Chemical mechanical planarization for polycrystalline silicon and amorphous silicon

Abstract

Present Chemical Mechanical Planarization (CMP) polishing compositions, methods and systems provide high polysilicon and high amorphous silicon removal rates, and a high selectivity of polysilicon / amorphous silicon removal rate to silicon nitride removal rate. The CMP polishing compositions comprise specifically in addition of other components, hydrophilic silicate to increase the polishing rate of amorphous silicon and at least two abrasive particles having different sizes to increase the initial polishing amount of polysilicon.

Description

Attorney Docket No.: P24-167-SEC-WO01Chemical Mechanical Planarization for Polycrystalline Silicon and Amorphous SiliconCROSS REFERENCE TO RELATED PATENT APPLICATIONS

[0001] The application claims the benefit of U.S. Application No. 63 / 700,220 filed on September 27, 2024, the entire disclosure of which is hereby incorporated by reference.BACKGROUND

[0002] The present invention relates to the chemical mechanical planarization (CMP) for polishing films containing polycrystalline silicon(polysilicon or Poly-Si) and amorphous silicon (a-Si) and various interconnect layers used in semiconductor integrated circuit manufacture with especially high selectivity to interlayer dielectric materials.

[0003] In a semiconductor device, a wafer or substrate usually contains silicon on which a plurality of transistors have been formed. Transistors are chemically and physically connected to the substrate by patterning regions in the substrate and layers on the substrate. The transistors and layers are separated by interlevel dielectrics (ILDs), comprised primarily of some form of silicon oxide (SiO2). The transistors are interconnected through the use of a stack of thin-films called multilevel interconnects to form functional circuits. The thin-films comprise materials metals, such as copper (Cu), tungsten (W), titanium (Ti), titanium nitride (TiN), tantalum (Ta), aluminum-copper (Al- Cu), aluminum-silicon (Al-Si), doped poly-silicon (Poly- Si). The transistors are isolated from each other often through the use of trenches filled with an insulating material such as silicon nitride or SiN4.

[0004] Chemical Mechanical Planarization (CMP) polishing is used to planarize the surface of the device during the various stages of device fabrication.

[0005] Polysilicon films may be deposited over a stop layer comprising films such as silicon oxide (SiO2) or silicon nitride (SiN). Selectivity is defined as the ratio of the removal rate of polysilicon film to the removal rate of the stop layer. A high selectivity of polysilicon films over stop layer film is usually desired to protect the stop layer.

[0006] The CMP polishing composition, slurry or formulation (they can be used interchangeably) is an important factor in providing an optimal chemical mechanical planarization polishing process.Attorney Docket No.: P24-167-SEC-WO01

[0007] In the CMP polishing process, poly-Si and amorphous-Si may both require high polishing speeds. However, it is difficult to satisfy a high removal rate in both polysilicon and amorphous silicon due to their different structures. Existing widely used amine-based chemicals increase the polishing amount of poly-Si, but there is a limit to increasing the polishing amount of amorphous-Si. Also in case of poly-Si, there are some grain boundary that is not easily polished chemically.

[0008] Accordingly, a need remains for new and improved polishing slurries having high polishing or removal rates for both polysilicon and amorphous silicon , and high selectivity to the stop layer containing insulator media.SUMMARY

[0009] This invention provides CMP polishing compositions for polishing films comprising polysilicon and amorphous silicon.

[0010] This invention provides Chemical Mechanical Planarization (CMP) polishing compositions, methods, and systems for polishing films comprising polysilicon and amorphous silicon.

[0011] This invention is also a CMP polishing composition that provides high selectivity towards polishing polysilicon and / or amorphous silicon in comparison to an interlevel dielectric layer (ILD) layer or Shallow Trench Isolation (STI) such as SIN4of an IC circuit.

[0012] This invention is also a method and / or a system for using the CMP polishing composition.

[0013] In one embodiment, this invention is an aqueous chemical mechanical planarization polishing composition comprises: at least two abrasive particles having different sizes; a silicate; a water soluble solvent; and optionally at least one of a quaternary ammonium compound; a surfactant; an amino acid; a biocide; and a pH adjuster.Attorney Docket No.: P24-167-SEC-WO01

[0014] In another aspect, the invention provides a method of a Chemical Mechanical Planarization polishing comprising steps of:1) providing a semiconductor substrate having at least one surface containing at least one first material and optionally at least one second material;2) providing a polishing pad;3) providing a chemical mechanical planarization polishing composition comprising: a) at least two abrasive particles having different sizes; b) a silicate; c) a water soluble solvent; and optionally at least one of d) a quaternary ammonium compound; e) a surfactant; f) an amino acid; g) a biocide; and h) a pH adjuster; and4) polishing the at least one surface of the semiconductor substrate; wherein the first material is selected from the group consisting of polycrystalline silicon (poly-Si), amorphous silicon (a-Si), and combinations thereof; the second material is selected from the group consisting of SiN, Ta, TaN, Ti, TiN film, dielectric layer material such as TEOS, low-k, ultra- low-k film, and combinations thereof.

[0015] In one embodiment, the ratio of the removal rate of the first material to the removal rate of the second material is equal or greater than 10, or 15.

[0016] In another embodiment, the ratio of the removal rate of the first material to the removal rate of the second material is equal or greater than 40, 50 or 60.

[0017] In yet another aspect, the invention provides a system of a Chemical Mechanical Planarization polishing comprising:Attorney Docket No.: P24-167-SEC-WO011) a semiconductor substrate having at least one surface containing at least one first material and optionally at least one second material;2) a polishing pad; and3) a chemical mechanical planarization polishing composition comprising: a) at least two abrasive particles having different sizes; b) a silicate; c) a water soluble solvent; and optionally at least one of d) a quaternary ammonium compound; e) a surfactant; f) an amino acid; g) a biocide; and h) a pH adjuster; wherein the at least one surface is in contact with the polishing pad and the chemical mechanical planarization polishing composition.

[0018] In one embodiment, the abrasive particles used include, but are not limited to: silica based abrasives such as colloidal silica, high purity colloidal silica, silica particles doped by other inorganic oxide within lattice of the colloidal silica such as alumina doped silica particles; colloidal aluminum oxide including alpha-, beta-, and gamma-types of aluminum oxides; colloidal and photoactive titanium dioxide; cerium oxide, colloidal cerium oxide; nano-sized inorganic metal oxide particles including alumina, titania, zirconia, ceria; nano-sized diamond particles; nano-sized silicon nitride particles; mono-modal, bi-modal, multi-modal colloidal abrasive particles; organic polymer-based soft abrasives; surface-coated or modified abrasives or other composite particles, and mixtures thereof. Silica based abrasives are preferred abrasive particles.

[0019] In another embodiment, the abrasive particles used are colloidal silica or high purity colloidal silica.

[0020] Abrasive particles may have various shapes including but are not limited to spherical, elongated, cocoon or chain like structures. Preferred particle shapes are sphere and cocoon. Cocoon shaped particles are characterized by aggregate ratioAttorney Docket No.: P24-167-SEC-WO01 which is the ratio of mean particle size measured by Dynamic Light Scattering (DLS) to primary particle diameter calculated based on specific surface area assuming nonporous spherical particles. Preferred aggregate ratio of cocoon shaped particles is >1.7 or more preferably between 1.7 and 2.3.

