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WO2024116910A1 - Composition and method for enhancing silicon nitride polishing rate selectivity - Google Patents

Composition and method for enhancing silicon nitride polishing rate selectivity Download PDF

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Publication number
WO2024116910A1
WO2024116910A1 PCT/JP2023/041499 JP2023041499W WO2024116910A1 WO 2024116910 A1 WO2024116910 A1 WO 2024116910A1 JP 2023041499 W JP2023041499 W JP 2023041499W WO 2024116910 A1 WO2024116910 A1 WO 2024116910A1
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weight
group
polishing
acid
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PCT/JP2023/041499
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French (fr)
Japanese (ja)
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ブランドン クロケット
ジミー グランストロム
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株式会社フジミインコーポレーテッド
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Publication of WO2024116910A1 publication Critical patent/WO2024116910A1/en

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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives

Definitions

  • Reverse shallow trench isolation (STI) architectures generally require polishing slurries that can obtain high SiN: SiO2 polishing selectivity, i.e., to remove bulk SiN from the device, the polishing slurry must be able to obtain a high ratio of SiN removal rate to SiO2 removal rate while maintaining a small amount of SiO2 dishing.
  • SiN: SiO2 polishing selectivity i.e., to remove bulk SiN from the device
  • the most common method to obtain high SiN: SiO2 selectivity is to formulate a slurry with a pH of 2.5-5, where SiN (+) and SiO2 (-) exhibit opposite zeta potentials, and then use a negatively charged abrasive.
  • the negatively charged abrasive electrostatically adsorbs to the SiN surface, thereby enhancing the SiN removal rate, and electrostatically repels to the SiO2 surface, thereby decreasing the SiO2 removal rate.
  • the selectivity achieved by such a method is limited by the maximum electrostatic interaction force between the polishing surface and the abrasive. Therefore, formulations and methods that can further enhance the electrostatic interaction between the abrasive and the SiN and SiO2 surfaces provide the advantage of enabling higher SiN: SiO2 removal rate selectivity.
  • the present disclosure relates to a polishing composition
  • a polishing composition comprising: an abrasive comprising silica particles modified with one or more organic acids immobilized on the surface of the silica particles; and a zwitterionic compound, wherein the composition has a pH of about 2.5 to about 5.
  • the one or more organic acids include sulfonic acid groups.
  • the abrasive has a primary particle size of about 5 nm to about 50 nm. In some embodiments, the abrasive has a primary particle size of about 10 nm to about 25 nm. In some embodiments, the abrasive is present in the composition at a concentration of about 0.1 wt % to about 5 wt %, based on the total weight of the composition. In some embodiments, the abrasive is present in the composition at a concentration of about 0.1 wt % to about 1 wt %, based on the total weight of the composition.
  • the zwitterionic compound comprises an SO 3 - anionic group and an NR 4 + cationic group, hi some embodiments, the zwitterionic compound comprises at least one selected from piperazino, morpholino, and hydroxyethylamino compounds.
  • the zwitterionic compound comprises at least one selected from the group consisting of 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid (HEPES), 3-[4-(2-hydroxyethyl)piperazin-1-yl]propane-1-sulfonic acid (HEPPS), 2-morpholinylethanesulfonic acid (MES), 3-(morpholinyl)propane-1-sulfonic acid, N,N-bis-(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES; N,N-bis-(2-hydroxyethyl)taurine), and 2- ⁇ [1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino ⁇ -ethane-1-sulfonic acid (TES).
  • HEPES 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid
  • HPPS 3-[4
  • the zwitterionic compound is present in the composition at a concentration of about 0.1% to about 1.0% by weight, based on the total weight of the composition. In some embodiments, the zwitterionic compound is present in the composition at a concentration of about 0.2% to about 0.5% by weight, based on the total weight of the composition.
  • the zwitterionic compound can improve the SiN: SiO2 removal rate selectivity of the composition by at least a factor of 4, as compared to a corresponding composition without the zwitterionic compound. In some embodiments, the zwitterionic compound can improve the SiN: SiO2 removal rate selectivity of the composition by at least a factor of 6, as compared to a corresponding composition without the zwitterionic compound.
  • the polishing composition includes a wetting agent present in the composition at a concentration of about 0.01 wt. % to about 1 wt. %, based on the total weight of the composition.
  • the wetting agent includes pullulan.
  • the polishing composition comprises a surfactant present in the composition at a concentration of about 0.0001 wt % to about 0.01 wt %, based on the total weight of the composition.
  • the surfactant comprises sodium isopropylated naphthalene sulfonate.
  • the polishing composition includes a pH adjuster.
  • the pH adjuster includes sulfuric acid.
  • the present disclosure relates to a method of polishing a substrate surface comprising a first material having a positive zeta potential at pH 2.5-5 and a second material having a negative zeta potential at pH 2.5-5, the method comprising polishing the substrate surface by applying the polishing composition of claim 1 to the substrate surface using a polishing pad, wherein the polishing achieves a removal rate selectivity of the first material relative to the second material of at least 20.
  • the removal rate selectivity is at least 40. In some embodiments, the removal rate selectivity is at least 60.
  • the first material is silicon nitride.
  • the second material includes silica.
  • the present invention also includes the following aspects and configurations:
  • a polishing composition comprising an abrasive containing silica particles modified with one or more organic acids immobilized on the surface of the silica particles and a zwitterionic compound, and having a pH of about 2.5 to about 5.
  • polishing composition according to 1. wherein the zwitterionic compound contains an SO 3 - anionic group and an NR 4 + cationic group.
  • the zwitterionic compound is a compound represented by N(R 1 )(R 2 )(R 3 ), in which R 1 , R 2 and R 3 are each independently a hydrogen atom, a hydroxyl group, an anionic group, or an alkyl group which may have a substituent selected from a hydroxyl group, an anionic group and a halogen atom, and at least one of R 1 , R 2 and R 3 is an anionic group or an alkyl group having an anionic group as a substituent.
  • R 4 and R 5 are each independently a hydrogen atom, a hydroxyl group, an anionic group, or an alkyl group which may have a substituent selected from a hydroxyl group, an anionic group, and a halogen atom, and at least one of R 4 and R 5 is an anionic group or an alkyl group having an anionic group as a substituent; and
  • R 6 is an anionic group or an alkyl group having an anionic group as a substituent.
  • polishing composition according to any one of 1 to 4, further comprising a polysaccharide.
  • polishing composition according to any one of 1 to 5, further comprising a surfactant containing a sulfo group.
  • polishing composition according to any one of 6. to 8., wherein the molecular weight of the surfactant is 1,000 or less.
  • polishing composition according to any one of 1 to 9, further comprising an acid containing a sulfo group.
  • polishing composition according to any one of 1. to 10., which contains a combination of a surfactant containing a sulfo group, an acid containing a sulfo group, and a zwitterionic compound containing a sulfo group.
  • polishing composition according to any one of 1. to 11., which contains a combination of colloidal silica having a sulfonic acid fixed to the surface, a surfactant containing a sulfo group, an acid containing a sulfo group, and a zwitterionic compound containing a sulfo group.
  • the polishing composition according to any one of 1. to 12. comprising at least one selected from the group consisting of 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid (HEPES); 3-[4-(2-hydroxyethyl)piperazin-1-yl]propane-1-sulfonic acid (HEPPS); 2-morpholinylethanesulfonic acid (MES); 3-(morpholinyl)propane-1-sulfonic acid; N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES); and 2- ⁇ [1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino ⁇ -ethane-1-sulfonic acid (TES), pullulan, sodium isopropylated naphthalenesulfonate, and sulfuric acid.
  • HPES 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane
  • polishing composition according to any one of 1. to 13., which has a silicon nitride polishing rate ( ⁇ /min) relative to the silicon oxide polishing rate ( ⁇ /min) of at least 20.
  • a method for polishing a substrate surface comprising a first material having a positive zeta potential at a pH of about 2.5 to about 5 and a second material having a negative zeta potential at a pH of about 2.5 to about 5, the method comprising polishing the substrate surface by applying to the substrate surface a polishing composition according to any one of 1. to 15. using a polishing pad, the polishing achieving a removal rate selectivity of the first material relative to the second material of at least 20.
  • FIG. 1 is a plot of zeta potential as a function of pH for silicon nitride (SiN) and silica ( SiO2 ). The dashed area highlights the pH range of interest for increasing SiN: SiO2 selectivity.
  • FIG. 1 illustrates the electrostatic interactions of the zwitterionic compound 4-(2-hydroxyethyl)-1-piperazine-ethanesulfonic acid (HEPES) with SiO2 abrasives, SiN surfaces, and SiO2 surfaces.
  • FIG. 1 shows SiN removal rates for compositions containing different zwitterionic selectivity enhancers.
  • FIG. 1 shows the SiO2 removal rates of compositions containing different zwitterion selectivity enhancers.
  • FIG. 13 shows SiN: SiO2 selectivity for compositions containing different zwitterion selectivity enhancers.
  • X to Y means “X or more and Y or less", including the numerical values (X and Y) written before and after it as the upper and lower limits.
  • X1 to Y1 or X2 to Y2 the disclosure of each numerical value as the upper limit, the disclosure of each numerical value as the lower limit, and the combination of the upper and lower limits are all disclosed (i.e., they are legal grounds for correction).
  • correction with X1 or more, correction with Y2 or less, correction with X1 or less, correction with Y2 or more, correction with X1 to X2, correction with X1 to Y2, etc. must all be considered legal.
  • the operation and measurement of physical properties are performed under the conditions of room temperature (20 to 25°C) / relative humidity 40 to 50% RH.
  • the concentration described in this specification may be the concentration at the POU (point of use) or the concentration before dilution to the POU concentration.
  • the dilution ratio may be 2 to 10 times.
  • the present disclosure relates to compositions and methods for improving the removal rate selectivity of SiN relative to SiO2 .
  • SiN exhibits a positive (+) zeta potential and SiO2 exhibits a negative (-) zeta potential.
  • the surfaces have opposing zeta potentials over this pH range, they undergo opposing electrostatic interactions with charged abrasives such as SiO2 (which has a negative zeta potential at pH 2.5 to 5).
  • the negatively charged abrasive is electrostatically attracted to the positively charged SiN surface, thereby increasing the degree of interaction between the negatively charged abrasive and the SiN surface, and increasing the SiN removal rate.
  • the negatively charged abrasive is electrostatically repelled by the SiO2 surface, thereby decreasing the degree of interaction between the abrasive and the SiO2 surface, and decreasing the SiO2 removal rate.
  • the selectivity achieved by such methods is limited by the maximum electrostatic interaction force between the polishing surface and the abrasive.
  • compositions of the present disclosure increase the maximum electrostatic interaction between the charged abrasive particles and the surfaces of the oppositely charged first material having a positive zeta potential and the second material having a negative zeta potential.
  • the zwitterionic compound When the zwitterionic compound is added to the composition within the appropriate pH range, the zwitterionic compound has at least two charged groups, a cation and an anion.
  • the zwitterionic form of 4-(2-hydroxyethyl)-1-piperazine-ethanesulfonic acid (HEPES) is shown below:
  • the anion of the zwitterionic compound associates (e.g., complexes) with the positively charged surface of a first material (e.g., SiN) and leaves the cation of the zwitterionic compound exposed to the composition to increase the charge-charge interaction between the positively charged surface of the first material (e.g., SiN) and the negatively charged abrasive (e.g., SiO 2 ), thereby increasing the polishing rate of the first material (e.g., SiN).
  • a first material e.g., SiN
  • the negatively charged abrasive e.g., SiO 2
  • the cation of the zwitterionic compound associates (e.g., complexes) with the negatively charged surface of a second material (e.g., SiO 2 ) and leaves the anion of the zwitterionic compound exposed to the composition to increase the charge-charge repulsion between the negatively charged surface of the second material (e.g., SiO 2 ) and the negatively charged abrasive (e.g., SiO 2 ), thereby decreasing the polishing rate of the second material (e.g., SiO 2 ).
  • the net electrostatic interaction between the abrasive and the zwitterionic surface complex increases the removal rate selectivity of the first material relative to the second material by increasing the removal rate of the first material and suppressing the removal rate of the second material.
  • the first material has silicon-nitrogen bonds, including silicon nitride (SiN), silicon oxynitride (SiON film), silicon carbonitride (SiCN), silicon oxycarbonitride (SiOCN), nitrogen-doped hafnium silicate (HfSiON), sialon (SiAlON film), etc.
  • the second material has silicon-oxygen bonds.
  • Examples of materials having silicon-oxygen bonds include silicon oxide (SiO 2 ) formed using TEOS (tetraethyl orthosilicate) as a raw material, silicon oxide formed by a HDP (High Density Plasma) process, USG (Undoped Silicate Glass), PSG (Phosphorous Silicate Glass), BPSG (Boron Phosphorous Silicate Glass), or silicon oxide formed by a RTO (Rapid Thermal Process) process.
  • silicon oxide (SiO 2 ) formed using TEOS as a raw material is preferred, and this is used as SiO 2 in this embodiment.
  • the abrasive has a positive zeta potential.
  • the nature of the net electrostatic interaction between the abrasive and the zwitterionic surface complex is opposite compared to the above embodiment using a negatively charged abrasive. That is, the anion of the zwitterionic compound associates (e.g., complexes) with the positively charged surface of the first material (e.g., SiN) and leaves the cation of the zwitterionic compound exposed to the composition to increase the charge-charge repulsion between the positively charged surface of the first material (e.g., SiN) and the positively charged abrasive, thereby inhibiting the polishing rate of the first material (e.g., SiN).
  • the anion of the zwitterionic compound associates (e.g., complexes) with the positively charged surface of the first material (e.g., SiN) and leaves the cation of the zwitterionic compound exposed to the composition to increase the charge-charge repulsion between the positively
  • the cation of the zwitterionic compound associates (e.g., complexes) with the negatively charged surface of the second material (e.g., SiO 2 ) and leaves the anion of the zwitterionic compound exposed to the composition to increase the charge-charge attraction between the negatively charged surface of the second material (e.g., SiO 2 ) and the positively charged abrasive, thereby increasing the polishing rate of the second material (e.g., SiO 2 ).
  • the net electrostatic interaction between the abrasive and the zwitterionic surface complexes in such embodiments increases the removal rate selectivity of the second material relative to the first material by increasing the removal rate of the second material and suppressing the removal rate of the first material.
  • the zwitterionic form of 4-(2-hydroxyethyl)-1-piperazine-ethanesulfonic acid has a negatively charged SO 3 - group and a positively charged NR 4 + group within the pH range of 2.5 to 5.
  • the anionic SO 3 - group of HEPES associates with the positively charged surface SiN, leaving the cationic NR 4 + group of the zwitterionic compound exposed to the composition, increasing the charge-charge interaction between the positively charged surface of SiN and the negatively charged SiO 2 abrasive, thereby increasing the polishing rate of SiN.
  • the cationic NR 4 + groups of HEPES associate with the negatively charged surface SiO 2 and leave the anionic SO 3 - groups of the zwitterionic compound exposed to the composition, increasing the charge-charge repulsion between the negatively charged surface of SiO 2 and the negatively charged SiO 2 abrasive, thereby decreasing the polishing rate of SiO 2.
  • the net electrostatic interaction between the abrasive and the HEPES surface complex increases the SiN removal rate and suppresses the SiO 2 removal rate, thereby increasing the SiN:SiO 2 removal rate selectivity.
  • SiN:SiO 2 is used herein to mean SiN relative to SiO 2 .
  • compositions and methods of the present application use zwitterions to complex a first material surface and a second material surface with opposite charge orientations.
  • the resulting complex increases the magnitude of charge-charge interactions between the abrasive and the first and second material surfaces, as described in more detail below.
  • the polishing composition according to the present disclosure comprises one or more zwitterionic compounds.
  • the term "zwitterion” or “zwitterionic compound” means an ion that includes both positively charged (cationic) and negatively charged (anionic) functional groups (e.g., has both a positive and a negative charge).
  • the anionic group is a sulfonate (SO 3 ⁇ ), a carboxylate (COO ⁇ ), or a phosphonate.
  • the cationic group is an ammonium group (e.g., NR 4 + ).
  • the anionic group includes a sulfur atom.
  • the anionic group is a sulfonate (SO 3 ⁇ ).
  • the zwitterionic compound comprises an SO 3 ⁇ anionic group and an NR 4 + cationic group.
  • the zwitterionic compound is an amino acid, a betaine (e.g., trimethylglycine, cocamidopropyl betaine, etc.), a sulfamic acid, an anthranilic acid, a piperazino compound, a morpholino compound, or a hydroxyethylamino compound.
  • the zwitterionic compound comprises at least one selected from piperazino, morpholino, and hydroxyethylamino compounds.
  • the zwitterionic compound includes a compound represented by N(R 1 )(R 2 )(R 3 ), where R 1 , R 2 , and R 3 are each independently a hydrogen atom, a hydroxyl group, an anionic group, or an alkyl group which may have a substituent selected from a hydroxyl group, an anionic group, and a halogen atom, and at least one of R 1 , R 2 , and R 3 is an anionic group or an alkyl group which has an anionic group as a substituent.
  • the number of carbon atoms in the alkyl group which may have a substituent is independently 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 or 2.
  • the zwitterionic compound is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N
  • R 4 and R 5 are each independently a hydrogen atom, a hydroxyl group, an anionic group, or an alkyl group which may have a substituent selected from a hydroxyl group, an anionic group, and a halogen atom, and at least one of R 4 and R 5 is an anionic group or an alkyl group which has an anionic group as a substituent.
  • the number of carbon atoms in the alkyl group which may have a substituent is independently 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 or 2.
  • the zwitterionic compound is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N
  • R 6 is an anionic group or an alkyl group having an anionic group as a substituent.
  • the number of carbon atoms in the alkyl group having an anionic group as a substituent is independently 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 or 2.
  • the zwitterionic compound is preferably a piperazino or morpholino compound, more preferably a piperazino compound.
  • the zwitterionic compound has a pKa value (pKa2 value in the case of a two-stage dissociation substance) of 6.0 or more, 6.1 or more, 6.2 or more, 6.3 or more, 6.4 or more, 6.5 or more, 6.6 or more, 6.6 or more, 6.7 or more, 6.8 or more, 6.9 or more, 7.0 or more, 7.1 or more, 7.2 or more, 7.3 or more, or 7.4 or more.
  • the zwitterionic compound has a pKa value of 8.5 or less, 8.4 or less, 8.3 or less, 8.2 or less, 8.1 or less, 8.0 or less, 7.9 or less, 7.8 or less, 7.7 or less, or 7.6 or less.
  • the number of carbon atoms in the sulfonylalkyl group bonded to the nitrogen (N) atom in the zwitterionic compound is generally 5 or less, preferably 4 or less, more preferably 3 or less, and most preferably 2 or less.
  • the zwitterionic compound is at least about 0.01 wt%, at least about 0.02 wt%, at least about 0.03 wt%, at least about 0.04 wt%, at least about 0.05 wt%, at least about 0.06 wt%, at least about 0.07 wt%, at least about 0.08 wt%, at least about 0.09 wt%, at least about 0.10 wt%, at least about 0.11 wt%, at least about 0.12 wt%, at least about 0.13 wt%, at least about 0.14 wt%, at least about 0.15 wt%, at least about 0.16 wt%, at least about 0.17 wt%, at least about 0.18 wt%, at least about 0.19 wt%, at least about 0.20 wt%, at least about 0.21 wt%, at least about 0.22 wt%, at least about 0.23 wt%, at least about 0.24 wt%, at least about 0.01
  • the zwitterionic compound is about 2.5 wt% or less, about 2.0 wt% or less, about 1.5 wt% or less, about 1.0 wt% or less, about 0.95 wt% or less, about 0.90 wt% or less, about 0.85 wt% or less, about 0.80 wt% or less, about 0.75 wt% or less, about 0.70 wt% or less, about 0.65 wt% or less, about 0.60 wt% or less, about 0.55 wt% or less, about 0.50 wt% or less, about 0.45 wt% or less, about 0.40 wt% or less, about 0.35 wt% or less, about 0.34 wt% or less, about 0.33 wt% or less, about 0.32 wt% or less, about 0.31 wt% or less, about 0.30 wt% or less, about 0.29 wt% or less, about 0.28 wt% or less, about 0.27 w
  • the zwitterionic compound is from about 0.01% to about 2.0% by weight, from about 0.01% to about 1.0% by weight, from about 0.01% to about 0.5% by weight, from about 0.01% to about 0.4% by weight, from about 0.01% to about 0.3% by weight, from about 0.01% to about 0.25% by weight, from 0.01% to about 0.2% by weight, from about 0.01% to about 0.1% by weight, from 0.05% to about 2.0% by weight, from about 0.05% to about 1.0% by weight, from about 0.05% to about 0.5% by weight, from about 0.05% to about 0.4% by weight, from about 0.05% to about 0.3% by weight, from about 0.05% to about 0.25% by weight, from 0.05% to about 0.2% by weight, from about 0.05% to about 0.
  • the composition may be present in an amount of 1 wt%, about 0.1 wt% to about 2.5 wt%, about 0.1 wt% to about 2.0 wt%, about 0.1 wt% to about 1.5 wt%, about 0.1 wt% to about 1.0 wt%, about 0.1 wt% to about 0.5 wt%, about 0.1 wt% to about 0.4 wt%, about 0.1 wt% to about 0.3 wt%, about 0.1 wt% to about 0.2 wt%, about 0.2 wt% to about 2.5 wt%, about 0.2 wt% to about 2.0 wt%, about 0.2 wt% to about 1.5 wt%, about 0.2 wt% to about 1.0 wt%, about 0.2 wt% to about 0.5 wt%, about 0.2 wt% to about 0.4 wt%, about 0.2 wt% to about 0.3 wt%, or any
  • the zwitterionic compound present in the composition is effective to obtain a removal rate selectivity of a first material (e.g., SiN) relative to a second material (e.g., SiO 2 ) of at least about 15, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95, at least about 100 , or more.
  • a first material e.g., SiN
  • a second material e.g., SiO 2
  • the composition is characterized by a removal rate selectivity of a first material (e.g., SiN) over a second material (e.g., SiO2) of at least about 15, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95, at least about 100, or more.
  • a first material e.g., SiN
  • a second material e.g., SiO2
  • the first material is SiN.
  • the second material is SiO2 .
  • the removal rate selectivity is a SiN: SiO2 removal rate selectivity.
  • the SiN:SiO2 removal rate selectivity is about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70, about 75, about 80, about 85, about 90, about 95, about 100, or more.
  • the zwitterionic compound present in the composition is effective to increase the removal rate selectivity of a first material over a second material (e.g., SiN:SiO2 removal rate selectivity) by at least about 1.1 times, at least about 1.2 times, at least about 1.5 times, at least about 2.0 times, at least about 2.5 times, at least about 3.0 times, at least about 3.5 times, at least about 4.0 times, at least about 4.5 times, at least about 5.0 times, at least about 5.5 times, at least about 6.0 times, at least about 6.5 times, at least about 7.0 times, at least about 7.5 times, at least about 8.0 times, at least about 8.5 times, at least about 9.0 times, at least about 9.5 times, at least about 10.0 times or more, when compared to the same composition but without the zwitterionic compound present.
  • a second material e.g., SiN:SiO2 removal rate selectivity
  • the polishing composition according to the present disclosure comprises abrasive particles suitable for polishing a first material and a second material having opposite charge orientations at the pH of the polishing composition.
  • the abrasive particles comprise one or more metal oxide particles, such as zirconia, hafnia, alumina, titania, silica, ceria, and any combination thereof.
  • the abrasive particles comprise colloidal silica, colloidal zirconia, or a combination thereof.
  • the abrasive particles comprise colloidal silica.
  • the abrasive particles may be commercially available, synthetic, or any combination thereof.
  • the abrasive particles may be anionic.
  • anionic particles have a negative surface charge or zeta potential charge at the pH of the polishing composition.
  • the abrasive particles may be cationic.
  • cationic particles have a positive surface charge or zeta potential charge at the pH of the polishing composition.
  • the abrasive may be simply referred to as abrasive particles.
  • the abrasive particles are surface modified with species covalently attached to the particle surface and having terminal anionic or cationic groups.
  • the abrasive particles include colloidal particles that are anionically modified, for example, by immobilization of an organic acid on the colloidal particle surface.
  • the organic acid can be immobilized on the surface of the abrasive particles (e.g., colloidal silica) in the polishing composition by chemically bonding the functional group of the organic acid to the surface of the abrasive particles (e.g., colloidal silica). Immobilization of the organic acid on the colloidal silica cannot be achieved by simply coexisting the colloidal silica with the organic acid. Immobilization of the organic acid (e.g., sulfonic acid) on the colloidal silica can be carried out, for example, by the method described in E.
  • the organic acid e.g., sulfonic acid
  • a silane coupling agent having a thiol group such as 3-mercaptopropyltrimethoxysilane ("MPS")
  • MPS 3-mercaptopropyltrimethoxysilane
  • the thiol group is oxidized with hydrogen peroxide to form a surface-immobilized sulfonic acid (e.g., surface-bound propanesulfonic acid, e.g., oxidized MPS), thereby obtaining colloidal silica with a sulfonic acid immobilized on the surface.
  • Carboxylic acid can be immobilized on colloidal silica by, for example, the method described in Y. Kazuo et al., Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel, 3 Chem. Lett. 228-29 (2000), the entirety of which is incorporated herein by reference.
  • a silane coupling agent containing a photoreactive 2-nitrobenzyl ester can be coupled to colloidal silica, followed by light irradiation, to obtain colloidal silica having a carboxylic acid immobilized on the surface.
  • organic acid immobilization on colloidal silica are intended to be illustrative and not limiting.
  • Other organic immobilization techniques using different organic acids and different abrasive particulate materials are intended to be encompassed within the scope of this disclosure.
  • the abrasive particles have an average primary particle size of about 7 nm or more, about 8 nm or more, about 9 nm or more, about 10 nm or more, about 11 nm or more, about 12 nm or more, about 13 nm or more, about 14 nm or more, about 15 nm or more, about 16 nm or more, about 17 nm or more, about 18 nm or more, about 19 nm or more, about 20 nm or more, about 25 nm or more, about 30 nm or more, about 35 nm or more, about 40 nm or more, about 45 nm or more, about 50 nm or more, about 55 nm or more, about 60 nm or more, about 65 nm or more, about 70 nm or more, about 75 nm or more, about 80 nm or more, about 85 nm or more, about 90 nm or more, about 95 nm or more, about 100 n
  • the abrasive particles have an average primary particle size of about 150 nm or less, about 140 nm or less, about 130 nm or less, about 120 nm or less, about 110 nm or less, about 100 nm or less, about 95 nm or less, about 90 nm or less, about 85 nm or less, about 80 nm or less, about 75 nm or less, about 70 nm or less, about 65 nm or less, about 60 nm or less, about 55 nm or less, about 50 nm or less, about 45 nm or less, about 40 nm or less, about 35 nm or less, about 30 nm or less, about 25 nm or less, about 20 nm or less, about 19 nm or less, about 18 nm or less, about 17 nm or less, about 16 nm or less, about 15 nm or less, about 14 nm or less, about 13 nm or less, about 12 n
  • the abrasive particles have a diameter of about 7 nm to about 150 nm, about 7 nm to about 100 nm, about 7 nm to about 90 nm, about 7 nm to about 80 nm, about 7 nm to about 70 nm, about 7 nm to about 60 nm, about 7 nm to about 50 nm, about 7 nm to about 45 nm, about 7 nm to about 40 nm, about 7 nm to about 35 nm, about 7 nm to about 30 nm, about 7 nm to about 25 nm, about 7 nm to about 20 nm, about 7 nm to about 15 nm, about 7 nm to about 14 nm, about 7 nm to about 13 nm, about 7 nm to about 12 nm, about 7 nm to about 15 nm, about 7 nm to about 14 nm, about 7 nm to about 13 nm
  • the abrasive particles have an average secondary particle size of about 10 nm or more, about 15 nm or more, about 20 nm or more, about 25 nm or more, about 30 nm or more, about 35 nm or more, about 40 nm or more, about 45 nm or more, about 50 nm or more, about 55 nm or more, about 60 nm or more, about 65 nm or more, about 70 nm or more, about 75 nm or more, about 80 nm or more, about 85 nm or more, about 90 nm or more, about 95 nm or more, about 100 nm or more, about 110 nm or more, about 120 nm or more, about 130 nm or more, about 140 nm or more, about 150 nm or more, about 160 nm or more, about 170 nm or more, about 180 nm or more, about 190 nm or more, about 200 nm or more, about 250
  • the abrasive particles have an average secondary diameter of about 500 nm or less, about 450 nm or less, about 400 nm or less, about 350 nm or less, about 300 nm or less, about 250 nm or less, about 200 nm or less, about 190 nm or less, about 180 nm or less, about 170 nm or less, about 160 nm or less, about 150 nm or less, about 140 nm or less, about 130 nm or less, about 120 nm or less, about 110 nm or less, about 100 nm or less, about 95 nm or less, about 90 nm or less, about 85 nm or less, about 80 nm or less, about 75 nm or less, about 70 nm or less, about 65 nm or less, about 60 nm or less, about 55 nm or less, about 50 nm or less, about 45 nm or less, about 40 nm or less, about 35
  • the abrasive particles have an average secondary particle size of about 10 nm to about 500 nm, about 10 nm to about 200 nm, about 10 nm to about 100 nm, about 10 nm to about 50 nm, about 10 nm to about 30 nm, about 20 nm to about 500 nm, about 20 nm to about 200 nm, about 20 nm to about 100 nm, about 20 nm to about 50 nm, about 20 nm to about 30 nm, about 30 nm to about 500 nm, about 30 nm to about 200 nm, about 30 nm to about 100 nm, about 30 nm to about 50 nm, about 30 nm to about 40 nm, or any range or value therein. In some embodiments, the abrasive particles have an average secondary particle size of about 20 nm to about 40 nm, or any range or value therein.
  • the abrasive particles are about 10 nm or more, about 15 nm or more, about 16 nm or more, about 17 nm or more, about 18 nm or more, about 19 nm or more, about 20 nm or more, about 21 nm or more, about 22 nm or more, about 23 nm or more, about 24 nm or more, about 25 nm or more, about 30 nm or more, about 35 nm or more, about 40 nm or more, about 45 nm or more, about 50 nm or more, about 55 nm or more, about 60 nm or more, about 65 nm or more, about 70 nm or more , about 75 nm or more, about 80 nm or more, about 85 nm or more, about 90 nm or more, about 95 nm or more, about 100 nm or more, about 110 nm or more, about 120 nm or more, about 130 nm or more, about
  • the average particle size can be measured using any suitable method known in the art (e.g., by light scattering, such as using a Malvern Panalytical ZetaSizer Nano light scattering system). Note that the term average particle size is used interchangeably with average secondary particle size.
  • the abrasive particles are about 300 nm or less, about 250 nm or less, about 200 nm or less, about 190 nm or less, about 180 nm or less, about 170 nm or less, about 160 nm or less, about 150 nm or less, about 140 nm or less, about 130 nm or less, about 120 nm or less, about 110 nm or less, about 100 nm or less, about 95 nm or less, about 90 nm or less, about 85 nm or less, about 80 nm or less, about 75 nm or less, about 70 nm or less, about 6 It has an average particle size of 5 nm or less, about 60 nm or less, about 55 nm or less, about 50 nm or less, about 45 nm or less, about 40 nm or less, about 35 nm or less, about 30 nm or less, about 25 nm or less, about 24 nm or less,
  • the abrasive particles have a diameter of about 10 nm to about 300 nm, about 10 nm to about 200 nm, about 10 nm to about 150 nm, about 10 nm to about 100 nm, about 10 nm to about 90 nm, about 10 nm to about 80 nm, about 10 nm to about 70 nm, about 10 nm to about 60 nm, about 10 nm to about 50 nm, about 10 nm to about 45 nm, about 10 nm to about 40 nm, about 10 nm to about 35 nm, about 10 nm to about 30 nm, about 10 nm to about 25 nm, about 10 nm to about 24 nm, about 10 nm to about 23 nm, about 10 nm to about 22 nm, about 10 nm to about 21 nm, about 10 nm to about 20 nm, about 10 nm to about 19 n
  • the abrasive particles comprise at least about 0.1 weight percent, at least about 0.15 weight percent, at least about 0.2 weight percent, at least about 0.25 weight percent, at least about 0.3 weight percent, at least about 0.35 weight percent, at least about 0.4 weight percent, at least about 0.45 weight percent, at least about 0.5 weight percent, at least about 0.55 weight percent, at least about 0.60 weight percent, at least about 0.65 weight percent, at least about 0.7 weight percent, at least about 0.75 weight percent, at least about 0.8 weight percent, at least about 0.85 weight percent, at least about 0.9 weight percent, at least about 0.95 weight percent, at least about 1.0 weight percent, at least about 1.1 weight percent, at least about 1.2 weight percent, at least about 1.3 weight percent, at least about 1.
  • the abrasive particles are present in the composition at a concentration by weight of about 4% or more, about 1.5% or more, about 1.6% or more, about 1.7% or more, about 1.8% or more, about 1.9% or more, about 2.0% or more, about 2.5% or more, about 3.0% or more, about 3.5% or more, about 4.0% or more, about 4.5% or more, about 5.0% or more, about 5.5% or more, about 6.0% or more, about 6.5% or more, about 7.0% or more, about 7.5% or more, about 8.0% or more, about 8.5% or more, about 9.0% or more, about 9.5% or more, about 10.0% or more, or any range or value therebetween.
  • the abrasive particles are present in the composition at a concentration by weight of about 0.01% or more, or about 0.05% or more, or any range or value therebetween, based on the total weight of the composition.
  • the abrasive particles are present in an amount, based on the total weight of the composition, of about 10.0 wt.% or less, about 9.5 wt.% or less, about 9.0 wt.% or less, about 8.5 wt.% or less, about 8.0 wt.% or less, about 7.5 wt.% or less, about 7.0 wt.% or less, about 6.5 wt.% or less, about 6.0 wt.% or less, about 5.5 wt.% or less, about 5.0 wt.% or less, about 4.5 wt.% or less, about 4.0 wt.% or less, about 3.5 wt.% or less, about 3.0 wt.% or less, about 2.5 wt.% or less, about 2.0 wt.% or less, about 1.9 wt.% or less, about 1.8 wt.% or less, about 1.7 wt.% or less, about 1.6 wt.%
  • the abrasive particles are present in an amount, based on the total weight of the composition, of about 0.1% to about 10.0% by weight, about 0.2% to about 10.0% by weight, about 0.3% to about 10.0% by weight, about 0.4% to about 10.0% by weight, about 0.5% to about 10.0% by weight, about 0.6% to about 10.0% by weight, about 0.7% to about 10.0% by weight, about 0.8% to about 10.0% by weight, about 0.9% to about 10.0% by weight, about 1.0% to about 10.0% by weight, about 2% to about 10.0% by weight, about 3% to about 10.0% by weight, about 4% to about 10.0% by weight, about 5% to about 10.0% by weight, about 0.
  • the abrasive particles are present in the composition at a concentration by weight of about 0.01% to about 10.0% by weight, or about 0.05% to about 10.0% by weight, or any range or value therein, based on the total weight of the composition.
  • the abrasive particles have a negative charge under the pH conditions used in the polishing compositions disclosed herein.
  • the abrasive particles e.g., colloidal silica or anionically modified colloidal silica
  • the zeta potential of the abrasive particles is more negative than -1 mV, -2 mV, -5 mV, -10 mV, -15 mV, -20 mV, -25 mV, -30 mV, -35 mV, or -40 mV, or any range or value therebetween.
  • the zeta potential of the anion-modified abrasive particles is more negatively charged (i.e., more negative) than the corresponding unmodified abrasive particles (e.g., unmodified colloidal silica) at the same pH conditions.
  • the zeta potential may be measured by a Zetasizer Nano ZSP from Spectris Corporation (a Malvern Division).
  • 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, 98% by weight or more, or 99% by weight or more of the abrasives contained in the composition of the present disclosure are silica particles modified with one or more organic acids immobilized on the surface of the silica particles.
  • 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, 98% by weight or more, or 99% by weight or more of the abrasives contained in the composition of the present disclosure are silica particles modified with one or more organic acids immobilized on the surface of the silica particles that have a negative charge under the pH conditions used in the polishing composition of the present disclosure (upper limit 100% by weight).
  • the composition according to the present disclosure includes a surfactant.
  • the composition further includes a surfactant containing a sulfo group.
  • "containing a sulfo group” means that the sulfo group is in the form of a salt such as sodium, potassium, or lithium.
  • a surfactant containing a sulfo group means that the sulfo group is in the form of a salt such as sodium, potassium, or lithium.
  • an example of a surfactant containing a sulfo group is sodium isopropylated naphthalene sulfonate.
  • the surfactant comprises an alkyl group. In some embodiments, the surfactant comprises a branched alkyl group. In some embodiments, the alkyl group in the surfactant (which may be a branched alkyl group) has 2 to 10 carbon atoms, 2 to 8 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms.
  • the surfactant has an aryl group.
  • the aryl group may be a phenyl group or a group containing a fused ring.
  • the surfactant has a fused ring.
  • the group containing a fused ring may be a naphthyl group, an anthracenyl group, or the like.
  • the molecular weight of the surfactant is 1000 or less, 800 or less, 600 or less, 400 or less, or 300 or less. In some embodiments, the molecular weight of the surfactant is 50 or more, 100 or more, 150 or more, 200 or more, or 250 or more.
  • the surfactant contains a sulfonic acid having a naphthalene structure or a salt thereof (the salt is sodium or the like).
  • sulfonic acids having a naphthalene structure include isopropylnaphthalenesulfonic acid (CAS: 31093-48-8), butylnaphthalenesulfonic acid (CAS: 28605-86-9), bis(isobutylnaphthalene)-1-sulfonic acid (CAS: 94247-74-2) (an example of diisopropylnaphthalenesulfonic acid), isobutylnaphthalenesulfonic acid, and diisobutylnaphthalenesulfonic acid.
  • isopropylnaphthalenesulfonic acid (CAS: 31093-48-8), bis(isobutylnaphthalene)-1-sulfonic acid (CAS: 94247-74-2) (an example of diisopropylnaphthalenesulfonic acid), isobutylnaphthalenesulfonic acid, and diisobutylnaphthalenesulfonic acid are preferred in terms of having a branched alkyl group.
  • the surfactant comprises a sulfonic acid having an anthracene structure or a salt thereof (the salt is sodium or the like).
  • sulfonic acids having an anthracene structure include anthracene-9-sulfonic acid (CAS: 22582-76-9), anthracene-2-sulfonic acid (CAS: 15100-53-5), and 9,10-dihydro-9,10-dioxoanthracene-1-sulfonic acid (82-49-5).
  • the surfactant improves the topography (e.g., wafer flatness) of polished objects including SiN and SiO2 .
  • the surfactant comprises or consists of sodium isopropylated naphthalene sulfonate.
  • the surfactant can be read as a surfactant containing a sulfo group, a surfactant containing a fused ring, a surfactant containing a branched alkyl, a surfactant with a molecular weight of 1000 or less, or sodium isopropylated naphthalene sulfonate.
  • the surfactant is at least about 0.0001% by weight, at least about 0.0002% by weight, at least about 0.0003% by weight, at least about 0.0004% by weight, at least about 0.0005% by weight, at least about 0.0006% by weight, at least about 0.0007% by weight, at least about 0.0008% by weight, at least about 0.0009% by weight, at least about 0.001% by weight, at least about 0.002% by weight, at least about 0.003% by weight, at least about 0.004% by weight, at least about 0.005% by weight, at least about 0.006 ...8% by weight, at least about 0.0008% by weight, at least about 0.0008% by weight, at least about 0.0008% by weight, at least about 0.0008% by weight, at least about 0.0008% by weight, at least about 0.0008% by weight, at least about 0.0008% by weight, at least about The surfactant is present in the composition at a concentration (by weight relative to the total weight of the composition) of at least about 0.007% by weight, at least about 0.008% by weight, at
  • the surfactant is present in the composition at at least about 0.00001% by weight, at least about 0.00003% by weight, at least about 0.00005% by weight, at least about 0.00007% by weight, at least about 0.00009% by weight.
  • the surfactant is about 1.0% by weight or less, about 0.5% by weight or less, about 0.2% by weight or less, about 0.1% by weight or less, about 0.09% by weight or less, about 0.08% by weight or less, about 0.07% by weight or less, about 0.06% by weight or less, about 0.05% by weight or less, about 0.04% by weight or less, about 0.03% by weight or less, about 0.02% by weight or less, about 0.01% by weight or less, about 0.009% by weight or less, about 0.008% by weight or less, about 0.007% by weight or less, about 0.006% by weight or less, about 0.005% by weight or less
  • the composition is present in a concentration (by weight relative to the total weight of the composition) of about 0.004% by weight or less, about 0.003% by weight or less, about 0.002% by weight or less, about 0.001% by weight or less, about 0.0009% by weight or less, about 0.0008% by weight or less, about 0.0007% by weight or less, about 0.0006%
  • the surfactant is present in the composition at a concentration (by weight relative to the total weight of the composition) of about 0.0001% to about 1.0% by weight, about 0.0001% to about 0.1% by weight, 0.0001% to about 0.01% by weight, about 0.0001% to about 0.001% by weight, about 0.0001% to about 0.0005% by weight, or any range or value therebetween.
  • the surfactant is present in the composition at a concentration (by weight relative to the total weight of the composition) of about 0.00001% to about 1.0% by weight, about 0.00003% to about 0.1% by weight, 0.00005% to about 0.01% by weight, about 0.00007% to about 0.001% by weight, about 0.00007% to about 0.0005% by weight, or any range or value therebetween.
  • compositions according to the present disclosure include one or more wetting agents (or “wetness controllers").
  • the wetting agent has one or more hydroxyl groups.
  • the composition has a saccharide.
  • the composition has a polysaccharide.
  • the composition has a polysaccharide consisting only of glucose.
  • the wetting agent can be read as a saccharide, a polysaccharide, a polysaccharide consisting only of glucose, or pullulan.
  • the wetting agent comprises one or more of hydroxyethyl cellulose, N,N-dimethyldodecylamine oxide, polyvinyl alcohol (PVA), sulfonic acid modified PVA, polyvinylpyrrolidone (PVP), poly(N-vinylacetamide) (PNVA), polypropylene glycol (PPG), polyethylene glycol (PEG), PEG-PPG copolymers or block copolymers (e.g., PEG-PPG, PEG-PPG-PEG, PPG-PEG-PPG, etc., and combinations thereof), dextrin, highly branched cyclic dextrin (e.g., Cluster DextrinTM), pullulan, and the like.
  • the wetting agent comprises or consists of pullulan.
  • the wetting agent is at least about 0.01 wt%, at least about 0.02 wt%, at least about 0.03 wt%, at least about 0.04 wt%, at least about 0.05 wt%, at least about 0.06 wt%, at least about 0.07 wt%, at least about 0.08 wt%, at least about 0.09 wt%, at least about 0.10 wt%, at least about 0.11 wt%, at least about 0.12 wt%, at least about 0.13 wt%, at least about 0.14 wt%, at least about 0.15 wt%, at least about 0.16 wt%, at least about 0.17 wt%, at least about 0.18 wt%, at least about 0.19 wt%, at least about 0.20 wt%, at least about 0.21 wt%, at least about 0.22 wt%, at least about 0.23 wt%, at least about 0.24 wt%, at least about 0.25
  • the wetting agent is about 2.5 wt% or less, about 2.0 wt% or less, about 1.5 wt% or less, about 1.0 wt% or less, about 0.95 wt% or less, about 0.90 wt% or less, about 0.85 wt% or less, about 0.80 wt% or less, about 0.75 wt% or less, about 0.70 wt% or less, about 0.65 wt% or less, about 0.60 wt% or less, about 0.55 wt% or less, about 0.50 wt% or less, about 0.45 wt% or less, about 0.40 wt% or less, about 0.35 wt% or less, about 0.34 wt% or less, about 0.33 wt% or less, about 0.32 wt% or less, about 0.31 wt% or less, about 0.30 wt% or less, about 0.29 wt% or less, about 0.28 wt% or less, about 0.27 wt% or
  • the wetting agent is from about 0.01% to about 1.0% by weight, from about 0.01% to about 0.5% by weight, from about 0.01% to about 0.4% by weight, from about 0.01% to about 0.3% by weight, from about 0.01% to about 0.25% by weight, from about 0.01% to about 0.2% by weight, from about 0.01% to about 0.1% by weight, from 0.05% to about 2.0% by weight, from about 0.05% to about 1.0% by weight, from about 0.05% to about 0.5% by weight, from about 0.05% to about 0.4% by weight, from about 0.05% to about 0.3% by weight, from about 0.05% to about 0.25% by weight, from about 0.05% to about 0.2% by weight, from about 0.05% to about 0.1% by weight, from about 0.1% by weight % to about 2.5 wt.%, about 0.1 wt.% to about 2.0 wt.%, about 0.1 wt.% to about 1.5 wt.%, about 0.1 wt.% to about 1.0
  • the composition according to the present disclosure may further comprise one or more pH adjusting agents for adjusting the pH to a selected pH value.
  • the zwitterionic compounds, surfactants, wetting agents, and organic acids immobilized on the abrasive particles described above, as well as the "additional components" described below, are not considered to be pH adjusting agents.
  • the pH adjusting agent comprises an acid containing a sulfo group.
  • the pH adjusting agent is read as an acid containing a sulfo group (e.g., sulfuric acid).
  • the pH adjusting agent is not particularly limited, and any suitable pH adjusting agent can be used to adjust the pH of the composition to any desired range, as described above.
  • one or more pH adjusting agents can include, consist essentially of, or consist of inorganic compounds, organic compounds, or combinations thereof.
  • one or more pH adjusting agents can include inorganic acids (e.g., hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and phosphoric acid); organic acids (e.g., carboxylic acids such as citric acid, formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, maleic acid, phthalic acid, malic acid, tartaric acid, and lactic acid); and/or organic sulfuric acids (e.g., methanesulfonic acid
  • the one or more pH adjusters may include divalent or higher acids of the above acid(s) (e.g., sulfuric acid, carbonic acid, phosphoric acid, oxalic acid, etc.) that may be in the form of a base where one or more protons (H + ) can be released (e.g., ammonium bicarbonate or ammonium hydrogen phosphate), although any counterion may be used (e.g., weakly basic cations such as ammonium, triethanolamine, etc.).
  • the one or more pH adjusters include sulfate.
  • the one or more pH adjusters may include one or more hydroxides of alkali metals (e.g., NaOH, KOH) or salts thereof (e.g., carbonates, bicarbonates, sulfates, acetates, etc.); quaternary ammonium compounds (e.g., tetramethylammonium, tetraethylammonium, tetrabutylammonium, etc.); quaternary ammonium hydroxides (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide) or salts thereof; ammonia; amines; or any other suitable pH adjuster.
  • alkali metals e.g., NaOH, KOH
  • salts thereof e.g., carbonates, bicarbonates, sulfates, acetates, etc.
  • quaternary ammonium compounds e.g
  • the composition includes a combination of a zwitterionic compound containing a sulfo group, a surfactant containing a sulfo group, and an acid containing a sulfo group.
  • the composition contains a combination of colloidal silica having a sulfonic acid immobilized on the surface, a zwitterionic compound containing a sulfo group, a surfactant containing a sulfo group, and an acid containing a sulfo group.
  • the pH adjuster may be present in any amount suitable to achieve a desired pH value to obtain oppositely charged surfaces of the first material (e.g., SiN) and the second material (e.g., SiO 2 ), as described above.
  • the pH of the polishing composition can be measured using any suitable method known in the art (e.g., using a ThermoFisher Scientific ORIONTM VERSA STAR PROTM pH/ISE/conductivity/dissolved oxygen multi-parameter benchtop meter).
  • the pH of the composition is acidic (e.g., less than 7). In some embodiments, the pH of the composition is about 6.9 or less, about 6.8 or less, about 6.7 or less, about 6.6 or less, about 6.5 or less, about 6.4 or less, about 6.3 or less, about 6.2 or less, about 6.1 or less, about 6.0 or less, about 5.9 or less, about 5.8 or less, about 5.7 or less, about 5.6 or less, about 5.5 or less, about 5.4 or less, about 5.3 or less, about 5.2 or less, about 5.1 or less, about 5.0 or less, about 4.9 or less, about 4.8 or less, about 4.7 or less, about 4.6 or less, about 4.5 or less, about 4.4 or less, about 4.3 or less.
  • the pH of the composition is about 1.5 or more, about 1.6 or more, about 1.7 or more, about 1.8 or more, about 1.9 or more, about 2.0 or more, about 2.1 or more, about 2.2 or more, about 2.3 or more, about 2.4 or more, about 2.5 or more, about 2.6 or more, about 2.7 or more, about 2.8 or more, about 2.9 or more, about 3.0 or more, about 3.1 or more, about 3.2 or more, about 3.3 or more, about 3.4 or more, about 3.5 or more.
  • the pH of the composition is about 1 to about 6, about 1.5 to about 5.5, about 2.0 to about 5.0, about 2.5 to about 5.0, about 3.0 to about 5.0, about 3.5 to about 5.0, about 4.0 to about 5.0, or about 4.5 to about 5.0.
  • the pH of the composition is about 2.5 to about 5.0, such as about 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, or any range or value therebetween.
  • the pH of the composition is about 1.5 to about 5.0, about 2.0 to about 5.0, about 3.5 to about 5.0, about 4.0 to about 5.0, about 4.1 to about 4.8, or about 4.2 to about 4.7.
  • the pH of the composition is basic (e.g., greater than 7). In some embodiments, the pH of the composition is greater than 7, 7.1 or more, 7.2 or more, 7.3 or more, 7.4 or more, 7.5 or more, 7.6 or more, 7.7 or more, 7.8 or more, 7.9 or more, 8.0 or more, 8.1 or more, 8.2 or more, 8.3 or more, 8.4 or more, 8.5 or more, 8.6 or more, 8.7 or more, 8.8 or more, 8.9 or more, 9.0 or more, 9.1 or more, 9.2 or more, 9.3 or more, 9.4 or more, 9.5 or more, 9.6 or more, 9.7 or more, 9.8 or more, 9.9 or more, 10.0 or more, or any range or value therebetween.
  • the pH of the composition is about 10.0 or less, about 9.9 or less, about 9.8 or less, about 9.7 or less, about 9.6 or less, about 9.5 or less, about 9.4 or less, about 9.3 or less, about 9.2 or less, about 9.1 or less, about 9.0 or less, about 8.9 or less, about 8.8 or less, about 8.7 or less, about 8.6 or less, about 8.5 or less, about 8.4 or less, about 8.3 or less, about 8.2 or less, about 8.1 or less, about 8.0 or less, about 7.9 or less, about 7.8 or less, about 7.7 or less, about 7.6 or less, about 7.5 or less, or any range or value therebetween.
  • the pH of the composition is 7-10, 7-9.5, 7-9, 7-8.5, 7-8, 7.5-10, 7.5-9.5, 7.5-9, 7.5-8.5, 7.5-8, 8-10, 8-9.5, 8-9, 8-8.5, 8.5-10, 8.5-9.5, 8.5-9, 9-10, 9-9.5, 9.5-10, or any range or value therebetween. In some embodiments, the pH of the composition is about 7, about 7.5, about 8, about 8.5, about 9, about 9.5, about 10, or any range or value therebetween.
  • the composition includes at least one selected from the group consisting of 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid (HEPES); 3-[4-(2-hydroxyethyl)piperazin-1-yl]propane-1-sulfonic acid (HEPPS); 2-morpholinylethanesulfonic acid (MES); 3-(morpholinyl)propane-1-sulfonic acid; N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES); and 2- ⁇ [1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino ⁇ -ethane-1-sulfonic acid (TES), pullulan, sodium isopropylated naphthalenesulfonate, and sulfuric acid.
  • HEPES 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid
  • the composition includes colloidal silica having a sulfonic acid immobilized on its surface, at least one selected from the group consisting of 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid (HEPES); 3-[4-(2-hydroxyethyl)piperazin-1-yl]propane-1-sulfonic acid (HEPPS); 2-morpholinylethanesulfonic acid (MES); 3-(morpholinyl)propane-1-sulfonic acid; N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES); and 2- ⁇ [1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino ⁇ -ethane-1-sulfonic acid (TES), pullulan, sodium isopropylated naphthalenesulfonate, and sulfuric acid.
  • HPES 2-[4-(2-hydroxyethyl)pipe
  • the polishing composition according to the present disclosure includes a liquid carrier.
  • the liquid carrier of the polishing composition is not particularly limited.
  • the liquid carrier is water, such as deionized water.
  • the liquid carrier may be, for example, an aqueous solution containing a suitable pH adjuster.
  • the liquid carrier may include one or more organic solvents, such as alcohol compounds, for example glycol ethers of aliphatic alcohols and alcohols having 2 to 6 carbon atoms and 3 to 10 carbon atoms.
  • Examples of aliphatic alcohols having 2 to 6 carbons include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, pentanol, hexanol, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,4-butanetriol, 1,2,6-hexanetriol, erythritol, D-threitol, L-threol, D-arabinitol, L-arabinitol, ribitol, xylitol, mannitol, and sorbitol.
  • glycol ethers having 3 to 10 carbons include methyl glycol, methyl diglycol, methyl triglycol, isopropyl glycol, isopropyl diglycol, butyl glycol, butyl diglycol, butyl triglycol, isobutyl glycol, isobutyl diglycol, hexyl glycol, hexyl diglycol, 2-ethylhexyl glycol, 2-ethylhexyl diglycol, aryl glycol, phenyl glycol, phenyl diglycol, benzyl glycol, methyl propylene glycol, methyl propylene diglycol, methyl propylene triglycol, propyl propylene glycol, propyl propylene diglycol, butyl propylene glycol, butyl propylene diglycol, and phenyl propylene glycol.
  • the liquid carrier contained in the polishing composition is 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, 98% by weight or more, or 99% by weight or more (up to 100% by weight) of water.
  • the composition may include other additives in any concentration. However, it is desirable not to add unnecessary components that may contribute to the presence of surface defects. Thus, any other additives, if present at all, are preferably present in relatively low concentrations (e.g., 0.1 wt.% or less, 0.05 wt.% or less, 0.01 wt.% or less, 0.005 wt.% or less, 0.001 wt.% or less, 0.0005 wt.% or less, 0.0001 wt.% or less, 0.0001 wt.% to 0.1 wt.%, 0.0001 wt.% to 0.01 wt.%, or 0.0001 wt.% to 0.001 wt.%, etc.).
  • relatively low concentrations e.g., 0.1 wt.% or less, 0.05 wt.% or less, 0.01 wt.% or less, 0.005 wt.% or less, 0.001 wt.% or less,
  • the other additives included in the composition have a concentration of at least about 0.000001 wt.%, at least about 0.000003 wt.%, or at least about 0.000005 wt.%.
  • other additives include preservatives, fungicides, biocides (e.g., isothiazolinones such as methylisothiazolinone ("MIT"), benzoisothiazolinone (“BIT”), and 2-methyl-4-isothiazolin-3-one), dispersants (additives that improve the redispersibility of abrasive grains that have once settled), electrical conductivity adjusters (additives that adjust the electrical conductivity of the polishing composition), abrasive grains other than the above-mentioned abrasive grains, chelating agents, oxidizing agents, reducing agents, and dissolved gases.
  • MIT methylisothiazolinone
  • BIT benzoisothiazolinone
  • a polishing composition in which the composition has a silicon nitride polishing rate ( ⁇ /min) relative to the silicon oxide polishing rate ( ⁇ /min) of at least 20, at least 40, or at least 60.
  • the polishing composition is used to polish silicon oxide and silicon nitride.
  • the present disclosure relates to a method of polishing a substrate surface comprising a first material having a positive zeta potential at a desired pH range and a second material having a negative zeta potential at a desired pH range, the method comprising polishing the substrate surface by applying a polishing composition of the present disclosure to the substrate surface, wherein the polishing achieves a removal rate selectivity of the first material relative to the second material (e.g., a removal rate selectivity of at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 or more).
  • a removal rate selectivity of at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 or more e.g., a removal rate selectivity of at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 or more.
  • a method for polishing a substrate surface comprising a first material having a positive zeta potential at a pH of about 2.5-5 and a second material having a negative zeta potential at a pH of about 2.5-5, the method comprising polishing the substrate surface by applying a polishing composition of the present invention to the substrate surface using a polishing pad, the polishing achieving a removal rate selectivity of the first material relative to the second material of at least 20.
  • the first material comprises silicon nitride. In some embodiments, the second material comprises silicon oxide. In some embodiments, the first material comprises silicon nitride and the second material comprises silicon oxide.
  • the first material is SiN. In some embodiments, the second material is SiO2 . In some embodiments, the first material is SiN and the second material is SiO2. In some embodiments, the pH is from about 1 to about 6. In some embodiments, the pH is from about 2 to about 5 (e.g., from about 2.5 to about 5, e.g., about 4.5 ).
  • polishing occurs at a rate of at least about 80 ⁇ /min, at least about 85 ⁇ /min, at least about 90 ⁇ /min, at least about 95 ⁇ /min, at least about 100 ⁇ /min, at least about 105 ⁇ /min, at least about 110 ⁇ /min, at least about 115 ⁇ /min, at least about 120 ⁇ /min, at least about 125 ⁇ /min, at least about 130 ⁇ /min, at least about 135 ⁇ /min, at least about 140 ⁇ /min, at least about 145 ⁇ /min, at least about 150 ⁇ /min, at least about 155 ⁇ /min, at least about 160 ⁇ /min, at least about 165 ⁇ /min.
  • /min at least about 170 ⁇ /min, at least about 175 ⁇ /min, at least about 180 ⁇ /min, at least about 185 ⁇ /min, at least about 190 ⁇ /min, at least about 195 ⁇ /min, at least about 200 ⁇ /min, at least about 210 ⁇ /min, at least about 220 ⁇ /min, at least about 225 ⁇ /min, at least about 230 ⁇ /min, at least about 240 ⁇ /min, at least about 250 ⁇ /min, at least about 275 ⁇ /min, at least about 300 ⁇ /min, at least about 400 ⁇ /min, at least about 500 ⁇ /min, or more.
  • polishing achieves a SiO2 removal rate of about 50 ⁇ /min or less, about 45 ⁇ /min or less, about 40 ⁇ /min or less, about 35 ⁇ /min or less, about 30 ⁇ /min or less, about 25 ⁇ /min or less, about 20 ⁇ /min or less, about 15 ⁇ /min or less, about 10 ⁇ /min or less, about 9 ⁇ /min or less, about 8 ⁇ /min or less, about 7 ⁇ / min or less, about 6 ⁇ /min or less, about 5 ⁇ /min, or less.
  • polishing achieves a SiN:SiO2 removal rate selectivity of at least about 10, at least about 11, at least about 12, at least about 13, at least about 14, at least about 15, at least about 16, at least about 17, at least about 18, at least about 19, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95, at least about 100, or more.
  • Example 1 Effect of Zwitterionic Compounds on SiN: SiO2 Removal Rate Selectivity
  • compositions were prepared according to the present disclosure with equimolar amounts of different zwitterionic compounds (A-F, H) or without zwitterionic compounds (G, I), as shown in Table 2.
  • the abrasive is silica with surface-bound organic acids bearing sulfonic acid groups, and the silica particles used in A-I have an average primary particle size of 14 nm and an average secondary particle size of 30 nm.
  • the silica particles are referred to as silicon dioxide.
  • the procedure for preparing the compositions is as follows: (1) 500 g of deionized water (DIW) was added to a container and stirring was started; (2) the zwitterionic compound was added to the water in the container and stirred/agitated for 5 minutes; (3) sodium isopropylated naphthalene sulfonate was added to the mixture from (2) and stirred/agitated for 5 minutes; (4) pullulan, biocide, sulfuric acid, and colloidal silica (sulfonic acid modified colloidal silica) were added one at a time to the mixture from (3) and stirred/agitated in turn; and (5) DIW was added to a final volume of 1000 g and stirred for 5 minutes to obtain the polishing compositions. The pH of each composition was adjusted to 4.5.
  • DIW deionized water
  • compositions described in Table 2 were applied to SiN (Advanced Materials Technology; LP-SiN; 5,000 ⁇ thick) and SiO 2 (Advanced Technologies; TEOS; 10,000 ⁇ thick) wafers and removal rates were measured using the following polishing conditions:
  • the film thickness was measured before and after polishing using a FILMETRICS® F50 film thickness mapping system to determine the thickness of material removed, which was then divided by the polishing time to determine the removal rate.
  • composition G (no zwitterionic compound) resulted in a SiN: SiO2 selectivity of 11.
  • the compositions containing zwitterionic compounds showed significantly higher SiN: SiO2 selectivities, ranging from 48 (composition E, BES) to 67 (composition A, HEPES).
  • composition E composition E
  • composition A composition A
  • all zwitterionic compounds tested improved SiN: SiO2 selectivity by at least 4-fold compared to composition G (no zwitterionic), with HEPES improving selectivity by more than 6-fold.
  • the SiN removal rate, SiO2 removal rate, and SiN: SiO2 selectivity as a function of zwitterionic compound are plotted in Figures 3A, 3B, and 3C, respectively.
  • compositions and methods illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations not specifically disclosed herein.
  • terms such as “comprising,” “including,” “containing,” and the like shall be read broadly and without limitation.
  • the terms and expressions used herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions to exclude any equivalents of the features shown and described or portions thereof. It is recognized that various modifications are possible within the scope of the disclosure claimed.

