A polishing composition containing zirconia particles and an oxidizing agent

Abstract

The present specification provides a CMP composition and method for polishing a surface including an amorphous carbon, spin-on carbon (SoC), and / or diamondlike carbon (DLC) film. The CMP composition of the present disclosure contains at least one abrasive grain having zirconia particles, and moreover, can contain at least one metal-containing oxidizing agent.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application incorporates by reference in its entirety U.S. Application No. 16 / 805,037, filed on February 28, 2020, and U.S. Application No. 17 / 100,072, filed on November 20, 2020.

[0002] The present technology generally relates to chemical - mechanical polishing compositions and methods for polishing surfaces including amorphous carbon, spin - on carbon (SoC), and / or diamond - like carbon (DLC) films.

Background Art

[0003] One of the major chemical - mechanical polishing (CMP) challenges in semiconductor manufacturing is selectively polishing specific materials. Carbon and DLC films are increasingly being used in the manufacture of integrated circuits (ICs). U.S. Patent 6,673,684; D.S. Hwang, et al., Diamond and Related Materials, 13(11 - 12):2207 - 2210(2004); Franz Kreupl, et al. Electron Devices Meeting, 2008. Conventional methods are ineffective for polishing DLC films (HY Tsai, et al., Diamond and Related Materials. 16(2)), and chemical enhancement including oxidation has been adopted to improve the removal rate (Zewei Yuan, et al., J.Manuf. Sci. Eng. 135(4):041006(2013); Evan L., et al., Carbon 68:473 - 479(2014); Jessica M. Werrell, et al., J.Sci.Techn.Adv.Materials 18(1):654 - 663; Soumen Mandal, et al., Carbon, 130:25 - 30(2018)). However, the removal rate is still too low for state - of - the - art CMP.

[0004] Accordingly, there is a need for a new CMP composition that can effectively and efficiently polish amorphous carbon, SoC, and / or DLC films. SUMMARY OF THE INVENTION

[0005] Provided herein are compositions and methods for polishing a surface comprising amorphous carbon, SoC, and / or DLC films.

[0006] Embodiments include methods of increasing the removal rate of amorphous carbon, SoC, or DLC from a surface, comprising contacting the surface with a slurry comprising abrasive grains having zirconia particles and a metal-containing oxidizing agent, and polishing the surface. In some embodiments, the removal rate is increased compared to the removal rate when using a similar slurry composition having silica and / or a non-metal-containing oxidizing agent instead of the zirconia particles and / or the metal-containing oxidizing agent. In some embodiments, the zirconia particles are aggregates comprising primary particles. In some embodiments, the zirconia particles comprise a primary particle size of about 8 - 10 nm and a secondary particle size of aggregates of about 70 nm. In some embodiments, the metal-containing oxidizing agent comprises an element selected from the group consisting of manganese, cerium, vanadium, and iron. In some embodiments, the metal-containing oxidizing agent is KMnO 4 , (NH 4 ) 2 Ce(NO 3 ) 6 , NaVO 3 , NH 4 VO 3 , and Fe(NO 3 ) 3Selected from the group consisting of. In some embodiments, the composition has a pH of from about 3 to about 6. In some embodiments, the zirconia particles are present in an amount of about 0.01 wt% or more or about 0.2 wt% or more. In some embodiments, the zirconia particles are present in an amount of about 2.5 wt% or less. In some embodiments, the metal-containing oxidant is present in an amount of about 0.05 mM or more or about 2 mM or more. In some embodiments, the zirconia particles include colloidal zirconia. In some embodiments, the zirconia particles include calcined zirconia. In some embodiments, the zirconia particles are doped with yttrium atoms as yttria. In some embodiments, the concentration of yttria in the zirconia particles is at least 9 mol%. In some embodiments, the yttria-doped zirconia particles have a particle size of less than 80 nm. In some embodiments, the pH of the composition containing the yttria-doped zirconia particles is from about 2 to 6.

[0007] Other embodiments include a chemical mechanical polishing (CMP) composition comprising colloidal zirconia particles and a metal-containing oxidant. In some embodiments, the colloidal zirconia particles are aggregates comprising primary particles. In some embodiments, the colloidal zirconia particles include primary particle sizes of about 8 to about 10 nm in diameter and secondary particle sizes of aggregates of about 70 nm in diameter. In some embodiments, the metal-containing oxidant includes an element selected from the group consisting of manganese, cerium, vanadium, and iron. In some embodiments, the metal-containing oxidant is KMnO 4 , (NH 4 ) 2 Ce(NO 3 ) 6 , NaVO 3 , NH 4 VO 3 , and Fe(NO 3 ) 3Selected from the group consisting of. In some embodiments, the composition has a pH of from about 3 to about 6. In some embodiments, the zirconia particles are present in an amount of about 0.01 wt% or more or about 0.2 wt% or more. In some embodiments, the zirconia particles are present in an amount of about 2.5 wt% or less. In some embodiments, the metal-containing oxidant is present in an amount of about 0.05 mM or more or about 2 mM or more. Embodiments also include reaction products formed by contacting the CMP composition of the embodiment with an amorphous carbon, SoC, or DLC surface. Embodiments also include a chemical mechanical polishing (CMP) composition comprising yttria-doped zirconia particles and a metal-containing oxidant, wherein the particle size of the particles is less than 80 nm. In some embodiments, the zirconia particles are doped with more than 9 mol% yttria. In some embodiments, the pH of the composition is from about 2 to 6.

[0008] Also, several of the following embodiments may be provided.

[0009] 1. A method for manufacturing a polished object to be polished, comprising polishing an object to be polished including amorphous carbon, spin-on carbon (SoC) or diamond-like carbon (DLC) using an abrasive grain including zirconia particles and a chemical mechanical polishing (CMP) composition including a metal-containing oxidant.

[0010] 2. The method according to 1., wherein the average primary particle size of the zirconia particles is from about 3 to 110 nm, and the average secondary particle size of the zirconia particles is from about 20 nm to about 2000 nm.

