from the group consisting of polyacrylic acid, a carbolic acid or its salt, a sulfuric ester or its salt, a sulfonic acid or its salt, a phosphoric acid or its salt, and a sulfosuccinic acid or its salt.
47. The method of claim 45, wherein said anionic surfactant is polyacrylic acid.
48. The method of claim 32, wherein said polishing slurry further comprises a cationic surfactant.
49. The method of claim 48, wherein said cationic surfactant comprises one or more selected from the group consisting of a primary amine or its salt, a secondary amine or its salt, a tertiary amine or its salt, and a quaternary amine or its salt.
50. The method of claim 48, wherein said cationic surfactant is cetyl pyridinium chloride.
51. The method of claim 32, further comprising a copper passivating agent.
52. The method of claim 51, wherein said copper passivating agent comprises a heterocyclic organic compound.
53. The method of claim 51, wherein the copper passivating agent comprises one or more selected from the group consisting of benzotriazole, triazole, and benzimidazole.
54. The method of claim 32 further comprising supplemental metal oxide particles.
55. The aqueous polishing slurry of claim 54, wherein said supplemental metal oxide particles comprise one or more selected from the group consisting of silica, ceria, aluminia, zirconia, titania, magnesia, iron oxide, tin oxide, and germania.
56. The method of claim 32, wherein said slurry further comprises molybdenum sulfide particles.
57. The method of claim 32, wherein said slurry further comprises about 0.1% to about 10% by weight molybdenum sulfide particles.
58. The method of claim 32, wherein said slurry further comprises about 0.5% to about 5% by weight molybdenum sulfide particles.
59. The method of claim 32, wherein said slurry further comprises about 1% by weight molybdenum sulfide particles.
60. The method of claim 32, further comprising additionally polishing the copper with a dilute suspension of H2O2, glycine, BTA, and colloidal silica in de-ionized water at a pH of 4.
US10/631,698 2003-07-30 2003-07-30 Polishing slurry and method for chemical-mechanical polishing of copper Abandoned US20050022456A1 (en)

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US10/631,698 US20050022456A1 (en) 2003-07-30 2003-07-30 Polishing slurry and method for chemical-mechanical polishing of copper
US10/846,718 US20050026444A1 (en) 2003-07-30 2004-05-13 Slurry and method for chemical-mechanical planarization of copper
TW093120127A TW200507097A (en) 2003-07-30 2004-07-05 Slurry and method for chemical-mechanical planarization of copper
KR1020067000223A KR20060118396A (en) 2003-07-30 2004-07-27 Slurries and methods for chemical-mechanical planarization of copper
CN200480021645.8A CN100569882C (en) 2003-07-30 2004-07-27 The slurry and the method that are used for the chemical-mechanical planarization of copper
JP2006521994A JP2007500943A (en) 2003-07-30 2004-07-27 Slurries and methods for chemically and mechanically smoothing copper
EP10009005A EP2256171A1 (en) 2003-07-30 2004-07-27 Methods for chemical-mechanical planarization of copper
EP04779276A EP1648974A4 (en) 2003-07-30 2004-07-27 Slurries and methods for chemical-mechanical planarization of copper
SG200805239-1A SG144929A1 (en) 2003-07-30 2004-07-27 Slurries and methods for chemical-mechanical planarization of copper
PCT/US2004/024143 WO2005012451A2 (en) 2003-07-30 2004-07-27 Slurries and methods for chemical-mechanical planarization of copper
US11/032,717 US7186653B2 (en) 2003-07-30 2005-01-11 Polishing slurries and methods for chemical mechanical polishing
US11/527,429 US20070043230A1 (en) 2003-07-30 2006-09-26 Polishing slurries and methods for chemical mechanical polishing
