Polishing compositions and methods of using the same

Abstract

A polishing composition comprising at least one abrasive, at least one pH adjuster, at least one guanamine compound, and water. The polishing composition can be used in a method of polishing a substrate comprising applying the polishing composition to a surface of a substrate, and contacting a pad with the surface of the substrate and moving the pad relative to the substrate. The surface of the substrate can comprise tungsten and / or molybdenum.

Description

Cross-reference to related applications

[0001] This application claims priority to U.S. Provisional Application No. 63 / 540,745, filed on September 27, 2023, the contents of which are incorporated herein by reference in their entirety. Background Technology

[0002] The semiconductor industry continuously improves chip performance by miniaturizing devices through process and integration innovations. Chemical mechanical polishing / planarization (CMP) is a powerful technology because it enables many complex integration schemes at the transistor level, thereby promoting increased chip density.

[0003] CMP (Carbon Dioxide Polishing) is a process used to planarize / planarize wafer surfaces by simultaneously removing material through abrasion-based physical processes and surface-based chemical reactions. Generally, a CMP process involves applying a CMP slurry (e.g., an aqueous chemical) 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 comprises an abrasive component 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, silicon nitride, etc.).

[0004] Many available CMP pastes are specifically designed to remove materials commonly found in older chip designs. However, as chip designs and architectures evolve, certain components in these older CMP pastes can lead to harmful and / or unacceptable numbers of defects. Summary of the Invention

[0005] This summary is provided to illustrate the selection of concepts, which will be further described in the detailed description below. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to help limit the scope of the claimed subject matter.

[0006] As defined herein, unless otherwise stated, all percentages expressed should be understood as weight percentages relative to the total weight of the chemical mechanical polishing composition.

[0007] In one aspect, the present disclosure is characterized by a polishing composition comprising at least one abrasive, at least one pH adjuster (e.g., selected from acids, bases, or mixtures thereof), at least one guanamine compound, and a solvent (e.g., water).

[0008] In some embodiments, the guanidine compound comprises the structure of formula (I): (I) or its salt, R can be any group described herein.

[0009] In some embodiments, the guanidine compound comprises the structure of formula (IA): (IA) or its salt. Where L can be any group described herein.

[0010] In another aspect, this disclosure is characterized by a method for polishing a substrate, the method comprising the steps of: applying a polishing composition described herein to a surface of the substrate; and bringing a pad into contact with the surface of the substrate and moving the pad relative to the substrate.

[0011] Other aspects and advantages of the claimed subject matter will become apparent from the following description and the appended claims. Detailed Implementation

[0012] The embodiments disclosed herein generally relate to a composition and a method of polishing a semiconductor substrate (e.g., a wafer) using the composition. In one or more embodiments, the compositions disclosed herein can be used to polish a semiconductor substrate comprising at least a tungsten portion, and more specifically, may comprise at least tungsten and silicon oxide and / or silicon nitride portions. In one or more embodiments, the polishing compositions described herein can provide a relatively low static etch rate (SER) for metals, particularly tungsten, without significantly reducing its removal rate. The ability to reduce this SER is important because it can reduce defects and other undesirable results occurring during the polishing process.

[0013] In one or more embodiments, the polishing composition described herein includes at least one abrasive, at least one pH adjuster selected from the group consisting of acids, bases, or mixtures thereof, and at least one guanidine compound, wherein the guanidine compound comprises the structure of formula (I): (I) or its salt, R is a group comprising a selectively substituted aliphatic (e.g., a selectively substituted alkyl), selectively substituted aromatic (e.g., a selectively substituted aryl), selectively substituted heterocyclic (e.g., a selectively substituted triazine), or selectively substituted aralkyl, and water.

[0014] In one or more embodiments, the guanidine compound comprises the structure of formula (IA): (IA) or its salt. Where L is a linker (e.g., a selectively substituted aliphatic, selectively substituted heteroaliphatic, or combination thereof, and any group described herein). In some embodiments, L is or Each Ak is independently covalently bonded, or optionally substituted aliphatic (e.g., optionally substituted alkylene) or optionally substituted heteroaliphatic (e.g., optionally substituted heteroalkylene); and Y 1 Y 2 Y 3 and Y 4 Each is independently an alkylene group (e.g., -CR) C1 R C2 -), oxygen (-O-), thio (-S-), or imino (-NR) N1 -).

[0015] In one or more embodiments, the polishing composition according to this disclosure may include about 0.1 wt% to about 50 wt% of an abrasive, about 0.001 wt% to about 10 wt% of an acid, a base or a mixture thereof, about 0.1 ppm to about 1000 ppm of a guanidine compound (such as any described herein), and the remaining weight percentage (e.g., about 40 wt% to about 99.9 wt%) of a solvent (e.g., deionized water). Alternatively, the polishing composition described herein may include at least one amino acid or poly(amino acid) other than the acid, in an amount of about 0.001 wt% to about 1 wt% of the composition, and / or at least one nitride inhibitor compound, in an amount of about 0.1 ppm to about 1000 ppm of the composition.

[0016] In one or more embodiments, this disclosure provides a concentrated polishing composition that can be diluted with water to up to two times, four times, six times, eight times, or ten times the concentration before use. In other embodiments, this disclosure provides a point-of-use (POU) polishing composition for use on a substrate (e.g., a substrate containing a tungsten portion), comprising the above-described polishing composition, water, and an optional oxidizing agent.

[0017] In one or more embodiments, a POU polishing composition may comprise about 0.1 wt% to about 12 wt% of an abrasive, about 0.001 wt% to about 5 wt% of a pH adjuster, about 0.1 ppm to about 500 ppm by weight of a guanidine compound (such as any described herein), optionally about 0.1 wt% to about 5 wt% of an oxidant, and the remaining weight percentage (e.g., about 88 wt% to about 99 wt%) of a solvent (e.g., deionized water). Furthermore, the POU polishing composition described herein may optionally comprise at least one amino acid or poly(amino acid) other than the acid, in an amount of about 0.0001 wt% to about 0.5 wt% of the composition, and / or at least one nitride inhibitor compound, in an amount of about 0.1 ppm to about 500 ppm of the composition.

[0018] In one or more embodiments, a concentrated polishing composition may include about 1% to about 50% by weight of an abrasive, about 0.01% to about 10% by weight of a pH adjuster, about 1 ppm to about 1000 ppm of a guanidine compound (as described herein), and the remaining weight percentage (e.g., about 40% to about 99.9% by weight) of a solvent (e.g., deionized water). Alternatively, the polishing composition described herein may include at least one amino acid or poly(amino acid) other than the acid, in an amount of about 0.001% to about 1% by weight of the composition, and / or at least one nitride inhibitor compound, in an amount of about 1 ppm to about 1000 ppm of the composition.

[0019] In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) abrasives. In one or more embodiments, the polishing composition may include a single type of abrasive. In some 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, silica, titanium dioxide, cerium oxide, zirconium oxide, co-formed products thereof (i.e., co-formed products of alumina, silica, 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, multi-component abrasives (e.g., composite abrasives), or abrasives surface-modified with Si-containing compounds (e.g., silanes). In some embodiments, the at least one abrasive is of high purity and may have less than about 100 ppm of alcohol, less than about 100 ppm of ammonia, and / or less than about 100 parts per billion (ppb) of alkali metal cations, such as sodium cations.

