Polishing compositions and methods of using the same

Abstract

This disclosure relates to an abrasive composition comprising (1) at least one abrasive; (2) at least one organic acid or a salt thereof; (3) at least one amine compound; (4) at least one nitride removal rate reducing agent; and (5) an aqueous solvent.

Description

[Technical Field]

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application Serial No. 63 / 166,340, filed on March 26, 2021, the contents of which are incorporated herein by reference in their entirety.

[0003] This invention relates to grinding compositions and methods of using them. [Previous Technology]

[0004] Background of the Invention

[0005] The semiconductor industry is constantly miniaturizing components through process and integration innovations, thereby improving wafer performance. Chemical mechanical polishing / planarization (CMP) is a powerful technology because it enables complex integration schemes at many transistor levels, thereby promoting increased wafer density.

[0006] CMP is a process that planarizes / planarizes a wafer surface by simultaneously removing material using abrasion-based physical processes and surface-based chemical reactions. Generally, the CMP process involves applying a CMP slurry (e.g., an aqueous chemical agent) to the wafer surface while simultaneously bringing the wafer surface into contact with and moving the polishing pad relative to the wafer. The slurry typically includes abrasive components and dissolved chemical components, which can vary significantly depending on the materials present on the wafer that will interact with the slurry and polishing pad during the CMP process (e.g., metals, metal oxides, metal nitrides, dielectric materials such as silicon oxide and silicon nitride).

[0007] Molybdenum is a transition metal with very low chemical reactivity, high hardness, excellent electrical conductivity, strong wear resistance, and high corrosion resistance. Molybdenum can also form heteropolymers and alloys with other elements. In the microelectronics industry, molybdenum and its alloys are used as interconnects, diffusion barrier layers, photomasks, and plug fillers. However, due to its hardness and chemical resistance, molybdenum is difficult to grind at high removal rates and low defect rates, which poses a significant challenge for CMP of molybdenum-containing substrates. [Summary of the Invention]

[0008] Summary of the Invention

[0009] The present invention is intended to provide options for incorporating concepts that will be further described in the following detailed description. This invention is not intended to identify key or essential features of the claimed subject matter, nor is it intended to serve as an aid in limiting the scope of the claimed subject matter.

[0010] This disclosure is based on the accidental discovery that certain polishing compositions can selectively remove molybdenum (Mo) and / or its alloys in a controlled manner relative to other materials (i.e., silicon nitride) in the semiconductor substrate during the CMP process, exhibiting excellent corrosion resistance to Mo and low static etching rate.

[0011] In one embodiment, the present disclosure is characterized by an abrasive composition comprising at least one abrasive; at least one organic acid or a salt thereof; at least one amine compound comprising an amino acid, an alkylamine having a 6-24 carbon alkyl chain, or a mixture thereof; at least one nitride removal rate reducing agent; and an aqueous solvent; wherein the abrasive composition has a pH of about 2 to about 9.

[0012] In another embodiment, the present disclosure is characterized by a method comprising (a) applying the abrasive composition described herein to a substrate having molybdenum or an alloy thereof on its surface; and (b) contacting a pad with the surface of the substrate and moving the pad relative to the substrate.

Implementation Method

[0013] Detailed Explanation of This Disclosure

[0014] This disclosure relates to an abrasive composition and a method of abrading a semiconductor substrate using the abrasive composition. In some embodiments, this disclosure relates to an abrasive composition for abrading a substrate comprising at least one portion of a molybdenum (Mo) metal or its alloy. In one or more embodiments, this disclosure relates to an abrasive composition for abrading a substrate comprising at least one portion of a molybdenum (Mo) metal or its alloy and having the ability to stop (i.e., substantially not remove) a dielectric material (e.g., a nitride, such as silicon nitride).

[0015] In one or more embodiments, the abrasive composition described herein may include at least one abrasive, at least one organic acid or a salt thereof, at least one amine compound, at least one nitride removal rate reducer, and an aqueous solvent. In one or more embodiments, the abrasive composition according to the present disclosure may include from about 0.01 wt% to about 50 wt% of at least one abrasive, from about 0.001 wt% to about 10 wt% of at least one organic acid, from about 0.001 wt% to about 5 wt% of at least one amine compound, from about 0.001 wt% to about 10 wt% of at least one nitride removal rate reducer, and the remaining weight percentage (e.g., from about 30 wt% to about 99.99 wt%) of an aqueous solvent (e.g., deionized water).

[0016] In one or more embodiments, this disclosure provides a concentrated grinding composition that can be diluted with water by a maximum of 2, 4, 6, 8, 10, 15, or 20 times before use. In other embodiments, this disclosure provides a point-of-use (POU) grinding composition comprising the above-described grinding composition, water, and optionally an oxidizing agent.

[0017] In one or more embodiments, a POU abrasive composition may include at least one abrasive from about 0.01% to about 25% by weight, at least one organic acid from about 0.001% to about 1% by weight, at least one amine compound from about 0.001% to about 0.5% by weight, at least one nitride removal rate reducer from about 0.001% to about 1% by weight, and an aqueous solvent (e.g., deionized water) in the remaining weight percentage (e.g., from about 65% to about 99.99% by weight).

[0018] In one or more embodiments, a concentrated abrasive composition may include at least one abrasive from about 0.02 wt% to about 50 wt%, at least one organic acid from about 0.01 wt% to about 10 wt%, at least one amine compound from about 0.01 wt% to about 5 wt%, at least one nitride removal rate reducer from about 0.01 wt% to about 10 wt%, and an aqueous solvent (e.g., deionized water) in the remaining weight percentage (e.g., from about 35 wt% to about 99.98 wt%).

[0019] In one or more embodiments, the abrasive composition described herein may comprise at least one (e.g., two or three) abrasives. In one or more embodiments, the at least one abrasive is selected from the group consisting of cationic abrasives, substantially neutral abrasives, and anionic abrasives. In one or more embodiments, the at least one abrasive is selected from the group consisting of: alumina, silicon dioxide, titanium dioxide, cerium oxide, zirconium oxide, co-formed products thereof (i.e., co-formed products of alumina, silicon dioxide, titanium dioxide, cerium oxide, or zirconium oxide), coated abrasives, surface-modified abrasives, and mixtures thereof. In some embodiments, the at least one abrasive does not include cerium oxide. In some embodiments, the at least one abrasive has high purity and may contain less than about 100 ppm of alcohol, less than about 100 ppm of ammonia, and less than about 100 ppb of basic cations such as sodium cations. Based on the total weight of the POU abrasive composition, the amount of abrasive present can range from about 0.01% to about 12% (e.g., from about 0.5% to about 10%) or any subrange thereof.

