WO2019151144A1 - Composition de polissage mecano-chimique et procédé de polissage - Google Patents

Composition de polissage mecano-chimique et procédé de polissage Download PDF

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WO2019151144A1
WO2019151144A1 PCT/JP2019/002526 JP2019002526W WO2019151144A1 WO 2019151144 A1 WO2019151144 A1 WO 2019151144A1 JP 2019002526 W JP2019002526 W JP 2019002526W WO 2019151144 A1 WO2019151144 A1 WO 2019151144A1
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Prior art keywords
chemical mechanical
mechanical polishing
titanium oxide
polishing composition
acid
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PCT/JP2019/002526
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English (en)
Japanese (ja)
Inventor
山田　裕也
昌宏 野田
達也 山中
昂輝 石牧
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Jsr株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00—Brightening metals by chemical means
    • C23F3/04—Heavy metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • 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
    • 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
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a chemical mechanical polishing composition and a polishing method using the same.
  • CMP chemical mechanical polishing
  • CMP while supplying a polishing composition containing abrasive grains and reagents onto a polishing pad, the semiconductor substrate is pressed against the polishing pad affixed on the surface plate, and the semiconductor substrate and the polishing pad are slid against each other.
  • This is a technique for chemically and mechanically polishing a semiconductor substrate.
  • unevenness on the surface of a semiconductor substrate can be removed by chemical reaction with a reagent and mechanical polishing with abrasive grains, and the surface can be flattened.
  • a ruthenium film polishing composition for planarizing a ruthenium film, which is a next-generation semiconductor material, by CMP has been studied (see, for example, Patent Documents 1 and 2).
  • a ruthenium film polishing composition in order to improve the ruthenium film polishing rate, a slurry in which abrasive grains such as alumina and titanium oxide and an oxidizing agent are used in combination has been studied.
  • titanium oxide particles when used as abrasive grains, the surface is chemically active, so it is easy to react with water, oxygen, nitrogen, etc. There was a problem of being easily damaged.
  • some embodiments according to the present invention can suppress the generation of ruthenium tetroxide, which is highly toxic to the human body, can polish a semiconductor substrate (particularly a ruthenium film-containing substrate) at high speed, and can polish polishing scratches on the surface to be polished.
  • An object of the present invention is to provide a chemical mechanical polishing composition capable of reducing the amount of polishing and a polishing method using the same.
  • Another object of the present invention is to provide a chemical mechanical polishing composition having excellent stability in which generation of foaming is further reduced, in addition to the above object.
  • the present invention has been made to solve at least a part of the above-described problems, and can be realized as the following aspects or application examples.
  • One aspect of the chemical mechanical polishing composition according to the present invention is: (A) titanium oxide-containing particles; (B) an organic acid; Containing The (A) titanium oxide-containing particles have a half width of less than 1 ° at the peak portion where the diffraction intensity in the powder X-ray diffraction pattern is maximum.
  • the (A) titanium oxide-containing particles further contain aluminum, wherein in (A) containing titanium oxide particles, it is possible the number of moles of titanium M Ti, the number of moles of aluminum is taken as M Al, the value of M Ti / M Al is 6-70.
  • the ratio (Rmax / Rmin) between the major axis (Rmax) and the minor axis (Rmin) of the (A) titanium oxide-containing particles may be 1.1 to 4.0.
  • the (C) oxidizing agent may be at least one selected from potassium periodate, potassium hypochlorite, and hydrogen peroxide.
  • the content of the (A) titanium oxide-containing particles can be 0.1% by mass or more and 10% by mass or less with respect to the total mass of the chemical mechanical polishing composition.
  • the pH can be 7 or more and 13 or less.
  • the chemical mechanical polishing composition of the above application example is It can be used to polish a semiconductor substrate containing a ruthenium film.
  • One aspect of the polishing method according to the present invention is: A step of polishing a semiconductor substrate using the chemical mechanical polishing composition of the above application example.
  • the semiconductor substrate may include a ruthenium film.
  • the generation of ruthenium tetroxide, which is highly toxic to the human body, can be suppressed, and a semiconductor substrate, particularly a ruthenium film-containing substrate can be polished at high speed, and the object to be polished Surface scratches can be reduced.
  • a semiconductor substrate, particularly a ruthenium film-containing substrate can be polished at high speed, and the object to be polished Surface scratches can be reduced.
  • a semiconductor substrate, particularly a ruthenium film-containing substrate can be polished at a high speed, and can be polished flat and with high throughput. .
  • FIG. 1 is a conceptual diagram schematically showing the major axis (Rmax) and minor axis (Rmin) of (A) titanium oxide-containing particles.
  • FIG. 2 is a cross-sectional view schematically showing an object to be processed suitable for use in the polishing method according to this embodiment.
  • FIG. 3 is a cross-sectional view schematically showing the object to be processed at the end of the first polishing process.