[0020] In some embodiments, the amount of the at least one abrasive is from at least about 0.1% by weight (e.g., at least about 0.5% by weight, at least about 1% by weight, at least about 2% by weight, at least about 4% by weight, at least about 5% by weight, at least about 10% by weight, at least about 12% by weight, at least about 15% by weight, or at least about 20% 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, or at most about 5% by weight) of the polishing composition described herein.

[0021] In one or more embodiments, the at least one abrasive may have an average particle size of 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, at most about 200 nm, at most about 150 nm, or at most about 100 nm). The average particle size (MPS) used herein is determined by dynamic light scattering techniques.

[0022] In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) pH adjusters selected from the group consisting of acids, bases, or mixtures thereof. In one or more embodiments, the polishing composition described herein may include a single pH adjuster. In one or more embodiments, at least one pH adjuster is a base selected from inorganic bases, organic bases, and mixtures thereof. In some embodiments, the inorganic base may be selected from the group consisting of ammonium hydroxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, and any combination thereof. In one or more embodiments, the organic base is a quaternary ammonium hydroxide (e.g., alkylammonium hydroxide, such as tetraalkylammonium hydroxide) or a quaternary phosphorus hydroxide (e.g., alkylphosphonium hydroxide, such as tetraalkylphosphonium hydroxide). In one or more embodiments, the quaternary ammonium hydroxide is selected from the group consisting of tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, diethyldimethylammonium hydroxide, dimethyldipropylammonium hydroxide, benzyltrimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, and any combination thereof. In one or more embodiments, the quaternary phosphonium hydroxide is selected from the group consisting of tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetrapentylphosphonium hydroxide, triethylmethylphosphonium hydroxide, tetra(hydroxymethyl)phosphonium hydroxide, tetraphenylphosphonium hydroxide, and any combination thereof. In one or more embodiments, the quaternary ammonium hydroxide or quaternary phosphonium hydroxide does not contain covalently bonded hydroxyl groups (e.g., does not contain choline hydroxide or tris(2-hydroxyethyl)methylammonium hydroxide).

[0023] In one or more embodiments, the pH adjuster is selected from acids comprising 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, glycine, phenoxyacetic acid, N,N-dihydroxyethylglycine (bicine), diglycolic acid, glyceric acid, tris(hydroxymethyl)methylglycine, alanine, histidine, valine, isoleucine, leucine, methionine, phenylalanine, cysteine, selenocysteine, glycine, proline, serine, threonine, asparagine, glutamine, aspartic acid, glutamic acid, arginine, histidine, lysine, tyrosine. Tryptophan, benzoic acid, 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, ethyl phosphoric acid, cyanoethyl phosphoric acid, phenyl phosphoric acid, vinyl phosphoric acid, poly(vinylphosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, aminotris(methylenephosphonic acid), diethylenetriaminepenta(methylphosphonic acid), N,N,N',N'-ethylenediaminetetra(methylenephosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, their salts, and mixtures thereof.

[0024] In one or more embodiments, the amount of the at least one pH adjuster is from about 0.001% by weight to 10% by weight of the polishing composition. For example, the at least one pH adjuster may be 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 0.5% by weight, at least about 1% by weight, at least about 2.5% by weight, or at least about 3% 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 2.5% by weight, or at most about 1% by weight) of the polishing composition described herein.

[0025] Unwilling to be bound by theory, the inventors were surprised to discover that using a pH adjuster to keep the pH of the polishing composition acidic could reduce tungsten surface corrosion that may occur during the polishing process.

[0026] In one or more embodiments, the polishing composition described herein comprises at least one (e.g., two or three) guanidine compound, wherein the guanidine compound comprises the structure of formula (I): (I) or its salt, Wherein R is a group comprising a selectively substituted aliphatic, selectively substituted aromatic, or selectively substituted heterocyclic group, or selectively substituted aromatic-aliphatic group. In one or more embodiments, R is a selectively substituted alkyl, selectively substituted aryl, selectively substituted aromatic, selectively substituted triazine, or selectively substituted aralkyl. In one or more embodiments, the polishing composition described herein may comprise a single guanidine compound according to formula (I). In one or more embodiments, R in formula (I) is a substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C2-C 20 Alkenyl, substituted or unsubstituted cycloalkyl, or substituted or unsubstituted aryl. In one or more embodiments, the guanidine compound comprises the structure of formula (IA): (IA) or its salt. Wherein L is a linking group (e.g., a selectively substituted aliphatic, selectively substituted heteroaliphatic, or combination thereof, and any group described herein). In one or more embodiments, L is or Each Ak is independently covalently bonded, or optionally substituted aliphatic (e.g., optionally substituted alkylene) or optionally substituted heteroaliphatic (e.g., optionally substituted heteroalkylene); and Y 1 Y 2 Y 3 and Y 4 Each is independently an alkylene group (e.g., -CR) C1 R C2 -, where R C1 and R C2 Each is independently hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein, oxygen (-O-), thio (-S-), or imino (-NR-). N1 -, where R N1(It is hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein). In one or more embodiments, the at least one guanidine may be a biguanidine. In one or more embodiments, the at least one guanidine is selected from the group consisting of: butyroguanamine, acetoguanamine, benzoguanamine, caprinoguanamine, adipoguanamine, stearoguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-undecyl-1,3,5-triazine. 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxospiro[5.5]undecane, 2,4-diamino-6-butanamino-1,3,5-triazine, 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(2-undecyl-1-imidazolyl)ethyl]-1,3,5-triazine, or mixtures thereof. Not wishing to be bound by theory, the inventors have surprisingly discovered that when a substrate is polished with the polishing composition described herein, this guanidine compound can highly effectively reduce the corrosion of certain materials (e.g., W / Mo) in semiconductor substrates.