[0020] In one or more embodiments, the abrasive is a silicon dioxide-based abrasive, such as one selected from the group consisting of colloidal silicon dioxide, fumed silicon dioxide, and mixtures thereof. In one or more embodiments, the abrasive may be surface-modified with organic groups and / or non-silicon inorganic groups. For example, the cationic abrasive may include an end group of formula (I): -Om-X-(CH2)nY (I), where m is an integer from 1 to 3; n is an integer from 1 to 10; X is Al, Si, Ti, Ce, or Zr; and Y is a cationic amino or thiol group. As another example, the anionic abrasive may include an end group of formula (I): -Om-X-(CH2)nY (I), where m is an integer from 1 to 3; n is an integer from 1 to 10; X is Al, Si, Ti, Ce, or Zr; and Y is an acid group.

[0021] In one or more embodiments, the abrasive described herein may have an average particle size from at least about 1 nm (e.g., at least about 5 nm, at least about 10 nm, at least about 20 nm, at least about 40 nm, at least about 50 nm, at least about 60 nm, at least about 80 nm, or at least about 100 nm) to at most about 1000 nm (e.g., at most about 800 nm, at most about 600 nm, at most about 500 nm, at most about 400 nm, or at most about 200 nm). The average particle size (MPS) used herein is determined by dynamic light scattering technique.

[0022] In one or more embodiments, the amount of the at least one abrasive is at least about 0.01% by weight (e.g., at least about 0.05% by weight, at least about 0.1% by weight, at least about 0.2% by weight, at least about 0.4% by weight, at least about 0.5% by weight, at least about 0.6% by weight, at least about 0.8% by weight, at least about 1% by weight, at least about 1.2% by weight, at least about 1.5% by weight, at least about 1.8% by weight, or at least about 2% by weight) to at most about 50% by weight (e.g., at most about 45% by weight, at most about 40% by weight, at most about 35% by weight, at most about 30% by weight, at most about 25% by weight, at most about 20% by weight, at most about 15% by weight, at most about 12% by weight, at most about 10% by weight, at most about 5% by weight, at most about 4% by weight, at most about 3% by weight, at most about 2% by weight, at most about 1% by weight) of the abrasive composition described herein.

[0023] In one or more embodiments, the grinding composition described herein includes at least one (e.g., two or three) organic acid or a salt of such organic acid. In some embodiments, the organic acid may be a carboxylic acid comprising one or more (e.g., two, three, or four) carboxylic acid groups, such as dicarboxylic acid or tricarboxylic acid. In one or more embodiments, the organic acid is selected from the group consisting of gluconic acid, lactic acid, citric acid, tartaric acid, malic acid, glycolic acid, malonic acid, formic acid, oxalic acid, acetic acid, propionic acid, peracetic acid, succinic acid, lactic acid, aminoacetic acid, phenoxyacetic acid, dihydroxyglycine, dihydroxyacetic acid, glyceric acid, and mixtures thereof. It is not intended to be theoretically constrained, but it is believed that organic acids (such as those mentioned above) can act as effective metal removal rate enhancers in the grinding composition described herein to improve the removal rate of molybdenum and / or its alloys in semiconductor substrates.

[0024] In one or more embodiments, the amount of the at least one organic acid or its salt is at least about 0.001% by weight (e.g., at least about 0.003% by weight, at least about 0.005% by weight, at least about 0.01% by weight, at least about 0.03% by weight, at least about 0.05% by weight, at least about 0.1% by weight, at least about 0.3% by weight, at least about 0.5% by weight, at least about 1% by weight, at least about 1.3% by weight, or at least about 1.5% by weight) to at most about 10% by weight of the milled composition described herein. (e.g., up to about 9% by weight, up to about 8% by weight, up to about 7% by weight, up to about 6% by weight, up to about 5% by weight, up to about 4% by weight, up to about 3% by weight, up to about 2.5% by weight, up to about 2.2% by weight, up to about 2% by weight, up to about 1.7% by weight, up to about 1.5% by weight, up to about 1.2% by weight, up to about 1% by weight, up to about 0.7% by weight, up to about 0.5% by weight, up to about 0.2% by weight, up to about 0.15% by weight, up to about 0.1% by weight, up to about 0.07% by weight, or up to about 0.05% by weight). In embodiments where the milled composition contains more than one organic acid, the above ranges may apply independently to each organic acid, or to the total amount of organic acids in the composition.

[0025] In one or more embodiments, the milling composition described herein comprises at least one (e.g., two or three) amine compound. In one or more embodiments, the amine compound may be an amino acid. In one or more embodiments, the amine compound may be an amino acid selected from the group consisting of: tris(hydroxymethyl)methylglycine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamine, arginine, lysine, tyrosine, serine, leucine, isoleucine, glycine, tryptophan, aspartic acid, cysteine, methionine, aspartate, glutamate, threonine, taurine, and mixtures thereof. In one or more embodiments, the amine compound may be an amino acid comprising at least two amino groups (e.g., histidine, lysine, arginine, etc.). In one or more embodiments, the amine compound may be an alkylamine compound having at least one (e.g., two or three) alkyl chains comprising 6 to 24 carbons (i.e., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24). In one or more embodiments, the alkyl chain may be straight-chain, branched, or cyclic alkyl. In one or more embodiments, the alkylamine compound may be a primary, secondary, tertiary, or cyclic amine compound. In one or more embodiments, the alkylamine compound may be an alkoxylated amine (e.g., including ethoxylated and / or propoxylated groups). In one or more embodiments, the alkoxylated amine may include 2 to 100 ethoxylated and / or propoxylated groups. In some embodiments, the at least one alkylamine compound has an alkyl chain comprising 6 to 18 carbons. In some embodiments, the alkylamine is selected from the group consisting of hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, cyclohexylamine, dicyclohexylamine, and mixtures thereof. In some embodiments, the grinding composition described herein may include both at least one amino acid and at least one alkylamine compound. Unwilling to be bound by theory, it is surprising that the aforementioned amine compounds can significantly reduce or minimize the corrosion or etching of molybdenum and / or its alloys in semiconductor substrates, thereby controlling the removal rate of molybdenum and / or its alloys.

[0026] In one or more embodiments, the amount of the at least one amine compound is at least about 0.001% by weight (e.g., at least about 0.003% by weight, at least about 0.005% by weight, at least about 0.01% by weight, at least about 0.03% by weight, at least about 0.05% by weight, at least about 0.1% by weight, at least about 0.3% by weight, at least about 0.5% by weight) to at most about 5% by weight of the milled composition described herein. (e.g., up to about 4.5% by weight, up to about 4% by weight, up to about 3.5% by weight, up to about 3% by weight, up to about 2.5% by weight, up to about 2% by weight, up to about 1.5% by weight, up to about 1% by weight, up to about 0.8% by weight, up to about 0.6% by weight, up to about 0.5% by weight, up to about 0.4% by weight, up to about 0.2% by weight, up to about 0.1% by weight, up to about 0.08% by weight, up to about 0.05% by weight, up to about 0.02% by weight, up to about 0.01% by weight, up to about 0.0075% by weight or up to about 0.005% by weight).

