Abrasive composition and method of use thereof

Abstract

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

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims priority to U.S. Provisional Application No. 63 / 166,340, filed on 26 March 2021, the contents of which are incorporated herein by reference in their entirety. [Background technology]

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

[0003] CMP (Chemical Polishing) is a process used to flatten / planarize wafer surfaces by removing material using a surface-based chemical reaction and a polishing-based physical process simultaneously. Generally, the CMP process involves applying a CMP slurry (e.g., an aqueous chemical formulation) to the wafer surface while bringing the wafer surface into contact with a polishing pad and moving the polishing pad across the wafer. The slurry typically contains polishing components and dissolved chemical components, which can vary considerably depending on the materials present on the wafer (e.g., metals, metal oxides, metal nitrides, dielectric materials such as silicon oxide and silicon nitride, etc.) that will interact with the slurry and polishing pad during the CMP process.

[0004] Molybdenum is a transition metal with very low chemical reactivity, high hardness, high conductivity, strong wear resistance, 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 defect rates, presenting challenges for CMP of molybdenum-containing substrates. [Overview of the project]

[0005] This summary is provided to introduce a selection of concepts that will be further explained in the detailed description below. This summary is not intended to identify any significant or essential features of the claimed subject matter, nor is it intended to be used to help limit 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 from other materials (e.g., silicon nitride) in a semiconductor substrate during the CMP process in a controlled manner with excellent corrosion resistance to Mo and a low static etch rate.

[0007] In one embodiment, the present disclosure features an abrasive composition comprising at least one abrasive; at least one organic acid or a salt thereof; at least one amine compound comprising an amino acid, an alkylamine having an alkyl chain of 6 to 24 carbon atoms, or a mixture thereof; at least one nitride removal rate reducing agent; and an aqueous solvent, wherein the pH is about 2 to about 9.

[0008] In yet another embodiment, the present disclosure is characterized by a method comprising (a) applying an abrasive composition described herein to a substrate having molybdenum or an alloy thereof on its surface, 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]

[0009] This disclosure relates to polishing compositions and methods for polishing semiconductor substrates using the same. 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. In one or more embodiments, this disclosure relates to polishing compositions used for polishing substrates comprising at least one portion containing molybdenum (Mo) metal and its alloys, having the ability to remain on (i.e., substantially not remove) a dielectric material (e.g., a nitride such as silicon nitride).

[0010] 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 amine compound, at least one nitride removal rate reducer, and an aqueous solvent. In one or more embodiments, the polishing compositions according to the 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 amine compound, about 0.001% to about 10% by weight of at least one nitride removal rate reducer, and the remaining weight percent (e.g., about 30% to about 99.99% by weight) of an aqueous solvent (e.g., deionized water).

[0011] In one or more embodiments, the Disclosure provides a concentrated polishing composition that can be diluted with water up to 2 times, 4 times, 6 times, 8 times, 10 times, 15 times, or 20 times before use. In other embodiments, the Disclosure provides a point-of-use (POU) polishing composition comprising the above polishing composition, water, and optionally an oxidizing agent.

[0012] In one or more embodiments, the POU polishing 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 amine compound, about 0.001% to about 1% by weight of at least one nitride removal rate reducer, and the remaining weight percent (e.g., about 65% to about 99.99% by weight) of an aqueous solvent (e.g., deionized water).

[0013] In one or more embodiments, the concentrated polishing composition may comprise 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 amine compound, about 0.01% to about 10% by weight of at least one nitride removal rate reducing agent, and the remaining weight percent (e.g., about 35% to about 99.98% by weight) of an aqueous solvent (e.g., deionized water).

[0014] In one or more embodiments, the polishing compositions described herein may comprise at least one (e.g., two or three) abrasive. In one or more embodiments, the at least one abrasive is selected from the group consisting of cationic abrasives, substantially neutral abrasives, and anionic abrasives. In one or more embodiments, the at least one abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, their co-formation products (i.e., co-formation products of alumina, silica, titania, ceria, or zirconia), coating abrasives, surface modifying abrasives, and mixtures thereof. In some embodiments, the at least one abrasive does not contain ceria. In some embodiments, the at least one abrasive is of high purity and may contain less than about 100 ppm of alcohol, less than about 100 ppm of ammonia, and less than about 100 ppb of alkaline 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%) based on the total weight of the POU polishing composition, or in any sub-range thereof.

[0015] In one or more embodiments, the abrasive is a silica-based abrasive such as those selected from the group consisting of colloidal silica, fumed silica, and mixtures thereof. In one or more embodiments, the abrasive can be surface-modified with organic groups and / or non-silica inorganic groups. For example, a cationic abrasive has the formula (I): -O m -X-(CH2) n -Y (I), and can contain end groups of, where m is an integer from 1 to 3; n is an integer from 1 to 10; X is Al, Si, Ti, Ce or Zr; Y is a cationic amino group or a thiol group. As another example, an anionic abrasive has the formula (I): -O m -X-(CH2) n -Y (I), and can contain end groups of, where m is an integer from 1 to 3; n is an integer from 1 to 10; X is Al, Si, Ti, Ce or Zr; Y is an acid group.

[0016] In one or more embodiments, the abrasive described herein can have an average particle size of about 1 nm or more (e.g., about 5 nm or more, about 10 nm or more, about 20 nm or more, about 40 nm or more, about 50 nm or more, about 60 nm or more, about 80 nm or more, or about 100 nm or more) to about 1000 nm or less (e.g., about 800 nm or less, about 600 nm or less, about 500 nm or less, about 400 nm or less, or about 200 nm or less). As used herein, the average particle size (MPS) is determined by dynamic light scattering techniques.

[0017] In one or more embodiments, at least one abrasive is present in the polishing composition described herein in an amount of from about 0.01 wt% or more (e.g., about 0.05 wt% or more, about 0.1 wt% or more, about 0.2 wt% or more, about 0.4 wt% or more, about 0.5 wt% or more, about 0.6 wt% or more, about 0.8 wt% or more, about 1 wt% or more, about 1.2 wt% or more, about 1.5 wt% or more, about 1.8 wt% or more, or about 2 wt% or more) to about 50 wt% or less (e.g., about 45 wt% or less, about 40 wt% or less, about 35 wt% or less, about 30 wt% or less, about 25 wt% or less, about 20 wt% or less, about 15 wt% or less, about 12 wt% or less, about 10 wt% or less, about 5 wt% or less, about 4 wt% or less, about 3 wt% or less, about 2 wt% or less, about 1 wt% or less).

