Chemical Mechanical Planarization Using Amino-Polyorganosiloxane-Coated Abrasives

Abstract

Chemical mechanical planarization (CMP) polishing compositions, methods and systems are provided that use a stable colloidal dispersion of abrasive particles. The abrasive particles in the dispersion are amino-polyorganosiloxane-coated abrasive particles. The amino-polyorganosiloxane-coated abrasive particles have an amino-functional polyorganosiloxane shell having a thickness of 0.1 nm to 10 nm, or 0.5 to 5 nm. The amino-polyorganosiloxane-coated abrasive particles have low silanol density and positive charge in the acidic low pH range.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of priority under 35 USC § 119(e) to earlier-filed U.S. patent application Ser. No. 63 / 269,585, filed March 18, 2022, which is incorporated herein by reference in its entirety. [Background technology]

[0002] The present invention relates to chemical mechanical planarization (CMP) compositions, chemical mechanical planarization (CMP) methods, and chemical mechanical planarization (CMP) systems.

[0003] More specifically, chemical mechanical planarization (CMP) polishing compositions, methods and systems are provided that use a stable colloidal dispersion of abrasive particles. The abrasive particles in the dispersion are amino-polyorganosiloxane-coated abrasive particles. The amino-polyorganosiloxane-coated abrasive particles have an amino-functional polyorganosiloxane shell. The amino-polyorganosiloxane-coated abrasive particles have low silanol density and positive charge in the acidic low pH range.

[0004] In the semiconductor industry, chemical mechanical planarization (CMP) is a well-known technique applied in the fabrication of advanced photonic, microelectromechanical, and microelectronic materials and devices, such as semiconductor wafers. CMP polishing is a key step for recovering selected materials and / or planarizing structures.

[0005] CMP utilizes the interplay of chemical and mechanical action to achieve planarity of the surface to be polished. The chemical action is provided by a chemical composition, also called a CMP slurry or CMP formulation. The mechanical action is usually performed by a polishing pad, which is typically pressed against the surface to be polished and attached to a moving platen. The motion of the platen is usually linear, rotational, or orbital.

[0006] In a typical CMP process step, a rotating wafer holder brings the wafer to be polished into contact with a polishing pad, and a CMP composition is usually applied between the wafer to be polished and the polishing pad.

[0007] CMP compositions typically contain an abrasive, usually colloidal particles, in an aqueous solution.

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

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

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

[0011] However, it is known that the addition of a large amount of aminosilane tends to destabilize the colloidal abrasive dispersion and reduce performance. Therefore, only colloidal abrasive dispersions with very low aminosilane loading (e.g., <1 wt.% per gram of abrasive) are available. Therefore, the performance derived from CMP compositions using such colloidal abrasive dispersions is limited.

[0012] It should therefore be readily apparent from the above that there remains a need in the art for stable colloidal dispersions of aminosilane-modified abrasive particles having higher aminosilane loadings to achieve higher charge densities and zeta potentials. There is also a continuing need for CMP compositions, methods, and systems that use stable colloidal dispersions of amino-polyorganosiloxane-coated abrasive particles to provide improved performance.

[0013] The present invention provides 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

[0014] The present invention provides stable colloidal dispersions of abrasive particles, such as stable colloidal dispersions of amino-polyorganosiloxane-coated silica abrasive particles having high charge density.

[0015] Also provided are CMP compositions, methods, and systems that use stable colloidal dispersions of amino-polyorganosiloxane-coated abrasive particles. Amino-polyorganosiloxane-coated abrasives refer to abrasive particles whose surfaces are completely coated or covered with amino-functional polyorganosiloxane.

[0016] Specifically, CMP compositions using dispersions of stable colloidal amino-polyorganosiloxane-coated abrasive particles have demonstrated high tungsten (W) removal rates, excellent selectivity (e.g., W:PECVD TEOS or W:SiN), especially in the acidic low pH range. x ) and chemical mechanical planarization of tungsten surfaces (i.e., W CMP).

[0017] In one embodiment, a stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles is provided, the surface of the amino-polyorganosiloxane-coated abrasive particles having an amino-functional polyorganosiloxane shell; 29 Stable colloidal dispersions of amino-polyorganosiloxane-coated abrasive particles are provided having a silanol density of SiOH / Si atoms of <60%, or <50%, as measured using Si-NMR spectroscopy, and the amino-polyorganosiloxane-coated abrasive particles have a positive charge of >15 mV, >25 mV, or >35 mV.

[0018] In another aspect, a. The general formula: (A x B y Si) z -R;(I) (wherein x and y are each independently 1 or 2, X+Y=3, and z is 1 or 2; A is a hydrolyzable group such as an alkoxy group selected from the group consisting of methoxy and ethoxy; B is a non-hydrolyzable group not having an amino group, such as an alkyl group having 1 to 6 carbon atoms; R is a non-hydrolyzable group selected from the group consisting of at least one of an aryl or alkyl group containing at least one amino group which can be a primary, secondary, tertiary, and quaternary amino group; b. providing a dispersion of colloidal base abrasive particles, the base abrasive particles having reactive groups on their surfaces; c. adding an aminosilane to the dispersion of colloidal base abrasive particles; d. forming amino-polyorganosiloxane-coated abrasive particles by interacting aminosilanes, their dimers, oligomers, and aminopolyorganosiloxanes (linear or cyclic) formed by interactions between aminosilanes with reactive groups on the surface of base abrasive particles to form amino-functional polyorganosiloxane shells on the surface of the base abrasive, said method comprising the steps of: the amino-functional polyorganosiloxane shell has a thickness of 0.1 nm to 10 nm, or 0.5 to 5 nm, and covers or coats the entire surface of the base abrasive particle; Methods are provided in which the amino-polyorganosiloxane-coated abrasive particles have a silanol density of <60%, or <50% of the SiOH / Si atoms, a positive charge of >15 mV, >25 mV, or >35 mV, and a surface charge density or potential charge carrier density of 0.012 to 1.0, 0.04 to 0.8, 0.06 to 0.6, or 0.08 to 0.5 mmol / g of silica.

[0019] The colloidal base abrasive particle dispersion contains base abrasive particles, which can be any suitable abrasive particles having reactive groups on the surface of the particles. The reactive groups can form covalent bonds with aminosilanes, their dimers, oligomers, and polymers (linear or cyclic), as disclosed above. The preferred abrasive particles contain Si-OH groups on the surface.

[0020] R is preferably an alkyl group containing at least one amino group, such as an aminomethylene group, an aminoethylene group, an aminopropylene group, an aminoisopropylene group, or an aminobutylene group.

[0021] Aminosilanes include, but are not limited to, methyl or ethyl substituted derivatives.

[0022] Specifically, the aminosilanes include n-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, n-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, (phenylaminomethyl)methyldimethoxysilane, n-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, n-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-(n,n-dimethylaminopropyl)aminopropylmethyldimethoxysilane, and 3-aminopropyldiisopropylethoxysilane. , 3-aminopropylmethyldiethoxysilane, 4-amino-3,3-dimethylbutylmethyldimethoxysilane, n,n-dimethyl-3-aminopropylmethyldimethoxysilane, n-methylaminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, (phenylaminomethyl)methyldimethoxysilane, bis(methyldimethoxysilylpropyl)-n-methylamine, 4-aminobutyldimethylmethoxysilane, and (4-aminobutyl)methyldiethoxysilane.