[0027] In one or more embodiments, the at least one (e.g., two or three different) nitride removal rate reducer comprises a compound (e.g., a non-polymeric compound) comprising a hydrophobic portion containing a C6 to C40 hydrocarbon group (e.g., containing alkyl, alkenyl, aryl (e.g., phenyl) and / or aralkyl (e.g., benzyl)); and a hydrophilic portion containing at least one group selected from the group consisting of: sulfinite group, sulfate group, sulfonate group, carboxylic acid ester group, phosphate ester group, and phosphonate group. In one or more embodiments, the hydrophobic portion and the hydrophilic portion are separated by 0 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, or 9) epoxy alkyl groups (e.g., -(CH2)nO- groups, where n can be 1, 2, 3, or 4). In one or more embodiments, the hydrophobic portion and the hydrophilic portion of the nitride removal rate reducer are separated by zero epoxy alkyl groups. Without wishing to be bound by theory, it is believed that in some embodiments, the presence of epoxy alkyl groups in the nitride removal rate reducer may not be preferred, as they may cause problems with slurry stability and increase the silicon nitride removal rate.

[0028] In one or more embodiments, the nitride removal rate reducing agent has a hydrophobic portion containing a hydrocarbon group, the hydrocarbon group comprising at least 6 carbon atoms (C6) (e.g., at least 8 carbon atoms (C8), at least 10 carbon atoms (C10), at least 12 carbon atoms (C12), at least 14 carbon atoms (C14), at least 16 carbon atoms (C16), at least 18 carbon atoms (C18), at least 20 carbon atoms (C20), or at least 22 carbon atoms (C22)) and / or up to 40 carbon atoms (C40). (e.g., up to 38 carbon atoms (C38), up to 36 carbon atoms (C36), up to 34 carbon atoms (C34), up to 32 carbon atoms (C32), up to 30 carbon atoms (C30), up to 28 carbon atoms (C28), up to 26 carbon atoms (C26), up to 24 carbon atoms (C24), or up to 22 carbon atoms (C22)). The hydrocarbon group referred to herein means a group containing carbon and hydrogen atoms and optionally substituted with one or more halogens (e.g., F, Cl, Br, or I), C1-C40 alkoxy or aryloxy groups. This hydrocarbon group may include saturated groups (e.g., straight-chain, branched, or cyclic alkyl groups) and unsaturated groups (e.g., straight-chain, branched, or cyclic alkenyl groups; straight-chain, branched, or cyclic alkynyl groups; or aromatic groups (e.g., phenyl, benzyl, or naphthyl groups)). In one or more embodiments, the hydrophilic portion of the nitride removal rate reducer contains at least one group selected from phosphate ester groups and phosphonate groups. It should be noted that the term "phosphonate group" is explicitly intended to include phosphonic acid groups.

[0029] In one or more embodiments, the nitride removal rate reducing agent is selected from the group consisting of: lauryl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, octadecylphosphonic acid, oleic acid ester, behenyl phosphate, octadecyl sulfate, tridodecyl phosphate, oleyl alcohol polyether-3-phosphate, oleyl alcohol polyether-10-phosphate, 1,4-phenylenediamine, dodecylphosphonic acid, decylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, 1,8-octyldiphosphonic acid, 2,3,4,5,6-pentafluorobenzylphosphonic acid, heptadecafluorodecylphosphonic acid, and 12-pentafluorophenoxydodecylphosphonic acid.

[0030] In one or more embodiments, the nitride removal rate reducer may include an anionic polymer. In one or more embodiments, the anionic polymer may include one or more anionic groups, such as sulfinite groups, sulfate groups, sulfonate groups, carboxylic acid groups, phosphate groups, and phosphonate groups. In one or more embodiments, the anionic polymer is formed from one or more monomers selected from the group consisting of: (meth)acrylic acid, maleic acid, acrylic acid, vinylphosphonic acid, vinyl phosphate, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, acrylamide, acrylamide propyl sulfonic acid, and sodium phosphinite. In a more specific embodiment, the anionic polymer may be selected from the group consisting of: poly(4-styrenesulfonic acid) (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamide-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), polyethyleneimine (PEI), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), polyaspartic acid (PASA), anionic poly(vinyl succinate) (PES), anionic polybutylene succinate (PBS), poly(vinyl alcohol) (PVA), monosodium salts of 2-acrylic acid and 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid and sodium hypophosphite. Copolymers of phosphinite, copolymers of 2-acrylic acid with monosodium salt of 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid and sodium salt of bisulfite, copolymers of 2-acrylamide-2-methyl-1-propanesulfonic acid-acrylic acid, terpolymers of poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid), and mixtures thereof. Not wishing to be bound by theory, it is believed that anionic polymers can dissolve hydrophobic abrasive materials and / or defects on wafer surfaces and facilitate their removal during CMP processes and / or post-CMP cleaning processes.

[0031] In one or more embodiments, the anionic polymer may have a weight average molecular weight ranging from at least about 250 g / mol (e.g., at least about 500 g / mol, at least about 1000 g / mol, at least about 2,000 g / mol, at least about 5,000 g / mol, at least about 50,000 g / mol, at least about 100,000 g / mol, at least about 200,000 g / mol or at least about 250,000 g / mol) to at most about 500,000 g / mol (e.g., at most about 400,000 g / mol, at most about 300,000 g / mol, at most about 200,000 g / mol, at most about 100,000 g / mol, or at most about 50,000 g / mol, or at most about 10,000 g / mol). In some embodiments, the at least one anionic polymer may have a weight-average molecular weight ranging from at least about 1000 g / mol to at most about 10,000 g / mol. In some embodiments, the anionic polymer may have a weight-average molecular weight ranging from at least about 2,000 g / mol to at most about 6,000 g / mol. In still other embodiments, the anionic polymer may have a weight-average molecular weight of about 5,000 g / mol.

[0032] In one or more embodiments, the at least one nitride removal rate reducer described herein may include (1) at least one (e.g., two or three) compound (e.g., a nonpolymer compound) comprising a hydrophobic portion and a hydrophilic portion and (2) at least one (e.g., two or three) anionic polymer.