[0021] Abrasive particles may have various size with a mean particle size or a primary size ranging from 4 to 500nm, from 10 to 400nm, from 10 to 300 nm, from 15 to 300nm, from 15 to 200 nm, or from 20 to 200nm.

[0022] The abrasive particles used in the aqueous chemical mechanical planarization polishing composition may have different sizes: small size abrasive particles and large size abrasive particles, where the mean particle size or the primary particle size of the small size abrasive particles is smaller than the mean particle size or the primary particle size of the large size abrasive particles.

[0023] In one embodiment, the small size abrasive particles have the mean particle size or the primary particle size of > 5 nm and < 60 nm, such as 55nm, 50 nm, 45nm, 40 nm, 35nm, 30 nm, 25nm, 20 nm or 10 nm.

[0024] In another embodiment, the small size abrasive particles have the mean particle size or the primary particle size of > 5 nm and < 60 nm, such as 5 to 60 nm, 5 to 55nm, 5 to 50 nm, 5 to 45nm, 5 to 40 nm, 5 to 35nm, 5 to 30 nm, 5 to 25nm, 5 to 20 nm or 5 to 10 nm.

[0025] In another embodiment, the large size abrasive particles have the mean particle size or the primary particle size of > 60 nm and < 250 nm, such as 61 to 250 nm, 65 to 220 nm, 65 to 200 nm, 65 to 190 nm, 65 to 180 nm; 70 to 250 nm, 70 to 220 nm, 70 to 200 nm, 70 to 190 nm, or 75 to 180 nm.

[0026] In yet another embodiment, the large size abrasive particles have the mean particle size or the primary particle size of > 60 nm and < 250 nm, such as 60 to 250 nm, 60 to 230 nm, 60 to 210 nm, 60 to 190 nm, 60 to 180 nm; 60 to 170 nm, 60 to 150 nm, 60 to 130 nm, 60 to 110 nm, or 60 to 100 nm.

[0027] In one of the embodiment, the concentration (weight percent wt. %) ratio of the at least two abrasive particles having different sizes have a concentration ratio of two different sizes from 1 :00 to 1 :00, 0.95 to1 :00, 0.90 to 1 :00, 0.85 to 1 :00, 0.80 to 1 :00, 0.75 to 1 :00, 0.70 to 1 :00, 0.65 to 1 :00, 0.60 to 1 :00, 0.55 to 1 :00, 0.50 to 1 :00, 0.45 to 1 :00, 0.4 to 1 :00, 0.35 to 1 :00, 0.3 to 1 :00, 0.25 to 1 :00, or 0.2 to 1 :00.Attorney Docket No.: P24-167-SEC-WO01

[0028] The concentrations of total abrasive particles relative to the total weight of the CMP composition range from 0.01 wt.% to 20 wt.%, from 0.05 wt.% to 10 wt.%, from 0.1 wt.% to 10 wt.%, 1 wt.% to 10 wt.%, or 1 wt.% to 6 wt.%.

[0029] Example of the silicate includes but is not limited to the inorganic silicate which is a salt of silicic acid selected from the group consisting of potassium silicate, sodium silicate, lithium silicate, aluminum silicate, calcium silicate or ammonium silicate such as tetramethylammonium silicate, tetrabutylammonium silicate, tetraethylammonium silicate, and combinations thereof.

[0030] In one embodiment, the concentrations of the silicate range from 0.01 wt.% to 20 wt.%, from 0.025 wt.% to 10 wt.%, from 0.05 wt.% to 5 wt.%, 0.075 wt.% to 2 wt.%, or 0.1 wt.% to 1 wt.%.

[0031] In one embodiment, the CMP composition optionally comprises a quaternary ammonium compound which includes but is not limited to ethyltrimethylammonium hydroxide (ETMAH), ethyltrimethylammonium bromide, ethyltrimethylammonium chloride, benzalkonium hydroxide, benzalkonium bromide, benzalkonium chloride, cetyltrimethylammonium hydroxide, cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride, lauryltrimethylammonium hydroxide, lauryltrimethylammonium bromide, lauryltrimethylammonium chloride (LTAC), stearalkonium hydroxide, stearalkonium bromide, stearalkonium chloride, hexadecylpyridinium hydroxide, hexadecylpyridinium bromide, hexadecylpyridinium chloride (Cetylpyridinium chloride), poly(dimethyldiallylammonium hydroxide), poly(dimethyldiallylammonium bromide), poly(dimethyldiallylammonium chloride) (PDMDAAC), trimethylstearylammonium hydroxide, trimethylstearylammonium bromide, trimethylstearylammonium chloride, dimethyldioctadecylammonium hydroxide, dimethyldioctadecylammonium bromide, dimethyldioctadecylammonium chloride, tetraalkylammonium hydroxides, tetraalkylammonium bromides, tetraalkylammonium chlorides, tetramethylammonium hydroxide (TMAH), tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride, tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium chloride, ethyltrimethylammonium hydroxide, ethyltrimethylammonium bromide, ethyltrimethylammonium chloride, diethyldimethylammonium hydroxide, diethyldimethylammonium bromide,Attorney Docket No.: P24-167-SEC-WO01 diethyldimethylammonium chloride, methyltriethylammonium hydroxide, methyltriethylammonium bromide, methyltriethylammonium chloride, choline hydroxide, choline bromide, choline chloride, choline bicarbonate, choline bitartrate, and other choline salts.

[0032] In another embodiment, the CMP composition optionally comprises ethyltrimethylammonium hydroxide (ETMAH).

[0033] The concentrations of the quaternary ammonium compound range from 0.00001 wt.% to 1 wt.%, 0.000025 wt.% to 0.75 wt.%, 0.00005 wt.% to 0.5 wt.%, 0.000075 wt.% to 0.1 wt.%, or 0.0001 wt.% to 0.05 wt.%.

[0034] In one embodiment, the CMP composition optionally comprises a surfactant. Example of the surfactant includes but is not limited to the group consisting of nonionic surfactant, anionic surfactant, cationic surfactant, ampholytic surfactant, and combinations thereof.

[0035] In one of the embodiment, the anionic surfactants include the surfactants having diphenyl disulfonic or sulfonic acid; such as Dowfax® series by Dow Chemical Company : Dowfax™ 2A1 , Dowfax™ 3b2 , Dowfax™ C6L and Dowfax™ ; and Calfax® series by Pilot Chemical Company: Calfax® DBA-70; Calfax®10L-45, Calfax®16L-35, and Calfax®6LA-70.

[0036] In another one of the embodiment, the non-ionic surfactants includes but is not limited to the types of long chain alcohols, ethoxylated alcohols, ethoxylated acetylenic diol surfactants, polyethylene glycol, polyethylene glycol alkyl ethers, proplylene glycol alkyl ethers, glucoside alkyl ethers, polyethylene glycol octylphenyl ethers, polyethylene glycol alkylpgenyl ethers, glycerol alkyl esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene glycol sorbiton alkyl esters, sorbiton alkyl esters, cocamide monoethanol amine, cocamide diethanol amine dodecyl dimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amines, fluorosurfactants.