[0018] In one or more embodiments, the polishing composition described herein includes at least one (e.g., two or three) organic acid or a salt thereof. In some embodiments, the organic acid can be a carboxylic acid containing one or more (e.g., two, three, or four) carboxylic acid groups such as a dicarboxylic acid or a tricarboxylic acid. In one or more embodiments, the organic acid is selected from the group consisting of gluconic acid, lactic acid, citric acid, tartaric acid, malic acid, glycolic acid, malonic acid, formic acid, oxalic acid, acetic acid, propionic acid, peracetic acid, succinic acid, lactic acid, aminoacetic acid, phenoxyacetic acid, bicine, diglycolic acid, glyceric acid, and mixtures thereof. The organic acid (such as the above organic acids) is believed to be able to be used as an effective metal removal rate improver in the polishing composition described herein to improve the removal rate of molybdenum and / or its alloys in a semiconductor substrate, but it is not desired to be bound by theory.

[0019] In one or more embodiments, at least one organic acid or a salt thereof is present in an amount of about 0.001% by weight or more (e.g., about 0.003% by weight or more, about 0.005% by weight or more, about 0.01% by weight or more, about 0.03% by weight or more, about 0.05% by weight or more, about 0.1% by weight or more, about 0.3% by weight or more, about 0.5% by weight or more, about 1% by weight or more, about 1.3% by weight or more, or about 1.5% by weight or more) to about 10% by weight or less (e.g., about 9% by weight or more) of the polishing composition described herein. The above amounts are approximately 8% by weight or more, approximately 7% by weight or more, approximately 6% by weight or more, approximately 5% by weight or more, approximately 4% by weight or more, approximately 3% by weight or more, approximately 2.5% by weight or more, approximately 2.2% by weight or less, approximately 2% by weight or less, approximately 1.7% by weight or less, approximately 1.5% by weight or less, approximately 1.2% by weight or less, approximately 1% by weight or less, approximately 0.7% by weight or less, approximately 0.5% by weight or less, approximately 0.2% by weight or less, approximately 0.15% by weight or less, approximately 0.1% by weight or less, approximately 0.07% by weight or less, or approximately 0.05% by weight or less. In embodiments in which the abrasive composition contains two or more organic acids, the above ranges may apply independently to each organic acid or to the total amount of organic acids in the composition.

[0020] In one or more embodiments, the polishing compositions described herein include at least one (e.g., two or three) amine compound. In one or more embodiments, the amine compound may be an amino acid. In one or more embodiments, the amine compound may be an amino acid selected from the group consisting of tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, serine, leucine, isoleucine, glycine, tryptophan, asparagine, cysteine, methionine, aspartate, glutamate, threonine, taurine, and mixtures thereof. In one or more embodiments, the amine compound may be an amino acid containing at least two amino groups (e.g., histidine, lysine, arginine, etc.). In one or more embodiments, the amine compound may be an alkylamine compound having at least one (e.g., two or three) alkyl chains containing 6 to 24 carbon atoms (i.e., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24). In one or more embodiments, the alkyl chain may be linear, branched, or cyclic alkyl. In one or more embodiments, the alkylamine compound may be a primary, secondary, tertiary, or cyclic amine compound. In one or more embodiments, the alkylamine compound may be an alkoxylated amine (e.g., containing 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, and mixtures thereof. In some embodiments, the polishing compositions described herein may contain both at least one amino acid and at least one alkylamine compound.It is remarkable that the above-mentioned amine compounds can significantly reduce or minimize the corrosion or etching of molybdenum and / or its alloys in semiconductor substrates, thereby controlling the removal rate of molybdenum and / or its alloys, but we do not wish to be bound by theory.

[0021] In one or more embodiments, at least one amine compound is present in an amount of about 0.001% by weight or more (e.g., about 0.003% by weight or more, about 0.005% by weight or more, about 0.01% by weight or more, about 0.03% by weight or more, about 0.05% by weight or more, about 0.1% by weight or more, about 0.3% by weight or more, about 0.5% by weight or more) to about 5% by weight or less (e.g., about 4.5% by weight or less, about 4% by weight or less, about 3.5% by weight or less) of the polishing composition described herein. This refers to amounts of % or less, approximately 3% by weight or less, approximately 2.5% by weight or less, approximately 2% by weight or less, approximately 1.5% by weight or less, approximately 1% by weight or less, approximately 0.8% by weight or less, approximately 0.6% by weight or less, approximately 0.5% by weight or less, approximately 0.4% by weight or less, approximately 0.2% by weight or less, approximately 0.1% by weight or less, approximately 0.08% by weight or less, approximately 0.05% by weight or less, approximately 0.02% by weight or less, approximately 0.01% by weight or less, approximately 0.0075% by weight or less, or approximately 0.005% by weight or less.

[0022] In one or more embodiments, at least one (e.g., two or three different) nitride removal rate reducing agent is C6~C 40 The present invention includes a compound (e.g., a nonpolymer compound) comprising a hydrophobic moiety containing a hydrocarbon group (e.g., an alkyl group, an alkenyl group, an aryl group (e.g., phenyl) and / or an arylalkyl group (e.g., benzyl)) and a hydrophilic moiety containing at least one group selected from the group consisting of sulfinite, sulfate, sulfonate, carboxylate, phosphate, and phosphonate groups. In one or more embodiments, the hydrophobic moiety and the hydrophilic moiety contain 0 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, or 9) alkylene oxide groups (e.g., -(CH2) nIt is separated by an O-group, where n can be 1, 2, 3, or 4. In one or more embodiments, the nitride removal rate reducer has 0 alkylene oxide groups that separate the hydrophobic portion and the hydrophilic portion. The presence of alkylene oxide groups in the nitride removal rate reducer can cause slurry stability problems and may increase the silicon nitride removal rate, so it is considered unfavorable in some embodiments, although it is not desired to be bound by theory.