[0033] In one or more embodiments, the amount of the nitride removal rate reducer is at least about 0.001% by weight (e.g., at least about 0.003% by weight, at least about 0.005% by weight, at least about 0.01% by weight, at least about 0.03% by weight, at least about 0.05% by weight, at least about 0.1% by weight, at least about 0.3% by weight, at least about 0.5% by weight) to at most about 10% by weight (e.g., at most about 9% by weight, at most about 8% by weight, at most about 7% by weight, at most about 6% by weight, at most about 5% by weight, at most about 4% by weight, at most about 3% by weight, at most about 2% by weight, at most about 1% by weight, at most about 0.8% by weight, at most about 0.6% by weight, at most about 0.5% by weight, at most about 0.4% by weight, at most about 0.2% by weight, at most about 0.1% by weight, at most about 0.08% by weight, at most about 0.05% by weight, at most about 0.02% by weight, at most about 0.0075% by weight, or at most about 0.005% by weight) of the grinding composition described herein. Without being bound by theory, it is believed that the aforementioned nitride removal rate reducer can significantly reduce the removal rate of the grinding composition on nitride substrate materials (e.g., silicon nitride), thereby providing the ability to stop on such substrate materials.

[0034] In one or more embodiments, the grinding composition described herein may optionally include at least one (e.g., two or three) pH adjuster, if desired, to adjust the pH to a desired value. In some embodiments, the at least one pH adjuster may be an acid (e.g., an organic or inorganic acid) or a base (e.g., an organic or inorganic base). For example, the pH adjuster may be selected from the group consisting of: nitric acid, hydrochloric acid, sulfuric acid, propionic acid, citric acid, malonic acid, hydrobromic acid, hydroiodic acid, perchloric acid, ammonia, ammonium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide, dimethyldipropylammonium hydroxide, benzyltrimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, choline hydroxide, and any combination thereof.

[0035] In one or more embodiments, the amount of the at least one pH adjuster is from at least about 0.001% by weight (e.g., at least about 0.005% by weight, at least about 0.01% by weight, at least about 0.05% by weight, at least about 0.1% by weight, at least about 0.2% by weight, at least about 0.4% by weight, at least about 0.5% by weight, at least about 1% by weight, or at least about 1.5% by weight) to at most about 2.5% by weight (e.g., at most about 2% by weight, at most about 1.5% by weight, at most about 1% by weight, at most about 0.5% by weight, at most about 0.1% by weight, or at most about 0.5% by weight) of the milled composition described herein.

[0036] In one or more embodiments, the abrasive composition described herein may be acidic or alkaline. In some embodiments, the abrasive composition may have a pH ranging from at least about 2 to at most about 9. For example, the pH range may be from at least about 2 (e.g., at least about 2.5, at least about 3, at least about 3.5, at least about 4, at least about 4.5, or at least about 5) to at most about 9 (e.g., at most about 8.5, at most about 8, at most about 7.5, at most about 7, at most about 6.5, at most about 6, at most about 6.5, or at most about 5). In one or more embodiments, the abrasive composition described herein may have an acidic pH, such as from about 2 to about 6 (e.g., from about 2 to about 4). It is not intended to be theoretically constrained, but it is believed that under these acidic conditions, the abrasive composition described herein may have an increased molybdenum removal rate and a decreased nitride material (e.g., silicon nitride) removal rate.

[0037] In one or more embodiments, the grinding composition described herein may include a solvent (e.g., a first solvent), such as an aqueous solvent (e.g., water or a solvent including water and an organic solvent). In some embodiments, the amount of the solvent (e.g., water) is at least about 20% by weight (e.g., at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, at least about 40% by weight, at least about 45% by weight, at least about 50% by weight, at least about 55% by weight, at least about 60% by weight, at least about 65% by weight, at least about 70% by weight, at least about 75% by weight, at least about 80% by weight, at least about 85% by weight, at least about 90% by weight, at least about 92% by weight, at least about 94% by weight, at least about 95% by weight, or at least about 97% by weight) to at most about 99% by weight (e.g., at most about 98% by weight, at most about 96% by weight, at most about 94% by weight, at most about 92% by weight, at most about 90% by weight, at most about 85% by weight, at most about 80% by weight, at most about 75% by weight, at most about 70% by weight, or at most about 65% by weight) of the milling composition described herein.

[0038] In one or more embodiments, an optional second solvent (e.g., an organic solvent) may be used in the milling composition disclosed herein (e.g., POU or concentrated milling composition) to help dissolve components (e.g., azole corrosion inhibitors, if present). In one or more embodiments, the second solvent may be one or more alcohols, alkyl glycols, or alkyl glycol ethers. In one or more embodiments, the second solvent includes one or more selected from the group consisting of ethanol, 1-propanol, 2-propanol, n-butanol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol propyl ether, and ethylene glycol.

[0039] In some embodiments, the amount of the second solvent is at least about 0.001% by weight (e.g., at least about 0.005% by weight, at least about 0.01% by weight, at least about 0.02% by weight, at least about 0.05% by weight, at least about 0.1% by weight, at least about 0.2% by weight, at least about 0.4% by weight, at least about 0.5% by weight, at least about 0.6% by weight, at least about 0.8% by weight, at least about 1% by weight, at least about 3% by weight, at least about 5% by weight, or at least about 10% by weight) to at most about 10% by weight (e.g., at most about 7.5% by weight, at most about 5% by weight, at most about 3% by weight, at most about 2% by weight, at most about 1% by weight, at most about 0.8% by weight, at most about 0.6% by weight, at most about 0.5% by weight, or at most about 0.1% by weight) of the grinding composition described herein.

[0040] In one or more embodiments, the grinding composition described herein may further include at least one additive selected from the group consisting of chelating agents, azole compounds, oxidizing agents, surfactants, corrosion inhibitors and water-soluble polymers.

[0041] There are no particular limitations on the chelating agent, but specific examples include the group consisting of: 1,2-ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, hydroxylamine O-sulfonic acid, methanesulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyanilinesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, acetoacetone, aminotris(methylenephosphonic acid), 1-hydroxyethylidene(1,1-diphosphonic acid), 2-phosphatidyl-1,2,4-butanetricarboxylic acid, hexamethylenediaminetetra(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), salts thereof, and mixtures thereof.

[0042] In some embodiments, the chelating agent may comprise at least about 0.001% by weight (e.g., at least about 0.002% by weight, at least about 0.003% by weight, at least about 0.004% by weight, at least about 0.005% by weight, at least about 0.006% by weight, at least about 0.007% by weight, at least about 0.008% by weight, at least about 0.009% by weight, or at least about 0.01% by weight) to at most about 10% by weight of the grinding composition described herein. (e.g., up to about 9% by weight, up to about 8% by weight, up to about 7% by weight, up to about 6% by weight, up to about 5% by weight, up to about 4% by weight, up to about 3% by weight, up to about 2% by weight, up to about 1% by weight, up to about 0.8% by weight, up to about 0.6% by weight, up to about 0.5% by weight, up to about 0.4% by weight, up to about 0.2% by weight, up to about 0.1% by weight, up to about 0.08% by weight, up to about 0.05% by weight, up to about 0.02% by weight, up to about 0.0075% by weight or up to about 0.005% by weight).

