WO2004053008A2 - Passivative chemical mechanical polishing composition for copper film planarization - Google Patents

Passivative chemical mechanical polishing composition for copper film planarization Download PDF

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WO2004053008A2
WO2004053008A2 PCT/US2003/038047 US0338047W WO2004053008A2 WO 2004053008 A2 WO2004053008 A2 WO 2004053008A2 US 0338047 W US0338047 W US 0338047W WO 2004053008 A2 WO2004053008 A2 WO 2004053008A2
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Prior art keywords
cmp composition
acid
tlie
ηie
composition
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PCT/US2003/038047
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French (fr)
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WO2004053008A3 (en
Inventor
Jun Liu
Peter Wrschka
David Bernhard
Mackenzie King
Michael Darsillo
Karl Boggs
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Advanced Technology Materials, Inc.
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Priority to EP03812786A priority Critical patent/EP1570015A4/en
Priority to AU2003297590A priority patent/AU2003297590A1/en
Publication of WO2004053008A2 publication Critical patent/WO2004053008A2/en
Publication of WO2004053008A3 publication Critical patent/WO2004053008A3/en

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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F3/00Brightening metals by chemical means
    • C23F3/04Heavy metals
    • C23F3/06Heavy metals with acidic solutions
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09GPOLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00Polishing compositions
    • C09G1/02Polishing compositions containing abrasives or grinding agents
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14Nitrogen-containing compounds
    • C23F11/141Amines; Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F3/00Brightening metals by chemical means
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/3205Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321After treatment
    • H01L21/32115Planarisation
    • H01L21/3212Planarisation by chemical mechanical polishing [CMP]