[0023] The amount of aminosilane is >1, 2, or 3.0% by weight and <20, 15, or 10% by weight per gram of abrasive.

[0024] In some embodiments, step a of the above method can provide at least one of a co-reactant silane in addition to the aminosilane.

[0025] Coreactant silanes include, but are not limited to, (1) alkoxysilanes and organically modified alkoxysilanes having at least one and up to two non-hydrolyzable substituents on the Si atom that are inert or have aliphatic, aromatic or cycloaliphatic functional groups, such as methyl, ethyl, propyl, or phenyl groups; (2) alkoxysilanes, such as methoxysilanes, ethoxysilanes, propoxysilanes, and the like, preferably tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), methyltriethoxysilane (MTEOS), trimethylmethoxysilane (MTMOS), or dimethyldimethoxysilane, or monomers (preferred) and preformed oligomers; and (3) silanes with other hydrolyzable groups, such as oximatosilanes, chlorosilanes, silazanes, and oligosilazanes.

[0026] The mix ratio (volume ratio) of the amount of aminosilane to the amount of co-reactant used is >1:99, >1:50, 1:40, 1:30, 1:20, or >1:10, for example, 1:9.

[0027] In yet another aspect, a CMP polishing composition is provided, the composition comprising: a stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles as disclosed above, and Contains a water-soluble solvent, The composition comprises: It has a pH of 2-10, 2-8, 2-6, 2-5, 2-4, or 2-3.

[0028] Water-soluble solvents include, but are not limited to, deionized (DI) water, distilled water, and alcoholic organic solvents.

[0029] 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 reducing agents. Examples of the polymers include hydrophilic polymers, -OH, -NR1R2R3R4 (R 1-4 are independently H, alkyl, or aryl), including, but not limited to, those with organic functional groups such as CN, ester, amide, halogen, and ether; Inorganic polymers, such as polymetal hydroxide clusters of single or mixed metals, polyanions, polycations, especially those containing Al, Ce, Zr, Fe as metal ions; It comprises at least one of surface active molecules / oligomers / polymers such as cationic, anionic or non-ionic surfactants and polymers that are attached either by physical adsorption, ionic or covalent bonding.

[0030] In another aspect, there is provided a method of chemical mechanical polishing (CMP) a substrate having at least one surface comprising tungsten using the above-described chemical mechanical polishing (CMP) composition.

[0031] The substrate having at least one surface comprising tungsten further comprises a silicon dioxide polished silicon oxide film, which can be a chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), high density deposition CVD (HDP), or spin-on silicon oxide film.

[0032] The removal selectivity of W:SiO2 is greater than 30, preferably greater than 50, 80, 100, 120, or 140. [Brief description of the drawings]

[0033] [Figure 1] 1 shows the zeta potential (mV) as a function of the amount of aminosilane charge carriers (in mmol / g silica) on the surface of amino-polyorganosiloxane-coated abrasive particles at pH 2.5. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] The present invention relates to chemical mechanical polishing (CMP) compositions (also known as slurries or formulations), methods, and systems that use dispersions of stable colloidal amino-polyorganosiloxane-coated abrasive particles, where amino-polyorganosiloxane-coated abrasive refers to abrasive particles having a surface that is completely coated or covered by an amino-functional polyorganosiloxane shell. The amino-functional polyorganosiloxane shell has a thickness of 0.1 nm to 10 nm, or 0.5 to 5 nm. The amino-polyorganosiloxane-coated abrasive particles have a high surface charge density or potential charge carrier density of 0.012 to 1.0, 0.04 to 0.8, 0.06 to 0.6, or 0.08 to 0.5 mmol / g of silica, and

[0035] Zeta potential and low silanol density ( 29 The amino-polyorganosiloxane-coated abrasive particles have a positive charge of >15 mV, >25 mV, or >35 mV (measured using Si-NMR spectroscopy).

[0036] A dispersion of colloidal amino-polyorganosiloxane-coated abrasive particles refers to amino-polyorganosiloxane-coated abrasive particles (usually having at least one dimension in the range of 1 nm to 500 nm) dispersed in a solvent, including water.

[0037] The term "polyorganosiloxane" refers to a polymer consisting of a silicon-oxygen backbone with organic alkyl (typically methyl) group(s) attached to the silicon atom(s), whereas the term "polysiloxane" refers to a polymer consisting of silicon-oxygen without alkyl (methyl) group(s) attached to the silicon atom. For example, polysiloxane formed with tetraethyl orthosilicate (TEOS).

[0038] To achieve superior performance, such as removal rate and selectivity, it is desirable to have abrasive particles with very high charge density and zeta potential. It is believed that the charge density on the abrasive particles can contribute significantly to the performance of the CMP composition, in addition to providing a repulsive force to stabilize the colloidal abrasive particles in the CMP composition.

[0039] For example, the higher charge density is believed to contribute to the low SiO2 removal rate, a desired characteristic of an abrasive for chemical mechanical planarization of tungsten surfaces, especially in the acidic pH region of W CMP compositions.

[0040] Therefore, it is desirable to attach a large / high amount of amino groups to the surface of the abrasive, which can then react with the positively charged ammonium groups at low pH.

[0041] However, it is known that the addition of large amounts of aminosilane tends to destabilize the dispersion of colloidal abrasive particles, decreasing removal rate and selectivity.

[0042] For example, aminosilane modification of silica is known to be difficult, often resulting in clumping and gelling if too much aminosilane is used, especially if not handled carefully.

[0043] Aminosilane as a modifier, especially as a surface modifier, is intended to convert isolated silanol groups to siloxanes on the surface of abrasive particles. The amount of aminosilane used is usually kept as low as possible so as to just reach a sufficiently high zeta potential. Therefore, typically, the aminosilane loading is very low (e.g., <1 wt.% per silica abrasive). After using low aminosilane loading, free silanol groups still remain.

[0044] Furthermore, for W CMP where good selectivity (e.g., W:PECVD TEOS or W:SiNx) is required, the aminosilane modified abrasive particles may need to have a low silanol content, a factor that could potentially reduce the selectivity of W CMP as silanol groups interact with SiO2 and SiN coatings and affect their removal rates.

[0045] Many of the problems associated with achieving high aminosilane loadings in dispersions of colloidal abrasive particles stem from the (1) -NH2, -NR1H, -NR2R3 (R 2,3 may be aliphatic, aromatic, with or without further functional groups), protonated cationic ammonium functional moieties, e.g., -N + H3 or -N + The present invention has demonstrated that this can be mitigated if one uses at least one amino-functional moiety containing R2R3H, (2) at least one Si moiety which can be a bidentate (e.g., bispropyldimethoxymethylsilylamine) or an oligomer, and (3) an amino-functional silane (aminosilane) having at least one hydrolyzable group and up to two hydrolyzable groups on (each) silicon atom.

[0046] In another aspect, a. The general formula: (A x B y Si) Z -R;(I) (wherein x and y are each independently 1 or 2, X+Y=3, and z is 1 or 2; A is a hydrolyzable group such as an alkoxy group selected from the group consisting of methoxy and ethoxy; B is a non-hydrolyzable group not having an amino group, such as an alkyl group having 1 to 6 carbon atoms; and R is a non-hydrolyzable group selected from the group consisting of at least one of an aryl or alkyl group containing at least one amino group which can be a primary, secondary, tertiary, and quaternary amino group; b. providing a dispersion of colloidal base abrasive particles, the base abrasive particles having reactive groups on their surfaces; c. adding an aminosilane to the dispersion of colloidal base abrasive particles; d. forming amino-polyorganosiloxane-coated abrasive particles by interacting aminosilanes, their dimers, oligomers, and aminopolyorganosiloxanes (linear or cyclic) formed by interactions between aminosilanes with reactive groups on the surface of the base abrasive particles to form an amino-functional polyorganosiloxane shell on the surface of the base abrasive, said method comprising the steps of: Methods are provided in which the amino-functional polyorganosiloxane shell has a thickness of 0.1 nm to 10 nm, or 0.5 to 5 nm, and covers or coats the entire surface of the base abrasive particle.