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Abstract

A composition and a method according to the present disclosure contain a zwitter ion compound and a silica polishing material in a polishing composition. The zwitter ion compound complexes the surfaces of SiN and SiO2 having opposite zeta potentials within a desired pH range (for example from 2.5 to 5), thereby increasing the electrostatic attractive force between the polishing material and the positively charged surface (SiN) so as to increase the SiN removal rate, while increasing the electrostatic repulsion between the polishing material and the negatively charged surface (SiO2) so as to suppress the SiO2 removal rate. Consequently, the composition and the method according to the present disclosure improve the SiN/SiO2 polishing selectivity.

Description

窒化ケイ素研磨速度選択性を増強するための組成物及び方法Compositions and methods for enhancing silicon nitride polishing rate selectivity - Patents.com
　本技術の背景に関する以下の説明は、単に本技術を理解するための補助として提供されるものであり、本技術の先行技術を説明又は構成すると認められるものではない。 The following description of the background of the present technology is provided merely as an aid in understanding the present technology and is not admitted to describe or constitute prior art to the present technology.
　リバース・シャロー・トレンチ・アイソレーション（ＳＴＩ）アーキテクチャは、一般に、高いＳｉＮ：ＳｉＯ２研磨選択性を得ることができる研磨スラリーを必要とする。すなわち、バルクＳｉＮをデバイスから除去するために、少量のＳｉＯ２ディッシングを維持しながら、研磨スラリーは、ＳｉＯ２除去速度に対するＳｉＮ除去速度の高い比を得ることができなければならない。 Reverse shallow trench isolation (STI) architectures generally require polishing slurries that can obtain high SiN: SiO2 polishing selectivity, i.e., to remove bulk SiN from the device, the polishing slurry must be able to obtain a high ratio of SiN removal rate to SiO2 removal rate while maintaining a small amount of SiO2 dishing.
　高いＳｉＮ：ＳｉＯ２選択性を得るための最も一般的な方法は、ＳｉＮ（＋）及びＳｉＯ２（－）が反対のゼータ電位を示す２．５～５のｐＨを有するスラリーを配合し、次いで負に帯電した研磨材を使用することである。負に帯電した研磨材は、ＳｉＮ表面に静電吸着し、それによってＳｉＮ除去速度を高め、ＳｉＯ２表面に静電反発し、それによってＳｉＯ２除去速度を低下させる。しかしながら、そのような方法によって達成される選択性は、研磨表面と研磨材との間の最大静電相互作用力によって制限される。したがって、研磨材とＳｉＮ及びＳｉＯ２表面との間の静電相互作用を更に高めることができる配合物及び方法は、より高いＳｉＮ：ＳｉＯ２除去速度選択性を可能にするという利点を提供する。 The most common method to obtain high SiN: SiO2 selectivity is to formulate a slurry with a pH of 2.5-5, where SiN (+) and SiO2 (-) exhibit opposite zeta potentials, and then use a negatively charged abrasive. The negatively charged abrasive electrostatically adsorbs to the SiN surface, thereby enhancing the SiN removal rate, and electrostatically repels to the SiO2 surface, thereby decreasing the SiO2 removal rate. However, the selectivity achieved by such a method is limited by the maximum electrostatic interaction force between the polishing surface and the abrasive. Therefore, formulations and methods that can further enhance the electrostatic interaction between the abrasive and the SiN and SiO2 surfaces provide the advantage of enabling higher SiN: SiO2 removal rate selectivity.
　任意の他の態様又は実施形態と組み合わせることができる一態様では、本開示は、シリカ粒子の表面に固定化された１つ又は複数の有機酸で修飾されたシリカ粒子を含む研磨材；及び双性イオン化合物を含む研磨用組成物に関し、組成物は約２．５～約５のｐＨを有する。 In one aspect that can be combined with any other aspect or embodiment, the present disclosure relates to a polishing composition comprising: an abrasive comprising silica particles modified with one or more organic acids immobilized on the surface of the silica particles; and a zwitterionic compound, wherein the composition has a pH of about 2.5 to about 5.
　いくつかの実施形態では、１つ又は複数の有機酸はスルホン酸基を含む。いくつかの実施形態では、研磨材は、約５ｎｍ～約５０ｎｍの一次粒子径を有する。いくつかの実施形態では、研磨材は、約１０ｎｍ～約２５ｎｍの一次粒子径を有する。いくつかの実施形態では、研磨材は、組成物の総重量に対して、約０．１重量％～約５重量％の濃度で組成物中に存在する。いくつかの実施形態では、研磨材は、組成物の総重量に対して、約０．１重量％～約１重量％の濃度で組成物中に存在する。 In some embodiments, the one or more organic acids include sulfonic acid groups. In some embodiments, the abrasive has a primary particle size of about 5 nm to about 50 nm. In some embodiments, the abrasive has a primary particle size of about 10 nm to about 25 nm. In some embodiments, the abrasive is present in the composition at a concentration of about 0.1 wt % to about 5 wt %, based on the total weight of the composition. In some embodiments, the abrasive is present in the composition at a concentration of about 0.1 wt % to about 1 wt %, based on the total weight of the composition.
　いくつかの実施形態では、双性イオン化合物は、ＳＯ３ －アニオン性基及びＮＲ４ ＋カチオン性基を含む。いくつかの実施形態では、双性イオン化合物は、ピペラジノ、モルホリノ及びヒドロキシエチルアミノ化合物から選択される少なくとも１つを含む。いくつかの実施形態では、双性イオン化合物は、２－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］エタン－１－スルホン酸（ＨＥＰＥＳ）；３－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］プロパン－１－スルホン酸（ＨＥＰＰＳ）；２－モルホリニルエタンスルホン酸（ＭＥＳ）；３－（モルホリニル）プロパン－１－スルホン酸；Ｎ，Ｎ－ビス－（２－ヒドロキシエチル）－２－アミノエタンスルホン酸（ＢＥＳ；Ｎ，Ｎ－ビス－（２－ヒドロキシエチル）タウリン））；及び２－｛［１，３－ジヒドロキシ－２－（ヒドロキシメチル）プロパン－２－イル］アミノ｝－エタン－１－スルホン酸（ＴＥＳ）からなる群から選択される少なくとも１つを含む。いくつかの実施形態では、双性イオン化合物は、ＨＥＰＥＳを含む。 In some embodiments, the zwitterionic compound comprises an SO 3 - anionic group and an NR 4 + cationic group, hi some embodiments, the zwitterionic compound comprises at least one selected from piperazino, morpholino, and hydroxyethylamino compounds. In some embodiments, the zwitterionic compound comprises at least one selected from the group consisting of 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid (HEPES), 3-[4-(2-hydroxyethyl)piperazin-1-yl]propane-1-sulfonic acid (HEPPS), 2-morpholinylethanesulfonic acid (MES), 3-(morpholinyl)propane-1-sulfonic acid, N,N-bis-(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES; N,N-bis-(2-hydroxyethyl)taurine), and 2-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino}-ethane-1-sulfonic acid (TES). In some embodiments, the zwitterionic compound comprises HEPES.
　いくつかの実施形態では、双性イオン化合物は、組成物の総重量に対して、約０．１重量％～約１．０重量％の濃度で組成物中に存在する。いくつかの実施形態では、双性イオン化合物は、組成物の総重量に対して、約０．２重量％～約０．５重量％の濃度で組成物中に存在する。 In some embodiments, the zwitterionic compound is present in the composition at a concentration of about 0.1% to about 1.0% by weight, based on the total weight of the composition. In some embodiments, the zwitterionic compound is present in the composition at a concentration of about 0.2% to about 0.5% by weight, based on the total weight of the composition.
　いくつかの実施形態では、双性イオン化合物は、双性イオン化合物を含まない対応する組成物と比較して、組成物のＳｉＮ：ＳｉＯ２除去速度選択性を少なくとも４倍改善することができる。いくつかの実施形態では、双性イオン化合物は、双性イオン化合物を含まない対応する組成物と比較して、組成物のＳｉＮ：ＳｉＯ２除去速度選択性を少なくとも６倍改善することができる。 In some embodiments, the zwitterionic compound can improve the SiN: SiO2 removal rate selectivity of the composition by at least a factor of 4, as compared to a corresponding composition without the zwitterionic compound. In some embodiments, the zwitterionic compound can improve the SiN: SiO2 removal rate selectivity of the composition by at least a factor of 6, as compared to a corresponding composition without the zwitterionic compound.
　いくつかの実施形態では、研磨用組成物は、組成物の総重量に対して、約０．０１重量％～約１重量％の濃度で組成物中に存在する濡れ剤を含む。いくつかの実施形態では、濡れ剤はプルランを含む。 In some embodiments, the polishing composition includes a wetting agent present in the composition at a concentration of about 0.01 wt. % to about 1 wt. %, based on the total weight of the composition. In some embodiments, the wetting agent includes pullulan.
　いくつかの実施形態では、研磨用組成物は、組成物の総重量に対して、約０．０００１重量％～約０．０１重量％の濃度で組成物中に存在する界面活性剤を含む。いくつかの実施形態では、界面活性剤は、イソプロピル化ナフタレンスルホン酸ナトリウムを含む。 In some embodiments, the polishing composition comprises a surfactant present in the composition at a concentration of about 0.0001 wt % to about 0.01 wt %, based on the total weight of the composition. In some embodiments, the surfactant comprises sodium isopropylated naphthalene sulfonate.
　いくつかの実施形態では、研磨用組成物は、ｐＨ調整剤を含む。いくつかの実施形態では、ｐＨ調整剤は硫酸を含む。 In some embodiments, the polishing composition includes a pH adjuster. In some embodiments, the pH adjuster includes sulfuric acid.
　任意の他の態様又は実施形態と組み合わせることができる別の態様では、本開示はｐＨ２．５～５で正のゼータ電位を有する第１の材料及びｐＨ２．５～５で負のゼータ電位を有する第２の材料を含む基板表面を研磨する方法に関し、方法は、研磨パッドを使用して基板表面に、請求項１に記載の研磨用組成物を適用することによって基板表面を研磨することを含み、研磨は、少なくとも２０の、第２の材料に対する第１の材料の除去速度選択性を達成する。いくつかの実施形態では、除去速度選択性は、少なくとも４０である。いくつかの実施形態では、除去速度選択性は、少なくとも６０である。 In another aspect that can be combined with any other aspect or embodiment, the present disclosure relates to a method of polishing a substrate surface comprising a first material having a positive zeta potential at pH 2.5-5 and a second material having a negative zeta potential at pH 2.5-5, the method comprising polishing the substrate surface by applying the polishing composition of claim 1 to the substrate surface using a polishing pad, wherein the polishing achieves a removal rate selectivity of the first material relative to the second material of at least 20. In some embodiments, the removal rate selectivity is at least 40. In some embodiments, the removal rate selectivity is at least 60.
　いくつかの実施形態では、第１の材料は窒化ケイ素である。いくつかの実施形態では、第２の材料はシリカを含む。 In some embodiments, the first material is silicon nitride. In some embodiments, the second material includes silica.
　本発明は、下記態様および形態も包含する。 The present invention also includes the following aspects and configurations:
　１．シリカ粒子の表面に固定化された１つ又は複数の有機酸で修飾されたシリカ粒子を含む研磨材と、双性イオン化合物と、を含み、約２．５～約５のｐＨを有する、研磨用組成物。 1. A polishing composition comprising an abrasive containing silica particles modified with one or more organic acids immobilized on the surface of the silica particles and a zwitterionic compound, and having a pH of about 2.5 to about 5.
　２．前記双性イオン化合物が、ＳＯ３ －アニオン性基及びＮＲ４ ＋カチオン性基を含む、１．に記載の研磨用組成物。 2. The polishing composition according to 1., wherein the zwitterionic compound contains an SO 3 - anionic group and an NR 4 + cationic group.
　３．前記双性イオン化合物が、ピペラジノ、モルホリノ及びヒドロキシエチルアミノ化合物から選択される少なくとも１つを含む、１．または２．に記載の研磨用組成物。 3. The polishing composition according to 1. or 2., wherein the zwitterionic compound includes at least one selected from piperazino, morpholino, and hydroxyethylamino compounds.
　４．前記双性イオン化合物は、Ｎ（Ｒ１）（Ｒ２）（Ｒ３）で示される化合物、この際、Ｒ１、Ｒ２及びＲ３は、それぞれ独立して、水素原子、水酸基、アニオン性基、又は、水酸基、アニオン性基及びハロゲン原子から選択される置換基を有してもよいアルキル基であり、Ｒ１、Ｒ２及びＲ３のうち少なくとも１つはアニオン性基又は置換基としてアニオン性基を有するアルキル基である、 4. The zwitterionic compound is a compound represented by N(R 1 )(R 2 )(R 3 ), in which R 1 , R 2 and R 3 are each independently a hydrogen atom, a hydroxyl group, an anionic group, or an alkyl group which may have a substituent selected from a hydroxyl group, an anionic group and a halogen atom, and at least one of R 1 , R 2 and R 3 is an anionic group or an alkyl group having an anionic group as a substituent.
で示される化合物、この際、Ｒ４及びＲ５は、それぞれ独立して、水素原子、水酸基、アニオン性基、又は、水酸基、アニオン性基及びハロゲン原子から選択される置換基を有してもよいアルキル基であり、Ｒ４及びＲ５のうち少なくとも１つはアニオン性基又は置換基としてアニオン性基を有するアルキル基である、及び、 wherein R 4 and R 5 are each independently a hydrogen atom, a hydroxyl group, an anionic group, or an alkyl group which may have a substituent selected from a hydroxyl group, an anionic group, and a halogen atom, and at least one of R 4 and R 5 is an anionic group or an alkyl group having an anionic group as a substituent; and
で示される化合物、この際、Ｒ６は、アニオン性基、又は、置換基としてアニオン性基を有するアルキル基である、から選択される少なくとも１つを含む、１．～３．のいずれかに記載の研磨用組成物。 wherein R 6 is an anionic group or an alkyl group having an anionic group as a substituent.
　５．多糖類を更に含む、１．～４．のいずれかに記載の研磨用組成物。 5. The polishing composition according to any one of 1 to 4, further comprising a polysaccharide.
　６．スルホ基を含む界面活性剤を更に含む、１．～５．のいずれかに記載の研磨用組成物。 6. The polishing composition according to any one of 1 to 5, further comprising a surfactant containing a sulfo group.
　７．前記界面活性剤が、分岐のアルキル基を含む、６．に記載の研磨用組成物。 7. The polishing composition according to 6., wherein the surfactant contains a branched alkyl group.
　８．前記界面活性剤が、縮合環を有する、６．または７．に記載の研磨用組成物。 8. The polishing composition according to 6. or 7., in which the surfactant has a condensed ring.
　９．前記界面活性剤の分子量が、１０００以下である、６．～８．のいずれかに記載の研磨用組成物。 9. The polishing composition according to any one of 6. to 8., wherein the molecular weight of the surfactant is 1,000 or less.
　１０．スルホ基を含む酸を更に含む、１．～９．のいずれかに記載の研磨用組成物。 10. The polishing composition according to any one of 1 to 9, further comprising an acid containing a sulfo group.
　１１．スルホ基を含む界面活性剤と、スルホ基を含む酸と、スルホ基を含む双性イオン化合物とを組み合わせて含む、１．～１０．のいずれかに記載の研磨用組成物。 11. The polishing composition according to any one of 1. to 10., which contains a combination of a surfactant containing a sulfo group, an acid containing a sulfo group, and a zwitterionic compound containing a sulfo group.
　１２．スルホン酸が表面に固定化されたコロイダルシリカと、スルホ基を含む界面活性剤と、スルホ基を含む酸と、スルホ基を含む双性イオン化合物と、を組み合わせて含む、１．～１１．のいずれかに記載の研磨用組成物。 12. The polishing composition according to any one of 1. to 11., which contains a combination of colloidal silica having a sulfonic acid fixed to the surface, a surfactant containing a sulfo group, an acid containing a sulfo group, and a zwitterionic compound containing a sulfo group.
　１３．２－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］エタン－１－スルホン酸（ＨＥＰＥＳ）；３－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］プロパン－１－スルホン酸（ＨＥＰＰＳ）；２－モルホリニルエタンスルホン酸（ＭＥＳ）；３－（モルホリニル）プロパン－１－スルホン酸；Ｎ，Ｎ－ビス（２－ヒドロキシエチル）－２－アミノエタンスルホン酸（ＢＥＳ）；及び２－｛［１，３－ジヒドロキシ－２－（ヒドロキシメチル）プロパン－２－イル］アミノ｝－エタン－１－スルホン酸（ＴＥＳ）からなる群から選択される少なくとも１つと、プルランと、イソプロピル化ナフタレンスルホン酸ナトリウムと、硫酸と、を含む、１．～１２．のいずれかに記載の研磨用組成物。 13. The polishing composition according to any one of 1. to 12., comprising at least one selected from the group consisting of 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid (HEPES); 3-[4-(2-hydroxyethyl)piperazin-1-yl]propane-1-sulfonic acid (HEPPS); 2-morpholinylethanesulfonic acid (MES); 3-(morpholinyl)propane-1-sulfonic acid; N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES); and 2-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino}-ethane-1-sulfonic acid (TES), pullulan, sodium isopropylated naphthalenesulfonate, and sulfuric acid.
　１４．酸化ケイ素の研磨速度（Å／分）に対する窒化ケイ素の研磨速度（Å／分）が少なくとも２０となる特性を有する、１．～１３．のいずれかに記載の研磨用組成物。 14. The polishing composition according to any one of 1. to 13., which has a silicon nitride polishing rate (Å/min) relative to the silicon oxide polishing rate (Å/min) of at least 20.
　１５．酸化ケイ素と、窒化ケイ素とを研磨するために用いられる、１．～１４．のいずれかに記載の研磨用組成物。 15. A polishing composition according to any one of 1 to 14, which is used to polish silicon oxide and silicon nitride.
　１６．ｐＨ約２．５～約５で正のゼータ電位を有する第１の材料及びｐＨ約２．５～約５で負のゼータ電位を有する第２の材料を含む基板表面を研磨する方法であって、前記方法が、研磨パッドを使用して、前記基板表面に１．～１５．のいずれかに記載の研磨用組成物を適用することによって、前記基板表面を研磨することを含み、前記研磨が、少なくとも２０の、前記第２の材料に対する前記第１の材料の除去速度選択性を達成する、方法。 16. A method for polishing a substrate surface comprising a first material having a positive zeta potential at a pH of about 2.5 to about 5 and a second material having a negative zeta potential at a pH of about 2.5 to about 5, the method comprising polishing the substrate surface by applying to the substrate surface a polishing composition according to any one of 1. to 15. using a polishing pad, the polishing achieving a removal rate selectivity of the first material relative to the second material of at least 20.
　１７．前記第１の材料は窒化ケイ素を含み、前記第２の材料が酸化ケイ素を含む、１６．に記載の方法。 17. The method according to claim 16, wherein the first material comprises silicon nitride and the second material comprises silicon oxide.
窒化ケイ素（ＳｉＮ）及びシリカ（ＳｉＯ２）のｐＨの関数としてのゼータ電位のプロットである。破線で囲まれた領域は、ＳｉＮ：ＳｉＯ２選択性を高めるための目的のｐＨ範囲を強調している。1 is a plot of zeta potential as a function of pH for silicon nitride (SiN) and silica ( SiO2 ). The dashed area highlights the pH range of interest for increasing SiN: SiO2 selectivity. 双性イオン化合物４－（２－ヒドロキシエチル）－１－ピペラジン－エタンスルホン酸（ＨＥＰＥＳ）とＳｉＯ２研磨材、ＳｉＮ表面及びＳｉＯ２表面との静電相互作用を示す図である。FIG. 1 illustrates the electrostatic interactions of the zwitterionic compound 4-(2-hydroxyethyl)-1-piperazine-ethanesulfonic acid (HEPES) with SiO2 abrasives, SiN surfaces, and SiO2 surfaces. 異なる双性イオン選択性エンハンサを含む組成物のＳｉＮ除去速度を示す図である。FIG. 1 shows SiN removal rates for compositions containing different zwitterionic selectivity enhancers. 異なる双性イオン選択性エンハンサを含む組成物のＳｉＯ２除去速度を示す図である。FIG. 1 shows the SiO2 removal rates of compositions containing different zwitterion selectivity enhancers. 異なる双性イオン選択性エンハンサを含む組成物に対するＳｉＮ：ＳｉＯ２選択性を示す図である。FIG. 13 shows SiN: SiO2 selectivity for compositions containing different zwitterion selectivity enhancers.
　ここで、本開示によって企図されるいくつかの特定の実施形態を詳細に参照する。様々な実施形態が本明細書に記載されているが、本技術を記載された実施形態に限定することは意図されていないことが理解されよう。対照的に、添付の特許請求の範囲によって定義される技術の趣旨及び範囲内に含まれ得る代替、修飾、及び均等物を網羅することが意図されている。 Reference will now be made in detail to some specific embodiments contemplated by the present disclosure. While various embodiments have been described herein, it will be understood that it is not intended to limit the technology to the described embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents that may be included within the spirit and scope of the technology as defined by the appended claims.
　本明細書において、「Ｘ～Ｙ」は、その前後に記載される数値（ＸおよびＹ）を下限値および上限値として含む意味で使用し、「Ｘ以上Ｙ以下」を意味する。「Ｘ～Ｙ」が複数記載されている場合、例えば、「Ｘ１～Ｙ１、あるいは、Ｘ２～Ｙ２」と記載されている場合、各数値を上限とする開示、各数値を下限とする開示、および、それらの上限・下限の組み合わせは全て開示されている（つまり、補正の適法な根拠となる）。具体的には、Ｘ１以上との補正、Ｙ２以下との補正、Ｘ１以下との補正、Ｙ２以上との補正、Ｘ１～Ｘ２との補正、Ｘ１～Ｙ２との補正等は全て適法とみなされなければならない。また、特記しない限り、操作および物性等の測定は室温（２０～２５℃）／相対湿度４０～５０％ＲＨの条件で測定する。なお、本明細書中に記載の濃度は、ＰＯＵ（ポイントオブユース）における濃度であっても、ＰＯＵの濃度に希釈する前の濃度であってもよい。希釈倍率は、２～１０倍であってよい。 In this specification, "X to Y" means "X or more and Y or less", including the numerical values (X and Y) written before and after it as the upper and lower limits. When multiple "X to Y" are written, for example, when "X1 to Y1 or X2 to Y2" is written, the disclosure of each numerical value as the upper limit, the disclosure of each numerical value as the lower limit, and the combination of the upper and lower limits are all disclosed (i.e., they are legal grounds for correction). Specifically, correction with X1 or more, correction with Y2 or less, correction with X1 or less, correction with Y2 or more, correction with X1 to X2, correction with X1 to Y2, etc. must all be considered legal. In addition, unless otherwise specified, the operation and measurement of physical properties are performed under the conditions of room temperature (20 to 25°C) / relative humidity 40 to 50% RH. The concentration described in this specification may be the concentration at the POU (point of use) or the concentration before dilution to the POU concentration. The dilution ratio may be 2 to 10 times.
　一態様では、本開示は、ＳｉＯ２に対するＳｉＮの除去速度選択性を改善するための組成物及び方法に関する。図１を参照すると、２．５～５のｐＨ範囲にわたって、ＳｉＮは正（＋）のゼータ電位を示し、ＳｉＯ２は負（－）のゼータ電位を示す。表面は、このｐＨ範囲にわたって対向するゼータ電位を有するため、ＳｉＯ２（ｐＨ２．５～５で負のゼータ電位を有する）等の帯電した研磨材との対向する静電相互作用を受ける。負に帯電した研磨材は、正に帯電したＳｉＮ表面に静電的に引き付けられ、それによって負に帯電した研磨材とＳｉＮ表面との間の相互作用の程度が増加し、ＳｉＮ除去速度が増加する。一方、負に帯電した研磨材は、ＳｉＯ２表面によって静電的に反発し、それによって研磨材とＳｉＯ２表面との間の相互作用の程度が低下し、ＳｉＯ２除去速度が低下する。そのような方法によって達成される選択性は、研磨表面と研磨材との間の最大静電相互作用力によって制限される。 In one aspect, the present disclosure relates to compositions and methods for improving the removal rate selectivity of SiN relative to SiO2 . With reference to Figure 1, over the pH range of 2.5 to 5, SiN exhibits a positive (+) zeta potential and SiO2 exhibits a negative (-) zeta potential. Because the surfaces have opposing zeta potentials over this pH range, they undergo opposing electrostatic interactions with charged abrasives such as SiO2 (which has a negative zeta potential at pH 2.5 to 5). The negatively charged abrasive is electrostatically attracted to the positively charged SiN surface, thereby increasing the degree of interaction between the negatively charged abrasive and the SiN surface, and increasing the SiN removal rate. Meanwhile, the negatively charged abrasive is electrostatically repelled by the SiO2 surface, thereby decreasing the degree of interaction between the abrasive and the SiO2 surface, and decreasing the SiO2 removal rate. The selectivity achieved by such methods is limited by the maximum electrostatic interaction force between the polishing surface and the abrasive.
　本開示による組成物は、荷電研磨粒子と、それとは反対に帯電した正のゼータ電位を有する第１の材料及び負のゼータ電位を有する第２の材料の表面との間の最大静電相互作用を増加させる。適切なｐＨ範囲内の組成物に双性イオン化合物を添加すると、双性イオン化合物は、少なくとも２つの荷電基、カチオン及びアニオンを有する。非限定的な例として、４－（２－ヒドロキシエチル）－１－ピペラジン－エタンスルホン酸（ＨＥＰＥＳ）の双性イオン形態を以下に示す： The compositions of the present disclosure increase the maximum electrostatic interaction between the charged abrasive particles and the surfaces of the oppositely charged first material having a positive zeta potential and the second material having a negative zeta potential. When the zwitterionic compound is added to the composition within the appropriate pH range, the zwitterionic compound has at least two charged groups, a cation and an anion. As a non-limiting example, the zwitterionic form of 4-(2-hydroxyethyl)-1-piperazine-ethanesulfonic acid (HEPES) is shown below:
　本開示による実施形態では、双性イオン化合物のアニオンは、第１の材料（例えば、ＳｉＮ）の正に帯電した表面（例えば、錯体）と会合し（例えば、錯体化し）、双性イオン化合物のカチオンを組成物に曝露したままにして、第１の材料（例えば、ＳｉＮ）の正に帯電した表面と負に帯電した研磨材（例えば、ＳｉＯ２）との間の電荷－電荷相互作用を増加させ、それによって第１の材料（例えば、ＳｉＮ）の研磨速度を増加させる。一方、双性イオン化合物のカチオンは、第２の材料（例えば、ＳｉＯ２）の負に帯電した表面と会合し（例えば、錯体化し）、双性イオン化合物のアニオンを組成物に曝露したままにして、第２の材料（例えば、ＳｉＯ２）の負に帯電した表面と負に帯電した研磨材（例えば、ＳｉＯ２）との間の電荷－電荷反発を増加させ、それによって第２の材料（例えば、ＳｉＯ２）の研磨速度を低下させる。全体として、研磨材と双性イオン表面錯体との間の正味の静電相互作用は、第１の材料の除去速度を増加させ、第２の材料の除去速度を抑制することによって、第２の材料に対する第１の材料の除去速度選択性を増加させる。 In embodiments according to the present disclosure, the anion of the zwitterionic compound associates (e.g., complexes) with the positively charged surface of a first material (e.g., SiN) and leaves the cation of the zwitterionic compound exposed to the composition to increase the charge-charge interaction between the positively charged surface of the first material (e.g., SiN) and the negatively charged abrasive (e.g., SiO 2 ), thereby increasing the polishing rate of the first material (e.g., SiN). Meanwhile, the cation of the zwitterionic compound associates (e.g., complexes) with the negatively charged surface of a second material (e.g., SiO 2 ) and leaves the anion of the zwitterionic compound exposed to the composition to increase the charge-charge repulsion between the negatively charged surface of the second material (e.g., SiO 2 ) and the negatively charged abrasive (e.g., SiO 2 ), thereby decreasing the polishing rate of the second material (e.g., SiO 2 ). Overall, the net electrostatic interaction between the abrasive and the zwitterionic surface complex increases the removal rate selectivity of the first material relative to the second material by increasing the removal rate of the first material and suppressing the removal rate of the second material.
　いくつかの実施形態では、第１の材料は、ケイ素－窒素結合を有する。ケイ素－窒素結合を有する材料としては、窒化ケイ素（ＳｉＮ）、シリコン酸窒化（ＳｉＯＮ膜）、シリコン炭窒化（ＳｉＣＮ）、シリコン酸炭窒化（ＳｉＯＣＮ）、窒素添加ハフニウムシリケート（ＨｆＳｉＯＮ）、サイアロン（ＳｉＡｌＯＮ膜）などが挙げられる。いくつかの実施形態では、第２の材料は、ケイ素－酸素結合を有する。ケイ素－酸素結合を有する材料として、ＴＥＯＳ（オルトケイ酸テトラエチル）を原料に成膜した酸化ケイ素（ＳｉＯ２）や、ＨＤＰ（Ｈｉｇｈ　Ｄｅｎｓｉｔｙ　Ｐｌａｓｍａ）プロセスで成膜した酸化ケイ素、ＵＳＧ（Ｕｎｄｏｐｅｄ　Ｓｉｌｉｃａｔｅ　Ｇｌａｓｓ）、ＰＳＧ（Ｐｈｏｓｐｈｏｒｏｕｓ　Ｓｉｌｉｃａｔｅ　Ｇｌａｓｓ）、ＢＰＳＧ（Ｂｏｒｏｎ　Ｐｈｏｓｐｈｏｒｏｕｓ　Ｓｉｌｉｃａｔｅ　Ｇｌａｓｓ）、あるいは、ＲＴＯ（Ｒａｐｉｄ　Ｔｈｅｒｍａｌ　Ｐｒｏｃｅｓｓ）プロセスで製膜した酸化ケイ素が挙げられる。これらの中でも、ＴＥＯＳを原料に成膜した酸化ケイ素（ＳｉＯ２）が好ましく、本実施例でもＳｉＯ２としてこれが用いられている。 In some embodiments, the first material has silicon-nitrogen bonds, including silicon nitride (SiN), silicon oxynitride (SiON film), silicon carbonitride (SiCN), silicon oxycarbonitride (SiOCN), nitrogen-doped hafnium silicate (HfSiON), sialon (SiAlON film), etc. In some embodiments, the second material has silicon-oxygen bonds. Examples of materials having silicon-oxygen bonds include silicon oxide (SiO 2 ) formed using TEOS (tetraethyl orthosilicate) as a raw material, silicon oxide formed by a HDP (High Density Plasma) process, USG (Undoped Silicate Glass), PSG (Phosphorous Silicate Glass), BPSG (Boron Phosphorous Silicate Glass), or silicon oxide formed by a RTO (Rapid Thermal Process) process. Among these, silicon oxide (SiO 2 ) formed using TEOS as a raw material is preferred, and this is used as SiO 2 in this embodiment.
　いくつかの実施形態では、研磨材は正のゼータ電位を有する。そのような実施形態では、研磨材と双性イオン表面錯体との間の正味の静電相互作用の性質は、負に帯電した研磨材を用いた上記の実施形態と比較して反対である。すなわち、双性イオン化合物のアニオンは、第１の材料（例えば、ＳｉＮ）の正に帯電した表面と会合し（例えば、錯体化し）、双性イオン化合物のカチオンを組成物に露出させたままにして、第１の材料（例えば、ＳｉＮ）の正に帯電した表面と正に帯電した研磨材との間の電荷－電荷反発を増加させ、それによって第１の材料（例えば、ＳｉＮ）の研磨速度を抑制する。一方、双性イオン化合物のカチオンは、第２の材料（例えば、ＳｉＯ２）の負に帯電した表面と会合し（例えば、錯体化し）、双性イオン化合物のアニオンを組成物に曝露したままにして、第２の材料（例えば、ＳｉＯ２）の負に帯電した表面と正に帯電した研磨材との間の電荷－電荷引力を増加させ、それによって第２の材料（例えば、ＳｉＯ２）の研磨速度を増加させる。全体として、そのような実施形態における研磨材と双性イオン表面錯体との間の正味の静電相互作用は、第２の材料の除去速度を増加させ、第１の材料の除去速度を抑制することによって、第１の材料に対する第２の材料の除去速度選択性を増加させる。 In some embodiments, the abrasive has a positive zeta potential. In such embodiments, the nature of the net electrostatic interaction between the abrasive and the zwitterionic surface complex is opposite compared to the above embodiment using a negatively charged abrasive. That is, the anion of the zwitterionic compound associates (e.g., complexes) with the positively charged surface of the first material (e.g., SiN) and leaves the cation of the zwitterionic compound exposed to the composition to increase the charge-charge repulsion between the positively charged surface of the first material (e.g., SiN) and the positively charged abrasive, thereby inhibiting the polishing rate of the first material (e.g., SiN). Meanwhile, the cation of the zwitterionic compound associates (e.g., complexes) with the negatively charged surface of the second material (e.g., SiO 2 ) and leaves the anion of the zwitterionic compound exposed to the composition to increase the charge-charge attraction between the negatively charged surface of the second material (e.g., SiO 2 ) and the positively charged abrasive, thereby increasing the polishing rate of the second material (e.g., SiO 2 ). Overall, the net electrostatic interaction between the abrasive and the zwitterionic surface complexes in such embodiments increases the removal rate selectivity of the second material relative to the first material by increasing the removal rate of the second material and suppressing the removal rate of the first material.