[0037] Commercial non-ionic surfactants include but are not limited to polysorbate (polyoxyethylene sorbitan monolaurate) Tween® 20 and Tween® 80 from ; and polyethylene glycol PEG 8000.

[0038] The concentrations of the surfactant range from 0.00001 wt.% to 1 wt.%, 0.000025 wt.% to 0.75 wt.%, 0.00005 wt.% to 0.5 wt.%, 0.000075 wt.% to 0.1 wt.%, or 0.0001 wt.% to 0.05 wt.%.

[0039] In one embodiment, the CMP composition optionally use an amino acid.Attorney Docket No.: P24-167-SEC-WO01

[0040] In one of the embodiment, the amino acid includes but is not limited to benzenesulfonic acid; benzylsulfonic acid (i.e., a-toluenesulfonic acid); alkylbenzenesulfonic acids such as toluenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetradecylbenzene sulfonic acid, hexadecylbenzene sulfonic acid, 4-methoxybenzenesulfonic acid; 4- hydroxybenzenesulfonic acid; 4-aminobenzenesulfonic acid; 4-nitrobenzenesulfonic acid; or the like; or a combination thereof. However, benzene-1 ,4-disulfonic acid provides sufficient activity.

[0041] The concentrations of the amino acid range from 0.001 wt.% to 5 wt.%, 0.0025 wt.% to 3 wt.%, 0.005 wt.% to 2 wt.%, 0.0075 wt.% to 1 .00 wt.%, or 0.0075 wt.% to 0.05 wt.%.

[0042] The water soluble solvent includes but is not limited to deionized (DI) water, distilled water, and alcoholic organic solvents. The preferred water soluble solvent is DI water.

[0043] The CMP composition optionally comprises a pH adjuster which includes but is not limited to (a)nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids, and mixtures thereof to lower the pH; and (b) potassium hydroxide(KOH), sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and mixtures thereof to raise the pH.

[0044] The pH of the aqueous chemical mechanical planarization polishing composition is from 2 to 12, such as 4 to 12, 4 to 11 , 4 to 10, 5 to 12, 5 to 11 , 5 to 10, 6 to 12, 6 to 11 , 6 to 10, 7 to 12, 7 to 11 , 7 to 10, 8 to 12, 8 to 11 , 8 to 10, 9 to 12, 9 to 11 , or 9 to 10.

[0045] Examples of the first material contained by the at least one surface of the semiconductor substrate includes but is not limited to polycrystalline silicon (poly-Si), amorphous silicon (a-Si), and combinations thereof.

[0046] Examples of the second material contained by the at least one surface of the semiconductor substrate includes but is not limited SiN, Ta, TaN, Ti, TiN, TEOS, low-k, and ultra-low-k film. The removal rate of the first material to the removal rate of the second material is equal or greater than (>)10:1 ; 15:1 ; 40:1 , 50:1 or 60:1.Attorney Docket No.: P24-167-SEC-WO01DETAILED DESCRIPTION

[0047] Semiconductor device manufacturing includes processes to from intricately patterned films on the substrate. Producing the patterned films involves steps such as deposition, etching, and Chemical Mechanical Planarization (CMP) polishing steps.

[0048] The present invention relates to the chemical mechanical planarization (CMP) for polishing films containing polycrystalline silicon(polysilicon or Poly-Si) and amorphous silicon (a-Si) and various interconnect layers used in semiconductor integrated circuit manufacture with especially high selectivity to interlayer dielectric materials.

[0049] CMP polishing for some semiconductor structures, high polishing rates or removal rates for both polysilicon and amorphous silicon are needed. However, it is difficult to use a same CPM polishing slurry to achieve high removal rates for both polysilicon and amorphous silicon due to different material structures. As an example, amorphous silicon is more hydrophilic than polysilicon since amorphous silicon is not high temperature treated.

[0050] It is known in the art that amine-based chemicals increase the polishing rate of polysilicon, but there is a limit to increase the polishing rate of amorphous silicon. In addition for polishing polysilicon it is not easily polished chemically due to the grain boundary.

[0051] The present invention satisfies the need by disclosing CMP polishing compositions comprising a more hydrophilic silicate to increase the polishing rate of amorphous silicon and at least two abrasive particles having different sizes to increase the initial polishing amount of polysilicon. Furthermore, the CMP compositions provide increased selectivity of amorphous silicon / SiN.

[0052] In one embodiment, this invention is an aqueous chemical mechanical planarization polishing composition comprises: at least two abrasive particles having different sizes; a silicate; a water soluble solvent; and optionally at least one of a quaternary ammonium compound; a surfactant;Attorney Docket No.: P24-167-SEC-WO01 an amino acid; a biocide; and a pH adjuster.

[0053] In another aspect, the invention provides a method of a Chemical Mechanical Planarization polishing comprising steps of:1) providing a semiconductor substrate having at least one surface containing at least one first material and optionally at least one second material;2) providing a polishing pad;3) providing a chemical mechanical planarization polishing composition comprising: a) abrasive particles have different sizes; b) a silicate; c) a water soluble solvent; and optionally at least one of d) a quaternary ammonium compound; e) a surfactant; f) an amino acid; g) a biocide; and h) a pH adjuster; and4) polishing the semiconductor substrate to selectively remove the first material; wherein the first material is selected from the group consisting of polycrystalline silicon, amorphous silicon, and combinations thereof; the second material is selected from the group consisting of SiN, Ta, TaN, Ti, TiN film, dielectric layer material such as TEOS, low-k, ultra- low-k film, and combinations thereof.

[0054] In one embodiment, the ratio of the removal rate of the first material to the removal rate of the second material is equal or greater than 10, or 15.

[0055] In another embodiment, the ratio of the removal rate of the first material to the removal rate of the second material is equal or greater than 40, 50 or 60.Attorney Docket No.: P24-167-SEC-WO01

[0056] In yet another aspect, the invention provides a system of a Chemical Mechanical Planarization polishing comprising:1) a semiconductor substrate having at least one surface containing at least one first material and optionally at least one second material;2) a polishing pad; and3) a chemical mechanical planarization polishing composition comprising: a) at least two abrasive particles having different sizes; b) a silicate; c) a water soluble solvent; and optionally at least one of d) a quaternary ammonium compound; e) a surfactant; f) an amino acid; g) a biocide; and h) a pH adjuster; wherein the at least one surface is in contact with the polishing pad and the chemical mechanical planarization polishing composition.

[0057] In one embodiment, the abrasive particles used include, but are not limited to: silica based abrasives such as colloidal silica, high purity colloidal silica, silica particles doped by other inorganic oxide within lattice of the colloidal silica such as alumina doped silica particles; colloidal aluminum oxide including alpha-, beta-, and gamma-types of aluminum oxides; colloidal and photoactive titanium dioxide; cerium oxide, colloidal cerium oxide; nano-sized inorganic metal oxide particles including alumina, titania, zirconia, ceria; nano-sized diamond particles; nano-sized silicon nitride particles; mono-modal, bi-modal, multi-modal colloidal abrasive particles; organic polymer-based soft abrasives; surface-coated or modified abrasives or other composite particles, and mixtures thereof. Silica based abrasives are preferred abrasive particles.