[0047] The amino-functional polyorganosiloxane shell has a thickness of 0.1 nm to 10 nm, or 0.5 to 5 nm. The amino-polyorganosiloxane-coated abrasive particles have a surface charge density or potential charge carrier density of 0.012 to 1.0, 0.04 to 0.8, 0.06 to 0.6, or 0.08 to 0.5 millimoles per gram of silica (mmol / g), a silanol density of <60%, or <50% of the SiOH / Si atoms, and a positive charge of >15 mV, >25 mV, or >35 mV.

[0048] The aminosilanes shown in formula (I) are most crosslinkable aminosilanes.

[0049] The colloidal base abrasive particle dispersion contains base abrasive particles, which can be any suitable abrasive particles having reactive groups on the surface of the particles. The reactive groups can form covalent bonds with aminosilanes, their dimers, oligomers, and polymers (linear or cyclic), as disclosed above. The preferred abrasive particles contain Si-OH groups on the surface.

[0050] R is preferably an alkyl group containing at least one amino group, such as an aminomethylene group, an aminoethylene group, an aminopropylene group, an aminoisopropylene group, or an aminobutylene group.

[0051] Aminosilanes include, but are not limited to, methyl or ethyl substituted derivatives.

[0052] Specifically, the aminosilanes include n-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, n-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, (phenylaminomethyl)methyldimethoxysilane, n-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, n-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-(n,n-dimethylaminopropyl)aminopropylmethyldimethoxysilane, and 3-aminopropyldiisopropylethoxysilane. , 3-aminopropylmethyldiethoxysilane, 4-amino-3,3-dimethylbutylmethyldimethoxysilane, n,n-dimethyl-3-aminopropylmethyldimethoxysilane, n-methylaminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, (phenylaminomethyl)methyldimethoxysilane, bis(methyldimethoxysilylpropyl)-n-methylamine, 4-aminobutyldimethylmethoxysilane, and (4-aminobutyl)methyldiethoxysilane.

[0053] The amount of aminosilane is >1, 2, or 3.0% by weight and <20, 15, or 10% by weight per gram of abrasive. For example, when colloidal silica is used as the base abrasive particle, the amount of aminosilane is >1, 2, or 3.0% by weight and <20, 15, or 10% by weight per gram of silica.

[0054] In some embodiments, step a of the above method, in addition to providing an aminosilane, can further provide at least one of a co-reactant silane.

[0055] When y=2 and z=1, a coreactant silane is required.

[0056] Coreactant silanes include, but are not limited to, (1) alkoxysilanes and organically modified alkoxysilanes having at least one and up to two non-hydrolyzable substituents on the Si atom that are inert or have aliphatic, aromatic or cycloaliphatic functional groups, such as methyl, ethyl, propyl, or phenyl groups; (2) alkoxysilanes, such as methoxysilanes, ethoxysilanes, propoxysilanes, and the like, preferably tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), methyltriethoxysilane (MTEOS), trimethylmethoxysilane (MTMOS), or dimethyldimethoxysilane, or monomers (preferred) and preformed oligomers; and (3) silanes with other hydrolyzable groups, such as oximatosilanes, chlorosilanes, silazanes, and oligosilazanes.

[0057] Among the co-reactants, tetraethyl orthosilicate (TEOS) and tetramethyl orthosilicate (TMOS) are network-forming silanes, while methyltriethoxysilane (MTEOS), trimethylmethoxysilane (MTMOS), and dimethyldimethoxysilane are network-modifying silanes. The co-reactant silanes act with aminosilanes, their dimers, oligomers, and polymers (linear or cyclic) to form an amino-functional polyorganosiloxane shell on the surface of the base abrasive particle.

[0058] The aminosilane and the co-reactant silane can be pre-reacted to form dimers, trimers, or oligomers prior to contacting the base abrasive particles.

[0059] The mixing ratio of the aminosilane and the co-reactant silane determines the mechanical and chemical properties of the polyorganosiloxane.

[0060] The mix ratio (volume ratio) of the amount of aminosilane to the amount of co-reactant used is >1:99, 1:50, 1:40, 1:30, 1:20, or >1:10, for example 1:9.

[0061] In yet another aspect, a CMP polishing composition is provided, the composition comprising: a stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles as disclosed above, and Contains a water-soluble solvent, It has a pH of 2-10, 2-8, 2-6, 2-5, 2-4, or 2-3.

[0062] Water-soluble solvents include, but are not limited to, deionized (DI) water, distilled water, and alcoholic organic solvents.

[0063] 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 reducing agents. Examples of the polymers include hydrophilic polymers, -OH, -NR1R2R3R4 (R 1~4 are independently H, alkyl, or aryl), organic polymers, including but not limited to those with organic functional groups such as CN, esters, amides, halogens, and ethers; Inorganic polymers, such as polymetal hydroxide clusters of single or mixed metals, polyanions, polycations, especially those containing Al, Ce, Zr, Fe as metal ions; It comprises at least one of surface active molecules / oligomers / polymers such as cationic, anionic or non-ionic surfactants and polymers that are attached either by physical adsorption, ionic or covalent bonding.

[0064] The aminosilane can be added at high loadings to a dispersion of colloidal base abrasive particles.

[0065] In general, the base abrasive particles can be any suitable CMP abrasive particles so long as the abrasive particles have reactive groups on their surface that can form covalent bonds with the aminosilanes disclosed above, etc. Preferred abrasive particles include Si-OH groups on the surface, such as silica.

[0066] The base abrasive particles can have any shape, and can be spherical or non-spherical, for example, elongated and / or branched, and the base abrasive particles can be partially agglomerated. Elongated shapes are preferred.

[0067] The base abrasive particles can be colloidal or fumed silica, alumina, homogeneous or gradient or core / shell particles of ceria (such as silica on alumina), composite particles (e.g., ceria-coated silica particles), or combinations thereof. Colloidal silica and fumed silica are preferred. Base colloidal silica can be synthesized by wet chemistry, thermally produced (e.g., fumed, fused, etc.), and doped (e.g., with Al, Ce ions) using mixed metal oxides (e.g., aluminosilicates, zirconium silicates).

[0068] The base abrasive particles can have a mean particle size (MPS) (for agglomerated or non-spherical particles) of 5-500 nm, 10-400 nm, 15-200 nm, or 25-150 nm, as measured by Dynamic Light Scattering (DLS).

[0069] The process for making the amino-polyorganosiloxane-coated abrasive particles begins with adding a sufficient amount of a crosslinkable aminosilane having the general formula (I) as shown above to a dispersion of base abrasive particles.

[0070] The total amount of reactive groups of the aminosilane used, or together with the co-reactant silanes (if they are added), must exceed the number of accessible silanol groups on the surface of the abrasive particle.

