WO2005109480A1 - 研磨用スラリー - Google Patents

研磨用スラリー Download PDF

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Publication number
WO2005109480A1
WO2005109480A1 PCT/JP2005/008131 JP2005008131W WO2005109480A1 WO 2005109480 A1 WO2005109480 A1 WO 2005109480A1 JP 2005008131 W JP2005008131 W JP 2005008131W WO 2005109480 A1 WO2005109480 A1 WO 2005109480A1
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WIPO (PCT)
Prior art keywords
polishing
metal
monomers
monomer
polishing slurry
Prior art date
Application number
PCT/JP2005/008131
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English (en)
French (fr)
Japanese (ja)
Inventor
Kiyotaka Shindo
Akinori Etoh
Tomokazu Ishizuka
Original Assignee
Mitsui Chemicals, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Chemicals, Inc. filed Critical Mitsui Chemicals, Inc.
Priority to US11/579,151 priority Critical patent/US20080248727A1/en
Priority to JP2006519522A priority patent/JPWO2005109480A1/ja
Publication of WO2005109480A1 publication Critical patent/WO2005109480A1/ja

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/04—Aqueous dispersions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]

Definitions

  • the present invention relates to a polishing slurry capable of polishing and flattening the surface of copper or the like without damaging the surface of copper or the like used in the production of semiconductor devices.
  • Mechanical Polishing is used. This is a method of mechanically polishing with a slurry in which munitions are dispersed.
  • the width of 1Z2 wiring on an insulating film has been further reduced from 130 nm to 90 nm and further to 65 nm, and the surface of the insulating film to be polished has become more complicated. It has a structure. As the wiring width becomes finer, polishing scratches on the metal surface due to scratches cause breaks, and dicing and erosion increase and vary the wiring resistance, as well as short-circuiting between wirings formed in upper layers. This significantly reduces the reliability of semiconductor devices and significantly reduces the yield.
  • This scratching is due to the hardness of the cannonball and partial overpolishing caused by the presence of agglomerate of the cannonball.
  • Erosion also prevents excessive polishing with hard cannonballs and diffusion of insulating films and metals This is because polishing selectivity with an underlayer such as a barrier layer is low.
  • the abrasive grains are made V and silica softer than alumina, and a polishing liquid for polishing is applied to the neutral side where no metal is eluted toward the alkaline side.
  • a polishing liquid for polishing is applied to the neutral side where no metal is eluted toward the alkaline side.
  • Japanese Patent No. 3172008 describes a method in which particles of an organic polymer compound are used as abrasive grit.
  • the organic polymer used here is made of methacrylic resin, polystyrene resin, and other components having no functional groups as the granules, and does not contain an oxidizing agent that oxidizes the metal surface.
  • the chemical action with the metal film, which is the polishing body, does not work at all, and a sufficient polishing rate is obtained, which is necessary for the wiring process of semiconductor device manufacturing!
  • Japanese Patent Application Laid-Open No. 2001-55559 discloses a water-based system for CMP containing organic particles having a functional group capable of reacting with a metal forming a surface to be polished. Dispersions are disclosed. This phenomenon, which is called dicing while the metal film in the wiring portion is polished more in the center portion while forming a concave shape, has not been solved. To prevent this, a technique in which a protective film forming agent such as benzotriazole is used is disclosed in Japanese Patent Application Laid-Open No. 8-83780, etc. Since a protective film forming agent such as benzotriazole has an extremely high effect, the polishing speed is reduced. Also had the disadvantage of significantly reducing
  • Patent Document 1 Patent No. 3172008
  • Patent Document 2 JP 2001-55559A
  • Patent Document 3 JP-A-8-38780 Disclosure of the invention
  • An object of the present invention is to provide a polishing slurry containing specific organic particles, and to provide a polishing slurry that remarkably suppresses the occurrence of scratching and dicing and erosion.
  • the present invention relates to a slurry containing the organic fine particles (A), wherein the organic fine particles (A) are formed on the surface of the organic particles (B) having a functional group capable of reacting with the metal to be polished.
  • the part is covered with! / Resin (C) that does not contain a functional group that can react with the metal to be polished.
  • the polishing slurry contains an oxidizing agent in that the reaction between the metal to be polished and the functional group is promoted.
