Soft polysiloxane core-shell abrasives for chemical mechanical planarization

Abstract

A soft polysiloxane core-shell abrasive is provided. The core and shell of the nanosized soft polysiloxane core-shell abrasive comprise different materials with different chemical and mechanical properties, and preferably the shell has a lower elastic modulus (E-modulus) than the core and is therefore mechanically softer. The shell comprises a polyorganosiloxane polymer, which is crosslinked, entangled, or a combination thereof. CMP polishing compositions, methods, and systems using the soft polysiloxane core-shell abrasive are provided to achieve high removal rates and low defectivity.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Application No. 63 / 490,412, filed March 15, 2023, which is incorporated herein by reference in its entirety. [Background technology]

[0002] The present invention relates to soft polysiloxane core-shell abrasives or abrasive particles. More specifically, soft polysiloxane core-shell abrasives or abrasive particles are provided for chemical mechanical planarization (CMP) with low defectivity.

[0003] In the semiconductor industry, chemical mechanical planarization (CMP) is a well-known technique applied in the fabrication of advanced photonics, microelectromechanical, and microelectronic materials and devices, such as semiconductor wafers. CMP polishing is a critical process for the recovery of certain materials and / or planarization of structures.

[0004] CMP uses the interplay of chemical and mechanical processes to achieve flatness on the surface being polished. The CMP process uses chemicals and nano-sized abrasives to smooth out irregularities that may have occurred during the deposition of the many different materials that make up semiconductor chips.

[0005] CMP polishing compositions typically contain abrasive nanoparticles (usually colloidal particles) in an aqueous solution. The size of the nanoparticles is strictly classified because oversized particles can scratch delicate structures and become a major source of defects. However, there are many cases where standard nanoparticles known in the prior art, typically silica-, ceria-, or alumina-based nanoparticles, still produce excessive defects. The reasons for this are manifold.

[0006] The structures to be planarized may be so delicate that even the presence of even small amounts of oversized nanoparticles in the CMP polishing composition or slurry will cause damage, irregularities in the shape of the abrasive may cause defects, or the material to be planarized may have such low mechanical strength or be so soft that even small, precisely sized nanoparticles will cause unacceptable damage.

[0007] Typically, nano-sized abrasives are at least partially surface-modified with organic groups, often carrying charged moieties, to adjust the particle's zeta potential to a desired range. For example, silica may be modified with a minimum amount of aminosilane necessary to exhibit a sufficiently high positive charge (positive zeta potential) at acidic pH.

[0008] Without being bound by theory, it is believed that to achieve a stable dispersion of colloidal abrasive particles, it is desirable for the abrasive particles to have a very high charge density and zeta potential. It is believed that the charge density on the abrasive particles, in addition to providing repulsive forces that result in stabilization of the colloidal abrasive particles, can significantly contribute to the performance of the composition.

[0009] Aminosilanes have been used to modify abrasive particles to have high charge density and zeta potential.

[0010] For example, U.S. Pat. No. 9,028,572 (B2) discloses a method for obtaining abrasive particles having a charge density and zeta potential through particle surface treatment with a compound selected from the group consisting of quaternary aminosilane compounds, dipodal aminosilane compounds, and combinations thereof.

[0011] The prior art teaches that very small amounts of silane are sufficient to significantly shift the zeta potential in the desired direction. Because silanes are typically much more expensive than unmodified abrasives, their concentrations are kept very low, typically well below the theoretically possible amount that can bond to reactive groups on the available surface of the unmodified abrasive.

[0012] Silane modification known in the art does not form a separate layer of material and does not substantially change the mechanical properties of the nanoparticles. This is because silanes typically bond to the abrasive but not, at least intentionally, to other silanes, and therefore do not form a separate layer by a combination of bonding to the surface and substantially bonding to each other. Small amounts of silane dimers or trimers that may accidentally form during surface modification are insufficient to change the mechanical properties of the abrasive.

[0013] Therefore, as discussed above, it is apparent that there remains a need in the art for nanosized abrasives for CMP processes that can significantly reduce defects, especially when used on delicate or soft materials such as spin-on dielectrics (SoD) and spin-on carbon (SoC).

[0014] The present invention provides nanosized abrasives for such improved CMP polishing compositions, methods, and systems. These and other advantages of the present invention, as well as additional inventive features, will be apparent from the description of the invention provided herein. Summary of the Invention

[0015] The present invention provides nanosized soft polysiloxane core-shell abrasives, as well as CMP polishing compositions, methods, and systems using the soft polysiloxane core-shell abrasives.

[0016] In one embodiment, a nanosized soft polysiloxane core-shell abrasive is provided, wherein the core and shell of the nanosized soft polysiloxane core-shell abrasive comprise different materials having different chemical and mechanical properties, and the shell preferably has a lower elastic modulus (E-modulus) than the core, making it mechanically softer. The shell comprises a crosslinked polyorganosiloxane polymer, an entangled polyorganosiloxane polymer, or a mixture of a crosslinked polyorganosiloxane polymer and an entangled polyorganosiloxane polymer. More specifically, the shell of the soft polysiloxane core-shell abrasive is a polyorganosiloxane shell.

[0017] The core of the nanosized soft polysiloxane core-shell abrasive comprises a material around its surface having reactive groups (preferably Si-OH groups), including but not limited to reactive OH- groups, which react with the polyorganosiloxane shell to form covalent bonds, bonding the polyorganosiloxane shell to the surface of the core.

[0018] The core of the nanosized soft polysiloxane core-shell abrasive includes, but is not limited to, an oxide, nitride, or mixture thereof of at least one element selected from the group consisting of Si, Al, Ce, La, Zr, and Ti. Preferably, the core of the nanosized soft polysiloxane core-shell abrasive is selected from the group consisting of colloidal silica, fumed silica, alumina, ceria, and combinations thereof.

[0019] The polyorganosiloxane polymer in the shell contains a silsesquioxane moiety RSiO 1.5Silicon moieties having zero or one non-hydrolyzable group R: Si(—O—) or SiR(—O—) ; and mixtures thereof, where R may be linear or cyclic alkyl or aryl, or a combination thereof, optionally containing heteroatoms such as O, S, N, and P, and R and R may each independently be aliphatic or aromatic groups, or a combination thereof, optionally containing heteroatoms such as O, S, N, and P.

[0020] Preferably, the polyorganosiloxane shell comprises greater than 50 mol%, greater than 75 mol%, greater than 85 mol%, 90 mol%, or 95 mol% of the silicone-like structure O—Si(RR)—O, where each R is independently an aliphatic and / or aromatic group and optionally has at least one heteroatom selected from the group consisting of S, N, O, and P.

[0021] Preferably, the polyorganosiloxane shell contains less than 20 mol%, less than 5 mol%, less than 2.5%, or 0% silicon moieties Si(—O—)4 having zero non-hydrolyzable groups, which function as crosslinkers.

[0022] The primary crosslinking species (crosslinkers) in the polyorganosiloxane polymer are silsesquioxane moieties, silicon moieties with zero non-hydrolyzable groups: Si(—O—)4, or a combination thereof. The crosslinkers may be present before or generated during the formation of the polyorganosiloxane shell.

[0023] The polyorganosiloxane shell contains non-ionic hydrophilic groups, and optionally organic C-OH groups or other hydrophilic groups. The non-ionic hydrophilic groups may be the sole component of the polyorganosiloxane shell.

[0024] The polyorganosiloxane shell may contain other groups, including, but not limited to, NR1R2R3 and / or NR1R2R3R4 groups, where each R is independently H, an organic aliphatic, and / or aromatic group.

[0025] The polyorganosiloxane shell contains charge carriers and other hydrophilic moieties to enhance the compatibility and colloidal stability of the nanosized soft polysiloxane core-shell abrasive particles with water or water-containing solvents.

[0026] The polyorganosiloxane polymer may be partially crosslinked, which may leave dangling ends of the polymer with terminal groups such as polymer-O-SiR1R2-OH or polymer-O-SiR(OH)2.

[0027] The polyorganosiloxane polymer may be completely uncrosslinked, in which case the dangling ends are merely physically entangled with one another.

[0028] The polyorganosiloxane polymer may additionally or solely be crosslinked by organic crosslinkers, which may be short- or long-chain alkyl or aryl groups as defined above, covalently bonded to at least two silicon moieties.

[0029] The shell may comprise crosslinked, entangled, or a mixture thereof, inorganic-organic hybrid polyorganosiloxane polymers, where the crosslinkers are both inorganic polysiloxane crosslinkers that utilize polysiloxane bonds and organic crosslinkers derived from shell-forming precursors with multiple crosslinker moieties.

[0030] The shell is a non-ionic or anionic modified polyorganosiloxane shell.

[0031] The shell is hydrophilic and may optionally contain charge carriers that are cationic, anionic, or zwitterionic at a given pH.

[0032] The shell thickness is greater than 0.2 nm and less than 20 nm, greater than 0.2 nm and less than 10 nm, greater than 0.2 nm and less than 5 nm, or greater than 0.2 nm and less than 2 nm.

[0033] The shell is bonded to the core by covalent bonds mainly via silicone and silicon moieties, and is either core-O-SiR1R2-O-, core-O-SiR(-O-)2, or core-O-Si(-O-)3, with core-O-SiR1R2-O- or core-O-SiR(-O-)2 being preferred. The core surface must contain OH- or Si-OH groups that react with the silicon moieties to form covalent bonds; for example, Si-OH groups react with the silicon moieties to form Si-O-Si covalent bonds.