　非限定的な例として、ここで図２を参照すると、４－（２－ヒドロキシエチル）－１－ピペラジン－エタンスルホン酸（ＨＥＰＥＳ）の双性イオン形態は、２．５～５のｐＨ範囲内で負に帯電したＳＯ３ －基及び正に帯電したＮＲ４ ＋基を有する。ＨＥＰＥＳのアニオン性ＳＯ３ －基は、正に帯電した表面ＳｉＮと会合し、双性イオン化合物のカチオン性ＮＲ４ ＋基を組成物に曝露したままにして、ＳｉＮの正に帯電した表面と負に帯電したＳｉＯ２研磨材との間の電荷－電荷相互作用を増加させ、それによってＳｉＮの研磨速度を増加させる。一方、ＨＥＰＥＳのカチオン性ＮＲ４ ＋基は、負に帯電した表面ＳｉＯ２と会合し、双性イオン化合物のアニオン性ＳＯ３ －基を組成物に曝露したままにして、ＳｉＯ２の負に帯電した表面と負に帯電したＳｉＯ２研磨材との間の電荷－電荷反発を増加させ、それによってＳｉＯ２の研磨速度を低下させる。全体として、研磨材とＨＥＰＥＳ表面錯体との間の正味の静電相互作用は、ＳｉＮ除去速度を増加させ、ＳｉＯ２除去速度を抑制することによって、ＳｉＮ：ＳｉＯ２除去速度選択性を増加させる。本明細書中、ＳｉＮ：ＳｉＯ２は、ＳｉＯ２に対するＳｉＮという意味で使用される。 As a non-limiting example, and referring now to Figure 2, the zwitterionic form of 4-(2-hydroxyethyl)-1-piperazine-ethanesulfonic acid (HEPES) has a negatively charged SO 3 - group and a positively charged NR 4 + group within the pH range of 2.5 to 5. The anionic SO 3 - group of HEPES associates with the positively charged surface SiN, leaving the cationic NR 4 + group of the zwitterionic compound exposed to the composition, increasing the charge-charge interaction between the positively charged surface of SiN and the negatively charged SiO 2 abrasive, thereby increasing the polishing rate of SiN. On the other hand, the cationic NR 4 + groups of HEPES associate with the negatively charged surface SiO 2 and leave the anionic SO 3 - groups of the zwitterionic compound exposed to the composition, increasing the charge-charge repulsion between the negatively charged surface of SiO 2 and the negatively charged SiO 2 abrasive, thereby decreasing the polishing rate of SiO 2. Overall, the net electrostatic interaction between the abrasive and the HEPES surface complex increases the SiN removal rate and suppresses the SiO 2 removal rate, thereby increasing the SiN:SiO 2 removal rate selectivity. SiN:SiO 2 is used herein to mean SiN relative to SiO 2 .
　したがって、本出願の組成物及び方法は、双性イオンを使用して、対向する電荷配向で第１の材料表面及び第２の材料表面を錯化する。得られた錯体は、以下で更に詳細に説明するように、研磨材と第１及び第２の材料表面との間の電荷－電荷相互作用の大きさを増加させる。 Thus, the compositions and methods of the present application use zwitterions to complex a first material surface and a second material surface with opposite charge orientations. The resulting complex increases the magnitude of charge-charge interactions between the abrasive and the first and second material surfaces, as described in more detail below.
　双性イオン化合物
　本開示による研磨用組成物は、１つ又は複数の双性イオン化合物を含む。本明細書で使用される場合、「双性イオン」又は「双性イオン化合物」という用語は、正に帯電した（カチオン性）及び負に帯電した（アニオン性）官能基の両方を含む（例えば、正電荷及び負電荷の両方を有する）イオンを意味する。いくつかの実施形態では、アニオン性基は、スルホナート（ＳＯ３ －）、カルボキシラート（ＣＯＯ－）又はホスホナートである。いくつかの実施形態では、カチオン性基は、アンモニウム基（例えば、ＮＲ４ ＋）である。いくつかの実施形態では、アニオン性基は、硫黄原子を含む。いくつかの実施形態では、アニオン性基はスルホナート（ＳＯ３ －）である。いくつかの実施形態では、双性イオン化合物が、ＳＯ３ －アニオン性基及びＮＲ４ ＋カチオン性基を含む。 Zwitterionic Compound The polishing composition according to the present disclosure comprises one or more zwitterionic compounds. As used herein, the term "zwitterion" or "zwitterionic compound" means an ion that includes both positively charged (cationic) and negatively charged (anionic) functional groups (e.g., has both a positive and a negative charge). In some embodiments, the anionic group is a sulfonate (SO 3 − ), a carboxylate (COO − ), or a phosphonate. In some embodiments, the cationic group is an ammonium group (e.g., NR 4 + ). In some embodiments, the anionic group includes a sulfur atom. In some embodiments, the anionic group is a sulfonate (SO 3 − ). In some embodiments, the zwitterionic compound comprises an SO 3 − anionic group and an NR 4 + cationic group.
　いくつかの実施形態では、双性イオン化合物は、アミノ酸、ベタイン（例えば、トリメチルグリシン、コカミドプロピルベタイン等）、スルファミン酸、アントラニル酸、ピペラジノ化合物、モルホリノ化合物、又はヒドロキシエチルアミノ化合物である。 In some embodiments, the zwitterionic compound is an amino acid, a betaine (e.g., trimethylglycine, cocamidopropyl betaine, etc.), a sulfamic acid, an anthranilic acid, a piperazino compound, a morpholino compound, or a hydroxyethylamino compound.
　いくつかの実施形態では、前記双性イオン化合物が、ピペラジノ、モルホリノ及びヒドロキシエチルアミノ化合物から選択される少なくとも１つを含む。 In some embodiments, the zwitterionic compound comprises at least one selected from piperazino, morpholino, and hydroxyethylamino compounds.
　いくつかの実施形態では、双性イオン化合物は、Ｎ（Ｒ１）（Ｒ２）（Ｒ３）で示される化合物を含み、この際、Ｒ１、Ｒ２及びＲ３は、それぞれ独立して、水素原子、水酸基、アニオン性基、又は、水酸基、アニオン性基及びハロゲン原子から選択される置換基を有してもよいアルキル基であり、Ｒ１、Ｒ２及びＲ３のうち少なくとも１つはアニオン性基又は置換基としてアニオン性基を有するアルキル基である。いくつかの実施形態では、置換基を有してもよいアルキル基の炭素数は、それぞれ独立して、１～６、１～５、１～４、１～３、又は、１もしくは２である。 In some embodiments, the zwitterionic compound includes a compound represented by N(R 1 )(R 2 )(R 3 ), where R 1 , R 2 , and R 3 are each independently a hydrogen atom, a hydroxyl group, an anionic group, or an alkyl group which may have a substituent selected from a hydroxyl group, an anionic group, and a halogen atom, and at least one of R 1 , R 2 , and R 3 is an anionic group or an alkyl group which has an anionic group as a substituent. In some embodiments, the number of carbon atoms in the alkyl group which may have a substituent is independently 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 or 2.
　いくつかの実施形態では、双性イオン化合物は、 In some embodiments, the zwitterionic compound is
で示される化合物を含み、この際、Ｒ４及びＲ５は、それぞれ独立して、水素原子、水酸基、アニオン性基、又は、水酸基、アニオン性基及びハロゲン原子から選択される置換基を有してもよいアルキル基であり、Ｒ４及びＲ５のうち少なくとも１つはアニオン性基又は置換基としてアニオン性基を有するアルキル基である。いくつかの実施形態では、置換基を有してもよいアルキル基の炭素数は、それぞれ独立して、１～６、１～５、１～４、１～３、又は、１もしくは２である。 wherein R 4 and R 5 are each independently a hydrogen atom, a hydroxyl group, an anionic group, or an alkyl group which may have a substituent selected from a hydroxyl group, an anionic group, and a halogen atom, and at least one of R 4 and R 5 is an anionic group or an alkyl group which has an anionic group as a substituent. In some embodiments, the number of carbon atoms in the alkyl group which may have a substituent is independently 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 or 2.
　いくつかの実施形態では、双性イオン化合物は、 In some embodiments, the zwitterionic compound is
で示される化合物を含み、この際、Ｒ６は、アニオン性基、又は、置換基としてアニオン性基を有するアルキル基である。いくつかの実施形態では、置換基としてアニオン性基を有するアルキル基の炭素数は、それぞれ独立して、１～６、１～５、１～４、１～３、又は、１もしくは２である。 wherein R 6 is an anionic group or an alkyl group having an anionic group as a substituent. In some embodiments, the number of carbon atoms in the alkyl group having an anionic group as a substituent is independently 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 or 2.
　いくつかの実施形態では、双性イオン化合物は、２－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］エタン－１－スルホン酸（ＨＥＰＥＳ；　ｐＫａ１＝３．０、ｐＫａ２＝７．５）；３－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］プロパン－１－スルホン酸（ＨＥＰＰＳ；　ｐＫａ＝８．０）；２－モルホリン－４－イルエタンスルホン酸（ＭＥＳ；ｐＫａ＝６．１５）；３－（モルホリン－４－イル）プロパン－ａ－スルホン酸（ＭＯＰＳ；ｐＫａ＝７．２）；Ｎ，Ｎ－ビス（２－ヒドロキシエチル）－２－アミノエタンスルホン酸（ＢＥＳ；Ｎ，Ｎ－ビス（２－ヒドロキシエチル）タウリン）；ｐＫａ＝７．１）；及び２－｛［１，３－ジヒドロキシ－２－（ヒドロキシメチル）プロパン－２－イル］アミノ｝エタン－１－スルホン酸（ＴＥＳ；ｐＫａ＝７．５）（表１を参照されたい）からなる群から選択される化合物の１つ又は複数を含む。いくつかの実施形態では、双性イオン化合物は、２－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］エタン－１－スルホン酸（ＨＥＰＥＳ）である。 In some embodiments, the zwitterionic compounds are 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid (HEPES; pKa1=3.0, pKa2=7.5); 3-[4-(2-hydroxyethyl)piperazin-1-yl]propane-1-sulfonic acid (HEPPS; pKa=8.0); 2-morpholin-4-ylethanesulfonic acid (MES; pKa=6.15); 3-(morpholin-4-yl)propane The zwitterionic compound includes one or more compounds selected from the group consisting of pan-a-sulfonic acid (MOPS; pKa=7.2); N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES; N,N-bis(2-hydroxyethyl)taurine; pKa=7.1); and 2-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino}ethane-1-sulfonic acid (TES; pKa=7.5) (see Table 1). In some embodiments, the zwitterionic compound is 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid (HEPES).
　いくつかの実施形態では、双性イオン化合物は、ＰＩＰＥＳ（１，４－ピペラジンジエタンスルホン酸；　ｐＫａ＝６．８）、ＡＣＥＳ（Ｎ－（２－アセトアミド）－２－アミノエタンスルホン酸；　ｐＫａ＝６．９）、コラミン塩酸（ｐＫａ＝７．１）、３－［Ｎ，Ｎ－ビス（２－ヒドロキシエチル）アミノ］－２－ヒドロキシプロパンスルホン酸（ＤＩＰＳＯ；　ｐＫａ＝７．６）、２－Ｈｙｄｒｏｘｙ－Ｎ－ｔｒｉｓ（ｈｙｄｒｏｘｙｍｅｔｈｙｌ）ｍｅｔｈｙｌ－３－ａｍｉｎｏｐｒｏｐａｎｅｓｕｌｆｏｎｉｃ　ａｃｉｄ（ＴＡＰＳＯ；　ｐＫａ＝７．６）、アセトアミドグリシン（ｐＫａ＝７．７）、２－Ｈｙｄｒｏｘｙ－３－［４－（２－ｈｙｄｒｏｘｙｅｔｈｙｌ）－１－ｐｉｐｅｒａｚｉｎｙｌ］ｐｒｏｐａｎｅｓｕｌｆｏｎｉｃ　ａｃｉｄ（ＨＥＰＰＳＯ；　ｐＫａ＝７．８）、ピペラジン－Ｎ、Ｎ’－ビス（２－ヒドロキシプロパンスルホン酸）（ＰＯＰＳＯ；　ｐＫａ＝７．８）、トリシン（Ｎ－（２－Ｈｙｄｒｏｘｙ－１，１－ｂｉｓ（ｈｙｄｒｏｘｙｍｅｔｈｙｌ）ｅｔｈｙｌ）ｇｌｙｃｉｎｅ；　ｐＫａ＝８．１５）、グリシンアミド（ｐＫａ＝８．２）、あるいは、ビシン（Ｎ，Ｎ－Ｂｉｓ（２－ｈｙｄｒｏｘｙｅｔｈｙｌ）ｇｌｙｃｉｎｅ；　ｐＫａ＝８．３５）、（トリス（ヒドロキシメチル）メチル－３－アミノプロパンスルホン酸（ＴＡＰＳ；　ｐＫａ＝８．４）である。 In some embodiments, the zwitterionic compound is PIPES (1,4-piperazinediethanesulfonic acid; pKa=6.8), ACES (N-(2-acetamido)-2-aminoethanesulfonic acid; pKa=6.9), cholamine hydrochloride (pKa=7.1), 3-[N,N-bis(2-hydroxyethyl)amino]-2-hydroxypropanesulfonic acid (DIPSO; pKa=7.6), 2-Hydroxy-N-tris(hydroxymethyl)methyl-3-aminopropanesulfonic acid (TAPSO; pKa=7.6), acetamidoglycine (pKa=7.7), 2-Hydroxy-3-[4-(2-h hydroxyethyl)-1-piperazineyl]propanesulfonic acid (HEPPSO; pKa = 7.8), piperazine-N,N'-bis(2-hydroxypropanesulfonic acid) (POPSO; pKa = 7.8), tricine (N-(2-hydroxy-1,1-bis(hydroxymethyl)ethyl)glycine; pKa = 8.15), glycine amide (pKa = 8.2), or bicine (N,N-Bis(2-hydroxyethyl)glycine; pKa = 8.35), (tris(hydroxymethyl)methyl-3-aminopropanesulfonic acid (TAPS; pKa = 8.4).
　双性イオン化合物は、ピペラジノまたはモルホリノ化合物が好ましく、ピペラジノ化合物がより好ましい。いくつかの実施形態では、双性イオン化合物は、ｐＫａの値（二段階乖離物質の場合はｐＫａ２の値）が、６．０以上、６．１以上、６，２以上、６．３以上、６．４以上、６．５以上、６．６以上、６．６以上、６．７以上、６，８以上、６．９以上、７．０以上、７．１以上、７．２以上、７．３以上、７．４以上である。 The zwitterionic compound is preferably a piperazino or morpholino compound, more preferably a piperazino compound. In some embodiments, the zwitterionic compound has a pKa value (pKa2 value in the case of a two-stage dissociation substance) of 6.0 or more, 6.1 or more, 6.2 or more, 6.3 or more, 6.4 or more, 6.5 or more, 6.6 or more, 6.6 or more, 6.7 or more, 6.8 or more, 6.9 or more, 7.0 or more, 7.1 or more, 7.2 or more, 7.3 or more, or 7.4 or more.
　また、いくつかの実施形態では、双性イオン化合物のｐＫａの値は、８．５以下、８．４以下、８．３以下、８．２以下、８．１以下、８．０以下、７．９以下、７．８以下、７．７以下、７．６以下である。また、いくつかの実施形態では、双性イオン化合物における窒素（Ｎ）原子に結合するスルホニルアルキル基の炭素数は一般的に５以下であり、４以下が好ましく、３以下がより好ましく、２以下が最も好ましい。 In some embodiments, the zwitterionic compound has a pKa value of 8.5 or less, 8.4 or less, 8.3 or less, 8.2 or less, 8.1 or less, 8.0 or less, 7.9 or less, 7.8 or less, 7.7 or less, or 7.6 or less. In some embodiments, the number of carbon atoms in the sulfonylalkyl group bonded to the nitrogen (N) atom in the zwitterionic compound is generally 5 or less, preferably 4 or less, more preferably 3 or less, and most preferably 2 or less.
　いくつかの実施形態では、双性イオン化合物は、少なくとも約０．０１重量％、少なくとも約０．０２重量％、少なくとも約０．０３重量％、少なくとも約０．０４重量％、少なくとも約０．０５重量％、少なくとも約０．０６重量％、少なくとも約０．０７重量％、少なくとも約０．０８重量％、少なくとも約０．０９重量％、少なくとも約０．１０重量％、少なくとも約０．１１重量％、少なくとも約０．１２重量％、少なくとも約０．１３重量％、少なくとも約０．１４重量％、少なくとも約０．１５重量％、少なくとも約０．１６重量％、少なくとも約０．１７重量％、少なくとも約０．１８重量％、少なくとも約０．１９重量％、少なくとも約０．２０重量％、少なくとも約０．２１重量％、少なくとも約０．２２重量％、少なくとも約０．２３重量％、少なくとも約０．２４重量％、少なくとも約０．２５重量％、少なくとも約０．２６重量％、少なくとも約０．２７重量％、少なくとも約０．２８重量％、少なくとも約０．２９重量％、少なくとも約０．３０重量％、少なくとも約０．３１重量％、少なくとも約０．３２重量％、少なくとも約０．３３重量％、少なくとも約０．３４重量％、少なくとも約０．３５重量％、少なくとも約０．３６重量％、少なくとも約０．３７重量％、少なくとも約０．３８重量％、少なくとも約０．３９重量％、少なくとも約０．４０重量％、少なくとも約０．４５重量％、少なくとも約０．５０重量％、少なくとも約０．５５重量％、少なくとも約０．６０重量％、少なくとも約０．６５重量％、少なくとも約０．７０重量％、少なくとも約０．７５重量％、少なくとも約０．８０重量％、少なくとも約０．８５重量％、少なくとも約０．９０重量％、少なくとも約０．９５重量％、少なくとも約１．０重量％、少なくとも約１．５重量％、少なくとも約２．０重量％、少なくとも約２．５重量％、又はそれらの間の任意の範囲若しくは値の濃度（組成物の総重量に対する重量による）で組成物中に存在する。 In some embodiments, the zwitterionic compound is at least about 0.01 wt%, at least about 0.02 wt%, at least about 0.03 wt%, at least about 0.04 wt%, at least about 0.05 wt%, at least about 0.06 wt%, at least about 0.07 wt%, at least about 0.08 wt%, at least about 0.09 wt%, at least about 0.10 wt%, at least about 0.11 wt%, at least about 0.12 wt%, at least about 0.13 wt%, at least about 0.14 wt%, at least about 0.15 wt%, at least about 0.16 wt%, at least about 0.17 wt%, at least about 0.18 wt%, at least about 0.19 wt%, at least about 0.20 wt%, at least about 0.21 wt%, at least about 0.22 wt%, at least about 0.23 wt%, at least about 0.24 wt%, at least about 0.25 wt%, at least about 0.26 wt%, at least about 0.27 wt%, at least about 0.28 wt%, at least about 0.29 wt%, at least about 0.30 wt%, at least about 0.31 wt%, at least about 0.32 wt%, at least about 0.33 wt%, at least about 0.34 wt%, at least about 0.35 wt%, at least about 0.36 wt%, at least about 0.37 wt%, at least about 0.38 wt%, at least about 0.39 wt%, at least about 0.40 wt%, at least about 0.41 wt%, at least about 0.42 wt%, at least about 0.43 wt%, at least about 0.44 wt%, at least about 0.45 wt%, at least about 0 at least about 0.14 wt%, at least about 0.15 wt%, at least about 0.16 wt%, at least about 0.17 wt%, at least about 0.18 wt%, at least about 0.19 wt%, at least about 0.20 wt%, at least about 0.21 wt%, at least about 0.22 wt%, at least about 0.23 wt%, at least about 0.24 wt%, at least about 0.25 wt%, at least about 0.26 wt%, at least about 0.27 wt%, at least about 0.28 wt%, at least about 0.29 wt%, at least about 0.30 wt%, at least about 0.31 wt%, at least about 0.32 wt%, at least about 0.33 wt%, at least about 0.29 wt%, at least about 0.30 wt%, at least about 0.31 wt%, at least about 0.32 wt%, at least about 0.33 wt%, at least about 0.34 wt%, at least about 0.35 wt%, at least about 0.36 wt%, at least about 0.37 wt%, at least about 0.38 wt%, at least about 0.39 wt%, at least about 0.40 wt%, at least about 0.45 wt%, at least about 0.50 wt%, at least about 0.55 wt%, is also present in the composition at a concentration (by weight relative to the total weight of the composition) of about 0.60% by weight, at least about 0.65% by weight, at least about 0.70% by weight, at least about 0.75% by weight, at least about 0.80% by weight, at least about 0.85% by weight, at least about 0.90% by weight, at least about 0.95% by weight, at least about 1.0% by weight, at least about 1.5% by weight, at least about 2.0% by weight, at least about 2.5% by weight, or any range or value therebetween.
　本明細書中、約Ｘ（Ｘは数値）とは、Ｘの±１０％あるいは±５％を更に含むことを意味し、具体的には、Ｘ×０．９～Ｘ×１．１を意味する。また、約Ｘは、Ｘ自体であってもよい。 In this specification, "about X" (X is a numerical value) means that it further includes ±10% or ±5% of X, and specifically means X x 0.9 to X x 1.1. In addition, "about X" may be X itself.
　いくつかの実施形態では、双性イオン化合物は、約２．５重量％以下、約２．０重量％以下、約１．５重量％以下、約１．０重量％以下、約０．９５重量％以下、約０．９０重量％以下、約０．８５重量％以下、約０．８０重量％以下、約０．７５重量％以下、約０．７０重量％以下、約０．６５重量％以下、約０．６０重量％以下、約０．５５重量％以下、約０．５０重量％以下、約０．４５重量％以下、約０．４０重量％以下、約０．３５重量％以下、約０．３４重量％以下、約０．３３重量％以下、約０．３２重量％以下、約０．３１重量％以下、約０．３０重量％以下、約０．２９重量％以下、約０．２８重量％以下、約０．２７重量％以下、約０．２６重量％以下、約０．２５重量％以下、約０．２４重量％以下、約０．２３重量％以下、約０．２２重量％以下、約０．２１重量％以下、約０．２０重量％以下、約０．１９重量％以下、約０．１８重量％以下、約０．１７重量％以下、約０．１６重量％以下、約０．１５重量％以下、約０．１４重量％以下、約０．１３重量％以下、約０．１２重量％以下、約０．１１重量％以下、約０．１０重量％以下、約０．０９重量％以下、約０．０８重量％以下、約０．０７重量％以下、約０．０６重量％以下、約０．０５重量％以下、約０．０４重量％以下、約０．０３重量％以下、約０．０２重量％以下、約０．０１重量％、又はそれらの間の任意の範囲若しくは値の濃度（組成物の総重量に対する重量による）で組成物中に存在する。 In some embodiments, the zwitterionic compound is about 2.5 wt% or less, about 2.0 wt% or less, about 1.5 wt% or less, about 1.0 wt% or less, about 0.95 wt% or less, about 0.90 wt% or less, about 0.85 wt% or less, about 0.80 wt% or less, about 0.75 wt% or less, about 0.70 wt% or less, about 0.65 wt% or less, about 0.60 wt% or less, about 0.55 wt% or less, about 0.50 wt% or less, about 0.45 wt% or less, about 0.40 wt% or less, about 0.35 wt% or less, about 0.34 wt% or less, about 0.33 wt% or less, about 0.32 wt% or less, about 0.31 wt% or less, about 0.30 wt% or less, about 0.29 wt% or less, about 0.28 wt% or less, about 0.27 wt% or less, about 0.26 wt% or less, about 0.25 wt% or less. 0.24% or less, about 0.23% or less, about 0.22% or less, about 0.21% or less, about 0.20% or less, about 0.19% or less, about 0.18% or less, about 0.17% or less, about 0.16% or less, about 0.15% or less, about 0.14% or less, about 0.13% or less, about 0.12% or less, about 0.11% or less, about 0.10% or less, about 0.09% or less, about 0.08% or less, about 0.07% or less, about 0.06% or less, about 0.05% or less, about 0.04% or less, about 0.03% or less, about 0.02% or less, about 0.01% or less, or any range or value therebetween (by weight relative to the total weight of the composition).
　いくつかの実施形態では、双性イオン化合物は、約０．０１重量％～約２．０重量％、約０．０１重量％～約１．０重量％、約０．０１重量％～約０．５重量％、約０．０１重量％～約０．４重量％、約０．０１重量％～約０．３重量％、約０．０１重量％～約０．２５重量％、０．０１重量％～約０．２重量％、約０．０１重量％～約０．１重量％、０．０５重量％～約２．０重量％、約０．０５重量％～約１．０重量％、約０．０５重量％～約０．５重量％、約０．０５重量％～約０．４重量％、約０．０５重量％～約０．３重量％、約０．０５重量％～約０．２５重量％、０．０５重量％～約０．２重量％、約０．０５重量％～約０．１重量％、約０．１重量％～約２．５重量％、約０．１重量％～約２．０重量％、約０．１重量％～約１．５重量％、約０．１重量％～約１．０重量％、約０．１重量％～約０．５重量％、約０．１重量％～約０．４重量％、約０．１重量％～約０．３重量％、約０．１重量％～約０．２重量％、約０．２重量％～約２．５重量％、約０．２重量％～約２．０重量％、約０．２重量％～約１．５重量％、約０．２重量％～約１．０重量％、約０．２重量％～約０．５重量％、約０．２重量％～約０．４重量％、約０．２重量％～約０．３重量％又はそれらの間の任意の範囲若しくは値（組成物の総重量に対する重量による）で組成物中に存在する。いくつかの実施形態では、双性イオン化合物は、０．２８４重量％～０．３１０重量％で組成物中に存在する。 In some embodiments, the zwitterionic compound is from about 0.01% to about 2.0% by weight, from about 0.01% to about 1.0% by weight, from about 0.01% to about 0.5% by weight, from about 0.01% to about 0.4% by weight, from about 0.01% to about 0.3% by weight, from about 0.01% to about 0.25% by weight, from 0.01% to about 0.2% by weight, from about 0.01% to about 0.1% by weight, from 0.05% to about 2.0% by weight, from about 0.05% to about 1.0% by weight, from about 0.05% to about 0.5% by weight, from about 0.05% to about 0.4% by weight, from about 0.05% to about 0.3% by weight, from about 0.05% to about 0.25% by weight, from 0.05% to about 0.2% by weight, from about 0.05% to about 0. [0033] The composition may be present in an amount of 1 wt%, about 0.1 wt% to about 2.5 wt%, about 0.1 wt% to about 2.0 wt%, about 0.1 wt% to about 1.5 wt%, about 0.1 wt% to about 1.0 wt%, about 0.1 wt% to about 0.5 wt%, about 0.1 wt% to about 0.4 wt%, about 0.1 wt% to about 0.3 wt%, about 0.1 wt% to about 0.2 wt%, about 0.2 wt% to about 2.5 wt%, about 0.2 wt% to about 2.0 wt%, about 0.2 wt% to about 1.5 wt%, about 0.2 wt% to about 1.0 wt%, about 0.2 wt% to about 0.5 wt%, about 0.2 wt% to about 0.4 wt%, about 0.2 wt% to about 0.3 wt%, or any range or value therebetween (by weight based on the total weight of the composition). In some embodiments, the zwitterionic compound is present in the composition at 0.284% to 0.310% by weight.
　いくつかの実施形態では、組成物中に存在する双性イオン化合物は、少なくとも約１５、少なくとも約２０、少なくとも約２５、少なくとも約３０、少なくとも約３５、少なくとも約４０、少なくとも約４５、少なくとも約５０、少なくとも約５５、少なくとも約６０、少なくとも約６５、少なくとも約７０、少なくとも約７５、少なくとも約８０、少なくとも約８５、少なくとも約９０、少なくとも約９５、少なくとも約１００、又はそれを超える、第２の材料（例えば、ＳｉＯ２）に対する第１の材料（例えば、ＳｉＮ）の除去速度選択性を得るのに有効である。 In some embodiments, the zwitterionic compound present in the composition is effective to obtain a removal rate selectivity of a first material (e.g., SiN) relative to a second material (e.g., SiO 2 ) of at least about 15, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95, at least about 100 , or more.
　いくつかの実施形態では、組成物は、少なくとも約１５、少なくとも約２０、少なくとも約２５、少なくとも約３０、少なくとも約３５、少なくとも約４０、少なくとも約４５、少なくとも約５０、少なくとも約５５、少なくとも約６０、少なくとも約６５、少なくとも約７０、少なくとも約７５、少なくとも約８０、少なくとも約８５、少なくとも約９０、少なくとも約９５、少なくとも約１００、又はそれを超える、第２の材料（例えば、ＳｉＯ２）に対する第１の材料（例えば、ＳｉＮ）の除去速度選択性をその特性として有する。 In some embodiments, the composition is characterized by a removal rate selectivity of a first material (e.g., SiN) over a second material (e.g., SiO2) of at least about 15, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95, at least about 100, or more.
　いくつかの実施形態では、第１の材料はＳｉＮである。いくつかの実施形態では、第２の材料はＳｉＯ２である。いくつかの実施形態では、除去速度選択性は、ＳｉＮ：ＳｉＯ２除去速度選択性である。いくつかの実施形態では、ＳｉＮ：ＳｉＯ２除去速度選択性は、約１５、約２０、約２５、約３０、約３５、約４０、約４５、約５０、約５５、約６０、約６５、約７０、約７５、約８０、約８５、約９０、約９５、約１００、又はそれを超える。 In some embodiments, the first material is SiN. In some embodiments, the second material is SiO2 . In some embodiments, the removal rate selectivity is a SiN: SiO2 removal rate selectivity. In some embodiments, the SiN:SiO2 removal rate selectivity is about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70, about 75, about 80, about 85, about 90, about 95, about 100, or more.
　いくつかの実施形態では、組成物中に存在する双性イオン化合物は、同一の組成物（ただし双性イオン化合物が存在しない場合）と比較した場合、少なくとも約１．１倍、少なくとも約１．２倍、少なくとも約１．５倍、少なくとも約２．０倍、少なくとも約２．５倍、少なくとも約３．０倍、少なくとも約３．５倍、少なくとも約４．０倍、少なくとも約４．５倍、少なくとも約５．０倍、少なくとも約５．５倍、少なくとも約６．０倍、少なくとも約６．５倍、少なくとも約７．０倍、少なくとも約７．５倍、少なくとも約８．０倍、少なくとも約８．５倍、少なくとも約９．０倍、少なくとも約９．５倍、少なくとも約１０．０倍以上、第２の材料よりも第１の材料の除去速度選択性（例えば、ＳｉＮ：ＳｉＯ２除去速度選択性）を高めるのに有効である。 In some embodiments, the zwitterionic compound present in the composition is effective to increase the removal rate selectivity of a first material over a second material (e.g., SiN:SiO2 removal rate selectivity) by at least about 1.1 times, at least about 1.2 times, at least about 1.5 times, at least about 2.0 times, at least about 2.5 times, at least about 3.0 times, at least about 3.5 times, at least about 4.0 times, at least about 4.5 times, at least about 5.0 times, at least about 5.5 times, at least about 6.0 times, at least about 6.5 times, at least about 7.0 times, at least about 7.5 times, at least about 8.0 times, at least about 8.5 times, at least about 9.0 times, at least about 9.5 times, at least about 10.0 times or more, when compared to the same composition but without the zwitterionic compound present.
　研磨材
　本開示による研磨用組成物は、研磨用組成物のｐＨにおいて反対の電荷配向を有する第１の材料及び第２の材料を研磨するのに適した研磨粒子を含む。いくつかの実施形態では、研磨粒子は、１つ又は複数の金属酸化物粒子、例えば、ジルコニア、ハフニア、アルミナ、チタニア、シリカ、セリア、及びそれらの任意の組合せを含む。いくつかの実施形態では、研磨粒子は、コロイダルシリカ、コロイダルジルコニア、又はそれらの組合せを含む。いくつかの実施形態では、研磨粒子はコロイダルシリカを含む。更に、研磨粒子は、市販品、合成品、又はそれらの任意の組合せであってもよい。いくつかの実施形態では、研磨粒子はアニオン性であり得る。本出願の文脈内で、「アニオン性」粒子は、研磨用組成物のｐＨにおいて負の表面電荷又はゼータ電位電荷を有する。いくつかの実施形態では、研磨粒子はカチオン性であり得る。本出願の文脈内で、「カチオン性」粒子は、研磨用組成物のｐＨにおいて正の表面電荷又はゼータ電位電荷を有する。本明細書中、研磨材を単に研磨粒子と称する場合もある。 Abrasive The polishing composition according to the present disclosure comprises abrasive particles suitable for polishing a first material and a second material having opposite charge orientations at the pH of the polishing composition. In some embodiments, the abrasive particles comprise one or more metal oxide particles, such as zirconia, hafnia, alumina, titania, silica, ceria, and any combination thereof. In some embodiments, the abrasive particles comprise colloidal silica, colloidal zirconia, or a combination thereof. In some embodiments, the abrasive particles comprise colloidal silica. Furthermore, the abrasive particles may be commercially available, synthetic, or any combination thereof. In some embodiments, the abrasive particles may be anionic. Within the context of this application, "anionic" particles have a negative surface charge or zeta potential charge at the pH of the polishing composition. In some embodiments, the abrasive particles may be cationic. Within the context of this application, "cationic" particles have a positive surface charge or zeta potential charge at the pH of the polishing composition. In this specification, the abrasive may be simply referred to as abrasive particles.
　いくつかの実施形態では、研磨粒子は、粒子表面に共有結合し、末端アニオン性基又はカチオン性基を有する化学種によって表面修飾される。いくつかの実施形態では、研磨粒子は、例えば、コロイド粒子表面上の有機酸の固定化によってアニオン修飾されたコロイド粒子を含む。 In some embodiments, the abrasive particles are surface modified with species covalently attached to the particle surface and having terminal anionic or cationic groups. In some embodiments, the abrasive particles include colloidal particles that are anionically modified, for example, by immobilization of an organic acid on the colloidal particle surface.
　いくつかの実施形態では、研磨用組成物中の研磨粒子（例えば、コロイダルシリカ）の表面への有機酸の固定は、有機酸の官能基を研磨粒子（例えば、コロイダルシリカ）の表面に化学的に結合させることによって行われ得る。コロイダルシリカに有機酸を固定化するには、単にコロイダルシリカと有機酸を共存させるだけでは達成できない。コロイダルシリカへの有機酸（例えば、スルホン酸）の固定化は、例えば、参照によりその全体が本明細書に組み込まれる、Ｅ．Ｃａｎｏ－Ｓｅｒｒａｎｏ　ｅｔ　ａｌ．，Ｓｕｌｆｏｎｉｃ　Ａｃｉｄ－Ｆｕｎｃｔｉｏｎａｌｉｚｅｄ　Ｓｉｌｉｃａ　Ｔｈｒｏｕｇｈ　Ｑｕａｎｔｉｔａｔｉｖｅ　Ｏｘｉｄａｔｉｏｎ　ｏｆ　Ｔｈｉｏｌ　Ｇｒｏｕｐｓ，Ｃｈｅｍ．Ｃｏｍｍｕｎ．２４６－４７（２００３）に記載される方法によって実行され得る。具体的には、３－メルカプトプロピルトリメトキシシラン（「ＭＰＳ」）等のチオール基を有するシランカップリング剤をコロイダルシリカにカップリングさせた後、過酸化水素によりチオール基を酸化して表面固定化スルホン酸（例えば、表面結合プロパンスルホン酸、例えば酸化ＭＰＳ）を形成することにより、スルホン酸が表面に固定化されたコロイダルシリカを得ることができる。 In some embodiments, the organic acid can be immobilized on the surface of the abrasive particles (e.g., colloidal silica) in the polishing composition by chemically bonding the functional group of the organic acid to the surface of the abrasive particles (e.g., colloidal silica). Immobilization of the organic acid on the colloidal silica cannot be achieved by simply coexisting the colloidal silica with the organic acid. Immobilization of the organic acid (e.g., sulfonic acid) on the colloidal silica can be carried out, for example, by the method described in E. Cano-Serrano et al., Sulfonic Acid-Functionalized Silica Through Quantitative Oxidation of Thiol Groups, Chem. Commun. 246-47 (2003), the entire contents of which are incorporated herein by reference. Specifically, a silane coupling agent having a thiol group, such as 3-mercaptopropyltrimethoxysilane ("MPS"), is coupled to colloidal silica, and then the thiol group is oxidized with hydrogen peroxide to form a surface-immobilized sulfonic acid (e.g., surface-bound propanesulfonic acid, e.g., oxidized MPS), thereby obtaining colloidal silica with a sulfonic acid immobilized on the surface.
　カルボン酸のコロイダルシリカへの固定化は、例えば、その全体が参照により本明細書に組み込まれる、Ｙ．Ｋａｚｕｏ　ｅｔ　ａｌ．，Ｎｏｖｅｌ　Ｓｉｌａｎｅ　Ｃｏｕｐｌｉｎｇ　Ａｇｅｎｔｓ　Ｃｏｎｔａｉｎｉｎｇ　ａ　Ｐｈｏｔｏｌａｂｉｌｅ　２－Ｎｉｔｒｏｂｅｎｚｙｌ　Ｅｓｔｅｒ　ｆｏｒ　Ｉｎｔｒｏｄｕｃｔｉｏｎ　ｏｆ　ａ　Ｃａｒｂｏｘｙ　Ｇｒｏｕｐ　ｏｎ　ｔｈｅ　Ｓｕｒｆａｃｅ　ｏｆ　Ｓｉｌｉｃａ　Ｇｅｌ，３　Ｃｈｅｍ．Ｌｅｔｔ．２２８－２９（２０００）に記載の方法によって実行され得る。具体的には、光反応性２－ニトロベンジルエステルを含むシランカップリング剤をコロイダルシリカにカップリングさせ、続いて光照射することにより、カルボン酸が表面に固定化されたコロイダルシリカを得ることができる。コロイダルシリカへの有機酸固定化のこれらの例は、例示的であることを意図しており、限定的であることを意図していない。異なる有機酸及び異なる研磨粒子材料（例えば、コロイダルシリカ以外）を使用する他の有機固定化技術は、本開示の範囲内に包含されることが意図されている。 Carboxylic acid can be immobilized on colloidal silica by, for example, the method described in Y. Kazuo et al., Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel, 3 Chem. Lett. 228-29 (2000), the entirety of which is incorporated herein by reference. Specifically, a silane coupling agent containing a photoreactive 2-nitrobenzyl ester can be coupled to colloidal silica, followed by light irradiation, to obtain colloidal silica having a carboxylic acid immobilized on the surface. These examples of organic acid immobilization on colloidal silica are intended to be illustrative and not limiting. Other organic immobilization techniques using different organic acids and different abrasive particulate materials (e.g., other than colloidal silica) are intended to be encompassed within the scope of this disclosure.
　いくつかの実施形態では、研磨粒子は、約７ｎｍ以上、約８ｎｍ以上、約９ｎｍ以上、約１０ｎｍ以上、約１１ｎｍ以上、約１２ｎｍ以上、約１３ｎｍ以上、約１４ｎｍ以上、約１５ｎｍ以上、約１６ｎｍ以上、約１７ｎｍ以上、約１８ｎｍ以上、約１９ｎｍ以上、約２０ｎｍ以上、約２５ｎｍ以上、約３０ｎｍ以上、約３５ｎｍ以上、約４０ｎｍ以上、約４５ｎｍ以上、約５０ｎｍ以上、約５５ｎｍ以上、約６０ｎｍ以上、約６５ｎｍ以上、約７０ｎｍ以上、約７５ｎｍ以上、約８０ｎｍ以上、約８５ｎｍ以上、約９０ｎｍ以上、約９５ｎｍ以上、約１００ｎｍ以上、約１１０ｎｍ以上、約１２０ｎｍ以上、約１３０ｎｍ以上、約１４０ｎｍ以上、約１５０ｎｍ以上、又はこれらの間の任意の範囲若しくは値の平均一次粒子径を有する。平均一次粒子径は、当技術分野で公知の任意の適切な方法（例えば、透過型電子顕微鏡法、走査型電子顕微鏡法、又はＨｉｔａｃｈｉ　Ｈｉｇｈ－Ｔｅｃｈ　ＨＤ－２７００　Ｓｃａｎｎｉｎｇ　Ｔｒａｎｓｍｉｓｓｉｏｎ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅを使用する等のＳＴＥＭによる）を使用して測定することができる。 In some embodiments, the abrasive particles have an average primary particle size of about 7 nm or more, about 8 nm or more, about 9 nm or more, about 10 nm or more, about 11 nm or more, about 12 nm or more, about 13 nm or more, about 14 nm or more, about 15 nm or more, about 16 nm or more, about 17 nm or more, about 18 nm or more, about 19 nm or more, about 20 nm or more, about 25 nm or more, about 30 nm or more, about 35 nm or more, about 40 nm or more, about 45 nm or more, about 50 nm or more, about 55 nm or more, about 60 nm or more, about 65 nm or more, about 70 nm or more, about 75 nm or more, about 80 nm or more, about 85 nm or more, about 90 nm or more, about 95 nm or more, about 100 nm or more, about 110 nm or more, about 120 nm or more, about 130 nm or more, about 140 nm or more, about 150 nm or more, or any range or value therebetween. The average primary particle size can be measured using any suitable method known in the art (e.g., by transmission electron microscopy, scanning electron microscopy, or STEM, such as using a Hitachi High-Tech HD-2700 Scanning Transmission Electron Microscope).