[0027] "Aliphatic" refers to a group of organisms with at least 1 carbon atom to 50 carbon atoms (C64- ... 1-50 The hydrocarbon group may have at least one carbon atom (C1), or at least two carbon atoms (C2), at least three carbon atoms (C3), at least four carbon atoms (C4), at least five carbon atoms (C5), at least six carbon atoms (C6), at least seven carbon atoms (C7), at least eight carbon atoms (C8), or at least ten carbon atoms (C9). 10 ), at least 12 carbon atoms (C 12 ), at least 14 carbon atoms (C 14 ), at least 16 carbon atoms (C 16 ), at least 18 carbon atoms (C 18 ) or at least 20 carbon atoms (C 20 )) and / or up to 50 carbon atoms (C 50 (e.g., a maximum of 49 carbon atoms (C)) 49 ), up to 48 carbon atoms (C 48 ), up to 47 carbon atoms (C 47 ), up to 46 carbon atoms (C 46 ), up to 45 carbon atoms (C 45 ), up to 44 carbon atoms (C44 ), up to 43 carbon atoms (C 43 ), up to 42 carbon atoms (C 42 ), up to 41 carbon atoms (C 41 ), up to 40 carbon atoms (C 40 ), up to 38 carbon atoms (C 38 ), up to 36 carbon atoms (C 36 ), up to 34 carbon atoms (C 34 ), up to 32 carbon atoms (C 32 ), up to 30 carbon atoms (C 30 ), up to 28 carbon atoms (C 28 ), up to 26 carbon atoms (C 26 ), up to 24 carbon atoms (C 24 ), up to 22 carbon atoms (C 22 ), up to 20 carbon atoms (C 20 ), up to 18 carbon atoms (C 18 ), up to 16 carbon atoms (C 16 ), up to 14 carbon atoms (C 14 ), up to 12 carbon atoms (C 12 ), up to 10 carbon atoms (C 10 The aliphatic group can have a maximum of 9 carbon atoms (C9), a maximum of 8 carbon atoms (C8), a maximum of 7 carbon atoms (C7), a maximum of 6 carbon atoms (C6), a maximum of 5 carbon atoms (C5), a maximum of 4 carbon atoms (C4), or a maximum of 3 carbon atoms (C3). The aliphatic group can include alkanes (or alkyl groups), alkenes (or alkenyl groups), alkynes (or ynyl groups), including their cyclic forms, and further including straight-chain and branched arrangements, as well as all stereoisomers and positional isomers. The aliphatic group can also be unsubstituted or substituted (e.g., substituted with one or more substituents of the alkyl group described herein). By removing one or more hydrogens to form a suitable connection with the parent molecule group, the aliphatic group can be monovalent or polyvalent (e.g., divalent), and can include monovalent or polyvalent forms of alkanes (or alkyl or alkylene groups), alkenes (or alkenyl or alkenyl groups), and alkynes (or ynyl or ynynyl groups).

[0028] "Alkenyl" refers to a group having at least 2 to 50 carbon atoms (C2+1 ... 2-50The unsaturated monovalent hydrocarbon group comprises at least two carbon atoms (C2), at least three carbon atoms (C3), at least four carbon atoms (C4), at least five carbon atoms (C5), at least six carbon atoms (C6), at least seven carbon atoms (C7), at least eight carbon atoms (C8), and at least ten carbon atoms (C9). 10 ), at least 12 carbon atoms (C 12 ), at least 14 carbon atoms (C 14 ), at least 16 carbon atoms (C 16 ), at least 18 carbon atoms (C 18 ) or at least 20 carbon atoms (C 20 )) and / or up to 50 carbon atoms (C 50 (e.g., a maximum of 49 carbon atoms (C)) 49 ), up to 48 carbon atoms (C 48 ), up to 47 carbon atoms (C 47 ), up to 46 carbon atoms (C 46 ), up to 45 carbon atoms (C 45 ), up to 44 carbon atoms (C 44 ), up to 43 carbon atoms (C 43 ), up to 42 carbon atoms (C 42 ), up to 41 carbon atoms (C 41 ), up to 40 carbon atoms (C 40 ), up to 38 carbon atoms (C 38 ), up to 36 carbon atoms (C 36 ), up to 34 carbon atoms (C 34 ), up to 32 carbon atoms (C 32 ), up to 30 carbon atoms (C 30 ), up to 28 carbon atoms (C 28 ), up to 26 carbon atoms (C 26 ), up to 24 carbon atoms (C 24 ), up to 22 carbon atoms (C 22 ), up to 20 carbon atoms (C 20 ), up to 18 carbon atoms (C 18 ), up to 16 carbon atoms (C 16 ), up to 14 carbon atoms (C 14 ), up to 12 carbon atoms (C 12 ), up to 10 carbon atoms (C 10The alkenyl group can have a maximum of 9 carbon atoms (C9), a maximum of 8 carbon atoms (C8), a maximum of 7 carbon atoms (C7), a maximum of 6 carbon atoms (C6), a maximum of 5 carbon atoms (C5), a maximum of 4 carbon atoms (C4), or a maximum of 3 carbon atoms (C3). The alkenyl group can be branched, linear, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). Examples of alkenyl groups include optionally substituted C atoms having one or more double bonds. 2-24 Alkyl group. The alkenyl group can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable connection with the parent molecule group. The alkenyl group can also be unsubstituted or substituted (e.g., substituted with one or more substituents of the alkyl group described herein).

[0029] "alkyl" refers to a compound having at least 1 carbon atom to 50 carbon atoms (C20-C50). 1-50 A saturated monovalent hydrocarbon group, wherein the saturated monovalent hydrocarbon group can be obtained by removing a hydrogen atom from a carbon atom of a parent compound (e.g., an alkane). For example, the saturated monovalent hydrocarbon group may have at least 1 carbon atom (C1) (e.g., at least 2 carbon atoms (C2), at least 3 carbon atoms (C3), at least 4 carbon atoms (C4), at least 5 carbon atoms (C5), at least 6 carbon atoms (C6), at least 7 carbon atoms (C7), at least 8 carbon atoms (C8), at least 10 carbon atoms (C9)). 10 ), at least 12 carbon atoms (C 12 ), at least 14 carbon atoms (C 14 ), at least 16 carbon atoms (C 16 ), at least 18 carbon atoms (C 18 ) or at least 20 carbon atoms (C 20 )) and / or up to 50 carbon atoms (C 50 (e.g., a maximum of 49 carbon atoms (C)) 49 ), up to 48 carbon atoms (C 48 ), up to 47 carbon atoms (C 47 ), up to 46 carbon atoms (C 46 ), up to 45 carbon atoms (C 45 ), up to 44 carbon atoms (C 44 ), up to 43 carbon atoms (C 43 ), up to 42 carbon atoms (C 42 ), up to 41 carbon atoms (C 41 ), up to 40 carbon atoms (C 40 ), up to 38 carbon atoms (C 38 ), up to 36 carbon atoms (C 36 ), up to 34 carbon atoms (C 34 ), up to 32 carbon atoms (C32 ), up to 30 carbon atoms (C 30 ), up to 28 carbon atoms (C 28 ), up to 26 carbon atoms (C 26 ), up to 24 carbon atoms (C 24 ), up to 22 carbon atoms (C 22 ), up to 20 carbon atoms (C 20 ), up to 18 carbon atoms (C 18 ), up to 16 carbon atoms (C 16 ), up to 14 carbon atoms (C 14 ), up to 12 carbon atoms (C 12 ), up to 10 carbon atoms (C 10 Alkyl groups can have a maximum of 9 carbon atoms (C9), a maximum of 8 carbon atoms (C8), a maximum of 7 carbon atoms (C7), a maximum of 6 carbon atoms (C6), a maximum of 5 carbon atoms (C5), a maximum of 4 carbon atoms (C4), or a maximum of 3 carbon atoms (C3). Alkyl groups can be branched, straight-chain, or cyclic (e.g., cycloalkyl). Examples of alkyl groups include branched or straight-chain saturated hydrocarbon groups with 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable connection with the parent molecule group. The alkyl group can also be unsubstituted or substituted. For example, the alkyl group may be substituted with one, two, or three substituents, or for alkyl groups having two or more carbons, with four substituents, the substituents being independently selected from the group consisting of: (1) alkoxy groups (e.g., -OR, where R is an alkyl group, such as C 1-6 (1) Alkyl); (2) Amino (e.g., -NR) 1 R 2 , where R 1 and R 2 Each is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 (3) Acylamino groups (e.g., -C(O)NR) can form heterocyclic groups as defined herein, together with the nitrogen atoms to which they are attached; 1 R 2 or -NHCOR 1 , where R 1 and R 2 Each is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2(4) aryl; (5) alkyl; (6) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl); (7) aryl acyl (e.g., -C(O)-R, where R is aryl); (8) azide (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C 3-8 (12) Cycloalkyl; (e.g., F, Cl, Br or I); (13) Heterocyclic (e.g., a 5-, 6- or 7-membered ring containing one, two, three or four non-carbon heteroatoms as defined herein); (14) Heterocyclic oxygen (e.g., -OR, where R is a heterocyclic group as defined herein); (15) Heterocyclic acyl (e.g., -C(O)-R, where R is a heterocyclic group as defined herein); (16) Hydroxyl (e.g., -OH); (17) Nitro (e.g., -NO2); (18) Lateral oxygen (oxo) (e.g., =O); (19) -CO2R 1 , where R 1 Selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein; (20) -C(O)NR 1 R 2 , where R 1 and R 2 Each is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein; (21) -SO2R 1 , where R 1 Selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein, and (22) -SO2NR 1 R 2 , where R 1 and R 2 Each is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein. The alkyl group may be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halogens or alkoxy groups). In some embodiments, the unsubstituted alkyl group is C10. 1-3 C 1-6 C 1-12 C 1-16 C 1-18 C 1-20 Or C 1-24 alkyl.