Definitions

  • the present invention relates to a chemical mechanical polishing composition and to a method of using same for the polishing of semiconductor substrates having copper thereon, e.g., copper interconnects, electrodes, or metallization, as part of a semiconductor device structure on a wafer substrate.
  • semiconductor substrates having copper thereon e.g., copper interconnects, electrodes, or metallization
  • Copper is widely employed in semiconductor manufacturing as a material of construction for components of semiconductor device structures on wafer substrates (e.g., contacts, electrodes, conductive vias, field emitter base layers, etc.), and it is rapidly becoming the interconnect metal of choice in semiconductor manufacturing due to its higher conductivity and increased electromigration resistance relative to aluminum and aluminum alloys.
  • the process scheme for utilizing copper in semiconductor manufacturing involves the damascene approach, wherein features are etched in a dielectric material. In the dual damascene process a single step is used to form both plugs and lines.
  • barrier layers such as Ta or TaN deposited by various deposition methods, are often used to seal the copper interconnects.
  • a thin seed layer of copper is deposited on the barrier material via physical vapor deposition, followed by electrodeposition of copper to fill the features.
  • the deposited copper must then be planarized to render it of suitable form to accommodate subsequent process steps in the fabrication of the finished semiconductor product, and in order to satisfactorily operate in the microcircuitry in which it is present.
  • the planarization typically involves chemical mechanical polishing (CMP), using a CMP composition formulated for such purpose.
  • the first step slurry (Step I) is used to rapidly planarize the topography and to uniformly remove the remaining copper, with the polish stopping at the barrier layer.
  • the second step slurry (Step II) removes the barrier layer material at a high removal rate and stops on the dielectric oxide layer, or alternatively on a cap layer that has been applied to protect the oxide.
  • Step I chemical mechanical polishing (CMP) compositions for planarization and polishing of copper typically are in the form of slurries containing an abrasive of suitable type, e.g., an abrasive selected from among silica, alumina, and other oxides and mineralic materials, in a solvent medium containing one or more solvent species, e.g., water, organic solvents, etc.
  • An abrasive of suitable type e.g., an abrasive selected from among silica, alumina, and other oxides and mineralic materials
  • solvent medium containing one or more solvent species, e.g., water, organic solvents, etc.
  • One type of CMP composition for planarizing copper surfaces includes an aqueous slurry of abrasive particles, containing hydrogen peroxide as an oxidizing component and glycine as a chelating agent.
  • step I CMP slurries containing abrasive particles, hydrogen peroxide and glycine, the
  • BTA compound benzotriazole
  • BTA FW: 119.13
  • insoluble Cu-BTA complex complexes with copper to form an insoluble Cu-BTA complex on the copper surface.
  • the resulting insoluble protective film facilitates the planarization of the topography of the device structure being fabricated, since the recessed areas on the wafer surface are protected from dissolution, while mechanical action of the abrasive species on the protruding areas enables material removal and polishing to be carried out.
  • the Cu-BTA complex minimizes corrosion and preserves the functional integrity of the copper device structures for their intended use.
  • BTA functions well as a copper corrosion inhibitor in the absence of OH radicals generated as a result of the Cu 2+ -glycine induced catalytic decomposition of hydrogen peroxide.
  • copper CMP slurries containing hydrogen peroxide and glycine the fo ⁇ nation of highly oxidizing OH radicals under dynamic CMP conditions cannot be avoided, since copper metal is readily oxidized in such CMP environment.
  • BTA is not effective in protecting the low features of copper wafer surfaces during the CMP process, and thus allows "dishing" to occur in high-density patterned areas when Cu + cation is present in the CMP composition.
  • An alternative to the use of BTA as a corrosion inhibitor in CMP compositions therefore is highly desirable. Specifically, an alternative corrosion inhibitor is desired, which is compatible with H 2 0 2 /glycine-based CMP compositions and effective to passivate copper surfaces when significant amounts of Cu ions are present in bulk solution and/or near the metal/solution interface during CMP processing.
  • the present invention relates to CMP compositions containing 5-aminotetrazole
  • the invention relates to a CMP composition for planarization of copper films, in which the composition includes oxidizing agent, chelating agent, and corrosion inhibitor, and the corrosion inhibitor includes 5-aminotetrazole.
  • the invention relates to a CMP composition for planarization of copper films.
  • the composition comprises an aqueous slurry medium including abrasive, solvent,
  • ATA, H 2 O 2 and glycine have the following concentrations by weight, based on the total weight of the composition: ATA 0.01 - 10 wt.%
  • Yet another aspect of the invention relates to a CMP composition including the following components by weight, based on the total weight of the composition:
  • Still another aspect of the invention relates to a method of polishing copper on a substrate having copper thereon, including contacting copper on the substrate under CMP conditions with a CMP composition effective for polishing the copper, wherein the CMP composition includes ATA.
  • Figure 1 is a graph of static etch rates of copper metal, in Angstroms per minute, as a function of added copper sulfate (CuS0 4 # 5H 2 0) concentration, in a H 2 0 2 /Glycine/Cu 2+ system at pH
  • Figure 2 is a graph of removal rate of copper metal, in Angstroms per minute, as a function of ATA concentration in wt%, based on the total weight of the CMP slurry composition. DETAILED DESCRIPTION OF THE INVENTION. AND PREFERRED EMBODIMENTS
  • the present invention is based on the discovery that 5-aminotetrazole
  • ATA s pw : 85.06
  • BTA copper corrosion inhibitor
  • ATA-containing CMP composition achieves active passivation of copper surfaces even when significant amounts of copper ions, e.g., Cu 2+ cations, are present in bulk solution and/or at the metal/solution interface during CMP processing.
  • copper ions e.g., Cu 2+ cations
  • the ATA-containing CMP composition of the invention in its broad contemplation, can be formulated with any suitable constituents, including any appropriate oxidizing agent(s), chelating agent(s), and corrosion inhibitor(s), abrasive media, solvent media, and optionally any suitable additives, adjuvants, excipients, etc., such as stabilizing agents, acids, bases (e.g., amines), surfactants, buffering agents, etc.
  • suitable constituents including any appropriate oxidizing agent(s), chelating agent(s), and corrosion inhibitor(s), abrasive media, solvent media, and optionally any suitable additives, adjuvants, excipients, etc., such as stabilizing agents, acids, bases (e.g., amines), surfactants, buffering agents, etc.
  • Oxidizing agents employed in the broad practice of the invention can be of any suitable type, including for example ferric nitrate, ferric ammonium oxalate, ferric ammonium citrate, permanganate salts (e.g., potassium permanganate), peroxyacids (e.g. peracetic acid), peroxoborate salts (e.g., potassium peroxoborate), urea-hydrogen peroxide, iodate salts (e.g., potassium iodate), perchlorate salts (e.g.
  • oxidizers include peracetic acid, urea-hydrogen peroxide, di-t-butyl peroxide, benzyl peroxide, hydrogen peroxide and compatible mixtures including two or more of such oxidizer species.
  • Chelating agents in tire CMP compositions of the invention can be of any appropriate type, including, for example: glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, lysine, etc.; polyamine complexes and their salts, including ethylenedi-iminetetraacetic acid, N-hydroxyethylemylenediaminetriacetic acid, nitrilotriacetic acid, iminodiacetic acid, diemylenefriaminepentaacetic acid, and ethanoldiglycinate; polycarboxylic acids, including phtlialic acid, oxalic acid, malic acid, succinic acid, mandelic acid, and mellitic acid; and compatible mixtures including two or more of the foregoing species.
  • Preferred chelating agents include arnino acids, with glycine being most preferred.
  • ATA is employed in CMP compositions of the invention in any suitable concentration. Suitable concentration of ATA in a specific formulation is readily empirically determinable within the skill of the art, based on the disclosure herein, to provide a CMP composition with suitable copper surface passivation characteristics even in CMP environments containing high levels of copper cations.
  • the amount of ATA in the CMP composition is in a range of from about 0.01 to about 10% by weight, based on the total weight of the CMP composition, with an amount of ATA in a range of from about 0.05 to about 5% by weight being more preferred, an amount of ATA in a range of from about 0.10 to about 1.0% by weight being even more preferred, and an amount of ATA in a range of from about 0.2 to 0.8% by weight being most preferred, on the same total weight basis, although greater or lesser percentages may be employed to advantage in specific applications within the broad scope of tire present invention.
  • the corrosion inhibitor component in the CMP composition of the invention comprises
  • ATA can additionally include other corrosion inhibitor components in combination with ATA, in specific embodiments of the invention.
  • Such other corrosion inhibitor components may be of any suitable type, including for example, imidazole, benzotriazole, benzimidazole, arnino, imino, carboxy, mercapto, nitro, alkyl, urea and thiourea compounds and derivatives, etc.
  • Preferred inhibitors include tetrazoles and their derivatives, and the invention therefore contemplates the provision of ATA alone or in combination with other tetrazole (or other corrosion inhibitor) species, as the corrosion inhibitor in compositions according to the present invention.
  • the abrasive can be of any suitable type, including, without limitation, metal oxides, silicon nitrides, carbides, etc. Specific examples include silica, alumina, silicon carbide, silicon nitride, iron oxide, ceria, zirconium oxide, tin oxide, titanium dioxide, and mixtures of two or more of such components in suitable form, such as grains, granules, particles, or other divided form.
  • the abrasive can include composite particles formed of two or more materials, e.g., NYACOL® alumina-coated colloidal silica (Nyacol Nano Technologies, Inc., Ashland, MA).
  • Alumina is a preferred inorganic abrasive and can be employed in the form of boehmite or transitional ⁇ , ⁇ or ⁇ phase alumina.
  • Organic polymer particles e.g., including thermoset and/or thermoplastic resin(s), can be utilized as abrasives.
  • Useful resins in the broad practice of the present invention include epoxies, urethanes, polyesters, polyamides, polycarbonates, polyolefins, polyvinylchloride, polystyrenes, polyolefins, and (meth)acryrics. Mixtures of two or more organic polymer particles can be used as the abrasive medium, as well as particles comprising both inorganic and organic components.
  • Bases can be optionally employed for pH adjustment in compositions of the invention.
  • Illustrative bases include, by way of example, potassium hydroxide, ammonium hydroxide and tefr-rmemylammoniumhydroxide (TMAH), tetraethylammonium hydroxide, trimethyl hydroxyethylammonium hydroxide, methyl tri (hydroxyethyl) ammonium hydroxide, tetra(hydroxyethyl)ammonium hydroxide, and benzyl trimethylammonium hydroxide.
  • Acids can also be optionally employed for pH adjustment in compositions of the invention.
  • the acids used can be of any suitable type, including, by way of example, formic acid, acetic acid, propanoic acid, butanoic acid, pentanoic acid, isovaleric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, lactic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, malic acid, fumaric acid, malonic acid, glutaric acid, glycolic acid, salicylic acid, 1,2,3-benzenetricarboxylic acid, tartaric acid, gluconic acid, citric acid, phthalic acid, pyrocatechoic acid, pyrogallol carboxylic acid, gallic acid, tannic acid, and mixtures including two or more acids of the foregoing or other types.
  • Amines when present can be of any suitable type, including, by way of example, hydroxylamine, monoethanolamine, diethanolamine, triethanolamine, diethyleneglycolamine, N- hydroxylethylpiperazine, N-methyletl anolamine, NN-dimethyletlianolamine, N-ethylethanolamine, NN-diethyletlianolamine, propanolamine, N,N-d ⁇ nemyl ⁇ ropanolamine, N-ethylpropanolamine, NN-dietliylpropanolainine, 4-(2-hydroxyeu ⁇ yl)mo ⁇ pholine, a inoetliylpiperazine, and mixtures including two or more of the foregoing or other amine species.
  • Surfactants when optionally employed in compositions of the invention can be of any suitable type, including non-ionic, anionic, cationic, and amphoteric surfactants, and polyelectrolytes including, for example: salts of organic acids; alkane sulfates (e.g., sodium dodecyl sulfate); alkane sulfonates; substituted amine salts (e.g., cetylpyridium bromide); betaines; polyethylene oxide; polyvinyl alcohol; polyvinyl acetate; polyacrylic acid; polyvinyl pyrrolidone; polyethyleneimine; and esters of anhydrosorbitols, such as those commercially available under the trademarks Tween ® and Span ® , as well as mixtures including two or more of the foregoing or other surfactant species.
  • alkane sulfates e.g., sodium dodecyl sulfate
  • the pH of CMP compositions of the invention can be at any suitable value that is efficacious for the specific polishing operation employed.
  • tire pH of the CMP composition can be in a range of from about 2 to about 11 , more preferably in a range of from about 2 to about 7.0, and most preferably in a range of from about 3 to about 6.
  • the solvents employed in CMP compositions of the invention can be single component solvents or multicomponent solvents, depending on tire specific application.
  • the solvent in tire CMP composition is water.
  • the solvent comprises an organic solvent, e.g., methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerin, etc.
  • the solvent comprises a water-alcohol solution.
  • a wide variety of solvent types and specific solvent media can be employed in the general practice of the invention to provide a solvating/suspending medium in which the abrasive is dispersed and in which the other components are incorporated to provide a composition of appropriate character, e.g., of slurry form, for application to the platen of the CMP unit to provide a desired level of polishing of the copper on the wafer substrate.
  • the invention provides a CMP composition useful for chemical mechanical polishing of substrates having copper thereon, e.g., copper interconnects, metallization, device structural elements, etc., in which the composition includes hydrogen peroxide, glycine, ATA, abrasive and solvent.
  • the CMP composition of tire invention is an aqueous slurry composition, and includes an aqueous medium, abrasive, ATA, H 2 0 2 and glycine, wherein ATA, H 2 0 2 and glycine have the following composition by weight, based on the total weight of the composition:
  • the CMP composition comprises the following components by weight, based on the total weight of the composition:
  • the CMP compositions of the invention can be readily formulated in a so-called 'day tank' or 'storage tank,' or the CMP composition can be provided as a two-part fonnulation or a multi-part formulation that is mixed at the point of use.
  • the advantage of a multi-part formulation resides in its extended shelf life, relative to single-package fomiulations.
  • a single package formulation is more susceptible to decomposition and change of its properties over time, in relation to a multi-part formulation, due to the presence of the oxidizer in the single-package CMP composition.
  • each single ingredient of the CMP composition is individually delivered to the polishing table for combination at the table with the other ingredients of the formulation, to constitute the CMP composition for use.
  • the CMP composition is formulated as a two-part composition in which the first part comprises abrasive and corrosion inliibitor in aqueous medium, and the second part comprises oxidizing agent and chelating agent.
  • the CMP composition is formulated as a two-part composition in which tlie first part comprises all components of the composition except the oxidizer, and the second part comprises the oxidizer.
  • tlie mixing of ingredients or parts to form the final composition occurs at the point of use, with mixing at the polishing table, polishing belt or tlie like, or in an appropriate container shortly before reaching the polishing table.
  • the copper CMP composition of tlie invention can be utilized in a conventional manner in tlie CMP operation, by application of tlie CMP composition to the copper surface on the wafer substrate in a conventional fashion, and polishing of the copper surface can be carried out using a conventional polishing element such as a polishing pad, polishing belt, or the like.
  • the CMP composition of tlie invention is advantageously employed to polish surfaces of copper elements on semiconductor substrates, without the occurrence of dishing or other adverse planarization deficiencies in the polished copper, even when significant amounts of copper ions, e.g., Cu 2+ ions, are present in the bulk CMP slurry composition and/or at the copper/CMP slurry interface during CMP processing.
  • CMP slurry compositions of tlie invention are highly effective for polishing copper on semiconductor wafer substrates, e.g., polishing of patterned copper wafers.
  • the CMP compositions of the invention can be readily prepared by mixing of ingredients in the desired single-package or multi-part formulations, consistent with Hie foregoing discussion herein of single-package and multipart formulations.
  • concentrations of the respective ingredients can be widely varied in specific formulations of the CMP composition, in the practice of the invention, and it will be appreciated that tlie CMP composition of the invention can variously and alternatively comprise, consist or consist essentially of any combination of ingredients consistent with the disclosure herein.
  • the features and advantages of the invention are more fully shown by the empirical examples and results discussed below. [0040] EXAMPLE 1 [0041]
  • Figure 1 is a graph of static etch rates of Cu metal, in Angstroms per minute, as a function of added copper sulfate (CuS0 4 '5H 2 0) concentration, in a H 2 0 2 /Glycine/Cu 2+ system at pH 3.5, with respective formulations incorporating the following ingredients: fonnulation (i) - 5% H 2 0 2 and 1% glycine, formulation (ii) - 5% H 2 0 2 , 1% glycine, and
  • Tlie corrosion potentials of ATA-containing solutions were measured, and determined to be constant within a range of from 0.28 to 0.35 volts when measured against a Ag/AgCl-in- saturated-KCl reference electrode.
  • slurry compositions were prepared with differing ATA concentrations.
  • a first part of tlie CMP formulation was delivered in slurry line 1
  • a second part of the CMP formulation was delivered in slurry line
  • Tlie first part of the CMP formulation in slurry line 1 contained 2% Nanotek alumina
  • aqueous medium deionized water
  • This first part of the CMP formulation was delivered to the platen at a flow rate of 125 mill-liters per minute.
  • Tlie second part of the CMP formulation in line 2 contained 10% hydrogen peroxide, 2% glycine, and ATA, in deionized water as the solvent, at a pH of 3.5.
  • the second part of the formulation was delivered to the platen at a flow rate of 125 milliliters per minute.
  • the concentration of ATA in such second part of the formulation was twice the concentration of the ATA desired in the final slurry, since the final slurry was produced by mixing tlie streams from slurry line 1 and slurry line 2 on tlie platen.
  • the final CMP composition produced by mixing the streams from slurry lines 1 and 2 therefore had a final composition of 5% hydrogen peroxide, 1% glycine, 1% ⁇ anotek alumina abrasive, and ATA, at a pH of 3.5.
  • Figure 2 is a graph of removal rate of copper metal, in Angstroms per minute, as a function of ATA concentration in wt%, based on the total weight of the slurry composition. The results show that the removal rates of copper in a range of about 2200 Angstroms per minute to about 4500 Angstroms per minute were achieved at ATA concentrations in a range of from 0.15 wt.% to 0.45 wt.%, with tlie rate of copper removal decreasing in a generally linear fashion over such ATA concentration range.
  • the polishing pad assembly included an ICIOOO polishing pad and a Suba IV subpad (commercially available from Rodel Corporation, Newark, Delaware). Polishing conditions included a 4 psi downforce, table and carrier speed of 90 rpm, and a slurry flow rate of 250 ml/min.
  • a Sematech (Austin, TX) 854 patterned wafer was used to investigate dishing of both isolated and array (50% pattern density) copper lines.
  • Formulation 1 contained 0.2% BTA, 1% alumina abrasive, 5% hydrogen peroxide and 1% glycine, at a pH of 3.5.
  • Formulation 2 contained 0.4% ATA, 2% glycine, 5% hydrogen peroxide and 1% alumina abrasive. The results showed a significant disparity between dishing in the isolated and array lines at endpoint (all Cu metal film was removed from the wafer) when BTA was used as the corrosion inhibitor (Formulation 1).

Abstract

A CMP composition containing 5-aminotetrazole, e.g., in combination with oxidizing agent, chelating agent, abrasive and solvent. Such CMP composition advantageously is devoid of BTA, and is useful for polishing surfaces of copper elements on semiconductor substrates, without the occurrence of dishing or other adverse planarization deficiencies in the polished copper, even in the presence of substantial levels of copper ions, e.g., Cu2+, in the bulk CMP composition at the copper/CMP composition interface during CMP processing.