　いくつかの実施形態では、研磨粒子は、約１５０ｎｍ以下、約１４０ｎｍ以下、約１３０ｎｍ以下、約１２０ｎｍ以下、約１１０ｎｍ以下、約１００ｎｍ以下、約９５ｎｍ以下、約９０ｎｍ以下、約８５ｎｍ以下、約８０ｎｍ以下、約７５ｎｍ以下、約７０ｎｍ以下、約６５ｎｍ以下、約６０ｎｍ以下、約５５ｎｍ以下、約５０ｎｍ以下、約４５ｎｍ以下、約４０ｎｍ以下、約３５ｎｍ以下、約３０ｎｍ以下、約２５ｎｍ以下、約２０ｎｍ以下、約１９ｎｍ以下、約１８ｎｍ以下、約１７ｎｍ以下、約１６ｎｍ以下、約１５ｎｍ以下、約１４ｎｍ以下、約１３ｎｍ以下、約１２ｎｍ以下、約１１ｎｍ以下、約１０ｎｍ以下、約９ｎｍ以下、約８ｎｍ以下、約７ｎｍ以下、又はこれらの間の任意の範囲若しくは値の平均一次粒子径を有する。 In some embodiments, the abrasive particles have an average primary particle size of about 150 nm or less, about 140 nm or less, about 130 nm or less, about 120 nm or less, about 110 nm or less, about 100 nm or less, about 95 nm or less, about 90 nm or less, about 85 nm or less, about 80 nm or less, about 75 nm or less, about 70 nm or less, about 65 nm or less, about 60 nm or less, about 55 nm or less, about 50 nm or less, about 45 nm or less, about 40 nm or less, about 35 nm or less, about 30 nm or less, about 25 nm or less, about 20 nm or less, about 19 nm or less, about 18 nm or less, about 17 nm or less, about 16 nm or less, about 15 nm or less, about 14 nm or less, about 13 nm or less, about 12 nm or less, about 11 nm or less, about 10 nm or less, about 9 nm or less, about 8 nm or less, about 7 nm or less, or any range or value therebetween.
　いくつかの実施形態では、研磨粒子は、約７ｎｍ～約１５０ｎｍ、約７ｎｍ～約１００ｎｍ、約７ｎｍ～約９０ｎｍ、約７ｎｍ～約８０ｎｍ、約７ｎｍ～約７０ｎｍ、約７ｎｍ～約６０ｎｍ、約７ｎｍ～約５０ｎｍ、約７ｎｍ～約４５ｎｍ、約７ｎｍ～約４０ｎｍ、約７ｎｍ～約３５ｎｍ、約７ｎｍ～約３０ｎｍ、約７ｎｍ～約２５ｎｍ、約７ｎｍ～約２０ｎｍ、約７ｎｍ～約１５ｎｍ、約７ｎｍ～約１４ｎｍ、約７ｎｍ～約１３ｎｍ、約７ｎｍ～約１２ｎｍ、約７ｎｍ～約１１ｎｍ、約７ｎｍ～約１０ｎｍ、約１０ｎｍ～約１５０ｎｍ、約１０ｎｍ～約１００ｎｍ、約１０ｎｍ～約９０ｎｍ、約１０ｎｍ～約８０ｎｍ、約１０ｎｍ～約７０ｎｍ、約１０ｎｍ～約６０ｎｍ、約１０ｎｍ～約５０ｎｍ、約１０ｎｍ～約４５ｎｍ、約１０ｎｍ～約４０ｎｍ、約１０ｎｍ～約３５ｎｍ、約１０ｎｍ～約３０ｎｍ、約１０ｎｍ～約２５ｎｍ、約１０ｎｍ～約２０ｎｍ、約１０ｎｍ～約１５ｎｍ、約１０ｎｍ～約１４ｎｍ、約１０ｎｍ～約１３ｎｍ、約１０ｎｍ～約１２ｎｍ、約２０ｎｍ～約１５０ｎｍ、約２０ｎｍ～約１００ｎｍ、約２０ｎｍ～約９０ｎｍ、約２０ｎｍ～約８０ｎｍ、約２０ｎｍ～約７０ｎｍ、約２０ｎｍ～約６０ｎｍ、約２０ｎｍ～約５０ｎｍ、約２０ｎｍ～約４５ｎｍ、約２０ｎｍ～約４０ｎｍ、約３０ｎｍ～約１５０ｎｍ、約３０ｎｍ～約１００ｎｍ、約３０ｎｍ～約９０ｎｍ、約３０ｎｍ～約８０ｎｍ、約３０ｎｍ～約７０ｎｍ、約３０ｎｍ～約６０ｎｍ、約３０ｎｍ～約５０ｎｍ、約３０ｎｍ～約４５ｎｍ、約３０ｎｍ～約４０ｎｍ、約４０ｎｍ～約１５０ｎｍ、約４０ｎｍ～約１００ｎｍ、約４０ｎｍ～約９０ｎｍ、約４０ｎｍ～約８０ｎｍ、約４０ｎｍ～約７０ｎｍ、約４０ｎｍ～約６０ｎｍ、約４０ｎｍ～約５０ｎｍ、約５０ｎｍ～約１５０ｎｍ、約５０ｎｍ～約１００ｎｍ、約５０ｎｍ～約９０ｎｍ、約５０ｎｍ～約８０ｎｍ、約５０ｎｍ～約７０ｎｍ、約５０ｎｍ～約６０ｎｍ、又はその中の任意の範囲若しくは値の平均一次粒子径を有する。 In some embodiments, the abrasive particles have a diameter of about 7 nm to about 150 nm, about 7 nm to about 100 nm, about 7 nm to about 90 nm, about 7 nm to about 80 nm, about 7 nm to about 70 nm, about 7 nm to about 60 nm, about 7 nm to about 50 nm, about 7 nm to about 45 nm, about 7 nm to about 40 nm, about 7 nm to about 35 nm, about 7 nm to about 30 nm, about 7 nm to about 25 nm, about 7 nm to about 20 nm, about 7 nm to about 15 nm, about 7 nm to about 14 nm, about 7 nm to about 13 nm, about 7 nm to about 12 nm, about 7 nm to about 15 nm, about 7 nm to about 14 nm, about 7 nm to about 13 nm, about 7 nm to about 12 nm, about 7 nm to about 15 nm, about 7 nm to about 15 nm, about 7 nm to about 15 nm, about 7 nm to about 16 nm, about 7 nm to about 17 nm, about 7 nm to about 18 nm, about 7 nm to about 19 nm, about 7 nm to about 20 nm, about 7 nm to about 25 nm, about 7 nm to about 20 nm, about 7 nm to about 25 nm, about 7 nm to about 20 nm, about 7 nm to about 15 nm, about 7 nm to about 14 nm, about 7 nm to about 13 nm, about 7 nm to about 12 nm, about 7 nm to about 25 nm, about 7 nm to about 20 ... nm to about 11 nm, about 7 nm to about 10 nm, about 10 nm to about 150 nm, about 10 nm to about 100 nm, about 10 nm to about 90 nm, about 10 nm to about 80 nm, about 10 nm to about 70 nm, about 10 nm to about 60 nm, about 10 nm to about 50 nm, about 10 nm to about 45 nm, about 10 nm to about 40 nm, about 10 nm to about 35 nm, about 10 nm to about 30 nm, about 10 nm to about 25 nm, about 10 nm to about 20 nm, about 10 nm to about 15 nm, about 10 nm to about 14 nm, about 10 nm to about 13 nm m, about 10 nm to about 12 nm, about 20 nm to about 150 nm, about 20 nm to about 100 nm, about 20 nm to about 90 nm, about 20 nm to about 80 nm, about 20 nm to about 70 nm, about 20 nm to about 60 nm, about 20 nm to about 50 nm, about 20 nm to about 45 nm, about 20 nm to about 40 nm, about 30 nm to about 150 nm, about 30 nm to about 100 nm, about 30 nm to about 90 nm, about 30 nm to about 80 nm, about 30 nm to about 70 nm, about 30 nm to about 60 nm, about 30 nm to about 50 nm, about The average primary particle size is 0 nm to about 45 nm, about 30 nm to about 40 nm, about 40 nm to about 150 nm, about 40 nm to about 100 nm, about 40 nm to about 90 nm, about 40 nm to about 80 nm, about 40 nm to about 70 nm, about 40 nm to about 60 nm, about 40 nm to about 50 nm, about 50 nm to about 150 nm, about 50 nm to about 100 nm, about 50 nm to about 90 nm, about 50 nm to about 80 nm, about 50 nm to about 70 nm, about 50 nm to about 60 nm, or any range or value therein.
　いくつかの実施形態では、研磨粒子は、約１０ｎｍ以上、約１５ｎｍ以上、約２０ｎｍ以上、約２５ｎｍ以上、約３０ｎｍ以上、約３５ｎｍ以上、約４０ｎｍ以上、約４５ｎｍ以上、約５０ｎｍ以上、約５５ｎｍ以上、約６０ｎｍ以上、約６５ｎｍ以上、約７０ｎｍ以上、約７５ｎｍ以上、約８０ｎｍ以上、約８５ｎｍ以上、約９０ｎｍ以上、約９５ｎｍ以上、約１００ｎｍ以上、約１１０ｎｍ以上、約１２０ｎｍ以上、約１３０ｎｍ以上、約１４０ｎｍ以上、約１５０ｎｍ以上、約１６０ｎｍ以上、約１７０ｎｍ以上、約１８０ｎｍ以上、約１９０ｎｍ以上、約２００ｎｍ以上、約２５０ｎｍ以上、約３００ｎｍ以上、約３５０ｎｍ以上、約４００ｎｍ以上、約４５０ｎｍ以上、約５００ｎｍ以上、又はこれらの間の任意の範囲若しくは値の平均二次粒子径を有する。平均二次粒子径は、当技術分野で公知の任意の適切な方法（例えば、Ｍａｌｖｅｒｎ　Ｐａｎａｌｙｔｉｃａｌ　ＺｅｔａＳｉｚｅｒ　Ｎａｎｏ光散乱システムを使用する等、光散乱によって）を使用して測定することができる。 In some embodiments, the abrasive particles have an average secondary particle size of about 10 nm or more, about 15 nm or more, about 20 nm or more, about 25 nm or more, about 30 nm or more, about 35 nm or more, about 40 nm or more, about 45 nm or more, about 50 nm or more, about 55 nm or more, about 60 nm or more, about 65 nm or more, about 70 nm or more, about 75 nm or more, about 80 nm or more, about 85 nm or more, about 90 nm or more, about 95 nm or more, about 100 nm or more, about 110 nm or more, about 120 nm or more, about 130 nm or more, about 140 nm or more, about 150 nm or more, about 160 nm or more, about 170 nm or more, about 180 nm or more, about 190 nm or more, about 200 nm or more, about 250 nm or more, about 300 nm or more, about 350 nm or more, about 400 nm or more, about 450 nm or more, about 500 nm or more, or any range or value therebetween. The average secondary particle size can be measured using any suitable method known in the art (e.g., by light scattering, such as using a Malvern Panalytical ZetaSizer Nano light scattering system).
　いくつかの実施形態では、研磨粒子は、約５００ｎｍ以下、約４５０ｎｍ以下、約４００ｎｍ以下、約３５０ｎｍ以下、約３００ｎｍ以下、約２５０ｎｍ以下、約２００ｎｍ以下、約１９０ｎｍ以下、約１８０ｎｍ以下、約１７０ｎｍ以下、約１６０ｎｍ以下、約１５０ｎｍ以下、約１４０ｎｍ以下、約１３０ｎｍ以下、約１２０ｎｍ以下、約１１０ｎｍ以下、約１００ｎｍ以下、約９５ｎｍ以下、約９０ｎｍ以下、約８５ｎｍ以下、約８０ｎｍ以下、約７５ｎｍ以下、約７０ｎｍ以下、約６５ｎｍ以下、約６０ｎｍ以下、約５５ｎｍ以下、約５０ｎｍ以下、約４５ｎｍ以下、約４０ｎｍ以下、約３５ｎｍ以下、約３０ｎｍ以下、約２５ｎｍ以下、約２０ｎｍ以下、約１５ｎｍ以下、又はこれらの間の任意の範囲若しくは値の平均二次直径を有する。 In some embodiments, the abrasive particles have an average secondary diameter of about 500 nm or less, about 450 nm or less, about 400 nm or less, about 350 nm or less, about 300 nm or less, about 250 nm or less, about 200 nm or less, about 190 nm or less, about 180 nm or less, about 170 nm or less, about 160 nm or less, about 150 nm or less, about 140 nm or less, about 130 nm or less, about 120 nm or less, about 110 nm or less, about 100 nm or less, about 95 nm or less, about 90 nm or less, about 85 nm or less, about 80 nm or less, about 75 nm or less, about 70 nm or less, about 65 nm or less, about 60 nm or less, about 55 nm or less, about 50 nm or less, about 45 nm or less, about 40 nm or less, about 35 nm or less, about 30 nm or less, about 25 nm or less, about 20 nm or less, about 15 nm or less, or any range or value therebetween.
　いくつかの実施形態では、研磨粒子は、約１０ｎｍ～約５００ｎｍ、約１０ｎｍ～約２００ｎｍ、約１０ｎｍ～約１００ｎｍ、約１０ｎｍ～約５０ｎｍ、約１０ｎｍ～約３０ｎｍ、約２０ｎｍ～約５００ｎｍ、約２０ｎｍ～約２００ｎｍ、約２０ｎｍ～約１００ｎｍ、約２０ｎｍ～約５０ｎｍ、約２０ｎｍ～約３０ｎｍ、約３０ｎｍ～約５００ｎｍ、約３０ｎｍ～約２００ｎｍ、約３０ｎｍ～約１００ｎｍ、約３０ｎｍ～約５０ｎｍ、約３０ｎｍ～約４０ｎｍ、又はその中の任意の範囲若しくは値の平均二次粒子径を有する。いくつかの実施形態では、研磨粒子は、約２０ｎｍ～約４０ｎｍ、又はその中の任意の範囲若しくは値の平均二次粒子径を有する。 In some embodiments, the abrasive particles have an average secondary particle size of about 10 nm to about 500 nm, about 10 nm to about 200 nm, about 10 nm to about 100 nm, about 10 nm to about 50 nm, about 10 nm to about 30 nm, about 20 nm to about 500 nm, about 20 nm to about 200 nm, about 20 nm to about 100 nm, about 20 nm to about 50 nm, about 20 nm to about 30 nm, about 30 nm to about 500 nm, about 30 nm to about 200 nm, about 30 nm to about 100 nm, about 30 nm to about 50 nm, about 30 nm to about 40 nm, or any range or value therein. In some embodiments, the abrasive particles have an average secondary particle size of about 20 nm to about 40 nm, or any range or value therein.
　いくつかの実施形態では、研磨粒子は、約１０ｎｍ以上、約１５ｎｍ以上、約１６ｎｍ以上、約１７ｎｍ以上、約１８ｎｍ以上、約１９ｎｍ以上、約２０ｎｍ以上、約２１ｎｍ以上、約２２ｎｍ以上、約２３ｎｍ以上、約２４ｎｍ以上、約２５ｎｍ以上、約３０ｎｍ以上、約３５ｎｍ以上、約４０ｎｍ以上、約４５ｎｍ以上、約５０ｎｍ以上、約５５ｎｍ以上、約６０ｎｍ以上、約６５ｎｍ以上、約７０ｎｍ以上、約７５ｎｍ以上、約８０ｎｍ以上、約８５ｎｍ以上、約９０ｎｍ以上、約９５ｎｍ以上、約１００ｎｍ以上、約１１０ｎｍ以上、約１２０ｎｍ以上、約１３０ｎｍ以上、約１４０ｎｍ以上、約１５０ｎｍ以上、約１６０ｎｍ以上、約１７０ｎｍ以上、約１８０ｎｍ以上、約１９０ｎｍ以上、約２００ｎｍ以上、約２５０ｎｍ以上、約３００ｎｍ以上、又はこれらの間の任意の範囲若しくは値の平均粒子径を有する。平均粒子径は、当技術分野で公知の任意の適切な方法（例えば、Ｍａｌｖｅｒｎ　Ｐａｎａｌｙｔｉｃａｌ　ＺｅｔａＳｉｚｅｒ　Ｎａｎｏ光散乱システムを使用する等、光散乱によって）を使用して測定することができる。なお、平均粒子径との用語は、平均二次粒子径と同じ意味で使用されている。 In some embodiments, the abrasive particles are about 10 nm or more, about 15 nm or more, about 16 nm or more, about 17 nm or more, about 18 nm or more, about 19 nm or more, about 20 nm or more, about 21 nm or more, about 22 nm or more, about 23 nm or more, about 24 nm or more, about 25 nm or more, about 30 nm or more, about 35 nm or more, about 40 nm or more, about 45 nm or more, about 50 nm or more, about 55 nm or more, about 60 nm or more, about 65 nm or more, about 70 nm or more , about 75 nm or more, about 80 nm or more, about 85 nm or more, about 90 nm or more, about 95 nm or more, about 100 nm or more, about 110 nm or more, about 120 nm or more, about 130 nm or more, about 140 nm or more, about 150 nm or more, about 160 nm or more, about 170 nm or more, about 180 nm or more, about 190 nm or more, about 200 nm or more, about 250 nm or more, about 300 nm or more, or any range or value therebetween. The average particle size can be measured using any suitable method known in the art (e.g., by light scattering, such as using a Malvern Panalytical ZetaSizer Nano light scattering system). Note that the term average particle size is used interchangeably with average secondary particle size.
　いくつかの実施形態では、研磨粒子は、約３００ｎｍ以下、約２５０ｎｍ以下、約２００ｎｍ以下、約１９０ｎｍ以下、約１８０ｎｍ以下、約１７０ｎｍ以下、約１６０ｎｍ以下、約１５０ｎｍ以下、約１４０ｎｍ以下、約１３０ｎｍ以下、約１２０ｎｍ以下、約１１０ｎｍ以下、約１００ｎｍ以下、約９５ｎｍ以下、約９０ｎｍ以下、約８５ｎｍ以下、約８０ｎｍ以下、約７５ｎｍ以下、約７０ｎｍ以下、約６５ｎｍ以下、約６０ｎｍ以下、約５５ｎｍ以下、約５０ｎｍ以下、約４５ｎｍ以下、約４０ｎｍ以下、約３５ｎｍ以下、約３０ｎｍ以下、約２５ｎｍ以下、約２４ｎｍ以下、約２３ｎｍ以下、約２２ｎｍ以下、約２１ｎｍ以下、約２０ｎｍ以下、約１９ｎｍ以下、約１８ｎｍ以下、約１７ｎｍ以下、約１６ｎｍ以下、約１５ｎｍ以下、約１０ｎｍ以下、又はこれらの間の任意の範囲若しくは値の平均粒子径を有する。 In some embodiments, the abrasive particles are about 300 nm or less, about 250 nm or less, about 200 nm or less, about 190 nm or less, about 180 nm or less, about 170 nm or less, about 160 nm or less, about 150 nm or less, about 140 nm or less, about 130 nm or less, about 120 nm or less, about 110 nm or less, about 100 nm or less, about 95 nm or less, about 90 nm or less, about 85 nm or less, about 80 nm or less, about 75 nm or less, about 70 nm or less, about 6 It has an average particle size of 5 nm or less, about 60 nm or less, about 55 nm or less, about 50 nm or less, about 45 nm or less, about 40 nm or less, about 35 nm or less, about 30 nm or less, about 25 nm or less, about 24 nm or less, about 23 nm or less, about 22 nm or less, about 21 nm or less, about 20 nm or less, about 19 nm or less, about 18 nm or less, about 17 nm or less, about 16 nm or less, about 15 nm or less, about 10 nm or less, or any range or value therebetween.
　いくつかの実施形態では、研磨粒子は、約１０ｎｍ～約３００ｎｍ、約１０ｎｍ～約２００ｎｍ、約１０ｎｍ～約１５０ｎｍ、約１０ｎｍ～約１００ｎｍ、約１０ｎｍ～約９０ｎｍ、約１０ｎｍ～約８０ｎｍ、約１０ｎｍ～約７０ｎｍ、約１０ｎｍ～約６０ｎｍ、約１０ｎｍ～約５０ｎｍ、約１０ｎｍ～約４５ｎｍ、約１０ｎｍ～約４０ｎｍ、約１０ｎｍ～約３５ｎｍ、約１０ｎｍ～約３０ｎｍ、約１０ｎｍ～約２５ｎｍ、約１０ｎｍ～約２４ｎｍ、約１０ｎｍ～約２３ｎｍ、約１０ｎｍ～約２２ｎｍ、約１０ｎｍ～約２１ｎｍ、約１０ｎｍ～約２０ｎｍ、約１０ｎｍ～約１９ｎｍ、約１０ｎｍ～約１８ｎｍ、約１０ｎｍ～約１７ｎｍ、約１０ｎｍ～約１６ｎｍ、約１０ｎｍ～約１５ｎｍ、約１０ｎｍ～約１４ｎｍ、約１０ｎｍ～約１３ｎｍ、約１０ｎｍ～約１２ｎｍ、約２０ｎｍ～約３００ｎｍ、約２０ｎｍ～約２００ｎｍ、約２０ｎｍ～約１５０ｎｍ、約２０ｎｍ～約１００ｎｍ、約２０ｎｍ～約９０ｎｍ、約２０ｎｍ～約８０ｎｍ、約２０ｎｍ～約７０ｎｍ、約２０ｎｍ～約６０ｎｍ、約２０ｎｍ～約５０ｎｍ、約２０ｎｍ～約４５ｎｍ、約２０ｎｍ～約４０ｎｍ、約２０ｎｍ～約３５ｎｍ、約２０ｎｍ～約３０ｎｍ、約２０ｎｍ～約２５ｎｍ、約２０ｎｍ～約２４ｎｍ、約２０ｎｍ～約２３ｎｍ、約２０ｎｍ～約２２ｎｍ、約３０ｎｍ～約３００ｎｍ、約３０ｎｍ～約２００ｎｍ、約３０ｎｍ～約１５０ｎｍ、約３０ｎｍ～約１００ｎｍ、約３０ｎｍ～約９０ｎｍ、約３０ｎｍ～約８０ｎｍ、約３０ｎｍ～約７０ｎｍ、約３０ｎｍ～約６０ｎｍ、約３０ｎｍ～約５０ｎｍ、約３０ｎｍ～約４５ｎｍ、約３０ｎｍ～約４０ｎｍ、約４０ｎｍ～約３００ｎｍ、約４０ｎｍ～約２００ｎｍ、約４０ｎｍ～約１５０ｎｍ、約４０ｎｍ～約１００ｎｍ、約４０ｎｍ～約９０ｎｍ、約４０ｎｍ～約８０ｎｍ、約４０ｎｍ～約７０ｎｍ、約４０ｎｍ～約６０ｎｍ、約４０ｎｍ～約５０ｎｍ、約５０ｎｍ～約３００ｎｍ、約５０ｎｍ～約２００ｎｍ、約５０ｎｍ～約１５０ｎｍ、約５０ｎｍ～約１００ｎｍ、約５０ｎｍ～約９０ｎｍ、約５０ｎｍ～約８０ｎｍ、約５０ｎｍ～約７０ｎｍ、約５０ｎｍ～約６０ｎｍ、又はその中の任意の範囲若しくは値の平均粒子径を有する。 In some embodiments, the abrasive particles have a diameter of about 10 nm to about 300 nm, about 10 nm to about 200 nm, about 10 nm to about 150 nm, about 10 nm to about 100 nm, about 10 nm to about 90 nm, about 10 nm to about 80 nm, about 10 nm to about 70 nm, about 10 nm to about 60 nm, about 10 nm to about 50 nm, about 10 nm to about 45 nm, about 10 nm to about 40 nm, about 10 nm to about 35 nm, about 10 nm to about 30 nm, about 10 nm to about 25 nm, about 10 nm to about 24 nm, about 10 nm to about 23 nm, about 10 nm to about 22 nm, about 10 nm to about 21 nm, about 10 nm to about 20 nm, about 10 nm to about 19 nm, about 10 nm to about 18 nm, about 10 nm to about 17 nm, about 10 nm to about 16 nm, about 10 nm to about 15 nm, about 10 nm to about 14 nm, about 10 nm to about 13 nm, about 10 nm to about 12 nm, about 20 nm to about 300 nm, about 20 nm to about 200 nm, about 20 nm to about 150 nm, about 20 nm to about 100 nm, about 20 nm to about 90 nm, about 20 nm to about 80 nm, about 20 nm to about 70 nm, about 20 nm to about 60 nm, about 20 nm to about 50 nm, about 20 nm to about 45 nm, about 20 nm to about 40 nm, about 20 nm to about 35 nm, about 20 nm to about 30 nm, about 20 nm to about 25 nm, about 20 nm to about 24 nm, about 20 nm to about 23 nm, about 20 nm to about 22 nm, about 30 nm to about 300 nm, about 30 nm to about 200 nm, about 30 nm to about 150 nm, about 30 nm to about 100 nm, about 30 nm to about 90 nm, about 30 nm to about 80 nm, about 30 nm to about 70 nm, about 30 nm to about 60 nm, about 30 nm to about 50 nm, about 30 nm to about 45 nm, about 30 nm to about 40 nm, about 40 nm to about It has an average particle size of 300 nm, about 40 nm to about 200 nm, about 40 nm to about 150 nm, about 40 nm to about 100 nm, about 40 nm to about 90 nm, about 40 nm to about 80 nm, about 40 nm to about 70 nm, about 40 nm to about 60 nm, about 40 nm to about 50 nm, about 50 nm to about 300 nm, about 50 nm to about 200 nm, about 50 nm to about 150 nm, about 50 nm to about 100 nm, about 50 nm to about 90 nm, about 50 nm to about 80 nm, about 50 nm to about 70 nm, about 50 nm to about 60 nm, or any range or value therein.
　いくつかの実施形態では、研磨粒子は、組成物の総重量に対して、約０．１重量％以上、約０．１５重量％以上、約０．２重量％以上、約０．２５重量％以上、約０．３重量％以上、約０．３５重量％以上、約０．４重量％以上、約０．４５重量％以上、約０．５重量％以上、約０．５５重量％以上、約０．６０重量％以上、約０．６５重量％以上、約０．７重量％以上、約０．７５重量％以上、約０．８重量％以上、約０．８５重量％以上、約０．９重量％以上、約０．９５重量％以上、約１．０重量％以上、約１．１重量％以上、約１．２重量％以上、約１．３重量％以上、約１．４重量％以上、約１．５重量％以上、約１．６重量％以上、約１．７重量％以上、約１．８重量％以上、約１．９重量％以上、約２．０重量％以上、約２．５重量％以上、約３．０重量％以上、約３．５重量％以上、約４．０重量％以上、約４．５重量％以上、約５．０重量％以上、約５．５重量％以上、約６．０重量％以上、約６．５重量％以上、約７．０重量％以上、約７．５重量％以上、約８．０重量％以上、約８．５重量％以上、約９．０重量％以上、約９．５重量％以上、約１０．０重量％以上、又はそれらの間の任意の範囲若しくは値の重量による濃度で組成物中に存在する。いくつかの実施形態では、研磨粒子は、組成物の総重量に対して、約０．０１重量％以上、あるいは、約０．０５重量％以上、又はそれらの間の任意の範囲若しくは値の重量による濃度で組成物中に存在する。 In some embodiments, the abrasive particles comprise at least about 0.1 weight percent, at least about 0.15 weight percent, at least about 0.2 weight percent, at least about 0.25 weight percent, at least about 0.3 weight percent, at least about 0.35 weight percent, at least about 0.4 weight percent, at least about 0.45 weight percent, at least about 0.5 weight percent, at least about 0.55 weight percent, at least about 0.60 weight percent, at least about 0.65 weight percent, at least about 0.7 weight percent, at least about 0.75 weight percent, at least about 0.8 weight percent, at least about 0.85 weight percent, at least about 0.9 weight percent, at least about 0.95 weight percent, at least about 1.0 weight percent, at least about 1.1 weight percent, at least about 1.2 weight percent, at least about 1.3 weight percent, at least about 1. The abrasive particles are present in the composition at a concentration by weight of about 4% or more, about 1.5% or more, about 1.6% or more, about 1.7% or more, about 1.8% or more, about 1.9% or more, about 2.0% or more, about 2.5% or more, about 3.0% or more, about 3.5% or more, about 4.0% or more, about 4.5% or more, about 5.0% or more, about 5.5% or more, about 6.0% or more, about 6.5% or more, about 7.0% or more, about 7.5% or more, about 8.0% or more, about 8.5% or more, about 9.0% or more, about 9.5% or more, about 10.0% or more, or any range or value therebetween. In some embodiments, the abrasive particles are present in the composition at a concentration by weight of about 0.01% or more, or about 0.05% or more, or any range or value therebetween, based on the total weight of the composition.
　いくつかの実施形態では、研磨粒子は、組成物の総重量に対して、約１０．０重量％以下、約９．５重量％以下、約９．０重量％以下、約８．５重量％以下、約８．０重量％以下、約７．５重量％以下、約７．０重量％以下、約６．５重量％以下、約６．０重量％以下、約５．５重量％以下、約５．０重量％以下、約４．５重量％以下、約４．０重量％以下、約３．５重量％以下、約３．０重量％以下、約２．５重量％以下、約２．０重量％以下、約１．９重量％以下、約１．８重量％以下、約１．７重量％以下、約１．６重量％以下、約１．５重量％以下、約１．４重量％以下、約１．３重量％以下、約１．２重量％以下、約１．１重量％以下、約１．０重量％以下、約０．９５重量％以下、約０．９重量％以下、約０．８５重量％以下、約０．８重量％以下、約０．７５重量％以下、約０．７重量％以下、約０．６５重量％以下、約０．６重量％以下、約０．５５重量％以下、約０．５重量％以下、約０．４５重量％以下、約０．４重量％以下、約０．３５重量％以下、約０．３重量％以下、約０．２５重量％以下、約０．２重量％以下、約０．１５重量％以下、約０．１重量％又はそれらの間の任意の範囲若しくは値の重量による濃度で組成物中に存在する。 In some embodiments, the abrasive particles are present in an amount, based on the total weight of the composition, of about 10.0 wt.% or less, about 9.5 wt.% or less, about 9.0 wt.% or less, about 8.5 wt.% or less, about 8.0 wt.% or less, about 7.5 wt.% or less, about 7.0 wt.% or less, about 6.5 wt.% or less, about 6.0 wt.% or less, about 5.5 wt.% or less, about 5.0 wt.% or less, about 4.5 wt.% or less, about 4.0 wt.% or less, about 3.5 wt.% or less, about 3.0 wt.% or less, about 2.5 wt.% or less, about 2.0 wt.% or less, about 1.9 wt.% or less, about 1.8 wt.% or less, about 1.7 wt.% or less, about 1.6 wt.% or less, about 1.5 wt.% or less, about 1.4 wt.% or less, It is present in the composition at a concentration by weight of about 1.3% or less, about 1.2% or less, about 1.1% or less, about 1.0% or less, about 0.95% or less, about 0.9% or less, about 0.85% or less, about 0.8% or less, about 0.75% or less, about 0.7% or less, about 0.65% or less, about 0.6% or less, about 0.55% or less, about 0.5% or less, about 0.45% or less, about 0.4% or less, about 0.35% or less, about 0.3% or less, about 0.25% or less, about 0.2% or less, about 0.15% or less, about 0.1% or less, or any range or value therebetween.
　いくつかの実施形態では、研磨粒子は、組成物の総重量に対して、約０．１重量％～約１０．０重量％、約０．２重量％～約１０．０重量％、約０．３重量％～約１０．０重量％、約０．４重量％～約１０．０重量％、約０．５重量％～約１０．０重量％、約０．６重量％～約１０．０重量％、約０．７重量％～約１０．０重量％、約０．８重量％～約１０．０重量％、約０．９重量％～約１０．０重量％、約１．０重量％～約１０．０重量％、約２重量％～約１０．０重量％、約３重量％～約１０．０重量％、約４重量％～約１０．０重量％、約５重量％～約１０．０重量％、約０．１重量％～約５重量％、約０．２重量％～約５重量％、約０．３重量％～約５重量％、約０．４重量％～約５重量％、約０．５重量％～約５重量％、約０．６重量％～約５重量％、約０．７重量％～約５重量％、約０．８重量％～約５重量％、約０．９重量％～約５重量％、約１．０重量％～約５重量％、約０．１重量％～約５．０重量％、約０．１重量％～約２．０重量％、約０．１重量％～約１．０重量％、約０．２重量％～約２．０重量％、約０．３重量％～約２．０重量％、約０．４重量％～約２．０重量％、約０．５重量％～約２．０重量％、約０．６重量％～約２．０重量％、約０．７重量％～約２．０重量％、約０．８重量％～約２．０重量％、約０．９重量％～約２．０重量％、約１．０重量％～約２．０重量％、約０．１重量％～約１．０重量％、約０．２重量％～約１．０重量％、約０．３重量％～約１．０重量％、約０．４重量％～約１．０重量％、約０．５重量％～約１．０重量％、約０．６重量％～約１．０重量％、約０．１重量％～約０．９重量％、約０．１重量％～約０．８重量％、約０．１重量％～約０．７重量％、約０．１重量％～約０．６重量％、約０．１重量％～約０．５重量％、約０．１重量％～約０．４重量％、約０．１重量％～約０．３重量％、約０．２重量％～約０．９重量％、約０．２重量％～約０．８重量％、約０．２重量％～約０．７重量％、約０．３重量％～約０．９重量％、約０．３重量％～約０．８重量％、約０．３重量％～約０．７重量％、約０．４重量％～約０．９重量％、約０．４重量％～約０．８重量％、約０．４重量％～約０．７重量％、約０．５重量％～約０．９重量％、約０．５重量％～約０．８重量％、約０．５重量％～約０．７重量％、約０．６重量％～約０．９重量％、約０．６重量％～約０．８重量％、又はその中の任意の範囲若しくは値の重量による濃度で組成物中に存在する。いくつかの実施形態では、研磨粒子は、組成物の総重量に対して、約０．０１重量％～約１０．０重量％、あるいは、約０．０５重量％～約１０．０重量％、又はその中の任意の範囲若しくは値の重量による濃度で組成物中に存在する。 In some embodiments, the abrasive particles are present in an amount, based on the total weight of the composition, of about 0.1% to about 10.0% by weight, about 0.2% to about 10.0% by weight, about 0.3% to about 10.0% by weight, about 0.4% to about 10.0% by weight, about 0.5% to about 10.0% by weight, about 0.6% to about 10.0% by weight, about 0.7% to about 10.0% by weight, about 0.8% to about 10.0% by weight, about 0.9% to about 10.0% by weight, about 1.0% to about 10.0% by weight, about 2% to about 10.0% by weight, about 3% to about 10.0% by weight, about 4% to about 10.0% by weight, about 5% to about 10.0% by weight, about 0. 1% to about 5% by weight, about 0.2% to about 5% by weight, about 0.3% to about 5% by weight, about 0.4% to about 5% by weight, about 0.5% to about 5% by weight, about 0.6% to about 5% by weight, about 0.7% to about 5% by weight, about 0.8% to about 5% by weight, about 0.9% to about 5% by weight, about 1.0% to about 5% by weight, about 0.1% to about 5.0% by weight, about 0.1% to about 2.0% by weight, about 0.1% to about 1.0% by weight, about 0.2% to about 2.0% by weight, about 0.3% to about 2.0% by weight, about 0.4% to about 2.0% by weight, about 0.5% to about 2.0% by weight, about 0.6% to about 2.0% by weight, about 0.7% to about 2.0% by weight, about 0.8% to about 2.0% by weight, about 0.9% to about 2.0% by weight, about 1.0% to about 2.0% by weight, about 0.1% to about 1.0% by weight, about 0.2% to about 1.0% by weight, about 0.3% to about 1.0% by weight, about 0.4% to about 1.0% by weight, about 0.5% to about 1.0% by weight, about 0.6% to about 1.0% by weight, about 0.1% to about 0.9% by weight, about 0.1% to about 0.8% by weight, about 0.1% to about 0.7% by weight, about 0.1% to about 0.6% by weight, about 0.1% to about 0.5% by weight, about 0.1% to about 0.4% by weight, about 0.1% to about [0046] The composition may be present in a concentration by weight of 0.3 wt.%, about 0.2 wt.% to about 0.9 wt.%, about 0.2 wt.% to about 0.8 wt.%, about 0.2 wt.% to about 0.7 wt.%, about 0.3 wt.% to about 0.9 wt.%, about 0.3 wt.% to about 0.8 wt.%, about 0.3 wt.% to about 0.7 wt.%, about 0.4 wt.% to about 0.9 wt.%, about 0.4 wt.% to about 0.8 wt.%, about 0.4 wt.% to about 0.7 wt.%, about 0.5 wt.% to about 0.9 wt.%, about 0.5 wt.% to about 0.8 wt.%, about 0.5 wt.% to about 0.7 wt.%, about 0.6 wt.% to about 0.9 wt.%, about 0.6 wt.% to about 0.8 wt.%, or any range or value therein. In some embodiments, the abrasive particles are present in the composition at a concentration by weight of about 0.01% to about 10.0% by weight, or about 0.05% to about 10.0% by weight, or any range or value therein, based on the total weight of the composition.
　いくつかの実施形態では、研磨粒子（例えば、コロイダルシリカ又はアニオン修飾コロイダルシリカ）は、本開示の研磨用組成物中に使用されるｐＨ条件下で負電荷を有する。いくつかの実施形態では、研磨粒子（例えば、コロイダルシリカ又はアニオン修飾コロイダルシリカ）は、約１、１．１、１．２、１．３、１．４、１．５、１．６、１．７、１．８、１．９、２．０、２．１、２．２、２．３、２．４、２．５、２．６、２．７、２．８、２．９、３．０、３．１、３．２、３．３、３．４、３．５、３．６、３．７、３．８、３．９、４．０、４．１、４．２、４．３、４．４、４．５、４．６、４．７、４．８、４．９、５．０、５．１、５．２、５．３、５．４、５．５、５．６、５．７、５．８、５．９、又は６．０のｐＨで負電荷を有する。いくつかの実施形態では、研磨粒子のゼータ電位は、－１ｍＶ、－２ｍＶ、－５ｍＶ、－１０ｍＶ、－１５ｍＶ、－２０ｍＶ、－２５ｍＶ、－３０ｍＶ、－３５ｍＶ、若しくは－４０ｍＶ、又はそれらの間の任意の範囲若しくは値を以上、負である。いくつかの実施形態では、アニオン変性研磨粒子のゼータ電位は、同じｐＨ条件で対応する非修飾研磨粒子（例えば、非修飾コロイダルシリカ）よりも大きい負電荷である（すなわち、より負である）。ゼータ電位は、スペクトリス株式会社製（マルバーン事業部）のＺｅｔａｓｉｚｅｒ　Ｎａｎｏ　ＺＳＰにより測定された値でありうる。 In some embodiments, the abrasive particles (e.g., colloidal silica or anionically modified colloidal silica) have a negative charge under the pH conditions used in the polishing compositions disclosed herein. In some embodiments, the abrasive particles (e.g., colloidal silica or anionically modified colloidal silica) have a negative charge at a pH of about 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, or 6.0. In some embodiments, the zeta potential of the abrasive particles is more negative than -1 mV, -2 mV, -5 mV, -10 mV, -15 mV, -20 mV, -25 mV, -30 mV, -35 mV, or -40 mV, or any range or value therebetween. In some embodiments, the zeta potential of the anion-modified abrasive particles is more negatively charged (i.e., more negative) than the corresponding unmodified abrasive particles (e.g., unmodified colloidal silica) at the same pH conditions. The zeta potential may be measured by a Zetasizer Nano ZSP from Spectris Corporation (a Malvern Division).
　いくつかの実施形態では、本開示による組成物に含まれる研磨材のうち、８０重量％以上、８５重量％以上、９０重量％以上、９５重量％以上、９８重量％以上、あるいは、９９重量％以上が、シリカ粒子の表面に固定化された１つ又は複数の有機酸で修飾されたシリカ粒子である。いくつかの実施形態では、本開示による組成物に含まれる研磨材のうち、８０重量％以上、８５重量％以上、９０重量％以上、９５重量％以上、９８重量％以上、あるいは、９９重量％以上が、本開示の研磨用組成物中に使用されるｐＨ条件下で負電荷を有する、シリカ粒子の表面に固定化された１つ又は複数の有機酸で修飾されたシリカ粒子である（上限は、１００重量％）。 In some embodiments, 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, 98% by weight or more, or 99% by weight or more of the abrasives contained in the composition of the present disclosure are silica particles modified with one or more organic acids immobilized on the surface of the silica particles. In some embodiments, 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, 98% by weight or more, or 99% by weight or more of the abrasives contained in the composition of the present disclosure are silica particles modified with one or more organic acids immobilized on the surface of the silica particles that have a negative charge under the pH conditions used in the polishing composition of the present disclosure (upper limit 100% by weight).
　界面活性剤