[0034] The shell may be attached to the core by physical adsorption of the polyorganosiloxane without a covalent chemical bond, although this is not preferred.

[0035] In another aspect, there is provided a method for producing a nanosized soft polysiloxane core-shell abrasive, comprising the steps of: a. providing a dispersion of core abrasives having reactive groups on their surfaces; b. providing a shell-forming precursor; c. adding the shell-forming precursor to the dispersion of the core abrasive to form a polyorganosiloxane shell on the surface of the core abrasive; and d. covalently bonding the polyorganosiloxane shell to the periphery of the surface of the core abrasive, thereby forming a nanosized soft polysiloxane core-shell abrasive; A method is provided that includes:

[0036] The core of the nanosized soft polysiloxane core-shell abrasive includes, but is not limited to, an oxide, nitride, or mixture thereof of at least one element selected from the group consisting of Si, Al, Ce, La, Zr, and Ti. Preferably, the core of the nanosized soft polysiloxane core-shell abrasive is selected from the group consisting of colloidal silica, fumed silica, alumina, ceria, and combinations thereof.

[0037] The shell-forming precursor may comprise an organosilane, organosiloxane, or a mixture thereof. Examples include, but are not limited to, chlorosilane, organoalkoxysilane, oximatosilane, silanols (such as diphenylsilanediol), siloxane oligomers having hydrolyzable or Si-OH groups (such as C5 (dimethylsiloxane with 5 repeating units and Si-OH end groups)), and combinations thereof. Here, the shell-forming precursor contains and / or generates Si-OH groups during shell formation.

[0038] Organoalkoxysilanes include, but are not limited to, hydrolyzable organoalkoxysilanes. Preferably, the organoalkoxysilanes have at least one or at least two non-hydrolyzable groups. This results in silicone-like, silsesquioxane-like, or mixed polyorganosiloxanes. The non-hydrolyzable groups may be aliphatic, aromatic, or a mixture thereof, and may have one or more heteroatoms, such as O, S, N, and P, attached to or contained within the structure.

[0039] Additionally, the non-hydrolyzable groups of the organoalkoxysilane may be covalently bonded to an unlimited number of more than one organoalkoxysilane moiety, such as less than 10, less than 6, or less than 4 organoalkoxysilane moieties.

[0040] When such shell-forming precursors are used to form polyorganosiloxane shells, the polyorganosiloxane shells comprise polyorganosiloxane polymers additionally or primarily crosslinked by non-hydrolyzable groups; thus, the polyorganosiloxane shells comprise inorganic-organic hybrid polymers crosslinked by both inorganic polysiloxane crosslinkers using polysiloxane bonds and organic crosslinkers derived from the shell-forming precursors having multiple crosslinker moieties.

[0041] Organoalkoxysilanes include, but are not limited to, 3-(dimethoxymethylsilyl)propylamine, N-[3-(trimethoxysilyl)propyl]aniline, 3-glycidoxypropyltrimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-(triethoxysilyl)propylsuccinic anhydride, 1,2-bis(triethoxysilyl)ethane, bis(3-trimethoxysilylpropyl)amine, N,N'-bis(3-trimethoxysilylpropyl)urea, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0042] Additionally, reactants other than the shell-forming precursors may be provided in the present method, including, but not limited to, organic monomers, oligomers, or polymers. Preferably, the non-silane reactant reacts with at least a portion of the polyorganosiloxane to be covalently incorporated into the shell structure during shell formation. Examples include, but are not limited to, glycidol, 1,2-diaminoethane, 1,4-diaminobutane, ethylene glycol-1,2-diglycidyl ether, or poly(ethylene glycol) diglycidyl ether.

[0043] The catalyst and process conditions in the method of the present invention are preferably selected to promote the hydrolysis and condensation of organoalkoxysilanes, so that the formation of polyorganosiloxanes can occur effectively.

[0044] Therefore, the method for producing nanosized soft polysiloxane core-shell abrasives may further comprise, as a step subsequent to step a, b, or c, adding a catalyst to the dispersion of the core abrasive.

[0045] The catalyst may be an acid, a base, or a metal ion, including, for example, a polymeric catalyst such as an ion exchanger.

[0046] The base includes, but is not limited to, NH3, amines, amino alcohols, and quaternary ammonium compounds. Preferably, the base is NH3.

[0047] The acid may be an inorganic or organic acid. Preferably, the acid used is an acid such as nitric acid, which is also used in CMP processes.

[0048] Metal ions that are used and / or at least tolerated in CMP processes include Ce, Al, Ti, Zr, W, and Cu.

[0049] The method for producing the nanosized soft polysiloxane core-shell abrasive may further include a process condition in which the pH is 2-5 or 8-11.

[0050] In yet another aspect, the nanosized soft polysiloxane core-shell abrasive disclosed above; and a solvent selected from the group consisting of water, a water-soluble solvent, and combinations thereof; A CMP polishing composition is provided, comprising: The pH of the composition is 2 to 10, 2 to 6, 2 to 5, 2 to 4, or 2 to 3.

[0051] Water includes, but is not limited to, deionized (DI) water and distilled water, and water-soluble solvents are not limited to alcoholic organic solvents.

[0052] The CMP polishing composition optionally comprises: Organic and inorganic salts as colloid stabilizers; acid / base buffers; Biocides; oxidizing agents; catalyst; corrosion inhibitors; Organic polymers as erosion, dishing, and corrosion reducers, including but not limited to hydrophilic polymers; polymers having organic functional groups such as -OH, -NH, CN, ester, amide, halogen, ether, etc.; Inorganic polymers, such as single or mixed metal polymetalhydroxide clusters, polyanions, and polycations (especially those containing Al, Ce, Zr, Fe as metal ions); and Surface-active molecules / oligomers / polymers such as cationic, anionic, or nonionic surfactants; and polymers that attach either by physical adsorption, ionic bonding, or covalent bonding; It may include at least one of the following:

[0053] In another aspect, there is provided a method for CMP polishing a substrate having at least one surface comprising at least one material selected from the group consisting of metals, including but not limited to, tungsten, copper, ruthenium, cobalt, aluminum, and combinations thereof; metal alloys; dielectric materials, including but not limited to, silicon dioxide and / or silicon nitride; spin-on dielectrics (SoD); and spin-on carbon (SoC); using the above-described CMP polishing composition.

[0054] Silicon dioxide polished silicon oxide films can be chemical vapor deposited (CVD), plasma enhanced CVD (PECVD), high density deposition CVD (HDP), or spin-on silicon oxide films. DETAILED DESCRIPTION OF THE INVENTION

[0055] The present invention relates to chemical mechanical planarization (CMP) polishing compositions (also known as slurries or formulations), methods, and systems using soft polysiloxane core-shell abrasives, more specifically soft polysiloxane core-shell abrasives having an amino-functional polyorganosiloxane shell.

[0056] The CMP polishing compositions, methods, and systems using soft polysiloxane core-shell abrasives are particularly suitable for low defect CMP applications, using the CMP polishing compositions to polish substrates having at least one surface comprising at least one material selected from the group consisting of metals, including but not limited to, tungsten, copper, ruthenium, cobalt, aluminum, and combinations thereof; metal alloys; dielectric materials, including but not limited to, silicon dioxide and / or silicon nitride; spin-on dielectrics (SoD); and spin-on carbon (SoC).

[0057] Soft polysiloxane core-shell abrasives have a core containing a standard abrasive or particle, such as silica or ceria, and a covalently bonded shell made of a material that is chemically and mechanically different from the core. The shell has a lower elastic modulus (E-modulus) and exhibits plastic and / or viscoelastic properties, unlike the core, making it softer. Preferably, the shell is made of polyorganosiloxane.

[0058] The shell exhibits cationic, anionic, nonionic, or zwitterionic charges depending on the pH, or independent of the pH by having so-called permanent charge carriers such as tetraalkylammonium ions.

[0059] Soft polysiloxane core-shell abrasive particles have a zeta potential of 20 mV or greater or -20 mV or less at a given pH in water; if the polymer is sufficiently hydrophilic and contains enough hydrophilic nonionic moieties to ensure steric stabilization, it is possible for the particles to have a zeta potential approaching zero without affecting colloidal stability.

[0060] The shell has sufficient thickness and differing mechanical properties compared to the core to effectively mitigate the consequences of the impact of the abrasive on the surface to be planarized, while not being excessively thick so as not to reduce the desired high removal rate.

[0061] The shell thickness is greater than 0.2 nm and less than 20 nm, greater than 0.2 nm and less than 10 nm, greater than 0.2 nm and less than 5 nm, or greater than 0.2 nm and less than 2 nm.

[0062] Without wishing to be bound by theory, it is believed that the shell having silicone-like or silsesquioxane-like moieties alters the microtribological behavior of the abrasive, reducing the generation of defects, particularly scratches. The shell thickness is significantly greater than the monolayer of silanes known from the prior art.

[0063] Surprisingly and unexpectedly, the removal rate of the soft polysiloxane core-shell abrasive was increased, or at least not decreased, compared to the original unmodified abrasive or the conventionally modified (silanized) abrasive. This is counterintuitive and could not reasonably be expected, since soft surface modification of a hard abrasive would also mean that the particle would be less abrasive in the CMP process.

[0064] The present invention provides a core-shell abrasive for CMP processes that combines the highest removal rates with extremely low defectivity for the needs of microelectronics manufacturing at today's and future nodes.

