WO2017221660A1 - 研磨液、化学的機械的研磨方法 - Google Patents

研磨液、化学的機械的研磨方法 Download PDF

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WO2017221660A1
WO2017221660A1 PCT/JP2017/020409 JP2017020409W WO2017221660A1 WO 2017221660 A1 WO2017221660 A1 WO 2017221660A1 JP 2017020409 W JP2017020409 W JP 2017020409W WO 2017221660 A1 WO2017221660 A1 WO 2017221660A1
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Prior art keywords
polishing
polishing liquid
rpm
acid
group
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PCT/JP2017/020409
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English (en)
French (fr)
Japanese (ja)
Inventor
上村　哲也
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富士フイルム株式会社
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Priority to CN201780033060.5A priority Critical patent/CN109312211A/zh
Priority to JP2018523645A priority patent/JP6761469B2/ja
Priority to KR1020187036008A priority patent/KR102169835B1/ko
Publication of WO2017221660A1 publication Critical patent/WO2017221660A1/ja

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    • 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
    • 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
    • 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
    • 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 polishing liquid used for chemical mechanical polishing and a chemical mechanical polishing method.
  • CMP chemical mechanical polishing
  • a general method of CMP is to apply a polishing pad on a circular polishing platen (platen), immerse the surface of the polishing pad with a polishing liquid, press the surface of the object to be polished against the pad, and apply a predetermined pressure from the back surface.
  • both the polishing platen and the object to be polished are rotated, and the surface of the object to be polished is flattened by the generated mechanical friction.
  • a polishing liquid having a good polishing rate “containing an oxidizing agent, a metal oxide dissolving agent, a metal anticorrosive agent, a water-soluble polymer and water, and the water-soluble polymer includes acrylic acid and methacrylic acid.
  • the copolymerization ratio of the methacrylic acid in the copolymer is 1 to 20 mol% based on the total of the acrylic acid and the methacrylic acid, and the viscosity at 25 ° C. is 0.5 Disclosed is a “polishing liquid for metal film having a viscosity of ⁇ 3.5 mPa ⁇ s”.
  • the inventors have used a polishing liquid described in Patent Document 1 to form an inorganic insulating film such as a silicon oxide film or silicon nitride, or a wafer on which a metal film mainly containing Cu, Ta, or the like is formed.
  • an inorganic insulating film such as a silicon oxide film or silicon nitride, or a wafer on which a metal film mainly containing Cu, Ta, or the like is formed.
  • the in-plane uniformity hereinafter simply referred to as “in-plane uniformity”
  • the cause is that the shearing force received from the polishing pad differs depending on the position in the plane of the object to be polished (for example, the wafer).
  • this invention makes it a subject to provide the polishing liquid which can give the to-be-polished body excellent in in-plane uniformity.
  • Another object of the present invention is to provide a chemical mechanical polishing method using the above polishing liquid.
  • the present inventors have found that the above-mentioned problems can be solved by a polishing liquid having a pseudo-plasticity with a viscosity ratio measured by a rotational viscometer,
  • the present invention has been completed. That is, it has been found that the above object can be achieved by the following configuration.
  • ⁇ 100 rpm is the viscosity of the polishing liquid measured at 40 rpm RH and a rotational viscometer at a rotation speed of 100 rpm at 23 ° C.
  • ⁇ 500 rpm is 40% RH, 23
  • the viscosity of the polishing liquid measured at 500 rpm with a rotational viscometer at ° C., and ⁇ 1000 rpm is the viscosity of the polishing liquid
  • the water-soluble polymer is at least one selected from the group consisting of polyacrylic acid, polymethacrylic acid, and a copolymer containing at least one of polyacrylic acid and polymethacrylic acid.
  • polishing liquid according to any one of (1) to (5) further comprising an oxidizing agent.
  • Polishing liquid as described in (6) whose content of the said oxidizing agent is 0.03 mass% or more with respect to polishing liquid total mass.
  • the oxidizing agent is hydrogen peroxide.
  • a chemical mechanical polishing method comprising a step of relatively moving a polishing object and the polishing pad to polish the surface to be polished to obtain a polished object.
  • the present invention it is possible to provide a polishing liquid that can provide an object to be polished having excellent in-plane uniformity. Moreover, according to this invention, the chemical mechanical polishing method using the said polishing liquid can be provided.
  • FIG. 1 is a schematic view showing a relative position between a wafer and a polishing pad in a process of performing CMP using a polishing pad on a wafer as an object to be polished.
  • FIG. 2 is a diagram showing the polishing rate (polishing amount) at each position in the plane of the wafer when CMP is performed using a polishing liquid exhibiting Newtonian properties. It is a figure which shows the grinding
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • 1 rpm corresponds to 1 rotation / minute.
  • 1 psi corresponds to 6894.76 Pa.
  • 1 cP corresponds to 1 ⁇ 10 3 Pa ⁇ s.
