Abrasive composition and method of use thereof

Abstract

Due to its hardness and chemical resistance, molybdenum has a high removal rate and low defect rate, making it difficult to polish, which presents a challenge for CMP (Chemical Polishing) of molybdenum-containing substrates. [Solution] 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 first amine compound comprising an alkylamine having 6 to 24 carbon alkyl chains; (4) at least one second amine compound containing at least two nitrogen atoms and different from the first amine compound; and (5) an aqueous solvent.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority to U.S. Provisional Patent Application No. 63 / 107,188, filed October 29, 2020.

Background Art

[0002] The semiconductor industry is continuously driven to improve chip performance through further miniaturization of devices via process and integration innovations. Chemical mechanical polishing / planarization (CMP) is a powerful technique as it enables many complex integration schemes at the transistor level, thereby facilitating an increase in chip density.

[0003] CMP is a process used to planarize / flat - polish a wafer surface by removing material using a wear - based physical process simultaneously with a surface - based chemical reaction. Generally, the CMP process involves applying a CMP slurry (e.g., an aqueous chemical formulation) to the wafer surface while contacting the wafer surface with a polishing pad and moving the polishing pad relative to the wafer. The slurry typically contains abrasive constituents and dissolution chemistry constituents that can vary significantly depending on the materials (e.g., metals, metal oxides, metal nitrides, dielectric materials such as silicon oxide and silicon nitride, etc.) present on the wafer that interact with the slurry and the polishing pad during the CMP process.

[0004] Molybdenum is a transition metal with very low chemical reactivity, high hardness, high conductivity, strong durability, and high corrosion resistance. Molybdenum can also form heteropoly and alloy compounds with other elements. Regarding its use in the microelectronics industry, molybdenum and its alloys can be used as interconnects, diffusion barriers, photomasks, and plug - filling materials. However, due to its hardness and chemical resistance, molybdenum is difficult to polish with high removal rates and low defectivity, presenting challenges for the CMP of molybdenum - containing substrates. [Overview of the project]

[0005] This summary is provided to introduce the selection of concepts that will be further described in the following detailed explanation. This summary is not intended to identify any important or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

[0006] This disclosure is based on the unexpected discovery that certain polishing compositions can selectively remove molybdenum (Mo) and / or its alloys in a controlled manner with superior corrosion resistance and low static etching rates to Mo, compared to other materials (e.g., dielectric materials) in semiconductor substrates during a CMP process.

[0007] In one embodiment, the present disclosure features an abrasive composition comprising: (1) at least one abrasive; (2) at least one organic acid or a salt thereof; (3) at least one first amine compound comprising an alkylamine having 6 to 24 carbon alkyl chains; (4) at least one second amine compound containing at least two nitrogen atoms and different from the first amine compound; and (5) an aqueous solvent.

[0008] In another embodiment, the present disclosure features an abrasive composition comprising: (1) at least one abrasive; (2) at least one organic acid or a salt thereof; (3) at least one first amine compound, the first amine compound comprising an alkylamine having 6 to 24 carbon alkyl chains; and (4) an aqueous solvent.

[0009] In yet another embodiment, the present disclosure is characterized by a method comprising (a) applying the polishing composition described herein to a substrate containing molybdenum or an alloy thereof on the surface of the substrate, and (b) bringing a pad into contact with the surface of the substrate and moving the pad relative to the substrate. [Modes for carrying out the invention]

[0010] This disclosure relates to polishing compositions and methods for polishing semiconductor substrates using polishing compositions. In some embodiments, this disclosure relates to polishing compositions used for polishing substrates, comprising at least one portion containing molybdenum (Mo) metal and its alloys.

[0011] In one or more embodiments, the polishing compositions described herein may comprise at least one abrasive, at least one organic acid or a salt thereof, at least one first amine compound comprising at least one alkylamine having at least 6 to 24 carbon alkyl chains, at least one second amine compound different from the first amine and containing at least two nitrogen atoms, and an aqueous solvent. In one or more embodiments, the polishing compositions according to the present disclosure may comprise about 0.01% to about 50% by weight of at least one abrasive, about 0.001% to about 10% by weight of at least one organic acid, about 0.001% to about 5% by weight of at least one first amine compound, about 0.001% to about 5% by weight of at least one second amine compound, and the remaining weight percent (e.g., about 30% to about 99.99% by weight) of an aqueous solvent (e.g., deionized water).

[0012] In one or more embodiments, the Disclosure provides a concentrated abrasive composition that can be diluted with water up to 2 times, or up to 4 times, or up to 6 times, or up to 8 times, or up to 10 times, or up to 15 times, or up to 20 times before use. In other embodiments, the Disclosure provides a point-of-use (POU) abrasive composition comprising the abrasive composition described above, water, and optionally an oxidizing agent.

[0013] In one or more embodiments, the POU abrasive composition may comprise about 0.01% to about 25% by weight of at least one abrasive, about 0.001% to about 1% by weight of at least one organic acid, about 0.001% to about 0.5% by weight of at least one first amine compound, about 0.001% to about 0.5% by weight of at least one second amine compound, and the remaining weight percent (e.g., about 65% to about 99.99% by weight) of an aqueous solvent (e.g., deionized water).