[0030] Unless otherwise stated, "aromatic" refers to a cyclic conjugated group or portion having 5 to 15 ring atoms, having a monocyclic (e.g., phenyl) or multiple fused rings, wherein at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridyl); that is, at least one ring, and optionally multiple fused rings, having a continuously delocalized π-electron system. For example, the cyclic conjugated group or portion may have at least 5 ring atoms (e.g., at least 6, 7, 8, 9, or 10 ring atoms) and / or up to 15 ring atoms (e.g., up to 14, 13, 12, 11, or 10 ring atoms). Typically, the number of out-of-plane π electrons corresponds to Huckel's rule (4n+2). The connection point with the parent structure is typically through the aromatic portion of the fused ring system. The aromatic group may include one or more heteroatoms (e.g., including, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the group, such as in a heteroaromatic group). The aromatic group may also be unsubstituted or substituted (e.g., substituted with one or more substituents of the alkyl group described herein). By removing one or more hydrogens to form a suitable connection with the parent molecule group, the aromatic group may be monovalent or polyvalent (e.g., divalent), and may include monovalent or polyvalent forms of aromatic (or aryl or arylene) or heteroaromatic (or heteroaryl or heteroarylene) groups.

[0031] "Aromatic-aliphatic" means an aromatic group coupled to or potentially coupled to compounds disclosed herein, wherein, as defined herein, the aromatic group is coupled or will be coupled via an aliphatic group. In some embodiments, the aromatic-aliphatic group is -LR, where L is an aliphatic group as defined herein, and R is an aromatic group as defined herein. In some embodiments, the aromatic-aliphatic group is -LR, where L is an alkylene group as defined herein, and R is an aryl group as defined herein.

[0032] "Aryl" refers to a group containing at least 5 to 15 carbon atoms (C64- ... 5-15 An aromatic carbocyclic group having a single ring or multiple fused rings. For example, the aromatic carbocyclic group may have at least 5 carbon atoms (C5) (e.g., at least 6 carbon atoms (C6), at least 7 carbon atoms (C7), at least 8 carbon atoms (C8), at least 9 carbon atoms (C9) or at least 10 carbon atoms (C10). 10 )) and / or up to 15 carbon atoms (C 15 (e.g., a maximum of 14 carbon atoms (C)) 14 ), up to 13 carbon atoms (C 13 ), up to 12 carbon atoms (C 12), up to 11 carbon atoms (C 11 ), or at most 10 carbon atoms (C 10 Examples of aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, etc. The term aryl also includes heteroaryl, defined as a group containing an aromatic group and having at least one heteroatom incorporated into a ring of that aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term non-heteroaryl is also included in the term aryl, defined as a group containing an aromatic group and lacking a heteroatom. The aryl group may be unsubstituted or substituted (e.g., substituted with one or more substituents of the alkyl group described herein). By removing one or more hydrogens to form a suitable connection with the parent molecule group, the aryl group may be monovalent or polyvalent (e.g., divalent).

[0033] Unless otherwise stated, “cycloalkyl” means a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group having 3 to 8 carbons, examples of which are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], etc. The cycloalkyl group may also be unsubstituted or substituted (e.g., substituted with one or more substituents of the alkyl group described herein).

[0034] "Heteroaliphatic" means an aliphatic group as defined herein that comprises at least one to 20 heteroatoms, which may be selected from, but is not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus and their oxidized forms within the group. For example, the aliphatic group may have at least one heteroatom (e.g., at least two heteroatoms, at least three heteroatoms, at least four heteroatoms, at least five heteroatoms, at least six heteroatoms, at least seven heteroatoms, at least eight heteroatoms, at least nine heteroatoms, at least ten heteroatoms, at least eleven heteroatoms, or at least twelve heteroatoms) and / or up to 20 heteroatoms (e.g., up to nineteen heteroatoms, up to eighteen heteroatoms, up to seventeen heteroatoms, up to sixteen heteroatoms, up to fifteen heteroatoms, up to fourteen heteroatoms, up to thirty heteroatoms, up to twelve heteroatoms, up to eleven heteroatoms, up to ten heteroatoms, up to nine heteroatoms, up to eight heteroatoms, up to seven heteroatoms, up to six heteroatoms, up to five heteroatoms, up to four heteroatoms, or up to three heteroatoms).

[0035] Unless otherwise stated, "heterocyclic" or "heterocyclic group" refers to a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halogen groups). The 5-membered ring has 0 to 2 double bonds, while the 6- and 7-membered rings have 0 to 3 double bonds. The term "heterocyclic group" also includes bicyclic, tricyclic, and tetracyclic groups, wherein any of these heterocyclic rings is fused to one, two, or three rings independently selected from the group consisting of aryl rings, cyclohexane rings, cyclohexene rings, cyclopentane rings, cyclopentene rings, and another monocyclic heterocyclic ring, such as indolyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, benzofuranyl, benzothiophene, etc. Heterocyclic compounds include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidine, imidazoleyl, imidazolelinyl, imidazoledinyl, pyridinyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidine, oxazolidineone, isoxazolyl, isoxazolidine, morpholinyl, thiomorpholinyl, and thiazolyl. Thiazolidine, isothiazolyl, isothiazolidine, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxoxazolyl, furanyl, thiophene, tetrahydrothiazolyl, isothiazolyl, isoindazole, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidinyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothiophene, dihydroindolyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxalkyl, dioxinyl, dithiaalkyl, trithiaalkyl, oxazinyl, thiaazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothiaphene, etc. The heterocyclic group can be unsubstituted or substituted (e.g., substituted with one or more substituents of the alkyl group described herein). The heterocyclic group can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable connection with the parent molecule group.