  • the description that does not indicate substitution and non-substitution includes those that have a substituent together with those that do not have a substituent, as long as the effects of the present invention are not impaired. It is included.
  • the “hydrocarbon group” includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group having a substituent (substituted hydrocarbon group). . This is synonymous also about each compound.
  • the polishing liquid of the present invention is A polishing liquid used for chemical mechanical polishing, Containing abrasive grains, organic acid, and water-soluble polymer, All of the following formulas (1) to (3) are satisfied. Equation (1): 1.5 ⁇ ⁇ 100rpm / ⁇ 1000rpm ⁇ 20 Formula (2): 1.2 ⁇ ⁇ 100 rpm / ⁇ 500 rpm ⁇ 10 Formula (3): ⁇ 100 rpm / ⁇ 1000 rpm > ⁇ 100 rpm / ⁇ 500 rpm
  • ⁇ 100 rpm is the viscosity of the polishing liquid measured at 40 rpm RH and a rotational viscometer at a rotation speed of 100 rpm at 23 ° C.
  • ⁇ 500 rpm is 40% RH, 23
  • the viscosity of the polishing liquid measured at 500 rpm with a rotational viscometer at ° C., and ⁇ 1000 rpm is the viscosity of the polishing
  • FIG. 1 is a schematic view showing a relative position between a wafer and a polishing pad in a process of performing CMP using a polishing pad on a wafer as an object to be polished.
  • FIG. 2 shows the polishing rate (polishing amount) at each position (center portion A and peripheral portions B and C) in the wafer plane when CMP is performed using a polishing liquid exhibiting Newtonian properties.
  • FIG. 1 and 2 in the plane of the wafer 1, the peripheral portions B and C are easily sheared with respect to the central portion A, and the peripheral portions B and C have a high polishing rate. For this reason, the amount of polishing of the object to be polished is larger at the peripheral portions B and C with respect to the central portion A. Note that the difference in polishing rate (shear difference) between the peripheral portions B and C is eliminated by the rotation of the wafer 1, and the polishing amounts at the peripheral portions B and C are substantially the same.
  • the object to be polished has a large amount of polishing at the peripheral portion with respect to the central portion and is inferior in in-plane uniformity.
  • the polishing liquid of the present invention is characterized in that all of the above formulas (1) to (3) are satisfied. Due to this feature, when CMP is performed on the object to be polished using the polishing liquid of the present invention, the viscosity of the polishing liquid becomes lower in the peripheral portions B and C on the plane of the wafer 1. That is, since the polishing liquid has a low viscosity, the shear from the polishing pad 2 is easily relaxed, and the polishing amount of the object to be polished is reduced.
  • the in-plane uniformity is excellent (see FIG. 3 above). Further, from the viewpoint of in-plane uniformity, the viscosity measured at a rotational speed between 100 rpm and 1000 rpm by a rotational viscometer is preferably lower at a location where the polishing rate (polishing amount) is larger, at least It is necessary to satisfy Expression (2) and Expression (3).
  • the polishing rate polishing amount
  • Expression (2) when eta is 100rpm / ⁇ 500rpm ⁇ 1.2, the polishing liquid shows Newtonian becomes inferior in in-plane uniformity.
  • ⁇ 100 rpm / ⁇ 500 rpm > 10 in the formula (2) the polishing amount in the central portion A becomes large, and the in-plane uniformity is inferior.
  • the viscosity measured with a rotational viscometer means a viscosity measured with a Brookfield rotational viscometer at 40% RH and 23 ° C.
  • the pH of the polishing liquid is preferably 2.0 to 8.0, and can be appropriately set depending on the material of the object to be polished.
  • the pH of the polishing liquid can be measured using a pH meter (for example, Toa Denpa Kogyo Co., Ltd., HM-30G).
  • a pH meter for example, Toa Denpa Kogyo Co., Ltd., HM-30G.
  • 2.0 to 6.0 is more preferable
  • 2.0 to 5.0 is more preferable from the viewpoint of further improving the polishing rate and in-plane uniformity.
  • 2.0 to 4.0 is particularly preferable.
  • 2.0 to 6.0 is more preferable from the viewpoint of further improving the in-plane uniformity.
  • the viscosity of the polishing liquid satisfies the relationships of the above formulas (1) to (3).
  • eta 100 rpm / eta 1000 rpm is preferably 1.5 to 10, more preferably from 1.5 to 5.
  • ⁇ 100 rpm / ⁇ 500 rpm is preferably 1.2 to 5, and more preferably 1.2 to 3.
  • ⁇ 100 rpm is preferably 1.0 to 10.0 cP, and more preferably 1.2 to 5.0 cP.
  • ⁇ 500 rpm is preferably 1.0 to 8.0 cP, and more preferably 1.2 to 4.0 cP.