[0043] There are no particular limitations on the azole compounds, but specific examples include heterocyclic azoles, substituted or unsubstituted triazoles (e.g., benzotriazole), substituted or unsubstituted tetraazoles, substituted or unsubstituted diazoles (e.g., imidazole, benzimidazole, thiadiazole, and pyrazole), and substituted or unsubstituted benzothiazoles. Here, substituted diazoles, triazoles, or tetraazoles mean products obtained by substituting one or more hydrogen atoms of the diazole, triazole, or tetraazole with, for example, a carboxyl group, an alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl), a halogen group (e.g., F, Cl, Br, or I), an amino group, or a hydroxyl group. In one or more embodiments, the azole compound may be selected from the group consisting of: tetrazolium, benzotriazole, tolyltriazole, methylbenzotriazole (e.g., 1-methylbenzotriazole, 4-methylbenzotriazole and 5-methylbenzotriazole), ethylbenzotriazole (e.g., 1-ethylbenzotriazole), propylbenzotriazole (e.g., 1-propylbenzotriazole), butylbenzotriazole (e.g., 1-butylbenzotriazole and 5-butylbenzotriazole), pentylbenzotriazole (e.g., 1-pentylbenzotriazole), hexylbenzotriazole (e.g., 1... -hexylbenzotriazole and 5-hexylbenzotriazole), dimethylbenzotriazole (e.g., 5,6-dimethylbenzotriazole), chlorobenzotriazole (e.g., 5-chlorobenzotriazole), dichlorobenzotriazole (e.g., 5,6-dichlorobenzotriazole), chloromethylbenzotriazole (e.g., 1-(chloromethyl)-1-H-benzotriazole), chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, aminobenzimidazole, pyrazole, imidazole, aminotetrazole, adenine, benzimazole, thiabendazole, 1,2,3-triazole, 1, 2,4-triazole, 1-hydroxybenzotriazole, 2-methylbenzothiazole, 2-aminobenzimidazole, 2-amino-5-ethyl-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-methylpyrazole, 4-amino-4H-1,2,4-triazole, aminotetrazole, tetrazolium, phenyltetrazole, phenyl-tetrazole-5-thiol, and combinations thereof. Not wishing to be bound by theory, it is believed that azole compounds can be used as corrosion inhibitors in the grinding compositions described herein to reduce the removal of certain materials (e.g., metals or dielectric materials) during the grinding process.

[0044] In some embodiments, the azole compound may comprise at least about 0.001% by weight (e.g., at least about 0.002% by weight, at least about 0.004% by weight, at least about 0.005% by weight, at least about 0.006% by weight, at least about 0.008% by weight, at least about 0.01% by weight, at least about 0.02% by weight, at least about 0.04% by weight, at least about 0.05% by weight, at least about 0.06% by weight, at least about 0.08% by weight, or at least about 0.1% by weight) to at most about 5% by weight of the milled composition described herein. (e.g., up to about 4.5% by weight, up to about 4% by weight, up to about 3.5% by weight, up to about 3% by weight, up to about 2.5% by weight, up to about 2% by weight, up to about 1.5% by weight, up to about 1% by weight, up to about 0.9% by weight, up to about 0.8% by weight, up to about 0.7% by weight, up to about 0.6% by weight, up to about 0.5% by weight, up to about 0.4% by weight, up to about 0.3% by weight, up to about 0.2% by weight, up to about 0.18% by weight, up to about 0.16% by weight, up to about 0.15% by weight, up to about 0.14% by weight, up to about 0.12% by weight, up to about 0.1% by weight, up to about 0.08% by weight, up to about 0.06% by weight, up to about 0.05% by weight, up to about 0.04% by weight, up to about 0.03% by weight, up to about 0.02% by weight or up to about 0.01% by weight).

[0045] There are no particular limitations on the oxidant, but specific examples include ammonium persulfate, potassium persulfate, hydrogen peroxide, ferric nitrate, diammonium cerium nitrate, ferric sulfate, hypochlorous acid, ozone, potassium periodate, and peracetic acid. It is not intended to be theoretically constrained, but the oxidant is believed to promote material removal during the grinding process.

[0046] In some embodiments, the oxidant may account for at least about 0.01% by weight (e.g., at least about 0.05% by weight, at least about 0.1% by weight, at least about 0.2% by weight, at least about 0.3% by weight, at least about 0.4% by weight, at least about 0.5% by weight, at least about 0.6% by weight, at least about 0.7% by weight, at least about 0.8% by weight, at least about 0.9% by weight, at least about 1% by weight, at least about 1.5% by weight, or at least about 2% by weight) to at most about 10% by weight (e.g., at most about 9% by weight, at most about 8% by weight, at most about 7% by weight, at most about 6% by weight, at most about 5% by weight, at most about 4% by weight, at most about 3% by weight, at most about 2% by weight, or at most about 1% by weight) of the grinding composition described herein.

[0047] In one or more embodiments, the grinding composition described herein may further include one or more surfactants selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, and mixtures thereof.

[0048] There are no particular limitations on the cationic surfactant, but specific examples include aliphatic amine salts and aliphatic ammonium salts.

[0049] There are no particular limitations on the nonionic surfactant, but specific examples include ether surfactants, ether ester surfactants, ester surfactants, and acetylene surfactants. There are no particular limitations on ether surfactants, but specific examples include polyethylene glycol mono-4-nonylphenyl ether, polyethylene glycol monooleyl ether, and triethylene glycol monododecyl ether. There are no particular limitations on ether ester surfactants, but specific examples are polyoxyethylene ethers of glycerol esters. There are no particular limitations on ester surfactants, but specific examples include polyethylene glycol fatty acid esters, glycerol esters, and sorbitan esters. There are no particular limitations on acetylene surfactants, but specific examples include ethylene oxide adducts of acetylene alcohol, acetylene glycol, and acetylene diol.

[0050] There are no particular limitations on the amphoteric surfactant, but specific examples include betaine surfactants.

[0051] There are no particular limitations on the anionic surfactant, but specific examples include carboxylates, sulfonates, sulfates, and phosphates. There are no particular limitations on the carboxylates, but specific examples include fatty acid salts (e.g., soaps) and alkyl ether carboxylates. Examples of sulfonates include alkylbenzene sulfonates, alkylnaphthalene sulfonates, and α-olefin sulfonates. There are no particular limitations on the sulfates, but specific examples include higher alcohol sulfates and alkyl sulfates. There are no particular limitations on the phosphates, but specific examples include alkyl phosphates and alkyl ester phosphates.