Description

PASSIVATIVE CHEMICAL MECHANICAL POLISHING COMPOSITION FOR COPPER FILM PLANARIZATION
FIELD OF THE INVENTION
[0001] The present invention relates to a chemical mechanical polishing composition and to a method of using same for the polishing of semiconductor substrates having copper thereon, e.g., copper interconnects, electrodes, or metallization, as part of a semiconductor device structure on a wafer substrate.
DESCRIPTION OF THE RELATED ART
[0002] Copper is widely employed in semiconductor manufacturing as a material of construction for components of semiconductor device structures on wafer substrates (e.g., contacts, electrodes, conductive vias, field emitter base layers, etc.), and it is rapidly becoming the interconnect metal of choice in semiconductor manufacturing due to its higher conductivity and increased electromigration resistance relative to aluminum and aluminum alloys. [0003] Typically, the process scheme for utilizing copper in semiconductor manufacturing involves the damascene approach, wherein features are etched in a dielectric material. In the dual damascene process a single step is used to form both plugs and lines. Since copper has a propensity to diffuse into the dielectric material, leading to leakage between metal lines, barrier layers, such as Ta or TaN deposited by various deposition methods, are often used to seal the copper interconnects. Following deposition of the barrier layer material, a thin seed layer of copper is deposited on the barrier material via physical vapor deposition, followed by electrodeposition of copper to fill the features. The deposited copper must then be planarized to render it of suitable form to accommodate subsequent process steps in the fabrication of the finished semiconductor product, and in order to satisfactorily operate in the microcircuitry in which it is present. The planarization typically involves chemical mechanical polishing (CMP), using a CMP composition formulated for such purpose. [0004] Due to the difference in chemical reactivity between copper and the (Ta or TaN) barrier layer, two chemically distinct slurries are often used in the copper CMP process. The first step slurry (Step I) is used to rapidly planarize the topography and to uniformly remove the remaining copper, with the polish stopping at the barrier layer. The second step slurry (Step II) removes the barrier layer material at a high removal rate and stops on the dielectric oxide layer, or alternatively on a cap layer that has been applied to protect the oxide.
[0005] Step I chemical mechanical polishing (CMP) compositions for planarization and polishing of copper typically are in the form of slurries containing an abrasive of suitable type, e.g., an abrasive selected from among silica, alumina, and other oxides and mineralic materials, in a solvent medium containing one or more solvent species, e.g., water, organic solvents, etc. [0006] One type of CMP composition for planarizing copper surfaces includes an aqueous slurry of abrasive particles, containing hydrogen peroxide as an oxidizing component and glycine as a chelating agent. Glycine has been found to react with solution phase Cu+2 ions formed by oxidation of Cu metal to form a Cu2+-glycine complex. The complexing of Cu+2 ions through formation of a water soluble Cu2+-glycine chelate assists in removal of Cu in protruded regions via a direct dissolution mechanism, and the Cu2+-glycine complex decomposes hydrogen peroxide to yield hydroxyl radicals having a higher oxidation potential than hydrogen peroxide itself. [0007] In step I CMP slurries containing abrasive particles, hydrogen peroxide and glycine, the
compound benzotriazole (BTA) is often used as a corrosion inhibitor. BTA (
Figure imgf000004_0001
FW: 119.13) complexes with copper to form an insoluble Cu-BTA complex on the copper surface. The resulting insoluble protective film facilitates the planarization of the topography of the device structure being fabricated, since the recessed areas on the wafer surface are protected from dissolution, while mechanical action of the abrasive species on the protruding areas enables material removal and polishing to be carried out. Additionally, the Cu-BTA complex minimizes corrosion and preserves the functional integrity of the copper device structures for their intended use. [0008] BTA functions well as a copper corrosion inhibitor in the absence of OH radicals generated as a result of the Cu2+-glycine induced catalytic decomposition of hydrogen peroxide. However, in first step copper CMP slurries containing hydrogen peroxide and glycine, the foπnation of highly oxidizing OH radicals under dynamic CMP conditions cannot be avoided, since copper metal is readily oxidized in such CMP environment.
[0009] Experiments with the addition of Cu2+ to an H202/glycine/BTA system have shown that the presence of Cu2+ increases the static etch rate of Cu dramatically, and at the same time, the Cu corrosion potential is shifted to less noble ranges.
[0010] The significance of this finding is that BTA is not effective in protecting the low features of copper wafer surfaces during the CMP process, and thus allows "dishing" to occur in high-density patterned areas when Cu + cation is present in the CMP composition. [0011] An alternative to the use of BTA as a corrosion inhibitor in CMP compositions therefore is highly desirable. Specifically, an alternative corrosion inhibitor is desired, which is compatible with H202/glycine-based CMP compositions and effective to passivate copper surfaces when significant amounts of Cu ions are present in bulk solution and/or near the metal/solution interface during CMP processing.
SUMMARY OF THE INVENTION
[0010] The present invention relates to CMP compositions containing 5-aminotetrazole
(ATA,
Figure imgf000005_0001
} FW: 85.06), and to copper CMP using such compositions.
[0011] In one aspect, the invention relates to a CMP composition for planarization of copper films, in which the composition includes oxidizing agent, chelating agent, and corrosion inhibitor, and the corrosion inhibitor includes 5-aminotetrazole.
[0012] In a further aspect, the invention relates to a CMP composition for planarization of copper films. The composition comprises an aqueous slurry medium including abrasive, solvent,
ATA, H2O2 and glycine. In the composition, ATA, H202 and glycine have the following concentrations by weight, based on the total weight of the composition: ATA 0.01 - 10 wt.%
H202 1 - 30 wt.%
Glycine 0.1 - 25 wt.%.
[0013] Yet another aspect of the invention relates to a CMP composition including the following components by weight, based on the total weight of the composition:
ATA 0.01 - 10 wt.%
H202 1 - 30 wt.%
Glycine 0.1 - 25 wt.%.
Abrasive 0 - 30 wt.%
Water 30 - 90 wt.% with the total wt.% of all components in the composition totaling to 100 wt.%. [0014] Still another aspect of the invention relates to a method of polishing copper on a substrate having copper thereon, including contacting copper on the substrate under CMP conditions with a CMP composition effective for polishing the copper, wherein the CMP composition includes ATA.
[0015] Other aspects, features and embodiments of the invention will be more fully apparent from the ensuing disclosure and appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 is a graph of static etch rates of copper metal, in Angstroms per minute, as a function of added copper sulfate (CuS04 #5H20) concentration, in a H202/Glycine/Cu2+ system at pH
3.5, for (i) 5% H202 and 1% glycine, (ii) 5% H202, 1% glycine, and 0.15% BTA, (iii) 5% H202, 1% glycine, and 0.15% 5-aιτrinotetrazole monohydrate, and (iv) 5% H202, 1% glycine, and 0.15% 1- hydroxybenzotriazole.
[0017] Figure 2 is a graph of removal rate of copper metal, in Angstroms per minute, as a function of ATA concentration in wt%, based on the total weight of the CMP slurry composition. DETAILED DESCRIPTION OF THE INVENTION. AND PREFERRED EMBODIMENTS
THEREOF
[0018] The present invention is based on the discovery that 5-aminotetrazole
(ATA,
Figure imgf000007_0001
s pw: 85.06) is unexpectedly effective as a replacement for BTA as a copper corrosion inhibitor in CMP compositions for planarizing copper films. ATA is compatible with
CMP compositions containing hydrogen peroxide as an oxidizer and glycine as a chelator. The
ATA-containing CMP composition achieves active passivation of copper surfaces even when significant amounts of copper ions, e.g., Cu2+ cations, are present in bulk solution and/or at the metal/solution interface during CMP processing.
[0019] The ATA-containing CMP composition of the invention, in its broad contemplation, can be formulated with any suitable constituents, including any appropriate oxidizing agent(s), chelating agent(s), and corrosion inhibitor(s), abrasive media, solvent media, and optionally any suitable additives, adjuvants, excipients, etc., such as stabilizing agents, acids, bases (e.g., amines), surfactants, buffering agents, etc.
[0020] Oxidizing agents employed in the broad practice of the invention can be of any suitable type, including for example ferric nitrate, ferric ammonium oxalate, ferric ammonium citrate, permanganate salts (e.g., potassium permanganate), peroxyacids (e.g. peracetic acid), peroxoborate salts (e.g., potassium peroxoborate), urea-hydrogen peroxide, iodate salts (e.g., potassium iodate), perchlorate salts (e.g. tetrametliylammonium perchlorate), persulfate salts, bromate salts, benzoquinone, chlorate salts, chlorite salts, hypochlorite salts, hypoiodite salts, oxybromide salts, percarbonate salts, periodate salts, eerie salts (e.g., ammonium eerie sulfate), chromate and dichromate compounds, cupricyanide and ferricyanide salts, ferriphenanthroline, ferripyridine and ferrocinium. Preferred oxidizers include peracetic acid, urea-hydrogen peroxide, di-t-butyl peroxide, benzyl peroxide, hydrogen peroxide and compatible mixtures including two or more of such oxidizer species.
[0021] Chelating agents in tire CMP compositions of the invention can be of any appropriate type, including, for example: glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, lysine, etc.; polyamine complexes and their salts, including ethylenedi-iminetetraacetic acid, N-hydroxyethylemylenediaminetriacetic acid, nitrilotriacetic acid, iminodiacetic acid, diemylenefriaminepentaacetic acid, and ethanoldiglycinate; polycarboxylic acids, including phtlialic acid, oxalic acid, malic acid, succinic acid, mandelic acid, and mellitic acid; and compatible mixtures including two or more of the foregoing species. Preferred chelating agents include arnino acids, with glycine being most preferred.
[0022] ATA is employed in CMP compositions of the invention in any suitable concentration. Suitable concentration of ATA in a specific formulation is readily empirically determinable within the skill of the art, based on the disclosure herein, to provide a CMP composition with suitable copper surface passivation characteristics even in CMP environments containing high levels of copper cations. In one preferred embodiment of the invention, the amount of ATA in the CMP composition is in a range of from about 0.01 to about 10% by weight, based on the total weight of the CMP composition, with an amount of ATA in a range of from about 0.05 to about 5% by weight being more preferred, an amount of ATA in a range of from about 0.10 to about 1.0% by weight being even more preferred, and an amount of ATA in a range of from about 0.2 to 0.8% by weight being most preferred, on the same total weight basis, although greater or lesser percentages may be employed to advantage in specific applications within the broad scope of tire present invention. [0023] The corrosion inhibitor component in the CMP composition of the invention comprises
ATA, and can additionally include other corrosion inhibitor components in combination with ATA, in specific embodiments of the invention. Such other corrosion inhibitor components may be of any suitable type, including for example, imidazole, benzotriazole, benzimidazole, arnino, imino, carboxy, mercapto, nitro, alkyl, urea and thiourea compounds and derivatives, etc. Preferred inhibitors include tetrazoles and their derivatives, and the invention therefore contemplates the provision of ATA alone or in combination with other tetrazole (or other corrosion inhibitor) species, as the corrosion inhibitor in compositions according to the present invention. [0024] The abrasive can be of any suitable type, including, without limitation, metal oxides, silicon nitrides, carbides, etc. Specific examples include silica, alumina, silicon carbide, silicon nitride, iron oxide, ceria, zirconium oxide, tin oxide, titanium dioxide, and mixtures of two or more of such components in suitable form, such as grains, granules, particles, or other divided form. Alternatively, the abrasive can include composite particles formed of two or more materials, e.g., NYACOL® alumina-coated colloidal silica (Nyacol Nano Technologies, Inc., Ashland, MA). Alumina is a preferred inorganic abrasive and can be employed in the form of boehmite or transitional δ, θ or γ phase alumina. Organic polymer particles, e.g., including thermoset and/or thermoplastic resin(s), can be utilized as abrasives. Useful resins in the broad practice of the present invention include epoxies, urethanes, polyesters, polyamides, polycarbonates, polyolefins, polyvinylchloride, polystyrenes, polyolefins, and (meth)acryrics. Mixtures of two or more organic polymer particles can be used as the abrasive medium, as well as particles comprising both inorganic and organic components.