[0058] In another embodiment, the abrasive particles used are colloidal silica or high purity colloidal silica.Attorney Docket No.: P24-167-SEC-WO01

[0059] Abrasive particles may have various shapes including but are not limited to spherical, elongated, cocoon or chain like structures. Preferred particle shapes are sphere and cocoon. Cocoon shaped particles are characterized by aggregate ratio which is the ratio of mean particle size measured by Dynamic Light Scattering (DLS) to primary particle diameter calculated based on specific surface area assuming nonporous spherical particles. Preferred aggregate ratio of cocoon shaped particles is >1.7 or more preferably between 1.7 and 2.3.

[0060] Abrasive particles may have various size with a mean particle size or a primary size ranging from 4 to 500nm, from 10 to 400nm, from 10 to 300 nm, from 15 to 300nm, from 15 to 200 nm, or from 20 to 200nm.

[0061] The abrasive particles used in the aqueous chemical mechanical planarization polishing composition may have different sizes: small size abrasive particles and large size abrasive particles, where the mean particle size or the primary particle size of the small size abrasive particles is smaller than the mean particle size or the primary particle size of the large size abrasive particles.

[0062] In one embodiment, the small size abrasive particles have the mean particle size or the primary particle size of > 5 nm and < 60 nm, such as 55nm, 50 nm, 45nm, 40 nm, 35nm, 30 nm, 25nm, 20 nm or 10 nm.

[0063] In another embodiment, the small size abrasive particles have the mean particle size or the primary particle size of > 5 nm and < 60 nm, such as 5 to 60 nm, 5 to 55nm, 5 to 50 nm, 5 to 45nm, 5 to 40 nm, 5 to 35nm, 5 to 30 nm, 5 to 25nm, 5 to 20 nm or 5 to 10 nm.

[0064] In another embodiment, the large size abrasive particles have the mean particle size or the primary particle size of > 60 nm and < 250 nm, such as 61 to 250 nm, 65 to 220 nm, 65 to 200 nm, 65 to 190 nm, 65 to 180 nm; 70 to 250 nm, 70 to 220 nm, 70 to 200 nm, 70 to 190 nm, or 75 to 180 nm.

[0065] In yet another embodiment, the large size abrasive particles have the mean particle size or the primary particle size of > 60 nm and < 250 nm, such as 60 to 250 nm, 60 to 230 nm, 60 to 210 nm, 60 to 190 nm, 60 to 180 nm; 60 to 170 nm, 60 to 150 nm, 60 to 130 nm, 60 to 110 nm, or 60 to 100 nm.

[0066] In one of the embodiment, the concentration (weight percent wt. %) ratio of the at least two abrasive particles having different sizes have a concentration ratio of two different sizes from 1 :00 to 1 :00, 0.95 to 1 :00, 0.90 to 1 :00, 0.85 to 1 :00, 0.80 to 1 :00,Attorney Docket No.: P24-167-SEC-WO010.75 to 1 :00, 0.70 to 1 :00, 0.65 to 1 :00, 0.60 to 1 :00, 0.55 to 1 :00, 0.50 to 1 :00, 0.45 to 1 :00, 0.4 to 1 :00, 0.35 to 1 :00, 0.3 to 1 :00, 0.25 to 1 :00, or 0.2 to 1 :00.

[0067] In one of the one embodiment, the concentration (weight percent wt. %) ratio of the small size abrasive particles to the large size abrasive particles may be 1 :1 , 1 :0.95, 90 to 1 , 85 to 1 , 80 to 1 , 75 to 1 , 70 to 1 , 0.65 to 1 , 0.60 to 1 , 0.55 to 1 , 0.50 to 1 , 0.45 to 1 , 0.4 to 1 , 0.35 to 1 , 0.3 to 1 , 0.25 to 1 , or 0.2 to 1 .

[0068] In another one of the one embodiment, the concentration (weight percent wt. %) ratio of the large size abrasive particles to the small size abrasive particles may be 1 :1 , 1:0.95, 90 to 1 , 85 to 1 , 80 to 1 , 75 to 1 , 70 to 1 , 0.65 to 1 , 0.60 to 1 , 0.55 to 1 , 0.50 to 1 , 0.45 to 1 , 0.4 to 1 , 0.35 to 1 , 0.3 to 1 , 0.25 to 1 , or 0.2 to 1 .

[0069] The concentrations of total abrasive particles relative to the total weight of the CMP composition range from 0.01 wt.% to 20 wt.%, from 0.05 wt.% to 10 wt.%, from 0.1 wt.% to 10 wt.%, 1 wt.% to 10 wt.%, or 1 wt.% to 6 wt.%.

[0070] Example of the silicate includes but is not limited to the inorganic silicate which is a salt of silicic acid selected from the group consisting of potassium silicate, sodium silicate, lithium silicate, aluminum silicate, calcium silicate or ammonium silicate such as tetramethylammonium silicate, tetrabutylammonium silicate, tetraethylammonium silicate, and combinations thereof.

[0071] In one embodiment, the concentrations of the silicate range from 0.01 wt.% to 20 wt.%, from 0.025 wt.% to 10 wt.%, from 0.05 wt.% to 5 wt.%, 0.075 wt.% to 2 wt.%, or 0.1 wt.% to 1 wt.%.

[0072] In one embodiment, the CMP polishing composition optionally comprises a quaternary ammonium compound which includes but is not limited to ethyltrimethylammonium hydroxide (ETMAH), ethyltrimethylammonium bromide, ethyltrimethylammonium chloride, benzalkonium hydroxide, benzalkonium bromide, benzalkonium chloride, cetyltrimethylammonium hydroxide, cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride, lauryltrimethylammonium hydroxide, lauryltrimethylammonium bromide, lauryltrimethylammonium chloride (LTAC), stearalkonium hydroxide, stearalkonium bromide, stearalkonium chloride, hexadecylpyridinium hydroxide, hexadecylpyridinium bromide, hexadecylpyridinium chloride (Cetylpyridinium chloride), poly(dimethyldiallylammonium hydroxide), poly(dimethyldiallylammonium bromide), poly(dimethyldiallylammonium chloride) (PDMDAAC), trimethylstearylammonium hydroxide, trimethylstearylammoniumAttorney Docket No.: P24-167-SEC-WO01 bromide, trimethylstearylammonium chloride, dimethyldioctadecylammonium hydroxide, dimethyldioctadecylammonium bromide, dimethyldioctadecylammonium chloride, tetraalkylammonium hydroxides, tetraalkylammonium bromides, tetraalkylammonium chlorides, tetramethylammonium hydroxide (TMAH), tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride, tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium chloride, ethyltrimethylammonium hydroxide, ethyltrimethylammonium bromide, ethyltrimethylammonium chloride, diethyldimethylammonium hydroxide, diethyldimethylammonium bromide, diethyldimethylammonium chloride, methyltriethylammonium hydroxide, methyltriethylammonium bromide, methyltriethylammonium chloride, choline hydroxide, choline bromide, choline chloride, choline bicarbonate, choline bitartrate, and other choline salts.