  • ⁇ 1000 rpm is preferably 0.8 to 5.0 cp, more preferably 1.0 to 3.5 cP.
  • the polishing liquid contains abrasive grains.
  • the abrasive grains are not particularly limited, and known abrasive grains can be used.
  • the abrasive grains include inorganic abrasive grains such as silica, alumina, zirconia, ceria, titania, germania, and silicon carbide; and organic abrasive grains such as polystyrene, polyacryl, and polyvinyl chloride.
  • silica particles or ceria particles are preferable, and silica particles are more preferable because the dispersion stability in the polishing liquid is excellent and the number of scratches generated by CMP is small.
  • the silica particles are not particularly limited, and examples thereof include precipitated silica, fumed silica, and colloidal silica. Of these, colloidal silica is preferable.
  • the average primary particle size of the abrasive grains is not particularly limited, but is preferably 1 to 100 nm in that the polishing liquid has more excellent dispersion stability.
  • the average primary particle size can be confirmed by a manufacturer's catalog or the like.
  • Examples of commercially available abrasive grains include, as colloidal silica, PL-1, PL-3, PL-7, PL-10H, etc. (all trade names, manufactured by Fuso Chemical Industry Co., Ltd.).
  • the content of the abrasive grains is not particularly limited and is preferably 0.01 to 10% by mass with respect to the total mass of the polishing liquid. Within the above range, when the polishing liquid is applied to CMP, the polishing rate is excellent and the in-plane uniformity can be further improved. From the viewpoint of further improving the in-plane uniformity, the lower limit of the content of the abrasive grains is more preferably 0.1% by mass or more, and further preferably 3% by mass or more with respect to the total mass of the polishing liquid.
  • an abrasive grain may be used individually by 1 type, or may use 2 or more types together. When two or more kinds of abrasive grains are used in combination, the total content is preferably within the above range.
  • the polishing liquid contains an organic acid.
  • the organic acid is a compound different from the oxidizing agent described later, and has an action of promoting the oxidation of the metal, adjusting the pH of the polishing liquid, and as a buffering agent.
  • As the organic acid a water-soluble organic acid is preferable. It does not restrict
  • Acid 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid Phthalic acid, malic acid, tartaric acid, citric acid, lactic acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, and salts such as ammonium salts and / or alkali metal salts thereof.
  • succinic acid, malic acid, malonic acid and citric acid is more preferable.
  • the content of the organic acid is preferably 10% by mass or less, more preferably 5% by mass or less, and further more preferably 3% by mass or less with respect to the total mass of the polishing liquid.
  • an organic acid may be used individually by 1 type, or may use 2 or more types together. When two or more organic acids are used in combination, the total content is preferably within the above range.
  • the polishing liquid of the present invention contains a water-soluble polymer.
  • the water-soluble polymer acts as a viscosity modifier for the polishing liquid.
  • examples of the water-soluble polymer include a polymer having a carboxyl group-containing monomer as a basic structural unit, a salt thereof, and a copolymer containing them.
  • polyacrylic acid and salts thereof, and copolymers containing them polymethacrylic acid and salts thereof, and copolymers containing them; polyamic acid and salts thereof, and copolymers containing them; Acid, polyitaconic acid, polyfumaric acid, poly (p-styrenecarboxylic acid), and polycarboxylic acids such as polyglyoxylic acid and salts thereof, and copolymers containing them.
  • vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrolein may be mentioned.
  • the object to be polished is a silicon substrate for a semiconductor integrated circuit or the like, contamination with alkali metal, alkaline earth metal and / or halide is not desirable. It is desirable to use it as it is or in its ammonium salt state.
  • water-soluble polymer among the above, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyacrylamide, polyacrylic acid ammonium salt, polyvinyl alcohol, polyvinylpyrrolidone or polyethylene glycol, or a copolymer containing these, or Polyoxyethylene-polyoxypropylene block polymers are preferred.
  • polyacrylic acid, polymethacrylic acid, and a copolymer containing at least one of polyacrylic acid and polymethacrylic acid (a copolymer containing at least one of the above polyacrylic acid and polymethacrylic acid and Contains a copolymer containing structural units derived from acrylic acid, a copolymer containing structural units derived from methacrylic acid, or a structural unit derived from acrylic acid and a structural unit derived from methacrylic acid
  • the copolymer is intended to be at least one selected from the group consisting of:
  • the weight average molecular weight of the water-soluble polymer As the weight average molecular weight of the water-soluble polymer, the viscosity of the polishing liquid is appropriately adjusted, and from the viewpoint of achieving good in-plane uniformity, the polystyrene conversion value by the GPC (gel permeation chromatography) method is used as the handleability. From the viewpoint, it is usually preferably 3000 to 100,000, more preferably 5000 to 100,000, still more preferably 10,000 to 50,000, and particularly preferably 15,000 to 30,000.
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as a column and THF as an eluent. Based on the method using (tetrahydrofuran).