  • Organic particles (B) —based on the weight of all monomers, a carboxylic group-containing vinyl monomer, a hydroxyl group-containing vinyl monomer, an amino group-containing vinyl monomer, and an acetoacetoxy group-containing vinyl monomer Glycidyl group-containing monomer monomer
  • a monomer composition containing 1 to 50% by weight of one or more selected monomer (s) and 99 to 50% by weight of another butyl monomer is polymerized.
  • the inclusion of the copolymer obtained in this manner is a preferred embodiment in terms of promoting the reaction with the metal to be polished.
  • the polishing slurry force contains at least one complexing agent selected from carboxylic acids, amines, amino acids, and ammonia force, and the ⁇ 5 force 5 to: L1 is in the range of polishing speed. Is an embodiment.
  • the fact that the oxidizing agent is hydrogen peroxide is preferred in terms of flatness and is an embodiment.
  • the polishing slurry of the present invention can reduce excess metal film on an insulating film processed by wiring at a high speed.
  • the surface of the object to be polished can be polished without causing scratches or scratches due to overpolishing, and there is no unevenness due to dicing or the like. is there.
  • the polishing slurry of the present invention which is composed of organic fine particles, has a decomposition temperature much lower than that of the insulating film. Therefore, heat treatment and plasma treatment do not damage the insulating film, and the polishing slurry can be removed with a residue. It is possible.
  • FIG. 1 is a view showing an SEM image of the organic particles obtained in Production Example 1.
  • FIG. 2 is a view showing an SEM image of the organic particles obtained in Comparative Production Example 1.
  • organic particles (A) a part of the surface of the organic particles (B) having a functional group capable of reacting with the metal to be polished is coated with a resin (C) containing no functional group capable of reacting with the metal to be polished.
  • reactable with the metal to be polished means the ability to accelerate the polishing rate of the metal to be polished by a chemical reaction.
  • Examples of the functional group of the organic particles (B) that can react with the metal to be polished include a carboxyl group, a hydroxyl group, an amine group, a ketone group, a glycidyl group, and an acetoacetoxy group. Particularly preferred is rubonic acid.
  • the organic particles (B) can be produced, for example, by polymerizing a monomer having a functional group capable of reacting with the metal to be polished and other vinyl monomers copolymerizable therewith. You.
  • the carboxyl group is dissociated by adding an alkali substance in an amount of 0.3 mol equivalent or more to the carboxyl group in the obtained copolymer emulsion, It is preferable to make the state easy to form a complex with a metal.
  • the carboxyl group-containing vinyl monomer used in the present invention includes, for example, acrylic acid, methacrylic acid, unsaturated monobasic acids such as crotonic acid, itaconic acid, fumaric acid, maleic acid and the like. Unsaturated dibasic acids or monoesters thereof These are one or more selected from acrylic acid and methacrylic acid.
  • Examples of the hydroxyl group-containing butyl monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl ( (Meth) acrylate.
  • Amino group-containing (meth) acrylate monomers containing a tertiary amino group include, for example, N, N-dimethylaminoethyl (meth) atalylate, , N-dimethylaminopropyl (meth) acrylate, N, N-t-butylaminoethyl (meth) acrylate, N, N-monomethylaminoethyl (meth) acrylate.
  • N-alkylamino (meth) acrylamide containing a tertiary amino group can be mentioned, for example, N, N-dimethyl (meth) acrylamide, N, N-getyl (meth) acrylamide, N, N —Dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N-isopropyl (meth) acrylamide and the like.
  • Examples of the vinyl monomer containing an acetoacetoxy group include acetoacetoxityl (meth) acrylate, and examples of the glycidyl group-containing vinyl monomer include glycidyl (meth) acrylate.
  • the amount of the monomer having a functional group capable of reacting with the metal to be polished is preferably 1 to 50 parts by weight, more preferably 3 to 45 parts by weight, of all the monomer components in the copolymer. And most preferably 5 to 40 parts by weight. If the amount is less than 1 part by weight, a desired polishing rate cannot be obtained, and if it exceeds 50 parts by weight, water resistance and alkali resistance may be poor.
  • the other vinyl monomers copolymerizable with the monomer having a functional group capable of reacting with the metal to be polished include, for example, styrene-based monomers such as styrene, ⁇ -methylstyrene, and toluene.