[0073] In another embodiment, the CMP polishing composition optionally comprises ethyltrimethylammonium hydroxide (ETMAH); tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide, or methyltriethylammonium hydroxide.

[0074] The concentrations of the quaternary ammonium compound range from 0.00001 wt.% to 1 wt.%, 0.000025 wt.% to 0.75 wt.%, 0.00005 wt.% to 0.5 wt.%, 0.000075 wt.% to 0.1 wt.%, or 0.0001 wt.% to 0.05 wt.%.

[0075] In one embodiment, the CMP composition optionally comprises a surfactant. Example of the surfactant includes but is not limited to the group consisting of nonionic surfactant, anionic surfactant, cationic surfactant, ampholytic surfactant, and combinations thereof.

[0076] In one of the embodiment, the anionic surfactants include the surfactants having diphenyl disulfonic or sulfonic acid; such as Dowfax® series by Dow Chemical Company : Dowfax™ 2A1 , Dowfax™ 3b2 , Dowfax™ C6L and Dowfax™ ; and Calfax® series by Pilot Chemical Company: Calfax® DBA-70; Calfax®10L-45, Calfax®16L-35, and Calfax®6LA-70.

[0077] In another one of the embodiment, the non-ionic surfactants includes but is not limited to the types of long chain alcohols, ethoxylated alcohols, ethoxylatedAttorney Docket No.: P24-167-SEC-WO01 acetylenic diol surfactants, polyethylene glycol, polyethylene glycol alkyl ethers, proplylene glycol alkyl ethers, glucoside alkyl ethers, polyethylene glycol octylphenyl ethers, polyethylene glycol alkylpgenyl ethers, glycerol alkyl esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene glycol sorbiton alkyl esters, sorbiton alkyl esters, cocamide monoethanol amine, cocamide diethanol amine dodecyl dimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amines, fluorosurfactants.

[0078] Commercial non-ionic surfactants include but are not limited to polysorbate (polyoxyethylene sorbitan monolaurate) Tween® 20 and Tween® 80 from ; and polyethylene glycol PEG 8000.

[0079] The concentrations of the surfactant range from 0.00001 wt.% to 1 wt.%, 0.000025 wt.% to 0.75 wt.%, 0.00005 wt.% to 0.5 wt.%, 0.000075 wt.% to 0.1 wt.%, or 0.0001 wt.% to 0.05 wt.%.

[0080] In one embodiment, the CMP composition optionally comprises an amino acid.

[0081] In one of the embodiment, the amino acid includes but is not limited to benzenesulfonic acid; benzylsulfonic acid (i.e., a-toluenesulfonic acid); alkylbenzenesulfonic acids such as toluenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetradecylbenzene sulfonic acid, hexadecylbenzene sulfonic acid, 4-methoxybenzenesulfonic acid; 4- hydroxybenzenesulfonic acid; 4-aminobenzenesulfonic acid; 4-nitrobenzenesulfonic acid; or the like; or a combination thereof. However, benzene-1 ,4-disulfonic acid provides sufficient activity.

[0082] The concentrations of the amino acid range from 0.001 wt.% to 5 wt.%, 0.0025 wt.% to 3 wt.%, 0.005 wt.% to 2 wt.%, 0.0075 wt.% to 1 .00 wt.%, or 0.0075 wt.% to 0.05 wt.%.

[0083] The water soluble solvent includes but is not limited to deionized (DI) water, distilled water, and alcoholic organic solvents. The preferred water soluble solvent is DI water.

[0084] The CMP composition optionally comprises a pH adjuster which includes but is not limited to (a)nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids, and mixtures thereof to lower the pH; and (b) potassium hydroxide(KOH), sodiumAttorney Docket No.: P24-167-SEC-WO01 hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and mixtures thereof to raise the pH.

[0085] The pH of the aqueous chemical mechanical planarization polishing composition is from 2 to 12, such as 4 to 12, 4 to 11 , 4 to 10, 5 to 12, 5 to 11 , 5 to 10, 6 to 12, 6 to 11 , 6 to 10, 7 to 12, 7 to 11 , 7 to 10, 8 to 12, 8 to 11 , 8 to 10, 9 to 12, 9 to 11 , or 9 to 10.

[0086] In one embodiment, the chemical mechanical planarization polishing composition comprises: silica particles with the small size abrasive particles having the mean particles size or the primary particle size of 30 to 50 nm and the large size abrasive particles having the mean particles size or the primary particle size of 70 to 120 nm; potassium silicate; ethyltrimethylammonium hydroxide; and DI water.

[0087] In another embodiment, chemical mechanical planarization polishing composition comprises: silica particles with the small size abrasive particles having the mean particles size or the primary particle size of 30 to 50 nm and the large size abrasive particles having the mean particles size or the primary particle size of 70 to 120 nm; potassium silicate; ethyltrimethylammonium hydroxide; benzenesulfonic acid; and DI water.

[0088] In yet another embodiment, the chemical mechanical planarization polishing composition comprises: silica particles with the small size abrasive particles having the mean particles size or the primary particle size of 30 to 50 nm and the large size abrasive particles having the mean particles size or the primary particle size of 70 to 120 nm; potassium silicate; ethyltrimethylammonium hydroxide; benzenesulfonic acid; a surfactant selected from the group consisting of alkyldiphenyloxide surfactant, disulfonate surfactant, polysorbate surfactant, polyethylene glycol, and combinations thereof; and DI water.

[0089] Examples of the first material contained by the at least one surface of the semiconductor substrate includes but is not limited to polycrystalline silicon (poly-Si), amorphous silicon (a-Si), and combinations thereof.

[0090] Examples of the second material contained by the at least one surface of the semiconductor substrate includes but is not limited SiN, Ta, TaN, Ti, TiN, TEOS, low-k, and ultra-low-k film. The removal rate of the first material to the removal rate of the second material is equal or greater than (>)10:1 ; 15:1 ; 40:1 , 50:1 or 60:1.Attorney Docket No.: P24-167-SEC-WO01

[0091] The CMP polishing compositions, methods and systems described herein will be illustrated in more detail with reference to the following examples, but it should be understood that it is not deemed to be limited thereto.CMP Methodology

[0092] In the examples presented below, CMP experiments were run using the procedures and experimental conditions given below.Metrology

[0093] Films were measured with KLA FX5 ellipsometry measurement system. Forty-nine-point diameter scan at 5mm edge exclusion for film was taken before and after polishing to measure the removal rates of polysilicon films, TECS films and SiN films.CMP Tool

[0094] The CMP tool that was used is 300mm Ebara Frex 300X manufactured by Ebara Technologies, Inc. 51 Main Avenue Sacramento, CA 95838. The polishing pad used fortesting is IC1070 pad supplied by Dupont, Inc, 451 Bellevue Rd., Newark, DE 19713. The polishing pads were break-in by conditioning the pad for 30 mins at 9lbf and 10min at 5lbf with DIW.Wafers

[0095] Polishing experiments were conducted using PECVD or LPCVD or HD TECS wafers purchased from Advantech (ADV) Co., Ltd, Hibiya-Kokusai, Chiyoda-ku, Tokyo in Japan. LP-SiN and polysilicon and amorphous silicon wafer were purchased from ADV Co., Ltd, Hibiya-Kokusai, Chiyoda-ku, Tokyo in Japan

[0096] The thickness of the wafers was measured by F5X from KLA-Tencor corporation 1 Technology Drive Milpitas, CA 95035.Polishing Experiments

[0097] In blanket wafer studies, oxide blanket wafers, and SiN blanket wafers were polished at baseline conditions. The tool baseline conditions were: table speed: 103 rpm: head speed: 97; polish down force; 2.5psi; slurry flow speed: 250ml / min.