[0071] Without being bound by theory, it is believed that the reaction involves (1) a reaction between the aminosilane and the base abrasive particle. More specifically, a portion of the aminosilane reacts with all of their alkoxy reactive sites with the Si-OH groups on the surface of the base abrasive particle to convert / shield / end-cap the Si-OH groups, and (2) a reaction between the excess portions of the aminosilanes themselves to form polyaminoorganosiloxane monomers, oligomers and / or polymers. Some of the aminopolyorganosiloxanes have multiple chemical bonds to the base abrasive particle, and some of the aminopolyorganosiloxanes are crosslinked to other aminopolyorganosiloxanes to form a shell on top of the base abrasive particle. Furthermore, the aminosilane monomers, oligomers and / or polymers used can be present in the dispersion of amino-polyorganosiloxane-coated abrasive particles either free without any type of bond to the abrasive particle, or associated with the abrasive particle via a non-covalent bond.

[0072] These free, unbound aminopolysiloxanes appear to play a critical role in the performance of amino-polyorganosiloxane-coated abrasive particles with respect to W removal rate.

[0073] The amino-polyorganosiloxane-coated abrasive particles have a core-shell structure with a base abrasive particle as a core and an aminopolyorganosiloxane shell, the thickness of the shell being 0.1 to 10 nm, preferably 0.5 to 5 nm.

[0074] Without wishing to be bound by theory, it is believed that amino-polyorganosiloxane-coated abrasive particles having such a core-shell structure contain significantly more aminosilane than other abrasive particles known in the state of the art.

[0075] It should be noted that the aminosilanes having the general formula (I) are different from the well-known and typically used trialkoxyamino-functional silanes. The aminosilanes having the general formula (I) are mono- or dialkoxysilanes having non-hydrolyzable group(s) that do not have an amino group. The typically used trialkoxyamino-functional silanes, in addition to not being mono- or dialkoxysilanes, do not have non-hydrolyzable group(s) that do not have an amino group.

[0076] Surprisingly, it has been discovered that abrasives having the same amount of unbound polysiloxane exhibit dramatically different W-RRs when known amino-functional trialkoxysilanes are used in place of mono- or dialkoxysilanes. The W-RR of the abrasives of the present invention can be 30-50 times higher than the W-RR of known abrasives having trialkoxy-aminosilanes.

[0077] It therefore appears that the presence of non-hydrolyzable group(s) on the Si atom may play a role in understanding the described effects. The non-hydrolyzable group(s) on the Si atom may affect the hydrolysis and condensation rates of the silanes, their adsorption onto the abrasive particle surface, and the structure of the dimers / oligomers that occur either on the particle surface or in solution.

[0078] The amino-polyorganosiloxane-coated abrasive particles are new particles and not simply aminosilane-modified abrasive particles known in the art.

[0079] The amino-functional polyorganosiloxane shell on the surface of the base abrasive particle has its own chemical and mechanical properties that are different from the base or core abrasive particle. Thus, the amino-polyorganosiloxane-coated abrasive particles are hybrid core / shell abrasive particles.

[0080] The amino groups in the amino-polyorganosiloxane shell are potential charge carriers that depend on the pH of the dispersion medium.

[0081] In acidic dispersion media (preferred), these amino groups are protonated to form ammonium ions and carry a positive charge, which is responsible for the desirable high zeta potential at these preferred low pHs (e.g., pH 2.5), which is a prerequisite for colloidally stable abrasive dispersions.

[0082] The zeta potential (mv) of aminosilane- and amino-polyorganosiloxane shell coated abrasive particles can be monitored as a function of charge carrier content (mmol / g silica).

[0083] FIG. 1 shows a chart of zeta potential values ​​measured for 90 nm SiO2 particles modified with increasing amounts of aminosilane (aminomethyldimethoxysilane) (units were mmol / g silica at pH 2.5).

[0084] It has been clearly shown that even a very small amount of charge carriers (amino groups) can result in a sufficiently high zeta potential of the abrasive, and furthermore, excess charge carriers do not necessarily increase the zeta potential further, but rather result in a plateau in the zeta potential.

[0085] The prior art does not teach that excess charge carriers beyond those required to reach the zeta potential plateau provide any advantage to colloidal stability or CMP performance.

[0086] It was therefore quite surprising to discover that when the aminopolyorganosiloxane shell contains many more excess potential charge carriers (amino groups) than are required to maintain a high zeta potential (>+25 mV@pH 2.5) for minimal colloidal stability, the abrasive exhibits the demonstrated high CMP performance removal rates and selectivity combined with excellent colloidal stability.

[0087] Without wishing to be bound by theory, this high charge carrier density on the surface of the abrasive may contribute to the combination of excellent selectivity and high removal rates of the abrasives of the present invention.

[0088] However, this effect of high charge carrier density only appears with the aminopolyorganosiloxane shells of the present invention, where the amino-functional polyorganosiloxane contains alkyl groups with 1-6 carbon atoms, and not with state-of-the-art aminosilane surface modifications that do not have these alkyl groups.

[0089] Also, the amino-polyorganosiloxane-coated abrasive particles are not simply aminosilane-modified abrasive particles known in the art.

[0090] In another aspect, there is provided a method of chemical mechanical polishing (CMP) a substrate having at least one surface comprising tungsten using the above-described chemical mechanical polishing (CMP) composition.

[0091] In another aspect, a system is provided for chemical mechanical polishing (CMP) a substrate having at least one surface comprising tungsten using the above-described chemical mechanical polishing (CMP) composition.

[0092] The substrate having at least one surface comprising tungsten further comprises a silicon dioxide polished silicon oxide film, which can be a chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), high density deposition CVD (HDP), or spin-on silicon oxide film.

[0093] The removal selectivity of W:SiO2 is greater than 30, preferably greater than 50, 80, 100, 120, or 140.

[0094] The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope.

[0095] CMP Methodology In the examples presented below, CMP experiments were performed using the procedures and experimental conditions set out below.

[0096] Glossary Parameters General Å or ​​A: Angstrom - unit of length

[0097] BP: Back pressure, unit is psi

[0098] CMP: Chemical mechanical planarization = chemical mechanical polishing

[0099] CS: Carrier Speed

[0100] DF: Downforce: pressure applied during CMP, unit: psi

[0101] min:minutes

[0102] mL: milliliter

[0103] mV: millivolt

[0104] psi: pounds per square inch

[0105] PS: Polishing tool platen rotation speed, in rpm (revolutions per minute)

[0106] SF: composition flow rate, mL / min

[0107] TEOS: Tetraethyl orthosilicate

[0108] Wt%: weight percent (of listed ingredients)

[0109] W: TEOS selectivity: (W removal rate) / (TEOS removal rate)

[0110] HDP: TEOS deposited by high density plasma

[0111] TEOS or HDP Removal Rate: The TEOS or HDP removal rate measured at a given down pressure.

[0112] measurement The films were measured using a ResMap CDE, Model 168, manufactured by Creative Design Engineering, Inc., 20565 Alves Dr., Cupertino, CA, 95014. The ResMap tool is a four-point probe sheet resistance tool. A 49-point diametric scan with 5 mm edge exclusion was performed on the film.

[0113] CMP Tools The CMP tools used were a 200 mm Mirra or a 300 mm Reflexion manufactured by Applied Materials, 3050 Boweres Avenue, Santa Clara, California, 95054. An IC1000 pad supplied by DOW, Inc. (451 Bellevue Rd., Newark, Del. 19713) was used on platen 1 for blanket and patterned wafer studies.