US11/540,297 US7553430B2 (en) 2003-07-30 2006-09-29 Polishing slurries and methods for chemical mechanical polishing
US12/163,385 US20080277378A1 (en) 2003-07-30 2008-06-27 Method for Chemical-Mechanical Planarization of Copper
US12/469,193 US20090224200A1 (en) 2003-07-30 2009-05-20 Polishing slurries for chemical-mechanical polishing
JP2011234230A JP2012084895A (en) 2003-07-30 2011-10-25 Slurry and method for chemical mechanical smoothing of copper

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050279733A1 (en) * 2004-06-18 2005-12-22 Cabot Microelectronics Corporation CMP composition for improved oxide removal rate
US7250369B1 (en) * 1998-12-28 2007-07-31 Hitachi, Ltd. Materials for polishing liquid for metal, polishing liquid for metal, method for preparation thereof and polishing method using the same
US20080277378A1 (en) * 2003-07-30 2008-11-13 Climax Engineered Materials, Llc Method for Chemical-Mechanical Planarization of Copper
US20100065530A1 (en) * 2007-02-06 2010-03-18 Advanced Technology Materials, Inc COMPOSITION AND PROCESS FOR THE SELECTIVE REMOVE OF TiSiN
EP2415849A1 (en) * 2009-03-30 2012-02-08 Toray Industries, Inc. Agent for removing conductive film and method for removing conductive film
US20130260558A1 (en) * 2010-12-24 2013-10-03 Hitachi Chemical Co., Ltd. Polishing liquid and method for polishing substrate using the polishing liquid
CN103831706A (en) * 2012-11-27 2014-06-04 安集微电子（上海）有限公司 Chemico-mechanical polishing technology
US9390938B2 (en) 2012-09-06 2016-07-12 Fujimi Incorporated Polishing composition
CN113122141A (en) * 2019-12-30 2021-07-16 安集微电子科技（上海）股份有限公司 Chemical mechanical polishing solution

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6732777B2 (en) * 2001-05-09 2004-05-11 Hewlett-Packard Development Company, L.P. Dispensing adhesive in a bookbinding system
US7247566B2 (en) * 2003-10-23 2007-07-24 Dupont Air Products Nanomaterials Llc CMP method for copper, tungsten, titanium, polysilicon, and other substrates using organosulfonic acids as oxidizers
US7514363B2 (en) * 2003-10-23 2009-04-07 Dupont Air Products Nanomaterials Llc Chemical-mechanical planarization composition having benzenesulfonic acid and per-compound oxidizing agents, and associated method for use
US7988878B2 (en) * 2004-09-29 2011-08-02 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Selective barrier slurry for chemical mechanical polishing
US8591763B2 (en) * 2006-03-23 2013-11-26 Cabot Microelectronics Corporation Halide anions for metal removal rate control
US7824568B2 (en) * 2006-08-17 2010-11-02 International Business Machines Corporation Solution for forming polishing slurry, polishing slurry and related methods
US8232624B2 (en) * 2009-09-14 2012-07-31 International Business Machines Corporation Semiconductor structure having varactor with parallel DC path adjacent thereto
WO2011101755A1 (en) * 2010-02-22 2011-08-25 Basf Se Chemical-mechanical planarization of substrates containing copper, ruthenium, and tantalum layers
CN102180540B (en) * 2011-03-24 2013-02-13 哈尔滨工业大学 Water treatment medicament for eliminating pollution through oxidation of high-activity intermediate state pentavalent manganese
US9646841B1 (en) 2015-10-14 2017-05-09 International Business Machines Corporation Group III arsenide material smoothing and chemical mechanical planarization processes
US9646842B1 (en) 2015-10-14 2017-05-09 International Business Machines Corporation Germanium smoothing and chemical mechanical planarization processes
US9916985B2 (en) 2015-10-14 2018-03-13 International Business Machines Corporation Indium phosphide smoothing and chemical mechanical planarization processes
CN105382676B (en) * 2015-11-17 2018-03-20 广东先导先进材料股份有限公司 A kind of polishing method of gallium arsenide wafer
CN109971357B (en) * 2017-12-27 2021-12-07 安集微电子（上海）有限公司 Chemical mechanical polishing solution