[0052] There are no particular limitations on the corrosion inhibitor, but specific examples include choline hydroxide, amino alcohols (e.g., monoethanolamine and 3-amino-4-octanol), amino acids (e.g., those described herein) and mixtures thereof.

[0053] There are no particular limitations on the water-soluble polymer, but specific examples include polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, hydroxyethyl cellulose, and copolymers including the polymers listed above. It is not intended to be theoretically limited, but the water-soluble polymer is believed to be usable as a removal rate inhibitor to reduce the removal rate of certain exposed materials on the substrate that are not intended to be removed or should be removed at a lower removal rate during the grinding process.

[0054] In one or more embodiments, the water-soluble polymer may account for at least about 0.01% by weight (e.g., at least about 0.02% by weight, at least about 0.03% by weight, at least about 0.04% by weight, at least about 0.05% by weight, at least about 0.06% by weight, at least about 0.07% by weight, at least about 0.08% by weight, at least about 0.09% by weight, or at least about 0.1% by weight) to at most about 1% by weight (e.g., at most about 0.8% by weight, at most about 0.6% by weight, at most about 0.5% by weight, at most about 0.4% by weight, at most about 0.2% by weight, at most about 0.1% by weight, at most about 0.08% by weight, at most about 0.06% by weight, or at most about 0.05% by weight) of the milling composition described herein.

[0055] In one or more embodiments, the grinding composition described herein may substantially be free of one or more specific components, such as organic solvents, pH adjusters, fluorinated compounds (e.g., fluorinated compounds or fluorinated compounds (e.g., fluorinated polymers / surfactants)), salts (e.g., halide salts or metal salts), polymers (e.g., nonionic, cationic, or anionic polymers), quaternary ammonium compounds (e.g., salts such as tetraalkylammonium salts or hydroxides such as tetraalkylammonium hydroxide), corrosion inhibitors (e.g., azole or nonazole corrosion inhibitors), bases (e.g., alkali metal hydroxides), silicon-containing compounds such as silanes (e.g., alkoxysilanes), nitrogen-containing compounds (e.g., amino acids, amines, amines, etc.). Amines (e.g., amidines, such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN)), amides or amides), polyols, inorganic acids (e.g., hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid), surfactants (e.g., cationic surfactants, anionic surfactants, nonpolymer surfactants or nonionic surfactants), plasticizers, oxidants (e.g., H2O2 and periodic acid), corrosion inhibitors (e.g., azole or nonazole corrosion inhibitors), electrolytes (e.g., polyelectrolytes) and / or certain abrasives (e.g., cerium oxide abrasives, nonionic abrasives, surface-modified abrasives or negatively / positively charged abrasives). Halide salts that can be excluded from the grinding composition include alkali metal halides (e.g., sodium halides or potassium halides) or ammonium halides (e.g., ammonium chloride), and may be fluorides, chlorides, bromides, or iodides. As used herein, a component “substantially absent” in the grinding composition means a component that is not intentionally added to the grinding composition. In some embodiments, the grinding composition described herein may have up to about 1000 ppm (e.g., up to about 500 ppm, up to about 250 ppm, up to about 100 ppm, up to about 50 ppm, up to about 10 ppm, or up to about 1 ppm) of one or more of the components described above that are substantially absent from the grinding composition. In some embodiments, the grinding composition may be completely free of one or more of the aforementioned components.

[0056] In one or more embodiments, the grinding composition described herein may have a removal rate ratio (i.e., removal rate ratio or selectivity) of molybdenum and / or its alloys to a nitride material (e.g., silicon nitride) ranging from at least about 2:1 (e.g., at least about 3:1, at least about 4:1, at least about 5:1, at least about 10:1, at least about 250:1, at least about 250:1, or at least about 300:1) to at most about 1000:1 (e.g., at most about 500:1, at most about 300:1, at most about 250:1, at most about 200:1, at most about 150:1, or at most about 100:1). In one or more embodiments, the grinding composition described herein may have a ratio from at least about 1:50 (e.g., at least about 1:45, at least about 1:40, at least about 1:35, at least about 1:30, at least about 1:25, at least about 1:20, at least about 1:15, at least about 1:10, at least about 1:8, at least about 1:6, at least about 1:5, at least about 1:4, at least about 1:2, or at least about 1:1) to at most about 50:1. The ratio (i.e., removal rate ratio or selectivity) of the removal rate of molybdenum and / or its alloys to the removal rate of oxide materials (e.g., silicon oxide such as TEOS) is the ratio of removal rates of molybdenum and / or its alloys to the removal rates of oxide materials (e.g., silicon oxide such as TEOS). In one or more embodiments, the above ratio may be applied when measuring the removal rates of blank wafers or patterned wafers (e.g., wafers including conductive layers, barrier layers, and / or dielectric layers).

[0057] In one or more embodiments, the molybdenum and / or TEOS removal rate may range from at least about 20 Å / min (e.g., at least about 30 Å / min, at least about 40 Å / min, at least about 50 Å / min, at least about 60 Å / min, at least about 70 Å / min, at least about 80 Å / min, at least about 90 Å / min or at least about 100 Å / min) to at most about 600 Å / min (e.g., at most about 550 Å / min, at most about 500 Å / min, at most about 450 Å / min, at most about 400 Å / min, at most about 350 Å / min, at most about 300 Å / min, at most about 250 Å / min, at most about 200 Å / min, at most about 150 Å / min or at most about 100 Å / min). In one or more embodiments, the nitride (e.g., silicon nitride) removal rate may be up to about 85 Å / min (e.g., up to about 80 Å / min, up to about 75 Å / min, up to about 70 Å / min, up to about 65 Å / min, up to about 60 Å / min, up to about 55 Å / min, up to about 50 Å / min, up to about 45 Å / min, up to about 40 Å / min, up to about 35 Å / min, up to about 30 Å / min, or up to about 25 Å / min, or up to about 20 Å / min, or up to about 15 Å / min, or up to about 10 Å / min, or up to about 5 Å / min or substantially 0 Å / min).

[0058] In one or more embodiments, the present disclosure is characterized by a polishing method which may include applying a polishing composition according to the present disclosure onto a substrate (e.g., a wafer, such as a blanket wafer or a patterned wafer); and contacting a pad (e.g., a polishing pad) with the surface of the substrate and moving the pad relative to the substrate. In one or more embodiments, the substrate may include at least one of the following: silica (e.g., tetraethyl orthosilicate (TEOS), high-density plasma oxide (HDP), high aspect ratio process oxide (HARP), or borosilicate silicate glass (BPSG)), spin-coated films (e.g., films based on inorganic particles or films based on crosslinkable carbon polymers), silicon nitride, silicon carbide, high-k dielectrics (e.g., metal oxides of hafnium, aluminum, or zirconium), silicon (e.g., polycrystalline silicon, monocrystalline silicon, or amorphous silicon), carbon, metals (e.g., tungsten, copper, cobalt, ruthenium, molybdenum, titanium, tantalum, or aluminum) or alloys thereof, metal nitrides (e.g., titanium nitride or tantalum nitride), and mixtures or combinations thereof. In one or more embodiments, the polishing method may include applying the polishing composition described herein to a substrate (e.g., a wafer) containing molybdenum and / or its alloys on a substrate surface.