  • FIG. 4 is a cross-sectional view schematically showing the object to be processed at the end of the second polishing process.
  • FIG. 5 is a perspective view schematically showing a chemical mechanical polishing apparatus.
  • a numerical range described using “to” means that numerical values described before and after “to” are included as a lower limit value and an upper limit value.
  • Chemical mechanical polishing composition contains (A) titanium oxide-containing particles and (B) an organic acid, and the (A) titanium oxide-containing particles are powder X.
  • the full width at half maximum of the peak portion where the diffraction intensity in the line diffraction pattern is maximum is less than 1 °.
  • Titanium oxide-containing particles The chemical mechanical polishing composition according to this embodiment includes (A) titanium oxide-containing particles.
  • “(A) Titanium oxide-containing particles” in the present invention may be particles formed only from titanium oxide, or may be particles containing other compounds than titanium oxide.
  • the titanium oxide contained in the titanium oxide-containing particles any of rutile type, anatase type, amorphous, and a mixture thereof can be used.
  • the upper limit of the full width at half maximum of the peak portion where the diffraction intensity in the powder X-ray diffraction pattern is maximum is less than 1 °, and preferably less than 0.7 °.
  • the lower limit value of the half width is preferably 0.2 ° or more.
  • the powder X-ray diffraction pattern is a diffraction measured at each incident angle in a two-dimensional graph with the incident angle as the horizontal axis and the diffraction intensity as the vertical axis when performing sample measurement by powder X-ray diffraction. Refers to the intensity plot line.
  • the (A) titanium oxide-containing particles in this embodiment have a ratio (Rmax / Rmin) of the major axis to the minor axis of 1.1 when the major axis of the (A) titanium oxide-containing particle is Rmax and the minor axis is Rmin. Is preferably 4.0 to 4.0, more preferably 1.5 to 3.8, and particularly preferably 2.0 to 3.5. If the ratio of the major axis to the minor axis (Rmax / Rmin) is 1.1 or more, the ruthenium film-containing substrate can be polished at high speed, and if the ratio of the major axis to the minor axis (Rmax / Rmin) is 4.0 or less. (A) Since the catch at the end of the titanium oxide-containing particles can be suppressed, polishing scratches on the polished surface of the ruthenium film-containing substrate can be reduced.
  • the ratio of the major axis to the minor axis (Rmax / Rmin) of the titanium oxide-containing particles can be adjusted by appropriately controlling the heat treatment conditions, acid addition conditions, pulverization conditions, and the like in production.
  • the major axis (Rmax) and minor axis (Rmin) of the titanium oxide-containing particles can be measured as follows. For example, when the image of one independent titanium oxide-containing particle 1 photographed by a transmission electron microscope is elliptical as shown in FIG. 1, the major axis a of the elliptical shape is defined as the major axis (Rmax of the titanium oxide-containing particle 1). ) And the short axis b of the elliptical shape is determined as the short diameter (Rmin) of the titanium oxide-containing particle 1.
  • the major axis (Rmax) and minor axis (Rmin) of 50 titanium oxide-containing particles are measured, and after calculating the average value of major axis (Rmax) and minor axis (Rmin), the major axis and The ratio to the minor axis (Rmax / Rmin) can be calculated and obtained.
  • titanium oxide-containing particles contain a compound other than titanium oxide
  • examples of the compound other than titanium oxide include aluminum hydroxide, aluminum oxide (alumina), aluminum chloride, aluminum nitride, aluminum acetate, and aluminum phosphate. And aluminum compounds such as aluminum sulfate, sodium aluminate, and potassium aluminate.
  • the (A) titanium oxide-containing particles containing an aluminum compound are also referred to as “aluminum / titanium oxide-containing particles”.
  • the value of Al is preferably 6 to 70, more preferably 10 to 65, and particularly preferably 20 to 60. If the value of M Ti / M Al is 6 or more, sufficient hardness for polishing can be obtained, so that the ruthenium film-containing substrate can be polished at high speed, and the titanium oxide-containing particles are chemically inert. As a result, the generation of foaming can be suppressed.
  • the value of M Ti / M Al is 70 or less, aggregation of the aluminum / titanium oxide-containing particles can be suppressed, so that polishing scratches on the surface to be polished can be reduced.
  • M Ti / M Al The value of M Ti / M Al is obtained by dissolving aluminum / titanium oxide-containing particles with dilute hydrofluoric acid and using ICP-MS (inductively coupled plasma mass spectrometer: manufactured by PerkinElmer, model number “ELAN DRC PLUS”). The content of titanium and aluminum in the aluminum / titanium oxide-containing particles can be measured and calculated from the measured values.
  • the aluminum / titanium oxide-containing particles are easily dispersed in a chemical mechanical polishing composition having a pH of 7 or more and 13 or less, and are excellent in stability.