[0025] Bases can be optionally employed for pH adjustment in compositions of the invention. Illustrative bases include, by way of example, potassium hydroxide, ammonium hydroxide and tefr-rmemylammoniumhydroxide (TMAH), tetraethylammonium hydroxide, trimethyl hydroxyethylammonium hydroxide, methyl tri (hydroxyethyl) ammonium hydroxide, tetra(hydroxyethyl)ammonium hydroxide, and benzyl trimethylammonium hydroxide. [0026] Acids can also be optionally employed for pH adjustment in compositions of the invention. The acids used can be of any suitable type, including, by way of example, formic acid, acetic acid, propanoic acid, butanoic acid, pentanoic acid, isovaleric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, lactic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, malic acid, fumaric acid, malonic acid, glutaric acid, glycolic acid, salicylic acid, 1,2,3-benzenetricarboxylic acid, tartaric acid, gluconic acid, citric acid, phthalic acid, pyrocatechoic acid, pyrogallol carboxylic acid, gallic acid, tannic acid, and mixtures including two or more acids of the foregoing or other types.
[0027] Amines when present can be of any suitable type, including, by way of example, hydroxylamine, monoethanolamine, diethanolamine, triethanolamine, diethyleneglycolamine, N- hydroxylethylpiperazine, N-methyletl anolamine, NN-dimethyletlianolamine, N-ethylethanolamine, NN-diethyletlianolamine, propanolamine, N,N-dύnemylρropanolamine, N-ethylpropanolamine, NN-dietliylpropanolainine, 4-(2-hydroxyeuιyl)moιpholine, a inoetliylpiperazine, and mixtures including two or more of the foregoing or other amine species.
[0028] Surfactants when optionally employed in compositions of the invention can be of any suitable type, including non-ionic, anionic, cationic, and amphoteric surfactants, and polyelectrolytes including, for example: salts of organic acids; alkane sulfates (e.g., sodium dodecyl sulfate); alkane sulfonates; substituted amine salts (e.g., cetylpyridium bromide); betaines; polyethylene oxide; polyvinyl alcohol; polyvinyl acetate; polyacrylic acid; polyvinyl pyrrolidone; polyethyleneimine; and esters of anhydrosorbitols, such as those commercially available under the trademarks Tween® and Span®, as well as mixtures including two or more of the foregoing or other surfactant species.
[0029] The pH of CMP compositions of the invention can be at any suitable value that is efficacious for the specific polishing operation employed. In one embodiment, tire pH of the CMP composition can be in a range of from about 2 to about 11 , more preferably in a range of from about 2 to about 7.0, and most preferably in a range of from about 3 to about 6.
[0030] The solvents employed in CMP compositions of the invention can be single component solvents or multicomponent solvents, depending on tire specific application. In one embodiment of the invention, the solvent in tire CMP composition is water. In another embodiment, the solvent comprises an organic solvent, e.g., methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerin, etc. In yet another embodiment, the solvent comprises a water-alcohol solution. A wide variety of solvent types and specific solvent media can be employed in the general practice of the invention to provide a solvating/suspending medium in which the abrasive is dispersed and in which the other components are incorporated to provide a composition of appropriate character, e.g., of slurry form, for application to the platen of the CMP unit to provide a desired level of polishing of the copper on the wafer substrate.
[0031] In one embodiment, the invention provides a CMP composition useful for chemical mechanical polishing of substrates having copper thereon, e.g., copper interconnects, metallization, device structural elements, etc., in which the composition includes hydrogen peroxide, glycine, ATA, abrasive and solvent. [0032] In another embodiment, the CMP composition of tire invention is an aqueous slurry composition, and includes an aqueous medium, abrasive, ATA, H202 and glycine, wherein ATA, H202 and glycine have the following composition by weight, based on the total weight of the composition:
ATA 0.01 - 10 wt.%
H202 1 - 30 wt.%
Glycine 0.1 - 25 wt.%.
[0033] In a further specific illustrative embodiment, the CMP composition comprises the following components by weight, based on the total weight of the composition:
ATA 0.01 - 10 wt.%
H202 1 - 30 wt.%
Glycine 0.1 - 25 wt.%.
Abrasive 0 - 30 wt.%
Water 30 - 90 wt.% with the total wt.% of all components in the composition totaling to 100 wt.%. [0034] The CMP compositions of the invention can be readily formulated in a so-called 'day tank' or 'storage tank,' or the CMP composition can be provided as a two-part fonnulation or a multi-part formulation that is mixed at the point of use. The advantage of a multi-part formulation resides in its extended shelf life, relative to single-package fomiulations. A single package formulation is more susceptible to decomposition and change of its properties over time, in relation to a multi-part formulation, due to the presence of the oxidizer in the single-package CMP composition. The individual parts of the multi-part fomiulation can be mixed at the polishing table, polishing belt or the like, or in an appropriate container shortly before reaching the polishing table. [0035] In one embodiment, each single ingredient of the CMP composition is individually delivered to the polishing table for combination at the table with the other ingredients of the formulation, to constitute the CMP composition for use. In another embodiment, the CMP composition is formulated as a two-part composition in which the first part comprises abrasive and corrosion inliibitor in aqueous medium, and the second part comprises oxidizing agent and chelating agent. In still another embodiment, the CMP composition is formulated as a two-part composition in which tlie first part comprises all components of the composition except the oxidizer, and the second part comprises the oxidizer. In all of these various embodiments, tlie mixing of ingredients or parts to form the final composition occurs at the point of use, with mixing at the polishing table, polishing belt or tlie like, or in an appropriate container shortly before reaching the polishing table. [0036] The copper CMP composition of tlie invention can be utilized in a conventional manner in tlie CMP operation, by application of tlie CMP composition to the copper surface on the wafer substrate in a conventional fashion, and polishing of the copper surface can be carried out using a conventional polishing element such as a polishing pad, polishing belt, or the like. [0037] The CMP composition of tlie invention is advantageously employed to polish surfaces of copper elements on semiconductor substrates, without the occurrence of dishing or other adverse planarization deficiencies in the polished copper, even when significant amounts of copper ions, e.g., Cu2+ ions, are present in the bulk CMP slurry composition and/or at the copper/CMP slurry interface during CMP processing.
[0038] CMP slurry compositions of tlie invention are highly effective for polishing copper on semiconductor wafer substrates, e.g., polishing of patterned copper wafers. The CMP compositions of the invention can be readily prepared by mixing of ingredients in the desired single-package or multi-part formulations, consistent with Hie foregoing discussion herein of single-package and multipart formulations. The concentrations of the respective ingredients can be widely varied in specific formulations of the CMP composition, in the practice of the invention, and it will be appreciated that tlie CMP composition of the invention can variously and alternatively comprise, consist or consist essentially of any combination of ingredients consistent with the disclosure herein. [0039] The features and advantages of the invention are more fully shown by the empirical examples and results discussed below. [0040] EXAMPLE 1 [0041]
In a comparative test of CMP slurry compositions, Cu corrosion rates were determined by electrochemical methods and are shown in Figure 1 as a function of Cu2+ concentration, with various corrosion inhibitors being tested. More specifically, Figure 1 is a graph of static etch rates of Cu metal, in Angstroms per minute, as a function of added copper sulfate (CuS04'5H20) concentration, in a H202/Glycine/Cu2+ system at pH 3.5, with respective formulations incorporating the following ingredients: fonnulation (i) - 5% H202 and 1% glycine, formulation (ii) - 5% H202, 1% glycine, and
0.15% BTA, formulation (iii) - 5% H202, 1% glycine, and 0.15% 5-aminotetrazole monohydrate, and formulation (iv) - 5% H202, 1% glycine, and 0.15% 1-hydroxybenzotriazole.
[0042] The results shown in Figure 1 reveal significant increase in corrosion rate with increasing concentration of Cu2+ as copper sulfate pentahydrate (CuS04«5H20) is added to the formulations (i), (ii) and (iv). By contrast, the passivation effect of ATA in composition (iii) is almost independent of tlie Cu2+ concentration change, compared to the formulations containing BTA and hydroxy-BTA. ATA thus provides an unexpected substantial improvement over BTA in the copper CMP slurry composition, and tlie results evidence tlie utility of ATA as a corrosion inhibitor that enables stable, consistent polishing of the copper on the microelectronic substrate to be achieved.
[0043] EXAMPLE 2
[0044] Tlie corrosion potentials of ATA-containing solutions were measured, and determined to be constant within a range of from 0.28 to 0.35 volts when measured against a Ag/AgCl-in- saturated-KCl reference electrode. These results show that copper is thermodynamically more stable in H202/glycine/ATA compositions than in H202/glycine compositions, since in the latter composition lacking ATA, the corrosion potential of copper was 0.17 volts when measured against a
Ag/AgCl-in-saturated-KCl reference electrode.
[0045] EXAMPLE 3
[0046] To evaluate ATA inliibitor-containing CMP slurries of the invention, slurry compositions were prepared with differing ATA concentrations. A first part of tlie CMP formulation was delivered in slurry line 1, and a second part of the CMP formulation was delivered in slurry line
2. The respective parts then were mixed on the platen of tlie CMP device to produce tlie CMP composition. [0047] Tlie first part of the CMP formulation in slurry line 1 contained 2% Nanotek alumina
(commercially available from Νanophase Technologies Corporation, Romeoville, Illinois) in an aqueous medium (deionized water) at a pH of 3.5. This first part of the CMP formulation was delivered to the platen at a flow rate of 125 mill-liters per minute. Tlie second part of the CMP formulation in line 2 contained 10% hydrogen peroxide, 2% glycine, and ATA, in deionized water as the solvent, at a pH of 3.5. The second part of the formulation was delivered to the platen at a flow rate of 125 milliliters per minute. The concentration of ATA in such second part of the formulation was twice the concentration of the ATA desired in the final slurry, since the final slurry was produced by mixing tlie streams from slurry line 1 and slurry line 2 on tlie platen. [0048] The final CMP composition produced by mixing the streams from slurry lines 1 and 2 therefore had a final composition of 5% hydrogen peroxide, 1% glycine, 1% Νanotek alumina abrasive, and ATA, at a pH of 3.5.
[0049] Copper-coated silicon wafers, with the film stack comprising c-Si bulk / 5,000
Angstroms TEOS Si02 / 250 Angstroms Ta liner / 1,000 Angstroms PVD Cu seed / 15,000 Angstroms ECD Cu, were polished using the respective slurry compositions of differing concentrations of ATA, and the removal rate of copper from tlie coated wafer using each of the respective slurry compositions was measured utilizing a 4-point probe. The results are shown in Figure 2.
[0050] Figure 2 is a graph of removal rate of copper metal, in Angstroms per minute, as a function of ATA concentration in wt%, based on the total weight of the slurry composition. The results show that the removal rates of copper in a range of about 2200 Angstroms per minute to about 4500 Angstroms per minute were achieved at ATA concentrations in a range of from 0.15 wt.% to 0.45 wt.%, with tlie rate of copper removal decreasing in a generally linear fashion over such ATA concentration range. [0051] EXAMPLE 4
[0052] Dishing of 10 micron copper lines was studied, using a Strasbaugh 6EC polishing tool
(commercially available from Strasbaugh Corporation, San Luis Obispo, California). The polishing pad assembly included an ICIOOO polishing pad and a Suba IV subpad (commercially available from Rodel Corporation, Newark, Delaware). Polishing conditions included a 4 psi downforce, table and carrier speed of 90 rpm, and a slurry flow rate of 250 ml/min. A Sematech (Austin, TX) 854 patterned wafer was used to investigate dishing of both isolated and array (50% pattern density) copper lines.
[0053] Two aqueous slurry copper CMP formulations were tested. Formulation 1 contained 0.2% BTA, 1% alumina abrasive, 5% hydrogen peroxide and 1% glycine, at a pH of 3.5. Formulation 2 contained 0.4% ATA, 2% glycine, 5% hydrogen peroxide and 1% alumina abrasive. The results showed a significant disparity between dishing in the isolated and array lines at endpoint (all Cu metal film was removed from the wafer) when BTA was used as the corrosion inhibitor (Formulation 1). When ATA replaced BTA as tlie corrosion inliibitor (Formulation 2), both the isolated and array 10 micron lines were dished to the same extent at endpoint of the CMP polishing operation, and tlie overall extent of dishing was substantially reduced.
[0054] While the invention has been described herein in reference to specific aspects, features and illustrative embodiments of the invention, it will be appreciated that the utility of the invention is not thus limited, but rather extends to and encompasses numerous other variations, modifications and alternative embodiments, as will suggest themselves to those of ordinary skill in the field of the present invention, based on the disclosure herein. Correspondingly, the invention as hereinafter claimed is intended to be broadly construed and interpreted, as including all such variations, modifications and alternative embodiments, within its spirit and scope.