  • the content of the water-soluble polymer is not particularly limited and is preferably 0.01 to 10% by mass with respect to the total mass of the polishing liquid. If the content of the water-soluble polymer is 0.01% by mass or more, the in-plane uniformity becomes better. Further, when the content of the water-soluble polymer is 10% by mass or less, the polishing rate is excellent and the in-plane uniformity is further improved. From the viewpoint of further improving the in-plane uniformity, the lower limit of the content of the water-soluble polymer is more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more with respect to the total mass of the polishing liquid.
  • the upper limit of the content of the water-soluble polymer is more preferably 5% by mass or less, and still more preferably 4% by mass or less, with respect to the total mass of the polishing liquid.
  • a water-soluble polymer may be used individually by 1 type, or may use 2 or more types together. When two or more water-soluble polymers are used in combination, the total content is preferably within the above range.
  • the polishing liquid preferably contains an oxidizing agent when applied to CMP for removing excess metal thin film during wiring formation.
  • the oxidizing agent has a function of oxidizing a metal to be polished existing on the surface to be polished of the object to be polished. It does not restrict
  • the oxidizing agent include hydrogen peroxide, peroxide, nitric acid, nitrate, iodate, periodate, hypochlorite, chlorite, chlorate, perchlorate, and persulfate. Examples thereof include salts, dichromates, permanganates, ozone water, silver (II) salts, and iron (III) salts. Of these, hydrogen peroxide is preferable.
  • the content is not particularly limited, but is preferably 0.005 to 10% by mass with respect to the total mass of the polishing liquid.
  • the content of the oxidizing agent is 0.005% by mass or more, a more excellent polishing rate can be obtained when the polishing liquid is applied to CMP.
  • the content of the oxidizing agent is 10% by mass or less, dishing is less likely to occur on the surface to be polished when the polishing liquid is applied to CMP.
  • the lower limit of the content of the oxidizing agent is more preferably 0.03% by mass or more, and still more preferably 1% by mass or more with respect to the total mass of the polishing liquid.
  • the upper limit of the content of the oxidizing agent is more preferably 5% by mass or less with respect to the total mass of the polishing liquid.
  • an oxidizing agent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of oxidizing agents together, it is preferable that total content is in the said range.
  • the polishing liquid preferably contains water.
  • the water contained in the polishing liquid is not particularly limited, but ion exchange water, pure water, or the like can be used.
  • the water content is not particularly limited, but is preferably 80 to 99% by mass based on the total mass of the polishing liquid.
  • the polishing liquid preferably contains an azole compound when applied to CMP such as removal of excess metal thin film during wiring formation.
  • the azole compound not only improves the oxidation action by the oxidant, which is an optional component described above, but also adsorbs on the surface of the object to be polished to form a film and controls the corrosion of the metal surface, so that dishing or erosion occurs. Can be suppressed.
  • the azole compound means a compound containing a hetero five-membered ring containing one or more nitrogen atoms, and the number of nitrogen atoms is preferably 1 to 4.
  • the azole compound may contain atoms other than nitrogen atoms as heteroatoms.
  • guide_body intends the compound which has the substituent which the said heterocyclic 5-membered ring can contain.
  • the azole compound examples include pyrrole skeleton, imidazole skeleton, pyrazole skeleton, isothiazole skeleton, isoxazole skeleton, triazole skeleton, tetrazole skeleton, imidazole skeleton, thiazole skeleton, oxazole skeleton, isoxazole skeleton, thiadiazole skeleton, and oxadiazole. Examples thereof include compounds having a skeleton and a tetrazole skeleton.
  • the azole compound may be an azole compound containing a polycyclic structure containing a condensed ring in the skeleton.
  • Examples of the azole compound containing a polycyclic structure include compounds containing an indole skeleton, a purine skeleton, an indazole skeleton, a benzimidazole skeleton, a carbazole skeleton, a benzoxazole skeleton, a benzothiazole skeleton, a benzothiadiazole skeleton, and a naphthimidazole skeleton. Is mentioned.
  • the substituent that the azole compound may contain is not particularly limited, and examples thereof include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group (a linear, branched, or cyclic alkyl group, A polycyclic alkyl group such as an alkyl group or an active methine group may be included), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (regarding the position of substitution), an acyl group, an alkoxycarbonyl group , Aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group (Examples of the carbamoyl group having a substituent include N-hydroxycarbamoyl group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl
  • a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom
  • an alkyl group (a linear, branched or cyclic alkyl group, even a polycyclic alkyl group such as a bicycloalkyl group, An active methine group may be included), an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group (regarding the position of substitution).
  • active methine group means a methine group substituted with two electron-attracting groups.
  • the “electron withdrawing group” is, for example, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, or A carbonimidoyl group is intended.
  • Two electron-withdrawing groups may be bonded to each other to form a cyclic structure.