[0014] In one or more embodiments, the concentrated polishing composition may comprise about 0.02% to about 50% by weight of at least one abrasive, about 0.01% to about 10% by weight of at least one organic acid, about 0.01% to about 5% by weight of at least one first amine compound, about 0.01% to about 5% by weight of at least one second amine compound, and the remaining weight percent (e.g., about 35% to about 99.98% by weight) of an aqueous solvent (e.g., deionized water).

[0015] In one or more embodiments, the abrasive compositions described herein may comprise at least one (e.g., two or three) abrasive. In one or more embodiments, at least one abrasive is selected from the group consisting of cationic abrasives, substantially neutral abrasives, and anionic abrasives. In one or more embodiments, at least one abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, their co-formation products (i.e., co-formation products of alumina, silica, titania, ceria, or zirconia), coated abrasives, surface-modifying abrasives, and mixtures thereof. In some embodiments, at least one abrasive does not contain ceria. In some embodiments, at least one abrasive may have high purity and contain less than about 100 ppm of alcohol, less than about 100 ppm of ammonia, and less than about 100 ppb of alkali cations, such as sodium cations. The abrasive may be present in an amount of about 0.01% to about 12% (e.g., about 0.5% to about 10%) or any sub-range thereof, based on the total weight of the POU abrasive composition.

[0016] In one or more embodiments, the abrasive is a silica-based abrasive, such as one selected from the group consisting of colloidal silica, fumed silica, 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, a cationic abrasive may contain terminal groups of formula (I), -O m -X-(CH2) n -Y(I), In the formula, 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, an anionic abrasive may contain the terminal group of formula (I), -O m -X-(CH2) n -Y(I), In the formula, m is an integer between 1 and 3, n is an integer between 1 and 10, X is Al, Si, Ti, Ce, or Zr, and Y is an acid group (e.g., a sulfonic acid group).

[0017] In one or more embodiments, the abrasives described herein 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 a maximum of about 1000 nm (e.g., a maximum of about 800 nm, a maximum of about 600 nm, a maximum of about 500 nm, a maximum of about 400 nm, a maximum of about 200 nm, a maximum of about 150 nm, or a maximum of about 100 nm). When used herein, the average particle size (MPS) is determined by dynamic light scattering techniques.

[0018] In one or more embodiments, at least one abrasive is present in an amount of 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 a maximum of about 50% by weight (e.g., a maximum of about 45% by weight, a maximum of about 40% by weight, a maximum of about 35% by weight, a maximum of about 30% by weight, a maximum of about 25% by weight, a maximum of about 20% by weight, a maximum of about 15% by weight, a maximum of about 12% by weight, a maximum of about 10% by weight, a maximum of about 5% by weight, a maximum of about 4% by weight, a maximum of about 3% by weight, a maximum of about 2% by weight, a maximum of about 1% by weight) of the abrasive composition described herein.

[0019] In one or more embodiments, the polishing compositions described herein comprise at least one (e.g., two or three) organic acid or a salt of an organic acid. In one or more embodiments, the organic acid (or a salt thereof) may be selected from the group consisting of carboxylic acids, amino acids, organic sulfonic acids, organic phosphonic acids, or mixtures thereof. 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 a dicarboxylic acid or tricarboxylic acid. In some embodiments, the organic acid or a salt thereof may be an amino acid comprising a carboxylic acid group. In one or more embodiments, the organic acid is 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, bicine, diglycolic acid, glyceric acid, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, 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 The organic acids are selected from the group consisting of hydroxyphosphonic acid, methanesulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyanetholesulfonic 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, nitrilotri(methylphosphonic acid), diethylenetriaminepentakis(methylphosphonic acid), N,N,N'N'-ethylenediaminetetrakis(methylenephosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, their salts, and mixtures thereof. Without wishing to be bound by theory, it is considered that organic acids (such as those listed above) can be used in the polishing compositions described herein as effective metal removal rate enhancers to improve the removal rate of molybdenum and / or its alloys from semiconductor substrates.

[0020] In one or more embodiments, at least one organic acid or salt thereof is present in an amount of 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 a maximum of about 10% by weight (e.g., The amounts are at least about 9% by weight, at least about 8% by weight, at least about 7% by weight, at least about 6% by weight, at least about 5% by weight, at least about 4% by weight, at least about 3% by weight, at least 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 in which two or more organic acids are included in the abrasive composition, the above ranges may apply independently to each organic acid or to the total amount of organic acids in the composition.

[0021] In one or more embodiments, the polishing compositions described herein comprise at least one (e.g., two or three) first amine compound. In one or more embodiments, the first amine compound may comprise only one amine group. In one or more embodiments, the first amine compound may be an alkylamine compound having at least one (e.g., two or three) alkyl chains comprising 6 to 24 (i.e., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24) carbon atoms. In one or more embodiments, the alkyl chain may be linear, branched, or cyclic alkyl. In one or more embodiments, the alkylamine compound may be a primary amine, secondary amine, tertiary amine, or cyclic amine compound. In one or more embodiments, the alkylamine compound may be an alkoxylated amine (e.g., comprising ethoxylate and / or propoxylate groups). In one or more embodiments, the alkoxylated amine may contain 2 to 100 ethoxylate and / or propoxylate groups. In some embodiments, at least one alkylamine compound has an alkyl chain containing 6 to 18 carbon atoms. In some embodiments, the alkylamine is selected from the group consisting of hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, cyclohexylamine, dicyclohexylamine, or mixtures thereof. Without wishing to be bound by theory, it is surprising that the above alkylamine compounds can significantly reduce or minimize the corrosion or etching of molybdenum and / or its alloys in semiconductor substrates.