　いくつかの実施形態では、本開示による組成物は界面活性剤を含む。いくつかの実施形態では、組成物はスルホ基を含む界面活性剤を更に含む。本開示において、「スルホ基を含む」とは、当該スルホ基が、ナトリウム、カリウム、あるいは、リチウム等の塩の形態になっている概念を含むことを意味する。つまり、本開示において、スルホ基を含む界面活性剤とは、当該スルホ基が、ナトリウム、カリウム、あるいは、リチウム等の塩の形態になっている概念を含むことを意味する。つまり、スルホ基を含む界面活性剤の一例として、イソプロピル化ナフタレンスルホン酸ナトリウムが挙げられる。 Surfactant In some embodiments, the composition according to the present disclosure includes a surfactant. In some embodiments, the composition further includes a surfactant containing a sulfo group. In the present disclosure, "containing a sulfo group" means that the sulfo group is in the form of a salt such as sodium, potassium, or lithium. In other words, in the present disclosure, a surfactant containing a sulfo group means that the sulfo group is in the form of a salt such as sodium, potassium, or lithium. In other words, an example of a surfactant containing a sulfo group is sodium isopropylated naphthalene sulfonate.
　いくつかの実施形態では、界面活性剤が、アルキル基を含む。いくつかの実施形態では、界面活性剤が、分岐のアルキル基を含む。いくつかの実施形態では、界面活性剤におけるアルキル基（アルキル基は分岐のアルキル基でもよい）の炭素数は、２～１０、２～８、２～６、あるいは、２～４である。 In some embodiments, the surfactant comprises an alkyl group. In some embodiments, the surfactant comprises a branched alkyl group. In some embodiments, the alkyl group in the surfactant (which may be a branched alkyl group) has 2 to 10 carbon atoms, 2 to 8 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms.
　いくつかの実施形態では、界面活性剤がアリール基を有する。アリール基はフェニル基であっても縮合環を含む基であってもよい。いくつかの実施形態では、界面活性剤が、縮合環を有する。いくつかの実施形態では、縮合環を含む基は、ナフチル基、あるいは、アントラセニル基などであってよい。 In some embodiments, the surfactant has an aryl group. The aryl group may be a phenyl group or a group containing a fused ring. In some embodiments, the surfactant has a fused ring. In some embodiments, the group containing a fused ring may be a naphthyl group, an anthracenyl group, or the like.
　いくつかの実施形態では、界面活性剤の分子量が、１０００以下、８００以下、６００以下、４００以下、あるいは、３００以下である。いくつかの実施形態では、界面活性剤の分子量が、５０以上、１００以上、１５０以上、２００以上、あるいは、２５０以上である。 In some embodiments, the molecular weight of the surfactant is 1000 or less, 800 or less, 600 or less, 400 or less, or 300 or less. In some embodiments, the molecular weight of the surfactant is 50 or more, 100 or more, 150 or more, 200 or more, or 250 or more.
　いくつかの実施形態では、界面活性剤がナフタレン構造を持つスルホン酸またはその塩（塩はナトリウム等）を含む。ナフタレン構造を持つスルホン酸としては、イソプロピルナフタレンスルホン酸（ＣＡＳ：３１０９３－４８－８）、ブチルナフタレンスルホン酸（ＣＡＳ：２８６０５－８６－９）、ビス（イソブチルナフタレン）－１－スルホン酸（ＣＡＳ：９４２４７－７４－２）（ジイソプロピルナフタレンスルホン酸の例）、イソブチルナフタレンスルホン酸、ジイソブチルナフタレンスルホン酸などが挙げられる。中でも、イソプロピルナフタレンスルホン酸（ＣＡＳ：３１０９３－４８－８）、ビス（イソブチルナフタレン）－１－スルホン酸（ＣＡＳ：９４２４７－７４－２）（ジイソプロピルナフタレンスルホン酸の例）、イソブチルナフタレンスルホン酸、あるいは、ジイソブチルナフタレンスルホン酸が分岐鎖のアルキル基を有する観点で好ましい。 In some embodiments, the surfactant contains a sulfonic acid having a naphthalene structure or a salt thereof (the salt is sodium or the like). Examples of sulfonic acids having a naphthalene structure include isopropylnaphthalenesulfonic acid (CAS: 31093-48-8), butylnaphthalenesulfonic acid (CAS: 28605-86-9), bis(isobutylnaphthalene)-1-sulfonic acid (CAS: 94247-74-2) (an example of diisopropylnaphthalenesulfonic acid), isobutylnaphthalenesulfonic acid, and diisobutylnaphthalenesulfonic acid. Among these, isopropylnaphthalenesulfonic acid (CAS: 31093-48-8), bis(isobutylnaphthalene)-1-sulfonic acid (CAS: 94247-74-2) (an example of diisopropylnaphthalenesulfonic acid), isobutylnaphthalenesulfonic acid, and diisobutylnaphthalenesulfonic acid are preferred in terms of having a branched alkyl group.
　いくつかの実施形態では、界面活性剤がアントラセン構造を持つスルホン酸またはその塩（塩はナトリウム等）を含む。アントラセン構造を持つスルホン酸としては、アントラセン－９－スルホン酸（ＣＡＳ：２２５８２－７６－９）、アントラセン－２－スルホン酸（ＣＡＳ：１５１００－５３－５）、９，１０－ジヒドロ－９，１０－ジオキソアントラセン－１－スルホン酸（８２－４９－５）などが挙げられる。 In some embodiments, the surfactant comprises a sulfonic acid having an anthracene structure or a salt thereof (the salt is sodium or the like). Examples of sulfonic acids having an anthracene structure include anthracene-9-sulfonic acid (CAS: 22582-76-9), anthracene-2-sulfonic acid (CAS: 15100-53-5), and 9,10-dihydro-9,10-dioxoanthracene-1-sulfonic acid (82-49-5).
　いくつかの実施形態では、界面活性剤は、ＳｉＮ及びＳｉＯ２を含む研磨対象物のトポグラフィ（例えば、ウェハの平坦度）を改善する。いくつかの実施形態では、界面活性剤は、イソプロピル化ナフタレンスルホン酸ナトリウムを含むか又はこれからなる。いくつかの実施形態では、界面活性剤は、スルホ基を含む界面活性剤、縮合環を含む界面活性剤、分岐のアルキルを含む界面活性剤、分子量１０００以下の界面活性剤、あるいは、イソプロピル化ナフタレンスルホン酸ナトリウムと読み替えられる。 In some embodiments, the surfactant improves the topography (e.g., wafer flatness) of polished objects including SiN and SiO2 . In some embodiments, the surfactant comprises or consists of sodium isopropylated naphthalene sulfonate. In some embodiments, the surfactant can be read as a surfactant containing a sulfo group, a surfactant containing a fused ring, a surfactant containing a branched alkyl, a surfactant with a molecular weight of 1000 or less, or sodium isopropylated naphthalene sulfonate.
　いくつかの実施形態では、界面活性剤は、少なくとも約０．０００１重量％、少なくとも約０．０００２重量％、少なくとも約０．０００３重量％、少なくとも約０．０００４重量％、少なくとも約０．０００５重量％、少なくとも約０．０００６重量％、少なくとも約０．０００７重量％、少なくとも約０．０００８重量％、少なくとも約０．０００９重量％、少なくとも約０．００１重量％、少なくとも約０．００２重量％、少なくとも約０．００３重量％、少なくとも約０．００４重量％、少なくとも約０．００５重量％、少なくとも約０．００６重量％、少なくとも約０．００７重量％、少なくとも約０．００８重量％、少なくとも約０．００９重量％、少なくとも約０．０１重量％、少なくとも約０．０２重量％、少なくとも約０．０３重量％、少なくとも約０．０４重量％、少なくとも約０．０５重量％、少なくとも約０．０６重量％、少なくとも約０．０７重量％、少なくとも約０．０８重量％、少なくとも約０．０９重量％、少なくとも約０．１重量％、少なくとも約０．５重量％、少なくとも約１．０重量％、又はそれらの間の任意の範囲若しくは値の濃度（組成物の総重量に対する重量による）で組成物中に存在する。いくつかの実施形態では、界面活性剤は、少なくとも約０．００００１重量％、少なくとも約０．００００３重量％、少なくとも約０．００００５重量％、少なくとも約０．００００７重量％、少なくとも約０．００００９重量％で組成物中に存在する。 In some embodiments, the surfactant is at least about 0.0001% by weight, at least about 0.0002% by weight, at least about 0.0003% by weight, at least about 0.0004% by weight, at least about 0.0005% by weight, at least about 0.0006% by weight, at least about 0.0007% by weight, at least about 0.0008% by weight, at least about 0.0009% by weight, at least about 0.001% by weight, at least about 0.002% by weight, at least about 0.003% by weight, at least about 0.004% by weight, at least about 0.005% by weight, at least about 0.006 ...8% by weight, at least about 0.0008% by weight, at least about 0.0008% by weight, at least about 0.0008% by weight, at least about 0.0008% by weight, at least about The surfactant is present in the composition at a concentration (by weight relative to the total weight of the composition) of at least about 0.007% by weight, at least about 0.008% by weight, at least about 0.009% by weight, at least about 0.01% by weight, at least about 0.02% by weight, at least about 0.03% by weight, at least about 0.04% by weight, at least about 0.05% by weight, at least about 0.06% by weight, at least about 0.07% by weight, at least about 0.08% by weight, at least about 0.09% by weight, at least about 0.1% by weight, at least about 0.5% by weight, at least about 1.0% by weight, or any range or value therebetween. In some embodiments, the surfactant is present in the composition at at least about 0.00001% by weight, at least about 0.00003% by weight, at least about 0.00005% by weight, at least about 0.00007% by weight, at least about 0.00009% by weight.
　いくつかの実施形態では、界面活性剤は、約１．０重量％以下、約０．５重量％以下、約０．２重量％以下、約０．１重量％以下、約０．０９重量％以下、約０．０８重量％以下、約０．０７重量％以下、約０．０６重量％以下、約０．０５重量％以下、約０．０４重量％以下、約０．０３重量％以下、約０．０２重量％以下、約０．０１重量％以下、約０．００９重量％以下、約０．００８重量％以下、約０．００７重量％以下、約０．００６重量％以下、約０．００５重量％以下、約０．００４重量％以下、約０．００３重量％以下、約０．００２重量％以下、約０．００１重量％以下、約０．０００９重量％以下、約０．０００８重量％以下、約０．０００７重量％以下、約０．０００６重量％以下、約０．０００５重量％以下、約０．０００４重量％以下、約０．０００３重量％以下、約０．０００２重量％以下、約０．０００１重量％以下、又はそれらの間の任意の範囲若しくは値の濃度（組成物の総重量に対する重量による）で組成物中に存在する。 In some embodiments, the surfactant is about 1.0% by weight or less, about 0.5% by weight or less, about 0.2% by weight or less, about 0.1% by weight or less, about 0.09% by weight or less, about 0.08% by weight or less, about 0.07% by weight or less, about 0.06% by weight or less, about 0.05% by weight or less, about 0.04% by weight or less, about 0.03% by weight or less, about 0.02% by weight or less, about 0.01% by weight or less, about 0.009% by weight or less, about 0.008% by weight or less, about 0.007% by weight or less, about 0.006% by weight or less, about 0.005% by weight or less The composition is present in a concentration (by weight relative to the total weight of the composition) of about 0.004% by weight or less, about 0.003% by weight or less, about 0.002% by weight or less, about 0.001% by weight or less, about 0.0009% by weight or less, about 0.0008% by weight or less, about 0.0007% by weight or less, about 0.0006% by weight or less, about 0.0005% by weight or less, about 0.0004% by weight or less, about 0.0003% by weight or less, about 0.0002% by weight or less, about 0.0001% by weight or less, or any range or value therebetween.
　いくつかの実施形態では、界面活性剤は、約０．０００１重量％～約１．０重量％、約０．０００１重量％～約０．１重量％、０．０００１重量％～約０．０１重量％、約０．０００１重量％～約０．００１重量％、約０．０００１重量％～約０．０００５重量％、又はそれらの間の任意の範囲若しくは値の濃度（組成物の総重量に対する重量による）で組成物中に存在する。いくつかの実施形態では、界面活性剤は、約０．００００１重量％～約１．０重量％、約０．００００３重量％～約０．１重量％、０．００００５重量％～約０．０１重量％、約０．００００７重量％～約０．００１重量％、約０．００００７重量％～約０．０００５重量％、又はそれらの間の任意の範囲若しくは値の濃度（組成物の総重量に対する重量による）で組成物中に存在する。 In some embodiments, the surfactant is present in the composition at a concentration (by weight relative to the total weight of the composition) of about 0.0001% to about 1.0% by weight, about 0.0001% to about 0.1% by weight, 0.0001% to about 0.01% by weight, about 0.0001% to about 0.001% by weight, about 0.0001% to about 0.0005% by weight, or any range or value therebetween. In some embodiments, the surfactant is present in the composition at a concentration (by weight relative to the total weight of the composition) of about 0.00001% to about 1.0% by weight, about 0.00003% to about 0.1% by weight, 0.00005% to about 0.01% by weight, about 0.00007% to about 0.001% by weight, about 0.00007% to about 0.0005% by weight, or any range or value therebetween.
　濡れ剤
　いくつかの実施形態では、本開示による組成物は、１つ又は複数の濡れ剤（又は「湿潤コントローラ」）を含む。 Wetting Agents In some embodiments, compositions according to the present disclosure include one or more wetting agents (or "wetness controllers").
　いくつかの実施形態では、濡れ剤は、水酸基を１つ又は複数有する。いくつかの実施形態では組成物は、糖類を有する。いくつかの実施形態では、組成物は、多糖類を有する。いくつかの実施形態では、組成物は、グルコースのみからなる多糖類を有する。いくつかの実施形態では、濡れ剤は、糖類、多糖類、グルコースのみからなる多糖類、あるいは、プルランと読み替えられる。 In some embodiments, the wetting agent has one or more hydroxyl groups. In some embodiments, the composition has a saccharide. In some embodiments, the composition has a polysaccharide. In some embodiments, the composition has a polysaccharide consisting only of glucose. In some embodiments, the wetting agent can be read as a saccharide, a polysaccharide, a polysaccharide consisting only of glucose, or pullulan.
　いくつかの実施形態では、濡れ剤は、ヒドロキシエチルセルロース、Ｎ，Ｎ－ジメチルドデシルアミンオキシド、ポリビニルアルコール（ＰＶＡ）、スルホン酸修飾ＰＶＡ、ポリビニルピロリドン（ＰＶＰ）、ポリ（Ｎ－ビニルアセトアミド）（ＰＮＶＡ）、ポリプロピレングリコール（ＰＰＧ）、ポリエチレングリコール（ＰＥＧ）、ＰＥＧ－ＰＰＧコポリマー又はブロックコポリマー（例えば、ＰＥＧ－ＰＰＧ、ＰＥＧ－ＰＰＧ－ＰＥＧ、ＰＰＧ－ＰＥＧ－ＰＰＧ等）、及びそれらの組合せ）、デキストリン、高度に分岐した環状デキストリン（例えば、Ｃｌｕｓｔｅｒ　Ｄｅｘｔｒｉｎ（商標））、プルラン等の１つ又は複数を含む。いくつかの実施形態では、濡れ剤はプルランを含むか、又はプルランからなる。 In some embodiments, the wetting agent comprises one or more of hydroxyethyl cellulose, N,N-dimethyldodecylamine oxide, polyvinyl alcohol (PVA), sulfonic acid modified PVA, polyvinylpyrrolidone (PVP), poly(N-vinylacetamide) (PNVA), polypropylene glycol (PPG), polyethylene glycol (PEG), PEG-PPG copolymers or block copolymers (e.g., PEG-PPG, PEG-PPG-PEG, PPG-PEG-PPG, etc., and combinations thereof), dextrin, highly branched cyclic dextrin (e.g., Cluster Dextrin™), pullulan, and the like. In some embodiments, the wetting agent comprises or consists of pullulan.
　いくつかの実施形態では、濡れ剤は、少なくとも約０．０１重量％、少なくとも約０．０２重量％、少なくとも約０．０３重量％、少なくとも約０．０４重量％、少なくとも約０．０５重量％、少なくとも約０．０６重量％、少なくとも約０．０７重量％、少なくとも約０．０８重量％、少なくとも約０．０９重量％、少なくとも約０．１０重量％、少なくとも約０．１１重量％、少なくとも約０．１２重量％、少なくとも約０．１３重量％、少なくとも約０．１４重量％、少なくとも約０．１５重量％、少なくとも約０．１６重量％、少なくとも約０．１７重量％、少なくとも約０．１８重量％、少なくとも約０．１９重量％、少なくとも約０．２０重量％、少なくとも約０．２１重量％、少なくとも約０．２２重量％、少なくとも約０．２３重量％、少なくとも約０．２４重量％、少なくとも約０．２５重量％、少なくとも約０．２６重量％、少なくとも約０．２７重量％、少なくとも約０．２８重量％、少なくとも約０．２９重量％、少なくとも約０．３０重量％、少なくとも約０．３１重量％、少なくとも約０．３２重量％、少なくとも約０．３３重量％、少なくとも約０．３４重量％、少なくとも約０．３５重量％、少なくとも約０．３６重量％、少なくとも約０．３７重量％、少なくとも約０．３８重量％、少なくとも約０．３９重量％、少なくとも約０．４０重量％、少なくとも約０．４５重量％、少なくとも約０．５０重量％、少なくとも約０．５５重量％、少なくとも約０．６０重量％、少なくとも約０．６５重量％、少なくとも約０．７０重量％、少なくとも約０．７５重量％、少なくとも約０．８０重量％、少なくとも約０．８５重量％、少なくとも約０．９０重量％、少なくとも約０．９５重量％、少なくとも約１．０重量％、少なくとも約１．５重量％、少なくとも約２．０重量％、少なくとも約２．５重量％、又はそれらの間の任意の範囲若しくは値の濃度（組成物の総重量に対する重量による）で組成物中に存在する。いくつかの実施形態では、濡れ剤は、少なくとも約０．００１重量％、少なくとも約０．００３重量％、少なくとも約０．００５重量％、あるいは、少なくとも約０．００７重量％である。 In some embodiments, the wetting agent is at least about 0.01 wt%, at least about 0.02 wt%, at least about 0.03 wt%, at least about 0.04 wt%, at least about 0.05 wt%, at least about 0.06 wt%, at least about 0.07 wt%, at least about 0.08 wt%, at least about 0.09 wt%, at least about 0.10 wt%, at least about 0.11 wt%, at least about 0.12 wt%, at least about 0.13 wt%, at least about 0.14 wt%, at least about 0.15 wt%, at least about 0.16 wt%, at least about 0.17 wt%, at least about 0.18 wt%, at least about 0.19 wt%, at least about 0.20 wt%, at least about 0.21 wt%, at least about 0.22 wt%, at least about 0.23 wt%, at least about 0.24 wt%, at least about 0.25 wt%, at least about 0.26 wt%, at least about 0.27 wt%, at least about 0.28 wt%, at least about 0.29 wt%, at least about 0.30 wt%, at least about 0.31 wt%, at least about 0.32 wt%, at least about 0.33 wt%, at least about 0.34 wt%, at least about 0.35 wt%, at least about 0.36 wt%, at least about 0.37 wt%, at least about 0.38 wt%, at least about 0.39 wt%, at least about 0.40 wt%, at least about 0.41 wt%, at least about 0.42 wt%, at least about 0.43 wt%, at least about 0.44 wt%, at least about 0.45 wt%, at least about 0.4 0.14% by weight, at least about 0.15% by weight, at least about 0.16% by weight, at least about 0.17% by weight, at least about 0.18% by weight, at least about 0.19% by weight, at least about 0.20% by weight, at least about 0.21% by weight, at least about 0.22% by weight, at least about 0.23% by weight, at least about 0.24% by weight, at least about 0.25% by weight, at least about 0.26% by weight, at least about 0.27% by weight, at least about 0.28% by weight, at least about 0.29% by weight, at least about 0.30% by weight, at least about 0.31% by weight, at least about 0.32% by weight, at least about 0.33% by weight, at least about 0.34% by weight, at least about 0.35% by weight, at least about 0.36% by weight, at least about 0.37% by weight, at least about 0.38% by weight, at least about 0.39% by weight, at least about 0.40% by weight, at least about 0.45% by weight, at least about 0.50% by weight, at least about 0.55% by weight, The wetting agent is present in the composition at a concentration (by weight relative to the total weight of the composition) of about 0.60%, at least about 0.65%, at least about 0.70%, at least about 0.75%, at least about 0.80%, at least about 0.85%, at least about 0.90%, at least about 0.95%, at least about 1.0%, at least about 1.5%, at least about 2.0%, at least about 2.5%, or any range or value therebetween. In some embodiments, the wetting agent is at least about 0.001%, at least about 0.003%, at least about 0.005%, or at least about 0.007% by weight.
　いくつかの実施形態では、濡れ剤は、約２．５重量％以下、約２．０重量％以下、約１．５重量％以下、約１．０重量％以下、約０．９５重量％以下、約０．９０重量％以下、約０．８５重量％以下、約０．８０重量％以下、約０．７５重量％以下、約０．７０重量％以下、約０．６５重量％以下、約０．６０重量％以下、約０．５５重量％以下、約０．５０重量％以下、約０．４５重量％以下、約０．４０重量％以下、約０．３５重量％以下、約０．３４重量％以下、約０．３３重量％以下、約０．３２重量％以下、約０．３１重量％以下、約０．３０重量％以下、約０．２９重量％以下、約０．２８重量％以下、約０．２７重量％以下、約０．２６重量％以下、約０．２５重量％以下、約０．２４重量％以下、約０．２３重量％以下、約０．２２重量％以下、約０．２１重量％以下、約０．２０重量％以下、約０．１９重量％以下、約０．１８重量％以下、約０．１７重量％以下、約０．１６重量％以下、約０．１５重量％以下、約０．１４重量％以下、約０．１３重量％以下、約０．１２重量％以下、約０．１１重量％以下、約０．１０重量％以下、約０．０９重量％以下、約０．０８重量％以下、約０．０７重量％以下、約０．０６重量％以下、約０．０５重量％以下、約０．０４重量％以下、約０．０３重量％以下、約０．０２重量％以下、約０．０１重量％、又はそれらの間の任意の範囲若しくは値の濃度（組成物の総重量に対する重量による）で組成物中に存在する。 In some embodiments, the wetting agent is about 2.5 wt% or less, about 2.0 wt% or less, about 1.5 wt% or less, about 1.0 wt% or less, about 0.95 wt% or less, about 0.90 wt% or less, about 0.85 wt% or less, about 0.80 wt% or less, about 0.75 wt% or less, about 0.70 wt% or less, about 0.65 wt% or less, about 0.60 wt% or less, about 0.55 wt% or less, about 0.50 wt% or less, about 0.45 wt% or less, about 0.40 wt% or less, about 0.35 wt% or less, about 0.34 wt% or less, about 0.33 wt% or less, about 0.32 wt% or less, about 0.31 wt% or less, about 0.30 wt% or less, about 0.29 wt% or less, about 0.28 wt% or less, about 0.27 wt% or less, about 0.26 wt% or less, about 0.25 wt% or less, It is present in the composition at a concentration (by weight relative to the total weight of the composition) of about 0.24% by weight or less, about 0.23% by weight or less, about 0.22% by weight or less, about 0.21% by weight or less, about 0.20% by weight or less, about 0.19% by weight or less, about 0.18% by weight or less, about 0.17% by weight or less, about 0.16% by weight or less, about 0.15% by weight or less, about 0.14% by weight or less, about 0.13% by weight or less, about 0.12% by weight or less, about 0.11% by weight or less, about 0.10% by weight or less, about 0.09% by weight or less, about 0.08% by weight or less, about 0.07% by weight or less, about 0.06% by weight or less, about 0.05% by weight or less, about 0.04% by weight or less, about 0.03% by weight or less, about 0.02% by weight or less, about 0.01% by weight, or any range or value therebetween.
　いくつかの実施形態では、濡れ剤は、約０．０１重量％～約１．０重量％、約０．０１重量％～約０．５重量％、約０．０１重量％～約０．４重量％、約０．０１重量％～約０．３重量％、約０．０１重量％～約０．２５重量％、０．０１重量％～約０．２重量％、約０．０１重量％～約０．１重量％、０．０５重量％～約２．０重量％、約０．０５重量％～約１．０重量％、約０．０５重量％～約０．５重量％、約０．０５重量％～約０．４重量％、約０．０５重量％～約０．３重量％、約０．０５重量％～約０．２５重量％、０．０５重量％～約０．２重量％、約０．０５重量％～約０．１重量％、約０．１重量％～約２．５重量％、約０．１重量％～約２．０重量％、約０．１重量％～約１．５重量％、約０．１重量％～約１．０重量％、約０．１重量％～約０．５重量％、約０．１重量％～約０．４重量％、約０．１重量％～約０．３重量％、約０．１重量％～約０．２重量％、約０．２重量％～約２．５重量％、約０．２重量％～約２．０重量％、約０．２重量％～約１．５重量％、約０．２重量％～約１．０重量％、約０．２重量％～約０．５重量％、約０．２重量％～約０．４重量％、約０．２重量％～約０．３重量％又はそれらの間の任意の範囲若しくは値（組成物の総重量に対する重量による）で組成物中に存在する。いくつかの実施形態では、濡れ剤は、約０．００１重量％～約１．０重量％、約０．００３重量％～約０．５重量％、約０．００５重量％～約０．３重量％、あるいは、約０．００７重量％～約０．１重量％で組成物中に存在する。 In some embodiments, the wetting agent is from about 0.01% to about 1.0% by weight, from about 0.01% to about 0.5% by weight, from about 0.01% to about 0.4% by weight, from about 0.01% to about 0.3% by weight, from about 0.01% to about 0.25% by weight, from about 0.01% to about 0.2% by weight, from about 0.01% to about 0.1% by weight, from 0.05% to about 2.0% by weight, from about 0.05% to about 1.0% by weight, from about 0.05% to about 0.5% by weight, from about 0.05% to about 0.4% by weight, from about 0.05% to about 0.3% by weight, from about 0.05% to about 0.25% by weight, from about 0.05% to about 0.2% by weight, from about 0.05% to about 0.1% by weight, from about 0.1% by weight % to about 2.5 wt.%, about 0.1 wt.% to about 2.0 wt.%, about 0.1 wt.% to about 1.5 wt.%, about 0.1 wt.% to about 1.0 wt.%, about 0.1 wt.% to about 0.5 wt.%, about 0.1 wt.% to about 0.4 wt.%, about 0.1 wt.% to about 0.3 wt.%, about 0.1 wt.% to about 0.2 wt.%, about 0.2 wt.% to about 2.5 wt.%, about 0.2 wt.% to about 2.0 wt.%, about 0.2 wt.% to about 1.5 wt.%, about 0.2 wt.% to about 1.0 wt.%, about 0.2 wt.% to about 0.5 wt.%, about 0.2 wt.% to about 0.4 wt.%, about 0.2 wt.% to about 0.3 wt.%, or any range or value therebetween (by weight based on the total weight of the composition). In some embodiments, the wetting agent is present in the composition at about 0.001% to about 1.0% by weight, about 0.003% to about 0.5% by weight, about 0.005% to about 0.3% by weight, or about 0.007% to about 0.1% by weight.
　ｐＨ調整剤
　いくつかの実施形態では、本開示による組成物は、ｐＨを選択されたｐＨ値に調整するための１つ又は複数のｐＨ調整剤を更に含み得る。いくつかの実施形態では、上述の双性イオン化合物、界面活性剤、濡れ剤、及び研磨粒子に固定化された有機酸、並びに以下に説明する「追加の成分」は、ｐＨ調整剤であると見なされない。いくつかの実施形態では、ｐＨ調整剤はスルホ基を含む酸を含む。いくつかの実施形態では、ｐＨ調整剤はスルホ基を含む酸（例えば、硫酸）と読み替えられる。 pH Adjusting Agent In some embodiments, the composition according to the present disclosure may further comprise one or more pH adjusting agents for adjusting the pH to a selected pH value. In some embodiments, the zwitterionic compounds, surfactants, wetting agents, and organic acids immobilized on the abrasive particles described above, as well as the "additional components" described below, are not considered to be pH adjusting agents. In some embodiments, the pH adjusting agent comprises an acid containing a sulfo group. In some embodiments, the pH adjusting agent is read as an acid containing a sulfo group (e.g., sulfuric acid).
　ｐＨ調整剤は特に限定されず、任意の適切なｐＨ調整剤を使用して、上述のように、組成物のｐＨを任意の所望の範囲にすることができる。いくつかの実施形態では、１つ又は複数のｐＨ調整剤は、無機化合物、有機化合物、又はそれらの組合せを含み得るか、それらから本質的になり得るか、又はそれらからなり得る。いくつかの実施形態では、１つ又は複数のｐＨ調整剤は、無機酸（例えば、塩酸、臭化水素酸、ヨウ化水素酸、硫酸、硝酸、ホウ酸、炭酸、次亜リン酸、亜リン酸及びリン酸）；有機酸（例えば、クエン酸、ギ酸、酢酸、プロピオン酸、安息香酸、サリチル酸、グリセリン酸、シュウ酸、マロン酸、コハク酸、マレイン酸、フタル酸、リンゴ酸、酒石酸、及び乳酸等のカルボン酸）；並びに／あるいは有機硫酸（例えば、メタンスルホン酸、エタンスルホン酸、イセチオン酸等）を含み得る。いくつかの実施形態では、１つ又は複数のｐＨ調整剤は、１つ又は複数のプロトン（Ｈ＋）が放出され得る場合（例えば、炭酸水素アンモニウム又はリン酸水素アンモニウム）に塩基の形態であり得る上記酸（複数可）（例えば、硫酸、炭酸、リン酸、シュウ酸等）の二価以上の酸を含み得るが、任意の対イオンが使用され得る（例えば、アンモニウム、トリエタノールアミン等の弱塩基性カチオン）。いくつかの実施形態では、１つ又は複数のｐＨ調整剤は硫酸を含む。 The pH adjusting agent is not particularly limited, and any suitable pH adjusting agent can be used to adjust the pH of the composition to any desired range, as described above.In some embodiments, one or more pH adjusting agents can include, consist essentially of, or consist of inorganic compounds, organic compounds, or combinations thereof.In some embodiments, one or more pH adjusting agents can include inorganic acids (e.g., hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and phosphoric acid); organic acids (e.g., carboxylic acids such as citric acid, formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, maleic acid, phthalic acid, malic acid, tartaric acid, and lactic acid); and/or organic sulfuric acids (e.g., methanesulfonic acid, ethanesulfonic acid, isethionic acid, etc.). In some embodiments, the one or more pH adjusters may include divalent or higher acids of the above acid(s) (e.g., sulfuric acid, carbonic acid, phosphoric acid, oxalic acid, etc.) that may be in the form of a base where one or more protons (H + ) can be released (e.g., ammonium bicarbonate or ammonium hydrogen phosphate), although any counterion may be used (e.g., weakly basic cations such as ammonium, triethanolamine, etc.). In some embodiments, the one or more pH adjusters include sulfate.
　いくつかの実施形態では、１つ又は複数のｐＨ調整剤は、アルカリ金属の１つ又は複数の水酸化物（例えば、ＮａＯＨ、ＫＯＨ）又はその塩（例えば、炭酸塩、炭酸水素塩、硫酸塩、酢酸塩等）；第４級アンモニウム化合物（例えば、テトラメチルアンモニウム、テトラエチルアンモニウム、テトラブチルアンモニウム等）；第４級アンモニウム水酸化物（例えば、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラブチルアンモニウム）又はその塩；アンモニア；アミン；又は任意の他の適切なｐＨ調整剤を含み得る。 In some embodiments, the one or more pH adjusters may include one or more hydroxides of alkali metals (e.g., NaOH, KOH) or salts thereof (e.g., carbonates, bicarbonates, sulfates, acetates, etc.); quaternary ammonium compounds (e.g., tetramethylammonium, tetraethylammonium, tetrabutylammonium, etc.); quaternary ammonium hydroxides (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide) or salts thereof; ammonia; amines; or any other suitable pH adjuster.
　いくつかの実施形態では、組成物が、スルホ基を含む双性イオン化合物と、スルホ基を含む界面活性剤と、スルホ基を含む酸とを組み合わせて含む。このようにスルホ基を含む化合物を重畳的に使用することによって、本発明の所期の効果を効率的に奏することができる。 In some embodiments, the composition includes a combination of a zwitterionic compound containing a sulfo group, a surfactant containing a sulfo group, and an acid containing a sulfo group. By using the compounds containing a sulfo group in this manner in a superimposed manner, the intended effect of the present invention can be efficiently achieved.
　いくつかの実施形態では、組成物が、スルホン酸が表面に固定化されたコロイダルシリカと、スルホ基を含む双性イオン化合物と、スルホ基を含む界面活性剤と、スルホ基を含む酸とを組み合わせて含む。このようにスルホ基を含む化合物を重畳的に使用することによって、本発明の所期の効果を効率的に奏することができる。 In some embodiments, the composition contains a combination of colloidal silica having a sulfonic acid immobilized on the surface, a zwitterionic compound containing a sulfo group, a surfactant containing a sulfo group, and an acid containing a sulfo group. By using the compounds containing a sulfo group in this manner in a superimposed manner, the intended effect of the present invention can be efficiently achieved.
　研磨用組成物のｐＨ
　ｐＨ調整剤は、上述のように、第１の材料（例えば、ＳｉＮ）及び第２の材料（例えば、ＳｉＯ２）の反対に帯電した表面を得るために所望のｐＨ値を達成するのに適した任意の量で存在してもよい。研磨用組成物のｐＨは、当該分野で公知の任意の適切な方法を使用して（例えば、ＴｈｅｒｍｏＦｉｓｈｅｒ　Ｓｃｉｅｎｔｉｆｉｃ　ＯＲＩＯＮ（商標）ＶＥＲＳＡ　ＳＴＡＲ　ＰＲＯ（商標）ｐＨ／ＩＳＥ／導電率／溶存酸素マルチパラメータベンチトップメータを使用して）測定され得る。 pH of the polishing composition
The pH adjuster may be present in any amount suitable to achieve a desired pH value to obtain oppositely charged surfaces of the first material (e.g., SiN) and the second material (e.g., SiO 2 ), as described above. The pH of the polishing composition can be measured using any suitable method known in the art (e.g., using a ThermoFisher Scientific ORION™ VERSA STAR PRO™ pH/ISE/conductivity/dissolved oxygen multi-parameter benchtop meter).
　いくつかの実施形態では、組成物のｐＨは酸性（例えば、７未満）である。いくつかの実施形態では、組成物のｐＨは、約６．９以下、約６．８以下、約６．７以下、約６．６以下、約６．５以下、約６．４以下、約６．３以下、約６．２以下、約６．１以下、約６．０以下、約５．９以下、約５．８以下、約５．７以下、約５．６以下、約５．５以下、約５．４以下、約５．３以下、約５．２以下、約５．１以下、約５．０以下、約４．９以下、約４．８以下、約４．７以下、約４．６以下、約４．５以下、約４．４以下、約４．３以下、約４．２以下、約４．１以下、約４．０以下、約３．９以下、約３．８以下、約３．７以下、約３．６以下、約３．５以下、約３．４以下、約３．３以下、約３．２以下、約３．１以下、約３．０以下、約２．９以下、約２．８以下、約２．７以下、約２．６以下、約２．５以下、約２．４以下、約２．３以下、約２．２以下、約２．１以下、約２．０以下、約１．９以下、約１．８以下、約１．７以下、約１．６以下、約１．５以下、又はそれより低い。 In some embodiments, the pH of the composition is acidic (e.g., less than 7). In some embodiments, the pH of the composition is about 6.9 or less, about 6.8 or less, about 6.7 or less, about 6.6 or less, about 6.5 or less, about 6.4 or less, about 6.3 or less, about 6.2 or less, about 6.1 or less, about 6.0 or less, about 5.9 or less, about 5.8 or less, about 5.7 or less, about 5.6 or less, about 5.5 or less, about 5.4 or less, about 5.3 or less, about 5.2 or less, about 5.1 or less, about 5.0 or less, about 4.9 or less, about 4.8 or less, about 4.7 or less, about 4.6 or less, about 4.5 or less, about 4.4 or less, about 4.3 or less. or less, about 4.2 or less, about 4.1 or less, about 4.0 or less, about 3.9 or less, about 3.8 or less, about 3.7 or less, about 3.6 or less, about 3.5 or less, about 3.4 or less, about 3.3 or less, about 3.2 or less, about 3.1 or less, about 3.0 or less, about 2.9 or less, about 2.8 or less, about 2.7 or less, about 2.6 or less, about 2.5 or less, about 2.4 or less, about 2.3 or less, about 2.2 or less, about 2.1 or less, about 2.0 or less, about 1.9 or less, about 1.8 or less, about 1.7 or less, about 1.6 or less, about 1.5 or less, or lower.