[0023] In one or more embodiments, the nitride removal rate reducer has a hydrophobic portion containing a hydrocarbon group having at least 6 carbon atoms (C6) (e.g., at least 8 carbon atoms (C8), at least 10 carbon atoms (C 10 ), at least 12 carbon atoms (C 11 ), 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 ), or at least 22 carbon atoms (C 22 )), and / or up to 40 carbon atoms (C 40 ) (e.g., 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 ), or up to 22 carbon atoms (C 22 )). The hydrocarbon groups referred to herein contain carbon atoms and hydrogen atoms and one or more kinds of halogens (e.g., F, Cl, Br, or I), C1-C 40This refers to a group that may be substituted with an alkoxy or aryloxy group. Hydrocarbon groups may include both saturated groups (e.g., linear, branched, or cyclic alkyl groups) and unsaturated groups (e.g., linear, branched, or cyclic alkyenyl groups; linear, branched, or cyclic alkynyl groups; or aromatic groups (e.g., phenyl, benzyl, or naphthyl)). In one or more embodiments, the hydrophilic portion of the nitride removal rate reducer contains at least one group selected from phosphate groups and phosphonate groups. Note that the term "phosphonate group" is explicitly intended to include phosphonic acid groups.

[0024] In one or more embodiments, the nitride removal rate reducing agent is selected from the group consisting of lauryl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, octadecylphosphonic acid, oleyl phosphate, behenyl phosphate, octadecyl sulfate, laceryl phosphate, oleth-3-phosphate, oleth-10-phosphate, 1,4-phenylenediphosphonic acid, dodecylphosphonic acid, decylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, 1,8-octyldiphosphonic acid, 2,3,4,5,6-pentafluorobenzylphosphonic acid, heptadecafluorodecylphosphonic acid, and 12-pentafluorophenoxidedodecylphosphonic acid.

[0025] In one or more embodiments, the nitride removal rate reducing agent may include an anionic polymer. In one or more embodiments, the anionic polymer may include one or more anionic groups, such as a sulfinite group, a sulfate group, a sulfonate group, a carboxylate group, a phosphate group, and a phosphonate group. In one or more embodiments, the anionic polymer is formed from one or more monomers selected from the group consisting of (meth)acrylic acid, maleic acid, acrylic acid, vinylphosphonic acid, vinyl phosphoric acid, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, acrylamide, acrylamidopropyl sulfonic acid, and sodium phosphinite. In more specific embodiments, the anionic polymer is poly(4-styrenesulfonic acid) (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), polyethyleneimine (PEI), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), polyaspartic acid (PASA), anionic poly(ethylene succinate) (PES), anionic polybutylene succinate (PBS), poly(vinyl alcohol) (PVA). The following groups may be selected: 2-propenoic acid copolymers having monosodium 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid and sodium phosphinite; 2-propenoic acid copolymers having monosodium 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid and sodium bisulfite; and 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymers; poly(4-styrenesulfonic acid-co(co)-acrylic acid-co(co)-vinylphosphonic acid) terpolymers; and mixtures thereof. Anionic polymers are thought to be able to solubilize hydrophobic polishing materials and / or defects on the wafer surface, facilitating their removal during the CMP process and / or post-CMP cleaning process, but we do not wish to be bound by theory.

[0026] In one or more embodiments, the anionic polymer may have a weight-average molecular weight in the range of about 250 g / mol or more (e.g., about 500 g / mol or more, about 1,000 g / mol or more, about 2,000 g / mol or more, about 5,000 g / mol or more, about 50,000 g / mol or more, about 100,000 g / mol or more, about 200,000 g / mol or more, or about 250,000 g / mol or more) to about 500,000 g / mol or less (e.g., about 400,000 g / mol or less, about 300,000 g / mol or less, about 200,000 g / mol or less, about 100,000 g / mol or less, or about 50,000 g / mol or less, or about 10,000 g / mol or less). In some embodiments, at least one anionic polymer may have a weight-average molecular weight in the range of about 1,000 g / mol or more to about 10,000 g / mol or less. In some embodiments, the anionic polymer may have a weight-average molecular weight in the range of about 2,000 g / mol or more to about 6,000 g / mol or less. Furthermore, in some embodiments, the anionic polymer may have a weight-average molecular weight of about 5,000 g / mol.

[0027] In one or more embodiments, the at least one nitride removal rate reducing agent described herein may include both (1) at least one (e.g., two or three) compound (e.g., a nonpolymer compound) comprising a hydrophobic portion and a hydrophilic portion, and (2) at least one (e.g., two or three) anionic polymer.

[0028] In one or more embodiments, the nitride removal rate reducing agent is in an amount of about 0.001% by weight or more (e.g., about 0.003% by weight or more, about 0.005% by weight or more, about 0.01% by weight or more, about 0.03% by weight or more, about 0.05% by weight or more, about 0.1% by weight or more, about 0.3% by weight or more, about 0.5% by weight or more) to about 10% by weight or less (e.g., about 9% by weight or less, about 8% by weight or less, about 7% by weight or less) of the polishing composition described herein. The amounts are less than or equal to % (approximately 6% by weight or less, approximately 5% by weight or less, approximately 4% by weight or less, approximately 3% by weight or less, approximately 2% by weight or less, approximately 1% by weight or less, approximately 0.8% by weight or less, approximately 0.6% by weight or less, approximately 0.5% by weight or less, approximately 0.4% by weight or less, approximately 0.2% by weight or less, approximately 0.1% by weight or less, approximately 0.08% by weight or less, approximately 0.05% by weight or less, approximately 0.02% by weight or less, approximately 0.0075% by weight or less, or approximately 0.005% by weight or less). The above nitride removal rate reducing agents are thought to significantly reduce the removal rate of polishing compositions from nitride substrate materials (e.g., silicon nitride) and thus provide the ability to stop on such substrate materials, but we do not wish to be bound by theory.

[0029] In one or more embodiments, the polishing compositions described herein may optionally include at least one (e.g., two or three) pH adjusters to adjust the pH to a desired value, as needed. In some embodiments, the at least one pH adjuster may be an acid (e.g., an organic or inorganic acid) or a base (e.g., an organic or inorganic base). For example, the pH adjuster may be selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, propionic acid, citric acid, malonic acid, hydrobromic acid, hydroiodic acid, perchloric acid, ammonia, ammonium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide, dimethyldipropylammonium hydroxide, benzyltrimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, choline hydroxide, and any combination thereof.