[0011] 3. The method according to 1. or 2., wherein the metal-containing oxidant includes an element selected from the group consisting of manganese, cerium, vanadium, and iron.

[0012] 4. The metal-containing oxidant is KMnO 4 , (NH 4 ) 2 Ce(NO 3 ) 6 , NaVO 3 , NH4 VO 3 、 and Fe(NO 3 ) 3 The method according to any one of 1. to 3., selected from the group consisting of

[0013] 5. The method according to any one of 1. to 4., wherein the composition has a pH of from about 2 to about 7.

[0014] 6. The method according to any one of 1. to 5., wherein the zirconia particles are present in an amount of about 0.01 wt% or more based on the chemical mechanical polishing (CMP) composition.

[0015] 7. The method according to any one of 1. to 6., wherein the zirconia particles are present in an amount of about 4.0 wt% or less based on the chemical mechanical polishing (CMP) composition.

[0016] 8. The method according to any one of 1. to 7., wherein the metal-containing oxidant is present in an amount of about 0.05 mM or more based on the chemical mechanical polishing (CMP) composition.

[0017] 9. The method according to any one of 1. to 8., wherein the zirconia particles comprise colloidal zirconia.

[0018] 10. The method according to any one of 1. to 8., wherein the zirconia particles comprise fired zirconia.

[0019] 11. The method according to any one of 1. to 8., wherein the zirconia particles are doped with yttria.

[0020] 12. The method according to 11., wherein the zirconia particles are doped with more than 9 mol% of yttria.

[0021] 13. A chemical mechanical polishing (CMP) composition for use in polishing an object to be polished comprising amorphous carbon, spin-on carbon (SoC), or diamond-like carbon (DLC), comprising zirconia particles and a metal-containing oxidant.

[0022] Detailed Description of the Invention Provided herein are CMP compositions and methods for polishing surfaces comprising amorphous carbon, SoC, and / or DLC films. As used herein, the term "chemical mechanical polishing" or "planarization" refers to the process of planarizing (polishing) a surface by a combination of surface chemical reaction and mechanical abrasion. In some embodiments, the chemical reaction is initiated by applying to the surface a composition capable of reacting with the surface material (which may be interchangeably referred to as "polishing slurry", "polishing composition", "composition", "slurry composition", or simply "slurry") to thereby convert the surface material into a product that can be more readily removed by simultaneous mechanical abrasion. In some embodiments, the mechanical abrasion is performed by contacting a polishing pad with the surface and moving the polishing pad relative to the surface. DLC is used herein according to how the term is understood in the art and includes various amorphous hydrogenated or non-hydrogenated forms of carbon that are metastable materials characterized by a mixture of sp2 and sp3 hybridized carbon bonds. DLC used in ICs is included within the meaning of the term.

[0023] Composition The CMP polishing compositions disclosed herein can comprise, consist essentially of, or consist of one or more of the following components.

[0024] Abrasive grains The CMP composition of the present disclosure includes at least one abrasive grain having zirconia particles. In some embodiments, the zirconia particles are colloidal zirconia particles or pulverized / fired zirconia particles. The abrasive grains in the CMP composition provide or enhance the mechanical polishing effect during the CMP process. The zirconia particles may be undoped or doped, for example, with yttrium (Y) or its oxide. In some embodiments, the pulverized / fired zirconia particles are produced through a pulverization process after calcination in a calcination furnace. More specifically, the object to be calcined is heated from room temperature (e.g., 20 - 25°C) over, for example, 1 - 10 hours, 1.2 - 5 hours, typically about 2 hours. The heating rate at that time is, for example, 100 - 1000°C / hour, or 200 - 800°C / hour. Then, the calcination temperature is set to be about 1300 - 1500°C, and it is held within that temperature range for, for example, 1 - 3 hours, typically about 2 hours. Then, natural cooling is performed at room temperature. The time from the start of heating the object to be calcined until it returns to room temperature by natural cooling is, for example, 3 - 20 hours, typically 7 - 8 hours.

[0025] In some embodiments, the zirconia particles are doped with yttria (Y-stabilized zirconia particles). In some embodiments, when the doped zirconia particles are made from calcined / pulverized zirconia, it is preferable to prepare them by mixing zirconia powder and yttria powder at a ratio such that yttria has a predetermined doping amount before the above-mentioned calcination and then calcining as described above. In some embodiments, when the doped zirconia particles are made from colloidal zirconia, it is common to prepare them by reacting the respective precursors of Y and Zr in the required molar amounts in advance and then granulating. Regarding the doping method, for example, the contents of JP-A-2010-523451 and U.S. Patent No. 3,110,681 can be appropriately referred to, and these contents are incorporated herein by reference in their entirety.

[0026] The concentration of yttria in the Y-stabilized zirconia particles is defined as follows.

[0027]

Number

[0028] The molar percentage of yttria can be determined by X-ray fluorescence (XRF) method or any other method known in the art. In some embodiments, the concentration of yttria in the yttria-stabilized zirconia particles is at least 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, 10 mol%, 11 mol%, 12 mol%, 13 mol%, 14 mol%, or 15 mol%. In some embodiments, the concentration of yttria in the yttria-stabilized zirconia particles is less than 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, or 20 mol%. In some embodiments, the concentration of yttria in the yttria-stabilized zirconia particles is about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 mol%, or in the range therebetween. In some embodiments, the concentration of yttria in the yttria-stabilized zirconia particles is about 1 mol% or more or less, about 2 mol% or more or less, about 3 mol% or more or less, about 4 mol% or more or less, about 5 mol% or more or less, about 6 mol% or more or less, about 7 mol% or more or less, about 8 mol% or more or less, about 9 mol% or more or less, about 10 mol% or more or less, about 11 mol% or more or less, about 12 mol% or more or less, about 13 mol% or more or less, about 14 mol% or more or less, about 15 mol% or more or less, about 16 mol% or more or less, about 17 mol% or more or less, about 18 mol% or more or less, about 19 mol% or more or less, about 20 mol% or more or less, about 21 mol% or more or less, about 22 mol% or more or less, about 23 mol% or more or less, about 24 mol% or more or less, or about 25 mol% or more or less. In some embodiments, the yttria-stabilized zirconia particles comprise a tetragonal phase (e.g., the yttria in the yttria-stabilized zirconia particles is at a concentration sufficient to result in a tetragonal phase). In some embodiments, the yttria-stabilized zirconia particles comprise a cubic phase (e.g., the yttria in the yttria-stabilized zirconia particles is at a concentration sufficient to result in a cubic phase).In some embodiments, the concentration of yttria in the yttria-stabilized zirconia particles is greater than 2.6 mol%, greater than 3.3 mol%, greater than 9.3 mol%, or greater than 10.6 mol%. As used herein, the expression "X (where X is a numerical value) or more or less" means that in this specification, it may be X or more or X or less. That is, when making corrections, the numerical value X can be used as the basis for the lower limit or the upper limit.

