EP4680687A1 - Abrasifs à noyau-enveloppe en polysiloxane mou pour planarisation chimico-mécanique - Google Patents

Abrasifs à noyau-enveloppe en polysiloxane mou pour planarisation chimico-mécanique

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Publication number
EP4680687A1
EP4680687A1 EP24771433.0A EP24771433A EP4680687A1 EP 4680687 A1 EP4680687 A1 EP 4680687A1 EP 24771433 A EP24771433 A EP 24771433A EP 4680687 A1 EP4680687 A1 EP 4680687A1
Authority
EP
European Patent Office
Prior art keywords
shell
core
group
nanosized
combinations
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24771433.0A
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German (de)
English (en)
Inventor
Gerhard Jonschker
Matthias Stender
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Versum Materials US LLC
Original Assignee
Versum Materials US LLC
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Filing date
Publication date
Application filed by Versum Materials US LLC filed Critical Versum Materials US LLC
Publication of EP4680687A1 publication Critical patent/EP4680687A1/fr
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
    • H10P52/40—Chemomechanical polishing [CMP]
    • H10P52/403—Chemomechanical polishing [CMP] of conductive or resistive materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1436—Composite particles, e.g. coated particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions

Definitions

  • This invention relates to soft polysiloxane core-shell abrasives or abrasive particles. More specifically, soft polysiloxane core-shell abrasives or abrasive particles are provided for the Chemical Mechanical Planarization (CMP) polishing with low defect rates.
  • CMP Chemical Mechanical Planarization
  • CMP Chemical Mechanical Planarization
  • CMP utilizes the interplay of chemical and mechanical action to achieve the planarity of the to-be-polished surfaces.
  • chemicals and nanosized abrasives are used to planarize any irregularities which may have been generated during the deposition of the many different materials which make up a semiconductor chip.
  • CMP polishing composition typically comprises abrasive nanoparticles (usually colloidal particles) in aqueous solution.
  • the nanoparticles are carefully classified in size, since too large particles may scratch the delicate structures which is a main cause for failure.
  • the standard nanoparticles which are known in the state of the art which are typically silica, ceria or alumina-based are still causing too many defects. The reasons for this are manifold.
  • the to-be-planarized structure is so delicate that even very few too big nanoparticles in a CMP polishing composition or slurry may cause damage, an irregular shape of the abrasives could cause defects, or the to-be-planarized materials are so mechanically weak or soft that even small and carefully classified nanoparticles cause inacceptable damage.
  • nanosized abrasives are often at least partially surface-modified with organic groups to carry charged moieties. This is done to tailor the zetapotential of the particles to be in a desired range.
  • silica may be modified with just enough aminosilanes so to exhibit a sufficiently high positive charge (positive zetapotential) at an acidic pH.
  • Aminosilane has been used to modify the abrasive particles to have high charge density and zeta potential.
  • US 9,028,572 B2 discloses a way to achieve abrasive particles with a charge density and zeta potential through the particle surface treatment with a compound selected from the group consisting of quaternary aminosilane compounds, dipodal aminosilane compounds, and combinations thereof.
  • the known silane modification in the art does not form a separate material layer nor changes the mechanical properties of the nanoparticle in a substantial way. This is because the silane is usually bonded to the abrasives, but not to other silanes, at least not intentionally, thus, a separate layer formed by a combination of silane bonded to the surface and substantially bonded to each other is not formed. Some dimers or trimers of silanes which may be formed by accident during surface modification are not enough to change the mechanical properties of the abrasives.
  • the present invention provides such nanosized abrasives for improved CMP polishing compositions, methods and systems.
  • the present invention provides nanosized soft polysiloxane core-shell abrasives.
  • the CMP polishing compositions, methods, and systems using the soft polysiloxane core-shell abrasives are also provided.
  • nanosized soft polysiloxane core-shell abrasives wherein the core and the shell of the nanosized soft polysiloxane core-shell abrasives comprise different materials with different chemical and mechanical properties, the shell is preferably mechanically softer as having lower E-modulus than the core.
  • the shell comprises crosslinked, entangled, or mixture of crosslinked and entangled polyorganosiloxane polymers. More specifically, the shell of the soft polysiloxane coreshell abrasives is polyorganosiloxane shell.
  • the core of nanosized soft polysiloxane core-shell abrasives comprises material having a reactive group including but being not limited to reactive OH- groups, preferably Si-OH groups around its surface to react with polyorganosiloxane shell and forming covalent bonds to bond the polyorganosiloxane shell to the surface of the core.
  • the core of nanosized soft polysiloxane core-shell abrasives includes but is not limited to oxides, nitrides or mixtures of at least one atom selected from the group consisting of: Si, Al, Ce, La, Zr, and Ti.