[0022] In one or more embodiments, at least one first amine compound is present in an amount of 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 a maximum of about 5% by weight (e.g., a maximum of about 4.5% by weight) of the polishing composition described herein. It is present in amounts of approximately 4% by weight, 3.5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.5% by weight, 1% by weight, 0.8% by weight, 0.6% by weight, 0.5% by weight, 0.4% by weight, 0.2% by weight, 0.1% by weight, 0.08% by weight, 0.05% by weight, 0.02% by weight, 0.01% by weight, 0.0075% by weight, or 0.005% by weight).

[0023] In one or more embodiments, the polishing compositions described herein optionally include at least one (e.g., two or three) second amine compound distinct from the first amine compound. In one or more embodiments, the second amine compound contains at least two (e.g., three or four) nitrogen atoms. In one or more embodiments, the second amine compound has a molecular weight of at least about 50 g / mol (e.g., at least about 100 g / mol, at least about 150 g / mol, at least about 200 g / mol, at least about 250 g / mol, at least about 300 g / mol, at least about 350 g / mol, at least about 400 g / mol, at least about 450 g / mol, or at least about 500 g / mol) to a maximum of about 1000 g / mol (e.g., a maximum of about 950 g / mol, a maximum of about 900 g / mol, a maximum of about 850 g / mol, a maximum of about 800 g / mol, a maximum of about 750 g / mol, a maximum of about 700 g / mol, a maximum of about 650 g / mol, a maximum of about 600 g / mol, a maximum of about 550 g / mol, or a maximum of about 500 g / mol).

[0024] In one or more embodiments, the second amine compound is a linear diamine, which is a molecule containing two primary amines separated by a linear alkyl chain. In one or more embodiments, the second amine compound is a non-linear diamine (e.g., a branched or cyclic diamine, or a diamine containing a secondary or tertiary amino group). In one or more embodiments, the second amine compound is selected from the group consisting of 1,3-pentanediamine, aminopropyldi-isopropanolamine, aminopropyldiethanolamine, ethylenediamine, 1,3-diaminopropane, butane-1,4-diamine, pentane-1,5-diamine, aminoethylethanolamine, trimethylethylenediamine, 1,2-diaminopropane, 1,12-diaminododecane, 1,2-diaminocyclohexane, and mixtures thereof.

[0025] In one or more embodiments, the second amine compound is present in the polishing composition described herein in an amount of at least about 0.001 wt% (e.g., at least about 0.003 wt%, at least about 0.005 wt%, at least about 0.01 wt%, at least about 0.03 wt%, at least about 0.05 wt%, at least about 0.1 wt%, at least about 0.3 wt%, at least about 0.5 wt%) to a maximum of about 5 wt% (e.g., a maximum of about 4 wt%, a maximum of about 3 wt%, a maximum of about 2 wt%, a maximum of about 1 wt%, a maximum of about 0.8 wt%, a maximum of about 0.6 wt%, a maximum of about 0.5 wt%, a maximum of about 0.4 wt%, a maximum of about 0.2 wt%, a maximum of about 0.1 wt%, a maximum of about 0.08 wt%, a maximum of about 0.05 wt%, a maximum of about 0.02 wt%, a maximum of about 0.0075 wt%, or a maximum of about 0.005 wt%). In one or more embodiments, the second amine compound can be omitted from the polishing composition described herein. Without wishing to be bound by theory, the second compound described above can significantly increase the removal rate of molybdenum and / or its alloys in a semiconductor substrate, and when used in combination with the first amine described above, can produce a synergistic effect (e.g., a relatively high Mo removal rate with relatively low Mo corrosion, as evidenced by a lower Mo static etching rate when the two amines are combined).

[0026] In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) pH adjuster, as necessary, to adjust the pH to a desired value. In some embodiments, at least one pH adjuster can be an acid (e.g., an organic acid or an inorganic acid) or a base (e.g., an organic base or an inorganic base). For example, the pH adjuster can 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 hydroxide tetrabutylammonium, 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.

[0027] In one or more embodiments, at least one pH adjuster is present in the polishing composition described herein in an amount of at least about 0.001 wt% (e.g., at least about 0.005 wt%, at least about 0.01 wt%, at least about 0.05 wt%, at least about 0.1 wt%, at least about 0.2 wt%, at least about 0.4 wt%, at least about 0.5 wt%, at least about 1 wt%, or at least about 1.5 wt%) to a maximum of about 2.5 wt% (e.g., a maximum of about 2 wt%, a maximum of about 1.5 wt%, a maximum of about 1 wt%, a maximum of about 0.5 wt%, a maximum of about 0.1 wt%, or a maximum of about 0.5 wt%).