Claims

THE CLAIMSWhat is claimed is:
1. A CMP composition, including 5-aminotetrazole.
2. The CMP composition of claim 1, further including oxidizing agent.
3. The CMP composition of claim 2, wherein the oxidizing agent comprises at least one agent selected from tlie group consisting of ferric nitrate, ferric ammonium oxalate, ferric ammonium citrate, permanganate salts, peroxyacids, peroxoborate salts, urea-hydrogen peroxide, iodate salts, perchlorate salts, persulfate salts, bromate salts, benzoquinone, chlorate salts, chlorite salts, hypochlorite salts, hypoiodite salts, oxybromide salts, percarbonate salts, periodate salts, eerie salts, cliromate and dicliromate compounds, cupricyanide and ferricyanide salts, ferriphenanthroline, fempyridine and ferrocinium.
4. Ηie CMP composition of claim 3, wherein the oxidizing agent comprises at least one agent selected from the group consisting of potassium permanganate, peracetic acid, potassium peroxoborate, potassium iodate, tetramethylammonium perchlorate, and ammonium eerie sulfate.
5. Ηie CMP composition of claim 2, wherein the oxidizing agent comprises at least one agent selected from the group consisting of peracetic acid, urea-hydrogen peroxide, di-t-butyl peroxide, benzyl peroxide, and hydrogen peroxide.
6. Ηie CMP composition of claim 2, wherein the oxidizing agent comprises at least one agent selected from tlie group consisting of ferric nitrate and hydrogen peroxide.
7. The CMP composition of claim 2, wherein tlie oxidizing agent comprises hydrogen peroxide.
8. The CMP composition of claim 1, further including chelating agent.
9. The CMP composition of claim 8, wherein the chelatmg agent comprises at least one agent selected from tlie group consisting of arnino acids, polyamine complexes and tlieir salts, and polycarboxylic acids.
10. Ηie CMP composition of claim 9, wherein the chelating agent comprises at least one agent selected from the group consisting of glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, lysine, etliylenediaminetetraacetic acid, N- hydroxyetliylethylenediaminetriacetic acid, nitrilotriacetic acid, diethylenefri-tminepentaacetic acid, etlianoldiglycinate, phtlialic acid, oxalic acid, malic acid, succinic acid, mandelic acid, and mellitic acid.
11. Ηie CMP composition of claim 9, wherein the chelating agent comprises at least one arnino acid.
12. Tlie CMP composition of claim 11, wherein tlie chelating agent comprises glycine.
13. Ηie CMP composition of claim 1, wherein tlie composition does not contain BTA.
14. The CMP composition of claim 1, wherein ATA has a concentration of from about 0.01 to about 10% by weight, based on total weight of the CMP composition.
15. The CMP composition of claim 1, wherein ATA has a concentration of from about 0.05 to about 5% by weight, based on total weight of tlie CMP composition.
16. Ηie CMP composition of claim 1, wherein ATA has a concentration of from about 0.1 to about 1.0% by weight, based on total weight of the CMP composition.
17. Ηie CMP composition of claim 1, wherein ATA has a concentration of from about 0.2 to about 0.8% by weight, based on total weight of tlie CMP composition.
18. Ηie CMP composition of claim 1, further comprising another corrosion inhibitor in combination with ATA.
19. The CMP composition of claim 18, wherein said another corrosion inhibitor comprises at least one inhibitor selected from tlie group consisting of imidazole, benzotriazole, benzimidazole, arnino, imino, carboxy, mercapto, nitro, alkyl, urea and thiourea compounds and derivatives.
20. Ηie CMP composition of claim 18, wherein said another corrosion inhibitor comprises at least one inhibitor selected from tlie group consisting of tetrazoles other than ATA, and their derivatives.
21. The CMP composition of claim 1, further comprising abrasive.
22. The CMP composition of claim 21, wherein the abrasive comprises at least one abrasive selected from tlie group consisting of metal oxides, silicon nitrides, and carbides.
23. The CMP composition of claim 21, wherein the abrasive comprises at least one abrasive selected from the group consisting of silica, alumina, silicon carbide, silicon nitride, iron oxide, ceria, zirconium oxide, tin oxide, titanium dioxide, and alumina-coated colloidal silica.
24. Ηie CMP composition of claim 21, wherein tlie abrasive is in divided form.
25. Ηie CMP composition of claim 24, wherein the abrasive is in particulate form.
26. Ηie CMP composition of claim 21, wherein the abrasive comprises alumina.
27. Tlie CMP composition of claim 26, wherein tlie alumina includes at least one form selected from tlie group consisting of boelimite and transitional δ, θ and γphase alumina forms.
28. Tlie CMP composition of claim 21, wherein tlie abrasive comprises composite particles formed of at least two materials.
29. The CMP composition of claim 21, wherein the abrasive comprises organic polymer particles.
30. Tlie CMP composition of claim 29, wherein tlie organic polymer particles are formed of at least one material selected from the group consisting of thermoset resins and thermoplastic resins.
31. Ηie CMP composition of claim 29, wherein the organic polymer particles comprise particles formed of at least two different materials.
32. The CMP composition of claim 21, wherein the abrasive comprises particles including both inorganic and organic components.
33. The CMP composition of claim 21, wherein the abrasive comprises particles formed of at least one resin selected from tlie group consisting of epoxies, urethanes, polyesters, polyamides, polycarbonates, polyolefins, polyvinylchloride, polystyrenes, polyolefins, and (meth)acrylic resins.
34. Tlie CMP composition of claim 1, further comprising a pH adjustment agent.
35. Ηie CMP composition of claim 34, wherein the pH adjustment agent comprises at least one acid.
36. Ηie CMP composition of claim 35, wherein the at least one acid comprises at least one acid selected from the group consisting of formic acid, acetic acid, propanoic acid, butanoic acid, pentanoic acid, isovaleric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, lactic acid, hydrochloric acid, nitric acid, phosphoric acid, ->uι-.-uι aciα, nyαronuoπc aciα, malic acid, fumaric acid, malonic acid, glutaric acid, glycolic acid, salicylic acid, 1,2,3-benzenetricarboxylic acid, tartaric acid, gluconic acid, citric acid, phthalic acid, pyrocatechoic acid, pyrogallol carboxylic acid, gallic acid, and tannic acid.
37. Ηie CMP composition of claim 34, wherein the pH adjustment agent comprises at least one base.
38. The CMP composition of claim 37, wherein the at least one base comprises at least one base selected from tlie group consisting of potassium hydroxide, ammonium hydroxide, tefrεu iethylammoniumliydroxide, tetraethylammonium hydroxide, trimethyl hydroxyetiiylammonium hydroxide, metliyl tri (hydroxyethyl) ammonium hydroxide, tetra(hydroxyethyl)ammonium hydroxide, and benzyl trimethylammonium hydroxide.
39. The CMP composition of claim 1, further comprising at least one amine.
40. The CMP composition of claim 39, wherein said at least one amine comprises at least one amine selected from the group consisting of hydroxylamine, monoem-molamine, diemanolamine, trietlianolamine, diethyleneglycolamine, N-hydroxylethylpiperazine, N-memyleth-mol-tniine, N,N- dimethylethanolamine, N-ethylethanolamine, NN-diethylethanolamine, propanolamine, N,N- dimethylpiOpanolamine, N-ethylpropanolamine, NN-diethylpropanolamine, 4-(2- hydroxyetlιyl)moφholine, and aminoethylpiperazine.
41. Ηie CMP composition of claim 1, further comprising at least one surfactant.
42. Ηie CMP composition of claim 41, wherein said at least one surfactant comprises at least one surfactant selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and polyelectrolytes.
43. The CMP composition of claim 41, wherein said at least one surfactant comprises at least one surfactant selected from tlie group consisting of: salts of organic acids; alkane sulfates; alkane sulfonates; substituted amine salts; betaines; polyethylene oxide; polyvinyl alcohol; polyvinyl acetate; polyacrylic acid; polyvinyl pyrrolidone; polyetliyleneimine; and esters of anhydrosorbitols.
44. Ηie CMP composition of claim 41, wherein said at least one surfactant comprises at least one surfactant selected from the group consisting of: sodium dodecyl sulfate and cetylpyridium bromide.
45. Ηie CMP composition of claim 1 , having a pH in a range of from about 2 to about 11.
46. The CMP composition of claim 1 , having a pH in a range of from about 2 to about 7.0.
47. Ηie CMP composition of claim 1, having a pH in a range of from about 3 to about 6.
48. Ηie CMP composition of claim 1, further comprising solvent.
49. Ηie CMP composition of claim 48, wherein the solvent comprises a single component solvent.
50. Tlie CMP composition of claim 48, wherein tlie solvent comprises a multicomponent solvent.
51. Tlie CMP composition of claim 48, wherein tlie solvent comprises at least one organic solvent.
52. Ηie CMP composition of claim 51, wherein the at least one organic solvent comprises at least one solvent selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, and glycerin.
53. Ηie CMP composition of claim 51, wherein tlie at least one organic solvent comprises at least one solvent selected from the group consisting of hydroxy-containing solvents.
54. The CMP composition of claim 48, wherein tl e solvent comprises at least one alcohol.
55. Ηie CMP composition of claim 48, wherein tlie solvent comprises at least one glycol solvent.
56. Ηie CMP composition of claim 48, wherein the solvent comprises water.
57. The CMP composition of claim 48, wherein the solvent comprises water and alcohol.
58. The CMP composition of claim 1, further comprising an oxidation inhibitor including at least one inhibitor selected from the group consisting of carboxylic acids and azole compounds other than ATA and BTA.
59. A CMP composition, comprising abrasive, solvent, ATA, H202 and glycine, wherein ATA, H202 and glycine have the following concentrations by weight, based on total weight of the composition:
ATA 0.01 - 10 wt.%
H202 1 - 30 wt.%
Glycine 0.1 - 25 wt.%.
60. A CMP composition comprising the following components by weight, based on total weight of the composition:
ATA 0.01 - 10 wt.%
H202 1 - 30 wt.%
Glycine 0.1 - 25 wt.%
Abrasive 0 - 30 wt.%
Water 30 - 90 wt.% with total wt.% of all components in tlie composition totaling to 100 wt.%.
61. The CMP composition of claim 60, wherein said abrasive comprises silica.
62. The CMP composition of claim 1, comprising a two-part formulation including a first part comprising abrasive and ATA in an aqueous medium, and a second part comprising oxidizing agent and chelating agent.
63. The CMP composition of claim 1, comprising a two-part formulation including a first part comprising abrasive, chelating agent and ATA in an aqueous medium, and a second part comprising oxidizing agent.
64. The CMP composition of claim 1, comprising abrasive, ATA, solvent, oxidizing agent and chelating agent, in a single package formulation.
65. A method of polishing copper on a substrate having copper thereon, including contacting copper on the substrate under CMP conditions with a CMP composition effective for polishing the copper, wherein tlie CMP composition includes ATA.
66. The method of claim 65, wherein said CMP conditions comprise use of a polishing element on said copper contacted with said CMP composition, wherein said polishing element includes at least one element selected from tlie group consisting of polishing pads and polishing belts.
67. Ηie method of claim 65, wherein said CMP composition further comprises abrasive, oxidizing agent, chelating agent and solvent.
68. The method of claim 65, wherein said CMP composition further comprises hydrogen peroxide, glycine, abrasive and water.
69. The metliod of claim 65, wherein said copper is on a semiconductor substrate and forms a constituent element of a microelectronic device.
70. Tlie method of claim 69, wherein said constituent element is selected from tlie group consisting of interconnects, contacts, conductive vias, metallization, electrodes, and conductive base layers for field emitter components.
71. The metliod of claim 65, wherein said CMP composition comprises abrasive, solvent, ATA, H202 and glycine, wherein ATA, H202 and glycine have the following concentrations by weight, based on total weight of tlie composition:
ATA 0.01 - 10 wt.%
H202 1 - 30 wt.%
Glycine 0.1 - 25 wt.%.
72. Ηie method of claim 65, wherein said CMP composition comprises Hie following components by weight, based on the total weight of the composition:
ATA 0.01 - 10 wt.%
H202 1 - 30 wt.%
Glycine 0.1 - 25 wt.%
Abrasive 0 - 30 wt.%
Water 30 - 90 wt.% with total wt.% of all components in the composition totaling to 100 wt.%.
73. Η e metliod of claim 65, wherein said contacting is conducted on a polishing table.
74. The metliod of claim 65, wherein said contacting is conducted with a polishing belt contacting tlie surface.
75. The metliod of claim 65, wherein tlie CMP composition comprises a two-part formulation including a first part comprising abrasive and ATA in an aqueous medium, and a second part comprising oxidizing agent and chelating agent, said metliod further comprising mixing the first part and tlie second part to produce said CMP composition.
76. The metliod of claim 65, wherein the CMP composition comprises a two-part formulation including a first part comprising abrasive, chelating agent and ATA in an aqueous medium, and a second part comprising oxidizing agent, said metliod further comprising mixing the first part and the second part to produce said CMP composition.
77. Ηie method of claim 65, wherein the CMP composition comprises abrasive, ATA, solvent, oxidizing agent and chelating agent, in a single package formulation.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008069781A1 (en) * 2006-12-04 2008-06-12 Basf Se Planarization composition for metal surfaces comprising an alumina hydrate abrasive
JP2010534934A (en) * 2007-07-26 2010-11-11 キャボット マイクロエレクトロニクス コーポレイション Compositions and methods for chemically and mechanically polishing phase change materials
CN102604542A (en) * 2012-02-21 2012-07-25 复旦大学 Polishing solution used in polishing process with metal ruthenium as adhesive barrier layer in copper interconnection
CN104449564A (en) * 2013-09-23 2015-03-25 中芯国际集成电路制造(上海)有限公司 Monodisperse grinding fluid and preparation method thereof and method for preparing inorganic oxide sol