  • Monomer methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isopropyl (meth) acrylate, (meth) atalylic acid (Meth) such as isobutyl, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobutyl (meth) acrylate
  • Acrylic acid ester monomers butyl esters such as butyl acetate and propyl propionate, bursiani conjugates such as (meth) acrylonitrile, butyl chloride, butyl chloride
  • a halogenated bilirui conjugate such as den is used.
  • As the functional group monomer (meth) acrylamide, N-
  • the amount of other vinyl monomers used is preferably from 99 to 50% by weight, more preferably from 95 to 70% by weight.
  • Such organic particles may or may not swell as a whole by adding an alkaline substance, but either may be used.
  • swelling means that the average particle diameter of the primary particles is increased by including water and other water-soluble substances which do not decompose or aggregate into the particles.
  • a crosslinkable monomer can be copolymerized as necessary.
  • the crosslinkable monomer is a monomer containing two or more polymerizable unsaturated bonds in one molecule, such as dibutylbenzene, butadiene, ethylene glycol dimethacrylate, trimethylol arovan trimethacrylate, and ethylene glycol. Examples thereof include diatalylate, 1,3-butylene glycol dimetharate and diatalylate.
  • the amount of the crosslinkable monomer used is preferably 20% by weight or less, more preferably 10% by weight or less based on the total amount of the monomers. It is used as appropriate depending on the type, amount, and type of the bullet copolymer.
  • the resin (C) coated on the surface of the organic particles (B) is composed of a polymer having no functional group capable of reacting with the metal to be polished, and is composed of a styrene monomer and Z or (meth) It is preferable to be composed of a polymer of an acrylate monomer.
  • Specific examples of the styrene monomer and the (meth) acrylate monomer include the other vinyl monomers copolymerizable with the monomer having a functional group capable of reacting with the metal to be polished as described above. Described in the above.
  • the method for synthesizing the organic particles is not particularly limited.
  • the organic particles can be synthesized by multi-stage polymerization of emulsion polymerization. That is, after synthesizing organic particles (B) having a functional group capable of reacting with the metal to be polished, and not containing a functional group capable of reacting with the metal to be polished! / ⁇ A method of additionally synthesizing the polymer (C) Conversely, a method of synthesizing a polymer (C) containing no functional group capable of reacting with the metal to be polished and then additionally synthesizing organic particles (B) having a functional group capable of reacting with the metal to be polished. And the like.
  • the amount of the monomer is adjusted so that a part of the surface of the organic particles (B) is covered with the resin (C).
  • the organic particles are preferably 10% or more and less than 100% of the surface, more preferably 30% or more and less than 95% of the surface, as long as a part of the surface is coated with the resin (C).
  • the particle diameter of the organic particles (A) covered with the resin layer (B) is preferably ⁇ ! 500500 Onm, more preferably 30 nm to 300 nm.
  • the molecular weight of the organic particles (A) is preferably 10,000 to 5,000,000, more preferably 100,000 to 1,000,000.
  • the molecular weight of the resin (B) is preferably 1,000 to 100,000, more preferably 10,000 to 500,000.
  • the content of the fine particles in the polishing slurry is preferably 0.1 to 20% by weight depending on the organic fine particles. If the content is less than 0.1% by weight, the effect of the organic fine particles cannot be sufficiently exerted, and the desired polishing rate may not be achieved. If the content exceeds 20% by weight, the viscosity of the polishing slurry is high, so that it may be difficult to supply the polishing slurry at a constant speed during polishing.
  • Metal components contained in the polishing slurry are used by adding an oxidizing agent such as hydrogen peroxide to the polishing slurry.
  • an oxidizing agent such as hydrogen peroxide
  • examples of the dispersant include polybutyl alcohol, modified polyvinyl alcohol, polybutylpyrrolidone, (meth) acrylic acid (co) polymer, and poly (meth) acrylamide (co) poly. And water-soluble polymers such as ethylene glycol.
  • examples of the surfactant include a-one type, non-one type and cationic type.
  • the ionic surfactant has an acidic group such as a sulfonic acid or a carboxylic acid as a hydrophilic group, but uses a metal salt such as Na or K as a counter ion thereof. be able to.
  • ammonium salts such as dodecylbenzenesulfonic acid, lauryl sulfate, alkyl difluoroether disulfonic acid, alkyl naphthalene sulfonic acid, dialkyl sulfosuccinic acid, stearic acid, oleic acid, octyl sulfosuccinate, and polyoxyethylene.