[0028] In one or more embodiments, the abrasive compositions described herein may be either acidic or basic. In some embodiments, the abrasive compositions may have a pH in the range of at least about 2 to a maximum of about 11. If the abrasive composition is acidic, the pH may be in the range of 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 a maximum of about 11 (e.g., at a maximum of about 10.5, at a maximum of about 10, at a maximum of about 9.5, at a maximum of about 9, at a maximum of about 8.5, at a maximum of about 8, at a maximum of about 7.5, at a maximum of about 7, at a maximum of about 6.5, at a maximum of about 6, at a maximum of about 5.5, at a maximum of about 5, at a maximum of about 4.5, or at a maximum of about 4). If the abrasive composition is acidic, the pH may range from at least about 3 (e.g., 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, at least about 6.5) to a maximum of about 7 (e.g., a maximum of about 6.5, a maximum of about 6, a maximum of about 5.5, a maximum of about 5, a maximum of about 4.5, or a maximum of about 4, a maximum of about 3.5).

[0029] In one or more embodiments, the polishing compositions described herein may include a solvent (e.g., a primary solvent) such as an aqueous solvent (e.g., water, or a solvent comprising water and an organic solvent). In some embodiments, the solvent (e.g., water) is in an amount of 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 a maximum of about 99% by weight (e.g., a maximum of about 98% by weight, a maximum of about 96% by weight, a maximum of about 94% by weight, a maximum of about 92% by weight, a maximum of about 90% by weight, a maximum of about 85% by weight, a maximum of about 80% by weight, a maximum of about 75% by weight, a maximum of about 70% by weight, or a maximum of about 65% by weight) of the abrasive composition described herein.

[0030] In one or more embodiments, an optional secondary solvent (e.g., an organic solvent) can be used in the polishing composition of the Disclosure (e.g., POU or concentrated polishing composition) to help dissolve the components (e.g., azole-containing corrosion inhibitors). In one or more embodiments, the secondary solvent may be one or more alcohols, alkylene glycols, or alkylene glycol ethers. In one or more embodiments, the secondary solvent includes 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.

[0031] In some embodiments, the second solvent is present in an amount of at least about 0.005% by weight (e.g., 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 a maximum of about 15% by weight (e.g., a maximum of about 12% by weight, a maximum of about 10% by weight, a maximum of about 5% by weight, a maximum of about 3% by weight, a maximum of about 2% by weight, a maximum of about 1% by weight, a maximum of about 0.8% by weight, a maximum of about 0.6% by weight, a maximum of about 0.5% by weight, or a maximum of about 0.1% by weight) of the polishing composition described herein.

[0032] In one or more embodiments, the polishing compositions described herein may further comprise at least one optional additive selected from the group consisting of azole compounds, oxidizing agents, chelating agents, surfactants, corrosion inhibitors, and water-soluble polymers.

[0033] Azole compounds are not particularly limited, but specific examples include heterocyclic azoles, substituted or unsubstituted triazoles (e.g., benzotriazole), substituted or unsubstituted tetrazoles, substituted or unsubstituted diazoles (e.g., imidazole, benzimidazole, thiadiazole, and pyrazole), and substituted or unsubstituted benzothiazole. In this specification, substituted diazoles, triazoles, or tetrazoles refer to products obtained by substituting one or more hydrogen atoms in a diazole, triazole, or tetrazole with, for example, a carboxyl group, an alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl group), 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 is tetrazole, 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, The following can be selected from the group consisting of 6-dichlorobenzotriazole, chloromethylbenzotriazole (e.g., 1-(chloromethyl)-1-H-benzotriazole), chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, aminobenzimidazole, pyrazole, imidazole, aminotetrazole, adenine, benzimidazole, 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, tetrazole, phenyltetrazole, phenyl-tetrazole-5-thiol, and combinations thereof. Without being constrained by theory, azole compounds can be considered as corrosion inhibitors in the polishing compositions described herein to reduce the removal of certain materials (e.g., metals or dielectric materials) during the polishing process.

[0034] In some embodiments, the azole compound is present in an amount of 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 a maximum of about 1% by weight of the polishing composition described herein. % (for example, up to approximately 0.9% by weight, up to approximately 0.8% by weight, up to approximately 0.7% by weight, up to approximately 0.6% by weight, up to approximately 0.5% by weight, up to approximately 0.4% by weight, up to approximately 0.3% by weight, up to approximately 0.2% by weight, up to approximately 0.18% by weight, up to approximately 0.16% by weight, up to approximately 0.15% by weight, up to approximately 0.14% by weight, up to approximately 0.12% by weight, up to approximately 0.1% by weight, up to approximately 0.08% by weight, up to approximately 0.06% by weight, up to approximately 0.05% by weight, up to approximately 0.04% by weight, up to approximately 0.03% by weight, up to approximately 0.02% by weight, or up to approximately 0.01% by weight) may be possible.

[0035] While oxidizing agents are not particularly limited, specific examples include ammonium persulfate, potassium persulfate, hydrogen peroxide, ferric nitrate, cerium diammonium nitrate, iron sulfate, hypochlorous acid, ozone, potassium periodate, and peracetic acid. Without being bound by theory, oxidizing agents are thought to facilitate the removal of material during the polishing process.