  • the core of nanosized soft polysiloxane core-shell abrasives is selected from the group consisting of colloidal silica, fumed silica, alumina, ceria, and combinations thereof.
  • R can be linear or cyclic alkyl or aryl, combinations thereof and optionally can comprise heteroatoms such as O, S, N, and P; and R1 and R 2 each independently can be aliphatic or aromatic group, combinations thereof; and optionally can comprise heteroatoms such as O, S, N, and P.
  • the polyorganosiloxane shell contains > 50 molar %, >75 molar % , > 85 molar%, 90 molar %, or 95 molar % of a silicone-like structure 0-Si(RiR2)-0 with each R independently being aliphatic and/or aromatic groups which may carry at least one heteroatom selected from the group consisting of S, N,O, and P.
  • the polyorganosiloxane shell contains ⁇ 20 mol%, ⁇ 5mol%, ⁇ 2.5 % or 0% silicon moieties with 0 non-hydrolyzable group Si(-O-)4 which function as crosslinkers.
  • the polyorganosiloxane shell comprises non-ionic hydrophilic groups and optionally organic C-OH groups or other hydrophilic groups.
  • Non-ionic hydrophilic groups can also be a single component of polyorganosiloxane shell.
  • the polyorganosiloxane shell may also contain other groups including but not being limited to NR1R2R3 groups and/or NR1R2R3R4 groups with each R independently being H, organic aliphatic and/or aromatic groups.
  • Polyorganosiloxane shell contains charge carriers and other hydrophilic moieties for enhancing good water or water-comprising solvents compatibility and good colloidal stability of the nanosized soft polysiloxane core-shell abrasives particles.
  • the polyorganosiloxane polymers can be partially crosslinked which might leave dangling ends of polymer with end groups, such as polymer-O-SiR1 R2-OH or polymer- O-SiR(OH)2. [0027] The polyorganosiloxane polymers can be completely uncrosslinked with dangling ends only physically entangled with each other.
  • the polyorganosiloxane polymers can be additionally or solely crosslinked by organic crosslinkers.
  • organic crosslinkers can be short- or long-chain alkyl or aryl groups as defined above and are covalently connected to at least 2 silicon moieties
  • the shell can comprise crosslinked, entangled, or mixtures thereof of inorganic-organic hybrid polyorganosiloxane polymers where the crosslinkers are both inorganic polysiloxane crosslinkers using polysiloxane bonds and organic crosslinkers which are from the shell-forming precursor having more than one crosslinker moieties.
  • the shell is a non-ionic or anionic modified polyorganosiloxane shell.
  • the shell is hydrophilic, optionally comprising charge carriers being either cationic, anionic or zwitterionic at a given pH.
  • the shell is mainly bonded to the core by covalent bonds via silicone moieties and silicon moieties, either Core-O-SiRiR2-O- or Core-O-SiR(-O-)2 or Core-O-Si(-O-)3 with Core-O-SiRiR2-O- or Core-O-SiR(-O-)2 being preferred.
  • the core surface need to contain OH- or Si-OH groups which react with silicon moieties to form covalent bonds, as an example Si-OH groups react with silicon moieties to form covalent Si-O-Si bonds.
  • a method of making nanosized soft polysiloxane core-shell abrasives 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 core abrasives to form polyorganosiloxane shells on surfaces of the core abrasives; d. forming the nanosized soft polysiloxane core-shell abrasives by covalently bonding the polyorganosiloxane shells around the surfaces of the core abrasives.
  • the core of nanosized soft polysiloxane core-shell abrasives includes but is not limited to oxides, nitrides or mixtures of at least one atom selected from the group consisting of: Si, Al, Ce, La, Zr, and Ti.
  • the core of nanosized soft polysiloxane core-shell abrasives is selected from the group consisting of colloidal silica, fumed silica, alumina, ceria, and combinations thereof.
  • the shell-forming precursor comprises organosilane, organosiloxane, or mixtures thereof. It includes but is not limited to chlorosilanes, organoalkoxysilanes, oximatosilanes, silanols (e.g. diphenylsilandiol), siloxane oligomers with hydrolysable groups or Si-OH groups like Cs (dimethylsiloxane with 5 repetitive units and Si-OH end groups), and combinations thereof; wherein the shell-forming precursor contains or/and generates Si-OH groups during formation of the shell.