[0114] The IK4250UH pad or other pads were conditioned and broken in for 18 minutes. The conditioner downforce was 7 pounds. To verify the tool settings and pad break-in, two tungsten monitors and two TEOS monitors were polished with Versum® STI2305 composition supplied by Versum Materials Inc. at baseline conditions.

[0115] All polishing data in the following examples was generated on a Mirra polisher using an IC 1010 pad at a polishing downforce of 2.5 psi.

[0116] Wafer Polishing experiments were performed using PECVD or LPCVD or HD, TEOS wafers. These blanket wafers were purchased from Silicon Valley Microelectronics, 2985 Kifer Rd., Santa Clara, CA 95051.

[0117] 1. Abrasive modification experiment a. Comparative example Example 1 Use of 3-aminopropyltrimethoxysilane Peanut-shaped colloidal silica particles IDISIL® KE40 were purchased from Evonik, and the average particle size was measured by DLS to be 53 nm.

[0118] In this example, peanut-shaped colloidal silica particles were surface modified with 3-aminopropyltrimethoxysilane.

[0119] In a 250 mL four-neck round-bottom flask equipped with a magnetic stirrer, an aqueous dispersion of peanut-shaped SiO2 nanoparticles (126.26 g, 0.42 mol of SiO2, average particle size 53 nm, pH 4.1), previously treated with an Amberlite IRN-150 ion exchanger, was stirred at room temperature.

[0120] In a 100 mL round bottom flask, nitric acid 65% (3.2 mL, 45.84 mmol) and methanol (31.22 mL, 0.77 mol) were mixed.

[0121] 3-Aminopropyltrimethoxysilane, 97% (2.69 mL, 15.28 mmol) was added, the mixture was shaken by hand for 5 seconds, and then quickly added to the dispersion of SiO2 particles. The mixture was continuously stirred at room temperature for 1 hour, then at 70° C. for 2 hours to form a reaction mixture.

[0122] 100 mL of deionized water was added to the reaction mixture and the resulting dispersion was concentrated on a rotary evaporator until the solids content reached approximately 20% by weight.

[0123] Yield: 104.1g, solids 23.5%, pH 0.99

[0124] Particle size: 53 nm (DLS), PDI 0.063, Zeta potential: 34.8 mV

[0125] Example 2 Use of 3-aminopropyltrimethoxysilane The elongated nanoparticles disclosed in U.S. Patent Application No. 63 / 177,539, filed April 21, 2021, were used.

[0126] In this example, elongated shaped colloidal silica particles were surface modified with 3-aminopropyltrimethoxysilane.

[0127] The same process steps used and described in Comparative Example 1 were used in this example.

[0128] A dispersion of elongated nanoparticles ion-exchanged with Amberlite IRN-150 (384.60 g, 0.42 mol SiO2, average particle size: 90.2 (DLS), PDI of 0.044, pH 4.0) was placed in a 1000 mL four-neck round bottom flask equipped with a magnetic stirrer and stirred at room temperature.

[0129] In a 100 mL round bottom flask, nitric acid 65% (2.52 mL, 36.09 mmol) and methanol (41.37 mL, 1.02 mol) were mixed. 3-Aminopropyltrimethoxysilane (2.1 mL, 12.03 mmol) was added, the mixture was shaken by hand for 5 seconds, and then quickly added to the dispersion of SiO2 particles. The mixture was continuously stirred at room temperature for 1 hour, then at 70° C. for 2 hours to form a reaction mixture.

[0130] 200 mL of deionized water was added to the reaction mixture and the resulting dispersion was concentrated on a rotary evaporator until the solids content reached approximately 20% by weight.

[0131] Yield: 112.3g, Solids: 20.6%, pH 1.03

[0132] Particle size: 87.9 nm (DLS), PDI: 0.041, Zeta potential: 41.2 mV

[0133] Example 3 Use of 2-aminoethyl-3-aminopropyl-trimethoxysilane The elongated nanoparticles disclosed in U.S. Patent Application No. 63 / 177,539, filed April 21, 2021, were used.

[0134] In this example, elongated shaped colloidal silica particles were surface modified with 2-aminoethyl-3-aminopropyl-trimethoxysilane.

[0135] The same process steps used and described in Comparative Example 1 were used in this example.

[0136] In a 250 mL four-neck round-bottom flask equipped with a magnetic stirrer, an aqueous dispersion of elongated shaped SiO2 nanoparticles (126.26 g, 0.42 mol of SiO2, average particle size 53 nm, pH 4.1), pre-treated with an Amberlite IRN-150 ion exchanger, was stirred at room temperature.

[0137] In a 100 mL round bottom flask, nitric acid 65% (6.39 mL, 91.68 mmol) and methanol (31.22 mL, 0.77 mol) were mixed. 2-Aminoethyl-3-aminopropyltrimethoxysilane (3.30 mL, 15.28 mmol) was added, the mixture was shaken by hand for 5 seconds, and then quickly added to the dispersion of SiO2 particles. The mixture was continuously stirred at room temperature for 1 hour, then at 70° C. for 2 hours to form a reaction mixture.

[0138] 100 mL of deionized water was added to the reaction mixture and the resulting dispersion was concentrated on a rotary evaporator until the solids content reached approximately 20% by weight.

[0139] Yield: 95.0 g, solids 17.2%, pH 0.91

[0140] Particle size: 53.1 nm (DLS) PDI: 0.058, Zeta potential: 36.9 mV.

[0141] Example 4 Use of 3-aminopropyltrimethoxysilane The elongated nanoparticles disclosed in U.S. Patent Application No. 63 / 177,539, filed April 21, 2021, were used.

[0142] In this example, elongated shaped colloidal silica particles were surface modified with 3-aminopropyltrimethoxysilane.

[0143] The same process steps used and described in Comparative Example 1 were used in this example.

[0144] A dispersion of elongated nanoparticles ion-exchanged with Amberlite IRN-150 (384.60 g, 0.42 mol SiO2, average particle size: 90.2 (DLS), PDI of 0.044, pH 4.0) was placed in a 1000 mL four-neck round bottom flask equipped with a magnetic stirrer and stirred at room temperature.

[0145] In a 100 mL round bottom flask, nitric acid 65% (0.157 mL, 2.25 mmol) and methanol (41.37 mL, 1.02 mol) were mixed. 3-Aminopropyltrimethoxysilane (0.13 mL, 0.752 mmol) was added, the mixture was shaken by hand for 5 seconds, and then quickly added to the dispersion of SiO2 particles. The mixture was continuously stirred at room temperature for 1 hour, then at 70 °C for 2 hours to form a reaction mixture.

[0146] 200 mL of deionized water was added to the reaction mixture and the resulting dispersion was concentrated on a rotary evaporator until the solids content reached approximately 20% by weight.

[0147] Yield: 110.1g, Solids: 20.1%, pH 1.13

[0148] Particle size: 85.7 nm (DLS), PDI: 0.039, Zeta potential: 36.4 mV

[0149] b. Example Example 1: Use of 3-aminopropyl-methyldimethoxysilane The same peanut-shaped colloidal silica particles, IDISIL® KE40, used and described in Comparative Example 1, as well as the same process steps used and described in Comparative Example 1, were used in this example.

[0150] However, the peanut-shaped colloidal silica particles were surface modified with 3-aminopropyl-methyldimethoxysilane in this example.