[0029] In some embodiments, the zirconia (e.g., colloidal zirconia or milled / fired zirconia or doped zirconia) particles are aggregates comprising primary particles and optionally secondary particles. The aggregates can be formed from combinations of individual particles, which are known in the art as primary particles, but it will be understood that the aggregated combinations of particles are known in the art as secondary particles. The abrasive grains in the polishing composition can be in the form of primary particles or in the form of secondary particles that are aggregates of primary particles. Alternatively, the abrasive grains can be present in both primary particle form and secondary particle form. In a preferred embodiment, the abrasive grains are present in the polishing composition at least partially in the form of secondary particles.

[0030] In some embodiments, the average primary particle diameter of the zirconia (e.g., colloidal zirconia (including doped ones)) particles is preferably at least the measurement limit value, 3 nm or more, or 5 nm or more. Also, the average primary particle diameter of the zirconia (e.g., colloidal zirconia (including doped ones)) particles is 15 nm or less, 10 nm or less, 9 nm or less, or 8 nm or less. In some embodiments, for example, it includes an average primary particle diameter (D P1 ) having a diameter of about 8 - 10 nm. In some embodiments, the zirconia (e.g., milled / fired zirconia (including doped ones)) particles have an average primary particle diameter (D P1) is included. In some embodiments, the zirconia (e.g., crushed / fired zirconia including doped ones) particles have an average primary particle diameter (D P1 ) is included. In some embodiments, the zirconia (e.g., crushed / fired zirconia including doped ones) particles have an average primary particle diameter (D P1 ) that is greater than 65 nm.

[0031] In some embodiments, the average primary particle size (D P1 ) of the abrasive grains can be determined, for example, from the specific surface area S (m P1 / g) measured by the BET method based on the formula of average primary particle diameter D 2 (nm) = 2727 / S. The specific surface area of the abrasive grains can be measured, for example, by using a surface area analyzer with the trade name "FLOW SORB II 2300" available from Micromeritics. In some embodiments, the average primary particle diameter of the abrasive grains can be calculated as the volume average particle diameter of 100 particles by taking pictures using the SEM SU8000 manufactured by Hitachi High-Technologies Corporation and using the image analysis type particle size distribution software MacView manufactured by Mounttech Co., Ltd.

[0032] In some embodiments, the average secondary particle diameter (D P2 ) of the abrasive grains (e.g., colloidal zirconia including doped ones) is not particularly limited. From the perspective of polishing speed and the like, it is 10 nm or more, 15 nm or more, 20 nm or more, 30 nm or more, 40 nm or more, 50 nm or more, 60 nm or more, 65 nm or more, 70 nm or more, 75 nm or more, or 80 nm or more. In some embodiments, the average secondary particle diameter D P2is 200 nm or less, 150 nm or less, 100 nm or less, 60 nm or less, less than 49 nm, less than 48 nm, less than 33 nm, less than 21 nm, or less than 17 nm. In some embodiments, the average secondary particle diameter of the aggregates is a diameter of about 40, 60, 65, 70, 75, or 80 nm, or in the range therebetween. In some embodiments, the average secondary particle diameter of the aggregates is about 40 nm or more or less, about 60 nm or more or less, about 65 nm or more or less, about 70 nm or more or less, about 75 nm or more or less, or about 80 nm or more or less.

[0033] In some embodiments, the zirconia (e.g., milled / fired zirconia, including doped) particles have an average secondary particle diameter (D P2 ) that includes a diameter of about 80 to 2000 nm. In some embodiments, the average secondary particle diameter of the aggregates (the average secondary particle diameter (D P2 ) of the zirconia (e.g., milled / fired zirconia) particles) is about 80, 90, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, or 2000 nm, or in the range therebetween. In some embodiments, the average secondary particle diameter (the average secondary particle diameter (D P2)) is about 80 nm or more or less, about 90 nm or more or less, about 100 nm or more or less, about 150 nm or more or less, about 200 nm or more or less, about 300 nm or more or less, about 400 nm or more or less, 500 nm or more or less, about 600 nm or more or less, about 700 nm or more or less, 800 nm or more or less, about 900 nm or more or less, about 1000 nm or more or less, about 1100 nm or more or less, about 1200 nm or more or less, about 1300 nm or more or less, about 1400 nm or more or less, about 1500 nm or more or less, about 1600 nm or more or less, about 1700 nm or more or less, about 1800 nm or more or less, about 1900 nm or more or less, or 2000 nm or more or less. In some embodiments, the average secondary particle diameter (the average secondary particle diameter (D of zirconia (e.g., pulverized / fired zirconia (including doped ones)) particles P2 )) is greater than 135 nm.

[0034] The average secondary particle diameter D of the abrasive grains P2 can be measured, for example, by dynamic light scattering using the model "UPA-UT151" available from Nikkiso Co., Ltd., for an aqueous dispersion of the target abrasive grains (a dispersion having a composition not containing a water-soluble polymer) as a measurement sample. In some embodiments, it can also be measured with a Malvern Zetasizer Nano ZS (measurement conditions: temperature 25 °C, sample dilution: none, measurement result: average value of 3 times).