[0059] In one or more embodiments, the method using the polishing composition described herein may further include producing a semiconductor device from a substrate treated with the polishing composition through one or more steps. For example, photolithography, ion implantation, dry / wet etching, plasma etching, deposition (e.g., PVD, CVD, ALD, ECD), wafer mounting, die dicing, packaging, and testing can be used to produce semiconductor devices from a substrate treated with the polishing composition described herein.

[0060] The specific examples below should be interpreted as illustrative only and do not limit the remainder of this disclosure in any way. No further explanation is needed; those skilled in the art will be able to fully utilize the invention based on the description herein. Examples

[0061] In these embodiments, the polishing is performed on a 300 mm wafer using an AMAT Reflexion LK CMP polisher with VP6000 pads or H804 pads and a slurry flow rate of 175 mL / min or 300 mL / min.

[0062] The common components used in the examples are shown in Table 1 below. The specific details of the differences in the test components will be explained in more detail when discussing the respective examples. Table 1 Components % by weight of the composition pH adjuster (alkali) 0.005 – 1 First organic acid 0.1 – 3 The first amine (an amino acid or an alkylamine containing 6-24 carbon alkyl groups). 0.001 – 1 (if used) Silicon nitride removal rate reducer 0.001 – 0.5 (if used) Abrasive (silicon dioxide) 0.1 – 5 Oxidizing agent 0.1 – 5 Solvent (DI water) 75-99 pH 2-6 Example 1

[0063] The removal rates of TEOS, SiN, and molybdenum (Mo) and the static etching rate (SER) of Mo were measured for the polishing compositions 1-5. The SER of Mo was measured by suspending the Mo sample in the polishing composition for 1 minute at 45°C. The removal rate was measured by polishing a blanket wafer of the specified material. Compositions 1-4 were identical except that (1) composition 1 was a control group and did not contain amine compounds, and (2) compositions 2-5 contained amino acids (amine compounds as described herein) at concentrations of 1X, 2X, 3X, and 4X, respectively. All compositions 1-5 contained 4X of the nitride removal rate reducer described herein. The test results are summarized in Table 2 below. Table 2 Composition 1 Composition 2 Composition 3 Composition 4 Composition 5 SiN RR (Å / min) not applicable 14 28 46 118 TEOS RR (Å / min) not applicable 146 142 110 120 Mo RR (Å / min) Cleared* 448 368 262 306 Mo SER (Å / min) Cleared* 28 twenty one 18 17 * Cleared indicates that RR / SER is too high to be measured because Mo on the wafer has been cleared.

[0064] The results showed that the amino acids (i.e., the amine compounds described herein) in compositions 2-5 effectively reduced the static etching rate of molybdenum, with the reduction increasing with increasing concentration. Composition 1, which did not contain amine compounds, completely removed the molybdenum material, indicating that the environment of this composition was highly corrosive to molybdenum. These results suggest that amino acid compounds can be used as corrosion inhibitors for Mo during CMP processes. Example 2

[0065] As described above, the removal rates of TEOS, SiN, and Mo, as well as the static etching rate (SER) of Mo, were measured for the grinding compositions 6-9. Compositions 6-9 were identical except for their pH values ​​(i.e., 2.5, 3, 4, and 5, respectively). Compositions 6-9 included 1X of an amino acid as the amine compound described herein and 4X of a nitride removal rate reducer. The test results are summarized in Table 3 below. Table 3 Composition 6 (pH 2.5) Composition 7 (pH 3) Composition 8 (pH 4) Composition 9 (pH 5) SiN RR (Å / min) 14 32 218 314 TEOS RR (Å / min) 162 178 178 150 Mo RR (Å / min) 524 440 204 175 Mo SER (Å / min) 31 30 26 28

[0066] The results showed that lower pH produced higher Mo RR, while SER was relatively stable from pH 2.5 to pH 5. RR for SiN increased significantly above pH 4. Example 3

[0067] The removal rates of TEOS, SiN, and Mo were measured for grinding compositions 10-13. Compositions 10-13 were identical, except that composition 10 did not contain any nitride removal rate reducer, while compositions 11-13 contained 1X, 2X, and 4X of the nitride removal rate reducers described herein, respectively. All compositions 10-13 contained 1X of an amino acid as an amine compound described herein. The test results are summarized in Table 4 below. Table 4 Composition 10 Composition 11 Composition 12 Composition 13 SiN RR (Å / min) 158 48 32 16 TEOS RR (Å / min) 190 194 178 168 Mo RR (Å / min) 366 436 440 440

[0068] The results show that the nitride removal rate reducer described herein significantly reduces SiN RR. Furthermore, this nitride removal rate reducer has no significant effect on the removal rates of TEOS or Mo. Example 4

[0069] As described above, the removal rates of TEOS, SiN, and Mo, as well as the Mo static etching rate (SER), were measured for the polishing compositions 14-17. Compositions 14-17 were identical except that they each included alkylamines comprising 6-24 carbon alkyl groups (0X, 1X, 2X, and 3X, respectively) as the amine compounds described herein. All compositions 14-17 included 2X of the nitride removal rate reducing agent described herein. The results are summarized in Table 5 below. Table 5 Composition 14 Composition 15 Composition 16 Composition 17 SiN RR (Å / min) not applicable 40 44 41 TEOS RR (Å / min) not applicable 216 204 266 Mo RR (Å / min) Cleared* 140 90 98 Mo SER (Å / min) Cleared* 3.8 3.4 0.2 * Cleared indicates that RR / SER is too high to measure because Mo on the wafer has been cleared.