[0030] In one or more embodiments, at least one pH adjusting agent is present in an amount of about 0.001% by weight or more (e.g., about 0.005% by weight or more, about 0.01% by weight or more, about 0.05% by weight or more, about 0.1% by weight or more, about 0.2% by weight or more, about 0.4% by weight or more, about 0.5% by weight or more, about 1% by weight or more, or about 1.5% by weight or more) to about 2.5% by weight or less (e.g., about 2% by weight or less, about 1.5% by weight or less, about 1% by weight or less, about 0.5% by weight or less, about 0.1% by weight or less, or about 0.5% by weight or less) of the polishing composition described herein.

[0031] In one or more embodiments, the polishing compositions described herein may be either acidic or basic. In some embodiments, the polishing compositions may have a pH in the range of about 2 to about 9. For example, the pH may be in the range of about 2 or more (e.g., about 2.5 or more, about 3 or more, about 3.5 or more, about 4 or more, about 4.5 or more, or about 5 or more) to about 9 (e.g., about 8.5 or less, about 8 or less, about 7.5 or less, about 7 or less, about 6.5 or less, about 6 or less, about 6.5 or less, or about 5 or less). In one or more embodiments, the polishing compositions described herein may have an acidic pH such as about 2 to about 6 (e.g., about 2 to about 4). Under such acidic conditions, it is thought that the polishing compositions described herein can increase the molybdenum removal rate and decrease the removal rate of nitride materials (e.g., silicon nitride), but we do not wish to be bound by theory.

[0032] In one or more embodiments, the polishing compositions described herein may include a solvent (e.g., a first solvent), such as an aqueous solvent (e.g., water, or a solvent comprising water and an organic solvent). In some embodiments, the amount of solvent (e.g., water) is about 20% by weight or more (e.g., about 25% by weight or more, about 30% by weight or more, about 35% by weight or more, about 40% by weight or more, about 45% by weight or more, about 50% by weight or more, about 55% by weight or more, about 60% by weight or more, about 65% by weight or more, about 70% by weight or more, about 75% by weight or more, about 80% by weight or more, about 85% by weight or more, about 90% by weight or more, about 92% by weight or more, about 94% by weight or more, about 95% by weight or more, or about 97% by weight or more) to about 99% by weight or less (e.g., about 98% by weight or less, about 96% by weight or less, about 94% by weight or less, about 92% by weight or less, about 90% by weight or less, about 85% by weight or less, about 80% by weight or less, about 75% by weight or less, about 70% by weight or less, or about 65% by weight or less) of the polishing composition described herein.

[0033] In one or more embodiments, an optional second solvent (e.g., an organic solvent) may be used in the polishing composition of the Disclosure (e.g., POU or concentrated polishing composition) which can help dissolve components (e.g., azole-containing corrosion inhibitors, if present). 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 may include 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.

[0034] In some embodiments, the second solvent is in an amount of about 0.001% by weight or more (e.g., about 0.005% by weight or more, about 0.01% by weight or more, about 0.02% by weight or more, about 0.05% by weight or more, about 0.1% by weight or more, about 0.2% by weight or more, about 0.4% by weight or more, about 0.5% by weight or more, about 0.6% by weight or more, about 0.8% by weight or more, about 1% by weight or more, about 3% by weight or more, about 5% by weight or more, or about 10% by weight or more) to about 10% by weight or less (e.g., about 7.5% by weight or less, about 5% by weight or less, about 3% by weight or less, about 2% by weight or less, about 1% by weight or less, about 0.8% by weight or less, about 0.6% by weight or less, about 0.5% by weight or less, or about 0.1% by weight or less) of the polishing composition described herein.

[0035] In one or more embodiments, the polishing compositions described herein may further comprise at least one optional additive selected from the group consisting of chelating agents, azole compounds, oxidizing agents, surfactants, corrosion inhibitors, and water-soluble polymers.

[0036] While not particularly limited, examples of chelating agents include 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), 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), ethylenediamine-tetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), salts thereof, and mixtures thereof.

[0037] In some embodiments, the chelating agent is in an amount of about 0.001% by weight or more (e.g., about 0.002% by weight or more, about 0.003% by weight or more, about 0.004% by weight or more, about 0.005% by weight or more, about 0.006% by weight or more, about 0.007% by weight or more, about 0.008% by weight or more, about 0.009% by weight or more, or about 0.01% by weight or more) to about 10% by weight or less (e.g., about 9% by weight or less, about 8% by weight) of the abrasive composition described herein. It may be less than %, less than or equal to approximately 7% by weight, less than or equal to approximately 6% by weight, less than or equal to approximately 5% by weight, less than or equal to approximately 4% by weight, less than or equal to approximately 3% by weight, less than or equal to approximately 2% by weight, less than or equal to approximately 1% by weight, less than or equal to approximately 0.8% by weight, less than or equal to approximately 0.6% by weight, less than or equal to approximately 0.5% by weight, less than or equal to approximately 0.4% by weight, less than or equal to approximately 0.2% by weight, less than or equal to approximately 0.1% by weight, less than or equal to approximately 0.08% by weight, less than or equal to approximately 0.05% by weight, less than or equal to approximately 0.02% by weight, less than or equal to approximately 0.0075% by weight, or less than or equal to approximately 0.005% by weight.

[0038] The above-mentioned 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 benzothiazoles. Here, substituted diazole, triazole, or tetrazole refers to a product 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. Azole compounds can be used 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, but we do not wish to be bound by theory.