[0036] Linking groups may include bonds (e.g., covalent bonds); arbitrarily substituted alkylene groups; arbitrarily substituted heteroalkylene groups (e.g., poly(ethylene glycol), such as -(OCH2CH2)). n- where n is an integer from 1 to 100; a optionally substituted arylene; or an optionally substituted heteroarylene. Alkylenes may include alkyl groups in polyvalent (e.g., divalent, trivalent, tetravalent, etc.) forms. Examples of alkylenes include methylene, ethylene, propylene, butylene, etc. For example, the alkylene may have at least 1 carbon atom (C1) (e.g., at least 2 carbon atoms (C2), at least 3 carbon atoms (C3), at least 4 carbon atoms (C4), at least 5 carbon atoms (C5), at least 6 carbon atoms (C6), at least 7 carbon atoms (C7), at least 8 carbon atoms (C8), at least 10 carbon atoms (C9)). 10 ), at least 12 carbon atoms (C 12 ), at least 14 carbon atoms (C 14 ), at least 16 carbon atoms (C 16 ), at least 18 carbon atoms (C 18 ) or at least 20 carbon atoms (C 20 )) and / or up to 50 carbon atoms (C 50 (e.g., a maximum of 49 carbon atoms (C)) 49 ), up to 48 carbon atoms (C 48 ), up to 47 carbon atoms (C 47 ), up to 46 carbon atoms (C 46 ), up to 45 carbon atoms (C 45 ), up to 44 carbon atoms (C 44 ), up to 43 carbon atoms (C 43 ), up to 42 carbon atoms (C 42 ), up to 41 carbon atoms (C 41 ), up to 40 carbon atoms (C 40 ), up to 38 carbon atoms (C 38 ), up to 36 carbon atoms (C 36 ), up to 34 carbon atoms (C 34 ), up to 32 carbon atoms (C 32 ), up to 30 carbon atoms (C 30 ), up to 28 carbon atoms (C 28 ), up to 26 carbon atoms (C 26 ), up to 24 carbon atoms (C 24 ), up to 22 carbon atoms (C 22 ), up to 20 carbon atoms (C 20 ), up to 18 carbon atoms (C 18 ), up to 16 carbon atoms (C 16 ), up to 14 carbon atoms (C 14 ), up to 12 carbon atoms (C 12 ), up to 10 carbon atoms (C10 The alkylene group can have a maximum of 9 carbon atoms (C9), a maximum of 8 carbon atoms (C8), a maximum of 7 carbon atoms (C7), a maximum of 6 carbon atoms (C6), a maximum of 5 carbon atoms (C5), a maximum of 4 carbon atoms (C4), or a maximum of 3 carbon atoms (C3). The alkylene group can be branched or unbranched. It can also be unsubstituted or substituted (e.g., substituted with one or more substituents of the alkyl group described herein). The heteroalkylene group can be an alkylene group containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halogen groups).

[0037] “Salt” refers to the ionic form of a compound or structure (e.g., any chemical formula, compound, or composition described herein), including cationic or anionic compounds to form electrically neutral compounds or structures. For example, nontoxic salts are described in Berge SM et al., “Pharmaceutical salts,” J. Pharm. Sci. 1977 January; 66(1):1-19; and “Handbook of Pharmaceutical Salts: Properties, Selection, and Use,” Wiley-VCH, April 2011 (2nd rev. ed., eds. PH Stahl and CG Wermuth). Such salts can be prepared in situ during the final separation and purification of the compounds of this invention, or individually by reacting a free base group with a suitable organic acid (to produce an anionic salt) or by reacting an acid group with a suitable metal or organic salt (to produce a cationic salt). Salts may include anionic salts (such as halide salts, carbonates, sulfates, sulfonates, phosphates, phosphonates, etc.) and cationic salts (such as metal salts, such as alkali metal salts or alkaline earth metal salts, such as barium, calcium, lithium, magnesium, potassium, sodium, etc.; other metal salts, such as aluminum, bismuth, iron and zinc; as well as non-toxic ammonium, quaternary ammonium and amine cations).

[0038] In one or more embodiments, the amount of guanidine compound contained in the polishing composition described herein is from at least about 0.1 ppm (e.g., at least about 0.5 ppm, at least about 1 ppm, at least about 5 ppm, at least about 10 ppm, at least about 25 ppm, at least about 50 ppm, at least about 75 ppm, or at least about 100 ppm) to at most about 1000 ppm (e.g., at most about 900 ppm, at most about 800 ppm, at most about 700 ppm, at most about 600 ppm, at most about 500 ppm, or at most about 250 ppm) based on the total weight of the composition.

[0039] In one or more embodiments, the polishing composition described herein may optionally comprise at least one (e.g., two or three) amino acids or poly(amino acids). In one or more embodiments, the composition described herein may optionally comprise a single amino acid or poly(amino acid). In one or more embodiments, the amino acid is chemically different from the pH adjuster. In one or more embodiments, the amino acid is selected from the group consisting of: alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, and mixtures thereof. In one or more embodiments, the poly(amino acid) is selected from the group consisting of: poly-DL-alanine, poly-L-arginine hydrochloride, poly-(α,β)-DL-aspartate sodium salt, poly-γ-benzyl-L-glutamate, poly-ε-Cbz-L-lysine, poly(γ-ethyl-L-glutamate), poly-D-glutamate sodium salt, poly-L-glutamate sodium salt, polyglycine, poly-L-histidine, poly(L-lactide), poly-D-lysine hydrobromide, poly-L-lysine hydrobromide, poly-DL-lysine hydrobromide, poly-L-ornithine hydrobromide, poly-DL-ornithine hydrobromide, poly-L-proline, poly-L-threonine, and mixtures thereof. Without being bound by theory, it is believed that amino acids or poly(amino acids) (such as those described above) can act as optional additional metal corrosion inhibitors, which further reduce the removal rate and / or static etching rate of metals (e.g., tungsten and / or molybdenum) in semiconductor substrates.

[0040] In one or more embodiments, the amount of the at least one amino acid is from about 0.0001% by weight to 1% by weight of the polishing composition. For example, the at least one amino acid may be from at least about 0.0001% by weight (e.g., at least about 0.0005% by weight, at least about 0.001% by weight, 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, or at least about 0.5% by weight) to at most about 1% by weight (e.g., at most about 0.5% by weight, at most about 0.25% by weight, at most about 0.1% by weight, or at most about 0.05% by weight) of the polishing composition described herein.