[0065] The present invention can even be demonstrated by using fumed silica as the core of a soft polysiloxane core-shell abrasive. Fumed silica abrasives are known in the art to cause undesirably high defect levels in CMP processes. It can be shown that the defect levels of soft polysiloxane core-shell abrasives using fumed silica as the core are even lower than those of colloidal silica, which is known in the art to exhibit low defect levels.

[0066] Typically, silicone-like and silsesquioxane-like structures are hydrophobic and tend to be destabilized in aqueous colloidal dispersions. The present invention overcomes this problem by using hydrophilic and / or charge-carrying silicone moieties to stabilize soft polysiloxane core-shell abrasives or abrasive particles against settling or agglomeration.

[0067] In one aspect, nanosized soft polysiloxane core-shell abrasives are provided, wherein the core and shell of the nanosized soft polysiloxane core-shell abrasive comprise different materials having different chemical and mechanical properties, with the shell preferably being mechanically softer, e.g., having a lower modulus of elasticity; and the shell comprises a crosslinked polyorganosiloxane polymer, an entangled polyorganosiloxane polymer, or a mixture of crosslinked and entangled polyorganosiloxane polymers.

[0068] Abrasive core of the present invention The core of the soft polysiloxane core-shell abrasive of the present invention may be inorganic or an inorganic / organic hybrid. The core may have a surface modified by conventional techniques, for example, silane bonded to the surface. The core may have any shape, including, but not limited to, round, oval, elongated, or branched. The surface of the core may have any quality or condition, including, but not limited to, smooth, rough, protruding, or non-protruding.

[0069] The core may be of any composition and may have reactive groups around its surface that can react with the polyorganosiloxane shell to form covalent bonds. For example, the core may have reactive OH-groups on its surface that can covalently bond with the OH-groups of the polyorganosiloxane shell. Examples of such compositions include, but are not limited to, oxides and / or nitrides containing at least one of Si, Al, Ce, La, Zr, and Ti atoms.

[0070] Preferably, the core is made of SiO2 with Si-OH groups around the surface. The core can be produced by either a wet process (e.g., Stober method) or a thermal process (flame synthesis, vapor phase synthesis).

[0071] The core has a mean particle size (MPS) measured by dynamic light scattering (DLS) of less than 500 nm, less than 400 nm, less than 300 nm, or less than 200 nm, and greater than 2 nm, greater than 10 nm, greater than 15 nm, or greater than 25 nm.

[0072] Raw materials as shell-forming precursors for producing shells All shell-forming precursor materials contain organosilanes, organosiloxanes, or a mixture of the two, which form a shell when reacted with reactive groups around the surface of the core, covalently bonding the shell to the surface of the core.

[0073] Examples of shell-forming precursors include, but are not limited to, chlorosilanes, organoalkoxysilanes, oximatosilanes, silanols (e.g., diphenylsilanediol), or siloxane oligomers having hydrolyzable or Si-OH groups, such as C5 (dimethylsiloxane with 5 repeating units and Si-OH end groups). Generally, all precursors can contain and / or generate Si-OH groups under the conditions for shell formation.

[0074] Organoalkoxysilanes include, but are not limited to, hydrolyzable organoalkoxysilanes. Preferably, the hydrolyzable organoalkoxysilane has at least one, preferably two, non-hydrolyzable groups, making it silicone-like, silsesquioxane-like, or a mixture thereof. The non-hydrolyzable groups may be aliphatic, aromatic, or a mixture thereof, and may have one or more heteroatoms, such as O, S, N, and P, attached thereto or included in its structure.

[0075] Additionally, the non-hydrolyzable groups of the organoalkoxysilane may be covalently bonded to an unlimited number of more than one organoalkoxysilane moiety, such as less than 10, less than 6, and preferably less than 4 organoalkoxysilane moieties.

[0076] One example is the reaction product of 3-glycidoxypropyltrimethoxysilane with 3-aminopropylmethyldimethoxysilane. The epoxy and amino groups react to form an organic crosslinker, which connects two silane moieties with hydrolyzable alkoxy groups. Another example is the reaction product of hexamethylene diisocyanate with 3-aminopropyltrimethoxysilane. Both reactions yield silanes with two organoalkoxysilane moieties covalently linked by a single non-hydrolyzable group. Another example is the reaction product of 3-aminopropylmethyldimethoxysilane with 3-(triethoxysilyl)propylsuccinic anhydride. Commercially available bipodal silanes, such as 1,2-bis(triethoxysilyl)ethane, bis(3-trimethoxysilylpropyl)amine, or N,N'-bis(3-trimethoxysilylpropyl)urea, can also be used.

[0077] When such organoalkoxysilanes are used to form polyorganosiloxane shells, the polyorganosiloxane shells contain both inorganic polysiloxane crosslinkers that use polysiloxane bonds and organic crosslinkers, resulting in inorganic-organic hybrid polymers.

[0078] Preferably, at least more than 25 mol%, more than 50 mol%, preferably more than 75 mol% of the hydrolyzable organoalkoxysilanes have hydrophilic groups and / or charge-carrying groups.

[0079] For planarization of particularly soft materials, it is preferred that at least some of the non-hydrolyzable groups contain aromatic moieties, more preferably those aromatic moieties are bonded to the Si atom via an aliphatic spacer that may contain one or more heteroatoms such as O, S, N, and P.

[0080] Shell of the abrasive of the present invention The shell of the soft polysiloxane core-shell abrasives of the present invention comprises an inorganic-organic polymer or an organic polymer, preferably an inorganic-organic polymer, and most preferably a polyorganosiloxane polymer.

[0081] Importantly, whereas in simple silane surface modification of the prior art, the silanes are bonded to the surface of the core but do not essentially crosslink or polymerize with each other, in the present invention, modification with polymers such as polyorganosiloxane polymers involves crosslinking, entanglement, or polymerization between the polymers.

[0082] The shell has different mechanical properties than the core: preferably, the shell is softer than the core, e.g., has a lower modulus of elasticity, and has viscoelastic or plastic deformability under the conditions of the CMP process, unlike the core.

[0083] The polyorganosiloxane polymer in the shell contains a silsesquioxane moiety RSiO 1.5Silicon moieties having zero or one non-hydrolyzable group R: Si(—O—) or SiR(—O—) ; and combinations thereof, where R may be linear or cyclic alkyl or aryl, or a combination thereof, optionally containing heteroatoms such as O, S, N, and P, and R and R may each independently be aliphatic or aromatic groups, or a combination thereof, optionally containing heteroatoms such as O, S, N, and P.

[0084] Preferably, the polyorganosiloxane shell comprises greater than 50 mol%, greater than 75 mol%, greater than 85 mol%, 90 mol%, or 95 mol% of the silicone-like structure O—Si(RR)—O, where each R is independently an aliphatic and / or aromatic group and optionally has at least one heteroatom selected from the group consisting of S, N, O, and P.

[0085] Preferably, the polyorganosiloxane shell contains less than 20 mol%, less than 5 mol%, less than 2.5%, or 0% silicon moieties Si(—O—)4 having zero non-hydrolyzable groups, which function as crosslinkers.

[0086] The primary crosslinking species (crosslinkers) in the polyorganosiloxane polymer are silsesquioxane moieties, silicon moieties with zero non-hydrolyzable groups: Si(—O—)4, or a combination thereof. The crosslinkers may be present before or generated during the formation of the polyorganosiloxane shell.

[0087] The polyorganosiloxane shell comprises crosslinked, entangled, or mixtures thereof polyorganosiloxane polymers. The polyorganosiloxane shell may have loose ends or may be fully bonded to the core surface.

[0088] The polyorganosiloxane shell is preferably covalently bonded to the core surface by Si-O-linkers.

[0089] The polyorganosiloxane shell comprises a crosslinked, entangled, or mixture thereof polyorganosiloxane polymer, and the crosslinker is an inorganic polysiloxane crosslinker using polysiloxane bonds. The polyorganosiloxane polymer may be partially crosslinked, in which case dangling ends of the polymer may remain with end groups such as polymer-O-SiR1R2-OH or polymer-O-SiR(OH)2. The polyorganosiloxane polymer may also be completely uncrosslinked, in which case the dangling ends are merely physically entangled with each other.

[0090] The polyorganosiloxane polymer may additionally or solely be crosslinked by organic crosslinkers, which may be short- or long-chain alkyl or aryl groups as defined above, covalently bonded to at least two silicon moieties.

[0091] Furthermore, the polyorganosiloxane shell comprises polyorganosiloxane polymers additionally or primarily crosslinked by non-hydrolyzable groups, and thus the polyorganosiloxane shell comprises an inorganic-organic hybrid polymer crosslinked to both inorganic polysiloxane crosslinkers using polysiloxane bonds and organic crosslinkers.

[0092] Optionally, the polyorganosiloxane shell includes hydrophilic groups such as nonionic hydrophilic groups and / or organic C-OH groups, either as part of the polyorganosiloxane shell or as the sole component.

[0093] The polyorganosiloxane shell may contain NR1R2R3 and / or NR1R2R3R4 groups, where each R is independently H, an organic aliphatic group, and / or an aromatic group.

[0094] The polyorganosiloxane shell contains charge carriers and other hydrophilic moieties to enhance the compatibility and colloidal stability of the nanosized soft polysiloxane core-shell abrasive particles with water or water-containing solvents.

[0095] The shell has mechanical properties that differ from those of the core by at least 10% or more, preferably by 20% or more, and most preferably by 50% or more, as measured by methods such as atomic force microscope (AFM) nanoindentation.

[0096] The soft polysiloxane core-shell abrasive has an amino-functional polyorganosiloxane shell that is less than 20 nm, less than 10 nm, less than 5 nm, or less than 2 nm in thickness, and greater than 0.2 nm.