  • the reason is that, in the chemical mechanical polishing composition having a pH of 7 or more and 13 or less, the zeta potential of the aluminum / titanium oxide-containing particles is increased, and therefore, the dispersibility is considered to be improved by electrostatic repulsion between the particles. .
  • the absolute value of the zeta potential of the aluminum / titanium oxide-containing particles in the chemical mechanical polishing composition having a pH of 7 or more and 13 or less is preferably 25 mV or more, more preferably 30 mV or more, and particularly preferably. Is 35 mV or more. If the absolute value of the zeta potential of the aluminum / titanium oxide-containing particles in the chemical mechanical polishing composition in the pH range is 25 mV or more, the dispersibility of the aluminum / titanium oxide-containing particles is improved, and the semiconductor substrate High-speed polishing can be performed while reducing polishing scratches (particularly a ruthenium film-containing substrate).
  • the average particle diameter of the titanium oxide-containing particles is preferably 10 nm or more and 300 nm or less, more preferably 20 nm or more and 200 nm or less, and particularly preferably 25 nm or more and 150 nm or less. If the (A) titanium oxide-containing particles having an average particle size in the above range, a sufficient polishing rate can be obtained, and a chemical mechanical polishing composition excellent in stability without causing sedimentation / separation of particles can be obtained. As a result, good performance can be achieved.
  • the average particle diameter of the (A) titanium oxide-containing particles is determined by measuring the specific surface area by the BET method using, for example, a flow-type specific surface area automatic measuring device (manufactured by Shimadzu Corporation, “micrometricsFlowSorbII2300”). It can be calculated.
  • the content of the titanium oxide-containing particles is preferably 0.1% by mass or more, and 0.3% by mass or more with respect to the total mass of the chemical mechanical polishing composition from the viewpoint of polishing the semiconductor substrate at high speed. Is more preferable, and 0.5% by mass or more is particularly preferable.
  • the content of the titanium oxide-containing particles is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less from the viewpoint of reducing the occurrence of polishing scratches on the polished surface.
  • the chemical mechanical polishing composition according to this embodiment contains (B) an organic acid.
  • the organic acid By containing the organic acid, the ruthenium film-containing substrate can be polished at a higher speed.
  • an ion composed of an element of a semiconductor material containing a metal such as ruthenium or an organic acid having a coordination ability with respect to the surface of the semiconductor material or the like is preferable.
  • an organic acid having at least one of a hydroxyl group and a carboxyl group is preferable. With such an organic acid, the coordination ability with respect to the surface of a semiconductor material containing a metal such as ruthenium is increased, and the polishing rate can be improved.
  • (B) organic acids include stearic acid, lauric acid, oleic acid, myristic acid, dodecylbenzenesulfonic acid, alkenyl succinic acid, lactic acid, tartaric acid, fumaric acid, glycolic acid, phthalic acid, maleic acid, formic acid, Acetic acid, oxalic acid, citric acid, malic acid, malonic acid, glutaric acid, succinic acid, benzoic acid, quinolinic acid, quinaldic acid, amidosulfuric acid; glycine, alanine, aspartic acid, glutamic acid, lysine, arginine, tryptophan, aromatic amino acid And amino acids such as heterocyclic amino acids.
  • At least one selected from stearic acid, lauric acid, oleic acid, myristic acid, dodecylbenzenesulfonic acid, alkenyl succinic acid and maleic acid is preferable.
  • These (B) organic acids may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the organic acid may be a salt of the organic acid, or may react with a base separately added in the chemical mechanical polishing composition to form a salt of the organic acid.
  • bases include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, organic alkali compounds such as tetramethylammonium hydroxide (TMAH), choline, and ammonia. Is mentioned.
  • the content of the organic acid (B) is preferably 0.001% by mass or more with respect to the total mass of the chemical mechanical polishing composition from the viewpoint of high-speed polishing of a semiconductor substrate containing a metal such as ruthenium. More preferably, it is more preferably at least 0.005% by mass.
  • the content of the organic acid is preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
  • the chemical mechanical polishing composition according to this embodiment may contain (C) an oxidizing agent within a range in which the ruthenium film is not oxidized during the CMP process to produce ruthenium tetroxide.
  • C By containing an oxidizing agent, it is possible to create a fragile modified layer on the surface to be polished by oxidizing a metal such as ruthenium and promoting a complexing reaction with a polishing liquid component. Has the effect of facilitating.
  • oxidizing agent examples include ammonium persulfate, potassium persulfate, hydrogen peroxide, ferric nitrate, diammonium cerium nitrate, potassium hypochlorite, ozone, potassium periodate, and peracetic acid. .
  • oxidants at least one selected from potassium periodate, potassium hypochlorite and hydrogen peroxide is preferable, and hydrogen peroxide is more preferable from the viewpoint of suppressing the generation of ruthenium tetroxide.