  • organosilane organosiloxane, or mixtures thereof. It includes but is not limited to chlorosilanes, organoalkoxysilanes, oximatosilanes, silanols (e.g. diphenylsilandiol), siloxane oligomers with hydrolysable groups or Si-OH groups like Cs (dimethylsiloxane with
  • the organoalkoxysilanes includes but is not limited to hydrolysable organoalkoxysilanes, preferably organoalkoxysilanes with at least 1, or at least 2 non- hydrolyzable groups, leading to a silicone-like, silsesquioxane-like, or mixture thereof of polyorganosiloxane; wherein the non-hydrolyzable groups can be aliphatic, aromatic, or mixtures, and may have one or more heteroatoms such as O, S, N, and P attached or included in their structure.
  • the non-hydrolyzable group of the organoalkoxysilane can be covalently bonded to more than one to non-limiting number of organoalkoxysilane moiety; such as ⁇ 10, ⁇ 6, or ⁇ 4 organoalkoxysilane moieties.
  • the polyorganosiloxane shell comprises polyorganosiloxane polymer being additionally or dominantly crosslinked by non-hydrolyzable groups so that the polyorganosiloxane shell comprises inorganic-organic hybrid polymer being crosslinked by both inorganic polysiloxane crosslinker using polysiloxane bonds and organic crosslinkers which are from the shell-forming precursor having more than one crosslinker moieties.
  • the organoalkoxysilane includes but is 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, 2-(3,4- epoxycyclohexyl)ethyltriethoxysilane.
  • non-silane reactant includes but is not limited to organic monomers, oligomers or polymers; preferably the non-silane reactant reacts with at least part of the polyorganosiloxane and is covalently incorporated in the shell structure during shell formation.
  • Example includes but is not limited to glycidol, 1 ,2- diaminoethan, 1,4-diaminobutan, ethyleneglycol-1 ,2 diglycidylether, or poly(ethylene glycol)diglycidyl ether.
  • Catalysts and the process conditions of the inventive method are preferably chosen to foster hydrolysis and condensation of the organoalkoxysilane, so that the formation of the polyorganosiloxane can take place effectively.
  • the method of making nanosized soft polysiloxane core-shell abrasives can further comprises a step after step a, b or c: adding a catalyst to the dispersion of core abrasives.
  • the catalysts can be acids, bases, or metal ions; such as polymeric catalysts like ion exchangers.
  • the bases include but are not limited to NH3, amines, amino alcohols, quaternary ammonium compounds.
  • the base is NH3.
  • the acids are mineral or organic acids.
  • the used acids are acids which are also used in CMP processes like nitric acid.
  • the metal ions are the ones used and/or at least tolerated in CMP processes, like Ce, Al, Ti, Zr, W, Cu.
  • the method of making nanosized soft polysiloxane core-shell abrasives can further have a process condition of: pH is from 2 to 5 or from 8 to 11.
  • a CMP polishing composition comprising: nanosized soft polysiloxane core-shell abrasives disclosed above; and a solvent selected from the group consisting of water, water-soluble solvent, and combinations thereof; wherein the composition has a pH of 2 to 10, 2 to 6, 2 to 5, 2 to 4, or 2 to 3.
  • the water includes but is not limited to deionized (DI) water, distilled water, and the water-soluble solvent t is not limited to alcoholic organic solvents.
  • the CMP polishing composition can optionally comprise at least one of: organic and inorganic salt as colloidal stabilizer; acid/base buffer agent; biocide; oxidizer; catalyst; corrosion inhibitor; organic polymers as erosion, dishing and corrosion reducer; wherein example polymers include but are not limited to hydrophilic polymers, polymers with organic functional groups like -OH, -NH, CN, ester, amide, halogen, ether, inorganic polymers for like mono-metal- or mixed-metal polymetalhydroxide clusters, polyanions, polycations, especially those containing Al, Ce, Zr, Fe as metal ions; surface-active molecules/oligomers/polymers like cationic-, anionic- or nonionic surfactants and polymers which attach by either physical adsorption, ionic or covalent bonding.
  • a method of CMP polishing a substrate having at least one surface comprising at least one material selected from the group consisting of a metal includes but is not limited to tungsten, copper, ruthenium, cobalt, aluminum, and combinations thereof; metal alloys; a dielectric material includes but is not limited to silicon dioxide and/or silicon nitride; spin-on dielectrics (SoD); and spin-on carbon(SoC); using the CMP polishing composition described above.
  • the silicon dioxide polished silicon oxide films can be Chemical vapor deposition (CVD), Plasma Enhance CVD (PECVD), High Density Deposition CVD(HDP), or spin on silicon oxide films.
  • CVD Chemical vapor deposition
  • PECVD Plasma Enhance CVD
  • HDP High Density Deposition
  • spin on silicon oxide films can be Chemical vapor deposition (CVD), Plasma Enhance CVD (PECVD), High Density Deposition CVD(HDP), or spin on silicon oxide films.