[0098] High purity colloidal silica used as abrasive particles having a mean particle size ranged from about 40 manometers (nm) to 120nm supplied by FUSO CHEMICAL Co ., LTD in Japan.Attorney Docket No.: P24-167-SEC-WO01

[0099] Potassium silicate was supplied by vanBaerle Silicates Taiwan Co Ltd, No. 99-1 , Sec. 2, Nanti Rd., Wuqi Distr. Polyethylene glycol (MW8000) (PEG 8000) was supplied by Sigma-Aldrich, St Louis, Mo. Ethyltrimethylammonium Hydroxide (ETMAH) was supplied by Sachem, Woodward St. Austin, Texas. KOH used as a pH adjustor was supplied by Samchun. in Korea; Calfax DBA was supplied by Pilot Chemical Company: 9075 Centre Pointe Drive Suite 400 West Chester, OH 45069. Tween 20, Tween80, from Sigma-Aldrich, St Louis, Mo.

[0100] Conditioners were used during CMP, supplied by Saesol Inc. Seonggok- dong, Ansan, in Korea.

[0101] In the working examples, the CMP polishing compositions were prepared by mixing abrasive, chemicals sequentially and adjusted pH with KOH.Working ExamplesExamplei . Initial Removal Amount on Polysilicon film

[0102] The surface of polysilicon is prone to oxidation in the air. In order to remove the oxidized surface, the initial polishing or removal amount need to be high.

[0103] The initial removal amounts (RA) of polysilicon film (the amount in A of the oxidized polysilicon removed with initial 5, 10 and 15 seconds) were measured using the CMP compositions having ETMAH (0.05 wt.%) and abrasive particles (total 3.5 wt.%) with different sizes and blended ratio of abrasives particles. pH range was 8 to 12.

[0104] The Small, Large 1 and Large 2 particles had size of 40, 80 and 120 nm respectively.

[0105] Concentration of Low, Middle and High were: 0.5 wt.%, 1.75 wt.% and 3 wt. % respectively. The total concentration of abrasive particles was 3 for one size abrasive particles and 3.5 wt.% for more than one size abrasive particles.

[0106] The removal rate slopes were calculated based on the initial removal amounts within 5, 10 and 15 seconds.Attorney Docket No.: P24-167-SEC-WO01

[0107] Results were shown in Table 1.Table 1

[0108] As shown in Table 1 , the particle size used in the CMP polishing composition affected the initial polishing amount of polysilicon. The initial polishing amount for High concentration Small particles was very low at 15 A. The initial polishing amount for High concentration of Large 1 or / and Large 2 size particles, and the mixed abrasives had higher amount of over 700 A within first 5 sec.Importantly, the mixture of any two different size of particles used in the CMP compositions provided the uniform increase of the removal rate slope which was missing with the single particle size used. Low concentration of Small size particles and High concentration of Large 2 size particles (Example 6) had the most uniform increase. The uniform increase of the removal rate slope is the key for a more controllable polishing of Polysilicon film.Example 2. Film Removal Rate And Selectivity

[0109] The CMP polishing composition was prepared as shown in Table 2. The pH of the compositions was in the range of 8 to 12, and 1x of potassium silicate was 0.35 wt.%.Attorney Docket No.: P24-167-SEC-WO01Table 2

[0110] The polishing results and the selectivities were shown in Table 3.Table 3

[0111] As shown in Table 3, with other chemical components unchanged, adding potassium silicate in the composition increased the removal rates(RR) for all film. Comparing to the reference composition. Specifically, adding 0.8X of potassium silicate increased the RR of polysilicon by 2.2%; silicon nitride by 268%, and amorphous silicon by 937%. The RR of polysilicon was increased minimal. While the RR of amorphous silicon was increased tremendously comparing to the other films.

[0112] As the result of increased RR for amorphous silicon, the selectivity of polishing amorphous silicon vs silicon nitride was also increased from 6.48 to 18.3.

[0113] As the result of more increased RR for silicon nitride, the selectivity of polishing polysilicon vs SiN was decreased from 230.8 to 64.06.

[0114] Adding more potassium silicate (0.9X and 1X) seemed continuously increasing the RR at much slower rate for all films.Example 3. Etch Rate and Defect MeasurementsAttorney Docket No.: P24-167-SEC-WO01

[0115] Eaxmplel in Table 4 was the same composition as Example 3 in Table 3. The same amount (0.005 wt.%) of different surfactants were used to replace PEG 8000 to obtain Examples 2, 3 and 4 in Table 4. Ref. composition was the same as Example 1 without PEG 8000.

[0116] The etch rate for amorphous silicon and the defects of > 90nm for polysilicon and >40 nm for SiN were measured. The results were shown in Table 4.Table 4

[0117] As shown in Table 4, the added surfactants functioned as inhibitors in the CMP polishing compositions Examples 1 to 4 which lowed the etch rates comparing with the Ref. composition which did not have a surfactant.

[0118] Additionally, the addition of the surfactants did not have a high impact on the RR of polysilicon and amorphous silicon..

[0119] Importantly, all examples having the surfactants showed better(reduced) defects than the ref. composition in polysilicon, as well as in silicon nitrate.

[0120] The embodiments listed above, including the working example, are exemplary of numerous embodiments that may be made of this disclosure. It is contemplated that numerous other configurations of the process may be used, and the materials used in the process may be elected from numerous materials other than those specifically disclosed.

Claims

Attorney Docket No.: P24-167-SEC-WO01CLAIMSWe claim:1 . A chemical mechanical planarization polishing composition comprising: at least two abrasive particles having different sizes; a silicate; a water soluble solvent; and optionally at least one of a quaternary ammonium compound; a surfactant; an amino acid; a biocide; and a pH adjuster; wherein the at least two abrasive particles having different sizes comprise small size abrasive particles and large size abrasive particles.

2. The chemical mechanical planarization polishing composition of claim 1 , wherein the at least two abrasive particles having different sizes are selected from the group consisting of silica based abrasives particles selected from the group consisting of colloidal silica, silica particles doped by other inorganic oxide within lattice of the colloidal silica including alumina doped silica particles; colloidal aluminum oxide selected from the group consisting of alpha-, beta-, and gammatypes of aluminum oxides; colloidal and photoactive titanium dioxide; cerium oxide; colloidal cerium oxide; nano-sized inorganic metal oxide particles selected from the group consisting of titania, zirconia and combinations thereof; nano-sized diamond particles; nano-sized silicon nitride particles; mono-modal, bi-modal, multi-modal colloidal abrasive particles; organic polymer-based soft abrasives; surface-coated or modified abrasives or other composite particles, and mixtures thereof.