  • These (C) oxidizing agents may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the (C) oxidizing agent is the total mass of the chemical mechanical polishing composition from the viewpoint of preventing the oxidation of a metal such as ruthenium from becoming insufficient and reducing the polishing rate. Is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and particularly preferably 0.01% by mass or more.
  • the content of the oxidizing agent is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less from the viewpoint of preventing ruthenium tetroxide from being generated due to excessive oxidation of ruthenium. .
  • the chemical mechanical polishing composition according to the present embodiment includes, in addition to water, which is a main liquid medium, a nitrogen-containing heterocyclic compound, a surfactant, an inorganic acid and a salt thereof, and water-soluble as necessary. It may contain a polymer or the like.
  • the chemical mechanical polishing composition according to this embodiment contains water as a main liquid medium.
  • the water is not particularly limited, but pure water is preferable. Water should just be mix
  • the chemical mechanical polishing composition according to this embodiment may contain a nitrogen-containing heterocyclic compound.
  • a nitrogen-containing heterocyclic compound By containing a nitrogen-containing heterocyclic compound, excessive etching of a metal such as ruthenium can be suppressed, and surface roughness after polishing such as corrosion can be prevented.
  • the nitrogen-containing heterocyclic compound is an organic compound containing at least one heterocyclic ring selected from a hetero five-membered ring and a hetero six-membered ring having at least one nitrogen atom.
  • the heterocyclic ring include hetero five-membered rings such as a pyrrole structure, an imidazole structure, and a triazole structure; and hetero six-membered rings such as a pyridine structure, a pyrimidine structure, a pyridazine structure, and a pyrazine structure.
  • the heterocyclic ring may form a condensed ring.
  • indole structure isoindole structure, benzimidazole structure, benzotriazole structure
  • quinoline structure isoquinoline structure, quinazoline structure, cinnoline structure, phthalazine structure, quinoxaline structure, acridine structure and the like.
  • heterocyclic compounds having such a structure heterocyclic compounds having a pyridine structure, a quinoline structure, a benzimidazole structure, or a benzotriazole structure are preferable.
  • nitrogen-containing heterocyclic compounds include aziridine, pyridine, pyrimidine, pyrrolidine, piperidine, pyrazine, triazine, pyrrole, imidazole, indole, quinoline, isoquinoline, benzoisoquinoline, purine, pteridine, triazole, triazolidine, benzotriazole, carboxy Examples thereof include benzotriazole, and further derivatives having these skeletons. Among these, at least one selected from benzotriazole and triazole is preferable.
  • These nitrogen-containing heterocyclic compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the nitrogen-containing heterocyclic compound is preferably 0.05 to 2% by mass, more preferably 0.8%, based on the total mass of the chemical mechanical polishing composition. 1 to 1% by mass.
  • the chemical mechanical polishing composition according to this embodiment may contain a surfactant.
  • the surfactant has the effect of imparting an appropriate viscosity to the chemical mechanical polishing composition, suppresses excessive etching of metals such as ruthenium, and prevents surface roughness after polishing such as corrosion. There are cases where it is possible.
  • the surfactant is not particularly limited, and examples thereof include anionic surfactants, cationic surfactants, and nonionic surfactants.
  • anionic surfactant include fatty acid soaps, carboxylates such as alkyl ether carboxylates; sulfonates such as alkylnaphthalene sulfonates and ⁇ -olefin sulfonates; higher alcohol sulfates, alkyl ethers.
  • examples thereof include sulfates such as sulfates and polyoxyethylene alkylphenyl ether sulfates; and fluorine-containing surfactants such as perfluoroalkyl compounds.
  • Examples of the cationic surfactant include aliphatic amine salts and aliphatic ammonium salts.
  • examples of the nonionic surfactant include nonionic surfactants having a triple bond such as acetylene glycol, acetylene glycol ethylene oxide adduct, and acetylene alcohol; polyethylene glycol type surfactants. These surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the surfactant is preferably 0.001% by mass or more and 5% by mass or less, more preferably 0.001 based on the total mass of the chemical mechanical polishing composition. It is not less than 3% by mass and particularly preferably not less than 0.01% and not more than 1% by mass.
  • the chemical mechanical polishing composition according to this embodiment may contain an inorganic acid and a salt thereof.
  • an inorganic acid and a salt thereof By containing an inorganic acid and a salt thereof, the polishing rate for a metal such as ruthenium may be further improved.
  • the inorganic acid for example, at least one selected from hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid is preferable.
  • a salt of an inorganic acid the salt of the above-mentioned inorganic acid may be sufficient, and the base added separately in the chemical mechanical polishing composition and the above-mentioned inorganic acid may form a salt.
  • Such bases include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; organic alkali compounds such as tetramethylammonium hydroxide (TMAH) and choline, and ammonia. Is mentioned.
  • alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide
  • organic alkali compounds such as tetramethylammonium hydroxide (TMAH) and choline, and ammonia. Is mentioned.