[0039] In some embodiments, the azole compound is present in an amount of about 0.001% by weight or more (e.g., about 0.002% by weight or more, about 0.004% by weight or more, about 0.005% by weight or more, about 0.006% by weight or more, about 0.008% by weight or more, about 0.01% by weight or more, about 0.02% by weight or more, about 0.04% by weight or more, about 0.05% by weight or more, about 0.06% by weight or more, about 0.08% by weight or more, or about 0.1% by weight or more) to about 5% by weight or less (e.g., about 4.5% by weight or less, about 4% by weight or less, about 3.5% by weight or less, about 3% by weight or less, about 2.5% by weight or less, about 2%) of the polishing composition described herein. It may be less than or equal to a certain amount, less than or equal to approximately 1.5% by weight, less than or equal to approximately 1% by weight, less than or equal to approximately 0.9% by weight, less than or equal to approximately 0.8% by weight, less than or equal to approximately 0.7% by weight, less than or equal to approximately 0.6% by weight, less than or equal to approximately 0.5% by weight, less than or equal to approximately 0.4% by weight, less than or equal to approximately 0.3% by weight, less than or equal to approximately 0.2% by weight, less than or equal to approximately 0.18% by weight, less than or equal to approximately 0.16% by weight, less than or equal to approximately 0.15% by weight, less than or equal to approximately 0.14% by weight, less than or equal to approximately 0.12% by weight, less than or equal to approximately 0.1% by weight, less than or equal to approximately 0.08% by weight, less than or equal to approximately 0.06% by weight, less than or equal to approximately 0.05% by weight, less than or equal to approximately 0.04% by weight, less than or equal to approximately 0.03% by weight, less than or equal to approximately 0.02% by weight, or less than or equal to approximately 0.01% by weight.

[0040] While not particularly limited, oxidizing agents include ammonium persulfate, potassium persulfate, hydrogen peroxide, ferric nitrate, cerium diammonium nitrate, iron sulfate, hypochlorous acid, ozone, potassium periodate, and peracetic acid. Oxidizing agents are thought to facilitate the removal of materials during the polishing process, but the theory is not to be constrained.

[0041] In some embodiments, the oxidizing agent may be in an amount of about 0.01% by weight or more (e.g., about 0.05% or more, about 0.1% or more, about 0.2% or more, about 0.3% or more, about 0.4% or more, about 0.5% or more, about 0.6% or more, about 0.7% or more, about 0.8% or more, about 0.9% or more, about 1% or more, about 1.5% or more, or about 2% or more) to about 10% by weight or less (e.g., about 9% or less, about 8% or less, about 7% or less, about 6% or less, about 5% or less, about 4% or less, about 3% or less, about 2% or less, or about 1% or less) of the polishing composition described herein.

[0042] 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.

[0043] Cationic surfactants are not particularly limited, but specific examples include aliphatic amine salts and aliphatic ammonium salts.

[0044] 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.

[0045] While there are no particular limitations on amphoteric surfactants, betaine-based surfactants are a specific example.

[0046] Anionic surfactants are not particularly limited, but specific examples include carboxylates, sulfonates, sulfates, and phosphates. Carboxylates are not particularly limited, but specific examples include fatty acid salts (e.g., soap) and alkyl ether carboxylates. Sulfonates include alkylbenzene sulfonates, alkylnaphthalene sulfonates, and α-olefin sulfonates. 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.

[0047] While not particularly limited, examples of corrosion inhibitors include choline hydroxide, amino alcohols (e.g., monoethanolamine and 3-amino-4-octanol), amino acids (e.g., those described herein), and mixtures thereof.

[0048] The water-soluble polymers are not particularly limited, but specific examples include polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, hydroxyethylcellulose, and copolymers containing the aforementioned polymers. The water-soluble polymers are thought to function as removal rate inhibitors to reduce the removal rate of certain exposed materials on the substrate that are not intended to be removed during the polishing process or should be removed at a lower removal rate, but we do not wish to be bound by theory.

[0049] In one or more embodiments, the water-soluble polymer may be in an amount of about 0.01% by weight or more (e.g., about 0.02% by weight or more, about 0.03% by weight or more, about 0.04% by weight or more, about 0.05% by weight or more, about 0.06% by weight or more, about 0.07% by weight or more, about 0.08% by weight or more, about 0.09% by weight or more, or about 0.1% by weight or more) to about 1% by weight or less (e.g., about 0.8% by weight or less, about 0.6% by weight or less, about 0.5% by weight or less, about 0.4% by weight or less, about 0.2% by weight or less, about 0.1% by weight or less, about 0.08% by weight or less, about 0.06% by weight or less, or about 0.05% by weight or less) of the abrasive composition described herein.

[0050] In one or more embodiments, the polishing compositions described herein include organic solvents, pH adjusters, fluorine-containing compounds (e.g., fluoride compounds or fluorinated compounds (fluorinated polymers / surfactants, etc.)), salts (e.g., halide salts or metal salts), polymers (e.g., nonionic, cationic, or anionic polymers), quaternary ammonium compounds (e.g., salts such as tetraalkylammonium salts, or hydroxides such as tetraalkylammonium hydroxide), corrosion inhibitors (e.g., azole or non-azole corrosion inhibitors), alkaline bases (e.g., alkaline hydroxides), silicon-containing compounds such as silanes (e.g., alkoxysilanes), nitrogen-containing compounds (e.g., amino acids, amines, imines (e.g., amidine, e.g., For example, it may substantially not contain one or more of the following specific components: 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN)), amides or imides), polyols, inorganic acids (e.g., hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid), surfactants (e.g., cationic surfactants, anionic surfactants, nonpolymeric surfactants, or nonionic surfactants), plasticizers, oxidizing agents (e.g., H2O2 and periodic acid), corrosion inhibitors (e.g., azole or non-azole corrosion inhibitors), electrolytes (e.g., polymeric electrolytes), and / or specific abrasives (e.g., ceria abrasives, nonionic abrasives, surface-modifying abrasives, or negatively / positively charged abrasives). Examples of 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 fluorides, chlorides, bromides, or iodides. As used herein, a component "substantially absent" from the abrasive composition means 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 substantially absent components in the abrasive composition at concentrations of about 1000 ppm or less (e.g., about 500 ppm or less, about 250 ppm or less, about 100 ppm or less, about 50 ppm or less, about 10 ppm or less, or about 1 ppm or less).In some embodiments, the polishing composition described may not contain one or more of the above components at all.