KR102216277B1 (en) * 2018-05-08 2021-02-17 엘지전자 주식회사 Water-soluble coating material and coating method thereof
WO2021130947A1 (en) * 2019-12-26 2021-07-01 ニッタ・デュポン株式会社 Polishing slurry
CN114231062A (en) * 2021-12-31 2022-03-25 佛山市胜锦洁金属表面技术有限公司 Copper material surface brightening repairing agent and preparation method thereof

Citations (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5244534A (en) * 1992-01-24 1993-09-14 Micron Technology, Inc. Two-step chemical mechanical polishing process for producing flush and protruding tungsten plugs
US5318927A (en) * 1993-04-29 1994-06-07 Micron Semiconductor, Inc. Methods of chemical-mechanical polishing insulating inorganic metal oxide materials
US5728308A (en) * 1995-05-26 1998-03-17 Sony Corporation Method of polishing a semiconductor substrate during production of a semiconductor device
US5735963A (en) * 1996-12-17 1998-04-07 Lucent Technologies Inc. Method of polishing
US5770103A (en) * 1997-07-08 1998-06-23 Rodel, Inc. Composition and method for polishing a composite comprising titanium
US5786275A (en) * 1996-06-04 1998-07-28 Nec Corporation Process of fabricating wiring structure having metal plug twice polished under different conditions
US5836806A (en) * 1993-11-03 1998-11-17 Intel Corporation Slurries for chemical mechanical polishing
US5958288A (en) * 1996-11-26 1999-09-28 Cabot Corporation Composition and slurry useful for metal CMP
US5993686A (en) * 1996-06-06 1999-11-30 Cabot Corporation Fluoride additive containing chemical mechanical polishing slurry and method for use of same
US6017463A (en) * 1997-11-21 2000-01-25 Advanced Micro Devices, Inc. Point of use mixing for LI/plug tungsten polishing slurry to improve existing slurry
US6027997A (en) * 1994-03-04 2000-02-22 Motorola, Inc. Method for chemical mechanical polishing a semiconductor device using slurry
US6093649A (en) * 1998-08-07 2000-07-25 Rodel Holdings, Inc. Polishing slurry compositions capable of providing multi-modal particle packing and methods relating thereto
US6143656A (en) * 1998-10-22 2000-11-07 Advanced Micro Devices, Inc. Slurry for chemical mechanical polishing of copper
US6270395B1 (en) * 1998-09-24 2001-08-07 Alliedsignal, Inc. Oxidizing polishing slurries for low dielectric constant materials
US20010013506A1 (en) * 1998-07-24 2001-08-16 Chamberlin Timothy Scott Slurry and use thereof for polishing
US6284151B1 (en) * 1997-12-23 2001-09-04 International Business Machines Corporation Chemical mechanical polishing slurry for tungsten
US6294105B1 (en) * 1997-12-23 2001-09-25 International Business Machines Corporation Chemical mechanical polishing slurry and method for polishing metal/oxide layers
US20010045063A1 (en) * 1997-10-31 2001-11-29 Nobuyuki Kambe Abrasive particles for surface polishing
US6348076B1 (en) * 1999-10-08 2002-02-19 International Business Machines Corporation Slurry for mechanical polishing (CMP) of metals and use thereof
US6358853B2 (en) * 1998-09-10 2002-03-19 Intel Corporation Ceria based slurry for chemical-mechanical polishing
US6362104B1 (en) * 1998-05-26 2002-03-26 Cabot Microelectronics Corporation Method for polishing a substrate using a CMP slurry
US6364744B1 (en) * 2000-02-02 2002-04-02 Agere Systems Guardian Corp. CMP system and slurry for polishing semiconductor wafers and related method
US6375545B1 (en) * 1999-01-18 2002-04-23 Kabushiki Kaisha Toshiba Chemical mechanical method of polishing wafer surfaces
US20020098701A1 (en) * 2000-11-30 2002-07-25 Jsr Corporation Polishing method
US6448182B1 (en) * 1998-11-24 2002-09-10 Texas Instruments Incorporated Stabilization of peroxygen-containing slurries used in a chemical mechanical planarization
US6520840B1 (en) * 1999-10-27 2003-02-18 Applied Materials, Inc. CMP slurry for planarizing metals