  • the content of the inorganic acid and the salt is preferably 3 to 8% by mass, more preferably 3 to 6% by mass with respect to the total mass of the chemical mechanical polishing composition. %.
  • the chemical mechanical polishing composition according to this embodiment may contain a water-soluble polymer.
  • a water-soluble polymer By containing a water-soluble polymer, it may be adsorbed on the surface of a semiconductor substrate (particularly a ruthenium film-containing substrate) to reduce polishing friction.
  • water-soluble polymers include polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, polyethyleneimine, polyvinyl methyl ether, polyallylamine, and hydroxyethyl cellulose.
  • the weight average molecular weight (Mw) of the water-soluble polymer is preferably 1,000 or more and 1,500,000 or less, more preferably 10,000 or more and 500,000 or less, and particularly preferably 30,000 or more and 100 or less. , 000 or less. If the weight average molecular weight of the water-soluble polymer is within the above range, the water-soluble polymer is easily adsorbed to the semiconductor substrate (particularly the ruthenium film-containing substrate), and the polishing friction is further reduced. As a result, generation of polishing flaws on the surface to be polished can be more effectively reduced.
  • “weight average molecular weight (Mw)” refers to a weight average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography).
  • the content of the water-soluble polymer is preferably 0.001% by mass or more based on the total mass of the chemical mechanical polishing composition from the viewpoint of effectively obtaining the effect of reducing the occurrence of polishing scratches on the surface to be polished. 0.003% by mass or more is more preferable, and 0.01% by mass or more is particularly preferable.
  • the content of the water-soluble polymer is preferably 1% by mass or less, more preferably 0.5% by mass or less, from the viewpoint of polishing at a sufficient polishing rate while suppressing generation of polishing scratches on the surface to be polished. .1% by mass or less is particularly preferable.
  • the content of the water-soluble polymer depends on the weight average molecular weight (Mw) of the water-soluble polymer, but is preferably adjusted so that the viscosity of the chemical mechanical polishing composition is less than 10 mPa ⁇ s. .
  • Mw weight average molecular weight
  • the viscosity of the chemical mechanical polishing composition is less than 10 mPa ⁇ s, it is easy to polish a semiconductor substrate (particularly a ruthenium film-containing substrate) at high speed, and the viscosity is appropriate.
  • a composition can be provided.
  • the pH of the chemical mechanical polishing composition according to this embodiment is preferably 7 to 13, and more preferably 8 to 12.5.
  • the absolute value of the zeta potential of the (A) titanium oxide-containing particles in the chemical mechanical polishing composition is increased and the dispersibility is improved, so that the semiconductor substrate (particularly the ruthenium film-containing substrate) High-speed polishing can be performed while reducing polishing scratches.
  • the absolute value of the zeta potential is particularly increased and the dispersibility is improved.
  • pH is 13 or less, the handleability at the time of production will improve.
  • the pH of the chemical mechanical polishing composition according to this embodiment can be adjusted by adding, for example, potassium hydroxide, ethylenediamine, TMAH (tetramethylammonium hydroxide), ammonia, or the like. The above can be used.
  • pH refers to a hydrogen ion index
  • the value can be measured using a commercially available pH meter (for example, a desktop pH meter manufactured by Horiba, Ltd.).
  • the chemical mechanical polishing composition according to this embodiment can suppress the generation of ruthenium tetroxide, which is highly toxic to the human body, and can polish a ruthenium film-containing substrate at high speed in CMP of a ruthenium film-containing substrate as described above. In addition, polishing scratches on the surface to be polished can be reduced. Therefore, the chemical mechanical polishing composition according to this embodiment is suitable as a polishing material for chemically mechanically polishing a ruthenium film-containing substrate in a semiconductor substrate in which a ruthenium film, which is a next-generation semiconductor material, is applied to a base of a copper film. It is.
  • the chemical mechanical polishing composition according to this embodiment can be prepared by dissolving or dispersing the above-described components in a liquid medium such as water.
  • the method for dissolving or dispersing is not particularly limited, and any method may be applied as long as it can be uniformly dissolved or dispersed. Further, the mixing order and mixing method of the components described above are not particularly limited.
  • the chemical mechanical polishing composition according to this embodiment can be prepared as a concentrated type stock solution and diluted with a liquid medium such as water when used.
  • polishing method includes a step of polishing a semiconductor substrate using the chemical mechanical polishing composition described above.
  • the chemical mechanical polishing composition described above suppresses the generation of ruthenium tetroxide, which is highly toxic to the human body, and can polish the ruthenium film at high speed when chemically rubbing the ruthenium film-containing substrate. It is possible to reduce polishing scratches. Therefore, the polishing method according to the present embodiment is suitable for polishing a semiconductor substrate in which a ruthenium film, which is a next-generation semiconductor material, is applied to a base of a copper film.
  • a specific example of the polishing method according to the present embodiment will be described in detail with reference to the drawings.