[0036] In some embodiments, the oxidizing agent may be 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 0.3% 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 a maximum of about 10% by weight (e.g., a maximum of about 9% by weight, a maximum of about 8% by weight, a maximum of about 7% by weight, a maximum of about 6% by weight, a maximum of about 5% by weight, a maximum of about 4% by weight, a maximum of about 3% by weight, a maximum of about 2% by weight, or a maximum of about 1% by weight) of the abrasive composition described herein.

[0037] In one or more embodiments, the chelating agent is 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, bicine, diglycolic acid, glyceric acid, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, benzoic acid, ammonia, 1,2-ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, hydroxylamine O-sulfonic acid The chelating agent is selected from the group consisting of methanesulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyanetholesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, acetylacetone, aminotri(methylenephosphonic acid), 1-hydroxyethylidene(1,1-diphosphonic acid), 2-phosphono-1,2,4-butanetricarboxylic acid, hexamethylenediaminetetra(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), salts thereof, and mixtures thereof. Without wishing to be bound by theory, it is thought that chelating agents may function as removal rate enhancers to facilitate the removal of certain materials on a substrate.

[0038] In some embodiments, the chelating agent may be 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 a maximum of about 10% by weight (e.g., a maximum of about 8% by weight, a maximum of about 6% by weight, a maximum of about 5% by weight, a maximum of about 4% by weight, a maximum of about 2% by weight, a maximum of about 1% by weight, a maximum of about 0.8% by weight, a maximum of about 0.6% by weight, or a maximum of about 0.5% by weight) of the abrasive composition described herein.

[0039] In one or more embodiments, the polishing compositions described herein may also include one or more surfactants selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, and mixtures thereof.

[0040] Cationic surfactants are not particularly limited, but specific examples include aliphatic amine salts and aliphatic ammonium salts.

[0041] Nonionic surfactants are not particularly limited, but specific examples include ether-type surfactants, ether ester-type surfactants, ester-type surfactants, and acetylene-based surfactants. Ether-type surfactants are not particularly limited, but specific examples include polyethylene glycol mono-4-nonylphenyl ether, polyethylene glycol monooleyl ether, and triethylene glycol monododecyl ether. Ether ester-type surfactants are not particularly limited, but specific examples include polyoxyethylene ether of glycerin ester. Ester-type surfactants are not particularly limited, but specific examples include polyethylene glycol fatty acid ester, glycerin ester, and sorbitan ester. Acetylene-based surfactants are not particularly limited, but specific examples include ethylene oxide adducts of acetylene alcohol, acetylene glycol, and acetylenediol.

[0042] While amphoteric surfactants are not particularly limited, a specific example is a betaine-based surfactant.

[0043] Anionic surfactants are not particularly limited, but specific examples include carboxylates, sulfons, sulfates, and phosphates. Carboxylates are not particularly limited, but specific examples include fatty acid salts (e.g., soaps) and alkyl ether carboxylates. Examples of sulfons include alkylbenzene sulfons, alkylnaphthalene sulfons, and α-olefin sulfons. Sulfates are not particularly limited, but specific examples include higher alcohol sulfates and alkyl sulfates. Phosphates are not particularly limited, but specific examples include alkyl phosphates and alkyl phosphate esters.

[0044] The corrosion inhibitors are not particularly limited, but specific examples include choline hydroxide, amino alcohols (e.g., monoethanolamine and 3-amino-4-octanol), ethylenediaminetetra(methylenephosphonic acid), and mixtures thereof.

[0045] While water-soluble polymers are not particularly limited, specific examples include polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, hydroxyethylcellulose, and copolymers containing the polymers listed above. Without wishing to be constrained by theory, water-soluble polymers can be thought to act as removal rate inhibitors, reducing the removal rate of certain exposed materials on a substrate that are not intended to be removed or should be removed at a lower removal rate during the polishing process.

[0046] In one or more embodiments, the water-soluble polymer may be 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 a maximum of about 1% by weight (e.g., a maximum of about 0.8% by weight, a maximum of about 0.6% by weight, a maximum of about 0.5% by weight, a maximum of about 0.4% by weight, a maximum of about 0.2% by weight, a maximum of about 0.1% by weight, a maximum of about 0.08% by weight, a maximum of about 0.06% by weight, or a maximum of about 0.05% by weight) of the abrasive composition described herein.