[0097] The shell is bonded to the core by a covalent bond mainly via silicon moieties, and is either core-O-SiR1R2-O-, core-O-SiR(-O-)2, or core-O-Si(-O-)3, with core-O-SiR1R2-O- or core-O-SiR(-O-)2 being preferred. The core surface must contain OH- or Si-OH groups that react with the silicon moieties to form covalent bonds; for example, Si-OH groups react with the silicon moieties to form Si-O-Si covalent bonds.

[0098] The shell may be attached to the core by physical adsorption of the polyorganosiloxane without a covalent chemical bond, although this is not preferred.

[0099] Soft polysiloxane core-shell abrasive The soft polysiloxane core-shell abrasive is hydrophilic and optionally contains charge carriers, which are either cationic, anionic, or zwitterionic at a given pH.

[0100] The soft polysiloxane core-shell abrasive is colloidally stable when dispersed in water or a water-containing solvent due to charge carriers or other hydrophilic groups (such as -OH or ethers). Preferably, the soft polysiloxane core-shell abrasive is colloidally stable up to 40% by weight solids.

[0101] The soft polysiloxane core-shell abrasives of the present invention may have a narrow or broad particle size distribution and may be unimodal or polymodal. The shape of the soft polysiloxane core-shell abrasive may be any shape, including, but not limited to, round, oval, elongated, irregular, or branched, or a combination thereof. The surface of the soft polysiloxane core-shell abrasive may be smooth, rough, protruding, or non-protruding.

[0102] The soft polysiloxane core-shell abrasives of the present invention are compatible with oxidizers, catalysts, surfactants, inhibitors, topo additives, and the like, typical CMP additives, even in concentrated CMP slurries, and are hydrophilic, providing good wetting of the surface being planarized.

[0103] Soft polysiloxane core-shell abrasives typically have an MPS measured by dynamic light scattering (DLS) in the range of 5 to 500 nm, 10 to 400 nm, 15 to 300 nm, 20 to 200 nm, or 30 to 150 nm.

[0104] Process for producing the soft polysiloxane core-shell abrasive of the present invention The process for making soft polysiloxane core-shell abrasives may begin with a dispersion of the core abrasive in a solvent, optionally including water.

[0105] The shell-forming precursor is added to the dispersion of core abrasive at a predetermined pH under stirring (acidic and alkaline processes are possible).

[0106] Preferably, the shell-forming precursor is a monomer, but may also comprise a dimer, trimer, oligomer, or polymer that has been preformed in a separate process step, which may include the addition of water to the precursor and, optionally, the addition of a catalyst.

[0107] The reaction medium includes any additional catalysts and reactants to promote shell formation. The pH is adjusted so that the shell is formed and the polymer reacts with the surface reactive groups of the core. Preferably, the pH is maintained below 5 or above 8, for example, between 2 and 5 or between 8 and 11.

[0108] Downstream processing includes at least one purification step to remove soluble and / or insoluble by-products of the reaction. Preferably, after the reaction, volatile organic reactants and by-products are removed from the dispersion and the solvent is replaced with water.

[0109] A preferred process for producing soft polysiloxane core-shell abrasives is to provide a dispersion of nanoparticles in a water-containing solvent with a pH of 2-3 or 10-11, and slowly add the shell-forming precursor dropwise under vigorous stirring and pH control. After a further 1-4 hours of reaction time, the volatile by-products are removed by distillation and replaced with water while maintaining a constant pH. The pH may then be adjusted by adding an acid or base, or by exposing the dispersion to an ion exchange resin. The dispersion may be further purified by centrifugation / redispersion or membrane filtration.

[0110] The catalyst may be an acid, a base, or a metal ion, such as a polymeric catalyst, for example an ion exchanger.

[0111] The base includes, but is not limited to, NH3, amines, amino alcohols, and quaternary ammonium compounds. Preferably, the base is NH3.

[0112] The acid may be an inorganic or organic acid. Preferably, the acid used is an acid such as nitric acid, which is also used in CMP processes.

[0113] Metal ions that are used and / or at least tolerated in CMP processes include Ce, Al, Ti, Zr, W, and Cu.

[0114] Solvents include, but are not limited to, water; alcohol (preferred); methanol; ethanol; propanol; and other common polar protic and aprotic solvents such as ketones, esters, ethers, and acetamides.

[0115] Preferably, the solvent is one that is at least partially compatible with water and does not react with the amino groups or other chemical groups of the polyorganosiloxane.

[0116] In another aspect, there is provided a method for producing a nanosized soft polysiloxane core-shell abrasive, comprising the steps of: a. providing a dispersion of core abrasives, the core abrasives having reactive groups around their surfaces; b. providing a shell-forming precursor; c. adding the shell-forming precursor to the dispersion of the core abrasive to form a polyorganosiloxane shell on the surface of the core abrasive; and d. covalently bonding the polyorganosiloxane shell to the periphery of the surface of the core abrasive, thereby forming a nanosized soft polysiloxane core-shell abrasive; A method is provided which includes:

[0117] The shell-forming precursor includes an organosilane, an organosiloxane, or a mixture thereof. Examples of the shell-forming precursor include, but are not limited to, chlorosilanes, alkoxysilanes, oximatosilanes, silanols (such as diphenylsilanediol), siloxane oligomers having hydrolyzable groups or Si-OH groups (such as C5 (dimethylsiloxane with 5 repeating units and Si-OH end groups)), and combinations thereof. Here, the shell-forming precursor contains or generates Si-OH groups during shell formation.

[0118] The organosiloxane includes, but is not limited to, hydrolyzable organoalkoxysilanes. Preferably, the organoalkoxysilane has at least one, preferably two, non-hydrolyzable groups. This results in silicone-like, silsesquioxane-like, or mixed polyorganosiloxanes. The non-hydrolyzable groups can be aliphatic, aromatic, or a mixture thereof, and can have one or more heteroatoms, such as O, S, N, and P, attached to or included in the structure.

[0119] Additionally, the non-hydrolyzable groups of the organoalkoxysilane may be covalently bonded to an unlimited number of more than one organoalkoxysilane moiety, such as less than 10, less than 6, and preferably less than 4 organoalkoxysilane moieties.

[0120] One example is the reaction product of 3-lycidoxypropyltrimethoxysilane with 3-aminopropylmethyldimethoxysilane. The epoxy and amino groups react to form an organic crosslinker, which connects two silane moieties bearing hydrolyzable alkoxy groups. Another example is the reaction product of hexamethylene diisocyanate with two moles of 3-aminopropyltrimethoxysilane. Both reactions yield silanes in which two organoalkoxysilane moieties are covalently linked by a single non-hydrolyzable group. Another example is the reaction product of 3-aminopropylmethyldimethoxysilane with 3-(triethoxysilyl)propylsuccinic anhydride. Commercially available bipodal silanes, such as 1,2-bis(triethoxysilyl)ethane, bis(3-trimethoxysilylpropyl)amine, or N,N'-bis(3-trimethoxysilylpropyl)urea, can also be used.

[0121] When such organosiloxanes are used to form polyorganosiloxane shells, the polyorganosiloxane shells are simultaneously crosslinked by both polysiloxane bonds and organic crosslinkers, resulting in inorganic-organic hybrid polymers.

[0122] Organosiloxanes include, but are not limited to, 3-(dimethoxymethylsilyl)propylamine, N-[3-(trimethoxysilyl)propyl]aniline, 3-glycidoxypropyltrimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-(triethoxysilyl)propylsuccinic anhydride, 1,2-bis(triethoxysilyl)ethane, bis(3-trimethoxysilylpropyl)amine, N,N'-bis(3-trimethoxysilylpropyl)urea, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0123] Additionally, non-organosiloxane reactants may be provided in the present method, including, but not limited to, organic monomers, oligomers, or polymers. Preferably, the non-silane reactants react with at least a portion of the polyorganosiloxane and become covalently incorporated into the shell structure during shell formation.

[0124] Examples of such reactants include, but are not limited to, glycidol, 1,2-diaminoethane, 1,4-diaminobutane, ethylene glycol-1,2-diglycidyl ether, or poly(ethylene glycol) diglycidyl ether.

[0125] The process conditions in the method of the present invention are preferably selected to promote the hydrolysis and condensation of silanes, thereby effectively forming polyorganosiloxanes. This can be achieved by any method known in the art, preferably by selecting an appropriate pH or introducing a catalyst. To eliminate the need for an additional catalyst, a pH of 2 to 5 or a pH of 8 to 11 is preferred.

[0126] In yet another aspect, the nanosized soft polysiloxane core-shell abrasive disclosed above; and a solvent selected from the group consisting of water, a water-soluble solvent, and combinations thereof; and a pH of 2 to 10, 2 to 8, 2 to 6, 2 to 5, 2 to 4, or 2 to 3.

[0127] Water includes, but is not limited to, deionized (DI) water and distilled water. Water-soluble solvents are not limited to alcoholic organic solvents.