[0051] In one or more embodiments, the polishing compositions described herein may have a ratio (i.e., removal rate ratio or selectivity) of the removal rate of molybdenum and / or its alloys to the removal rate of nitride materials (e.g., silicon nitride) of about 2:1 or more (e.g., about 3:1 or more, about 4:1 or more, about 5:1 or more, about 10:1 or more, about 25:1 or more, about 50:1 or more, about 60:1 or more, about 75:1 or more, about 100:1 or more, about 150:1 or more, about 200:1 or more, about 250:1 or more, or about 300:1 or more) to about 1000:1 or less (e.g., about 500:1 or less, about 300:1 or less, about 250:1 or less, about 200:1 or less, about 150:1 or less, or about 100:1 or less). In one or more embodiments, the polishing compositions described herein are in a ratio of about 1:50 or more (e.g., about 1:45 or more, about 1:40 or more, about 1:35 or more, about 1:30 or more, about 1:25 or more, about 1:20 or more, about 1:15 or more, about 1:10 or more, about 1:8 or more, about 1:6 or more, about 1:5 or more, about 1:4 or more, about 1:2 or more, or about 1:1 or more) to about 50:1 or less (e.g., about 45:1 or less, about 40 The ratio (i.e., removal rate ratio or selectivity) of the removal rate of molybdenum and / or its alloys to the removal rate of oxide materials (e.g., silicon oxide such as TEOS) may be 1 or less, approximately 35:1 or less, approximately 30:1 or less, approximately 25:1 or less, approximately 20:1 or less, approximately 15:1 or less, approximately 10:1 or less, approximately 8:1 or less, approximately 6:1 or less, approximately 5:1 or less, approximately 4:1 or less, approximately 2:1 or less, or approximately 1:1 or less. In one or more embodiments, the above ratio may be applicable 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).

[0052] In one or more embodiments, the molybdenum and / or TEOS removal rate may be in the range of about 20 Å / min or more (e.g., about 30 Å / min or more, about 40 Å / min or more, about 50 Å / min or more, about 60 Å / min or more, about 70 Å / min or more, about 80 Å / min or more, about 90 Å / min or more, or about 100 Å / min or more) to about 600 Å / min or less (e.g., about 550 Å / min or less, about 500 Å / min or less, about 450 Å / min or less, about 400 Å / min or less, about 350 Å / min or less, about 300 Å / min or less, about 250 Å / min or less, about 200 Å / min or less, about 150 Å / min or less, or about 100 Å / min or less). In one or more embodiments, the nitride (e.g., silicon nitride) removal rate may be about 85 Å / min or less (e.g., about 80 Å / min or less, about 75 Å / min or less, about 70 Å / min or less, about 65 Å / min or less, about 60 Å / min or less, about 55 Å / min or less, about 50 Å / min or less, about 45 Å / min or less, about 40 Å / min or less, about 35 Å / min or less, about 30 Å / min or less, or about 25 Å / min or less, or about 20 Å / min or less, or about 15 Å / min or less, or about 10 Å / min or less, or about 5 Å / min or less, or essentially 0 Å / min).

[0053] In one or more embodiments, the Disclosure features a polishing method which may include applying a polishing composition according to the Disclosure to a substrate (e.g., a wafer such as a blanket wafer or a patterned 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 silicon oxides (e.g., tetraethyl orthosilicate (TEOS), high-density plasma oxide (HDP), high-aspect-ratio process oxide (HARP), or borosilicate glass (BPSG)), spin-on films (e.g., films based on inorganic particles or films based on crosslinkable carbon polymers), silicon nitride, silicon carbide, high-K dielectrics (e.g., metal oxides of hafnium, aluminum, or zirconium), silicon (e.g., 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 its surface.

[0054] In one or more embodiments, a method using the polishing compositions described herein may further include manufacturing a semiconductor device from a substrate treated with the polishing composition through one or more steps. For example, a semiconductor device can be manufactured 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.

[0055] The following specific examples should be construed as illustrative only and in no way limit the remainder of this disclosure. Without further detail, those skilled in the art will be able to make the most of the present invention based on the description herein. [Examples]

[0056] In these embodiments, polishing was performed on a 300 mm wafer using an AMAT Reflexion LK CMP polisher with a VP6000 pad or an H804 pad at a slurry flow rate of 175 mL / min or 300 mL / min.

[0057] Table 1 below shows the general compositions used in the examples. Specific details regarding the differences between the tested compositions will be explained in more detail when discussing each example.

[0058] [Table 1]

[0059] Example 1 The removal rates of TEOS, SiN, and molybdenum (Mo), as well as the static etch rate (SER) of Mo, were measured for polishing compositions 1 to 5. The SER of Mo was measured by suspending a Mo coupon in the polishing composition at 45°C for 1 minute. The removal rate was measured by polishing a blanket wafer of the indicated material. Compositions 1 to 4 were identical except that (1) composition 1 was the control and did not contain any amine compounds, and (2) compositions 2 to 5 contained amino acids (as amine compounds as specified herein) at concentrations of 1X, 2X, 3X, and 4X, respectively. Compositions 1 to 5 all contained 4X of the nitride removal rate reducing agent as specified herein. The test results are summarized in Table 2 below.

[0060] [Table 2]

[0061] The results show that the amino acids in compositions 2-5 (i.e., the amine compounds described herein) effectively reduce the static etch rate of molybdenum, and the reduction increases with increasing amounts. Composition 1, which does not contain the amine compound, showed that the molybdenum material was completely removed, indicating that this composition is too aggressive to the molybdenum environment. These results suggest that amino acid compounds can be used as corrosion inhibitors for Mo during the CMP process.

[0062] Example 2 The removal rates of TEOS, SiN, and Mo, as well as the static etch rate (SER) of Mo, were measured for polishing compositions 6-9 as described above. Compositions 6-9 were identical except for their different pH values ​​(i.e., 2.5, 3, 4, and 5, respectively). Compositions 6-9 contained 1X amino acids as amine compounds as specified herein and 4X nitride removal rate reducing agents as specified herein. The test results are summarized in Table 3 below.

[0063] [Table 3]

[0064] The results showed that lower pH resulted in higher Mo RR, but SER was relatively stable between pH 2.5 and pH 5. SiN RR increased significantly above pH 4.