[0070] The results showed that the addition of alkylamines containing 6-24 carbon alkyl groups as amine compounds significantly reduced Mo RR and SER, but did not significantly affect the removal rates of TEOS or SiN. Example 5

[0071] The Mo SER was measured for the milled compositions 18-22 as described above. Composition 18 is a control group that does not contain any amine compounds. Compositions 19-22 contain the same components as composition 18, except that compositions 19-22 contain the same weight percentage of 6-carbon, 8-carbon, 12-carbon, and 16-carbon alkylamine compounds, respectively. All compositions contain the same amount of all other components, except that composition 18 contains slightly more water due to the lack of alkylamines. The results are summarized in Table 6 below. Table 6 Composition 18 Composition 19 Composition 20 Composition 21 Composition 22 Mo SER (Å / min) 21.67 10.72 4.42 0.86 0.6

[0072] The results showed that, compared with the control group (composition 18), the addition of alkylamine compounds resulted in a significant reduction in Mo SER. Furthermore, the reduction in Mo SER increased as the carbon chain length increased from 6 carbons to 16 carbons. SER measurements for compositions 21 and 22 indicated very little Mo corrosion and provided a very protective environment for Mo, which should provide a controlled grinding rate for a small number of defects. Example 6

[0073] The removal rates of TEOS, SiN, and Mo were measured for the grinding compositions 23-25. Compositions 23-25 ​​were identical, except that they each included C6, C12, and C18 nitride removal rate reducers, respectively. All compositions 23-25 ​​contained the same amino acid as the amine compound described herein. The test results are summarized in Table 7 below. Table 7 Composition 23 Composition 24 Composition 25 SiN RR (Å / min) 84.5 15.6 5.35 TEOS RR (Å / min) 600 531 381 Mo RR (Å / min) 553 518 410

[0074] The results show that the silicon nitride removal rate gradually decreases with increasing carbon chain length in the nitride removal rate reducer. TEOS and Mo removal rates show similar progress, but to a smaller extent. Therefore, the above results indicate that a longer carbon chain in the nitride removal rate reducer may provide a more effective ability to stop nitride formation. Example 7

[0075] For the grinding compositions 26-29, the Mo SER and removal rates of TEOS, SiN, and Mo were measured. Compositions 26-29 are identical, except that they each include different amino acids as amine compounds described herein. All compositions 26-29 include the same nitride removal rate reducing agent. The test results are summarized in Table 8 below. Table 8 Composition 26 (histidine) Composition 27 (arginine) Composition 28 (glycine) Composition 29 (lysine) SiN RR (Å / min) 30 30 116 40 TEOS RR (Å / min) 178 204 218 186 Mo RR (Å / min) 440 362 728 312 Mo SER (Å / min) 30 30 116 40

[0076] The results showed that, compared with other compositions, composition 28 could not adequately protect Mo (i.e., high SER and RR). Furthermore, composition 28 also showed a significant increase in SiN RR. These results indicate that amino acids containing at least two amino groups (e.g., histidine, arginine, and lysine) exhibit superior corrosion inhibition against Mo compared to amino acids containing only one amino group (e.g., glycine).

[0077] Although this disclosure has been described with reference to the examples set forth herein, it should be understood that other modifications and variations are possible without departing from the spirit and scope of this disclosure as defined by the scope of the invention application.

Claims

1. A grinding composition comprising: at least one abrasive; at least one organic acid or a salt thereof, wherein the at least one organic acid is selected from the group consisting of gluconic acid, citric acid, tartaric acid, malic acid, glycolic acid, malonic acid, formic acid, oxalic acid, acetic acid, propionic acid, peracetic acid, succinic acid, lactic acid, aminoacetic acid, phenoxyacetic acid, dihydroxyglycine, dihydroxyacetic acid, glyceric acid, and mixtures thereof; at least one amine compound comprising: an amino acid comprising at least two amino groups, an alkylamine having a 6-24 carbon alkyl chain, or mixtures thereof; at least one nitride removal rate reducing agent; and an aqueous solvent; wherein the grinding composition has a pH of 2 to 9, and wherein the grinding composition is free of polymers.

2. The abrasive composition of claim 1, wherein the at least one abrasive is selected from the group consisting of: alumina, silicon dioxide, titanium dioxide, cerium oxide, zirconium oxide; co-formed products of alumina, silicon dioxide, titanium dioxide, cerium oxide or zirconium oxide; coated abrasives, surface-modified abrasives, and mixtures thereof.

3. The abrasive composition of claim 1, wherein the amount of the at least one abrasive is from 0.01% by weight to 50% by weight of the composition.

4. The milled composition of claim 1, wherein the amount of the at least one organic acid is from 0.001% to 10% by weight of the composition.

5. The milling composition of claim 1, wherein the at least one amine compound is selected from the group consisting of: histidine, glutamine, arginine, lysine, tryptophan, aspartic acid, hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, and mixtures thereof.

6. The milling composition of claim 1, wherein the amount of the at least one amine compound is from 0.001% by weight to 5% by weight of the composition.

7. The grinding composition of claim 1, wherein the at least one nitride removal rate reducing agent comprises: a hydrophobic portion comprising a C6 to C40 hydrocarbon group; and a hydrophilic portion comprising at least one group selected from the group consisting of: sulfinite group, sulfate group, sulfonate group, carboxylic acid ester group, phosphate ester group and phosphonate group; and wherein the hydrophobic portion and the hydrophilic portion are separated by 0 to 10 epoxy alkyl groups.

8. The grinding composition of claim 7, wherein the hydrophobic portion comprises C12 to C32 hydrocarbon groups.

9. The grinding composition of claim 7, wherein the hydrophilic portion comprises a phosphate ester group or a phosphonate ester group.

10. The grinding composition of claim 7, wherein the hydrophobic portion and the hydrophilic portion of the at least one nitride removal rate reducer are separated by zero epoxy alkyl groups.

11. The grinding composition of claim 1, wherein the at least one nitride removal rate reducing agent is selected from the group consisting of: lauryl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, octadecylphosphonic acid, oleic acid ester, behenyl phosphate, octadecyl sulfate, tridodecyl phosphate, oleyl alcohol polyether-3-phosphate, oleyl alcohol polyether-10-phosphate, 1,4-phenylenediamine, dodecylphosphonic acid, decylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, 1,8-octyldiphosphonic acid, 2,3,4,5,6-pentafluorobenzylphosphonic acid, heptadecafluorodecylphosphonic acid, and 12-pentafluorophenoxydodecylphosphonic acid.

12. The grinding composition of claim 1, wherein the at least one nitride removal rate reducing agent accounts for 0.001% to 10% by weight of the composition.

13. The grinding composition of claim 1, further comprising at least one azole compound.

14. The milled composition of claim 13, wherein the at least one azole compound accounts for 0.001% to 5% by weight of the composition.

15. The grinding composition of claim 1 further comprises: an organic solvent in an amount of 0.001% to 10% by weight of the composition.

16. The grinding composition of claim 15, wherein the organic solvent is selected from the group consisting of ethanol, 1-propanol, 2-propanol, n-butanol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol propyl ether, ethylene glycol, and any combination thereof.

17. A method for polishing a substrate, comprising: applying an polishing composition as claimed in any one of claims 1-16 onto the substrate, wherein the surface of the substrate contains molybdenum or an alloy thereof; and contacting a pad with the surface of the substrate and moving the pad relative to the substrate.

18. The method of claim 17, further comprising forming a semiconductor element from the substrate.