Families Citing this family (143)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040175942A1 (en) * 2003-01-03 2004-09-09 Chang Song Y. Composition and method used for chemical mechanical planarization of metals
US7736405B2 (en) * 2003-05-12 2010-06-15 Advanced Technology Materials, Inc. Chemical mechanical polishing compositions for copper and associated materials and method of using same
US8158532B2 (en) * 2003-10-20 2012-04-17 Novellus Systems, Inc. Topography reduction and control by selective accelerator removal
US7972970B2 (en) * 2003-10-20 2011-07-05 Novellus Systems, Inc. Fabrication of semiconductor interconnect structure
US8372757B2 (en) 2003-10-20 2013-02-12 Novellus Systems, Inc. Wet etching methods for copper removal and planarization in semiconductor processing
TWI244498B (en) * 2003-11-20 2005-12-01 Eternal Chemical Co Ltd Chemical mechanical abrasive slurry and method of using the same
US20050189322A1 (en) * 2004-02-27 2005-09-01 Lane Sarah J. Compositions and methods for chemical mechanical polishing silica and silicon nitride
US20050279964A1 (en) * 2004-06-17 2005-12-22 Ming-Tseh Tsay Chemical mechanical polishing slurry for polishing copper layer on a wafer
US20060000808A1 (en) * 2004-07-01 2006-01-05 Fuji Photo Film Co., Ltd. Polishing solution of metal and chemical mechanical polishing method
US7144599B2 (en) 2004-07-15 2006-12-05 Birchwood Laboratories, Inc. Hybrid metal oxide/organometallic conversion coating for ferrous metals
US20060021972A1 (en) * 2004-07-28 2006-02-02 Lane Sarah J Compositions and methods for chemical mechanical polishing silicon dioxide and silicon nitride
US8178482B2 (en) * 2004-08-03 2012-05-15 Avantor Performance Materials, Inc. Cleaning compositions for microelectronic substrates
KR100672941B1 (en) * 2004-10-06 2007-01-24 삼성전자주식회사 Solution of inhibiting Copper erosion and CMP process using the solution
JP5026665B2 (en) * 2004-10-15 2012-09-12 株式会社フジミインコーポレーテッド Polishing composition and polishing method using the same
US20060116313A1 (en) * 2004-11-30 2006-06-01 Denise Geitz Compositions comprising tannic acid as corrosion inhibitor
US20060124026A1 (en) * 2004-12-10 2006-06-15 3M Innovative Properties Company Polishing solutions
US7446046B2 (en) * 2005-01-06 2008-11-04 Intel Corporation Selective polish for fabricating electronic devices
US7427362B2 (en) * 2005-01-26 2008-09-23 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Corrosion-resistant barrier polishing solution
KR20060101396A (en) * 2005-03-17 2006-09-22 후지 샤신 필름 가부시기가이샤 Metal polishing solution and polishing method
US20060216935A1 (en) * 2005-03-28 2006-09-28 Ferro Corporation Composition for oxide CMP in CMOS device fabrication
US7467988B2 (en) * 2005-04-08 2008-12-23 Ferro Corporation Slurry composition and method for polishing organic polymer-based ophthalmic substrates
US7294044B2 (en) * 2005-04-08 2007-11-13 Ferro Corporation Slurry composition and method for polishing organic polymer-based ophthalmic substrates
US20110045741A1 (en) * 2005-04-28 2011-02-24 Techno Semichem Co., Ltd. Auto-Stopping Abrasive Composition for Polishing High Step Height Oxide Layer
KR100661273B1 (en) * 2005-04-28 2006-12-26 테크노세미켐 주식회사 Abrasive composition for polishing of wafer
SG127749A1 (en) * 2005-05-11 2006-12-29 Agency Science Tech & Res Method and solution for forming anatase titanium dioxide, and titanium dioxide particles, colloidal dispersion and film
WO2006133249A2 (en) * 2005-06-06 2006-12-14 Advanced Technology Materials, Inc. Integrated chemical mechanical polishing composition and process for single platen processing
US20060283093A1 (en) * 2005-06-15 2006-12-21 Ivan Petrovic Planarization composition
US7718536B2 (en) * 2005-06-16 2010-05-18 United Microelectronics Corp. Planarization process for pre-damascene structure including metal hard mask
JP4679277B2 (en) * 2005-07-11 2011-04-27 富士通セミコンダクター株式会社 Manufacturing method of semiconductor device
WO2007019342A2 (en) * 2005-08-05 2007-02-15 Advanced Technology Materials, Inc. High throughput chemical mechanical polishing composition for metal film planarization
KR20070017762A (en) * 2005-08-08 2007-02-13 엘지.필립스 엘시디 주식회사 Etchant composition, method of patterning electroconductive film using the same and method of fabricating flat panel display using the same
KR100734274B1 (en) * 2005-09-05 2007-07-02 삼성전자주식회사 Method of forming gate using the cleaning composition
WO2008048240A2 (en) * 2005-09-22 2008-04-24 Pantheon Chemical, Inc. Copper chelating agent, composition including the agent, and methods of forming and using the agent and composition
JP2007088379A (en) * 2005-09-26 2007-04-05 Fujifilm Corp Aqueous polishing slurry and chemical mechanical polishing method
CN101283441B (en) * 2005-10-12 2011-07-20 日立化成工业株式会社 Polishing slurry for CMP and polishing method
US7435162B2 (en) * 2005-10-24 2008-10-14 3M Innovative Properties Company Polishing fluids and methods for CMP
KR20080072905A (en) 2005-11-09 2008-08-07 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 Composition and method for recycling semiconductor wafers having low-k dielectric materials thereon
US7534753B2 (en) * 2006-01-12 2009-05-19 Air Products And Chemicals, Inc. pH buffered aqueous cleaning composition and method for removing photoresist residue
US20070218692A1 (en) * 2006-01-31 2007-09-20 Nissan Chemical Industries, Ltd. Copper-based metal polishing compositions and polishing processes
KR20070088245A (en) * 2006-02-24 2007-08-29 후지필름 가부시키가이샤 Polishing liquid for metals
US20070209287A1 (en) * 2006-03-13 2007-09-13 Cabot Microelectronics Corporation Composition and method to polish silicon nitride
US7820067B2 (en) * 2006-03-23 2010-10-26 Cabot Microelectronics Corporation Halide anions for metal removal rate control
CN100491072C (en) * 2006-06-09 2009-05-27 河北工业大学 Method for controlling disc-like pit during chemically mechanical polishing for ULSI multiple-layered copper wiring
US7396768B2 (en) * 2006-10-20 2008-07-08 Hitachi Global Storage Technologies Netherlands B.V. Copper damascene chemical mechanical polishing (CMP) for thin film head writer fabrication
CN101225282B (en) * 2007-01-19 2013-05-01 安集微电子(上海)有限公司 Low-dielectric material lapping liquid
US20100087065A1 (en) * 2007-01-31 2010-04-08 Advanced Technology Materials, Inc. Stabilization of polymer-silica dispersions for chemical mechanical polishing slurry applications
JP5121273B2 (en) * 2007-03-29 2013-01-16 富士フイルム株式会社 Polishing liquid for metal and polishing method
US20100112728A1 (en) * 2007-03-31 2010-05-06 Advanced Technology Materials, Inc. Methods for stripping material for wafer reclamation
US7670497B2 (en) * 2007-07-06 2010-03-02 International Business Machines Corporation Oxidant and passivant composition and method for use in treating a microelectronic structure
US20090031636A1 (en) * 2007-08-03 2009-02-05 Qianqiu Ye Polymeric barrier removal polishing slurry
US20090032765A1 (en) * 2007-08-03 2009-02-05 Jinru Bian Selective barrier polishing slurry
CN101451047B (en) * 2007-11-30 2013-10-23 安集微电子(上海)有限公司 Chemico-mechanical polishing liquid
US8425797B2 (en) * 2008-03-21 2013-04-23 Cabot Microelectronics Corporation Compositions for polishing aluminum/copper and titanium in damascene structures
US8247326B2 (en) * 2008-07-10 2012-08-21 Cabot Microelectronics Corporation Method of polishing nickel-phosphorous
US8361237B2 (en) * 2008-12-17 2013-01-29 Air Products And Chemicals, Inc. Wet clean compositions for CoWP and porous dielectrics
KR101279966B1 (en) * 2008-12-29 2013-07-05 제일모직주식회사 CMP slurry composition for polishing metal wiring and polishing method using the same
KR20100091436A (en) * 2009-02-10 2010-08-19 삼성전자주식회사 Composition of solution for chemical mechanical polishing
JP5516426B2 (en) 2009-02-16 2014-06-11 日立化成株式会社 Abrasive and polishing method
CN102318042B (en) 2009-02-16 2015-07-01 日立化成株式会社 Polishing agent for copper polishing and polishing method using same
EP2226374B1 (en) * 2009-03-06 2012-05-16 S.O.I. TEC Silicon Etching composition, in particular for silicon materials, method for characterizing defects of such materials and process of treating such surfaces with etching composition
CN101906269A (en) * 2009-06-08 2010-12-08 安集微电子科技(上海)有限公司 Slurry for metal chemical and mechanical polishing and using method thereof
KR20120080595A (en) 2009-09-02 2012-07-17 노벨러스 시스템즈, 인코포레이티드 Reduced isotropic etchant material consumption and waste generation
CN102640275B (en) 2009-11-30 2015-12-02 巴斯夫欧洲公司 Remove the method for bulk material layer from substrate and be suitable for the chemical mechnical polishing agent of the method
US9028708B2 (en) 2009-11-30 2015-05-12 Basf Se Process for removing a bulk material layer from a substrate and a chemical mechanical polishing agent suitable for this process
KR20130136593A (en) 2010-03-12 2013-12-12 히타치가세이가부시끼가이샤 Slurry, polishing fluid set, polishing fluid, and substrate polishing method using same
CN102220133B (en) * 2010-04-19 2014-02-12 深圳富泰宏精密工业有限公司 Stripping solution of titanium carbide and/or titanium nitride film and stripping method
TWI471458B (en) * 2010-04-30 2015-02-01 Fih Hong Kong Ltd An etching solution for removing titanium carbide and titanium nitride films and method for removing the films
CN102337079B (en) * 2010-07-23 2015-04-15 安集微电子(上海)有限公司 Chemically mechanical polishing agent
JP6101421B2 (en) * 2010-08-16 2017-03-22 インテグリス・インコーポレーテッド Etching solution for copper or copper alloy
KR20130099948A (en) 2010-08-20 2013-09-06 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 Sustainable process for reclaiming precious metals and base metals from e-waste