[0128] The CMP polishing composition optionally comprises: Organic and inorganic salts as colloid stabilizers; acid / base buffers; Biocides; oxidizing agents; catalyst; corrosion inhibitors; Organic polymers as erosion, dishing, and corrosion reducers, including but not limited to hydrophilic polymers; polymers having organic functional groups such as -OH, -NH, CN, ester, amide, halogen, ether, etc.; Inorganic polymers, such as single or mixed metal polymetal hydroxide clusters, polyanions, and polycations (especially those containing Al, Ce, Zr, Fe as metal ions); and Surface-active molecules / oligomers / polymers such as cationic, anionic, or nonionic surfactants; and polymers that attach either by physical adsorption, ionic bonding, or covalent bonding; It may include at least one of the following:

[0129] In another aspect, there is provided a method of chemical-mechanical polishing (CMP) a substrate having at least one surface comprising at least one material selected from the group consisting of: metals, including but not limited to, tungsten, copper, ruthenium, cobalt, aluminum, and combinations thereof; metal alloys; dielectric materials, including but not limited to, silicon dioxide and / or silicon nitride; spin-on dielectrics (SoD); and spin-on carbon (SoC); using the above-described CMP polishing composition.

[0130] The silicon dioxide film can be a chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), high density deposition CVD (HDP), or spin-on silicon oxide film. [Example]

[0131] CMP Methodology In the examples presented below, CMP experiments were carried out using the procedures and experimental conditions set out below. Glossary Parameters general

[0132] A: Angstrom - unit of length

[0133] BP: Back pressure, unit psi

[0134] CMP: Chemical mechanical planarization = chemical mechanical polishing

[0135] CS: Carrier Speed

[0136] DF: Downforce: Pressure applied during CMP, unit: psi

[0137] min:minutes

[0138] ml: milliliter

[0139] mV: millivolt

[0140] psi: pounds per square inch

[0141] PS: Polishing tool platen rotation speed, in rpm (revolutions per minute)

[0142] SF: composition flow rate, ml / min

[0143] wt.%: mass% (of the listed components)

[0144] TEOS: Tetraethyl orthosilicate

[0145] SOC: Spin-on carbon

[0146] SoD: Spin-on dielectric

[0147] W: TEOS selectivity: (W removal rate) / (TEOS removal rate)

[0148] HDP: High density plasma deposition TEOS

[0149] TEOS or HDP removal rate: The removal rate of TEOS or HDP measured at a given down pressure.

[0150] Synthesis of soft polysiloxane core-shell abrasives 1. Synthesis of soft polysiloxane core-shell structured abrasives using fumed silica as core particles Example 1 In a 1000 ml four-neck flask equipped with a condenser and a KPG stirrer, 397 g of a dispersion of fumed silica powder in water (806.3 mmol SiO2; Brunauer-Emmett-Teller (BET) specific surface area approximately 300 m) was added. 2 / g; trade name Aerosil (registered trademark) 300; manufactured by Evonik) was adjusted to pH 2 with nitric acid while vigorously stirring.

[0151] In a 250 ml round-bottom flask, concentrated nitric acid (65 wt %; 4.87 ml; 69.88 mmol) was added to methanol (120.42 ml; 2968.92 mmol) under magnetic stirring, followed by 3-(dimethoxymethylsilyl)propylamine (3.80 g; 23.29 mmol), and this mixture was quickly added to the vigorously stirred fumed silica dispersion.

[0152] After the addition, the temperature of the fumed silica dispersion was increased from room temperature to 30° C., after which the dispersion was allowed to cool. After 1 hour, the temperature was increased to 70° C. and held for 2 hours under continuous stirring.

[0153] The reaction mixture was transferred to a round-bottom flask and the volatile organic solvent was removed and replaced with deionized water to give a soft core-shell silica solids content of approximately 20 wt %.

[0154] Yield 293.3 g; solids 18.0 wt%; pH 1.15; MPS 66.6 nm (measured by DLS); polydispersity index (PDI) 0.157; zeta potential 31.1 mV

[0155] Example 2 In a 1000 ml four-neck flask equipped with a condenser and a KPG stirrer, 318.6 g of a dispersion of fumed silica powder in water (915.4 mmol SiO; BET specific surface area approximately 50 m 2 / g; trade name Aerosil (registered trademark) OX50; manufactured by Evonik) was adjusted to pH 2 with nitric acid while vigorously stirring.

[0156] In a 250 ml round-bottom flask, concentrated nitric acid (65 wt%; 5.45 ml; 79.20 mmol) was added to methanol (102.57 ml; 2529.03 mmol) under magnetic stirring, followed by 3-(dimethoxymethylsilyl)propylamine (4.54 ml; 26.40 mmol), and this mixture was quickly added to the vigorously stirred fumed silica dispersion.

[0157] After the addition, the temperature of the fumed silica dispersion was increased from room temperature to 30° C., after which the dispersion was allowed to cool. After 1 hour, the temperature was increased to 70° C. and held for 2 hours under continuous stirring.

[0158] The reaction mixture was transferred to a round-bottom flask and the volatile organic solvent was removed and replaced with deionized water to give a soft core-shell silica solids content of approximately 20 wt %.

[0159] Yield 269.6 g; Solids 21.9%; MPS 237.7 nm (measured by DLS); PDI 0.142; Zeta potential 49.2 mV

[0160] Example 3 In a 2000 ml four-neck flask equipped with a condenser and a KPG stirrer, 1150.00 g of fumed silica dispersion (supplied by Evonik as dispersed product Aerodisp® W7622; 3827.97 mmol SiO2; ion-exchanged until the pH was less than 4.5) was adjusted to pH 3 with nitric acid.

[0161] In a 250 mL round-bottom flask, concentrated nitric acid (65 wt%; 15.41 mL; 224.06 mmol) was added to methanol (170.28 mL; 4198.29 mmol) under magnetic stirring, followed by 3-(dimethoxymethylsilyl)propylamine (11.9 mL; 69.19 mmol), and this mixture was quickly added to the vigorously stirred fumed silica dispersion.

[0162] After the addition, the temperature of the silica dispersion was increased from room temperature to 27°C, after which the dispersion was allowed to cool. After 1 hour, the temperature was increased to 70°C and maintained under continuous stirring for 2 hours.

[0163] The reaction mixture was transferred to a round-bottom flask, and the volatile organic solvent was removed and replaced with deionized water to give a soft core-shell silica solids content of approximately 20 wt %. The product was pressure filtered through a 2 μm filter.

[0164] Yield 1132.6 g; Solids 21.6 wt%; MPS 117.0 nm (measured by DLS); PDI 0.169; Zeta potential 32.0 mV

[0165] 2. Comparative Example Synthesis of Abrasives Using Fumed Silica as the Core Particle but Without a Soft Polysiloxane Core-Shell Structure Comparative Example 1 In a 1000 ml four-neck flask equipped with a condenser and a KPG stirrer, 399 g of a dispersion of fumed silica powder in water (806.3 mmol SiO2; BET specific surface area approximately 300 m) was added. 2 / g; trade name Aerosil (registered trademark) 300; manufactured by Evonik) was adjusted to pH 2 with nitric acid while vigorously stirring.

[0166] In a 250 mL round-bottom flask, concentrated nitric acid (65 wt%; 0.304 mL; 4.36 mmol) was added to methanol (30.1 mL; 742.23 mmol) under magnetic stirring, followed by 3-(dimethoxymethylsilyl)propylamine (0.237 g; 1.455 mmol), and this mixture was quickly added to the vigorously stirred fumed silica dispersion.

[0167] After the addition, the temperature of the fumed silica dispersion was increased from room temperature to 22° C., after which the dispersion was allowed to cool. After 1 hour, the temperature was increased to 70° C. and held for 2 hours under continuous stirring.

[0168] The reaction mixture was transferred to a round-bottom flask and the volatile organic solvent was removed and replaced with deionized water to give a core-shell silica solids content of approximately 20 wt %.

[0169] Yield 282.1 g; solids 18.5 wt%; pH 1.9; MPS 158.3 nm (measured by DLS); PDI 0.147; zeta potential 27.3 mV

[0170] Comparative Example 2 In a 1000 ml four-neck flask equipped with a condenser and a KPG stirrer, 321.9 g of a dispersion of fumed silica powder in water (921.1 mmol SiO2; BET specific surface area approximately 50 m) was added. 2 / g; trade name Aerosil (registered trademark) OX50; manufactured by Evonik) was adjusted to pH 2 with nitric acid while vigorously stirring.

[0171] In a 250 mL round-bottom flask, concentrated nitric acid (65 wt%; 0.059 mL; 0.856 mmol) was added to methanol (24.42 mL; 602.15 mmol) under magnetic stirring, followed by 3-(dimethoxymethylsilyl)propylamine (4.54 mL; 0.2855 mmol), and this mixture was quickly added to the vigorously stirred fumed silica dispersion.

[0172] After the addition, the temperature of the fumed silica dispersion was increased from room temperature to 21° C., after which the dispersion was allowed to cool. After 1 hour, the temperature was increased to 70° C. and held for 2 hours under continuous stirring.

[0173] The reaction mixture was transferred to a round-bottom flask and the volatile organic solvent was removed and replaced with deionized water to give a core-shell silica solids content of approximately 20 wt %.

[0174] Yield 260.8 g; solids 21.2 wt%; pH 1.9; MPS 231.2 nm (measured by DLS); PDI 0.148; zeta potential 31.4 mV

[0175] Comparative Example 3 In a 2000 ml four-neck flask equipped with a condenser and a KPG stirrer, 1150.00 g of fumed silica dispersion (supplied by Evonik as dispersed product Aerodisp® W7622; 3827.97 mmol SiO2; ion-exchanged until the pH was less than 4) was adjusted to pH 3 with nitric acid.

[0176] In a 250 mL round-bottom flask, concentrated nitric acid (65 wt%; 1.54 mL; 22.41 mmol) was added to methanol (17.03 mL; 419.83 mmol) under magnetic stirring, followed by 3-(dimethoxymethylsilyl)propylamine (1.19 mL; 6.92 mmol), and this mixture was quickly added to the vigorously stirred fumed silica dispersion.