  • FIG. 2 is a cross-sectional view schematically showing a target object suitable for use in the polishing method according to this embodiment.
  • the target object 100 is formed through the following steps (1) to (4).
  • a base 10 is prepared.
  • the substrate 10 may be composed of, for example, a silicon substrate and a silicon oxide film formed thereon. Furthermore, a functional device such as a transistor (not shown) may be formed on the base 10. Next, a silicon oxide film 12 that is an insulating film is formed on the substrate 10 by using a thermal oxidation method.
  • the silicon oxide film 12 is patterned. Using the obtained pattern as a mask, wiring trenches 14 are formed in the silicon oxide film 12 by photolithography.
  • a ruthenium film 16 is formed on the surface of the silicon oxide film 12 and the inner wall surface of the wiring groove 14.
  • the ruthenium film 16 can be formed, for example, by chemical vapor deposition (CVD) using a ruthenium precursor, atomic layer deposition (ALD), or physical vapor deposition (PVD) such as sputtering.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • PVD physical vapor deposition
  • a 10,000 to 15,000 mm copper film 18 is deposited by chemical vapor deposition or electroplating.
  • a material of the copper film not only high-purity copper but also an alloy containing copper can be used.
  • the copper content in the alloy containing copper is preferably 95% by mass or more.
  • FIG. 3 is a cross-sectional view schematically showing the workpiece 100 at the end of the first polishing step.
  • the first polishing step is a step of polishing the copper film 18 until the ruthenium film 16 is exposed using the chemical mechanical polishing composition for the copper film.
  • FIG. 4 is a cross-sectional view schematically showing the workpiece 100 at the end of the second polishing step.
  • the second polishing step is a step of polishing the ruthenium film 16 and the copper film 18 until the silicon oxide film 12 is exposed using the chemical mechanical polishing composition described above.
  • the chemical mechanical polishing composition described above since the chemical mechanical polishing composition described above is used, the generation of ruthenium tetroxide, which is highly toxic to the human body, is suppressed, the ruthenium film can be polished at a high speed, and polishing scratches on the surface to be polished can be removed. Can be reduced.
  • FIG. 5 is a perspective view schematically showing the polishing apparatus 200.
  • the slurry (chemical mechanical polishing composition) 44 is supplied from the slurry supply nozzle 42, and the semiconductor substrate is rotated while the turntable 48 to which the polishing cloth 46 is attached is rotated. This is done by bringing the carrier head 52 holding 50 into contact.
  • FIG. 5 also shows the water supply nozzle 54 and the dresser 56.
  • the polishing load of the carrier head 52 can be selected within a range of 0.7 to 70 psi, and preferably 1.5 to 35 psi. Further, the rotation speeds of the turntable 48 and the carrier head 52 can be appropriately selected within the range of 10 to 400 rpm, and preferably 30 to 150 rpm.
  • the flow rate of the slurry (chemical mechanical polishing composition) 44 supplied from the slurry supply nozzle 42 can be selected within the range of 10 to 1,000 mL / min, and preferably 50 to 400 mL / min.
  • polishing apparatuses examples include: “EPO-112”, “EPO-222” manufactured by Ebara Manufacturing Co., Ltd .; “LGP-510”, “LGP-552” manufactured by Lappmaster SFT, “Applied Materials” Model “Mirra”, “Reflexion”; G & P manufactured by TECHNOLOGY, model “POLI-400L”; manufactured by AMAT, model “Reflexion LK”, and the like.
  • the slurry was heated to 50 ° C., and 12.5 kg of 35% hydrochloric acid was added at this temperature over 4 minutes with stirring.
  • the hydrochloric acid concentration in the slurry after addition of hydrochloric acid was 40 g / L in terms of 100% HCl. It was made to become.
  • the hydrochloric acid addition rate was 0.11 kg / min per 1 kg of TiO 2 .
  • ⁇ Preparation of aluminum / titanium oxide-containing particles B, C, G to I> The powder obtained by mixing the titanium oxide particles A and aluminum hydroxide obtained above was baked in the range of 100 to 1000 ° C., and then washed with a 1% aqueous sodium hydroxide solution. Subsequently, it was washed with water, dried and pulverized to obtain aluminum / titanium oxide-containing particles. At this time, the mixing ratio of the titanium oxide particles A and aluminum hydroxide is appropriately adjusted, and the firing temperature is appropriately changed within the range of 100 to 1000 ° C., whereby the aluminum / titanium oxide-containing particles B shown in Tables 1 and 2 are used. , C, G to I were obtained respectively.
  • TiO 2 ⁇ Preparation of titanium oxide particles D>
  • the titanyl sulfate solution was hydrolyzed by a conventional method, and 40 kg of a 48% aqueous sodium hydroxide solution was added to 35 kg of hydrous titanium dioxide cake (titanium dioxide hydrate) (10 kg in terms of TiO 2 ) that had been filtered and washed.