CN102373014A (en) * 2010-08-24 2012-03-14 安集微电子(上海)有限公司 Chemical-mechanical polishing solution
CN103080256B (en) 2010-09-08 2015-06-24 巴斯夫欧洲公司 Aqueous polishing composition and process for chemically mechanically polishing substrates containing silicon oxide dielectric and polysilicon films
RU2608890C2 (en) 2010-09-08 2017-01-26 Басф Се Aqueous polishing composition containing n-substituted diazenium dioxides and/or salts of n-substituted n'-hydroxy-diazenium oxides
MY164859A (en) 2010-09-08 2018-01-30 Basf Se Aqueous polishing composition and process for chemically mechanically polishing substrate materials for electrical, mechanical and optical devices
CN102399494B (en) * 2010-09-10 2014-12-31 安集微电子(上海)有限公司 Chemical mechanical polishing solution
KR101827031B1 (en) 2010-10-06 2018-02-07 엔테그리스, 아이엔씨. Composition and process for selectively etching metal nitrides
RU2589482C2 (en) 2010-10-07 2016-07-10 Басф Се Aqueous polishing composition and method for chemical-mechanical polishing of substrates, having structured or unstructured dielectric layers with low dielectric constant
TWI502065B (en) 2010-10-13 2015-10-01 Entegris Inc Composition for and method of suppressing titanium nitride corrosion
CN102453439B (en) * 2010-10-22 2015-07-29 安集微电子(上海)有限公司 A kind of chemical mechanical polishing liquid
US9881801B2 (en) 2010-11-22 2018-01-30 Hitachi Chemical Company, Ltd. Slurry, polishing liquid set, polishing liquid, method for polishing substrate, and substrate
WO2012070544A1 (en) 2010-11-22 2012-05-31 日立化成工業株式会社 Method for producing abrasive grains, method for producing slurry, and method for producing polishing liquid
JP5590144B2 (en) * 2010-11-22 2014-09-17 日立化成株式会社 Slurry, polishing liquid set, polishing liquid, and substrate polishing method
KR101919750B1 (en) 2010-12-10 2018-11-19 바스프 에스이 Aqueous polishing composition and process for chemically mechanically polishing substrates containing silicon oxide dielectric and polysilicon films
KR102064487B1 (en) 2011-01-13 2020-01-10 엔테그리스, 아이엔씨. Formulations for the removal of particles generated by cerium-containing solutions
KR20140012660A (en) 2011-03-11 2014-02-03 바스프 에스이 Method for forming through-base wafer vias
KR20140019401A (en) * 2011-03-22 2014-02-14 바스프 에스이 A chemical mechanical polishing (cmp) composition comprising a polymeric polyamine
US8790160B2 (en) * 2011-04-28 2014-07-29 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Chemical mechanical polishing composition and method for polishing phase change alloys
US8309468B1 (en) * 2011-04-28 2012-11-13 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Chemical mechanical polishing composition and method for polishing germanium-antimony-tellurium alloys
JP5933950B2 (en) 2011-09-30 2016-06-15 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 Etching solution for copper or copper alloy
CN102504705B (en) * 2011-10-17 2014-07-09 河南省化工研究所有限责任公司 Polishing solution used for precision machining of optical communication ZrO2 ceramic stub and preparation method thereof
JP6044630B2 (en) 2012-02-21 2016-12-14 日立化成株式会社 Abrasive, abrasive set, and substrate polishing method
KR102004570B1 (en) 2012-02-21 2019-07-26 히타치가세이가부시끼가이샤 Abrasive, abrasive set, and method for abrading substrate
WO2013175859A1 (en) 2012-05-22 2013-11-28 日立化成株式会社 Slurry, polishing-solution set, polishing solution, substrate polishing method, and substrate
JP5943073B2 (en) 2012-05-22 2016-06-29 日立化成株式会社 Slurry, polishing liquid set, polishing liquid and polishing method for substrate
JP5943072B2 (en) 2012-05-22 2016-06-29 日立化成株式会社 Slurry, polishing liquid set, polishing liquid and polishing method for substrate
US9039914B2 (en) 2012-05-23 2015-05-26 Cabot Microelectronics Corporation Polishing composition for nickel-phosphorous-coated memory disks
US9765288B2 (en) 2012-12-05 2017-09-19 Entegris, Inc. Compositions for cleaning III-V semiconductor materials and methods of using same
KR101933529B1 (en) * 2012-12-28 2019-03-15 동우 화인켐 주식회사 Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same
CN103450812B (en) * 2013-01-10 2014-09-17 湖南皓志新材料股份有限公司 Polishing solution for sapphire substrate
CN105102584B (en) 2013-03-04 2018-09-21 恩特格里斯公司 Composition and method for selective etch titanium nitride
JP6203525B2 (en) * 2013-04-19 2017-09-27 関東化學株式会社 Cleaning liquid composition
TWI651396B (en) 2013-06-06 2019-02-21 美商恩特葛瑞斯股份有限公司 Compositions and methods for selectively etching titanium nitride
US8974692B2 (en) 2013-06-27 2015-03-10 Air Products And Chemicals, Inc. Chemical mechanical polishing slurry compositions and method using the same for copper and through-silicon via applications
WO2015017659A1 (en) 2013-07-31 2015-02-05 Advanced Technology Materials, Inc. AQUEOUS FORMULATIONS FOR REMOVING METAL HARD MASK AND POST-ETCH RESIDUE WITH Cu/W COMPATIBILITY
SG10201801575YA (en) 2013-08-30 2018-03-28 Entegris Inc Compositions and methods for selectively etching titanium nitride
CN105793471B (en) * 2013-12-02 2019-11-05 艺康美国股份有限公司 Corrosion inhibitor based on tetrazolium
US10340150B2 (en) 2013-12-16 2019-07-02 Entegris, Inc. Ni:NiGe:Ge selective etch formulations and method of using same
JP6776125B2 (en) 2013-12-20 2020-10-28 インテグリス・インコーポレーテッド Use of non-oxidizing strong acids for removal of ion-implanted resists
WO2015103146A1 (en) 2013-12-31 2015-07-09 Advanced Technology Materials, Inc. Formulations to selectively etch silicon and germanium
WO2015116818A1 (en) 2014-01-29 2015-08-06 Advanced Technology Materials, Inc. Post chemical mechanical polishing formulations and method of use
US11127587B2 (en) 2014-02-05 2021-09-21 Entegris, Inc. Non-amine post-CMP compositions and method of use
CN103789770B (en) * 2014-02-14 2016-08-31 东莞宜安科技股份有限公司 Large block amorphous and nanometer crystal alloy Surface Chemical Polishing technique
US10946494B2 (en) * 2015-03-10 2021-03-16 Showa Denko Materials Co., Ltd. Polishing agent, stock solution for polishing agent, and polishing method
CN104746082B (en) * 2015-03-12 2017-05-17 深圳新宙邦科技股份有限公司 Water-based copper anti-rusting agent and preparation method thereof
US9978609B2 (en) 2015-04-27 2018-05-22 Versum Materials Us, Llc Low dishing copper chemical mechanical planarization
CN105002498A (en) * 2015-07-24 2015-10-28 金川集团股份有限公司 GH625 high-temperature alloy metallographic etchant and preparation and application method thereof
CN105086836A (en) * 2015-08-19 2015-11-25 三峡大学 Cerium oxide polishing solution and preparation method thereof
WO2017156304A1 (en) 2016-03-09 2017-09-14 Entegris, Inc. Tungsten post-cmp cleaning compositions
CN105802582A (en) * 2016-05-23 2016-07-27 昆山金城试剂有限公司 Rare earth grinding fluid
WO2017214995A1 (en) * 2016-06-17 2017-12-21 深圳市恒兆智科技有限公司 Polishing agent, copper part and polishing treatment method therefor
KR101943704B1 (en) * 2016-06-27 2019-01-29 삼성에스디아이 주식회사 Cmp slurry composition for metal film and polishing method
CN106119855B (en) * 2016-08-17 2018-08-21 安徽红桥金属制造有限公司 A kind of preparation method of stainless steel material polishing agent
KR102522528B1 (en) * 2016-09-21 2023-04-17 가부시끼가이샤 레조낙 Slurry and Grinding Method
KR102337333B1 (en) * 2017-05-25 2021-12-13 생-고뱅 세라믹스 앤드 플라스틱스, 인코포레이티드 Oxidizing fluids for chemical mechanical polishing of ceramic materials
CN107164764A (en) * 2017-06-09 2017-09-15 大连理工大学 A kind of environment protection chemical mechanical polishing method of copper
CN110832043A (en) * 2017-07-03 2020-02-21 深圳市宏昌发科技有限公司 Polishing agent, copper piece and polishing treatment method thereof
US11401441B2 (en) 2017-08-17 2022-08-02 Versum Materials Us, Llc Chemical mechanical planarization (CMP) composition and methods therefore for copper and through silica via (TSV) applications
US10465096B2 (en) 2017-08-24 2019-11-05 Versum Materials Us, Llc Metal chemical mechanical planarization (CMP) composition and methods therefore
WO2019113005A1 (en) * 2017-12-04 2019-06-13 Chemtreat, Inc. Methods and compositions for inhibiting corrosion on metal surfaces
US11560533B2 (en) 2018-06-26 2023-01-24 Versum Materials Us, Llc Post chemical mechanical planarization (CMP) cleaning
CN111378972A (en) * 2018-12-29 2020-07-07 安集微电子(上海)有限公司 Chemical mechanical polishing solution
US20200277514A1 (en) 2019-02-28 2020-09-03 Versum Materials Us, Llc Chemical Mechanical Polishing For Copper And Through Silicon Via Applications
JP2022530669A (en) * 2019-05-01 2022-06-30 フジフイルム エレクトロニック マテリアルズ ユー.エス.エー., インコーポレイテッド Etching composition
CN110256968B (en) * 2019-05-29 2021-01-01 湖南皓志科技股份有限公司 Aluminum oxide polishing solution for copper polishing and preparation method thereof
US11268025B2 (en) * 2019-06-13 2022-03-08 Fujifilm Electronic Materials U.S.A., Inc. Etching compositions
WO2021061591A1 (en) * 2019-09-24 2021-04-01 Versum Materials Us, Llc With-in die non-uniformities (wid-nu) in planarization
KR20220070026A (en) * 2019-09-30 2022-05-27 버슘머트리얼즈 유에스, 엘엘씨 Low dishing copper chemical mechanical planarization
CN111235579A (en) * 2019-12-31 2020-06-05 南方科技大学 Metal polishing method
CN111362883B (en) * 2020-04-16 2022-04-19 安美科技股份有限公司 Benzotriazole derivative corrosion inhibitor and preparation method and application thereof
CN112160002B (en) * 2020-09-15 2021-05-28 深圳市崇辉表面技术开发有限公司 Method for carrying out surface activation treatment on copper alloy surface
CN114686115A (en) * 2020-12-30 2022-07-01 安集微电子科技(上海)股份有限公司 Chemical mechanical polishing solution and use method thereof
CN114855156A (en) * 2022-05-09 2022-08-05 如皋市凯源电器设备有限公司 Preparation process of corrosion-resistant conductive strip
CN115449302A (en) * 2022-09-20 2022-12-09 江西鑫铂瑞科技有限公司 Use method of novel polishing solution for electrolytic copper foil cathode titanium roller