  • This invention relates to soft polysiloxane core-shell abrasives, more specifically, the Chemical Mechanical Planarization (CMP) polishing composition (also known as slurry or formulation), methods, and systems using soft polysiloxane core-shell abrasives with amino-functional polyorganosiloxane shell.
  • CMP Chemical Mechanical Planarization
  • the CMP polishing compositions, method and system using soft polysiloxane core-shell abrasives are specifically suitable for low defects CMP applications for polishing a substrate having at least one surface comprising at least one material selected from the group consisting of a metal includes but is not limited to tungsten, copper, ruthenium, cobalt, aluminum, and combinations thereof; metal alloys; dielectric material includes but is not limited to silicon dioxide and/or silicon nitride; spin-on dielectrics (SoD); and spin-on carbon(SoC) using the CMP polishing composition described above.
  • a metal includes but is not limited to tungsten, copper, ruthenium, cobalt, aluminum, and combinations thereof; metal alloys; dielectric material includes but is not limited to silicon dioxide and/or silicon nitride; spin-on dielectrics (SoD); and spin-on carbon(SoC) using the CMP polishing composition described above.
  • the soft polysiloxane core-shell abrasive has a core containing standard abrasive materials or particles such as silica or ceria; and a covalently bonded shell consisting of a chemical and mechanical different material from the core.
  • the shell is softer by exhibiting a lower Young's modulus or E-modulus and showing plastic and/or viscoelastic properties unlike the core.
  • the shell consists of polyorganosiloxane(s).
  • the shell showing either cationic, anionic, non-ionic or zwitterionic charge depending on the pH or independent of the pH by carrying so called permanent charge carriers like tetraalkylammonium ions.
  • the soft polysiloxane core-shell abrasive particles have a zetapotential of > 20 mV or ⁇ -20 mV at a given pH in water; having a zetapotential near zero is possible without affecting the colloidal stability when the polymer is hydrophilic enough and comprises enough hydrophilic non-ionic moieties to ensure a steric stabilization.
  • the shell is thick enough with different mechanical properties compared to the core, so that the consequences of an impact of the abrasive on the to-be-planarized surfaces are effectively mitigated. On the other hand, the shell is not too thick so to degrade the desired high removal rate.
  • the shell has a thickness of >0.2 nm and ⁇ 20 nm, >0.2 nm and ⁇ 10nm, >0.2 and ⁇ 5 nm, or >0.2 nm and ⁇ 2 nm.
  • the shell with silicone- or silsesquioxane-like moieties changes the micro-tribological behavior of the abrasives so that defects, especially scratch generation is mitigated.
  • the thickness of the shell is significantly larger than a monolayer of silanes which is known by the state of the art.
  • the removal rates of the soft polysiloxane coreshell abrasives increased or at least did not decrease compared to the original unmodified or state of the art modified (silanized) abrasive. This is counterintuitive and could not reasonably be expected, since a soft surface modification of a hard abrasive is meant to also decrease the abrasiveness of the particles in the CMP process.
  • the present invention provides the core-shell abrasives for CMP process making it possible to combine both highest removal rates and exceptionally low detectivity for the needs of the microelectronic fabrication of todays and future nodes.
  • the invention can even be demonstrated by using fumed silica as cores for the soft polysiloxane core-shell abrasives.
  • the fumed silica abrasives are well known in the art for causing an undesirably high defect level in the CMP process.
  • the defect level for soft polysiloxane core-shell abrasives using fumed silica as the cores can be shown to be even below the level of colloidal silica which is known to have low defect level in the art.
  • silicone- and silsesquioxane-like structures are hydrophobic and tend to destabilize in water-borne colloidal dispersions.
  • the present invention overcomes the problem by using hydrophilic and/or charge-carrying silicone moieties to make the soft polysiloxane core-shell abrasives or abrasive particles stable against precipitation or flocculation.
  • nanosized soft polysiloxane core-shell abrasives wherein the core and the shell of the nanosized soft polysiloxane core-shell abrasives comprise different materials with different chemical and mechanical properties preferably the shell is mechanically softer such as having lower E-modulus; and the shell comprises crosslinked, entangled, or mixture of crosslinked and entangled polyorganosiloxane polymers.
  • the cores of the inventive soft polysiloxane core-shell abrasives can be inorganic or inorganic/organic hybrids.
  • the cores may have a surface modification according to the state of the art like silanes attached to their surface.
  • the cores can have any shape includes but is not limited to round, egg shape, elongated or branched shapes.
  • the surface of the core can be any quality or condition, includes but is not limited to smooth, rough, with or without protrusions.
  • the core consists of SiC>2 with Si-OH groups around the surface.