[0151] In a 250 mL four-neck round-bottom flask equipped with a magnetic stirrer, an aqueous dispersion of elongated shaped SiO2 nanoparticles (126.26 g, 0.42 mol of SiO2, average particle size 53 nm, pH 4.1), pre-treated with an Amberlite IRN-150 ion exchanger, was stirred at room temperature.

[0152] In a 100 mL round bottom flask, nitric acid 65% (3.20 mL, 45.84 mmol) and methanol (31.22 mL, 0.77 mol) were mixed. 3-Aminopropyl-methyldimethoxysilane (2.63 mL, 15.28 mmol) was added, the mixture was shaken by hand for 5 seconds, and then quickly added to the dispersion of SiO2 particles. The mixture was continuously stirred at room temperature for 1 hour, then at 70° C. for 2 hours to form a reaction mixture.

[0153] 100 mL of deionized water was added to the reaction mixture and the resulting dispersion was concentrated on a rotary evaporator until the solids content reached approximately 20% by weight.

[0154] Yield: 110.2 g, solids 22.6%, pH=1.09

[0155] Particle size: 53.7 nm (DLS), PDI: 0.078, Zeta potential: 34.9 mV

[0156] Example 2: Use of 3-aminopropyl-dimethylmethoxysilane The same peanut-shaped colloidal silica particles IDISIL® KE40 used and described in Comparative Example 1 were used in this example, as well as the same process steps.

[0157] However, in this example, the peanut-shaped colloidal silica particles were surface modified with 3-aminopropyl-dimethylmethoxysilane.

[0158] In a 250 mL four-neck round-bottom flask equipped with a magnetic stirrer, an aqueous dispersion of elongated shaped SiO2 nanoparticles (126.26 g, 0.42 mol of SiO2, average particle size 53 nm, pH 4.1), pre-treated with an Amberlite IRN-150 ion exchanger, was stirred at room temperature.

[0159] In a 100 mL round bottom flask, nitric acid 65% (3.20 mL, 45.84 mmol) and methanol (31.22 mL, 0.77 mol) were mixed. 3-Aminopropyl-dimethylmethoxysilane (2.59 mL, 15.28 mmol) and methyltriethoxysilane (3.06 mL, 15.28 mmol) were added, the mixture was shaken by hand for 5 seconds, and then quickly added to the dispersion of SiO2 particles. The mixture was continuously stirred at room temperature for 1 hour, then at 70 °C for 2 hours to form a reaction mixture.

[0160] 100 mL of deionized water was added to the reaction mixture and the resulting dispersion was concentrated on a rotary evaporator until the solids content reached approximately 20% by weight.

[0161] Yield: 109.3 g, solids 22.9%, pH 1.07

[0162] Particle size: 53 nm (DLS) PDI: 0.060, Zeta potential: 34.1 mV.

[0163] Example 3: Use of 3-aminopropyl-methyldimethoxysilane The elongated nanoparticles disclosed in U.S. Patent Application No. 63 / 177,539, filed April 21, 2021, were used.

[0164] The same process steps used and described in Comparative Example 1 were used in this example.

[0165] However, in this example, the peanut-shaped colloidal silica particles were surface modified with 3-aminopropyl-methyldimethoxysilane.

[0166] A dispersion of elongated nanoparticles (384.60 g, 0.42 mol SiO2, average particle size: 90.29 (DLS), PDI of 0.044, pH 4.0) previously ion-exchanged with Amberlite IRN-150 was placed in a 1000 mL four-neck round-bottom flask equipped with a magnetic stirrer and stirred at room temperature.

[0167] In a 100 mL round bottom flask, nitric acid 65% (2.52 mL, 36.09 mmol) and methanol (41.37 mL, 1.02 mol) were mixed. 3-Aminopropyl-methyldimethoxysilane (2.07 mL, 12.03 mmol) was added, the mixture was shaken by hand for 5 seconds, and then quickly added to the dispersion of SiO2 particles. The mixture was continuously stirred at room temperature for 1 hour, then at 70 °C for 2 hours to form a reaction mixture.

[0168] 200 mL of deionized water was added to the reaction mixture and the resulting dispersion was concentrated on a rotary evaporator until the solids content reached approximately 20% by weight.

[0169] Yield: 107.8 g, solids 20.3%, pH=1.03

[0170] Particle size: 87.9 nm (DLS), PDI: 0.045, Zeta potential: 46.7 mV

[0171] Example 4: Use of 3-aminopropyl-dimethylmethoxysilane The elongated nanoparticles disclosed in U.S. Patent Application No. 63 / 177,539, filed April 21, 2021, were used.

[0172] The same process steps used and described in Comparative Example 1 were used in this example.

[0173] However, in this example, the peanut-shaped colloidal silica particles were surface modified with 3-aminopropyl-methyldimethoxysilane.

[0174] A dispersion of elongated nanoparticles (384.60 g, 0.42 mol SiO2, average particle size: 90.29 (DLS), PDI of 0.044, pH 4.0) previously ion-exchanged with Amberlite IRN-150 was placed in a 1000 mL four-neck round-bottom flask equipped with a magnetic stirrer and stirred at room temperature.

[0175] In a 100 mL round bottom flask, nitric acid 65% (2.52 mL, 36.09 mmol) and methanol (41.37 mL, 1.02 mol) were mixed. 3-Aminopropyl-dimethylmethoxysilane (2.04 mL, 12.03 mmol) and methyltriethoxysilane (2.41 mL, 12.03 mmol) were added, the mixture was shaken by hand for 5 seconds, and then quickly added to the dispersion of SiO2 particles. The mixture was continuously stirred at room temperature for 1 hour, then at 70 °C for 2 hours to form a reaction mixture.

[0176] 200 mL of deionized water was added to the reaction mixture and the resulting dispersion was concentrated on a rotary evaporator until the solids content reached approximately 20% by weight.

[0177] Yield: 112.3g, Solids: 20.6%, pH 1.03

[0178] Particle size: 89.6 nm (DLS), PDI: 0.032, Zeta potential: 37.9 mV

[0179] 2. Silanol Density Measurement The silanol density is 29 Measurements were performed by Si-NMR spectroscopy.

[0180] Q from the deconvoluted spectrum 1 -Q 4 Quantify the signal (Σ(Q 1 ,...,Q 4 )=100%), and the silanol density was calculated according to the following formula: Q 1 : 3 silanol groups per silicon atom (300%) Q 2 : 2 silanol groups per silicon atom (200%) Q 3 : 1 silanol group per silicon atom (100%) Q 4 : 0 silanol groups per silicon atom (0%) Silanol density (% silanol per Si atom) = Q 1* 300+Q 2*200+Q 3* 100

[0181] The results of the silanol density on the surface of the abrasive particles obtained in Comparative Example 2, Examples 3 and 4 are shown in Table 1. [Table 1]

[0182] As shown in Table 1, the number of silanol groups detected from the abrasive particles treated with 3-aminopropyl-dimethylmethoxysilane (not of the present invention) is significantly higher than the number of silanol groups detected from the abrasive particles treated with 3-aminopropyl-methyldimethoxysilane (Example 3 of the present invention) or 3-aminopropyltrialkoxysilane (Example 4 of the present invention). This may help provide a further explanation for the exceptionally good CMP performance of the abrasives of the present invention.

[0183] 3. CMP Polishing Experiment Removal rate and selectivity The modified SiO2 dispersion obtained from the abrasive modification experiment was used to formulate a typical W-CMP slurry. The removal rates (RR) of tungsten wafers and CVD-TEOS(SiO2) coatings were measured using a Mirra polisher (2.5 psi, IC1010). [Table 2]

[0184] CMP slurries are disclosed in US Pat. No. 11,111,435 (B2), the entirety of which is incorporated herein by reference.