[0177] After the addition, the temperature of the silica dispersion was increased from room temperature to 20° C., after which the dispersion was allowed to cool. After 1 hour, the temperature was increased to 70° C. and maintained for 2 hours under continuous stirring.

[0178] The reaction mixture was transferred to a round-bottom flask and the volatile organic solvent was removed and replaced with deionized water to give a core-shell silica solids content of approximately 20 wt %.

[0179] The product was pressure filtered through a 2 μm filter.

[0180] Yield 1139.1 g; Solids 20.9 wt%; MPS 108.0 nm (measured by DLS); PDI 0.159; Zeta potential 23.3 mV

[0181] 3. Synthesis of soft polysiloxane core-shell structured abrasives using elongated silica nanoparticles as core particles The synthesis of elongated silica nanoparticles is disclosed in WO 2022 / 226471 A1, the disclosure of which is incorporated herein by reference.

[0182] Example 4 Synthesis of an abrasive having an amino-functional soft polysiloxane core-shell structure A dispersion of elongated nanoparticles (384.60 g; 0.42 mol SiO2) previously ion-exchanged with Amberlite IRN-150 was prepared in a 1000 ml four-neck round-bottom flask equipped with a magnetic stirrer (particle size 90.29 (DLS); PDI 0.044; pH 4.0).

[0183] In a 100 mL round-bottom flask, 65% nitric acid (2.52 mL; 36.09 mmol) and methanol (41.37 mL; 1.02 mol) were mixed. 3-[Dimethoxy(methyl)silyl]propylamine (2.07 mL; 12.03 mmol) was added, and the mixture was manually shaken for 5 seconds before being quickly added to the vigorously stirred dispersion of SiO particles. Stirring was continued for 1 hour at room temperature and 2 hours at 70 °C.

[0184] 200 ml of deionized water was added to the reaction mixture, and the resulting dispersion was concentrated on a rotary evaporator until the solid content was about 20% by weight.

[0185] Yield 107.8 g; solids 20.3%; pH=1.03; mean particle size 87.9 nm (by DLS); PDI 0.045; zeta potential 46.7 mV.

[0186] Example 5 Synthesis of an abrasive having a soft polysiloxane shell containing an aromatic amine A dispersion of ion-exchanged elongated silica nanoparticles (MPS 87 nm (measured by DLS); pH 4.1; 232.98 g / 665.78 mmol SiO2) was transferred to a 500 ml four-neck flask equipped with a condenser and a KPG stirrer. The dispersion was heated to 70 °C with stirring.

[0187] The two solutions were added simultaneously within 1 h via two pumps equipped with tubing while the dispersion was being vigorously stirred. The two reactant streams were mixed by connecting the tubing with a Y-connector just before adding them to the dispersion.

[0188] Solution A was prepared by mixing N-[3-(trimethoxysilyl)propyl]aniline (3.69 ml; 14.40 mmol) and methanol (29.50 ml; 727.40 mmol).

[0189] Solution B was prepared by mixing nitric acid (65 wt %; 1.09 ml; 15.84 mmol) and methanol (32.10 ml; 791.57 mmol).

[0190] After addition of the reactant solution, the dispersion was stirred at 70° C. for an additional 2 hours and then allowed to cool to room temperature.

[0191] 200 ml of deionized water was added, and the dispersion was concentrated on a rotary evaporator until the solid content was about 20 wt %. The dispersion was filtered through a 5 μm syringe filter and then through a 1 μm syringe filter.

[0192] Yield 197.19 g (dispersion); solids 21.50 wt%; pH=1.81; MPS 89.6 nm (by DLS); PDI 0.026.

[0193] Example 6 Synthesis of abrasive with soft polysiloxane nonionic core-shell structure In a 1000 ml four-neck round-bottom flask equipped with a magnetic stirrer, a dispersion of elongated SiO2 nanoparticles in water (83,217 mmol; 60.02 g; SiO2 content 8.3 wt%; mean particle size 48.3 nm as measured by DLS) was prepared by ion exchange with Amberlite IRN-150 and then adjusted to pH 3 with HNO3.

[0194] In a 100 mL round-bottom flask, 65% nitric acid (2.18 mmol; 0.21 g; 0.149 mL) and methanol (1.900 mmol; 0.023 equiv; 3.740 g; 0.077 mL) were mixed. 3-Glycidoxypropyltrimethoxysilane (1.80 mmol; 0.425 g; 0.448 mL) was added, and the mixture was manually shaken for 5 seconds before being rapidly added to the vigorously stirred dispersion of SiO particles. Stirring was continued for 1 hour at room temperature and 2 hours at 70 °C.

[0195] 500 ml of deionized water was added to the reaction mixture, and the resulting dispersion was concentrated on a rotary evaporator until the solid content was about 20% by weight.

[0196] Yield 25.8 g; solids 19.8%; pH 2.73; mean particle size 49.5 nm (by DLS); PDI 0.039.

[0197] Example 7 Synthesis of abrasive with soft polysiloxane nonionic core-shell structure A dispersion of elongated SiO2 nanoparticles in water (166.426 mmol; 57.14 g; SiO2 content 17.5 wt%; mean particle size measured by DLS 79.5 nm; pH 9.6) was prepared in a 1000 ml four-neck round-bottom flask equipped with a magnetic stirrer.

[0198] Deionized water was added under stirring to adjust the concentration of SiO2 nanoparticles to 10 wt %. The dispersion was heated to 70 °C under continuous stirring.

[0199] Within 12 hours, a solution of 3-glycidoxypropyltrimethoxysilane (2.40 mmol; 0.568 g; 0.60 ml) in ethanol (0.11 mol; 5.112 g; 6.47 ml) was added dropwise with continuous stirring of the reaction mixture. During the reaction, the pH was adjusted to above pH 9 by adding aqueous ammonia as needed.

[0200] 500 ml of 0.05 mol / l aqueous ammonia was added to the reaction mixture in two portions, and the dispersion obtained each time was concentrated using a rotary evaporator to a solid content of about 20 wt %.

[0201] Yield 51.3 g; solids 19.4%; pH 8.9; mean particle size 82.2 nm (by DLS); PDI 0.065.

[0202] Example 8 Synthesis of abrasive with soft polysiloxane nonionic core-shell structure A dispersion of elongated SiO2 nanoparticles in water (166.426 mmol; 57.14 g; SiO2 content 17.5 wt%; mean particle size measured by DLS 79.5 nm; pH 9.6) was prepared in a 1000 ml four-neck round-bottom flask equipped with a magnetic stirrer.

[0203] Deionized water was added under stirring to adjust the concentration of SiO2 nanoparticles to 10 wt %. The dispersion was heated to 70 °C under continuous stirring.

[0204] Within 12 hours, a solution of 3-glycidoxypropylmethyldimethoxysilane (2.40 mmol; 0.529 g) in ethanol (0.11 mol; 5.112 g; 6.47 ml) was added dropwise with continuous stirring of the reaction mixture. During the reaction, the pH was adjusted to above pH 9 by adding aqueous ammonia as needed.

[0205] 500 ml of 0.05 mol / l aqueous ammonia was added to the reaction mixture in two portions, and the dispersion obtained each time was concentrated using a rotary evaporator to a solid content of about 20 wt %.

[0206] Yield 50.8 g; solids 19.7%; pH 9.0; mean particle size 80.7 nm (by DLS); PDI 0.061.

[0207] Example 9 Abrasive with a Soft Polysiloxane Anionic Carboxy-Functional Core-Shell Structure A dispersion of elongated SiO2 nanoparticles in water (166.426 mmol; 57.14 g; SiO2 content 17.5 wt%; mean particle size measured by DLS 79.5 nm; pH 9.6) was prepared in a 1000 ml four-neck round-bottom flask equipped with a magnetic stirrer.

[0208] Deionized water was added under stirring to adjust the concentration of SiO2 nanoparticles to 10 wt %. The dispersion was heated to 70 °C under continuous stirring.

[0209] Within 12 hours, a solution of 3-(triethoxysilyl)propylsuccinic anhydride (2.40 mmol; 0.731 g) in ethanol (0.11 mol; 5.112 g; 6.47 ml) was added dropwise with continuous stirring of the reaction mixture. During the reaction, the pH was adjusted and maintained above pH 9 by adding aqueous ammonia.

[0210] 500 ml of 0.05 mol / l aqueous ammonia was added to the reaction mixture in two portions, and the dispersion obtained each time was concentrated using a rotary evaporator to a solid content of about 20 wt %.

[0211] Yield 50.9 g; solids 19.9%; pH 9.1; mean particle size 81.9 nm (by DLS); PDI 0.071.

[0212] 4. Comparative Example: Synthesis of an abrasive using elongated nanoparticles surface-modified with aminosilane as the core Comparative Example 4 A dispersion of elongated nanoparticles (374.20 g; 0.409 mol SiO2) previously ion-exchanged with Amberlite IRN-150 was prepared in a 1000 ml four-neck round-bottom flask equipped with a magnetic stirrer (particle size 90.29 nm by DLS; PDI 0.044; pH 4.1).

[0213] In a 100 ml round-bottom flask, 65% nitric acid (0.0265 ml; 0.38 mmol) and methanol (4.14 ml; 0.1 mol) were mixed. 3-[Dimethoxy(methyl)silyl]propylamine (0.127 ml; 0.7365 mmol) was added, and the mixture was shaken manually for 5 seconds before being added quickly to the vigorously stirred dispersion of SiO particles, which was continued for 1 hour at room temperature and 2 hours at 70 °C.