[0047] In one or more embodiments, the polishing compositions described herein include organic solvents, pH adjusters (e.g., acids or bases), amines, alkaline bases (e.g., alkaline hydroxides), fluorine-containing compounds (e.g., fluorine compounds or fluorinated compounds (e.g., fluorinated polymers / surfactants)), silicon-containing compounds (e.g., silanes (e.g., alkoxysilanes)), nitrogen-containing compounds (e.g., amino acids, amines, or imines (e.g., amidines, e.g., 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN))), salts (e.g., halide salts or metal salts), and polymers (e.g., nonionic, cationic) The composition may substantially be free of one or more of the following specific components: on- or anionic polymers, non-organic acids (e.g., hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid), surfactants (e.g., cationic surfactants, anionic surfactants, or nonionic surfactants), plasticizers, oxidizing agents (e.g., H2O2), quaternary ammonium compounds (e.g., salts, e.g., tetraalkylammonium salts and hydroxides, e.g., tetramethylammonium hydroxide), corrosion inhibitors (e.g., azole or non-azole corrosion inhibitors), electrolytics (e.g., polyelectrolytics), and / or certain abrasives (e.g., ceria abrasives, nonionic abrasives, surface-modifying abrasives, or negatively / positively charged abrasives). Halide salts that may be excluded from the abrasive composition include alkali metal halides (e.g., sodium halide or potassium halide) or ammonium halides (e.g., ammonium chloride), which may be chlorides, bromides, or iodides. As used herein, a component "substantially absent" from an abrasive composition refers to a component that is not intentionally added to the abrasive composition. In some embodiments, the abrasive compositions described herein may contain one or more of the above-mentioned components substantially absent from an abrasive composition in 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). In some embodiments, the described abrasive compositions may not contain one or more of the above-mentioned components at all.

[0048] In one or more embodiments, the polishing compositions described herein may have a ratio of the removal rate of molybdenum and / or its alloys to the removal rate of dielectric material (e.g., TEOS) of at least about 3:1 (e.g., at least about 4:1, at least about 5:1, at least about 10:1, at least about 25:1, at least about 50:1, at least about 60:1, at least about 75:1, at least about 100:1, at least about 150:1, at least about 200:1, at least about 250:1, or at least about 300:1) to a maximum of about 1000:1 (e.g., or a maximum of about 500:1) (i.e., removal rate ratio or selectivity). In one or more embodiments, the molybdenum removal rate may range from at least about 500 Å / min (e.g., at least about 750 Å / min, at least about 1000 Å / min, at least about 1250 Å / min, at least about 1500 Å / min, at least about 1750 Å / min, or at least about 2000 Å / min) to a maximum of about 10000 Å / min. In one or more embodiments, the above removal rates and ratios may be applied when measuring the removal rate for polishing either a blanket wafer or a patterned wafer (e.g., a wafer including a conductive layer, a barrier layer, and / or a dielectric layer).

[0049] In one or more embodiments, the present disclosure features a polishing method which may include applying a polishing composition according to the present disclosure to a substrate (e.g., a wafer), and bringing a pad (e.g., a polishing pad) into contact 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: silicon oxides (e.g., tetraethyl orthosilicate (TEOS), high-density plasma oxide (HDP), high-aspect-ratio process oxide (HARP), or borosilicate glass (BPSG)), spin on a film (e.g., a film based on inorganic particles or a film based on a crosslinkable carbon polymer), silicon nitride, silicon carbide, high-K dielectrics (e.g., metal oxides of hafnium, aluminum, or zirconium), silicon (e.g., polysilicon, single-crystal 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 an alloy thereof on the surface of the substrate.

[0050] In one or more embodiments, a method using the polishing compositions described herein may further include producing a semiconductor device from a substrate treated with the polishing composition through one or more steps. For example, a semiconductor device can be produced from a substrate treated with the polishing composition described herein using photolithography, ion implantation, dry / wet etching, plasma etching, deposition (e.g., PVD, CVD, ALD, ECD), wafer mounting, die cutting, packaging, and testing.

[0051] The following specific embodiments should be construed as illustrative examples only and in no way limit the remainder of this disclosure. Those skilled in the art will likely be able to make the most of the present invention based on the description herein without further detail. [Examples]

[0052] In these examples, polishing was performed on a 300 mm wafer using an AMAT Reflexion LK CMP polishing machine with a VP6000 pad and a slurry flow rate of 300 mL / min.

[0053] Table 1 below shows the typical compositions used in the examples. Specific details regarding the differences between the compositions being tested will be explained in more detail when considering each example. [Table 1]

[0054] Example 1 The static etching rate (SER) of molybdenum was measured by suspending molybdenum coupons in compositions 1-4 at 45°C for 1 minute, and the molybdenum removal rate (RR) was measured by polishing blanket molybdenum wafers with compositions 2-4. Compositions 1-4 were identical except that (1) composition 1 was the control and did not contain any of the amine compounds listed in Table 1 above, and (2) compositions 2-4 contained the same alkylamine containing a single amine group and 6-24 carbon alkyl groups at concentrations of 1x, 1.5x, and 2x, respectively. Compositions 1-4 did not contain the second amine. The test results are summarized in Table 2 below. [Table 2]

[0055] The results indicate that the alkylamine compound (i.e., the first amine) effectively reduced the static etching rate of molybdenum, with the increase indicating a greater reduction. Composition 1, which did not contain the alkylamine compound, completely removed Mo during the SER test. These results suggest that alkylamine compounds can be used as corrosion inhibitors of Mo during the CMP process.