[0041] In one or more embodiments, the at least one (e.g., two or three different) nitride inhibitory compound comprises compounds containing C4 to C6. 40The hydrophobic portion comprises a hydrocarbon group (e.g., containing alkyl and / or alkenyl groups); and a hydrophilic portion comprises at least one group selected from the group consisting of: sulfinate, sulfate, sulfonate, carboxylate, phosphate, and phosphonate groups (e.g., including their protonated forms). In one or more embodiments, the hydrophobic and hydrophilic portions contain zero to ten (e.g., 1, 2, 3, 4, 5, 6, 7, 8, or 9) epoxy alkyl groups (e.g., -(CH2)). n O- groups, where n can be 1, 2, 3, or 4, are separated. In one or more embodiments, the nitride inhibitor compound has zero epoxy alkyl groups separating the hydrophobic and hydrophilic portions. It is not desirable to be bound by theory, but it is believed that in some embodiments, the presence of epoxy alkyl groups in the nitride inhibitor compound may not be preferred, as they may cause slurry stability problems and increase the silicon nitride removal rate.

[0042] In one or more embodiments, the nitride inhibitory compound has a hydrophobic portion containing a hydrocarbon group comprising at least 4 carbon atoms (C4) (e.g., at least 6 carbon atoms (C6), at least 8 carbon atoms (C8), or at least 10 carbon atoms (C5)). 10 ), at least 12 carbon atoms (C 12 ), at least 14 carbon atoms (C 14 ), at least 16 carbon atoms (C 16 ), at least 18 carbon atoms (C 18 ), at least 20 carbon atoms (C 20 ), at least 22 carbon atoms (C 22 )) and / or up to 40 carbon atoms (C 40 (e.g., a maximum of 38 carbon atoms (C)) 38 ), up to 36 carbon atoms (C 36 ), up to 34 carbon atoms (C 34 ), up to 32 carbon atoms (C 32 ), up to 30 carbon atoms (C 30 ), up to 28 carbon atoms (C 28 ), up to 26 carbon atoms (C 26 ), up to 24 carbon atoms (C 24 ), or up to 22 carbon atoms (C 22The hydrocarbon groups mentioned herein refer to groups containing only carbon and hydrogen atoms, and 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 or naphthyl groups)). In one or more embodiments, the hydrophilic portion of the nitride inhibitor compound contains at least one group selected from phosphate groups and phosphonic acid groups (e.g., including their protonated forms). It should be noted that the term "phosphonic acid group" is explicitly intended to include phosphonic acid groups, which may include protonated or deprotonated forms.

[0043] In one or more embodiments, the nitride inhibitory compound is selected from the group consisting of: naphthalenesulfonic acid-formalin condensate, lauryl phosphate, myristyl phosphate, stearyl phosphate, octadecylphosphonic acid, oleyl phosphate, behenyl phosphate, octadecyl phosphate, lacteryl phosphate, oleth-3-phosphate, and oleth-10-phosphate.

[0044] In one or more embodiments, the nitride inhibitory compound is present in the polishing composition described herein at a content of at least about 0.1 ppm (e.g., at least about 0.5 ppm, at least about 1 ppm, at least about 5 ppm, at least about 10 ppm, at least about 25 ppm, at least about 50 ppm, at least about 75 ppm, or at least about 100 ppm) to at most about 1000 ppm (e.g., at most about 900 ppm, at most about 800 ppm, at most about 700 ppm, at most about 600 ppm, at most about 500 ppm, or at most about 250 ppm) by weight of the total composition.

[0045] In one or more embodiments, the pH range of the polishing composition 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, at least about 5, at least about 5.5, at least about 6, or at least about 6.5) to at most about 14 (e.g., at most about 13.5, at most about 13, at most about 12.5, at most about 12, at most about 11.5, at most about 11, at most about 10.5, at most about 10, at most about 9.5, at most about 9, 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 5.5, at most about 5, at most about 4.5, at most about 4, at most about 3.5, or at most about 3). It is not desirable to be bound by theory; it is believed that polishing compositions with a pH below 2 will significantly increase corrosion and particulate residue. However, in some embodiments, polishing compositions with a pH higher than 7 can lead to reduced solubility of guanidine compounds in solution and increased corrosion of tungsten surfaces; therefore, a pH of 7 or lower may be preferred in certain cases. To obtain the desired pH, the relative concentrations of the components in the polishing compositions described herein can be adjusted.

[0046] In one or more embodiments, the polishing composition described herein may optionally include at least one (e.g., two or three) azole-containing corrosion inhibitor. In one or more embodiments, the polishing composition may include a single azole-containing corrosion inhibitor. In some embodiments, the at least one azole-containing corrosion inhibitor is selected from the group consisting of: substituted or unsubstituted triazoles, substituted or unsubstituted tetraazoles, substituted or unsubstituted benzotriazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted imidazoles, substituted or unsubstituted benzimidazoles, substituted or unsubstituted thiadiazoles, substituted or unsubstituted thiabendazoles, substituted or unsubstituted adenines, substituted or unsubstituted xanthines, and substituted or unsubstituted guanines. In one or more embodiments, the azole-containing corrosion inhibitor may be selected from the group consisting of: 1,2,4-triazole, 1,2,3-triazole, tetraazole, benzotriazole, tolyltriazole, methylbenzotriazole (e.g., 1-methylbenzotriazole, 4-methylbenzotriazole, or 5-methylbenzotriazole), ethylbenzotriazole (e.g., 1-ethylbenzotriazole), propylbenzotriazole (e.g., 1-propylbenzotriazole), butylbenzotriazole (e.g., 1-butylbenzotriazole or 5-butylbenzotriazole), pentylbenzotriazole (e.g., 1-pentylbenzotriazole), hexylbenzotriazole (e.g., 1-hexylbenzotriazole or 5-hexylbenzotriazole), dimethylbenzotriazole (e.g., 5,6-dimethylbenzotriazole). (e.g., chlorobenzotriazole), chlorobenzotriazole (e.g., 5-chlorobenzotriazole), dichlorobenzotriazole (e.g., 5,6-dichlorobenzotriazole), chloromethylbenzotriazole (e.g., 1-(chloromethyl)-1-H-benzotriazole), chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, aminobenzimidazole, aminotetrazole, pyrazole, imidazole, adenine, xanthine, guanine, benzimidazole, thiabendazole, 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 and mixtures thereof.) Without being bound by theory, it is believed that azole-containing corrosion inhibitors (such as those mentioned above) can significantly reduce or minimize the removal rate of metals (e.g., copper) in semiconductor substrates.

[0047] In some embodiments, the amount of the at least one azole-containing corrosion inhibitor is at least about 0.0001% by weight (e.g., at least about 0.0002% by weight, at least about 0.0005% by weight, at least about 0.001% by weight, at least about 0.002% by weight, 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, or at least about 0.5% 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 0.05% by weight, at most about 0.02% by weight, at most about 0.01% by weight, or at most about 0.005% by weight) of the polishing composition described herein.