[0214] 200 ml of deionized water was added to the reaction mixture, and the resulting dispersion was concentrated on a rotary evaporator until the solid content was about 20% by weight.

[0215] Yield 121.9 g; solids 20.1%; pH=1.73; mean particle size 84.7 nm (by DLS); PDI 0.048; zeta potential 31.1 mV. Comparative Example 5 A dispersion of elongated nanoparticles (357.80 g; 0.409 mol SiO2) previously ion-exchanged with Amberlite IRN-150 was prepared in a 1000 ml four-neck round-bottom flask equipped with a magnetic stirrer (particle size: 45.29 nm by DLS; PDI 0.034; pH 4.3).

[0216] In a 100 mL round-bottom flask, 65% nitric acid (0.0265 mL; 0.38 mmol) and methanol (4.14 mL; 0.1 mol) were mixed. 3-[Dimethoxy(methyl)silyl]propylamine (0.127 mL; 0.7365 mmol) was added, and the mixture was manually shaken for 5 seconds before being quickly added to the vigorously stirred dispersion of SiO particles. Stirring was continued for 1 hour at room temperature and 2 hours at 70 °C.

[0217] 200 ml of deionized water was added to the reaction mixture, and the resulting dispersion was concentrated on a rotary evaporator until the solid content was about 20% by weight.

[0218] Yield 120.8 g; solids 19.9%; pH=1.84; average particle size 47.9 nm (by DLS); PDI 0.038; zeta potential 29.8 mV.

[0219] CMP polishing experiment CMP Tools 300 mm diameter wafers with suitable layers were polished using a Reflexeon LK-300 mm CMP tool, IC-1000 polishing pads (Dow Chemicals), and AK45 conditioner (Seasol) at a downforce of 3 psi and a slurry flow rate of 200 ml / min. The removal rates of W, TEOS, and SOC spin-on carbon films were measured using a four-point probe (RS-100, KLA Tencor) and ellipsometry (Spectra FX100, KLA Tencor). Defect counts were obtained using an SP2 Surfscan tool (KLA Tencor).

[0220] wafer Polishing experiments were performed using W and PECVD TEOS wafers. These blanket wafers were purchased from Silicon Valley Microelectronics (2985 Kifer Rd., Santa Clara, CA 95051).

[0221] CMP slurries are disclosed in US Pat. No. 11,111,435 (B2), which is incorporated herein by reference in its entirety.

[0222] Example 10 CMP using a soft polysiloxane core-shell structured abrasive having fumed silica as the core In this example, the polishing rates (removal rates) and the number of defects on tungsten (W) and TEOS layers were evaluated for CMP polishing compositions containing different abrasives using fumed silica as core particles.

[0223] Each CMP polishing composition contained 0.1 wt % of the abrasive particles shown in Table 1. Before polishing testing, the CMP polishing compositions were filtered (Pall CMP StarKleen Capsule, filter size 0.3 μm).

[0224] The abrasives, removal rates (RR), and number of defects are shown in Table 1. [Table 1]

[0225] The CMP performance of the tested abrasives shows clear trends in terms of removal rate and defectivity. The abrasives with the soft core-shell structure of the present invention exhibit better selectivity, with a favorably high W removal rate and a low TEOS removal rate, and more importantly, significantly reduced defectivity.

[0226] Example 11 CMP using an abrasive having elongated nanoparticles as core particles In this example, compositions containing different abrasives were evaluated for polishing rate and defectivity of tungsten and TEOS layers. Each polishing composition contained 0.1 wt. % abrasive particles.

[0227] Composition 1A contained the aminosilane-modified abrasive of Comparative Example 4, Composition 1B contained the abrasive having an amino-functional soft polysiloxane core-shell structure of Example 4, and Composition 1C contained the aminosilane-modified abrasive of Comparative Example 5. All compositions were filtered (Pall CMP StarKleen Capsule, filter size 0.3 μm) before polishing testing.

[0228] The results are shown in Table 2. [Table 2]

[0229] Composition 1B, which uses the amino-functional soft polysiloxane core-shell structure prepared in Example 4, surprisingly demonstrates a significantly reduced number of defects as well as a slightly higher removal rate than the aminosilane-modified abrasive without the silicone-like shell, despite having a silicone-like shell.

[0230] The above-listed embodiments of the present invention, including the working examples, are only examples of many that may be practiced from the present invention. It is contemplated that many other configurations may be used in the process and that the materials used in the process may be selected from many other materials than those specifically disclosed.

Claims

1. A nanosized soft polysiloxane core-shell abrasive comprising a core and a shell, the core and the shell comprise different materials having different chemical and mechanical properties, preferably the shell having a lower E-modulus and being mechanically softer than the core; the core comprises reactive groups around the surface of the core; the shell comprises a crosslinked polyorganosiloxane polymer, an entangled polyorganosiloxane polymer, or a combination of a crosslinked polyorganosiloxane polymer and an entangled polyorganosiloxane polymer; Abrasive.

2. 2. The nanosized soft polysiloxane core-shell abrasive according to claim 1, wherein the reactive group is selected from the group consisting of an OH-group, an Si-OH group, and a combination thereof, preferably an Si-OH group.

3. 3. The nanosized soft polysiloxane core-shell abrasive according to claim 1, wherein the core comprises at least one oxide, nitride, or combination thereof of an atom selected from the group consisting of Si, Al, Ce, La, Zr, and Ti.

4. The nanosized soft polysiloxane core-shell abrasive according to any one of claims 1 to 3, wherein the core is selected from the group consisting of colloidal silica, fumed silica, alumina, ceria, and combinations thereof.

5. The core is SiO having Si—OH groups around the surface of the core. ２ The nanosized soft polysiloxane core-shell abrasive according to any one of claims 1 to 4, comprising:

6. 6. The nanosized soft polysiloxane core-shell abrasive according to claim 1, wherein the core is a colloidal silica or fumed silica having Si-OH groups around the surface of the core.

7. 7. The nanosized soft polysiloxane core-shell abrasive of claim 1, wherein the core has a mean particle size (MPS) of 5 to 500 nm, 10 to 400 nm, 15 to 300 nm, 20 to 200 nm, or 30 to 150 nm, as measured by dynamic light scattering (DLS).

8. The polyorganosiloxane polymer has a silsesquioxane moiety RSiO １．５ Silicone part R １ R ２ SiO moiety; silicon moiety having 0 or 1 non-hydrolyzable group R: Si(—O—) ４ or SiR(—O—) ３ and combinations thereof; R is selected from the group consisting of linear or cyclic alkyl, linear or cyclic aryl, and combinations thereof, optionally containing at least one heteroatom selected from the group consisting of O, S, N, and P; R １ and R ２ are each independently selected from the group consisting of aliphatic groups, aromatic groups, and combinations thereof, and may optionally contain at least one heteroatom selected from the group consisting of O, S, N, and P; The nano-sized soft polysiloxane core-shell abrasive according to any one of claims 1 to 7.

9. The polyorganosiloxane polymer contains a silsesquioxane portion, a silicon portion Si(—O—) having 0 non-hydrolyzable groups, ４ and combinations thereof; and the crosslinker may be present before or generated during the formation of the polyorganosiloxane shell.

10. The nanosized soft polysiloxane core-shell abrasive according to any one of claims 1 to 9, wherein the polyorganosiloxane polymer is an inorganic-organic hybrid polymer.

11. The nanosized soft polysiloxane core-shell abrasive according to any one of claims 1 to 10, wherein the polyorganosiloxane polymer has a chain whose end groups are bonded only to the surface periphery of the core, and the polyorganosiloxane polymers are entangled with each other.

12. 12. The nanosized soft polysiloxane core-shell abrasive of any one of claims 1 to 11, wherein the shell comprises non-ionic hydrophilic groups, and optionally organic C-OH groups or other hydrophilic groups.

13. The shell further comprises NR １ R ２ R ３ group, NR １ R ２ R ３ R ４ 13. The nanosized soft polysiloxane core-shell abrasive of any one of claims 1 to 12, wherein each R is independently selected from the group consisting of H, an organic aliphatic group, an aromatic group, and combinations thereof.

14. The shell has a silicone structure O—Si(R １ R ２ )—O, wherein each R is independently an aliphatic or aromatic group, optionally having at least one heteroatom selected from the group consisting of O, S, N, and P; and the shell is a silicon moiety Si(—O—) having 0 non-hydrolyzable groups. ４ 14. The nanosized soft polysiloxane core-shell abrasive according to any one of claims 1 to 13, comprising less than 20 mol%, less than 10 mol%, less than 5 mol%, less than 2.5 mol%, or 0 mol% of:

15. The nanosized soft polysiloxane core-shell abrasive according to any one of claims 1 to 14, wherein the shell is a nonionic or anionic modified polyorganosiloxane shell.

16. 16. The nanosized soft polysiloxane core-shell abrasive of any one of claims 1 to 15, wherein the shell is hydrophilic and optionally contains charge carriers selected from the group consisting of cationic, anionic, and zwitterionic at a predetermined pH.

17. 17. The nanosized soft polysiloxane core-shell abrasive of any one of claims 1 to 16, wherein the shell has a thickness greater than 0.2 nm and less than 20 nm, less than 10 nm, less than 5 nm, or less than 2 nm.

18. 18. The nanosized soft polysiloxane core-shell abrasive according to any one of claims 1 to 17, wherein the core has a surface modification with an organosilane.