  • the core can be either made by wet processes (e.g. Stober process) or thermal processes (flame synthesis, gas phase synthesis).
  • the cores have a mean particle size(MPS) measured by Dynamic Light Scattering (DLS) ⁇ 500 nm, ⁇ 400 nm, ⁇ 300 nm, or ⁇ 200 nm; and > 2 nm, > 10 nm, >15 nm, or > 25 nm.
  • MPS Dynamic Light Scattering
  • All raw materials as shell-forming precursors comprise organosilane, organosiloxane, or mixtures of the two.
  • the shell-forming precursors form the shell and covalently bond the shell around the surfaces of the cores upon reacting with the reactive groups around the surfaces of the cores.
  • shell-forming precursors include but are not limited to: chlorosilanes, organoalkoxysilanes, oximatosilanes, silanols (e.g. diphenylsilandiol), or siloxane oligomers with hydrolysable groups or Si-OH groups like C5 (dimethylsiloxane with 5 repetitive units and Si-OH end groups): generally all precursors contain or/and can generate Si-OH groups under the conditions of the shell formation.
  • the organoalkoxysilanes include but are not limited to hydrolysable organoalkoxysilanes.
  • the hydrolysable organoalkoxysilanes have at least 1 , preferably 2 non-hydrolyzable groups, leading to a silicone-like, silsesquioxane-like, or mixtures thereof; wherein the non-hydrolyzable groups can be aliphatic, aromatic, or mixtures, and may have one or more heteroatoms such as O, S, N, and P attached or included in their structure.
  • the non-hydrolyzable group of the organoalkoxysilanes can be covalently bonded to more than one and non-limiting number of organoalkoxysilane moiety; such as ⁇ 10, ⁇ 6, and preferably ⁇ 4 organoalkoxysilane moieties.
  • An example is the reaction product of 3-glycidoxypropyltrimethoxysilane with 3- aminopropylmethyldimethoxysilane.
  • the epoxy group and the amino group react to form an organic crosslinker which connects 2 silane moieties with hydrolysable alkoxy groups.
  • Another example is the reaction product of hexamethylendiisocyanate with 3- aminopropyltrimethoxysilane. Both reactions yield a silane in which 2 organoalkoxysilane moieties are covalently linked by one non-hydrolyzable group.
  • Another example is the reaction product of 3-aminopropylmethyldimethoxysilane with (3- triethoxysilyl)propylsuccinic anhydride.
  • bipodal silanes like e.g. 1 ,2-bis(triethoxysilyl)ethane, bis-(3-trimethoxysilylpropyl)amine or N,N’-bis(3- trimethoxysilylpropyl)urea can be used.
  • the polyorganosiloxane shell comprises both inorganic polysiloxane crosslinker using polysiloxane bonds and organic crosslinkers yielding an inorganic-organic hybrid polymer.
  • the polyorganosiloxane shell comprises polyorganosiloxane polymer being crosslinked, entangled with each other, or the mixtures of both.
  • the polyorganosiloxane shell can have loose ends or can be completely bonded to the core surface.
  • the shell has mechanical properties which are different from the core by at least > 10% different, preferably > 20% and most preferably > 50% different, such as measured by Atomic Force Microscopy (AFM) nanoindentation or other method.
  • AFM Atomic Force Microscopy
  • the shell is mainly bonded to the core by covalent bonds via silicon moiety, either Core-O-SiRiR2-O- or Core-O-SiR(-O-)2 or Core-O-Si(-O-)3 with Core-O-SiRiR2-O- or Core-O-SiR(-O-)2 being preferred.
  • the core surface must contain OH- or Si-OH groups which react with silicon moieties to form covalent bonds, as an example Si-OH groups react with silicon moieties to form covalent Si-O-Si bonds.
  • the shell may also but is not preferred to be bonded to the core by physisorption of the polyorganosiloxane without a covalent chemical bond.
  • the soft polysiloxane core-shell abrasives are hydrophilic, optionally comprising charge carriers.
  • Charge carriers are either cationic, anionic or zwitterionic at a given pH.
  • the soft polysiloxane core-shell abrasives are colloidally stable upon dispersion in water or water-comprising solvents either by charge carriers or other hydrophilic groups (e.g. -OH, ether).
  • the soft polysiloxane core-shell abrasives are colloidally stable up to a solid content of 40 wt.%
  • the inventive soft polysiloxane core-shell abrasives can have narrow or broad, monomodal or polymodal size distributions.
  • the shape of the soft polysiloxane core-shell abrasives can be any shape; includes but is not limited to round, egg, elongated, irregular or branched, or combinations thereof.
  • the surface of the soft polysiloxane coreshell abrasives can be smooth, rough, with or without protrusions.