  • Ammonium salts such as alkyl ether sulfuric acid, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene alkyl ether ether sulfuric acid, dialkyl sulfosuccinic acid, stearic acid, oleic acid, tert-octyl phenoxyethoxy polyethoxysulfuric acid, etc. Salt.
  • non-ionic surfactants generally have an ethylene glycol chain as a hydrophilic group and do not contain a metal.
  • polyoxyethylene lauryl ether polyoxyethylene octyl phenyl ether, polyoxyethylene phenyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene oxy propylene block copolymer, tert-octyl phenyl Shetyl polyethoxyhetanol, nourfenoxhetyl polyethoxyethanol, and the like.
  • the cationic surfactant for example, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, alkylbenzyl dimethyl ammonium chloride, Lauryl betaine, stearyl betaine, lauryl dimethylamine oxide, lauryl carboxymethylhydroxyethyl imidazoly-dumbetaine, coconutamine acetate, stearylamine acetate, alkyl amminazine polyoxyethanol, alkyl picolium chloride, etc. .
  • these dispersants can be selected.
  • metal-free polymerization initiator examples include, for example, hydrogen peroxide, ammonium persulfate, azobiscyanovaleric acid, 2,2, -azobis (2-amidinopropane) dihydrochloride, 2,2,1-azobis [2 — (N-Feramidino) propane] dihydrochloride, 2,2, azobis ⁇ 2— [N- (4-cyclohexyl) amidino] propane ⁇ dihydrochloride, 2,2, azobis ⁇ 2— [ N- (4-hydroxyphenyl) amidino] propane ⁇ dihydrochloride, 2,2, -azobis [2- (N-benzylamidino) propane] dihydrochloride, 2,2, -azobis [2- (N-arylamidino) propa Dihydrochloride, 2,2, azobis ⁇ 2- [N- (2-hydroxyethyl) amidino] propane ⁇ Dihydrochloride, azobisisobutyral-tolyl, 2, 2
  • the initiator is water-soluble, and more preferred are ammonium persulfate, azobiscyanovaleric acid and 2,2,1-azobis (2-amidinopropane) dihydrochloride
  • Typical initiator amounts are from 0.1 to 5% by weight, based on the total weight of the monomers to be (co) polymerized.
  • mercaptans such as t-dodecylmercaptan and n-dodecylmercaptan
  • arylsulfonic acid metharylsulfonic acid
  • soda salts thereof may be used.
  • An aryl conjugate may also be used as a molecular weight regulator.
  • the organic particles can be produced by a conventionally known emulsion polymerization method, suspension polymerization method, or mechanical emulsification method.
  • emulsion polymerization method there are a method in which various monomers are collectively charged and polymerized in the presence of a dispersant and an initiator, and a method in which polymerization is performed while monomers are continuously supplied.
  • the polymerization temperature at that time is usually 30 to 90 ° C., and an aqueous dispersion of organic particles can be substantially obtained.
  • Emulsion polymerization is a more preferable polymerization method because it is possible to obtain organic particles having a small particle diameter and excellent dispersion stability.
  • Acrylic resin emulsions have excellent dispersibility, and the time observed in abrasives using organic fine particles other than alumina, silica, and emulsion, such as metharyl resin, phenol resin, and urea resin, as abrasive grains. It is most preferable because separation over time (formation of a supernatant and a precipitate) and formation of aggregates do not occur, and a stable polishing rate can always be obtained.
  • carboxylic acids such as acetic acid, oxalic acid, malic acid, tartaric acid, succinic acid, and citric acid, which are preferably water-soluble conjugates capable of forming a complex with a metal, methylamine, dimethylamine, triethylamine, Examples thereof include amines such as ethylamine, getylamine, and triethylamine; amino acids such as glycine, aspartic acid, glutamic acid, and cysteine; ketones such as acetylacetone; and N-containing cyclic conjugates such as imidazole.
  • oxalic acid, malic acid, and ethylamine are exemplified.
  • the content of the complexing agent varies depending on the complexing agent, but is preferably in the range of 0.1 to 10% by weight in the polishing slurry. If the amount is less than 0.1% by weight, the effect cannot be sufficiently exhibited, and the desired polishing rate may not be achieved. On the other hand, if the content exceeds 10% by weight, complex formation with the metal to be polished proceeds excessively, so that the dipping in which the metal to be polished that is not polished elutes may not be suppressed.