3. The chemical mechanical planarization polishing composition according to any one of claims 1 -2, wherein the at least two abrasive particles having different sizes are selected from the group consisting of silica based abrasives particles.

4. The chemical mechanical planarization polishing composition according to any one of claims 1-3, wherein mean particle size or primary particle size of the small size abrasive particles is smaller than mean particle size or primary particle size of the large size abrasive particles.Attorney Docket No.: P24-167-SEC-WO015. The chemical mechanical planarization polishing composition according to any one of claims 1-4, wherein the small size abrasive particles have a mean particles size or a primary particle size of > 5 nm and < 60 nm.

6. The chemical mechanical planarization polishing composition according to any one of claims 1-5, wherein the small size abrasive particles have a mean particles size or a primary particle size of 5 to 60 nm, 5 to 55nm, 5 to 50 nm, 5 to 45nm, 5 to 40 nm, 5 to 35nm, 5 to 30 nm, 5 to 25nm, 5 to 20 nm or 5 to 10 nm.

7. The chemical mechanical planarization polishing composition according to any one of claims 1-6, wherein the large size abrasive particles have a mean particles size or a primary particle size of > 60 nm and < 250 nm.

8. The chemical mechanical planarization polishing composition according to any one of claims 1-7, where the large size abrasive particles have a mean particles size or a primary particle size of 60 to 250 nm, 60 to 230 nm, 60 to 210 nm, 60 to 190 nm, 60 to 180 nm; 60 to 170 nm, 60 to 150 nm, 60 to 130 nm, 60 to 1 10 nm, or 60 to 100 nm, .

9. The chemical mechanical planarization polishing composition according to any one of claims 1-8, wherein a concentration ratio of the at least two abrasive particles having different sizes is from 1 :00 to 1 :00, 0.95 to 1 :00, 0.90 to 1 :00, 0.85 to 1 :00, 0.80 to 1 :00, 0.75 to 1 :00, 0.70 to 1 :00, 0.65 to 1 :00, 0.60 to 1 :00, 0.55 to 1 :00, 0.50 to 1 :00, 0.45 to 1 :00, 0.4 to 1 :00, 0.35 to 1 :00, 0.3 to 1 :00, 0.25 to 1 :00, or 0.2 to 1 :00.

10. The chemical mechanical planarization polishing composition according to any one of claims 1 -9, wherein the at least two abrasive particles having different sizes have a total concentration from 0.01 wt.% to 20 wt.%, from 0.05 wt.% to 10 wt.%, from 0.1 wt.% to 10 wt.%, 1 wt.% to 10 wt.%, or 1 wt.% to 6 wt.%.1 1 . The chemical mechanical planarization polishing composition according to any one of claims 1-10, wherein the silicate is selected from the group consisting of inorganic silicate selected from the group consisting of potassium silicate, sodium silicate, lithium silicate, aluminum silicate, calcium silicate or ammonium silicate such as tetramethylammonium silicate, tetrabutylammonium silicate, tetraethylammonium silicate, and combinations thereof.

12. The chemical mechanical planarization polishing composition according to any one of claims 1-1 1 , wherein concentrations of the silicate range from 0.01 wt.% to 20 wt.%, from 0.025 wt.% to 10 wt.%, from 0.05 wt.% to 5 wt.%, 0.075 wt.% to 2 wt.%, or 0.1 wt.% to 1 wt.%.Attorney Docket No.: P24-167-SEC-WO0113. The chemical mechanical planarization polishing composition according to any one of claims 1-12, wherein the chemical mechanical planarization polishing composition comprise a quaternary ammonium compound selected from the group consisting of ethyltrimethylammonium hydroxide (ETMAH), ethyltrimethylammonium bromide, ethyltrimethylammonium chloride, benzalkonium hydroxide, benzalkonium bromide, benzalkonium chloride, cetyltrimethylammonium hydroxide, cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride, lauryltrimethylammonium hydroxide, lauryltrimethylammonium bromide, lauryltrimethylammonium chloride (LTAC), stearalkonium hydroxide, stearalkonium bromide, stearalkonium chloride, hexadecylpyridinium hydroxide, hexadecylpyridinium bromide, hexadecylpyridinium chloride (Cetylpyridinium chloride), poly(dimethyldiallylammonium hydroxide), poly(dimethyldiallylammonium bromide), poly(dimethyldiallylammonium chloride) (PDMDAAC), trimethylstearylammonium hydroxide, trimethylstearylammonium bromide, trimethylstearylammonium chloride, dimethyldioctadecylammonium hydroxide, dimethyldioctadecylammonium bromide, dimethyldioctadecylammonium chloride, tetraalkylammonium hydroxides, tetraalkylammonium bromides, tetraalkylammonium chlorides, tetramethylammonium hydroxide (TMAH), tetramethylammonium bromide, tetramethylammonium chloride tetraethylammonium hydroxide, tetraethylammonium bromide tetraethylammonium chloride, tetrapropylammonium hydroxide tetrapropylammonium bromide, tetrapropylammonium chloride tetrabutylammonium hydroxide, tetrabutylammonium bromide tetrabutylammonium chloride, ethyltrimethylammonium hydroxide, ethyltrimethylammonium bromide, ethyltrimethylammonium chloride, diethyldimethylammonium hydroxide, diethyldimethylammonium bromide, diethyldimethylammonium chloride, methyltriethylammonium hydroxide, methyltriethylammonium bromide, methyltriethylammonium chloride, choline hydroxide, choline bromide, choline chloride, choline bicarbonate, choline bitartrate, and combinations thereof.

14. The chemical mechanical planarization polishing composition according to any one of claims 1-13, wherein the chemical mechanical planarization polishing composition comprise a quaternary ammonium compound selected from the group consisting of ethyltrimethylammonium hydroxide (ETMAH); tetraalkylammoniumAttorney Docket No.: P24-167-SEC-WO01 hydroxides selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide, methyltriethylammonium hydroxide, and combinations thereof.

15. The chemical mechanical planarization polishing composition according to any one of claims 1-14, wherein concentration of the quaternary ammonium compound ranges from 0.00001 wt.% to 1 wt.%, 0.000025 wt.% to 0.75 wt.%, 0.00005 wt.% to 0.5 wt.%, 0.000075 wt.% to 0.1 wt.%, or 0.0001 wt.% to 0.05 wt.%.

16. The chemical mechanical planarization polishing composition according to any one of claims 1-15, wherein the chemical mechanical planarization polishing composition comprises a surfactant selected from the group consisting of non-ionic surfactant, anionic surfactant, cationic surfactant, ampholytic surfactant, and combinations thereof.

17. The chemical mechanical planarization polishing composition according to any one of claims 1-16, wherein the chemical mechanical planarization polishing composition comprises a surfactant having at least one of diphenyl disulfonic or diphenyl sulfonic acid, long chain alcohol, ethoxylated alcohol, ethoxylated acetylenic diol surfactant, polyethylene glycol, polyethylene glycol alkyl ethers, proplylene glycol alkyl ethers, glucoside alkyl ethers, polyethylene glycol octylphenyl ethers, polyethylene glycol alkylpgenyl ethers, glycerol alkyl esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene glycol sorbiton alkyl esters, sorbiton alkyl esters, cocamide monoethanol amine, cocamide diethanol amine dodecyl dimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amines, and fluorosurfactants.