　いくつかの実施形態では、組成物のｐＨは、約１．５以上、約１．６以上、約１．７以上、約１．８以上、約１．９以上、約２．０以上、約２．１以上、約２．２以上、約２．３以上、約２．４以上、約２．５以上、約２．６以上、約２．７以上、約２．８以上、約２．９以上、約３．０以上、約３．１以上、約３．２以上、約３．３以上、約３．４以上、約３．５以上、約３．６以上、約３．７以上、約３．８以上、約３．９以上、約４．０以上、約４．１以上、約４．２以上、約４．３以上、約４．４以上、約４．５以上、約４．６以上、約４．７以上、約４．８以上、約４．９以上、約５．０以上、約５．１以上、約５．２以上、約５．３以上、約５．４以上、約５．５以上、又はこれらの間の任意の範囲若しくは値である。 In some embodiments, the pH of the composition is about 1.5 or more, about 1.6 or more, about 1.7 or more, about 1.8 or more, about 1.9 or more, about 2.0 or more, about 2.1 or more, about 2.2 or more, about 2.3 or more, about 2.4 or more, about 2.5 or more, about 2.6 or more, about 2.7 or more, about 2.8 or more, about 2.9 or more, about 3.0 or more, about 3.1 or more, about 3.2 or more, about 3.3 or more, about 3.4 or more, about 3.5 or more. or more, about 3.6 or more, about 3.7 or more, about 3.8 or more, about 3.9 or more, about 4.0 or more, about 4.1 or more, about 4.2 or more, about 4.3 or more, about 4.4 or more, about 4.5 or more, about 4.6 or more, about 4.7 or more, about 4.8 or more, about 4.9 or more, about 5.0 or more, about 5.1 or more, about 5.2 or more, about 5.3 or more, about 5.4 or more, about 5.5 or more, or any range or value therebetween.
　いくつかの実施形態では、組成物のｐＨは、約１～約６、約１．５～約５．５、約２．０～約５．０、約２．５～約５．０、約３．０～約５．０、約３．５～約５．０、約４．０～約５．０又は約４．５～約５．０である。いくつかの実施形態では、組成物のｐＨは、約２．５～約５．０、例えば約２．６、２．７、２．８、２．９、３．０、３．１、３．２、３．３、３．４、３．５、３．６、３．７、３．８、３．９、４．０、４．１、４．２、４．３、４．４、４．５、４．６、４．７、４．８、４．９、５．０、又はそれらの間の任意の範囲若しくは値である。いくつかの実施形態では、組成物のｐＨは、約１．５～約５．０、約２．０～約５．０、約３．５～約５．０、約４．０～約５．０、約４．１～約４．８、あるいは、約４．２～約４．７である。 In some embodiments, the pH of the composition is about 1 to about 6, about 1.5 to about 5.5, about 2.0 to about 5.0, about 2.5 to about 5.0, about 3.0 to about 5.0, about 3.5 to about 5.0, about 4.0 to about 5.0, or about 4.5 to about 5.0. In some embodiments, the pH of the composition is about 2.5 to about 5.0, such as about 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, or any range or value therebetween. In some embodiments, the pH of the composition is about 1.5 to about 5.0, about 2.0 to about 5.0, about 3.5 to about 5.0, about 4.0 to about 5.0, about 4.1 to about 4.8, or about 4.2 to about 4.7.
　いくつかの実施形態では、組成物のｐＨは塩基性（例えば、７より大きい）である。いくつかの実施形態では、組成物のｐＨは、７超、７．１以上、７．２以上、７．３以上、７．４以上、７．５以上、７．６以上、７．７以上、７．８以上、７．９以上、８．０以上、８．１以上、８．２以上、８．３以上、８．４以上、８．５以上、８．６以上、８．７以上、８．８以上、８．９以上、９．０以上、９．１以上、９．２以上、９．３以上、９．４以上、９．５以上、９．６以上、９．７以上、９．８以上、９．９以上、１０．０以上、又はそれらの間の任意の範囲若しくは値である。 In some embodiments, the pH of the composition is basic (e.g., greater than 7). In some embodiments, the pH of the composition is greater than 7, 7.1 or more, 7.2 or more, 7.3 or more, 7.4 or more, 7.5 or more, 7.6 or more, 7.7 or more, 7.8 or more, 7.9 or more, 8.0 or more, 8.1 or more, 8.2 or more, 8.3 or more, 8.4 or more, 8.5 or more, 8.6 or more, 8.7 or more, 8.8 or more, 8.9 or more, 9.0 or more, 9.1 or more, 9.2 or more, 9.3 or more, 9.4 or more, 9.5 or more, 9.6 or more, 9.7 or more, 9.8 or more, 9.9 or more, 10.0 or more, or any range or value therebetween.
　いくつかの実施形態では、組成物のｐＨは、約１０．０以下、約９．９以下、約９．８以下、約９．７以下、約９．６以下、約９．５以下、約９．４以下、約９．３以下、約９．２以下、約９．１以下、約９．０以下、約８．９以下、約８．８以下、約８．７以下、約８．６以下、約８．５以下、約８．４以下、約８．３以下、約８．２以下、約８．１以下、約８．０以下、約７．９以下、約７．８以下、約７．７以下、約７．６以下、約７．５以下、又はそれらの間の任意の範囲若しくは値である。 In some embodiments, the pH of the composition is about 10.0 or less, about 9.9 or less, about 9.8 or less, about 9.7 or less, about 9.6 or less, about 9.5 or less, about 9.4 or less, about 9.3 or less, about 9.2 or less, about 9.1 or less, about 9.0 or less, about 8.9 or less, about 8.8 or less, about 8.7 or less, about 8.6 or less, about 8.5 or less, about 8.4 or less, about 8.3 or less, about 8.2 or less, about 8.1 or less, about 8.0 or less, about 7.9 or less, about 7.8 or less, about 7.7 or less, about 7.6 or less, about 7.5 or less, or any range or value therebetween.
　いくつかの実施形態では、組成物のｐＨは、７～１０、７～９．５、７～９、７～８．５、７～８、７．５～１０、７．５～９．５、７．５～９、７．５～８．５、７．５～８、８～１０、８～９．５、８～９、８～８．５、８．５～１０、８．５～９．５、８．５～９、９～１０、９～９．５、９．５～１０、又はその間の任意の範囲若しくは値である。いくつかの実施形態では、組成物のｐＨは、約７、約７．５、約８、約８．５、約９、約９．５、約１０、又はそれらの間の任意の範囲若しくは値である。 In some embodiments, the pH of the composition is 7-10, 7-9.5, 7-9, 7-8.5, 7-8, 7.5-10, 7.5-9.5, 7.5-9, 7.5-8.5, 7.5-8, 8-10, 8-9.5, 8-9, 8-8.5, 8.5-10, 8.5-9.5, 8.5-9, 9-10, 9-9.5, 9.5-10, or any range or value therebetween. In some embodiments, the pH of the composition is about 7, about 7.5, about 8, about 8.5, about 9, about 9.5, about 10, or any range or value therebetween.
　いくつかの実施形態では、組成物は、２－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］エタン－１－スルホン酸（ＨＥＰＥＳ）；３－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］プロパン－１－スルホン酸（ＨＥＰＰＳ）；２－モルホリニルエタンスルホン酸（ＭＥＳ）；３－（モルホリニル）プロパン－１－スルホン酸；Ｎ，Ｎ－ビス（２－ヒドロキシエチル）－２－アミノエタンスルホン酸（ＢＥＳ）；及び２－｛［１，３－ジヒドロキシ－２－（ヒドロキシメチル）プロパン－２－イル］アミノ｝－エタン－１－スルホン酸（ＴＥＳ）からなる群から選択される少なくとも１つと、プルランと、イソプロピル化ナフタレンスルホン酸ナトリウムと、硫酸と、を含む。このような組み合わせの化合物を含むことによって、本発明の所期の効果をよりさらに効率的に奏することができる。 In some embodiments, the composition includes at least one selected from the group consisting of 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid (HEPES); 3-[4-(2-hydroxyethyl)piperazin-1-yl]propane-1-sulfonic acid (HEPPS); 2-morpholinylethanesulfonic acid (MES); 3-(morpholinyl)propane-1-sulfonic acid; N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES); and 2-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino}-ethane-1-sulfonic acid (TES), pullulan, sodium isopropylated naphthalenesulfonate, and sulfuric acid. By including such a combination of compounds, the intended effect of the present invention can be achieved even more efficiently.
　いくつかの実施形態では、組成物は、スルホン酸が表面に固定化されたコロイダルシリカと、２－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］エタン－１－スルホン酸（ＨＥＰＥＳ）；３－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］プロパン－１－スルホン酸（ＨＥＰＰＳ）；２－モルホリニルエタンスルホン酸（ＭＥＳ）；３－（モルホリニル）プロパン－１－スルホン酸；Ｎ，Ｎ－ビス（２－ヒドロキシエチル）－２－アミノエタンスルホン酸（ＢＥＳ）；及び２－｛［１，３－ジヒドロキシ－２－（ヒドロキシメチル）プロパン－２－イル］アミノ｝－エタン－１－スルホン酸（ＴＥＳ）からなる群から選択される少なくとも１つと、プルランと、イソプロピル化ナフタレンスルホン酸ナトリウムと、硫酸と、を含む。このような組み合わせの化合物を含むことによって、本発明の所期の効果をよりさらに効率的に奏することができる。 In some embodiments, the composition includes colloidal silica having a sulfonic acid immobilized on its surface, at least one selected from the group consisting of 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid (HEPES); 3-[4-(2-hydroxyethyl)piperazin-1-yl]propane-1-sulfonic acid (HEPPS); 2-morpholinylethanesulfonic acid (MES); 3-(morpholinyl)propane-1-sulfonic acid; N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES); and 2-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino}-ethane-1-sulfonic acid (TES), pullulan, sodium isopropylated naphthalenesulfonate, and sulfuric acid. By including such a combination of compounds, the intended effect of the present invention can be achieved even more efficiently.
　液体担体
　本開示による研磨用組成物は、液体担体を含む。研磨用組成物の液体担体は、特に限定されない。いくつかの実施形態では、液体担体は、脱イオン水等の水である。液体担体は、例えば、適切なｐＨ調整剤を含有する水溶液であってもよい。いくつかの実施形態では、液体担体は、アルコール化合物、例えば脂肪族アルコールのグリコールエーテル及び２～６個の炭素原子を有する３～１０個の炭素原子等の１つ又は複数の有機溶媒を含むことができる。２～６個の炭素を有する脂肪族アルコールの例としては、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、ｔｅｒｔ－ブタノール、ペンタノール、ヘキサノール、エチレングリコール、プロピレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、グリセリン、１，２，４－ブタントリオール、１，２，６－ヘキサントリオール、エリスリトール、Ｄ－トレイトール、Ｌ－トレイロール、Ｄ－アラビニトール、Ｌ－アラビニトール、リビトール、キシリトール、マンニトール及びソルビトールが挙げられる。３～１０個の炭素を有するグリコールエーテルの例としては、メチルグリコール、メチルジグリコール、メチルトリグリコール、イソプロピルグリコール、イソプロピルジグリコール、ブチルグリコール、ブチルジグリコール、ブチルトリグリコール、イソブチルグリコール、イソブチルジグリコール、ヘキシルグリコール、ヘキシルジグリコール、２－エチルヘキシルグリコール、２－エチルヘキシルジグリコール、アリールグリコール、フェニルグリコール、フェニルジグリコール、ベンジルグリコール、メチルプロピレングリコール、メチルプロピレンジグリコール、メチルプロピレントリグリコール、プロピルプロピレングリコール、プロピルプロピレンジグリコール、ブチルプロピレングリコール、ブチルプロピレンジグリコール、及びフェニルプロピレングリコールが挙げられる。 Liquid Carrier The polishing composition according to the present disclosure includes a liquid carrier. The liquid carrier of the polishing composition is not particularly limited. In some embodiments, the liquid carrier is water, such as deionized water. The liquid carrier may be, for example, an aqueous solution containing a suitable pH adjuster. In some embodiments, the liquid carrier may include one or more organic solvents, such as alcohol compounds, for example glycol ethers of aliphatic alcohols and alcohols having 2 to 6 carbon atoms and 3 to 10 carbon atoms. Examples of aliphatic alcohols having 2 to 6 carbons include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, pentanol, hexanol, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,4-butanetriol, 1,2,6-hexanetriol, erythritol, D-threitol, L-threol, D-arabinitol, L-arabinitol, ribitol, xylitol, mannitol, and sorbitol. Examples of glycol ethers having 3 to 10 carbons include methyl glycol, methyl diglycol, methyl triglycol, isopropyl glycol, isopropyl diglycol, butyl glycol, butyl diglycol, butyl triglycol, isobutyl glycol, isobutyl diglycol, hexyl glycol, hexyl diglycol, 2-ethylhexyl glycol, 2-ethylhexyl diglycol, aryl glycol, phenyl glycol, phenyl diglycol, benzyl glycol, methyl propylene glycol, methyl propylene diglycol, methyl propylene triglycol, propyl propylene glycol, propyl propylene diglycol, butyl propylene glycol, butyl propylene diglycol, and phenyl propylene glycol.
　いくつかの実施形態において、研磨用組成物中に含まれる液体担体のうち、８０重量％以上、８５重量％以上、９０重量％以上、９５重量％以上、９８重量％以上、あるいは、９９重量％以上が、水である（上限は、１００重量％）。 In some embodiments, the liquid carrier contained in the polishing composition is 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, 98% by weight or more, or 99% by weight or more (up to 100% by weight) of water.
　追加成分
　いくつかの実施形態では、組成物は、任意の濃度で他の添加剤を含んでもよい。しかしながら、表面欠陥の存在の原因となり得る不要な成分を添加しないことが望ましい。したがって、任意の他の添加剤は、とにかくそれらが存在する場合、比較的低い濃度（例えば、０．１重量％以下、０．０５重量％以下、０．０１重量％以下、０．００５重量％以下、０．００１重量％以下、０．０００５重量％以下、０．０００１重量％以下、０．０００１重量％～０．１重量％、０．０００１重量％～０．０１重量％、又は０．０００１重量％～０．００１重量％等）で存在することが好ましい。いくつかの実施形態では、組成物に含まれる他の添加剤は、少なくとも約０．０００００１重量％、少なくとも約０．０００００３重量％、あるいは、少なくとも約０．０００００５重量％の濃度を有する。他の添加剤の例としては、防腐剤、防カビ剤、殺生物剤（例えば、メチルイソチアゾリノン（「ＭＩＴ」）、ベンゾイソチアゾリノン（「ＢＩＴ」）、２－メチル－４－イソチアゾリン－３－オン等のイソチアゾリノン）、分散剤（一旦沈降した研磨材砥粒の再分散性を向上させる添加剤）、電気伝導度調整剤（研磨用組成物の電気伝導度を調整する添加剤）、上記研磨材砥粒以外の研磨材砥粒、キレート剤、酸化剤、還元剤、及び溶存ガスが挙げられる。 Additional Components In some embodiments, the composition may include other additives in any concentration. However, it is desirable not to add unnecessary components that may contribute to the presence of surface defects. Thus, any other additives, if present at all, are preferably present in relatively low concentrations (e.g., 0.1 wt.% or less, 0.05 wt.% or less, 0.01 wt.% or less, 0.005 wt.% or less, 0.001 wt.% or less, 0.0005 wt.% or less, 0.0001 wt.% or less, 0.0001 wt.% to 0.1 wt.%, 0.0001 wt.% to 0.01 wt.%, or 0.0001 wt.% to 0.001 wt.%, etc.). In some embodiments, the other additives included in the composition have a concentration of at least about 0.000001 wt.%, at least about 0.000003 wt.%, or at least about 0.000005 wt.%. Examples of other additives include preservatives, fungicides, biocides (e.g., isothiazolinones such as methylisothiazolinone ("MIT"), benzoisothiazolinone ("BIT"), and 2-methyl-4-isothiazolin-3-one), dispersants (additives that improve the redispersibility of abrasive grains that have once settled), electrical conductivity adjusters (additives that adjust the electrical conductivity of the polishing composition), abrasive grains other than the above-mentioned abrasive grains, chelating agents, oxidizing agents, reducing agents, and dissolved gases.
　いくつかの実施形態では、組成物が、酸化ケイ素の研磨速度（Å／分）に対する窒化ケイ素の研磨速度（Å／分）が少なくとも２０となる特性を有する、少なくとも４０となる特性を有する、あるいは、少なくとも６０となる特性を有する、研磨用組成物が提供される。 In some embodiments, a polishing composition is provided in which the composition has a silicon nitride polishing rate (Å/min) relative to the silicon oxide polishing rate (Å/min) of at least 20, at least 40, or at least 60.
　いくつかの実施形態では、研磨用組成物は、酸化ケイ素と、窒化ケイ素とを研磨するために用いられる。 In some embodiments, the polishing composition is used to polish silicon oxide and silicon nitride.
　研磨方法
　別の態様において、本開示は、所望のｐＨ範囲において正のゼータ電位を有する第１の材料及び所望のｐＨ範囲において負のゼータ電位を有する第２の材料を含む基板表面を研磨する方法に関し、方法は、本開示の研磨用組成物を基板表面に適用することによって基板表面を研磨することを含み、研磨は、第２の材料に対する第１の材料の除去速度選択性（例えば、少なくとも１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０、６５、７０、７５、８０、８５、９０、９５、１００以上の除去速度選択性）を達成する。 Polishing Method In another aspect, the present disclosure relates to a method of polishing a substrate surface comprising a first material having a positive zeta potential at a desired pH range and a second material having a negative zeta potential at a desired pH range, the method comprising polishing the substrate surface by applying a polishing composition of the present disclosure to the substrate surface, wherein the polishing achieves a removal rate selectivity of the first material relative to the second material (e.g., a removal rate selectivity of at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 or more).
　いくつかの実施形態では、ｐＨ約２．５～５で正のゼータ電位を有する第１の材料及びｐＨ約２．５～５で負のゼータ電位を有する第２の材料を含む基板表面を研磨する方法であって、前記方法が、研磨パッドを使用して、前記基板表面に本発明の研磨用組成物を適用することによって、前記基板表面を研磨することを含み、前記研磨が、少なくとも２０の、前記第２の材料に対する前記第１の材料の除去速度選択性を達成する、方法が提供される。 In some embodiments, a method is provided for polishing a substrate surface comprising a first material having a positive zeta potential at a pH of about 2.5-5 and a second material having a negative zeta potential at a pH of about 2.5-5, the method comprising polishing the substrate surface by applying a polishing composition of the present invention to the substrate surface using a polishing pad, the polishing achieving a removal rate selectivity of the first material relative to the second material of at least 20.
　ｐＨ、第１の材料、第２の材料、研磨用組成物、除去速度選択性についての説明は上記で行った説明が適用されうる。 The explanations given above regarding pH, the first material, the second material, the polishing composition, and the removal rate selectivity can be applied.
　いくつかの実施形態では、前記第１の材料は窒化ケイ素を含む。いくつかの実施形態では、前記第２の材料が酸化ケイ素を含む。いくつかの実施形態では、前記第１の材料は窒化ケイ素を含み、前記第２の材料が酸化ケイ素を含む。 In some embodiments, the first material comprises silicon nitride. In some embodiments, the second material comprises silicon oxide. In some embodiments, the first material comprises silicon nitride and the second material comprises silicon oxide.
　いくつかの実施形態では、第１の材料はＳｉＮである。いくつかの実施形態では、第２の材料はＳｉＯ２である。いくつかの実施形態では、第１の材料はＳｉＮであり、第２の材料はＳｉＯ２である。いくつかの実施形態では、ｐＨは、約１～約６である。いくつかの実施形態では、ｐＨは、約２～約５（例えば、約２．５～約５、例えば約４．５）である。 In some embodiments, the first material is SiN. In some embodiments, the second material is SiO2 . In some embodiments, the first material is SiN and the second material is SiO2. In some embodiments, the pH is from about 1 to about 6. In some embodiments, the pH is from about 2 to about 5 (e.g., from about 2.5 to about 5, e.g., about 4.5 ).
　いくつかの実施形態では、研磨は、少なくとも約８０Å／分、少なくとも約８５Å／分、少なくとも約９０Å／分、少なくとも約９５Å／分、少なくとも約１００Å／分、少なくとも約１０５Å／分、少なくとも約１１０Å／分、少なくとも約１１５Å／分、少なくとも約１２０Å／分、少なくとも約１２５Å／分、少なくとも約１３０Å／分、少なくとも約１３５Å／分、少なくとも約１４０Å／分、少なくとも約１４５Å／分、少なくとも約１５０Å／分、少なくとも約１５５Å／分、少なくとも約１６０Å／分、少なくとも約１６５Å／分、少なくとも約１７０Å／分、少なくとも約１７５Å／分、少なくとも約１８０Å／分、少なくとも約１８５Å／分、少なくとも約１９０Å／分、少なくとも約１９５Å／分、少なくとも約２００Å／分、少なくとも約２１０Å／分、少なくとも約２２０Å／分、少なくとも約２２５Å／分、少なくとも約２３０Å／分、少なくとも約２４０Å／分、少なくとも約２５０Å／分、少なくとも約２７５Å／分、少なくとも約３００Å／分、少なくとも約４００Å／分、少なくとも約５００Å／分、又はそれを超えるＳｉＮ除去速度を達成する。 In some embodiments, polishing occurs at a rate of at least about 80 Å/min, at least about 85 Å/min, at least about 90 Å/min, at least about 95 Å/min, at least about 100 Å/min, at least about 105 Å/min, at least about 110 Å/min, at least about 115 Å/min, at least about 120 Å/min, at least about 125 Å/min, at least about 130 Å/min, at least about 135 Å/min, at least about 140 Å/min, at least about 145 Å/min, at least about 150 Å/min, at least about 155 Å/min, at least about 160 Å/min, at least about 165 Å/min. /min, at least about 170 Å/min, at least about 175 Å/min, at least about 180 Å/min, at least about 185 Å/min, at least about 190 Å/min, at least about 195 Å/min, at least about 200 Å/min, at least about 210 Å/min, at least about 220 Å/min, at least about 225 Å/min, at least about 230 Å/min, at least about 240 Å/min, at least about 250 Å/min, at least about 275 Å/min, at least about 300 Å/min, at least about 400 Å/min, at least about 500 Å/min, or more.
　いくつかの実施形態では、研磨は、約５０Å／分以下、約４５Å／分以下、約４０Å／分以下、約３５Å／分以下、約３０Å／分以下、約２５Å／分以下、約２０Å／分以下、約１５Å／分以下、約１０Å／分以下、約９Å／分以下、約８Å／分以下、約７Å／分以下、約６Å／分以下、約５Å／分、又はそれ未満のＳｉＯ２除去速度を達成する。 In some embodiments, polishing achieves a SiO2 removal rate of about 50 Å/min or less, about 45 Å/min or less, about 40 Å/min or less, about 35 Å/min or less, about 30 Å/min or less, about 25 Å/min or less, about 20 Å/min or less, about 15 Å/min or less, about 10 Å/min or less, about 9 Å/min or less, about 8 Å/min or less, about 7 Å/ min or less, about 6 Å/min or less, about 5 Å/min, or less.
　いくつかの実施形態では、研磨は、少なくとも約１０、少なくとも約１１、少なくとも約１２、少なくとも約１３、少なくとも約１４、少なくとも約１５、少なくとも約１６、少なくとも約１７、少なくとも約１８、少なくとも約１９、少なくとも約２０、少なくとも約２５、少なくとも約３０、少なくとも約３５、少なくとも約４０、少なくとも約４５、少なくとも約５０、少なくとも約５５、少なくとも約６０、少なくとも約６５、少なくとも約７０、少なくとも約７５、少なくとも約８０、少なくとも約８５、少なくとも約９０、少なくとも約９５、少なくとも約１００、又はそれを超えるＳｉＮ：ＳｉＯ２除去速度選択性を達成する。 In some embodiments, polishing achieves a SiN:SiO2 removal rate selectivity of at least about 10, at least about 11, at least about 12, at least about 13, at least about 14, at least about 15, at least about 16, at least about 17, at least about 18, at least about 19, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95, at least about 100, or more.
　実施例１．ＳｉＮ：ＳｉＯ２除去速度選択性に対する双性イオン化合物の効果
　ＳｉＮ：ＳｉＯ２選択性に対する双性イオンタイプの効果を試験するために、等モル量の異なる双性イオン化合物（Ａ～Ｆ、Ｈ）を含むか、又は双性イオン化合物を含まずに（Ｇ、Ｉ）、表２に示すように、本開示に従って組成物を調製した。全ての組成物において、研磨材は、スルホン酸基を有する表面結合有機酸を有するシリカであり、Ａ～Ｉで使用したシリカ粒子は、１４ｎｍの平均一次粒子径及び３０ｎｍの平均二次粒子径を有する。表中では、シリカ粒子を二酸化ケイ素と表している。 Example 1. Effect of Zwitterionic Compounds on SiN: SiO2 Removal Rate Selectivity To test the effect of zwitterionic type on SiN: SiO2 selectivity, compositions were prepared according to the present disclosure with equimolar amounts of different zwitterionic compounds (A-F, H) or without zwitterionic compounds (G, I), as shown in Table 2. In all compositions, the abrasive is silica with surface-bound organic acids bearing sulfonic acid groups, and the silica particles used in A-I have an average primary particle size of 14 nm and an average secondary particle size of 30 nm. In the table, the silica particles are referred to as silicon dioxide.
　組成物を調製するための手順は以下の通りである：（１）脱イオン水（ＤＩＷ）５００ｇを容器に添加し、撹拌を開始した；（２）双性イオン化合物を容器内の水に添加し、５分間撹拌し／かき混ぜた；（３）イソプロピル化ナフタレンスルホン酸ナトリウムを（２）からの混合物に添加し、５分間撹拌し／かき混ぜた；（４）プルラン、殺生物剤、硫酸、及びコロイダルシリカ（スルホン酸修飾コロイダルシリカ）を（３）からの混合物に一度に１つずつ添加し、順番に撹拌し／かき混ぜた；並びに（５）ＤＩＷを最終体積１０００ｇまで添加し、５分間撹拌して、研磨用組成物を得る。各組成物のｐＨを４．５に調整した。 The procedure for preparing the compositions is as follows: (1) 500 g of deionized water (DIW) was added to a container and stirring was started; (2) the zwitterionic compound was added to the water in the container and stirred/agitated for 5 minutes; (3) sodium isopropylated naphthalene sulfonate was added to the mixture from (2) and stirred/agitated for 5 minutes; (4) pullulan, biocide, sulfuric acid, and colloidal silica (sulfonic acid modified colloidal silica) were added one at a time to the mixture from (3) and stirred/agitated in turn; and (5) DIW was added to a final volume of 1000 g and stirred for 5 minutes to obtain the polishing compositions. The pH of each composition was adjusted to 4.5.
　研磨のために、以下の研磨条件を使用して、表２に記載の組成物をＳｉＮ（Ａｄｖａｎｃｅｄ　Ｍａｔｅｒｉａｌｓ　Ｔｅｃｈｎｏｌｏｇｙ；ＬＰ－ＳｉＮ；５，０００Å厚）及びＳｉＯ２（Ａｄｖａｎｔｉｖ　Ｔｅｃｈｎｏｌｏｇｉｅｓ；ＴＥＯＳ；１０，０００Å厚）ウェハに適用して除去速度を測定した。 For polishing, the compositions described in Table 2 were applied to SiN (Advanced Materials Technology; LP-SiN; 5,000 Å thick) and SiO 2 (Advanced Technologies; TEOS; 10,000 Å thick) wafers and removal rates were measured using the following polishing conditions:
　・研磨機：２００ｍｍ研磨機（Ｗｅｓｔｅｃｈ）；
　・研磨パッド：ＩＣ１０１０；
　・ダウンフォース：１．５ｐｓｉ
　・プラテン回転：６６ｒｐｍ；
　・ヘッド回転：５８ｒｐｍ；
　・スラリー流量：１５０ｍＬ／分；
　・研磨時間：６０秒（ＳｉＮ）；３００秒（ＳｉＯ２）。 Polisher: 200mm polisher (Westech);
Polishing pad: IC1010;
Downforce: 1.5 psi
Platen rotation: 66 rpm;
Head rotation: 58 rpm;
Slurry flow rate: 150 mL/min;
Polishing time: 60 seconds (SiN); 300 seconds ( SiO2 ).
　研磨用組成物によって達成される除去速度を評価するために、ＦＩＬＭＥＴＲＩＣＳ（登録商標）Ｆ５０膜厚マッピングシステムを使用して研磨前後の膜厚を測定して、除去された材料の厚さを決定し、これを研磨時間で割って除去速度を決定した。 To evaluate the removal rate achieved by the polishing composition, the film thickness was measured before and after polishing using a FILMETRICS® F50 film thickness mapping system to determine the thickness of material removed, which was then divided by the polishing time to determine the removal rate.
　表２に示すように、組成物Ｇ（双性イオン化合物なし）は、１１のＳｉＮ：ＳｉＯ２選択性をもたらした。双性イオン化合物を含む組成物は、４８（組成物Ｅ、ＢＥＳ）から６７（組成物Ａ、ＨＥＰＥＳ）まで、著しくより高いＳｉＮ：ＳｉＯ２選択性を示した。したがって、試験した全ての双性イオン化合物は、組成物Ｇ（双性イオンなし）と比較して、ＳｉＮ：ＳｉＯ２選択性を少なくとも４倍改善し、ＨＥＰＥＳは選択性を６倍超改善した。ＳｉＮ除去速度、ＳｉＯ２除去速度、及びＳｉＮ：ＳｉＯ２選択性を、双性イオン化合物の関数としてそれぞれ図３Ａ、図３Ｂ、及び図３Ｃにプロットする。 As shown in Table 2, composition G (no zwitterionic compound) resulted in a SiN: SiO2 selectivity of 11. The compositions containing zwitterionic compounds showed significantly higher SiN: SiO2 selectivities, ranging from 48 (composition E, BES) to 67 (composition A, HEPES). Thus, all zwitterionic compounds tested improved SiN: SiO2 selectivity by at least 4-fold compared to composition G (no zwitterionic), with HEPES improving selectivity by more than 6-fold. The SiN removal rate, SiO2 removal rate, and SiN: SiO2 selectivity as a function of zwitterionic compound are plotted in Figures 3A, 3B, and 3C, respectively.
　特定の実施形態を図示及び説明してきたが、以下の特許請求の範囲に定義されるそのより広い態様の技術から逸脱することなく、当業者に従って変更及び修飾を行うことができることを理解されるべきである。 Although particular embodiments have been shown and described, it should be understood that changes and modifications can be made by those skilled in the art without departing from the technology in its broader aspects as defined in the following claims.
　本明細書に例示的に記載される組成物及び方法は、本明細書に具体的に開示されていない任意の１つ又は複数の要素、１つ又は複数の制限がない状態で適切に実施され得る。したがって、例えば、「含むこと（ｃｏｍｐｒｉｓｉｎｇ）」、「含むこと（ｉｎｃｌｕｄｉｎｇ）」、「含有すること（ｃｏｎｔａｉｎｉｎｇ）」等の用語は、広範に、限定することなく読まれるものとする。更に、本明細書で使用される用語及び表現は、限定ではなく説明の用語として使用されており、そのような用語及び表現の使用において、示され説明された特徴又はその一部のあらゆる均等物を除外する意図はない。特許請求される開示の範囲内で様々な修飾が可能であることが認識される。したがって、本開示は好ましい実施形態及び任意選択の特徴によって具体的に開示されているが、本明細書に開示されている、そこに具体化された開示の修飾及び変形が当業者によって行われてもよく、そのような修飾及び変形は本開示の範囲内にあると見なされることを理解されるべきである。 The compositions and methods illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations not specifically disclosed herein. Thus, for example, terms such as "comprising," "including," "containing," and the like, shall be read broadly and without limitation. Furthermore, the terms and expressions used herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions to exclude any equivalents of the features shown and described or portions thereof. It is recognized that various modifications are possible within the scope of the disclosure claimed. Thus, although the present disclosure has been specifically disclosed by preferred embodiments and optional features, it should be understood that modifications and variations of the disclosure embodied therein disclosed herein may be made by those skilled in the art, and such modifications and variations are considered to be within the scope of the present disclosure.
　本開示は、本明細書において広く一般的に説明されている。一般的な開示に含まれるより狭い種及び亜属のグループ化のそれぞれも、方法の一部を形成する。これは、切除された材料が本明細書に具体的に列挙されているか否かにかかわらず、属から任意の主題を除去するという条件又は否定的限定を伴う方法の一般的な説明を含む。本技術は、本技術の個々の態様の単一の例示として意図される本出願に記載された特定の実施形態に関して限定されるべきではない。当業者には明らかなように、本技術の趣旨及び範囲から逸脱することなく、本技術の多くの修飾及び変形を行うことができる。本明細書に列挙されたものに加えて、本技術の範囲内の機能的に等価な方法及び装置は、前述の説明から当業者には明らかであろう。そのような修飾及び変形は、本技術の範囲内に含まれることが意図される。この本技術は、特定の方法、試薬、化合物組成物又は生物学的系に限定されず、当然のことながら変化し得ることを理解されたい。本明細書で使用される用語は、特定の実施形態を説明することのみを目的としており、限定することを意図していないことも理解されたい。 The disclosure has been described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the method. This includes the general description of the method with a proviso or negative limitation that removes any subject matter from the genus, whether or not the excised material is specifically recited herein. The technology should not be limited with respect to the specific embodiments described in this application, which are intended as single illustrations of individual aspects of the technology. As will be apparent to those skilled in the art, many modifications and variations of the technology can be made without departing from the spirit and scope of the technology. Functionally equivalent methods and apparatuses within the scope of the technology, in addition to those recited herein, will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to be included within the scope of the technology. It is to be understood that the technology is not limited to specific methods, reagents, compounds compositions or biological systems, which may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
　当業者は、本開示が目的を実行し、言及された目的及び利点、並びにそれらに固有の目的及び利点を得るのによく適合していることを容易に理解する。その中の修飾及び他の使用が当業者には思い浮かぶであろう。これらの修飾は、本開示の趣旨の範囲内に包含され、本開示の非限定的な実施形態を示す特許請求の範囲によって定義される。 Those skilled in the art will readily appreciate that the present disclosure is well adapted to carry out the objects and obtain the objects and advantages mentioned, as well as those inherent therein. Modifications therein and other uses will occur to those skilled in the art. These modifications are encompassed within the spirit of the disclosure and are defined by the claims which represent non-limiting embodiments of the disclosure.
　更に、本開示の特徴又は態様がマーカッシュ群に関して記載されている場合、当業者は、本開示がそれによってマーカッシュ群の任意の個々のメンバー又はメンバーのサブグループに関しても記載されていることを認識するであろう。 Furthermore, when features or aspects of the present disclosure are described in terms of a Markush group, one of skill in the art will recognize that the present disclosure is also thereby described in terms of any individual members or subgroups of members of the Markush group.
　本明細書で引用される全ての参考文献、論文、刊行物、特許、特許公報、及び特許出願は、あらゆる目的のためにその全体が参照により組み込まれる。しかしながら、本明細書で引用される任意の参考文献、論文、出版物、特許、特許出版物、及び特許出願の言及は、それらが有効な先行技術を構成するか、又は世界のあらゆる国における共通の一般知識の一部を形成するという承認又は任意の形態の提案ではなく、またそのように解釈されるべきではない。 All references, articles, publications, patents, patent publications, and patent applications cited herein are incorporated by reference in their entirety for all purposes. However, the mention of any references, articles, publications, patents, patent publications, and patent applications cited herein is not, and should not be construed as, an acknowledgment or any form of suggestion that they constitute valid prior art or form part of the common general knowledge in any country in the world.
　本出願は、２０２２年１１月３０日に出願された米国仮出願６３／４２８９５５に基づいており、その開示内容は、その全体が参照により本明細書に組みこまれる。 This application is based on U.S. Provisional Application No. 63/428,955, filed November 30, 2022, the disclosure of which is incorporated herein by reference in its entirety.
　他の実施形態は、以下の特許請求の範囲に記載される。 Other embodiments are described in the following claims.