  • the metal of the object to be polished contains a functional group contained in the organic fine particles and Z or
  • the metal complex may also have a ligand force between the ligand of the organic fine particles and the complexing agent, or the complex formation between the organic fine particles and the metal promotes the complexing agent-metal complex formation, or The agent-metal complex formation may promote organic fine particle-metal complex formation.
  • the oxidizing agent potassium iodate or hydrogen peroxide is preferable, and hydrogen peroxide is more preferable.
  • the content of these oxidizing agents is preferably in the range of 0.1 to 15% by weight in the polishing composition, and particularly preferably in the range of 0.5 to 5% by weight. If the content is less than 0.1% by weight, the chemical reaction between the metal and the organic particles does not proceed, and the desired polishing rate may not be achieved. On the other hand, if the content exceeds 15% by weight, the oxide film formed on the metal surface is passivated, the polishing does not proceed, and the desired polishing rate may not be achieved.
  • the pH of the polishing slurry of the present invention is in the range of 5 to: L1, more preferably in the range of 7 to 10. If the pH is less than 5, the elution of the metal cannot be suppressed, so that dicing may occur. If the pH exceeds 1, the insulating film is dissolved or partially separated at the point where the semiconductor insulating film and the metal wiring, which are the final points of metal film polishing, are present on the same surface. May be solved.
  • the substance used for adjusting the pH of the abrasive is not particularly limited.
  • the alkaline substance include amines such as ammonia, triethylamine, getylamine, ethylamine, trimethylamine, dimethylamine, and methylamine; And inorganic compounds such as KOH.
  • the acidic substance include inorganics such as hydrochloric acid and nitric acid, and organic acids such as acetic acid, oxalic acid, and citric acid.
  • These P H adjusting agent may also function as a complex it ⁇ which can be a ligand of the metal indicated above. These substances may be used in combination of two or more kinds.
  • a method for producing a polishing slurry for example, after mixing organic fine particles, a complexing agent, an oxidizing agent, and water, the pH is adjusted, and a slurry serving as an abrasive can be produced.
  • This production method is not particularly limited, but it is preferable to add an aqueous solution of a complexing agent capable of forming a ligand with a metal whose pH has been adjusted to a pH-adjusted resin emulsion, and mix well with stirring. Thereafter, the oxidizing agent is gradually added, and the mixture is further stirred and mixed.
  • Additives include nitrogen-containing heterocyclic compounds such as benzotriazole and quinaldic acid, and water-soluble polymers such as polyacrylic acid, polybutyl alcohol, polyethylene glycol, and glucose, and surfactants alone or in combination. Or two or more kinds may be added in combination.
  • the amount and type of addition are not particularly limited as long as the object of the present invention can be achieved.
  • the particle size of the organic particles in the polishing composition was measured by the following method.
  • Measuring device MICROTRAC II MODEL: 9230 (Leeds & Northrup) Concentration conditions: sample stock solution
  • Polishing slurry polishing composition of the present invention
  • Polishing object Thermal oxidation film 5000 Ta film formed by AZ sputtering method on silicon wafer substrate 300 Seed copper film for plating formed by AZCVD method 1500 AZ Copper film formed by AZ plating method 15000A laminated 8 Inch silicon wafer
  • Polishing pad 340mm IC—1000Zsuba400 grid
  • the object to be polished was washed with ultrapure water and ultrasonic cleaning, and then dried.
  • the film thickness before and after polishing was measured by measuring the sheet resistance using a four-terminal probe.
  • the average polishing rate was calculated from the change in film thickness and the polishing time.
  • a groove with a thickness of 500 ⁇ and a width of 100 ⁇ m is formed in the oxide film on the silicon wafer by dry etching. Copper is buried in the groove by a plating method to obtain an object to be polished. Polishing composition of the present invention After polishing with a polishing object under the above polishing conditions, the thickness of the concave portion at the center of the groove is measured by a cross-sectional SEM photograph. The polishing was completed when the copper polishing of the portion where the groove was not formed was completed.
  • the abrasive was allowed to stand at atmospheric pressure and room temperature for 6 hours. Thereafter, the state of the abrasive was visually observed.