[0065] Example 3 The removal rates of TEOS, SiN, and Mo were measured for polishing compositions 10 to 13. Compositions 10 to 13 were identical except that composition 10 did not contain a nitride removal rate reducing agent, and compositions 11 to 13 contained 1X, 2X, and 4X nitride removal rate reducing agents as specified herein, respectively. All compositions 10 to 13 contained 1X of an amino acid as an amine compound as specified herein. The test results are summarized in Table 4 below.

[0066] [Table 4]

[0067] The results indicate that the nitride removal rate reducing agents described herein significantly reduced the SiN RR. Furthermore, the nitride removal rate reducing agents had little effect on the TEOS or Mo removal rates.

[0068] Example 4 The removal rates of TEOS, SiN, and Mo, as well as the static etch rate (SER) of Mo, were measured for polishing compositions 14-17 as described above. Compositions 14-17 were identical except that they contained alkylamines with 6-24 carbon alkyl groups as amine compounds as described herein, in concentrations of 0X, 1X, 2X, and 3X, respectively. All compositions 14-17 contained 2X of the nitride removal rate reducing agent as described herein. The results are summarized in Table 5 below.

[0069] [Table 5]

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

[0071] Example 5 Mo SER was measured for polishing compositions 18-22 as described above. Composition 18 was a control that did not contain amine compounds. Compositions 19-22 contained the same components as composition 18, except that they contained the same wt% of alkylamine compounds with 6 carbon, 8 carbon, 12 carbon, and 16 carbon atoms, respectively. All compositions contained the same amounts of all other components, and composition 18 contained slightly more water due to the absence of alkylamines. The results are summarized in Table 6 below.

[0072] [Table 6]

[0073] The results show that the addition of alkylamine compounds significantly reduced Mo SER compared to the control (composition 18). Furthermore, the reduction in Mo SER increased as the carbon chain length increased from 6 carbon atoms to 16 carbon atoms. The SER measurements for compositions 21 and 22 indicate that very minimal Mo corrosion occurred, providing a highly protective environment for Mo, which should result in a controlled polishing rate with fewer defects.

[0074] Example 6 The removal rates of TEOS, SiN, and Mo were measured for polishing compositions 23-25. Compositions 23-25 ​​were identical except that they contained C6, C12, and C18 nitride removal rate reducing agents, respectively. All compositions 23-25 ​​contained the same amino acid as the amine compound described herein. The test results are summarized in Table 7 below.

[0075] [Table 7]

[0076] The results indicate that the silicon nitride removal rate gradually decreases as the carbon chain length of the nitride removal rate reducing agent increases. The removal rates of TEOS and Mo show similar progression, but at a smaller magnitude. Therefore, these results suggest that longer carbon chains in the nitride removal rate reducing agent can provide more effective stop-on nitrides.

[0077] Example 7 The removal rates of Mo SER, as well as TEOS, SiN, and Mo, were measured for polishing compositions 26-29. Compositions 26-29 were identical except that each contained a different amino acid as an amine compound as described herein. All compositions 26-29 contained the same nitride removal rate reducing agent. The test results are summarized in Table 8 below.

[0078] [Table 8]

[0079] The results indicate that composition 28 failed to adequately protect Mo compared to the other compositions (i.e., high SER and RR). Furthermore, composition 28 also showed a significant increase in SiN RR. The above results suggest that amino acids containing at least two amino groups (e.g., histidine, arginine, and lysine) exhibit superior corrosion protection against Mo compared to amino acids containing only one amino group (e.g., glycine).

[0080] While this disclosure describes examples as set forth 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. Furthermore, this application includes the following aspects: [Section 1] At least one type of abrasive; At least one organic acid or a salt thereof; At least one amine compound comprising an amino acid, an alkylamine having an alkyl chain of 6 to 24 carbon atoms, or a mixture thereof; At least one nitride removal rate reducing agent; and aqueous solvent Includes, The pH is approximately 2 to 9. Polishing composition. [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, a co-formation product of alumina, silica, titania, ceria, or zirconia, coating abrasives, surface modifying abrasives, and mixtures thereof. [Section 3] The polishing composition according to claim 1, wherein the amount of at least one abrasive is 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 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, and mixtures thereof. [Section 5] The polishing composition according to claim 1, wherein the amount of at least one organic acid is about 0.001% to about 10% by weight of the composition. [Section 6] The polishing composition according to claim 1, wherein the at least one amine compound is selected from the group consisting of tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, serine, leucine, isoleucine, glycine, tryptophan, asparagine, cysteine, methionine, aspartate, glutamate, threonine, taurine, hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, and mixtures thereof. [Section 7] The polishing composition according to claim 1, wherein the amount of at least one amine compound is about 0.001% to about 5% by weight of the composition. [Section 8] The above-mentioned at least one nitride removal rate reducing agent is C 6 ~C 40 A hydrophobic moiety containing a hydrocarbon group; A hydrophilic moiety comprising at least one group selected from the group consisting of sulfinite, sulfate, sulfonate, carboxylate, phosphate, and phosphonate groups; Includes, The hydrophobic portion and the hydrophilic portion are separated by 0 to 10 alkylene oxide groups. The polishing composition described in item 1. [Section 9] The hydrophobic portion is C 12 ~C 32 The polishing composition according to item 8, comprising a hydrocarbon group. [Section 10] The polishing composition according to claim 8, wherein the hydrophilic portion comprises a phosphate group or a phosphonate group. [Section 11] The polishing composition according to claim 8, wherein the at least one nitride removal rate reducing agent has zero alkylene oxide groups that separate the hydrophobic portion from the hydrophilic portion. [Section 12] The polishing composition according to claim 1, wherein the at least one nitride removal rate reducing agent is selected from the group consisting of lauryl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, octadecylphosphonic acid, oleyl phosphate, behenyl phosphate, octadecyl sulfate, laceryl phosphate (lacceryl phosphate), oleth-3-phosphate, oleth-10-phosphate, 1,4-phenylenediphosphonic acid, dodecylphosphonic acid, decylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, 1,8-octyldiphosphonic acid, 2,3,4,5,6-pentafluorobenzylphosphonic acid, heptadecafluorodecylphosphonic acid, and 12-pentafluorophenoxidedodecylphosphonic acid. [Section 13] The polishing composition according to claim 1, wherein the at least one nitride removal rate reducing agent comprises an anionic polymer. [Section 14] The aforementioned at least one nitride removal rate reducing agent is poly(4-styrenesulfonic acid) (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), polyaspartic acid (PASA), anionic poly(ethylene succinate) (PES), anionic polybutylene succinate (PBS), poly(vinyl alcohol) (PVA), 2-methyl-2- The polishing composition according to item 13, comprising a 2-propenoic acid copolymer having ((1-oxo-2-propenyl)amino)-1-propanesulfonic acid monosodium salt and sodium phosphinite, a 2-propenoic acid copolymer having 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid monosodium salt and sodium bisulfite sodium salt, a 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, poly(4-styrenesulfonic acid-co(co)-acrylic acid-co(co)-vinylphosphonic acid) terpolymer, or a mixture thereof. [Section 15] The polishing composition according to claim 1, wherein the at least one nitride removal rate reducing agent is present in an amount of 0.001% to about 10% by weight of the composition. [Section 16] The polishing composition according to item 1, further comprising at least one azole compound. [Section 17] The polishing composition according to claim 16, wherein the at least one azole compound is present in an amount of 0.001% to about 5% by weight of the composition. [Section 18] The polishing composition according to item 1, further comprising an organic solvent in an amount of about 0.001% to about 10% by weight of the composition. [Section 19] The polishing composition according to claim 18, 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 20] Applying the polishing composition described in any one of paragraphs 1 to 19 to a substrate containing molybdenum or an alloy thereof on its surface; and The pad is brought into contact with the surface of the substrate, and the pad is moved relative to the substrate. Methods that include... [Section 21] The method according to claim 20, further comprising forming a semiconductor device from the substrate.