  • inventive soft polysiloxane core-shell abrasives are also compatible with typical CMP additives like oxidizers, catalysts, surfactants, inhibitors, topo additives and the like, also in concentrated CMP slurries, and are hydrophilic and good-wetting of to- be-planarized surfaces
  • the soft polysiloxane core-shell abrasives usually have a MPS measured by Dynamic Light Scattering (DLS) ranging from 5 to 500 nm, 10 to 400 nm, 15 to 300nm, 20 to 200 nm, or 30 to 150 nm.
  • DLS Dynamic Light Scattering
  • the process to make soft polysiloxane core-shell abrasives can start with a dispersion of core abrasives in a solvent optionally comprising water.
  • the shell-forming precursor(s) are added to the dispersion of core abrasives at a given pH under agitation (acid and alkaline processes are possible).
  • the shell-forming precursors are monomers, but can also comprise dimers, trimers, oligomers or polymers which have been pre-formed by a separate process step which may comprise adding water and optionally a catalyst to the precursors.
  • the reaction medium contains optional additional catalysts and reactants to foster shell formation.
  • the pH is adjusted so that the shell forms and the polymer reacts with the surface reactive groups of the core.
  • the pH is either kept ⁇ 5 or > 8; such as a pH from 2 to 5 or a pH from 8-11.
  • the downstream processing involves at least one purification step to remove soluble and/or insoluble byproducts of the reaction.
  • the volatile organic reactants and byproducts are removed from the dispersion and the solvent is replaced by water.
  • the preferred process to make soft polysiloxane core-shell abrasives is to provide a dispersion of a nanoparticle dispersion in a solvent which comprises water at a pH of either 2-3 or 10-11 and add the shell-forming precursors slowly dropwise under intensive agitation and pH control. Then, after an additional reaction time of 1-4 hours, the volatile byproducts are removed by distillation and replaced by water while the pH is kept constant. Then the pH may be adjusted by adding acid or base or exposing the dispersion to an ion-exchanger resin. The dispersion may be further purified by centrifugation/redispersion or membrane filtration.
  • the catalysts can be acids, bases, or metal ions; such as polymeric catalysts like ion exchangers.
  • the bases include but are not limited to NH3, amines, amino alcohols, quaternary ammonium compounds.
  • the base is NH3.
  • the acids are mineral or organic acids.
  • the used acids are acids which are also used in CMP processes like nitric acid.
  • the metal ions are the ones used and/or at least tolerated in CMP processes, like Ce, Al, Ti, Zr, W, Cu.
  • Solvents include but are not limited to water, alcohols (preferred), methanol, ethanol, propanol; and other common polar protic and aprotic solvents like ketones, esters, ethers, acetamides, xxx
  • a method of making nanosized soft polysiloxane core-shell abrasives comprising the steps of: a. providing a dispersion of core abrasives wherein the core abrasives have reactive groups around its surface; b. providing a shell-forming precursor; c. adding the shell-forming precursor to the dispersion of core abrasives to form polyorganosiloxane shells on surfaces of the core abrasives; d. forming the nanosized soft polysiloxane core-shell abrasives by covalently bonding the polyorganosiloxane shells around the surfaces of the core abrasives.
  • the shell-forming precursor comprises organosilane, organosiloxane, or mixtures.
  • the shell-forming precursor includes but is not limited to of chlorosilanes, alkoxysilanes, oximatosilanes, silanols (e.g. diphenylsilandiol), siloxane oligomers with hydrolysable groups or Si-OH groups like Cs (dimethylsiloxane with 5 repetitive units and Si-OH end groups), and combinations thereof; wherein the shell-forming precursor contains or generates Si-OH groups during formation of the shell.
  • the organosiloxane includes but is not limited to hydrolysable organoalkoxysilanes, preferably organoalkoxysilanes with at least 1, preferably 2 non- hydrolyzable groups, leading to a silicone-like, silsesquioxane-like, or mixture thereof of polyorganosiloxane; wherein the non-hydrolyzable groups can be aliphatic, aromatic, or mixtures thereof, and may have one or more heteroatoms such as O, S, N, and P attached or included in their structure.
  • the non-hydrolyzable group of the organoalkoxysilanes can be covalently bonded to more than one and non-limiting number of organoalkoxysilane moiety; such as ⁇ 10, ⁇ 6, and preferably ⁇ 4 organoalkoxysilane moieties.
  • An example is the reaction product of 3-lycidoxypropyltrimethoxysilane with 3- aminopropylmethyldimethoxysilane.
  • the epoxy group and the amino group react to form an organic crosslinker which connects 2 silane moieties with hydrolysable alkoxy groups.