US6530968B2 (en) * 2000-11-24 2003-03-11 Nec Electronics Corporation Chemical mechanical polishing slurry
US20030047710A1 (en) * 2001-09-13 2003-03-13 Nyacol Nano Technologies, Inc Chemical-mechanical polishing
US6544892B2 (en) * 1999-12-08 2003-04-08 Eastman Kodak Company Slurry for chemical mechanical polishing silicon dioxide
US6558570B2 (en) * 1998-07-01 2003-05-06 Micron Technology, Inc. Polishing slurry and method for chemical-mechanical polishing
US20030092271A1 (en) * 2001-09-13 2003-05-15 Nyacol Nano Technologies, Inc. Shallow trench isolation polishing using mixed abrasive slurries
US6569350B2 (en) * 1996-12-09 2003-05-27 Cabot Microelectronics Corporation Chemical mechanical polishing slurry useful for copper substrates
US6585568B2 (en) * 2000-11-24 2003-07-01 Nec Electronics Corporation Chemical mechanical polishing slurry
US6585786B2 (en) * 2000-11-24 2003-07-01 Nec Electronics Corporation Slurry for chemical mechanical polishing
US6589099B2 (en) * 2001-07-09 2003-07-08 Motorola, Inc. Method for chemical mechanical polishing (CMP) with altering the concentration of oxidizing agent in slurry
US6726990B1 (en) * 1998-05-27 2004-04-27 Nanogram Corporation Silicon oxide particles
US6805615B1 (en) * 1999-04-09 2004-10-19 Micron Technology, Inc. Planarizing solutions, planarizing machines and methods for mechanical or chemical-mechanical planarization of microelectronic-device substrate assemblies
US6863592B2 (en) * 2002-08-16 2005-03-08 Samsung Electronics Co., Ltd. Chemical/mechanical polishing slurry and chemical mechanical polishing method using the same

Family Cites Families (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5996594A (en) * 1994-11-30 1999-12-07 Texas Instruments Incorporated Post-chemical mechanical planarization clean-up process using post-polish scrubbing
JP3150095B2 (en) * 1996-12-12 2001-03-26 日本電気株式会社 Method of manufacturing multilayer wiring structure
US5981378A (en) * 1997-07-25 1999-11-09 Vlsi Technology, Inc. Reliable interconnect via structures and methods for making the same
US6142855A (en) * 1997-10-31 2000-11-07 Canon Kabushiki Kaisha Polishing apparatus and polishing method
JP2000158331A (en) * 1997-12-10 2000-06-13 Canon Inc Precise polishing method and device for substrate
US6015499A (en) * 1998-04-17 2000-01-18 Parker-Hannifin Corporation Membrane-like filter element for chemical mechanical polishing slurries
TW369947U (en) * 1998-04-24 1999-09-11 United Microelectronics Corp A filter set
US6723143B2 (en) * 1998-06-11 2004-04-20 Honeywell International Inc. Reactive aqueous metal oxide sols as polishing slurries for low dielectric constant materials
US6551367B2 (en) * 1998-09-22 2003-04-22 Cheil Industries Inc. Process for preparing metal oxide slurry suitable for semiconductor chemical mechanical polishing
US6260709B1 (en) * 1998-11-09 2001-07-17 Parker-Hannifin Corporation Membrane filter element for chemical-mechanical polishing slurries
US6276996B1 (en) * 1998-11-10 2001-08-21 Micron Technology, Inc. Copper chemical-mechanical polishing process using a fixed abrasive polishing pad and a copper layer chemical-mechanical polishing solution specifically adapted for chemical-mechanical polishing with a fixed abrasive pad
SG78405A1 (en) * 1998-11-17 2001-02-20 Fujimi Inc Polishing composition and rinsing composition
KR100447551B1 (en) * 1999-01-18 2004-09-08 가부시끼가이샤 도시바 Composite Particles and Production Process Thereof, Aqueous Dispersion, Aqueous Dispersion Composition for Chemical Mechanical Polishing, and Process for Manufacture of Semiconductor Apparatus
JP3941284B2 (en) * 1999-04-13 2007-07-04 株式会社日立製作所 Polishing method
US6419554B2 (en) * 1999-06-24 2002-07-16 Micron Technology, Inc. Fixed abrasive chemical-mechanical planarization of titanium nitride