  • the term “salt” is intended to include cations such as alkali metals, alkaline earth metals, and heavy metals; organic cations such as ammonium ions and phosphonium ions.
  • azole compound examples include 5-methylbenzotriazole, 5-aminobenzotriazole, benzotriazole, 5,6-dimethylbenzoatriazole, 3-amino-1,2,4-triazole, 1,2, Examples include 4-triazole, 3,5-dimethylpyrazole, pyrazole, and imidazole.
  • a benzotriazole compound (a compound containing a benzotriazole skeleton) and a compound different from the benzotriazole compound (a compound not containing a benzotriazole skeleton) may be contained.
  • a compound containing a benzotriazole skeleton is strongly coordinated with copper oxidized by an oxidizing agent.
  • a compound that does not contain a benzotriazole skeleton is relatively weak and easy to coordinate with oxidized copper.
  • the compound not containing the benzotriazole skeleton is not particularly limited, but 3-amino-1,2,4-triazole, 1,2,4-triazole, or imidazole is preferable from the viewpoint of further improving the polishing rate.
  • the content of the azole compound is not particularly limited, but is preferably 0.001 to 5% by mass and more preferably 0.001 to 2% by mass with respect to the total mass of the polishing liquid from the viewpoint of further improving the polishing rate. .
  • the total amount is contained in the said range.
  • the polishing liquid may contain an organic solvent. It does not restrict
  • methyl ethyl ketone, tetrahydrofuran, dioxane, N-methylpyrrolidone, methanol, ethanol, ethylene glycol and the like are preferable.
  • the content is not particularly limited, but is preferably 0.001 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass with respect to the total mass of the polishing liquid.
  • the content of the organic solvent is in the range of 0.01 to 2.0% by mass, a polishing solution that is superior in stability of the polishing rate can be obtained.
  • the organic solvent may be used individually by 1 type, or may use 2 or more types together. When two or more organic solvents are used in combination, the total content is preferably within the above range.
  • the polishing liquid When applied to the CMP of the inorganic insulating layer, the polishing liquid preferably contains a polishing accelerator.
  • a polishing accelerator By containing a polishing accelerator, it is easier to improve the in-plane uniformity of the inorganic insulating layer on the surface of the object to be polished.
  • the polishing accelerator include sulfonic acid compounds and phosphonic acid compounds, which are compounds having a sulfo group (—SO 3 H) and an amino group (—NH 2 , —NHR or —NRR ′) in the molecule. preferable.
  • said R and R ' represent an alkyl group, an aryl group, or each substituent each independently.
  • polishing accelerator examples include 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid (sulfanilic acid), aminomethanesulfonic acid, 1-aminoethanesulfonic acid, 2-amino-1-ethanesulfonic acid (taurine). And aminosulfonic acids such as 1-aminopropane-2-sulfonic acid, amide sulfuric acid (sulfamic acid), N-methylsulfamic acid, phenylsulfamic acid, and sulfamic acids such as N-cyclohexylsulfamic acid.
  • benzenesulfonic acids such as 3-aminobenzenesulfonic acid or 4-aminobenzenesulfonic acid, or amidosulfuric acid is more preferable, and 4-aminobenzenesulfonic acid is preferable.
  • amide sulfuric acid is still more preferable.
  • the content is not particularly limited, but is preferably 0.001 to 5% by mass with respect to the total mass of the polishing liquid from the viewpoint of improving in-plane uniformity and polishing rate. 0.01 to 3% by mass is more preferable.
  • a polishing accelerator may be used individually by 1 type, or may use 2 or more types together. When two or more kinds of polishing accelerators are used in combination, the total content is preferably within the above range.
  • the polishing liquid may further contain a pH adjusting agent and / or a pH buffering agent so as to have a predetermined pH.
  • the pH adjusting agent and / or pH buffering agent include acid agents and / or alkali agents.
  • the pH adjusting agent and the pH buffering agent are compounds different from the organic acid. Although it does not restrict
  • the alkali agent is not particularly limited, but ammonia; ammonium hydroxide and organic ammonium hydroxide (for example, tetrabutylammonium hydroxide); alkanolamines such as diethanolamine, triethanolamine, and triisopropanolamine; sodium hydroxide, water Alkali metal hydroxides such as potassium oxide and lithium hydroxide; carbonates such as sodium carbonate; phosphates such as trisodium phosphate; borate and tetraborate; hydroxybenzoate; It is done.
  • the content of the pH adjusting agent and / or pH buffering agent is not particularly limited as long as it is an amount necessary to maintain the pH in a desired range, and is usually 0.01 to 1 in the total mass of the polishing liquid. Mass% is preferred.
  • the chemical mechanical polishing method using the polishing liquid of the present invention is not particularly limited, and a known chemical mechanical polishing method can be applied.
  • a chemical mechanical polishing method according to an embodiment in which the polishing liquid of the present invention can be used the polishing surface of the object to be polished is polished while supplying the polishing liquid to the polishing pad attached to the polishing surface plate.