18. The chemical mechanical planarization polishing composition according to any one of claims 1-17, wherein the chemical mechanical planarization polishing composition comprises a surfactant comprising one selected from the group consisting of polyoxyethylene sorbitan monolaurate, diphenyl disulfonic sulfonic acid, and diphenyl sulfonic acid.

19. The chemical mechanical planarization polishing composition according to any one of claims 1-18, wherein the chemical mechanical planarization polishing composition comprises a surfactant having a concentration of from 0.00001 wt.% to 1 wt.%, 0.000025 wt.% to 0.75 wt.%, 0.00005 wt.% to 0.5 wt.%, 0.000075 wt.% to 0.1 wt.%, or 0.0001 wt.% to 0.05 wt.%.Attorney Docket No.: P24-167-SEC-WO0120. The chemical mechanical planarization polishing composition according to any one of claims 1-19, wherein the chemical mechanical planarization polishing composition comprises an amino acid selected from the group consisting of benzenesulfonic acid; benzylsulfonic acid; benzene-1 ,4-disulfonic acid; alkylbenzenesulfonic acid selected from the group consisting of toluenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetradecylbenzene sulfonic acid, hexadecylbenzene sulfonic acid, 4-methoxybenzenesulfonic acid; 4-hydroxybenzenesulfonic acid; 4- aminobenzenesulfonic acid; 4-nitrobenzenesulfonic acid; and combinations thereof.21 . The chemical mechanical planarization polishing composition according to any one of claims 1-20, wherein the chemical mechanical planarization polishing composition comprises an amino acid having a concentration from 0.001 wt.% to 5 wt.%, 0.0025 wt.% to 3 wt.%, 0.005 wt.% to 2 wt.%, 0.0075 wt.% to 1 .00 wt.%, or 0.0075 wt.% to 0.05 wt.%.

22. The chemical mechanical planarization polishing composition according to any one of claims 1-21 , wherein the chemical mechanical planarization polishing composition comprises a pH adjuster selected from the group consisting of (a)nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids, and mixtures thereof to lower the pH; and (b) potassium hydroxide(KOH), sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and mixtures thereof to raise the pH.

23. The chemical mechanical planarization polishing composition according to any one of claims 1-22, wherein the chemical mechanical planarization polishing composition has a pH of 2 to 12, 4 to 12, 4 to 1 1 , 4 to 10, 5 to 12, 5 to 1 1 , 5 to 10, 6 to 12, 6 to 1 1 , 6 to 10, 7 to 12, 7 to 1 1 , 7 to 10, 8 to 12, 8 to 11 , 8 to 10, 9 to 12, 9 to 1 1 , or 9 to 10.

24. The chemical mechanical planarization polishing composition according to any one of claims 1-23, wherein the water soluble solvent is selected from the group consisting of deionized (DI) water, distilled water, and alcoholic organic solvents.Attorney Docket No.: P24-167-SEC-WO0125. The chemical mechanical planarization polishing composition according to any one of claims 1-24, wherein the water soluble solvent is DI water.

26. The chemical mechanical planarization polishing composition according to any one of claims 1-25, wherein the chemical mechanical planarization polishing composition comprises: silica particles with the small size abrasive particles having the mean particles size or the primary particle size of 30 to 50 nm and the large size abrasive particles having the mean particles size or the primary particle size of 70 to 120 nm; potassium silicate; and DI water.

27. The chemical mechanical planarization polishing composition according to any one of claims 1-26, wherein the chemical mechanical planarization polishing composition comprises: silica particles with the small size abrasive particles having the mean particles size or the primary particle size of 30 to 50 nm and the large size abrasive particles having the mean particles size or the primary particle size of 70 to 120 nm; potassium silicate; ethyltrimethylammonium hydroxide; and DI water.

28. The chemical mechanical planarization polishing composition according to any one of claims 1-27, wherein the chemical mechanical planarization polishing composition comprises: silica particles with the small size abrasive particles having the mean particles size or the primary particle size of 30 to 50 nm and the large size abrasive particles having the mean particles size or the primary particle size of 70 to 120 nm; potassium silicate; ethyltrimethylammonium hydroxide; benzenesulfonic acid; and DI water.

29. The chemical mechanical planarization polishing composition according to any one of claims 1-28, wherein the chemical mechanical planarization polishing composition comprises: silica particles with the small size abrasive particles having the mean particles size or the primary particle size of 30 to 50 nm and the large size abrasive particles having the mean particles size or the primary particle size of 70 to 120 nm; potassium silicate; ethyltrimethylammonium hydroxide; benzenesulfonic acid; a surfactant having one selected from the group consisting of polyoxyethylene sorbitan monolaurate, diphenyl disulfonic sulfonic acid, and diphenyl sulfonic sulfonic acid, and DI water.

30. The chemical mechanical planarization polishing composition according to any one of claims 1-29, wherein the chemical mechanical planarization polishing composition has a pH of 7 to 12 or 8 to 12.Attorney Docket No.: P24-167-SEC-WO0131 . A method of a Chemical Mechanical Planarization polishing comprising steps of:1) providing a semiconductor substrate having at least one surface containing at least one first material and optionally at least one second material;2) providing a polishing pad;3) providing a chemical mechanical planarization polishing composition according to any one of claims 1-30; and4) polishing the at least one surface of the semiconductor substrate; wherein the first material is selected from the group consisting of polycrystalline silicon (poly-Si), amorphous silicon (a-Si), and combinations thereof; the second material is selected from the group consisting of SiN, Ta, TaN, Ti, TiN film, dielectric layer material such as TEOS, low-k, ultra-low-k film, and combinations thereof.

32. The method of a Chemical Mechanical Planarization polishing of claim 31 , wherein ratio of removal rate of the first material to removal rate of the second material is equal or greater than 10, or 15.

33. The method of a Chemical Mechanical Planarization polishing of claim 32, wherein ratio of removal rate of the first material to removal rate of the second material is equal or greater than 40, 50 or 60.

34. A system of a Chemical Mechanical Planarization polishing comprising:1) a semiconductor substrate having at least one surface containing at least one first material and optionally at least one second material;2) a polishing pad; and3) the chemical mechanical planarization polishing composition according to any one of claims 1-30; and wherein the first material is selected from the group consisting of polycrystalline silicon (poly-Si), amorphous silicon (a-Si), and combinations thereof; and the second material is selected from the group consisting of SiN, Ta, TaN, Ti, TiN film, dielectric layer material such as TEOS, low-k, ultra-low-k film, and combinations thereof; andAttorney Docket No.: P24-167-SEC-WO01 the at least one surface is in contact with the polishing pad and the chemical mechanical planarization polishing composition.

35. The system of a Chemical Mechanical Planarization polishing of claim 34, wherein ratio of removal rate of the first material to removal rate of the second material is equal or greater than 10, or 15.

36. The system of a Chemical Mechanical Planarization polishing of claim 35, wherein ratio of removal rate of the first material to removal rate of the second material is equal or greater than 40, 50 or 60.

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