[0035] In some embodiments, the doped zirconia has a particle diameter (average secondary particle diameter) of from about 10 to about 80 nm, such as about 10, 20, 30, 40, 50, 60, 70, or 80 nm. In some embodiments, the doped zirconia has a particle diameter (average secondary particle diameter) of, for example, about 10 nm or more or less, about 20 nm or more or less, about 30 nm or more or less, about 40 nm or more or less, about 50 nm or more or less, about 60 nm or more or less, about 70 nm or more or less, or about 80 nm or more or less. In some embodiments, the doped zirconia has a particle diameter (average secondary particle diameter) of 10 to 50 nm, or 10 to 40 nm. In some embodiments, the average secondary particle diameter D of the doped zirconia P2 is less than 49 nm, less than 48 nm, less than 33 nm, less than 21 nm, or less than 17 nm.

[0036] In some embodiments, the CMP composition comprises from about 0.01 wt% to about 4 wt% of zirconia (e.g., colloidal zirconia, crushed / fired zirconia, or doped zirconia) particulate abrasive grains. In some embodiments, the CMP composition comprises from about 0.1 wt% to about 3 wt% of zirconia (e.g., colloidal zirconia, crushed / fired zirconia, or doped zirconia) particulate abrasive grains. For example, the CMP composition comprises about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 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, or 3.0 wt% of zirconia (e.g., colloidal zirconia, crushed / fired zirconia, or doped zirconia) particulate abrasive grains. For example, the CMP composition comprises about 0.1 wt% or more or less, about 0.2 wt% or more or less, about 0.3 wt% or more or less, about 0.4 wt% or more or less, about 0.5 wt% or more or less, about 0.6 wt% or more or less, about 0.7 wt% or more or less, about 0.8 wt% or more or less, about 0.9 wt% or more or less, about 1.0 wt% or more or less, about 1.1 wt% or more or less, about 1.2 wt% or more or less, about 1.3 wt% or more or less, about 1.4 wt% or more or less, about 1.5 wt% or more or less, about 1.6 wt% or more or less, about 1.7 wt% or more or less, about 1.8 wt% or more or less, about 1.9 wt% or more or less, about 2.0 wt% or more or less, about 2.1 wt% or more or less, about 2.2 wt% or more or less, about 2.3 wt% or more or less, about 2.4 wt% or more or less, about 2.5 wt% or more or less, about 2.6 wt% or more or less, about 2.7 wt% or more or less, about 2.8 wt% or more or less, about 2.9 wt% or more or less, about 3.0 wt% or more or less, or about 4.0 wt% or more or less of zirconia (e.g., colloidal zirconia, crushed / fired zirconia, or doped zirconia) particulate abrasive grains.In some embodiments, the CMP composition comprises more than 0.05 wt%, more than 0.1 wt%, more than 0.3 wt%, or more than 0.5 wt% of zirconia (e.g., colloidal zirconia, crushed / fired zirconia, or doped zirconia) particulate abrasive grains. In some embodiments, the CMP composition comprises less than 3.0 wt% of zirconia (e.g., colloidal zirconia, crushed / fired zirconia, or doped zirconia) particulate abrasive grains.

[0037] In some embodiments, the CMP composition comprises from about 0.01 wt% to about 0.3 wt% of zirconia (e.g., colloidal zirconia, crushed / fired zirconia, or doped zirconia) particulate abrasive grains. For example, the CMP composition comprises about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, or 0.3 wt% of zirconia (e.g., colloidal zirconia, crushed / fired zirconia, or doped zirconia) particulate abrasive grains. In some embodiments, for example, the CMP composition comprises about 0.01 wt% or more or less, about 0.02 wt% or more or less, about 0.03 wt% or more or less, about 0.04 wt% or more or less, about 0.05 wt% or more or less, about 0.06 wt% or more or less, about 0.07 wt% or more or less, about 0.08 wt% or more or less, about 0.09 wt% or more or less, about 0.1 wt% or more or less, about 0.11 wt% or more or less, about 0.12 wt% or more or less, about 0.13 wt% or more or less, about 0.14 wt% or more or less, about 0.15 wt% or more or less, about 0.16 wt% or more or less, about 0.17 wt% or more or less, about 0.18 wt% or more or less, about 0.19 wt% or more or less, about 0.2 wt% or more or less, about 0.21 wt% or more or less, about 0.22 wt% or more or less, about 0.23 wt% or more or less, about 0.24 wt% or more or less, 0.25 wt% or more or less, about 0.26 wt% or more or less, about 0.27 wt% or more or less, about 0.28 wt% or more or less, about 0.29 wt% or more or less, or about 0.3 wt% wt% or more or less of zirconia (e.g., colloidal zirconia, crushed / fired zirconia, or doped zirconia) particulate abrasive grains.

[0038] Metal-containing oxidizing agent The CMP compositions of the present disclosure may also include at least one metal-containing oxidizing agent. An oxidizing agent can be added to the CMP composition to oxidize the surface of the object to be polished, thereby increasing the removal rate of the CMP process. In some embodiments, the oxidizing agent is added to the CMP composition only prior to use. In other embodiments, the oxidizing agent is mixed with other components of the CMP composition substantially simultaneously during the manufacturing procedure. In some embodiments, the composition is manufactured and sold as a stock composition, and the end customer can choose to dilute the stock composition as needed and / or add an appropriate amount of the oxidizing agent prior to use.

[0039] Examples of metals in the metal-containing oxidizing agents that can be used include, but are not limited to, manganese, cerium, vanadium, and iron. Examples of metal-containing oxidizing agents that can be used include, but are not limited to, KMnO 4 , (NH 4 ) 2 Ce(NO 3 ) 6 , NaVO 3 , NH 4 VO 3 , and Fe(NO 3 ) 3 are included.