  • a chemical mechanical polishing method (hereinafter also referred to as “CMP method”), which includes a step of obtaining a polished target object by polishing the surface to be polished by relatively moving the target object and the polishing pad. .).
  • the object to be polished to which the CMP method according to the above embodiment can be applied is not particularly limited.
  • substrate which has at least 1 sort (s) chosen from the group which consists of a metal layer and an inorganic insulating layer on the surface is mentioned. That is, the metal layer or the inorganic insulating layer described above is polished by the CMP method according to the above embodiment. Note that these layers may be stacked.
  • the semiconductor substrate which consists of a single layer, and the semiconductor substrate which consists of a multilayer are contained.
  • the material constituting the semiconductor substrate composed of a single layer is not particularly limited, and is generally preferably composed of a Group III-V compound such as silicon, silicon germanium, GaAs, or any combination thereof.
  • the configuration is not particularly limited.
  • a metal layer The wiring layer which can form wiring, a barrier metal layer, etc. are mentioned.
  • the metal component contained in the wiring layer that can form the wiring examples include a copper-based metal (such as copper or a copper alloy). Moreover, it does not restrict
  • the material constituting the inorganic insulating layer is not particularly limited, and examples thereof include silicon oxide, silicon nitride, silicon carbide, silicon carbonitride, silicon oxycarbide, and silicon oxynitride. Of these, silicon oxide or silicon nitride is preferable.
  • the polishing apparatus is not particularly limited, and a known chemical mechanical polishing apparatus (hereinafter also referred to as “CMP apparatus”) to which the CMP method according to the above embodiment can be applied can be used.
  • CMP apparatus for example, a holder that holds an object to be polished (for example, a semiconductor substrate) having a surface to be polished and a polishing pad to which a polishing pad is attached (a motor that can change the number of revolutions is attached).
  • a general CMP apparatus provided with a board can be used.
  • FREX300 made by Ebara Chemical Co., Ltd.
  • FREX300 made by Ebara Chemical Co., Ltd.
  • polishing is preferably performed at a polishing pressure, that is, a pressure generated on the contact surface between the surface to be polished and the polishing pad of 3000 to 25000 Pa, and more preferably 6500 to 14000 Pa. .
  • the polishing is preferably performed at a rotation speed of the polishing platen of 50 to 200 rpm, more preferably 60 to 150 rpm.
  • the holder may be further rotated and / or swayed, the polishing platen may be rotated on a planetary surface, or the belt-like polishing pad may be elongated. It may be moved linearly in one direction.
  • the holder may be in a fixed, rotating, or swinging state.
  • polishing liquid supply method In the CMP method according to the above embodiment, the polishing liquid is continuously supplied to the polishing pad on the polishing surface plate by a pump or the like while the surface to be polished is polished. Although there is no restriction
  • the aspect of the polishing liquid is as described above.
  • Each raw material and each catalyst used in each Example shown below are those purified by distillation, ion exchange, filtration or the like in advance using a high purity grade having a purity of 99% or more.
  • polishing liquids of Examples 1 to 27 and Comparative Examples 1 to 4 and their evaluation [Example 1] Each component shown below was mixed to prepare a polishing liquid.
  • dilute sulfuric acid or potassium hydroxide was appropriately added so that the pH of the polishing liquid became the value described in Table 1.
  • Colloidal silica (average primary particle size: 35 nm, product name “PL3”, manufactured by Fuso Chemical Industries, applicable to abrasive grains) 3.0% by mass ⁇ Malic acid (corresponds to organic acid) 0.5% by mass PAA (Mw 25000) (corresponds to polyacrylic acid having a weight average molecular weight of 25000 and a water-soluble polymer) 1.0% by mass ⁇ Hydrogen peroxide (corresponds to oxidizing agent) 0.03% by mass ⁇ Methanol (corresponding to organic solvent) 1.0% by mass -BTA (corresponds to an azole compound containing a benzotriazole or benzotriazole skeleton) 0.5% by mass ⁇ Water (ultra pure water) Balance (mass%)
  • Polishing device FREX300 (manufactured by Sugawara Chemical Co., Ltd.) -Object to be polished (wafer): A 12-inch blanket wafer in which a Cu film having a thickness of 1.5 ⁇ m is formed on a silicon substrate (note that 1 inch corresponds to 25.4 mm) 12-inch in which a Ta film having a thickness of 0.2 ⁇ m is formed on a silicon substrate Blanket wafer, polishing pad: IC1400 XY-k-pad (Rodel Nitta Co., Ltd.) ⁇ Polishing conditions: Polishing pressure (contact pressure between polished surface and polishing pad); 1.5 psi Polishing liquid supply speed; 300 ml / min Polishing platen rotation speed: 112 rpm Polishing head rotation speed: 113 rpm
  • polishing rate The blanket wafer was polished for 60 seconds, and the metal film thickness before and after polishing was determined using 49 contact-type film thickness measuring instruments at 49 equally spaced locations on the wafer surface. The average value obtained by dividing the film thickness by the polishing time was defined as the polishing rate (unit: nm / min). The results are shown in Table 1.