[0056] Example 2 The static etching rate (SER) of molybdenum was measured by suspending molybdenum coupons in compositions 5-8 at 45°C for 1 minute, and the molybdenum and TEOS removal rates (RR) were measured by polishing blanket wafers with compositions 5-8. Compositions 5-8 all contained the same primary amine (i.e., an alkylamine compound containing a single amine group and 6-24 carbon alkyl groups) at the same concentration. Compositions 6-8 also contained the same secondary amine (i.e., an amine compound containing at least two nitrogen atoms) in 1x, 2x, and 3x amounts, respectively. The test results are summarized in Table 3 below. [Table 3]

[0057] The results indicate that the inclusion of an amine compound containing at least two nitrogen atoms (i.e., a second amine) significantly increased the rate of molybdenum removal by polishing. However, the SER of Mo actually decreased upon the addition of the second amine compound. This is a surprising result, suggesting a unique synergistic effect between the first and second amine compounds present in the composition (e.g., having a relatively high Mo removal rate along with relatively low Mo corrosion). Specifically, it is expected that the SER of the composition would increase upon the addition of a compound that dramatically increases the RR. The fact that compositions 6-8 exhibit the opposite effect on SER suggests that the composition delivers a more controlled polishing that is not significantly dependent on molybdenum etching for molybdenum removal. This is important because high etching / corrosion typically leads to an increased introduction of defects during polishing, potentially reducing the final yield of usable devices.

[0058] Example 3 The static etching rate (SER) of molybdenum was measured by suspending molybdenum coupons in compositions 9-11 at 45°C for 1 minute, and the molybdenum and TEOS removal rates (RR) were measured by polishing blanket wafers with compositions 9-11. Compositions 9-11 contained equal amounts of alkylamine compounds (i.e., first amines) containing a single amine group and 6-24 carbon alkyl groups, and equal amounts of amine compounds (i.e., second amines) containing at least 2 nitrogen atoms. Composition 9 contained silica with a negative charge due to surface modification by sulfonic acid group addition. Composition 10 contained silica with a positive charge due to surface modification by amino group addition. Composition 11 was unmodified (i.e., natural) silica without surface modification. All silica samples used had comparable particle sizes. The test results are summarized in Table 3 below. [Table 4]

[0059] The results show that composition 9, which has negatively charged silica, has a significantly higher Mo / TEOS removal rate ratio compared to compositions 10 and 11.

[0060] While this disclosure has been described in relation to the embodiments described herein, it is understood that other modifications and variations are possible without departing from the spirit and scope of this disclosure as defined in the appended claims. This application includes the following aspects: [Section 1] Abrasive composition, At least one abrasive, At least one organic acid or a salt thereof, At least one first amine compound comprising an alkylamine having 6 to 24 carbon alkyl chains, A second amine compound comprising at least two nitrogen atoms, wherein the second amine compound is different from the first amine compound, An abrasive composition comprising an aqueous solvent. [Section 2] The polishing composition according to claim 1, wherein the at least one abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia; co-formation products of alumina, silica, titania, ceria, or zirconia; coated abrasives, surface-modifying abrasives, and mixtures thereof. [Section 3] The abrasive composition according to claim 1, wherein the at least one abrasive is present in an amount of about 0.01% to about 50% by weight of the composition. [Section 4] The polishing composition according to claim 1, wherein the at least one organic acid is selected from the group consisting of carboxylic acids, amino acids, sulfonic acids, phosphonic acids, and mixtures thereof. [Section 5] The aforementioned at least one organic acid or salt thereof is 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, bicine, diglycolic acid, glyceric acid, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, 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, meta The polishing composition according to item 1, selected from the group consisting of phosphonic acid, m-xylene-4-sulfonic acid, poly(4-styrene sulfonic acid), polyanethole sulfonic acid, p-toluenesulfonic acid, trifluoromethane-sulfonic acid, ethyl phosphoric acid, cyanoethyl phosphoric acid, phenyl phosphoric acid, vinyl phosphoric acid, poly(vinylphosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, nitrilotri(methylphosphonic acid), diethylenetriaminepentakis(methylphosphonic acid), N,N,N'N'-ethylenediaminetetrakis(methylenephosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, salts thereof, and mixtures thereof. [Section 6] The abrasive composition according to claim 1, wherein the at least one organic acid or salt thereof is present in an amount of about 0.001% to about 10% by weight of the composition. [Section 7] The polishing composition according to claim 1, wherein the at least one first amine compound comprises an alkylamine having an alkyl chain containing 6 to 18 carbon atoms. [Section 8] The polishing composition according to claim 1, wherein the at least one first amine compound is present in an amount of about 0.001% to about 5% by weight of the composition. [Section 9] The polishing composition according to claim 1, wherein the at least one second amine compound has a molecular weight of about 50 g / mol to about 1000 g / mol. [Section 10] The polishing composition according to claim 1, wherein the at least one second amine compound comprises a nonlinear diamine. [Section 11] The polishing composition according to claim 1, wherein the at least one second amine compound is selected from the group consisting of 1,3-pentanediamine, aminopropyldiisopropanolamine, aminopropyldiethanolamine, ethylenediamine, 1,3-diaminopropane, butane-1,4-diamine, pentane-1,5-diamine, aminoethylethanolamine, trimethylethylenediamine, 1,2-diaminopropane, and mixtures thereof. [Section 12] The polishing composition according to claim 1, wherein the at least one second amine compound is present in an amount of about 0.001% to about 5% by weight of the composition. [Section 13] The polishing composition according to claim 1, further comprising an organic solvent in an amount of about 0.001% to about 10% by weight of the composition. [Section 14] The polishing composition according to claim 13, 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. [Section 15] The abrasive composition according to claim 1, wherein the composition has a pH in the range of about 2 to about 11. [Section 16] Applying the polishing composition described in any one of items 1 to 15 to the substrate containing molybdenum or an alloy thereof on the surface of the substrate, A method comprising bringing a pad into contact with the surface of the substrate and moving the pad relative to the substrate. [Section 17] The method according to claim 16, further comprising forming a semiconductor device from the substrate. [Section 18] Abrasive composition, At least one abrasive, At least one organic acid or a salt thereof, At least one first amine compound comprising an alkylamine having 6 to 24 carbon alkyl chains, An abrasive composition comprising an aqueous solvent.