[0040] The appropriate content of the metal-containing oxidizing agent can be determined based on specific requirements. In some embodiments, the content of the metal-containing oxidizing agent in the CMP composition is about 0.05 mM or more, or about 2 mM or more. For example, the content of the metal-containing oxidizing agent is about 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75 mM, or in the range therebetween. In some embodiments, the content of the metal-containing oxidizing agent in the CMP composition is about 2 mM or less, about 3 mM or less, about 4 mM or less, about 5 mM or less, about 6 mM or less, about 7 mM or less, about 8 mM or less, about 9 mM or less, about 10 mM or less, about 15 mM or less, about 20 mM or less, about 25 mM or less, about 30 mM or less, about 35 mM or less, about 40 mM or less, about 45 mM or less, about 50 mM or less, about 55 mM or less, about 60 mM or less, about 65 mM or less, about 70 mM or less, or about 75 mM or less. In some embodiments, the content of the metal-containing oxidizing agent in the CMP composition is about 0.05 mM or more, about 0.1 mM or more, about 0.15 mM or more, about 0.2 mM or more, about 0.3 mM or more, about 0.4 mM or more, about 0.5 mM or more, about 0.6 mM or more, about 0.7 mM or more, about 0.8 mM or more, about 0.9 mM or more, about 1.0 mM or more, about 1.1 mM or more, about 1.2 mM or more, about 1.3 mM or more, about 1.4 mM or more, about 1.5 mM or more, about 1.6 mM or more, about 1.7 mM or more, about 1.8 mM or more, about 1.9 mM or more, or about 2.0 mM or more.For example, the content of the metal-containing oxidizing agent is about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75 mM, or in the range therebetween.In some embodiments, the content of the metal-containing oxidant in the CMP composition is about 0.01 mM or more or less, about 0.02 mM or more or less, about 0.03 mM or more or less, about 0.04 mM or more or less, about 0.05 mM or more or less, about 0.06 mM or more or less, about 0.07 mM or more or less, about 0.08 mM or more or less, about 0.09 mM or more or less, about 0.1 mM or more or less, about 0.15 mM or more or less, about 0.20 mM or more or less, about 0.25 mM or more or less, about 0.30 mM or more or less, about 0.35 mM or more or less, about 0.40 mM or more or less, about 0.45 mM or more or less, about 0.50 mM or more or less, about 0.55 mM or more or less, about 0.60 mM or more or less, about 0.65 mM or more or less, about 0.70 mM or more or less, about 0.75 mM or more or less, about 0.8 mM or more or less, about 0.85 mM or more or less, about 0.9 mM or more or less, about 0.95 mM or more or less, about 1 mM or more or less, about 1.1 mM or more or less, about 1.2 mM or more or less, about 1.3 mM or more or less, about 1.4 mM or more or less, about 1.5 mM or more or less, about 1.6 mM or more or less, about 1.7 mM or more or less, about 1.8 mM or more or less, about 1.9 mM or more or less, about 2 mM or more or less, about 3 mM or more or less, about 4 mM or more or less, about 5 mM or more or less, about 6 mM or more or less, about 7 mM or more or less, about 8 mM or more or less, about 9 mM or more or less, about 10 mM or more or less, about 15 mM or more or less, about 20 mM or more or less, about 25 mM or more or less, about 30 mM or more or less, about 35 mM or more or less, about 40 mM or more or less, about 45 mM or more or less, about 50 mM or more or less, about 55 mM or more or less, about 60 mM or more or less, about 65 mM or more or less, about 70 mM or more or less, or about 75 mM or more or less. In some embodiments, the content of the metal-containing oxidant in the CMP composition is more than 0.1 mM, more than 1.2 mM, more than 3.2 mM, more than 6.3 mM, or more than 25 mM.

[0041] pH adjuster In some embodiments, the CMP composition further comprises at least one pH adjuster. In some embodiments, the pH of the CMP composition is not particularly limited, but is in the range of about 2 to about 7, including the end points. The pH of the CMP composition is not particularly limited, but is in the range of about 3 to about 6, including the end points. For example, in some embodiments, the pH of the CMP composition is about 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6, or 6.2, or in the range therebetween. In some embodiments, the pH of the CMP composition is about 1.8 or more or less, about 2 or more or less, about 2.2 or more or less, about 2.4 or more or less, about 2.6 or more or less, about 2.8 or more or less, about 3 or more or less, about 3.2 or more or less, about 3.4 or more or less, about 3.6 or more or less, about 3.8 or more or less, about 4 or more or less, about 4.2 or more or less, about 4.4 or more or less, about 4.6 or more or less, about 4.8 or more or less, about 5 or more or less, about 5.2 or more or less, about 5.4 or more or less, about 5.6 or more or less, about 5.8 or more or less, about 6 or more or less, about 6.2 or more or less, or about 7 or more or less. In some embodiments (e.g., when using colloidal zirconia as the abrasive), the pH of the CMP composition is greater than 2.3. In some embodiments (e.g., when using colloidal zirconia as the abrasive), the pH of the CMP composition is less than 6.7, or less than 5.2. In some embodiments (e.g., when using doped zirconia as the abrasive), the pH of the CMP composition is greater than 2.21. In some embodiments (e.g., when using doped zirconia as the abrasive), the pH of the CMP composition is less than 5.52, less than 4.61, or less than 4.01.

[0042] In some embodiments, an acid is used as a pH adjuster. The acid used in connection with the present invention can be an organic compound or an inorganic compound. Examples of acids include inorganic acids such as sulfuric acid, nitric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and phosphoric acid; carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, lactic acid; and organic acids such as organic sulfuric acids including methanesulfonic acid, ethanesulfonic acid, and isothionic acid.

[0043] The content of the acid in the CMP composition is not particularly limited as long as the CMP composition is enabled to be within the aforementioned pH range.

[0044] Other components The CMP composition of the present invention can optionally contain other components such as preservatives, biocides, reducing agents, polymers, surfactants, etc.