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010008828A1 (en) * 2000-01-12 2001-07-19 Jsr Corporation Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing process

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5332341B2 (en) * 1973-03-27 1978-09-07
US4468339B1 (en) * 1982-01-21 1989-05-16 Aqueous compositions containing overbased materials
JP2781954B2 (en) * 1994-03-04 1998-07-30 メック株式会社 Copper and copper alloy surface treatment agent
US20020111024A1 (en) * 1996-07-25 2002-08-15 Small Robert J. Chemical mechanical polishing compositions
ATE312895T1 (en) * 1996-07-25 2005-12-15 Dupont Air Prod Nanomaterials COMPOSITION AND METHOD FOR CHEMICAL-MECHANICAL POLISHING
US5954997A (en) * 1996-12-09 1999-09-21 Cabot Corporation Chemical mechanical polishing slurry useful for copper substrates
US6126853A (en) * 1996-12-09 2000-10-03 Cabot Microelectronics Corporation Chemical mechanical polishing slurry useful for copper substrates
US6099604A (en) * 1997-08-21 2000-08-08 Micron Technology, Inc. Slurry with chelating agent for chemical-mechanical polishing of a semiconductor wafer and methods related thereto
US6168508B1 (en) * 1997-08-25 2001-01-02 Lsi Logic Corporation Polishing pad surface for improved process control
US6068879A (en) * 1997-08-26 2000-05-30 Lsi Logic Corporation Use of corrosion inhibiting compounds to inhibit corrosion of metal plugs in chemical-mechanical polishing
US6190237B1 (en) * 1997-11-06 2001-02-20 International Business Machines Corporation pH-buffered slurry and use thereof for polishing
JP4163785B2 (en) * 1998-04-24 2008-10-08 スピードファム株式会社 Polishing composition and polishing method
US6114215A (en) * 1998-07-06 2000-09-05 Lsi Logic Corporation Generating non-planar topology on the surface of planar and near-planar substrates
JP4095731B2 (en) * 1998-11-09 2008-06-04 株式会社ルネサステクノロジ Semiconductor device manufacturing method and semiconductor device
US6184141B1 (en) * 1998-11-24 2001-02-06 Advanced Micro Devices, Inc. Method for multiple phase polishing of a conductive layer in a semidonductor wafer
JP4053165B2 (en) * 1998-12-01 2008-02-27 株式会社フジミインコーポレーテッド Polishing composition and polishing method using the same
US6783434B1 (en) * 1998-12-25 2004-08-31 Hitachi Chemical Company, Ltd. CMP abrasive, liquid additive for CMP abrasive and method for polishing substrate
JP2001015460A (en) * 1999-06-30 2001-01-19 Toshiba Corp Fabrication of semiconductor device
US6159077A (en) * 1999-07-30 2000-12-12 Corning Incorporated Colloidal silica polishing abrasive
TW499471B (en) * 1999-09-01 2002-08-21 Eternal Chemical Co Ltd Chemical mechanical/abrasive composition for semiconductor processing
JP4505891B2 (en) 1999-09-06 2010-07-21 Jsr株式会社 Chemical mechanical polishing aqueous dispersion used in the manufacture of semiconductor devices
JP2001077060A (en) * 1999-09-08 2001-03-23 Toshiba Corp Manufacture of semiconductor device
DE19942984A1 (en) * 1999-09-09 2001-03-15 Schaeffler Waelzlager Ohg Radial-axial bearing unit
US6656842B2 (en) * 1999-09-22 2003-12-02 Applied Materials, Inc. Barrier layer buffing after Cu CMP
JP2001187877A (en) * 1999-12-28 2001-07-10 Nec Corp Slurry for chemical mechanical polishing
JP3490038B2 (en) * 1999-12-28 2004-01-26 Necエレクトロニクス株式会社 Metal wiring formation method
JP2001269859A (en) 2000-03-27 2001-10-02 Jsr Corp Aqueous dispersing element for polishing chemical machine
JP4078787B2 (en) * 2000-03-31 2008-04-23 Jsr株式会社 Aqueous dispersion for chemical mechanical polishing
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
US6612911B2 (en) * 2001-01-16 2003-09-02 Cabot Microelectronics Corporation Alkali metal-containing polishing system and method
US6811470B2 (en) * 2001-07-16 2004-11-02 Applied Materials Inc. Methods and compositions for chemical mechanical polishing shallow trench isolation substrates
US6805812B2 (en) * 2001-10-11 2004-10-19 Cabot Microelectronics Corporation Phosphono compound-containing polishing composition and method of using same
KR100428787B1 (en) * 2001-11-28 2004-04-28 삼성전자주식회사 Slurry supply appratus having a mixing unit at a point of use and a slurry storage unit
US7132058B2 (en) * 2002-01-24 2006-11-07 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Tungsten polishing solution
US20030162398A1 (en) * 2002-02-11 2003-08-28 Small Robert J. Catalytic composition for chemical-mechanical polishing, method of using same, and substrate treated with same
US6936543B2 (en) * 2002-06-07 2005-08-30 Cabot Microelectronics Corporation CMP method utilizing amphiphilic nonionic surfactants
EP1628334A4 (en) 2003-05-09 2006-08-02 Sanyo Chemical Ind Ltd Polishing liquid for cmp process and polishing method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010008828A1 (en) * 2000-01-12 2001-07-19 Jsr Corporation Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1570015A2 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008069781A1 (en) * 2006-12-04 2008-06-12 Basf Se Planarization composition for metal surfaces comprising an alumina hydrate abrasive
JP2010534934A (en) * 2007-07-26 2010-11-11 キャボット マイクロエレクトロニクス コーポレイション Compositions and methods for chemically and mechanically polishing phase change materials
CN102604542A (en) * 2012-02-21 2012-07-25 复旦大学 Polishing solution used in polishing process with metal ruthenium as adhesive barrier layer in copper interconnection
CN104449564A (en) * 2013-09-23 2015-03-25 中芯国际集成电路制造(上海)有限公司 Monodisperse grinding fluid and preparation method thereof and method for preparing inorganic oxide sol

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US7300601B2 (en) 2007-11-27
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US20050255693A1 (en) 2005-11-17

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