  • methyl methacrylate 222.2 parts, methacrylic acid 59 Of dibutylbenzene and 15 parts of dibutylbenzene were mixed with 120 parts of water and 0.25 part of alkyl diphenyl ether disulfonic acid to prepare an emulsion of the monomer, and the emulsion was poured into a flask for 4 hours. Then, the mixture was kept at 70 ° C. for 30 minutes. Subsequently, an emulsion prepared by mixing 60 parts of styrene, 23.7 parts of water, and 0.05 part of alkyl diphenyl ether disulfonate ammonium was added dropwise over 15 minutes, and kept at 70 ° C for 4 hours.
  • the obtained emulsion had a solid content of 32.6%, an average particle size of 140 ⁇ m by light scattering, and a pH of 2.9.
  • the obtained emulsion had a solid content of 19.8%, an average particle size of 183 nm by light scattering, and a pH of 3.2.
  • the mixture was mixed in 3 parts to prepare an emulsion of the monomer, and the emulsion was dropped into the flask over 4 hours, and then kept at 70 ° C for 4 hours.
  • the resulting emulsion had a solids content of 34.2%, an average particle size by light scattering of 140.8 nm, and a pH of 2.4.
  • Figure 2 shows an SEM image of the obtained organic particles.
  • a 10% solution of oxalic acid was adjusted to pH 7.2 using ammonia. This solution was mixed well with the pH-adjusted emulsion of Production Example 1, pure water, 30% hydrogen peroxide, and benzotriazole, and the organic particles (solid content) concentration was 5.0% by weight, and hydrogen peroxide was 2. 0% by weight, oxalic acid
  • a 10% solution of oxalic acid was adjusted to pH 7.2 using ammonia. This solution was mixed well with the pH-adjusted emulsion of Production Example 2, pure water, 30% hydrogen peroxide, and benzotriazole, and the organic particles (solid content) concentration was 5.0% by weight, and the concentration of hydrogen peroxide was 2. 0% by weight, oxalic acid
  • a 10% solution of oxalic acid was adjusted to pH 7.2 using ammonia. This solution was mixed well with the pH-adjusted emulsion of Production Example 3, pure water, 30% hydrogen peroxide, and benzotriazole, and the organic particles (solid content) concentration was 5.0% by weight, and hydrogen peroxide was 2. 0% by weight, oxalic acid
  • a 10% solution of glycine was adjusted to pH 7.5 using ammonia. This solution was mixed well with the pH-adjusted emulsion of Production Example 1, pure water, 30% hydrogen peroxide, and benzotriazole, and the organic particles (solid content) concentration was 5.0% by weight, and hydrogen peroxide was 2. 0% by weight, glycine
  • Example 1 The same operations and evaluations as in Example 1 were performed, except that the organic fine particles of Example 1 were replaced with commercially available colloidal silica (PL-1 manufactured by Fuso Chemical Co., Ltd.). Table 1 shows the polishing results.
  • the polishing slurry of the present invention can quickly polish an excessive metal film on an insulating film subjected to wiring processing, and can produce scratches and scratches due to excessive polishing on the surface of an object to be polished.
  • Polishing can be performed without any irregularities such as dating and erosion, and polishing with high flatness can be performed.
  • the polishing slurry of the present invention having a solid content of organic fine particles, since the decomposition temperature is considerably lower than that of the insulating film, heat treatment and plasma treatment can be performed, and the polishing slurry is not damaged.
  • the industrial applicability is extremely high because it is possible to remove the residue.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
PCT/JP2005/008131 2004-05-06 2005-04-28 研磨用スラリー WO2005109480A1 (ja)

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US11/579,151 US20080248727A1 (en) 2004-05-06 2005-04-28 Polishing Slurry
JP2006519522A JPWO2005109480A1 (ja) 2004-05-06 2005-04-28 研磨用スラリー

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JP2004-137235 2004-05-06
JP2004137235 2004-05-06

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JP (1) JPWO2005109480A1 (zh)
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CN (1) CN1943018A (zh)
TW (1) TWI282801B (zh)
WO (1) WO2005109480A1 (zh)

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KR20070012426A (ko) 2007-01-25
US20080248727A1 (en) 2008-10-09
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TWI282801B (en) 2007-06-21
JPWO2005109480A1 (ja) 2008-03-21

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