[0045] In some embodiments, the CMP composition according to the present disclosure may also contain a biocide or other preservative. Examples of preservatives and biocides that can be used in connection with the present invention include isothiazolin-based preservatives such as 2-methyl-4-isothiazolin-3-one or 5-chloro-2-methyl-4-isothiazolin-3-one, paraoxybenzoic acid esters, and phenoxyethanol. These preservatives and biocides can be used alone or in combination of two or more.

[0046] In some embodiments, the CMP composition is H 2 O 2 , NH 4 IO 4 , and (NH 4 ) 2 S 2 O8 It substantially does not contain a non-metal-containing oxidizing agent such as this. In this specification, "substantially does not contain" means that it contains none at all in the CMP composition, or also includes cases where it contains 50 ppm by weight or less, 20 ppm by weight or less, or 10 ppm by weight or less. Note that in this specification, "weight" can be read as "mass".

[0047] In some embodiments, the CMP composition does not contain abrasive grains other than zirconia grains such as silica, alumina, ceria, and titania particles. In some embodiments, the CMP composition substantially does not contain abrasive grains other than colloidal zirconia particles.

[0048] Methods and Compositions In some embodiments, provided is a method for manufacturing a polished object to be polished, including polishing an object to be polished including amorphous carbon, spin-on carbon (SoC), or diamond-like carbon (DLC) using a chemical mechanical polishing (CMP) composition including abrasive grains containing zirconia particles and a metal-containing oxidizing agent. Also provided is a chemical mechanical polishing (CMP) composition for use in polishing amorphous carbon, spin-on carbon (SoC), or diamond-like carbon (DLC), including zirconia particles and a metal-containing oxidizing agent.

[0049] In another aspect of the present disclosure, provided herein is a method for CMP of an object having at least one surface. This method includes the steps of contacting the surface with a polishing pad, delivering a CMP composition according to the present disclosure to the surface, and polishing the surface with the CMP composition. In some embodiments, the surface includes amorphous carbon, SoC, and / or DLC. By performing CMP, a method for manufacturing a polished object to be polished can be manufactured.

[0050] Examples of the object to be polished (object to be polished) can include silicon nitride, silicon oxide, amorphous silicon (a-Si), or polysilicon.

[0051] In this regard, examples of the workpiece containing silicon oxide (silicon dioxide) include tetraethyl orthosilicate (TEOS) type silicon oxide films (hereinafter also simply referred to as "TEOS") formed using tetraethyl orthosilicate as a precursor, high density plasma (HDP) films, undoped silicate glass (USG) films, phosphosilicate glass (PSG) films, borophosphosilicate glass (BPSG) films, and rapid thermal oxide (RTO) films and the like.

[0052] In another aspect of the present disclosure, provided herein is a method for increasing the removal rate of amorphous carbon, SoC, or DLC from a surface, including contacting the surface with a slurry comprising abrasive grains having zirconia particles and a metal-containing oxidizing agent, and polishing the surface. In some embodiments, the removal rate is increased as compared to the removal rate when using a similar slurry composition having silica and / or a non-metal-containing oxidizing agent instead of the zirconia particles and / or the metal-containing oxidizing agent. In some embodiments, the slurry is a CMP composition according to the present disclosure.

[0053] In another aspect of the present disclosure, provided herein is a system for chemical mechanical polishing (CMP). The system includes a substrate including at least one surface having an amorphous carbon, SoC, or DLC material, a polishing pad, and a CMP composition according to the present disclosure.

[0054] In yet another aspect of the present disclosure, provided herein is a substrate including at least one surface having amorphous carbon, SoC, or DLC, the substrate being contacted with a chemical mechanical polishing (CMP) composition according to the present disclosure.

[0055] In some embodiments, the methods and compositions of the present invention are suitable for polishing amorphous carbon, SoC, or DLC surfaces. The equipment or conditions commonly used for co-polishing can be adopted and modified according to specific requirements. The selection of appropriate equipment and / or conditions for carrying out the method is within the knowledge of those skilled in the art.

[0056] In some embodiments, the method provides an amorphous carbon, SoC, or DLC removal rate greater than about 40, 60, 80, 85, 90, 100, 120, 140, 160, 180, 200, 300, 400, 500, 600, 700, 800, 900, or 1,000 Å / min.

[0057] Note that as used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise. Further, note that the claims may be drafted to exclude any element. Thus, this description is intended to serve as a basis for the use of exclusive terms such as "solely", "only", etc. in connection with the recitation of claim elements or the use of "negative" limitations.

[0058] The term "about" is understood by those skilled in the art and will vary to some extent depending on the context in which it is used. Where there is use of a term that is not clear to those skilled in the art in the context in which it is used, "about" will mean plus or minus 10% of the particular term. Specific ranges are presented herein with the term "about" preceding a numerical value. The term "about" is used herein to provide literal support for the exact number preceding it, as well as for a number that is near to, or approximately the number preceding it. When determining whether a number is near to, or approximately, a particular recited number, an unrecited number that is near to, or approximates, the recited number may be a number that provides a substantial equivalent of the particular recited number in the context in which it is presented.

[0059] When ranges of values are provided, each intermediate value, unless the context clearly dictates otherwise, is understood to be included within the invention between one-tenth of the unit of the lower limit, between the upper and lower limits of the range, and between any other recited value or intermediate value within the recited range. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are included within the invention subject to any specifically excluded limitations within the recited range. When the recited range includes one or both of those included limitations, ranges excluding one or both of those included limitations are also included in the invention.

[0060] The present disclosure is not limited to the specific embodiments described and may, of course, be modified. Further, since the scope of the present invention is limited only by the appended claims, the terms used herein have the sole purpose of describing specific embodiments and are not intended to be limiting.

[0061] As will be apparent to those skilled in the art upon reading this disclosure, each of the embodiments described and illustrated herein has discrete components and features that can be readily separated from or combined with the features of some other embodiments without departing from the scope and spirit of the present invention. Any of the recited methods can be performed in the order of the recited events or in any other logically possible order.