Claims

1. At least one type of abrasive; At least one organic acid or a salt thereof; At least one amine compound comprising an amino acid, an alkylamine having an alkyl chain of 6 to 24 carbon atoms, or a mixture thereof; At least one nitride removal rate reducing agent; and aqueous solvent Includes, The pH is between 2 and 9. The removal rate ratio of molybdenum and / or its alloys to the removal rate of silicon nitride is at least 2:1 and at most 1000:

1. The removal rate ratio of molybdenum and / or its alloys to the removal rate of silicon oxide is at least 1:50 and at most 50:

1. Polishing composition.

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

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

4. The polishing composition according to claim 1, wherein the at least one organic acid is selected from the group consisting of gluconic acid, lactic acid, citric acid, tartaric acid, malic acid, glycolic acid, malonic acid, formic acid, oxalic acid, acetic acid, propionic acid, peracetic acid, succinic acid, aminoacetic acid, phenoxyacetic acid, bicine, diglycolic acid, glyceric acid, and mixtures thereof.

5. The polishing composition according to claim 1, wherein the amount of at least one organic acid is 0.001% to 10% by weight of the composition.

6. The polishing composition according to claim 1, wherein the at least one amine compound is selected from the group consisting of tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, serine, leucine, isoleucine, glycine, tryptophan, asparagine, cysteine, methionine, aspartate, glutamate, threonine, taurine, hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, and mixtures thereof.

7. The polishing composition according to claim 1, wherein the amount of at least one amine compound is 0.001% to 5% by weight of the composition.

8. The at least one nitride removal rate reducing agent is C ６ ~C ４０ A hydrophobic moiety containing a hydrocarbon group; A hydrophilic moiety comprising at least one group selected from the group consisting of sulfinite, sulfate, sulfonate, carboxylate, phosphate, and phosphonate groups; Includes, The hydrophobic portion and the hydrophilic portion are separated by 0 to 10 alkylene oxide groups. The polishing composition according to claim 1.

9. The hydrophobic portion is C １２ ~C ３２ The polishing composition according to claim 8, comprising a hydrocarbon group.

10. The polishing composition according to claim 8, wherein the hydrophilic portion comprises a phosphate group or a phosphonate group.

11. The polishing composition according to claim 8, wherein the at least one nitride removal rate reducing agent has zero alkylene oxide groups that separate the hydrophobic portion from the hydrophilic portion.

12. The polishing composition according to claim 1, wherein the at least one nitride removal rate reducing agent is selected from the group consisting of lauryl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, octadecylphosphonic acid, oleyl phosphate, behenyl phosphate, octadecyl sulfate, laceryl phosphate, oleth-3-phosphate, oleth-10-phosphate, 1,4-phenylenediphosphonic acid, dodecylphosphonic acid, decylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, 1,8-octyldiphosphonic acid, 2,3,4,5,6-pentafluorobenzylphosphonic acid, heptadecafluorodecylphosphonic acid, and 12-pentafluorophenoxidedodecylphosphonic acid.

13. The polishing composition according to claim 1, wherein the at least one nitride removal rate reducing agent comprises an anionic polymer.

14. The aforementioned at least one nitride removal rate reducing agent is poly(4-styreneyl sulfonate) acid (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), polyaspartic acid (PASA), anionic poly(ethylene succinate) (PES), anionic polybutylene succinate (PBS), poly(vinyl alcohol) (PVA), 2-methyl- The polishing composition according to claim 13, comprising a 2-propenoic acid copolymer having 2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid monosodium salt and sodium phosphinite, a 2-propenoic acid copolymer having 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid monosodium salt and sodium bisulfite, a 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, a poly(4-styrenesulfonic acid-co(co)-acrylic acid-co(co)-vinylphosphonic acid) terpolymer, or a mixture thereof.

15. The polishing composition according to claim 1, wherein the at least one nitride removal rate reducing agent is present in an amount of 0.001% to 10% by weight of the composition.

16. The polishing composition according to claim 1, further comprising at least one azole compound.

17. The polishing composition according to claim 16, wherein the at least one azole compound is present in an amount of 0.001% to 5% by weight of the composition.

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

19. The polishing composition according to claim 18, 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.

20. Applying the polishing composition described in any one of claims 1 to 19 to a substrate containing molybdenum or an alloy thereof on its surface; and The pad is brought into contact with the surface of the substrate, and the pad is moved relative to the substrate. Methods that include...

21. The method according to claim 20, further comprising forming a semiconductor device from the substrate.

Images