US6630433B2 (en) * 1999-07-19 2003-10-07 Honeywell International Inc. Composition for chemical mechanical planarization of copper, tantalum and tantalum nitride
US6538853B1 (en) * 1999-09-13 2003-03-25 Maxtor Corporation E-block having improved resonance characteristics and improved fragility
JP4273475B2 (en) * 1999-09-21 2009-06-03 株式会社フジミインコーポレーテッド Polishing composition
WO2001032799A1 (en) * 1999-11-04 2001-05-10 Nanogram Corporation Particle dispersions
US6242351B1 (en) * 1999-12-27 2001-06-05 General Electric Company Diamond slurry for chemical-mechanical planarization of semiconductor wafers
US6451200B1 (en) * 2000-01-13 2002-09-17 W. R. Grace & Co.-Conn. Hydrothermally stable high pore volume aluminum oxide/swellable clay composites and methods of their preparation and use
JP3945964B2 (en) * 2000-06-01 2007-07-18 株式会社ルネサステクノロジ Abrasive, polishing method and method for manufacturing semiconductor device
US6569222B2 (en) * 2000-06-09 2003-05-27 Harper International Corporation Continuous single stage process for the production of molybdenum metal
JP3837277B2 (en) * 2000-06-30 2006-10-25 株式会社東芝 Chemical mechanical polishing aqueous dispersion for use in polishing copper and chemical mechanical polishing method
KR100481651B1 (en) * 2000-08-21 2005-04-08 가부시끼가이샤 도시바 Slurry for chemical mechanical polishing and method for manufacturing semiconductor device
US6511912B1 (en) * 2000-08-22 2003-01-28 Micron Technology, Inc. Method of forming a non-conformal layer over and exposing a trench
JP2002075927A (en) * 2000-08-24 2002-03-15 Fujimi Inc Composition for polishing and polishing method using it
US6551935B1 (en) * 2000-08-31 2003-04-22 Micron Technology, Inc. Slurry for use in polishing semiconductor device conductive structures that include copper and tungsten and polishing methods
US6602117B1 (en) * 2000-08-30 2003-08-05 Micron Technology, Inc. Slurry for use with fixed-abrasive polishing pads in polishing semiconductor device conductive structures that include copper and tungsten and polishing methods
US6468497B1 (en) 2000-11-09 2002-10-22 Cyprus Amax Minerals Company Method for producing nano-particles of molybdenum oxide
TW591089B (en) * 2001-08-09 2004-06-11 Cheil Ind Inc Slurry composition for use in chemical mechanical polishing of metal wiring
US6692546B2 (en) * 2001-08-14 2004-02-17 Advanced Technology Materials, Inc. Chemical mechanical polishing compositions for metal and associated materials and method of using same
US20030211747A1 (en) * 2001-09-13 2003-11-13 Nyacol Nano Technologies, Inc Shallow trench isolation polishing using mixed abrasive slurries
US6660638B1 (en) * 2002-01-03 2003-12-09 Taiwan Semiconductor Manufacturing Company CMP process leaving no residual oxide layer or slurry particles
US7524346B2 (en) * 2002-01-25 2009-04-28 Dupont Air Products Nanomaterials Llc Compositions of chemical mechanical planarization slurries contacting noble-metal-featured substrates
US6548409B1 (en) * 2002-02-19 2003-04-15 Silicon Integrated Systems Corp. Method of reducing micro-scratches during tungsten CMP
KR100442873B1 (en) * 2002-02-28 2004-08-02 삼성전자주식회사 Chemical mechanical polishing slurry and chemical mechanical polishing method using the same
US6726535B2 (en) * 2002-04-25 2004-04-27 Taiwan Semiconductor Manufacturing Co., Ltd. Method for preventing localized Cu corrosion during CMP
US7087187B2 (en) * 2002-06-06 2006-08-08 Grumbine Steven K Meta oxide coated carbon black for CMP
US6803353B2 (en) * 2002-11-12 2004-10-12 Atofina Chemicals, Inc. Copper chemical mechanical polishing solutions using sulfonated amphiprotic agents
US20050022456A1 (en) * 2003-07-30 2005-02-03 Babu S. V. Polishing slurry and method for chemical-mechanical polishing of copper