[0062] All publications and patents cited herein are incorporated by reference into this application as if each individual publication or patent were specifically and individually indicated to be incorporated by reference, and are incorporated by reference for the purpose of disclosing and describing the methods and / or materials associated with which the publication is cited. Any citation of a publication is for its disclosure prior to the filing date and should not be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the provided publication dates may be different from the actual publication dates which may need to be independently confirmed.

[0063] The following examples are provided for the purpose of illustrating various embodiments of the present disclosure and are not meant to limit the present disclosure in any way. Those skilled in the art will readily understand that the present disclosure is well adapted to carry out the above objects and obtain the above results and advantages as well as those that are specific to this specification. These examples, along with the methods described herein, are presently representative of embodiments and are exemplary and are not intended as limitations on the scope of the present disclosure. Changes and other uses within the spirit of the present disclosure as defined by the claims will be apparent to those skilled in the art.

Example

[0064] Example 1: Effects of Particles and Oxidants on Removal Rate A slurry containing silica or zirconia particles and certain oxidants was prepared, and the surface of a diamond-like carbon (DLC) film was polished using a bench-top polishing machine. The results are shown in Table 1.

[0065] Hereinafter, when simply described as zirconia or zirconia particles, it is colloidal zirconia.

[0066]

Table 1

[0067] Slurries containing only silica or zirconia particles result in very low removal rates. Therefore, an oxidant is added to oxidize the surface of the carbon film in order to mechanically polish the film. Slurries based on zirconia particles with periodate and persulfate also do not result in high removal rates (only 5 Å / min and 14 Å / min, respectively). A slurry containing zirconia particles and a permanganate oxidant results in a much higher removal rate (121 Å / min) than slurries containing periodate and persulfate (5 Å / min and 14 Å / min).

[0068] Synergistic Effect of Zirconia and Permanganate: As shown above, slurries based on zirconia particles with strong non-metal-containing oxidants such as persulfate and periodate do not produce high removal rates. Slurries containing silica and permanganate do not produce high removal rates. The combination of metal-oxidized zirconia particles and metal-containing permanganate produces a much higher removal rate. Therefore, there is a synergistic effect by combination between zirconia particles and permanganate oxidant. Without being bound by theory, it is considered that permanganate oxidizes the surface of the carbon film and helps to form C-O-Mn bonds, while zirconia particles are attracted to the surface and enhance mechanical polishing. Zirconia particles and permanganate oxidant cooperate to produce a very high removal rate.

[0069] Example 2: Effect of pH CMP compositions containing the same concentrations of zirconia and permanganate were prepared at different pH values. The DLC surface was polished using a bench-top polishing machine with various CMP compositions. The results are shown in Table 2.

[0070] [Table 2]

[0071] In Table 2, it is shown that the removal rate is higher at pH 3.6 - 5.2 than at pH 2.3 and pH 6.7 (weak acidic pH). Without being bound by theory, the observed effect of removal rate vs. pH is considered to be a combined effect of multiple processes including the pH effect on the oxidation of the DLC film by permanganate, the pH effect on the zeta potential of zirconia particles and the DLC film, and the pH effect on the charge-charge interaction between the particles and the film.

[0072] Example 3: Effect of Zirconia Concentration on Removal Rate CMP compositions containing the same concentration of permanganate and pH were prepared with different concentrations of zirconia. The results are shown in Table 3.

[0073]

Table 3

[0074] Table 3 shows that the weight percentage of zirconia particles in the range exceeding 0.1 wt% and less than 3 wt% has a significant effect on the removal rate.

[0075] Example 4: Effect of KMnO in Removal Rate 4 Effect of Concentration CMP compositions containing the same concentration of zirconia and pH were prepared with different concentrations of permanganate. The results are shown in Table 4.

[0076]

Table 4

[0077] Table 4 shows that the removal rate increases when the permanganate increases from 3.2 mM to 25 mM (especially 63 mM).

[0078] Example 5: Effect of Zirconia Particles CMP compositions containing the same concentration of zirconia, permanganate and pH were prepared with different types of zirconia. The results are shown in Table 5.

[0079]

Table 5

[0080] Table 5 shows that the removal rate with fired zirconia is as efficient as that with colloidal zirconia.

[0081] Example 6: SoC Polishing

[0082]

Table 6

[0083] Table 6 shows that slurries based on 0.03 wt% colloidal zirconia do not produce high SoC removal rates even when using peroxides and persulfates, i.e., H 2 O 2 and (NH 4 ) 2 S 2 O 8 as oxidants. However, when using KMnO 4 as an oxidant, a 0.03 wt% colloidal zirconia slurry produces a very high SoC removal rate. Moreover, as described above, the concentration of zirconia and / or the oxidant can be varied while maintaining the polishing performance. As described above, these slurries achieve very high SoC / TEOS and SoC / a-Si selectivities even with very low concentrations of zirconia and KMnO 4 .

[0084] Example 7: Y-Stabilized Zirconia Particles and KMnO 4 Oxidant The following slurries were tested and the removal rates of the amorphous carbon film were measured.

[0085]

Table 7

[0086] Slurries 1a, 1b, and 1d containing silica, zirconia, or Y-stabilized zirconia particles produce only very low removal rates (4, 8, and 9 Å / min, respectively). Therefore, an oxidant is required to oxidize the surface of the carbon film in order to mechanically polish the film at a high removal rate. Peroxides (H 2 O 2Slurries 1e and 1f, which are based on Y-stabilized zirconia particles and contain persulfate, also do not result in a high removal rate (only 14 Å / min and 23 Å / min respectively). Therefore, slurries containing strong oxidizing agents such as peroxides and persulfates do not result in a high removal rate. Slurries 1c and 1g, which contain zirconia or Y-stabilized zirconia particles and a permanganate oxidizing agent, result in much higher removal rates (199 Å / min and 314 Å / min respectively). Therefore, KMnO 4 is a unique oxidizing agent that enables a high removal rate of the carbon film by slurries based on zirconia and Y-stabilized zirconia particles. The slurry 1g based on Y-stabilized zirconia particles and KMnO 4 results in a significantly higher removal rate than the slurry 1c based on zirconia particles and KMnO 4 (314 Å / min vs. 199 Å / min).