[0048] In one or more embodiments, the polishing composition described herein may optionally include at least one (e.g., two or three) oxidizing agents. In one or more embodiments, the polishing composition may optionally include a single oxidizing agent. In some embodiments, the oxidizing agent may be added when diluting the concentrated composition to form a POU composition. The oxidizing agent may be selected from the group consisting of: hydrogen peroxide, ammonium persulfate, silver nitrate (AgNO3), ferric nitrate or ferric chloride, peracids or salts, ozonated water, potassium ferricyanide, potassium dichromate, potassium iodate, potassium bromate, potassium periodate, periodic acid, vanadium trioxide, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, magnesium hypochlorite, ferric nitrate, potassium permanganate, other inorganic or organic peroxides and mixtures thereof. In some embodiments, the oxidizing agent is hydrogen peroxide.

[0049] In some embodiments, the amount of the oxidant is at least about 0.05% by weight (e.g., 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, at least about 1.5% by weight, at least about 2% by weight, at least about 2.5% by weight, at least about 3% by weight, at least about 3.5% by weight, at least about 4% by weight, or at least about 4.5% by weight) to at most about 5% by weight (e.g., at most about 4.5% by weight, at most about 4% by weight, at most about 3.5% by weight, at most about 3% by weight, at most about 2.5% by weight, 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, or at most about 0.1% by weight) of the polishing composition. In some embodiments, the oxidant may shorten the shelf life of the polishing composition. In such embodiments, the oxidant may be added to the polishing composition at the point of use before polishing.

[0050] In one or more embodiments, the polishing composition described herein may include a solvent (e.g., a primary solvent), such as water. In some embodiments, the amount of the solvent (e.g., water) is from 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 polishing composition described herein.

[0051] In one or more embodiments, an optional second solvent (e.g., an organic solvent) may be used in the polishing compositions of this disclosure (e.g., POU or concentrated polishing compositions) to aid in the dissolution of one or more components (e.g., guanidine compounds or azole-containing corrosion inhibitors) in the polishing composition. In one or more embodiments, the second solvent may be one or more alcohols, alkylene glycols, or alkylene glycol ethers. In one or more embodiments, the second solvent comprises one or more solvents 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.

[0052] In some embodiments, the amount of the second solvent is at least about 0.0025% 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 0.6% by weight, at least about 0.8% by weight, or at least about 1% by weight) to at most about 2% by weight (e.g., at most about 1.8% by weight, at most about 1.6% by weight, at most about 1.5% by weight, at most about 1.4% by weight, at most about 1.2% 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 polishing composition described herein.

[0053] In one or more embodiments, the polishing compositions described herein may be substantially free of one or more of the following components: organic solvents, pH adjusters (e.g., organic acids, inorganic acids, organic bases, or inorganic bases), quaternary ammonium compounds (e.g., salts such as tetraalkylammonium salts and hydroxides such as tetramethylammonium hydroxide), alkali metal bases (e.g., alkali metal hydroxides), fluorinated compounds (e.g., fluoride compounds or fluorinated compounds (e.g., fluorinated polymers / surfactants)), silicon-containing compounds, such as silanes (e.g., alkoxysilanes or aminosilanes), nitrogen-containing compounds (e.g., amino acids, amino alcohols, amines, alkylamines, or imines (e.g., amidines, such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0]-7-undecene). The composition may contain: non-5-ene (DBN), amides or imides, salts (e.g., halide salts or metal salts), polymers (e.g., nonionic, cationic, anionic, or water-soluble polymers), inorganic acids (e.g., hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid), surfactants (e.g., cationic surfactants, anionic surfactants, nonpolymer surfactants, amphoteric surfactants, or nonionic surfactants), plasticizers, oxidants (e.g., hydrogen peroxide and periodic acid), corrosion inhibitors (e.g., azole, thiazole, or nonazole corrosion inhibitors), electrolytes (e.g., polyelectrolytes), and / or certain abrasives (e.g., polymeric abrasives, fumed silica, cerium oxide abrasives, nonionic abrasives, surface-modified abrasives, negatively / positively charged abrasives, or ceramic abrasive composites). Halide salts excluded from the polishing 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 polishing composition that is “substantially free” means an ingredient that is not intentionally added to the polishing composition. In some embodiments, the polishing 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 ingredients that are substantially free of the polishing composition. In some embodiments, the polishing composition described herein may be completely free of one or more of the above ingredients.

[0054] This disclosure also contemplates methods for using any of the above-described polishing compositions (e.g., concentrates or POU slurries). For the concentrate, the method may include the steps of: diluting the concentrate (e.g., at least twice) to form a POU slurry, and then contacting a substrate surface at least partially containing tungsten or molybdenum with the POU slurry. In some embodiments, an oxidant may be added to the slurry before, during, or after the dilution. For the POU slurry, the method may include the step of contacting the substrate surface at least partially containing tungsten or molybdenum with the polishing composition.

[0055] In one or more embodiments, this disclosure features a polishing method that may include applying a polishing composition of this disclosure to a surface of a substrate (e.g., a wafer having at least tungsten or molybdenum on the surface of the substrate); and contacting a pad with the surface of the substrate and moving the pad relative to the substrate. Furthermore, in some embodiments, after polishing the substrate with the polishing composition described herein, the polished substrate may undergo a rinse-polishing process, wherein a composition comprising all components of the polishing composition described herein (excluding abrasives) is applied to the polished substrate in a polishing tool, and a pad in the polishing tool is contacted with and moved relative to the substrate to produce a rinse-polished substrate. In some embodiments, after the polishing process and / or the rinse-polishing process, the substrate may be removed from the polishing tool and subjected to CMP post-cleaning in a cleaning tool (e.g., a brush scrubber or a rotary rinse dryer).

[0056] In some embodiments, the method of using the polishing composition described herein may further include producing a semiconductor device from a substrate treated with the polishing composition by one or more steps. For example, photolithography, ion implantation, dry / wet etching, plasma ashing, deposition (e.g., PVD, CVD, ALD, ECD), wafer mounting, die cutting, packaging, and testing may be used to produce a semiconductor device from a substrate treated with the polishing composition described herein.

[0057] The specific examples below should be interpreted as illustrative only and do not limit the remainder of this disclosure in any way. Without further detail, it is believed that those skilled in the art will be able to make the most of the invention based on the description herein.

[0058] Example In these examples, polishing was performed on 200 mm wafers using an AMAT Mirra CMP polisher, Fujibo H804 pads, a downforce of 1–2 psi, a platen head speed between 50 / 45 and 120 / 112 rpm, and a slurry flow rate between 175 mL / min and 225 mL / min. The static etch rate (SER) experiment was conducted by immersing a tungsten or molybdenum sample in 100 g of polishing composition at 60 °C for five minutes and measuring the concentration of metal ions in the solution using a four-point probe or by measuring the concentration in Å / min.

[0059] The general compositions used in the examples are shown in Table 1 below. Specific details regarding the differences between the tested compositions will be explained in further detail when discussing the individual examples.

[0060] Table 1 Example 1 Table 2 below shows the static etching rate (W SER), static etching rate (Mo SER), and removal rates (RR) of silicon oxide (TEOS), silicon nitride (SiN), polycrystalline silicon (pSi), tungsten (W), and molybdenum (Mo) films for six different example compositions. Example 1 is a control sample without any guanidine compounds. Examples 2-6 have the same composition as Example 1, except that guanidine compounds are added. The guanidine compounds in Examples 2-6 (i.e., G1-G5) are all different from each other, all added in the same weight percentage, and all covered by formula (I) in the specific embodiments. The surface of the silica used as the abrasive in this example is not chemically modified. Each formulation contains the same weight percentage of amino acids and oxidants, but no organic solvents.