JP2006324584A (en) * 2005-05-20 2006-11-30 Sharp Corp Semiconductor device and manufacturing method thereof
CN101641291A (en) * 2006-11-16 2010-02-03 雅宝荷兰有限责任公司 By molybdenum glance purified molybdenum technical oxide

Patent Citations (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5244534A (en) * 1992-01-24 1993-09-14 Micron Technology, Inc. Two-step chemical mechanical polishing process for producing flush and protruding tungsten plugs
US5318927A (en) * 1993-04-29 1994-06-07 Micron Semiconductor, Inc. Methods of chemical-mechanical polishing insulating inorganic metal oxide materials
US6178585B1 (en) * 1993-11-03 2001-01-30 Intel Corporation Slurries for chemical mechanical polishing
US6375552B1 (en) * 1993-11-03 2002-04-23 Intel Corporation Slurries for chemical mechanical polishing
US5836806A (en) * 1993-11-03 1998-11-17 Intel Corporation Slurries for chemical mechanical polishing
US5954975A (en) * 1993-11-03 1999-09-21 Intel Corporation Slurries for chemical mechanical polishing tungsten films
US6046099A (en) * 1993-11-03 2000-04-04 Intel Corporation Plug or via formation using novel slurries for chemical mechanical polishing
US6027997A (en) * 1994-03-04 2000-02-22 Motorola, Inc. Method for chemical mechanical polishing a semiconductor device using slurry
US5728308A (en) * 1995-05-26 1998-03-17 Sony Corporation Method of polishing a semiconductor substrate during production of a semiconductor device
US5786275A (en) * 1996-06-04 1998-07-28 Nec Corporation Process of fabricating wiring structure having metal plug twice polished under different conditions
US5993686A (en) * 1996-06-06 1999-11-30 Cabot Corporation Fluoride additive containing chemical mechanical polishing slurry and method for use of same
US5958288A (en) * 1996-11-26 1999-09-28 Cabot Corporation Composition and slurry useful for metal CMP
US6569350B2 (en) * 1996-12-09 2003-05-27 Cabot Microelectronics Corporation Chemical mechanical polishing slurry useful for copper substrates
US5735963A (en) * 1996-12-17 1998-04-07 Lucent Technologies Inc. Method of polishing
US5770103A (en) * 1997-07-08 1998-06-23 Rodel, Inc. Composition and method for polishing a composite comprising titanium
US20010045063A1 (en) * 1997-10-31 2001-11-29 Nobuyuki Kambe Abrasive particles for surface polishing
US6017463A (en) * 1997-11-21 2000-01-25 Advanced Micro Devices, Inc. Point of use mixing for LI/plug tungsten polishing slurry to improve existing slurry
US6284151B1 (en) * 1997-12-23 2001-09-04 International Business Machines Corporation Chemical mechanical polishing slurry for tungsten
US6294105B1 (en) * 1997-12-23 2001-09-25 International Business Machines Corporation Chemical mechanical polishing slurry and method for polishing metal/oxide layers
US6362104B1 (en) * 1998-05-26 2002-03-26 Cabot Microelectronics Corporation Method for polishing a substrate using a CMP slurry
US6726990B1 (en) * 1998-05-27 2004-04-27 Nanogram Corporation Silicon oxide particles
US6558570B2 (en) * 1998-07-01 2003-05-06 Micron Technology, Inc. Polishing slurry and method for chemical-mechanical polishing
US20010013506A1 (en) * 1998-07-24 2001-08-16 Chamberlin Timothy Scott Slurry and use thereof for polishing
US6093649A (en) * 1998-08-07 2000-07-25 Rodel Holdings, Inc. Polishing slurry compositions capable of providing multi-modal particle packing and methods relating thereto
US6358853B2 (en) * 1998-09-10 2002-03-19 Intel Corporation Ceria based slurry for chemical-mechanical polishing
US6270395B1 (en) * 1998-09-24 2001-08-07 Alliedsignal, Inc. Oxidizing polishing slurries for low dielectric constant materials
US6143656A (en) * 1998-10-22 2000-11-07 Advanced Micro Devices, Inc. Slurry for chemical mechanical polishing of copper
US6448182B1 (en) * 1998-11-24 2002-09-10 Texas Instruments Incorporated Stabilization of peroxygen-containing slurries used in a chemical mechanical planarization