  • the mixture was heated and stirred at a temperature range of 95 to 105 ° C. for 2 hours.
  • the slurry was then filtered and washed thoroughly to obtain a base-treated titanium dioxide hydrate. Water was added to the hydrate cake to make a slurry, and the hydrated TiO 2 concentration was adjusted to 110 g / L. While stirring the slurry, 35% hydrochloric acid was added to adjust the pH to 7.0.
  • the slurry was heated to 50 ° C., and 9.1 kg of 35% hydrochloric acid was added at this temperature over 4 minutes with stirring.
  • the hydrochloric acid concentration in the slurry after addition of hydrochloric acid was 30 g / L in terms of 100% HCl. It was made to become.
  • the hydrochloric acid addition rate is 0.08 kg / min per 1 kg of TiO 2 .
  • the aluminum / titanium oxide-containing particles E and F shown in Table 3 were respectively adjusted by appropriately adjusting the mixing ratio of the titanium oxide particles and aluminum hydroxide and appropriately changing the firing temperature within the range of 100 to 1000 ° C. Obtained.
  • ⁇ Silica particles> To a mixed solution of 787.9 g of pure water, 786.0 g of 26% ammonia water, and 12924 g of methanol, a mixed solution of 1522.2 g of tetramethoxysilane and 413.0 g of methanol was dropped over 55 minutes while maintaining the liquid temperature at 35 ° C. Thus, a silica sol using water and methanol as liquid media was obtained. This silica sol was heated and concentrated to 5000 mL under normal pressure to obtain silica particles.
  • ⁇ Alumina particles> As the alumina particles, Advanced Alumina Series AA-04 manufactured by Sumitomo Chemical Co., Ltd. was used.
  • Polishing device G & P TECHNOLOGY, model “POLI-400L” ⁇ Polishing pad: Fuji Spinning Co., Ltd., “Multi-rigid polyurethane pad; H800-type1 (3-1S) 775” ⁇
  • Chemical mechanical polishing composition supply rate 100 mL / min ⁇
  • Surface plate rotation speed: 100 rpm -Head rotation speed: 90 rpm -Head pressing pressure: 2 psi Polishing rate ( ⁇ / min) (film thickness before polishing ⁇ film thickness after polishing) / polishing time
  • the evaluation criteria for the polishing rate are as follows. Tables 1 to 3 show the ruthenium film polishing rate and its evaluation results. (Evaluation criteria) -When the polishing rate is 300 ⁇ / min or more, the polishing rate is high, so in actual semiconductor polishing, the speed balance with the polishing of the other material film can be easily secured, and it is determined to be good because it is practical. It was written. When the polishing rate was less than 300 ⁇ / min, the polishing rate was low, so that it was difficult to put into practical use and was judged as defective, and indicated as “B”.
  • the total number of defects of 90 nm or more was counted using the defect inspection apparatus (the model "Surfscan SP1" by KLA-Tencor Corporation).
  • the evaluation criteria are as follows.
  • the total number of defects per wafer and the evaluation results are also shown in Tables 1 to 3. (Evaluation criteria)
  • the case where the total number of defects per wafer was less than 500 was judged good, and “A” was indicated in the table.
  • Evaluation results Tables 1 to 3 show the compositions of the chemical mechanical polishing compositions of the examples and the comparative examples and the evaluation results.
  • Examples 1 to 19 by using a chemical mechanical polishing composition containing titanium oxide-containing particles and an organic acid having a half-value width of less than 1 ° in the peak portion where the diffraction intensity in the powder X-ray diffraction pattern is maximum, It was found that the ruthenium film can be polished at a high speed and polishing scratches on the surface to be polished can be reduced.
  • Comparative Example 1 is an example in which a chemical mechanical polishing composition containing titanium oxide particles A having a half-width of less than 1 ° at the peak portion where the diffraction intensity in the powder X-ray diffraction pattern is maximum and containing no organic acid is used. It is. In this case, since the organic acid was not contained, the ruthenium film could not be polished at a high speed, and in the defect evaluation, many defects were recognized on the surface of the surface to be polished.
  • Comparative Example 2 is an example using a chemical mechanical polishing composition containing silica particles and an organic acid (stearic acid).
  • the ruthenium film could not be polished at high speed because the mechanical polishing force of the silica particles was too low.
  • Comparative Example 3 is an example in which a chemical mechanical polishing composition containing alumina particles and an organic acid (stearic acid) having a half-value width of less than 1 ° at the peak portion where the diffraction intensity is maximum in the powder X-ray diffraction pattern is used. is there.
  • a chemical mechanical polishing composition containing alumina particles and an organic acid (stearic acid) having a half-value width of less than 1 ° at the peak portion where the diffraction intensity is maximum in the powder X-ray diffraction pattern is used. is there.
  • the mechanical polishing power of the alumina particles is too low, the ruthenium film cannot be polished at a high speed, and in the defect evaluation, a large number of defects were found on the surface of the surface to be polished.