[0185] The polishing results (removal rate and selectivity) are shown in Table 2.

[0186] The measured removal rates clearly show the advantage of using metal- or dimethyl-derivatives compared to trimethoxysilane: the particles of the present invention show a 30-fold higher W removal rate and 35-fold higher selectivity than the comparative example with the commonly used silane, a very surprising difference that has not been described before.

[0187] Defect Measurement For defect measurement, the abrasives produced in Comparative Example 4 were used in addition to the abrasives obtained from Examples 3 and 4. The total defect rate and total scratch count were measured (0.13μ threshold, n=3). The results for 2.5PSI, Mirra, and IC1010 defects are shown in Table 3. [Table 3]

[0188] The total defects and scratches using the abrasives of the examples of the present invention were found to be significantly lower than those of Comparative Example 4.

[0189] CMP polishing results obtained from CMP compositions containing stable colloidal amino-polyorganosiloxane-coated abrasive particle dispersions using 3-aminopropyl-methyl-dimethoxysilane or 3-aminopropyl-dimethylmethoxysilane and high amounts of methyltriethoxysilane (as a coreactant silane) surprisingly performed better than 3-aminopropyl-trimethoxysilane in terms of both removal rate and selectivity.

[0190] The CMP polishing results also showed that the CMP composition using amino-polyorganosiloxane-coated abrasive particles surprisingly suppressed defects during CMP compared to the state-of-the-art known abrasive prepared as shown in Comparative Example 4.

[0191] Without wishing to be bound by theory, it is believed that the unique properties of the amino-modified polyorganosiloxane shell are the determining factor in reducing the number of defects compared to the simple "surface-modified silica" of the benchmark (Comparative Example 4).

[0192] The embodiments of the invention listed above, including the examples, are illustrative of the numerous embodiments that may be made from the present invention. It is contemplated that numerous other configurations of the process may be used and that the materials used in the process may be selected from numerous materials other than those specifically disclosed.

Claims

1. A stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles, A stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles, wherein the amino-polyorganosiloxane-coated abrasive particles have an amino-functional polyorganosiloxane shell as their surface, and the amino-functional polyorganosiloxane contains an alkyl group having 1 to 6 carbon atoms.

2. A stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles according to claim 1, wherein the amino-polyorganosiloxane-coated abrasive particles have a silanol density of less than 60% of SiOH / Si atoms and a positive charge greater than 15 mV.

3. The stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles according to claim 1, wherein the amino-functionalized polyorganosiloxane shell has a thickness of 0.1 to 10 nm.

4. A method for preparing a stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles, a. The following general formula: (A x B y Si) z -R;(I) (In the equation, x and y are independently 1 or 2, x + y = 3, and z is 1 or 2.) A is a hydrolyzable group selected from the group consisting of methoxy, ethoxy, and combinations thereof. B is a non-hydrolyzable group selected from the group consisting of alkyl groups and phenyl groups having 1 to 6 carbon atoms, and B does not have an amino group. The present invention provides an aminosilane having R, which is a non-hydrolyzable group selected from the group consisting of at least one aryl group or alkyl group containing at least one amino group that can be a primary, secondary, tertiary, or quaternary amino group. b. To provide a dispersion of colloidal base abrasive particles, wherein the base abrasive particles have reactive groups on their surface. c. Adding the aminosilane to the dispersion of the colloidal base abrasive particles, d. The method involves interacting an aminosilane, its dimer, an oligomer, and an amino-polyorganosiloxane (linear or cyclic) formed by the interaction between the aminosilanes with the reactive groups on the surface of the base abrasive particles to form an amino-functional polyorganosiloxane shell on the surface of the base abrasive particles, thereby forming amino-polyorganosiloxane-coated abrasive particles. The amino-functional polyorganosiloxane shell has a thickness of 0.1 nm to 10 nm and covers or coats the entire surface of the base abrasive particles. A method wherein the amino-polyorganosiloxane-coated polished particles have a silanol density of less than 60% SiOH / Si atoms and a positive charge greater than 15 mV.

5. A method for producing a stable colloidal amino-polyorganosiloxane-coated abrasive particle dispersion according to claim 4, wherein the base abrasive particles are selected from the group consisting of homogeneous or gradient or core / shell particles of colloidal silica, fumed silica, alumina, ceria, and combinations thereof, and the reactive group on the surface of the base abrasive particles is a Si-OH group.

6. A method for producing a stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles according to claim 4, wherein the amount of aminosilane is greater than 1% and less than 20% per gram of the base abrasive particles.

7. A method for producing a stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles according to claim 4, wherein B is methyl.

8. A method for producing a stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles according to claim 4, wherein R is selected from the group consisting of an aminomethylene group, an aminoethylene group, an aminopropylene group, an aminoisopropylene group, an aminobutylene group, an (aminoethyl)aminopropyl group, and combinations thereof.

9. A method for producing a stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles according to claim 4, wherein the reactive group on the surface of the base abrasive particles is a Si-OH group.

10. The aminosilanes mentioned above are n-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, n-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, (phenylaminomethyl)methyldimethoxysilane, n-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, n-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-(n,n-dimethylaminopropyl)aminopropylmethyldimethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-amino-3,3 A method for producing a stable colloidal amino-polyorganosiloxane-coated abrasive particle dispersion according to claim 4, selected from the group consisting of -dimethylbutylmethyldimethoxysilane, n,n-dimethyl-3-aminopropylmethyldimethoxysilane, n-methylaminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, (phenylaminomethyl)methyldimethoxysilane, bis(methyldimethoxysilylpropyl)-n-methylamine, 4-aminobutyldimethylmethoxysilane, (4-aminobutyl)methyldiethoxysilane, and combinations thereof.

11. A method for producing a stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles according to claim 4, wherein the aminosilane is a methyl-substituted derivative selected from the group consisting of aminopropyldimethoxymethylsilane and aminopropyldimethylmethoxysilane.

12. A method for producing a stable colloidal amino-polyorganosiloxane-coated abrasive particle dispersion according to claim 4, wherein the aminosilane is (3-aminopropyl)dimethoxymethylsilane or (3-aminopropyl)(methoxy)dimethylsilane, the colloidal base abrasive particle is colloidal silica, and the dispersion of the stable colloidal amino-polyorganosiloxane-coated abrasive particle is a dispersion of stable colloidal amino-polyorganosiloxane-coated silica.

13. A method for producing a stable colloidal dispersion of amino-polyorganosiloxane-coated polished particles according to claim 4, wherein the amino-functionalized polyorganosiloxane shell has a thickness of 0.1 nm to 10 nm.

14. A method for producing a stable colloidal dispersion of amino-polyorganosiloxane-coated abrasive particles according to claim 4, wherein the amino-polyorganosiloxane-coated abrasive particles have a silanol density of less than 60% of SiOH / Si atoms and a positive charge greater than 15 mV.

15. A method for producing a stable colloidal amino-polyorganosiloxane-coated abrasive particle dispersion according to claim 4, wherein step a further provides at least one co-reactant silane selected from the group consisting of (1) an organically modified alkoxysilane having at least one and up to two non-hydrolyzable substituents on a Si atom selected from the group consisting of an alkoxysilane and a methyl group, an ethyl group, a propyl group, and a phenyl group, and (2) a silane having a hydrolyzable group selected from the group consisting of an oximatosilane, a chlorosilane, a silazane, an oligosilazane, and combinations thereof, wherein the co-reactant silane further interacts with the reactive group and aminosilane on the surface of the base abrasive particles to form an amino-functional polyorganosiloxane shell on the surface of the base abrasive particles, and the ratio of the amount of aminosilane to the amount of co-reactant silane is greater than 1:

99.