  • in-plane uniformity in the outer periphery exclusion area (Edge Exclusion: EE) of the blanket wafer was also evaluated.
  • EE 3 mm means in-plane uniformity excluding the area of 3 mm on the outer peripheral side of the blanket wafer
  • EE 10 mm is in-plane uniformity excluding the area of 10 mm on the outer peripheral side of the blanket wafer. Means sex. The results are shown in Table 1.
  • Examples 2 to 27, Comparative Examples 1 to 4 The polishing liquids of Examples 2 to 27 and Comparative Examples 1 to 4 were prepared and evaluated in the same manner as in Example 1 except that the blending amount or pH of each component was changed. The results are shown in Table 1.
  • each component amount (% by mass) in the polishing liquid composition means an amount relative to the total mass of the composition.
  • other components used in Table 1 are shown.
  • PAA (Mw 3000) (corresponds to polyacrylic acid having a weight average molecular weight of 3000, water-soluble polymer)
  • PAA (Mw 5000) (corresponds to polyacrylic acid having a weight average molecular weight of 5000 and a water-soluble polymer)
  • PAA (Mw 15000) (corresponds to polyacrylic acid having a weight average molecular weight of 15000 and a water-soluble polymer)
  • PAA (Mw 50000) (corresponds to polyacrylic acid having a weight average molecular weight of 50000, water-soluble polymer)
  • PAA (Mw 100,000) (corresponds to polyacrylic acid having a weight average molecular weight of 100,000, water-soluble polymer)
  • PVA (Mw 10000) (corresponds to polyvinyl alcohol having a weight average molecular weight of 10,000, water-soluble polymer)
  • CMC (Mw 10000) (corresponds to carboxymethyl cellulose having a weight average mo
  • Example 1 From comparison between Examples 1, 22, and 23, it was confirmed that in-plane uniformity was more excellent when the content of the oxidizing agent was 0.03% by mass or more. From the comparison of Examples 1 and 24 to 26, it was confirmed that the in-plane uniformity was more excellent when the pH was 2.0 to 5.0 (preferably 2.0 to 4.0). From the comparison of Examples 1 to 4, when the organic acid content is 3% by mass or less, the polishing rate is excellent, and in particular, in-plane uniformity is more excellent when CMP is performed on the Cu film. confirmed.
  • a comparison between Example 1 and Examples 13 to 14 confirms that when polyacrylic acid is used as the water-soluble polymer, it is more excellent in in-plane uniformity, particularly when CMP is performed on the Cu film. It was. By comparing Example 27 with Example 1 and Examples 17 to 19, when malic acid, malonic acid, or citric acid was used as the organic acid, it was more effective especially when CMP was performed on the Cu film. It was confirmed that the inner uniformity was excellent.
  • polishing Liquids of Examples 28 to 42 and Comparative Example 5 Each component shown below was mixed to prepare a polishing liquid. In addition, dilute sulfuric acid or potassium hydroxide was appropriately added so that the pH of the polishing liquid became the value described in Table 2.
  • Ceria particles (Ceria abrasive dispersion, secondary particle size: 350 nm, manufactured by Hitachi Chemical Co., Ltd., product name “GPX series”, pH 8-9, applicable to abrasive grains) 3.0% by mass ⁇
  • Citric acid (corresponds to organic acid) 0.5% by mass
  • PAA (Mw 25000) (corresponds to polyacrylic acid having a weight average molecular weight of 25000 and a water-soluble polymer) 1.0% by mass ⁇ 4-Aminobenzenesulfonic acid (corresponds to polishing accelerator) 2.0% by mass ⁇ Water (ultra pure water) Balance (mass%)
  • Example 28 The resulting polishing liquid of Example 28 was subjected to viscosity measurement using a rotational viscometer in the same manner as in Example 1. Further, in the same manner as in Example 1, polishing rate evaluation and in-plane uniformity evaluation were performed. In addition, about polishing rate evaluation and in-plane uniformity evaluation, the to-be-polished body (wafer) was made into the blanket wafer shown below, and the film thickness before and behind grinding
  • Example 29 to 42, Comparative Example 5 The polishing liquids of Examples 29 to 42 and Comparative Example 5 were prepared and evaluated in the same manner as in Example 28 except that the blending amount or pH of each component was changed. The results are shown in Table 2.
  • each component amount (% by mass) in the polishing liquid composition means an amount relative to the total mass of the composition.
  • the other components used in Table 2 are the same as those shown in Table 1 above.