Claims (17)

  1. 　シリカ粒子の表面に固定化された１つ又は複数の有機酸で修飾されたシリカ粒子を含む研磨材と、
    　双性イオン化合物と、
    を含み、約２．５～約５のｐＨを有する、研磨用組成物。     an abrasive comprising silica particles modified with one or more organic acids immobilized on the surface of the silica particles;
    A zwitterionic compound,
    and having a pH of about 2.5 to about 5.
  2. 　前記双性イオン化合物が、ＳＯ３ －アニオン性基及びＮＲ４ ＋カチオン性基を含む、請求項１に記載の研磨用組成物。 2. The polishing composition of claim 1, wherein the zwitterionic compound comprises an SO 3 - anionic group and an NR 4 + cationic group.
  3. 　前記双性イオン化合物が、ピペラジノ、モルホリノ及びヒドロキシエチルアミノ化合物から選択される少なくとも１つを含む、請求項１に記載の研磨用組成物。 The polishing composition according to claim 1, wherein the zwitterionic compound comprises at least one selected from piperazino, morpholino, and hydroxyethylamino compounds.
  4. 　前記双性イオン化合物は、
    　Ｎ（Ｒ１）（Ｒ２）（Ｒ３）で示される化合物、この際、Ｒ１、Ｒ２及びＲ３は、それぞれ独立して、水素原子、水酸基、アニオン性基、又は、水酸基、アニオン性基及びハロゲン原子から選択される置換基を有してもよいアルキル基であり、Ｒ１、Ｒ２及びＲ３のうち少なくとも１つはアニオン性基又は置換基としてアニオン性基を有するアルキル基である、