Claims

1. Abrasive composition, At least one abrasive, At least one organic acid or a salt thereof, At least one first amine compound comprising an alkylamine having 6 to 24 carbon alkyl chains, At least one second amine compound, which is a diamine comprising a linear alkyl group, a branched alkyl group, a cyclic alkyl group, or a mixture thereof, and which is different from the first amine compound, It contains an aqueous solvent, The at least one organic acid is selected from the group consisting of carboxylic acids, amino acids, sulfonic acids, phosphonic acids, and mixtures thereof. The at least one organic acid or a salt thereof is present in an amount of 0.001% to 10% by weight of the composition. The at least one first amine compound is present in an amount of 0.001% to 5% by weight of the composition. An abrasive composition wherein the at least one second amine compound is present in an amount of 0.001% to 5% by weight of the composition.

2. The at least one abrasive is, Alumina, silica, titania, ceria, zirconia, Co-formation products of alumina, silica, titania, ceria, or zirconia, Coated abrasive, Surface modifying abrasive, and The polishing composition according to claim 1, selected from the group consisting of mixtures thereof.

3. The at least one abrasive is present in an amount of 0.01% to 50% by weight of the composition. The polishing composition according to claim 1.

4. The aforementioned at least one organic acid or salt thereof is 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, bicine, diglycolic acid, glyceric acid, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, 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 The polishing composition according to claim 1, selected from the group consisting of sulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyanetholesulfonic 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, nitrilotri(methylphosphonic acid), diethylenetriaminepentakis(methylphosphonic acid), N,N,N'N'-ethylenediaminetetrakis(methylenephosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, salts thereof, and mixtures thereof.

5. The polishing composition according to claim 1, wherein the at least one organic acid or a salt thereof is present in an amount of 0.003% to 9% by weight of the composition.

6. The polishing composition according to claim 1, wherein the at least one first amine compound comprises an alkylamine having an alkyl chain containing 6 to 18 carbon atoms.

7. The polishing composition according to claim 1, wherein the at least one first amine compound is present in an amount of 0.003% to 4.5% by weight of the composition.

8. The polishing composition according to claim 1, wherein the at least one second amine compound has a molecular weight of 50 g / mol to 1000 g / mol.

9. The polishing composition according to claim 1, wherein the at least one second amine compound comprises a primary amino group, a secondary amino group, a tertiary amino group, or a mixture thereof.

10. The polishing composition according to claim 1, wherein the at least one second amine compound is selected from the group consisting of 1,3-pentanediamine, aminopropyldiisopropanolamine, aminopropyldiethanolamine, ethylenediamine, 1,3-diaminopropane, butane-1,4-diamine, pentane-1,5-diamine, aminoethylethanolamine, trimethylethylenediamine, 1,2-diaminopropane, and mixtures thereof.

11. The polishing composition according to claim 1, wherein the at least one second amine compound is present in an amount of 0.003% to 4% by weight of the composition.

12. The polishing composition according to claim 1, further comprising 0.001% to 10% by weight of an organic solvent in the composition.

13. The polishing composition according to claim 12, 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.

14. The polishing composition according to claim 1, wherein the polishing composition has a pH in the range of 2 to 11.

15. The polishing composition according to claim 1, wherein the polishing composition is for polishing molybdenum, tungsten, or an alloy thereof.

16. Applying the polishing composition according to any one of claims 1 to 15 to the substrate containing molybdenum, tungsten, or an alloy thereof to the surface of the substrate, A method comprising bringing a pad into contact with the surface of the substrate and moving the pad relative to the substrate.

17. The method according to claim 16, further comprising forming a semiconductor device from the substrate.

18. A polishing composition for polishing molybdenum, tungsten, or alloys thereof, At least one abrasive, At least one organic acid or a salt thereof, At least one first amine compound comprising an alkylamine having 6 to 24 carbon alkyl chains, It contains an aqueous solvent, The at least one organic acid is selected from the group consisting of carboxylic acids, amino acids, sulfonic acids, phosphonic acids, and mixtures thereof. The at least one organic acid or a salt thereof is present in an amount of 0.001% to 10% by weight of the composition. An abrasive composition wherein the at least one first amine compound is present in an amount of 0.001% to 5% by weight of the composition.

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