US6375545B1 (en) * 1999-01-18 2002-04-23 Kabushiki Kaisha Toshiba Chemical mechanical method of polishing wafer surfaces
US6805615B1 (en) * 1999-04-09 2004-10-19 Micron Technology, Inc. Planarizing solutions, planarizing machines and methods for mechanical or chemical-mechanical planarization of microelectronic-device substrate assemblies
US6348076B1 (en) * 1999-10-08 2002-02-19 International Business Machines Corporation Slurry for mechanical polishing (CMP) of metals and use thereof
US6520840B1 (en) * 1999-10-27 2003-02-18 Applied Materials, Inc. CMP slurry for planarizing metals
US6544892B2 (en) * 1999-12-08 2003-04-08 Eastman Kodak Company Slurry for chemical mechanical polishing silicon dioxide
US6364744B1 (en) * 2000-02-02 2002-04-02 Agere Systems Guardian Corp. CMP system and slurry for polishing semiconductor wafers and related method
US6585568B2 (en) * 2000-11-24 2003-07-01 Nec Electronics Corporation Chemical mechanical polishing slurry
US6585786B2 (en) * 2000-11-24 2003-07-01 Nec Electronics Corporation Slurry for chemical mechanical polishing
US6530968B2 (en) * 2000-11-24 2003-03-11 Nec Electronics Corporation Chemical mechanical polishing slurry
US20020098701A1 (en) * 2000-11-30 2002-07-25 Jsr Corporation Polishing method
US6589099B2 (en) * 2001-07-09 2003-07-08 Motorola, Inc. Method for chemical mechanical polishing (CMP) with altering the concentration of oxidizing agent in slurry
US20030092271A1 (en) * 2001-09-13 2003-05-15 Nyacol Nano Technologies, Inc. Shallow trench isolation polishing using mixed abrasive slurries
US20030047710A1 (en) * 2001-09-13 2003-03-13 Nyacol Nano Technologies, Inc Chemical-mechanical polishing
US6863592B2 (en) * 2002-08-16 2005-03-08 Samsung Electronics Co., Ltd. Chemical/mechanical polishing slurry and chemical mechanical polishing method using the same

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7250369B1 (en) * 1998-12-28 2007-07-31 Hitachi, Ltd. Materials for polishing liquid for metal, polishing liquid for metal, method for preparation thereof and polishing method using the same
US20080277378A1 (en) * 2003-07-30 2008-11-13 Climax Engineered Materials, Llc Method for Chemical-Mechanical Planarization of Copper
US20050279733A1 (en) * 2004-06-18 2005-12-22 Cabot Microelectronics Corporation CMP composition for improved oxide removal rate
US20090191710A1 (en) * 2004-06-18 2009-07-30 Cabot Microelectronics Corporation CMP method for improved oxide removal rate
US20100065530A1 (en) * 2007-02-06 2010-03-18 Advanced Technology Materials, Inc COMPOSITION AND PROCESS FOR THE SELECTIVE REMOVE OF TiSiN
EP2415849A1 (en) * 2009-03-30 2012-02-08 Toray Industries, Inc. Agent for removing conductive film and method for removing conductive film
EP2415849A4 (en) * 2009-03-30 2014-12-17 Toray Industries Agent for removing conductive film and method for removing conductive film
US20130260558A1 (en) * 2010-12-24 2013-10-03 Hitachi Chemical Co., Ltd. Polishing liquid and method for polishing substrate using the polishing liquid
US9564337B2 (en) * 2010-12-24 2017-02-07 Hitachi Chemical Co., Ltd. Polishing liquid and method for polishing substrate using the polishing liquid
US9390938B2 (en) 2012-09-06 2016-07-12 Fujimi Incorporated Polishing composition
CN103831706A (en) * 2012-11-27 2014-06-04 安集微电子（上海）有限公司 Chemico-mechanical polishing technology
CN113122141A (en) * 2019-12-30 2021-07-16 安集微电子科技（上海）股份有限公司 Chemical mechanical polishing solution

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JP2012084895A (en) 2012-04-26
CN1863883A (en) 2006-11-15
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CN100569882C (en) 2009-12-16
US20080277378A1 (en) 2008-11-13

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