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018199751A (ja) * 2017-05-25 2018-12-20 ニッタ・ハース株式会社 研磨用スラリー
JP2019131641A (ja) * 2018-01-29 2019-08-08 ニッタ・ハース株式会社 研磨用組成物
WO2020255921A1 (ja) * 2019-06-17 2020-12-24 株式会社フジミインコーポレーテッド 研磨用組成物
JP2021057093A (ja) * 2019-09-30 2021-04-08 株式会社フジミインコーポレーテッド 研磨用組成物
JP2022512431A (ja) * 2018-12-12 2022-02-03 ビーエーエスエフ ソシエタス・ヨーロピア 銅及びルテニウムを含有する基板の化学機械研磨
CN114227527A (zh) * 2020-09-09 2022-03-25 中国科学院微电子研究所 研磨试剂及其制备方法、化学机械研磨方法及其装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109746771B (zh) * 2019-02-14 2020-11-20 南京航空航天大学 一种CsPbX3无机钙钛矿晶体材料的抛光方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008539581A (ja) * 2005-04-28 2008-11-13 テクノ セミケム シーオー．， エルティーディー． 高段差酸化膜の平坦化のための自動研磨停止機能を有する化学機械的研磨組成物
JP2009105455A (ja) * 2009-02-10 2009-05-14 Hitachi Chem Co Ltd 素子分離形成方法
JP2010028081A (ja) * 2008-02-18 2010-02-04 Jsr Corp 化学機械研磨用水系分散体およびその製造方法、ならびに化学機械研磨方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5176078A (en) * 1974-12-23 1976-07-01 Hitachi Ltd Handaboshokumakuo hodokoshita handotaisochi
KR100661273B1 (ko) * 2005-04-28 2006-12-26 테크노세미켐 주식회사 고단차 산화막의 평탄화를 위한 화학기계적 연마조성물
US20090302266A1 (en) * 2006-04-03 2009-12-10 Jsr Corporation Aqueous dispersion for chemical mechanical polishing, chemical mechanical polishing method, and kit for preparing aqueous dispersion for chemical mechanical polishing
WO2008044477A1 (fr) * 2006-10-06 2008-04-17 Jsr Corporation Dispersion aqueuse pour polissage chimico-mécanique et procédé de polissage chimico-mécanique pour dispositif semi-conducteur
US20100087065A1 (en) * 2007-01-31 2010-04-08 Advanced Technology Materials, Inc. Stabilization of polymer-silica dispersions for chemical mechanical polishing slurry applications
US20110081780A1 (en) * 2008-02-18 2011-04-07 Jsr Corporation Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method
EP2273537A4 (en) 2008-04-15 2012-07-25 Hitachi Chemical Co Ltd POLISHING SOLUTION FOR METALLIC FILMS AND METHOD OF POLISHING USING THE SAME
WO2013152894A1 (de) * 2012-04-13 2013-10-17 Boehringer Ingelheim International Gmbh Zerstäuber mit kodiermitteln

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008539581A (ja) * 2005-04-28 2008-11-13 テクノ セミケム シーオー．， エルティーディー． 高段差酸化膜の平坦化のための自動研磨停止機能を有する化学機械的研磨組成物
JP2010028081A (ja) * 2008-02-18 2010-02-04 Jsr Corp 化学機械研磨用水系分散体およびその製造方法、ならびに化学機械研磨方法
JP2009105455A (ja) * 2009-02-10 2009-05-14 Hitachi Chem Co Ltd 素子分離形成方法

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018199751A (ja) * 2017-05-25 2018-12-20 ニッタ・ハース株式会社 研磨用スラリー
JP2019131641A (ja) * 2018-01-29 2019-08-08 ニッタ・ハース株式会社 研磨用組成物
JP7002354B2 (ja) 2018-01-29 2022-02-04 ニッタ・デュポン株式会社 研磨用組成物
JP2022512431A (ja) * 2018-12-12 2022-02-03 ビーエーエスエフ ソシエタス・ヨーロピア 銅及びルテニウムを含有する基板の化学機械研磨
JP7504886B2 (ja) 2018-12-12 2024-06-24 ビーエーエスエフ ソシエタス・ヨーロピア 銅及びルテニウムを含有する基板の化学機械研磨
WO2020255921A1 (ja) * 2019-06-17 2020-12-24 株式会社フジミインコーポレーテッド 研磨用組成物
EP3985078A4 (en) * 2019-06-17 2023-08-02 Fujimi Incorporated POLISHING COMPOSITION
JP2021057093A (ja) * 2019-09-30 2021-04-08 株式会社フジミインコーポレーテッド 研磨用組成物
JP7368997B2 (ja) 2019-09-30 2023-10-25 株式会社フジミインコーポレーテッド 研磨用組成物
CN114227527A (zh) * 2020-09-09 2022-03-25 中国科学院微电子研究所 研磨试剂及其制备方法、化学机械研磨方法及其装置

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