    で示される化合物、この際、Ｒ４及びＲ５は、それぞれ独立して、水素原子、水酸基、アニオン性基、又は、水酸基、アニオン性基及びハロゲン原子から選択される置換基を有してもよいアルキル基であり、Ｒ４及びＲ５のうち少なくとも１つはアニオン性基又は置換基としてアニオン性基を有するアルキル基である、及び、

    で示される化合物、この際、Ｒ６は、アニオン性基、又は、置換基としてアニオン性基を有するアルキル基である、
    から選択される少なくとも１つを含む、請求項１に記載の研磨用組成物。     The zwitterionic compound is
    A compound represented by N(R 1 )(R 2 )(R 3 ), in which R 1 , R 2 and R 3 are each independently a hydrogen atom, a hydroxyl group, an anionic group, or an alkyl group which may have a substituent selected from a hydroxyl group, an anionic group and a halogen atom, and at least one of R 1 , R 2 and R 3 is an anionic group or an alkyl group which has an anionic group as a substituent;

    wherein R 4 and R 5 are each independently a hydrogen atom, a hydroxyl group, an anionic group, or an alkyl group which may have a substituent selected from a hydroxyl group, an anionic group, and a halogen atom, and at least one of R 4 and R 5 is an anionic group or an alkyl group having an anionic group as a substituent; and

    wherein R 6 is an anionic group or an alkyl group having an anionic group as a substituent;
    The polishing composition according to claim 1 , comprising at least one selected from the following:
  5. 　多糖類を更に含む、請求項１に記載の研磨用組成物。 The polishing composition according to claim 1, further comprising a polysaccharide.
  6. 　スルホ基を含む界面活性剤を更に含む、請求項１に記載の研磨用組成物。 The polishing composition according to claim 1, further comprising a surfactant containing a sulfo group.
  7. 　前記界面活性剤が、分岐のアルキル基を含む、請求項６に記載の研磨用組成物。 The polishing composition according to claim 6, wherein the surfactant contains a branched alkyl group.
  8. 　前記界面活性剤が、縮合環を有する、請求項６または７に記載の研磨用組成物。 The polishing composition according to claim 6 or 7, wherein the surfactant has a condensed ring.
  9. 　前記界面活性剤の分子量が、１０００以下である、請求項６または７に記載の研磨用組成物。 The polishing composition according to claim 6 or 7, wherein the molecular weight of the surfactant is 1000 or less.
  10. 　スルホ基を含む酸を更に含む、請求項１に記載の研磨用組成物。 The polishing composition according to claim 1, further comprising an acid containing a sulfo group.
  11. 　スルホ基を含む界面活性剤と、スルホ基を含む酸と、スルホ基を含む双性イオン化合物と、を組み合わせて含む、請求項１に記載の研磨用組成物。 The polishing composition according to claim 1, which contains a combination of a surfactant containing a sulfo group, an acid containing a sulfo group, and a zwitterionic compound containing a sulfo group.
  12. 　スルホン酸が表面に固定化されたコロイダルシリカと、スルホ基を含む界面活性剤と、スルホ基を含む酸と、スルホ基を含む双性イオン化合物と、を含む、請求項１に記載の研磨用組成物。 The polishing composition according to claim 1, comprising colloidal silica having a sulfonic acid fixed to its surface, a surfactant containing a sulfo group, an acid containing a sulfo group, and a zwitterionic compound containing a sulfo group.
  13. 　２－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］エタン－１－スルホン酸（ＨＥＰＥＳ）；３－［４－（２－ヒドロキシエチル）ピペラジン－１－イル］プロパン－１－スルホン酸（ＨＥＰＰＳ）；２－モルホリニルエタンスルホン酸（ＭＥＳ）；３－（モルホリニル）プロパン－１－スルホン酸；Ｎ，Ｎ－ビス（２－ヒドロキシエチル）－２－アミノエタンスルホン酸（ＢＥＳ）；及び２－｛［１，３－ジヒドロキシ－２－（ヒドロキシメチル）プロパン－２－イル］アミノ｝－エタン－１－スルホン酸（ＴＥＳ）からなる群から選択される少なくとも１つと、
    　プルランと、
    　イソプロピル化ナフタレンスルホン酸ナトリウムと、
    　硫酸と、
    を含む、請求項１に記載の研磨用組成物。     at least one selected from the group consisting of 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane-1-sulfonic acid (HEPES); 3-[4-(2-hydroxyethyl)piperazin-1-yl]propane-1-sulfonic acid (HEPPS); 2-morpholinylethanesulfonic acid (MES); 3-(morpholinyl)propane-1-sulfonic acid; N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES); and 2-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino}-ethane-1-sulfonic acid (TES);
    Pullulan and
    Sodium isopropylated naphthalene sulfonate;
    Sulfuric acid,
    The polishing composition of claim 1 , comprising:
  14. 　酸化ケイ素の研磨速度（Å／分）に対する窒化ケイ素の研磨速度（Å／分）が少なくとも２０となる特性を有する、請求項１に記載の研磨用組成物。 The polishing composition according to claim 1, which has a silicon nitride polishing rate (Å/min) relative to the silicon oxide polishing rate (Å/min) of at least 20.
  15. 　酸化ケイ素と、窒化ケイ素とを研磨するために用いられる、請求項１に記載の研磨用組成物。 The polishing composition according to claim 1, which is used to polish silicon oxide and silicon nitride.
  16. 　ｐＨ約２．５～約５で正のゼータ電位を有する第１の材料及びｐＨ約２．５～約５で負のゼータ電位を有する第２の材料を含む基板表面を研磨する方法であって、前記方法が、
    　研磨パッドを使用して、前記基板表面に請求項１に記載の研磨用組成物を適用することによって、前記基板表面を研磨することを含み、
    　前記研磨が、少なくとも２０の、前記第２の材料に対する前記第１の材料の除去速度選択性を達成する、方法。     1. A method for polishing a substrate surface comprising a first material having a positive zeta potential at a pH of about 2.5 to about 5 and a second material having a negative zeta potential at a pH of about 2.5 to about 5, the method comprising:
    polishing the surface of the substrate by applying the polishing composition of claim 1 to the surface of the substrate using a polishing pad;
    The method of claim 1, wherein the polishing achieves a removal rate selectivity of the first material relative to the second material of at least 20.
  17. 　前記第１の材料は窒化ケイ素を含み、前記第２の材料が酸化ケイ素を含む、請求項１５に記載の方法。 The method of claim 15, wherein the first material comprises silicon nitride and the second material comprises silicon oxide.
PCT/JP2023/041499 2022-11-30 2023-11-17 Composition and method for enhancing silicon nitride polishing rate selectivity WO2024116910A1 (en)

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JP2001035820A (en) * 1999-07-21 2001-02-09 Hitachi Chem Co Ltd Cmp polishing solution
JP2019070114A (en) * 2017-09-28 2019-05-09 ローム アンド ハース エレクトロニック マテリアルズ シーエムピー ホウルディングス インコーポレイテッド Aqueous anionic functional silica slurry and amine carboxylic acid composition for selective nitride removal in polishing, and application method therefor
JP2020050700A (en) * 2018-09-25 2020-04-02 株式会社フジミインコーポレーテッド Tungsten dissolution inhibitor, and polishing composition and surface-treated composition including the same
JP2020186380A (en) * 2019-05-16 2020-11-19 ローム アンド ハース エレクトロニック マテリアルズ シーエムピー ホウルディングス インコーポレイテッド Chemical mechanical polishing compositions and methods that enhance defect suppression and selectively polish silicon nitride over silicon dioxide in acidic environments.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001035820A (en) * 1999-07-21 2001-02-09 Hitachi Chem Co Ltd Cmp polishing solution
JP2019070114A (en) * 2017-09-28 2019-05-09 ローム アンド ハース エレクトロニック マテリアルズ シーエムピー ホウルディングス インコーポレイテッド Aqueous anionic functional silica slurry and amine carboxylic acid composition for selective nitride removal in polishing, and application method therefor
JP2020050700A (en) * 2018-09-25 2020-04-02 株式会社フジミインコーポレーテッド Tungsten dissolution inhibitor, and polishing composition and surface-treated composition including the same
JP2020186380A (en) * 2019-05-16 2020-11-19 ローム アンド ハース エレクトロニック マテリアルズ シーエムピー ホウルディングス インコーポレイテッド Chemical mechanical polishing compositions and methods that enhance defect suppression and selectively polish silicon nitride over silicon dioxide in acidic environments.

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