16. A method for producing a stable colloidal amino-polyorganosiloxane-coated abrasive particle dispersion according to claim 4, wherein step a further provides at least one alkoxysilane selected from the group consisting of methoxysilane, ethoxysilane, propoxysilane, preferably tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), methyltriethoxysilane (MTEOS), methyltrimethoxysilane (MTMOS), and dimethyldimethoxysilane, a monomer of the alkoxysilane, and a pre-formed oligomer of the alkoxysilane.

17. A method for producing a stable colloidal amino-polyorganosiloxane-coated abrasive particle dispersion according to claim 4, wherein the aminosilane has y=2 and z=1, and step a further provides at least one alkoxysilane selected from the group consisting of methoxysilane, ethoxysilane, propoxysilane, preferably tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), methyltriethoxysilane (MTEOS), methyltrimethoxysilane (MTMOS), and dimethyldimethoxysilane, a monomer of the alkoxysilane, and a pre-formed oligomer of the alkoxysilane.

18. A method for producing a stable colloidal amino-polyorganosiloxane-coated abrasive particle dispersion according to claim 4, wherein the colloidal base abrasive particles are colloidal silica, the aminosilane is (3-aminopropyl)(methoxy)dimethylsilane, step a further provides methyltriethoxysilane, the ratio of the amount of (3-aminopropyl)(methoxy)dimethylsilane to the amount of methyltriethoxysilane is greater than 1:50, and the dispersion of the stable colloidal amino-polyorganosiloxane-coated abrasive particles is a dispersion of stable colloidal amino-polyorganosiloxane-coated silica.

19. A chemical mechanical polishing (CMP) composition, A dispersion of stable colloidal amino-polyorganosiloxane-coated abrasive particles according to claim 1, and Containing a water-soluble solvent, Optionally, Organic and inorganic salts as colloidal stabilizers; Acid / base buffering agent; Biocides; Oxidizing agent; catalyst; Corrosion inhibitor; Organic polymers as erosion, dishing, and corrosion reducers, examples of which include, but are not limited to, hydrophilic polymers, and organic polymers having organic functional groups such as -OH, -NR1 R2 R3 R4 (where R1-4 are independently H, alkyl, or aryl), CN, esters, amides, halogens, and ethers; Inorganic polymers, for example, polymetal hydroxide clusters of a single metal or mixed metal, polyanions, polycations, in particular those containing Al, Ce, Zr, Fe as metal ions; Cationic, anionic, or nonionic surfactants, and surface-active molecules / oligomers / polymers such as polymers that adhere by physical adsorption, ionic bonding, or covalent bonding. Includes at least one of the following: A chemical mechanical polishing (CMP) composition having a pH of 2 to 10.

20. A chemical mechanical polishing (CMP) method, To provide a semiconductor substrate having at least one surface containing tungsten, A dispersion of stable colloidal amino-polyorganosiloxane-coated abrasive particles according to claim 1, and Water-soluble solvent Includes, Optionally, Organic and inorganic salts as colloidal stabilizers; Acid / base buffering agent; Biocides; Oxidizing agent; catalyst; Corrosion inhibitor; Organic polymers as erosion, dishing, and corrosion reducers, examples of which include, but are not limited to, hydrophilic polymers, and organic polymers having organic functional groups such as -OH, -NR1 R2 R3 R4 (where R1-4 are independently H, alkyl, or aryl), CN, esters, amides, halogens, and ethers; Inorganic polymers, for example, polymetal hydroxide clusters of a single metal or mixed metal, polyanions, polycations, in particular those containing Al, Ce, Zr, Fe as metal ions; Cationic, anionic, or nonionic surfactants, and surface-active molecules / oligomers / polymers such as polymers that adhere by physical adsorption, ionic bonding, or covalent bonding. To provide a chemical mechanical polishing (CMP) composition comprising at least one of the following: The CMP composition has a pH of 2 to 10, and to provide this, The surface of the semiconductor substrate is brought into contact with the polishing pad and the chemical mechanical polishing composition, A chemical mechanical polishing (CMP) method comprising polishing at least one surface containing tungsten.

21. The surface of the semiconductor substrate further comprises a silicon dioxide film, W:SiO 2 The chemical mechanical polishing (CMP) method according to claim 20, wherein the removal selectivity is greater than 30.

22. A chemical mechanical polishing (CMP) system, Polishing pad and A semiconductor substrate having at least one surface containing tungsten, A dispersion of stable colloidal amino-polyorganosiloxane-coated abrasive particles according to claim 1, and Water-soluble solvent Includes, Optionally, Organic and inorganic salts as colloidal stabilizers; Acid / base buffering agent; Biocides; Oxidizing agent; catalyst; Corrosion inhibitor; Organic polymers as erosion, dishing, and corrosion reducers, examples of which include, but are not limited to, hydrophilic polymers, and organic polymers having organic functional groups such as -OH, -NR1 R2 R3 R4 (where R1-4 are independently H, alkyl, or aryl), CN, esters, amides, halogens, and ethers; Inorganic polymers, for example, polymetal hydroxide clusters of a single metal or mixed metal, polyanions, polycations, in particular those containing Al, Ce, Zr, Fe as metal ions; Cationic, anionic, or nonionic surfactants, and surface-active molecules / oligomers / polymers such as polymers that adhere by physical adsorption, ionic bonding, or covalent bonding. A chemical mechanical polishing (CMP) composition comprising at least one of the following, Includes, The CMP composition has a pH of 2 to 10. A chemical mechanical polishing (CMP) system in which the surface of the semiconductor substrate is in contact with the polishing pad and the chemical mechanical polishing composition.

23. The surface of the semiconductor substrate further comprises a silicon dioxide film, W:SiO 2 The chemical mechanical polishing (CMP) system according to claim 22, wherein the removal selectivity is greater than 30.

24. The stable colloidal amino-polyorganosiloxane-coated abrasive particle dispersion according to claim 1, which is a stable colloidal amino-polyorganosiloxane-coated silica dispersion.

25. A chemical mechanical polishing (CMP) composition, A dispersion of stable colloidal amino-polyorganosiloxane-coated abrasive particles according to claim 4, and Water-soluble solvent Includes, Optionally, Organic and inorganic salts as colloidal stabilizers; Acid / base buffering agent; Biocides; Oxidizing agent; catalyst; Corrosion inhibitor; Organic polymers as erosion, dishing, and corrosion reducers, examples of which include, but are not limited to, hydrophilic polymers, and organic polymers having organic functional groups such as -OH, -NR1 R2 R3 R4 (where R1-4 are independently H, alkyl, or aryl), CN, esters, amides, halogens, and ethers; Inorganic polymers, for example, polymetal hydroxide clusters of a single metal or mixed metal, polyanions, polycations, in particular those containing Al, Ce, Zr, Fe as metal ions; Cationic, anionic, or nonionic surfactants, and surface-active molecules / oligomers / polymers such as polymers that adhere by physical adsorption, ionic bonding, or covalent bonding. Includes at least one of the following: A chemical mechanical polishing (CMP) composition having a pH of 2 to 10.

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