19. 19. The nanosized soft polysiloxane core-shell abrasive of any one of claims 1 to 18, wherein the silicone and silicon moieties in the shell react with the reactive groups on the surface of the core to form covalent bonds, bonding the shell to the core.

20. 1. A method for making a nanosized soft polysiloxane core-shell abrasive, comprising: a. providing a dispersion of cores, said cores having reactive groups around the surface of said cores; b. providing a shell-forming precursor; c. adding the shell-forming precursor to the dispersion of the core to form a shell; and d. forming the nanosized soft polysiloxane core-shell abrasive; Including, the shell-forming precursor is selected from the group consisting of organosilanes, organosiloxanes, and combinations thereof; the shell comprises a crosslinked polyorganosiloxane polymer, an entangled polyorganosiloxane polymer, or a combination of a crosslinked polyorganosiloxane polymer and an entangled polyorganosiloxane polymer; the shell is covalently bonded to the periphery of the surface of the core; method.

21. 21. The method for producing nanosized soft polysiloxane core-shell abrasive according to claim 20, wherein the reactive groups around the surface of the core are --OH groups, preferably Si--OH groups.

22. 22. The method for producing a nanosized soft polysiloxane core-shell abrasive according to claim 20 or 21, wherein the core is selected from the group consisting of colloidal silica, fumed silica, alumina, ceria, and combinations thereof.

23. 23. The method for producing a nanosized soft polysiloxane core-shell abrasive according to any one of claims 20 to 22, wherein the core is selected from the group consisting of colloidal silica, fumed silica, and combinations thereof, and the reactive groups around the surface of the core are Si-OH groups.

24. The shell is a silsesquioxane moiety RSiO １．５ Silicone part R １ R ２ SiO moiety: a silicon moiety Si(—O—) having 0 or 1 non-hydrolyzable group R ４ or SiR(—O—) ３ and combinations thereof; R is selected from the group consisting of linear or cyclic alkyl, linear or cyclic aryl, and combinations thereof, optionally containing at least one heteroatom selected from the group consisting of O, S, N, and P; R １ and R ２ are each independently selected from the group consisting of aliphatic groups, aromatic groups, and combinations thereof, and may optionally contain at least one heteroatom selected from the group consisting of O, S, N, and P; A method for producing the nano-sized soft polysiloxane core-shell abrasive according to any one of claims 20 to 23.

25. 25. The method for producing a nanosized soft polysiloxane core-shell abrasive according to any one of claims 20 to 24, wherein the shell-forming precursor is selected from the group consisting of chlorosilanes, alkoxysilanes, oximatosilanes, silanols (preferably diphenylsilanediol), siloxane oligomers having hydrolyzable groups or Si-OH groups (preferably dimethylsiloxanes having 5 repeating units and having Si-OH terminal groups), and combinations thereof; and the shell-forming precursor contains or generates Si-OH groups during the formation of the shell.

26. 26. A method for producing a nanosized soft polysiloxane core-shell abrasive according to any one of claims 20 to 25, wherein the shell-forming precursor is a hydrolyzable organoalkoxysilane, preferably an organoalkoxysilane having at least one or at least two non-hydrolyzable groups, to form a polyorganosiloxane polymer that is silicone-like, silsesquioxane-like, or a mixture thereof.

27. 27. The method for producing a nanosized soft polysiloxane core-shell abrasive according to claim 26, wherein the non-hydrolyzable group is selected from the group consisting of an aliphatic group, an aromatic group, and a combination thereof, and optionally has at least one heteroatom selected from the group consisting of O, S, N, and P bonded thereto or included in its structure.

28. The method for producing a nanosized soft polysiloxane core-shell abrasive according to any one of claims 20 to 27, wherein the shell-forming precursor comprises at least two organoalkoxysilane moieties that share the same non-hydrolyzable group; the polyorganosiloxane polymer comprises both a polysiloxane crosslinker that uses a polysiloxane bond and a non-hydrolyzable organic group; and the polyorganosiloxane polymer is an inorganic-organic hybrid polymer.

29. 29. The method for producing a nanosized soft polysiloxane core-shell abrasive according to any one of claims 20 to 28, wherein the shell-forming precursor is selected from the group consisting of 3-(dimethoxymethylsilyl)propylamine, N-[3-(trimethoxysilyl)propyl]aniline, 3-glycidoxypropyltrimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-(triethoxysilyl)propylsuccinic anhydride, 1,2-bis(triethoxysilyl)ethane, bis(3-trimethoxysilylpropyl)amine, N,N'-bis(3-trimethoxysilylpropyl)urea, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and combinations thereof.

30. 30. The method of any one of claims 20 to 29, wherein at least more than 25 mol%, more than 50 mol%, or more than 75 mol% of the shell-forming precursors have hydrophilic groups, charge-carrying groups, or a combination thereof.

31. 31. The method for producing a nanosized soft polysiloxane core-shell abrasive according to any one of claims 20 to 30, wherein the core is selected from the group consisting of colloidal silica, fumed silica, and combinations thereof, and the shell-forming precursor is selected from the group consisting of 3-(dimethoxymethylsilyl)propylamine, N-[3-(trimethoxysilyl)propyl]aniline, 3-glycidoxypropyltrimethoxysilane, (3-triethoxysilyl)propylsuccinic anhydride, and combinations thereof.

32. 32. The method for producing a nanosized soft polysiloxane core-shell abrasive according to any one of claims 20 to 31, further comprising, as a step subsequent to step a, b, or c, providing a reactant selected from the group consisting of an organic monomer, oligomer, or polymer, wherein preferably the non-silane reactant reacts with at least a portion of the polyorganosiloxane to become covalently incorporated into the shell structure during shell formation, the reactant is not a shell-forming precursor, and the reactant accounts for less than 75 mol%, less than 50 mol%, or less than 25 mol% of the mass of the shell.

33. 33. The method for producing nanosized soft polysiloxane core-shell abrasives according to claim 32, wherein the reactant is selected from the group consisting of glycidol, 1,2-diaminoethane, 1,4-diaminobutane, ethylene glycol-1,2-diglycidyl ether, polyethylene glycol diglycidyl ether, and combinations thereof.

34. further comprising, as a step subsequent to step a, b or c, providing a catalyst; The catalyst is an inorganic or organic acid; NH ３ 34. The method for producing the nanosized soft polysiloxane core-shell abrasive according to any one of claims 20 to 33, wherein the base is selected from the group consisting of amines, amino alcohols, and quaternary ammonium compounds; metal ions selected from the group consisting of Ce, Al, Ti, Zr, W, and Cu; and combinations thereof.

35. The method for producing the nanosized soft polysiloxane core-shell abrasive according to any one of claims 20 to 34, which is carried out at a pH of 2 to 5 or a pH of 8 to 11.

36. 36. The method for producing the nanosized soft polysiloxane core-shell abrasive according to any one of claims 20 to 35, wherein the reactive groups around the surface of the core react with the silicone moieties and silicon moieties in the shell to form covalent bonds, bonding the shell to the surface of the core.

37. 1. A chemical mechanical polishing (CMP) composition comprising: The nanosized soft polysiloxane core-shell abrasive according to any one of claims 1 to 19; and a solvent selected from the group consisting of water, water-soluble solvents, and combinations thereof; Including, the pH is 2 to 10, 2 to 8, 2 to 6, 2 to 5, 2 to 4, or 2 to 3; composition.

38. providing a substrate; providing a chemical-mechanical polishing (CMP) composition comprising the nanosized soft polysiloxane core-shell abrasive of any one of claims 1 to 19; and a solvent selected from the group consisting of water, a water-soluble solvent, and combinations thereof; and having a pH of 2 to 10, 2 to 8, 2 to 6, 2 to 5, 2 to 4, or 2 to 3; contacting the surface of the semiconductor substrate with a polishing pad and the chemical-mechanical polishing composition; and polishing said surface; Including, the substrate having at least one surface comprising at least one material selected from the group consisting of: a metal selected from the group consisting of tungsten, copper, ruthenium, cobalt, aluminum, and combinations thereof; a metal alloy; a dielectric material selected from the group consisting of silicon dioxide and / or silicon nitride; a spin-on dielectric (SoD); and a spin-on carbon (SoC); Chemical mechanical polishing (CMP) method.

39. the surface of the semiconductor substrate includes W and a silicon dioxide film, and W:SiO ２ 39. The chemical mechanical polishing (CMP) method of claim 38, wherein the removal selectivity is greater than 30, 50, 80, 100, 120, or 140.

40. polishing pads; a substrate; and A chemical-mechanical polishing (CMP) composition comprising the nanosized soft polysiloxane core-shell abrasive of any one of claims 1 to 19; and a solvent selected from the group consisting of water, water-soluble solvents, and combinations thereof; and having a pH of 2 to 10, 2 to 8, 2 to 6, 2 to 5, 2 to 4, or 2 to 3; Equipped with the substrate has a surface comprising at least one material selected from the group consisting of: a metal selected from the group consisting of tungsten, copper, ruthenium, cobalt, aluminum, and combinations thereof; a metal alloy; a dielectric material selected from the group consisting of silicon dioxide and / or silicon nitride; a spin-on dielectric (SoD); and a spin-on carbon (SoC); a surface of the semiconductor substrate is in contact with the polishing pad and the chemical-mechanical polishing composition, thereby polishing the surface; Chemical Mechanical Polishing (CMP) system.

41. the surface of the semiconductor substrate includes W and a silicon dioxide film, and W:SiO ２ 41. The chemical mechanical polishing (CMP) system of claim 40, wherein the removal selectivity is greater than 30, 50, 80, 100, 120, or 140.

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