[0087] Example 8: Effect of the molar% ratio of yttria in Y-stabilized zirconia particles The following slurries were tested and the removal rates of the amorphous carbon film were measured.

[0088]

Table 8

[0089] Table 8 shows that as the molar% ratio of yttria in the Y-stabilized zirconia particles increases, the removal rate increases.

[0090] The improvement in the removal rate due to Y stabilization is thought to be due to both physical and chemical changes resulting from the substitution of Zr 3+ ions by Y 4+ ions. Pure zirconia has a monoclinic phase. As the molar% ratio of yttria increases, the crystal phase changes to a tetragonal phase and a cubic phase. Y-stabilized zirconia particles improve the mechanical polishing rate with Y 2 O 3It is considered that as the mol% of 3+ increases, the crystal phase changes (from monoclinic to tetragonal, cubic) and becomes harder. On the other hand, the substitution of Zr by Y 4+ strengthens the chemical interaction between the particles and the carbon film. Specifically, vacancies of O 2- occur in the particles, and the vacancies of O 2 increase according to the mol% of Y 3 O 2- . The vacancies of O 2- in the particles are assumed to enhance the oxidation of the carbon film by KMnO 4 , resulting in an improvement in the chemical polishing rate. Such an improvement in the removal rate increases as the density of the vacancies of O 2- increases with the increase in the mol% of Y 2 O 3 in the Y-stabilized zirconia particles.

[0091] Example 9: Effect of Particle Size The following slurries were tested to measure the removal rate of the amorphous carbon film.

[0092]

Table 9

[0093] The data in Table 9 were prepared to determine the possible effect of particle size on the removal rate. For 9.3 mol% Y 2 O 3 Y-stabilized zirconia particles in the range of 16 - 29 nm, no clear effect of particle size on the removal rate was observed. Mechanically, larger particles typically produce a higher mechanical polishing rate. Chemically, smaller particles usually enhance the chemical polishing rate due to a larger surface portion interacting with the surface of the carbon film to be polished.

[0094] Example 10: Effect of pH The following slurries were tested to measure the removal rate of the amorphous carbon film.

[0095]

Table 10

[0096] Table 10 shows the effect of slurry pH on the removal rate. The highest removal rate was obtained at around pH 3.43 by using acetic acid to adjust the pH of the slurry. Overall, a pH of about 2.2 to about 4.6 is a particularly useful pH range for generating high carbon removal rates for CMP applications.

Claims

1. A method for manufacturing a polished object to be polished, comprising polishing an object to be polished containing amorphous carbon, spin-on carbon (SoC), or diamond-like carbon (DLC) using a chemical mechanical polishing (CMP) composition containing abrasive grains containing zirconia particles and a metal-containing oxidizing agent, wherein an average primary particle diameter of the zirconia particles is 3 to 110 nm, and an average secondary particle diameter of the zirconia particles is 20 nm to 2000 nm.

2. A method for manufacturing a polished object to be polished, comprising polishing an object to be polished containing amorphous carbon, spin-on carbon (SoC), or diamond-like carbon (DLC) using a chemical mechanical polishing (CMP) composition containing abrasive grains containing zirconia particles and a metal-containing oxidizing agent, wherein the metal-containing oxidizing agent is selected from the group consisting of KMnO₄, (NH₄)₂Ce(NO₃)₆, NaVO₃, NH₄VO₃, and Fe(NO₃)₃.

3. A method for manufacturing a polished object to be polished, comprising polishing an object to be polished containing amorphous carbon, spin-on carbon (SoC), or diamond-like carbon (DLC) using a chemical mechanical polishing (CMP) composition containing abrasive grains containing zirconia particles and a metal-containing oxidizing agent, wherein the zirconia particles include colloidal zirconia or fired zirconia, or the zirconia particles are doped with yttria.

4. The method according to claim 1 or 3, wherein the metal-containing oxidizing agent contains an element selected from the group consisting of manganese, cerium, vanadium, and iron.

5. The method according to any one of claims 1 to 3, wherein the chemical mechanical polishing (CMP) composition has a pH of 2 to 7.

6. The method according to any one of claims 1 to 3, wherein the zirconia particles are present in an amount of 0.01% by weight or more based on the chemical mechanical polishing (CMP) composition.

7. The method according to any one of claims 1 to 3, wherein the zirconia particles are present in an amount of 4.0% by weight or less based on the chemical mechanical polishing (CMP) composition.

8. The method according to any one of claims 1 to 3, wherein the metal-containing oxidizing agent is present in an amount of 0.05 mM or more based on the chemical mechanical polishing (CMP) composition.

9. The method according to any one of claims 1 to 3, wherein the zirconia particles are doped with more than 9 mol% of yttria.

10. A chemical mechanical polishing (CMP) composition for use in polishing an object to be polished, which comprises zirconia particles and a metal-containing oxidizing agent, wherein the average primary particle size of the zirconia particles is 3 to 110 nm, and the average secondary particle size of the zirconia particles is 20 nm to 2000 nm, and the object to be polished comprises amorphous carbon, spin-on carbon (SoC), or diamond-like carbon (DLC).

11. A chemical mechanical polishing (CMP) composition for use in polishing an object to be polished, which comprises zirconia particles and a metal-containing oxidizing agent, wherein the metal-containing oxidizing agent is selected from the group consisting of KMnO4, (NH4)2Ce(NO3)6, NaVO3, NH4VO3, and Fe(NO3)3, and the object to be polished comprises amorphous carbon, spin-on carbon (SoC), or diamond-like carbon (DLC).

12. A chemical mechanical polishing (CMP) composition for use in polishing an object to be polished, which comprises zirconia particles and a metal-containing oxidizing agent, wherein the zirconia particles comprise colloidal zirconia or fired zirconia, or the zirconia particles are doped with yttria, and the object to be polished comprises amorphous carbon, spin-on carbon (SoC), or diamond-like carbon (DLC).

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