  • Comparative Example 4 is a chemical mechanical polishing composition containing aluminum / titanium oxide-containing particles E having a half-value width of 2.1 ° at the peak portion where the diffraction intensity is maximum in the powder X-ray diffraction pattern and an organic acid (stearic acid). It is an example using a thing. In this case, since the hardness of the aluminum / titanium oxide-containing particles E was low and the mechanical polishing power was too low, the ruthenium film could not be polished at high speed.
  • Comparative Example 5 is a chemical mechanical polishing composition containing aluminum / titanium oxide-containing particles F having a half-value width of 1.4 ° at the peak portion where the diffraction intensity is maximum in the powder X-ray diffraction pattern and an organic acid (stearic acid). It is an example using a thing. In this case, since the hardness of the aluminum / titanium oxide-containing particles F was slightly lowered, the ruthenium film could not be polished at high speed, and in the defect evaluation, many defects were recognized on the surface of the surface to be polished. .
  • Comparative Example 6 and Comparative Example 7 are examples in which the titanium oxide particles A having a half-value width of less than 1 ° at the peak portion where the diffraction intensity is maximum in the powder X-ray diffraction pattern, and nitric acid and sulfuric acid were used in place of the organic acid, respectively. It is. In this case, a number of defects were observed on the surface of the surface to be polished due to the etching action of nitric acid or sulfuric acid.
  • the chemical mechanical polishing composition according to the present invention can polish a semiconductor substrate (particularly a ruthenium film-containing substrate) at high speed and reduce polishing scratches on the surface to be polished.
  • the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment.
  • the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced.
  • the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object.
  • the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.
  • SYMBOLS 1 Titanium oxide containing particle, 10 ... Base

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Abstract

L'invention concerne : une composition de polissage mécano-chimique qui peut polir un substrat semi-conducteur (en particulier, un substrat contenant un film de ruthénium) à grande vitesse et réduire les rayures de polissage sur une surface à polir tout en supprimant la génération de tétraoxyde de ruthénium qui est hautement toxique pour le corps humain ; et un procédé de polissage utilisant ladite composition. Cette composition de polissage mécano-chimique contient des particules contenant de l'oxyde de titane (A) et un acide organique (B), les particules contenant de l'oxyde de titane (A) ont une largeur totale à mi-hauteur d'une partie de pic, au niveau de laquelle l'intensité de diffraction dans un motif de diffraction de rayons X de poudre est maximale, en dessous de 1°.
PCT/JP2019/002526 2018-02-05 2019-01-25 Composition de polissage mecano-chimique et procédé de polissage WO2019151144A1 (fr)

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WO2021060234A1 (fr) * 2019-09-27 2021-04-01 株式会社トクヤマ AGENT INHIBANT LA GENERATION DE GAZ RuO4 ET PROCEDE INHIBANT LA GENERATION DE GAZ RuO4
US11674230B2 (en) 2019-09-27 2023-06-13 Tokuyama Corporation Treatment liquid for semiconductor with ruthenium and method of producing the same

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TW202132527A (zh) * 2019-12-12 2021-09-01 日商Ｊｓｒ股份有限公司 化學機械研磨用組成物及研磨方法

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JP2015168818A (ja) * 2014-03-11 2015-09-28 信越化学工業株式会社 研磨組成物及び研磨方法並びに研磨組成物の製造方法
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JP2009010031A (ja) * 2007-06-26 2009-01-15 Fujifilm Corp 金属用研磨液及びそれを用いた研磨方法
JP2009206240A (ja) * 2008-02-27 2009-09-10 Jsr Corp 化学機械研磨用水系分散体、化学機械研磨用水系分散体の製造方法および化学機械研磨方法
JP2015168818A (ja) * 2014-03-11 2015-09-28 信越化学工業株式会社 研磨組成物及び研磨方法並びに研磨組成物の製造方法
WO2016140246A1 (fr) * 2015-03-04 2016-09-09 日立化成株式会社 Liquide de polissage cmp et procédé de polissage l'utilisant

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WO2021060234A1 (fr) * 2019-09-27 2021-04-01 株式会社トクヤマ AGENT INHIBANT LA GENERATION DE GAZ RuO4 ET PROCEDE INHIBANT LA GENERATION DE GAZ RuO4
JP6874231B1 (ja) * 2019-09-27 2021-05-19 株式会社トクヤマ ＲｕＯ４ガスの発生抑制剤及びＲｕＯ４ガスの発生抑制方法
US11674230B2 (en) 2019-09-27 2023-06-13 Tokuyama Corporation Treatment liquid for semiconductor with ruthenium and method of producing the same
US11932590B2 (en) 2019-09-27 2024-03-19 Tokuyama Corporation Inhibitor for RuO4 gas generation and method for inhibiting RuO4 gas generation

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