  • Another example is the reaction product of hexamethylendiisocyanate with 2 moles of 3- aminopropyltrimethoxysilane. Both reactions yield a silane in which 2 organoalkoxysilane moieties are covalently linked by one non-hydrolyzable group.
  • Another example is the reaction product of 3-aminopropylmethyldimethoxysilane with (3- triethoxysilyl) propylsuccinic anhydride.
  • bipodal silanes like e.g. 1 ,2-bis(triethoxysilyl)ethane, bis-(3-trimethoxysilylpropyl)amine or N,N’-bis(3- trimethoxysilylpropyl)urea can be used.
  • the polyorganosiloxane shell will be crosslinked by both polysiloxane bonds and organic crosslinkers at the same time yielding an inorganic- organic hybrid polymer.
  • the organosiloxane includes but is not limited to 3-
  • non- organosiloxane reactant can also be provided in the method, wherein non-silane reactant includes but is not limited to organic monomers, oligomers or polymers; preferably the non-silane reactant reacts with at least part of the polyorganosiloxane and is covalently incorporated in the shell structure during shell formation.
  • Example of the reactant includes but is not limited to glycidol, 1 ,2-diaminoethan, 1 ,4-diaminobutan, ethyleneglycol- 1,2 diglycidylether or poly(ethylene glycol)diglycidyl ether.
  • the process conditions of the inventive method are preferably chosen to foster hydrolysis and condensation of the silane, so that the formation of the polyorganosiloxane can take place effectively. This can be done by any method known in the art, preferably by choosing a suitable pH or by introducing catalysts. It is preferred to have a pH either from 2 to 5 or from 8-11 to avoid further catalysts.
  • a CMP polishing composition comprises: nanosized soft polysiloxane core-shell abrasives disclosed above; and a solvent selected from the group consisting of water, water-soluble solvent, and combinations thereof; wherein the composition has a pH of 2 to 10, 2 to 8, 2 to 6, 2 to 5, 2 to 4, or 2 to 3.
  • the water includes but is not limited to deionized (DI) water, distilled water, and the water-soluble solvent t is not limited to alcoholic organic solvents.
  • DI deionized
  • distilled water distilled water
  • water-soluble solvent t is not limited to alcoholic organic solvents.
  • the CMP polishing composition can optionally comprise at least one of: organic and inorganic salt as colloidal stabilizer; acid/base buffer agent; biocide; oxidizer; catalyst; corrosion inhibitor; organic polymers as erosion, dishing and corrosion reducer; wherein example polymers include but are not limited to hydrophilic polymers, polymers with organic functional groups like -OH, -NH, -CN, ester, amide, halogen, ether, inorganic polymers for like mono-metal- or mixed-metal polymetalhydroxide clusters, polyanions, polycations, especially those containing AL, Ce, Zr, Fe as metal ions; surface-active molecules/oligomers/polymers like cationic-, anionic- or nonionic surfactants and polymers which attach by either physical adsorption, ionic or covalent bonding.
  • a method of chemical mechanical polishing a substrate having at least one surface comprising at least one material selected from the group consisting of a metal includes but is not limited to tungsten, copper, ruthenium, cobalt, aluminum, and combinations thereof; metal alloys; a dielectric material includes but is not limited to silicon dioxide and/or silicon nitride; spin-on dielectrics (SoD); and spin-on carbon(SoC); using the CMP polishing composition described above.
  • the silicon dioxide films can be Chemical vapor deposition (CVD), Plasma Enhance CVD (PECVD), High Density Deposition CVD(HDP), or spin on silicon oxide films.
  • CVD Chemical vapor deposition
  • PECVD Plasma Enhance CVD
  • HDP High Density Deposition
  • a or A angstrom(s) - a unit of length
  • BP back pressure, in psi units
  • DF Down force: pressure applied during CMP, units: psi
  • PS platen rotational speed of polishing tool, in rpm (revolution(s) per minute)
  • TEOS tetraethyl orthosilicate
  • SoD spin-on-dielectric
  • W TEOS Selectivity: (removal rate of W)/ (removal rate of TEOS)
  • HDP high density plasma deposited TEOS
  • TEOS or HDP Removal Rates Measured TEOS or HDP removal rate at a given down pressure.
  • reaction mixture was transferred to a round flask and the volatile organic solvents were removed and replaced by deionized water so that a solid content of soft core-shell silica of approximately 20 wt.% was achieved.
  • reaction mixture was transferred to a round flask and the volatile organic solvents were removed and replaced by deionized water so that a solid content of soft core-shell silica of approximately 20 wt.% was achieved.
  • reaction mixture was transferred to a round flask and the volatile organic solvents were removed and replaced by deionized water so that a solid content of soft core-shell silica of approximately 20 wt.% was achieved.