[0061] Table 2 Surprisingly, the results showed that, compared to the values ​​obtained in Example 1, the guanidine compound reduced the SER on the Mo sample by approximately 8% (Example 5) to 84% (Example 6). Furthermore, the guanidine compound maintained the SER on the W sample (Examples 3-5) or significantly reduced the SER (Examples 2 and 6). Importantly, compared to the polishing composition using Example 1, neither the W RR nor the Mo RR decreased significantly with the addition of the guanidine compound, and this, combined with the lower SER values, indicates a more controlled and defect-free polishing process.

[0062] Example 2 Table 3 below shows the tungsten static etching rate (W SER), molybdenum static etching rate (MoSER), and removal rates (RR) of TEOS, SiN, tungsten, and molybdenum films for four different example compositions. Example 7 is a control sample without any guanidine compound. Examples 8-10 have the same composition as Example 7, except that the same guanidine compound (G6) is added in different amounts. The guanidine compound used in Examples 8-10 is different from that added in the examples in Table 2 and is covered by formula (I) in the specific embodiments. The surface of the silica used as the abrasive in this example is chemically modified with sulfonic acid, resulting in a negatively charged surface. These formulations contain organic solvents but no oxidants or amino acids.

[0063] Table 3 Surprisingly, the results showed that the presence of guanidine compounds gradually reduced the SER on both Mo and W samples with increasing amounts of guanidine compounds. Importantly, neither the W RR nor the Mo RR decreased significantly with the addition of guanidine compounds compared to the polishing composition used in Example 7. This combined with the lower SER values ​​indicates that the polishing process was more controlled and defect-free.

[0064] Although only a few exemplary embodiments have been described in detail above, those skilled in the art will readily understand that many modifications can be made to the exemplary embodiments without substantially departing from the invention. Therefore, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims.

Claims

1. A polishing composition comprising: At least one abrasive; At least one pH adjuster selected from the group consisting of acids, bases or mixtures thereof; At least one guanidine compound, wherein the guanidine compound comprises the structure of formula (I): (I) or its salt, Wherein R is a selectively substituted aliphatic group (e.g., selectively substituted alkyl group), a selectively substituted aromatic group (e.g., selectively substituted aryl group), a selectively substituted heterocyclic group (e.g., selectively substituted triazine group), or a selectively substituted aromatic-aliphatic group (e.g., selectively substituted aralkyl group); and water.

2. The polishing composition of claim 1, wherein the at least one abrasive is selected from the group consisting of cationic abrasives, substantially neutral abrasives, and anionic abrasives.

3. The polishing 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.

4. The polishing composition of claim 1, wherein the amount of the at least one abrasive is from about 0.05% by weight to about 50% by weight of the composition.

5. The polishing composition of claim 1, wherein the 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, aminoacetic acid, phenoxyacetic acid, N,N-dihydroxyethylglycine, diethanolic acid, glyceric acid, tris(hydroxymethyl)methylglycine, alanine, histidine, valine, isoleucine, leucine, methionine, phenylalanine, cysteine, selenocysteine, glycine, proline, serine, threonine, asparagine, glutamine, aspartic acid, glutamic acid, arginine, histidine, lysine, tyrosine, and tryptophan. Benzoic acid, 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, ethyl phosphoric acid, cyanoethyl phosphoric acid, phenyl phosphoric acid, vinyl phosphoric acid, poly(vinylphosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, aminotris(methylenephosphonic acid), diethylenetriaminepenta(methylphosphonic acid), N,N,N',N'-ethylenediaminetetra(methylenephosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, their salts, and mixtures thereof.

6. The polishing composition of claim 1, wherein the alkali is selected from the group consisting of inorganic alkalis, organic alkalis, and mixtures thereof.

7. The polishing composition of claim 1, wherein the amount of the pH adjuster is from about 0.001% by weight to about 10% by weight of the composition.

8. The polishing composition of claim 1, wherein R in formula (I) is a substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C2-C 20 Alkenyl, substituted or unsubstituted cycloalkyl, or substituted or unsubstituted aryl.

9. The polishing composition of claim 1, wherein the guanidine compound is selected from the group consisting of: butyroguanidine, acetylguanidine, benzoguanidine, decanoguanidine, adipicoguanidine, stearoylguanidine, 2,4-diamine-6-nonyl-1,3,5-triazine, 2,4-diamino-6-undecyl-1,3,5-triazine, 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4, 8,10-tetraoxospiro[5.5]undecane, 2,4-diamino-6-butanamino-1,3,5-triazine, 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(2-undecyl-1-imidazolyl)ethyl]-1,3,5-triazine, and mixtures thereof.

10. The polishing composition of claim 1, wherein the guanidine compound comprises the structure of formula (IA): (IA) or its salt. Where L is a linker (e.g., a selectively substituted aliphatic, a selectively substituted heteroaliphatic, or a combination thereof).

11. The polishing composition of claim 10, wherein L is or Each Ak is independently covalently bonded, or optionally substituted aliphatic (e.g., optionally substituted alkylene) or optionally substituted heteroaliphatic (e.g., optionally substituted heteroalkylene); and Y 1 Y 2 Y 3 and Y 4 Each is independently an alkylene group (e.g., -CR) C1 R C2 -), oxygen (-O-), thio (-S-), or imino (-NR) N1 -).

12. The polishing composition of claim 1, wherein the amount of the guanidine compound is from about 0.1 ppm to about 1000 ppm of the composition.

13. The polishing composition of claim 1, further comprising at least one amino acid or poly(amino acid), wherein the amino acid is chemically different from the pH adjuster.

14. The polishing composition of claim 13, wherein the amount of the amino acid or poly(amino acid) is from about 0.001% by weight to about 1% by weight of the composition.

15. The polishing composition of claim 1, further comprising a nitride inhibition compound, comprising: The hydrophobic portion contains C4 to C 40 hydrocarbon groups; and The hydrophilic portion comprises at least one group selected from the group consisting of: sulfinic acid group, sulfate group, sulfonic acid group, carboxylic acid group, phosphate group, and phosphonic acid group; and The hydrophobic portion and the hydrophilic portion are separated by zero to ten epoxy alkyl groups.

16. The polishing composition of claim 15, wherein the amount of the compound is from about 0.1 ppm to about 1000 ppm of the composition.

17. The polishing composition of claim 1, wherein the polishing composition has a pH of about 2 to about 7.

18. A method for polishing a substrate, comprising the following steps: Apply the polishing composition as described in any one of claims 1 to 17 to the surface of a substrate; and The pad is brought into contact with the surface of the substrate and moved relative to the substrate.

19. The method of claim 18, wherein the surface of the substrate comprises Mo and / or W.

20. The method of claim 18 or claim 19, further comprising forming a semiconductor device from the substrate.

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