  • the product was pressure- filtered over a 2 pm filter
  • reaction mixture was transferred to a round flask and the volatile organic solvents were removed and replaced by deionized water so that a solid content of coreshell silica of approximately 20 wt.% was achieved.
  • reaction mixture was transferred to a round flask and the volatile organic solvents were removed and replaced by deionized water so that a solid content of coreshell silica of approximately 20 wt.% was achieved.
  • reaction mixture was transferred to a round flask and the volatile organic solvents were removed and replaced by deionized water so that a solid content of coreshell silica of approximately 20 wt.% was achieved.
  • a dispersion of ion-exchanged, elongated silica nanoparticles 87 nm MPS, measured by DLS; pH 4.1; 232.98 g/665.78 mmol SiO2) was transferred to a 500 ml 4- neck flask, equipped with condenser and KPG stirrer. The dispersion was heated to 70°C while being stirred.
  • Solution A was made by mixing N-[3-(trimethoxysilyl)propyl]aniline (3.69 ml; 14.40 mmol) with methanol (29.50 ml; 727.40 mmol).
  • Solution B was made by mixing nitric acid (65wt.%, 1.09 ml; 15.84 mmol) with methanol (32.10 ml; 791.57 mmol).
  • Deionized water was added while stirring to adjust the concentration of SiC>2 nanoparticles to 10 wt.%. Under continuous stirring, the dispersion was heated to 70 °C.
  • polishing results were obtained by polishing 300 mm diameter wafers having the appropriate layers using a Reflexeon LK-300mm CMP tool, IC-1000 polishing pad (Dow Chemicals) and AK45 conditioner (Seasol) at a downforce of 3 psi and a slurry flow rate of 200 ml/min. Removal rates for W, TECS, and SOC spin-on-carbon films were measured using 4-point probe (RS-100, KLA Tencor) and Ellipsometry (Spectra FX100, KLA Tencor). Defect counts were obtained using SP2 surfscan tool (KLA Tencor).
  • Polishing experiments were conducted using W, and PECVD TECS wafers. These blanket wafers were purchased from Silicon Valley Microelectronics, 2985 Kifer Rd., Santa Clara, CA 95051.
  • Example 10 CMP using Soft Polysiloxane Core-Shell Structure Abrasives Having Fumed Silica As Core
  • Each of the CMP polishing compositions included 0.1 wt.% abrasive particles as shown in Table 1.
  • the CMP polishing compositions were filtered prior to polish tests (Pall CMP StarKleen Capsule 0.3 pm filter size).
  • Example 11 CMP Using Abrasives Having Elongated-Shaped Nanoparticles As Core Particles
  • polishing rates and detectivity of Tungsten and TEOS layers were evaluated in this example for compositions containing different abrasives.
  • Each of the polishing compositions included 0.1 wt% abrasive particles.
  • Composition 1A contained the aminosilane-modified abrasives from Comparative Example 4;
  • Composition 1 B contained abrasives with aminofunctional soft polysiloxane core-shell structure from Example 4; and
  • Composition 1C contained the aminosilane-modified abrasives from Comparative Example 5. All compositions were filtered prior to polish tests (Pall CMP StarKleen Capsule 0.3 pm filter size).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Polishing Bodies And Polishing Tools (AREA)

Abstract

L'invention concerne des abrasifs à noyau-enveloppe en polysiloxane mou. Le noyau et l'enveloppe des abrasifs à noyau-enveloppe en polysiloxane mou de taille nanométrique comprennent différents matériaux ayant des propriétés chimiques et mécaniques différentes, de préférence l'enveloppe a un module E inférieur et est ainsi mécaniquement plus souple que le noyau. L'enveloppe comprend des polymères de polyorganosiloxane qui sont réticulés, enchevêtrés ou des combinaisons de ceux-ci. Les compositions de polissage CMP, les procédés et les systèmes utilisant les abrasifs à noyau-enveloppe de polysiloxane mou sont fournis pour obtenir des taux d'élimination élevés et une faible détectivité.
EP24771433.0A 2023-03-15 2024-03-07 Abrasifs à noyau-enveloppe en polysiloxane mou pour planarisation chimico-mécanique Pending EP4680687A1 (fr)

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PCT/US2024/018863 WO2024191746A1 (fr) 2023-03-15 2024-03-07 Abrasifs à noyau-enveloppe en polysiloxane mou pour planarisation chimico-mécanique

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US7182798B2 (en) * 2004-07-29 2007-02-27 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Polymer-coated particles for chemical mechanical polishing
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US20150174734A1 (en) * 2012-06-13 2015-06-25 Konica Minolta, Inc. Polishing Material Composition And Production Method Therefor
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