Polishing composition and method of use thereof
A polishing composition with specific components and pH levels addresses the challenge of cobalt corrosion in CMP processes, achieving effective and selective polishing of cobalt and dielectric materials in semiconductor manufacturing.
Patent Information
- Application Number
- JP2022523015
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2019-10-15
- Filing Date
- 2020-10-06
- Publication Date
- 2025-08-26
- Estimated Expiration
- 2040-10-06
AI Technical Summary
Current CMP slurries are ineffective in polishing cobalt-containing surfaces without causing significant corrosion, and they lack selectivity in removing other metals and metal nitrides or oxides, which is critical for advanced semiconductor manufacturing.
A polishing composition comprising an abrasive, pH adjuster, barrier film removal rate enhancer, TEOS removal rate inhibitor, cobalt removal rate enhancer, azole-containing corrosion inhibitor, and cobalt corrosion inhibitor, with specific concentrations and pH levels to minimize cobalt corrosion and achieve selective polishing of cobalt and dielectric materials.
The composition effectively polishes cobalt and dielectric materials at moderate rates while minimizing cobalt corrosion and maintaining selectivity in polishing rates of other metals and metal nitrides or oxides, ensuring smooth surface topography for semiconductor substrates.
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Abstract
Description
[Technical Field]
[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application Serial No. 62 / 915,290, filed October 15, 2019, the contents of which are incorporated herein by reference in their entirety. [Background technology]
[0002] The semiconductor industry is continually driven to improve chip performance by further miniaturizing devices through process, material, and integration innovations. Early material innovations included the introduction of copper, replacing aluminum as the conductive material in interconnect structures, and the use of tantalum (Ta) / tantalum nitride (TaN) (or titanium (Ti) / titanium nitride (TiN)) as a diffusion barrier to separate the Cu conductive material from the non-conductive / insulating dielectric material. Copper (Cu) was chosen as the interconnect material due to its low resistivity and excellent resistance to electromigration.
[0003] However, as new-generation chip features shrink, maintaining effective interconnect resistivity at the back-end-of-line (BEOL) requires multilayer Cu / barrier / dielectric stacks to become thinner and more conformal. Thinner Cu and Ta / TaN barrier film schemes present challenges related to resistivity and flexibility in deposition. For example, resistivity worsens exponentially with smaller dimensions and advanced manufacturing nodes, and transistor circuit speed improvements (at the front-end-of-line (FEOL)) are halved by delays due to conductive Cu / barrier interconnects (BEOL). Cobalt (Co) has emerged as a leading candidate for use as a liner material, barrier layer, and conductive layer. Additionally, cobalt is also being investigated as a replacement for tungsten (W) metal in multiple applications, such as W metal contacts, plugs, vias, and gate materials.
[0004] Many currently available CMP slurries were specifically designed to remove materials more common in older chip designs, such as the aforementioned copper and tungsten. Because cobalt is susceptible to chemical attack, certain components in these older CMP slurries can be harmful to the cobalt and cause unacceptable defects. As a result, using copper polishing slurries on cobalt layers often results in unacceptable corrosion, wafer topography, and removal rate selectivity.
[0005] With the increasing use of cobalt (Co) as a metal component in semiconductor manufacturing, there is a market need for CMP slurries that can effectively polish dielectric or barrier components on Co-containing surfaces without significant Co corrosion. Summary of the Invention
[0006] This Summary is provided to introduce a selection of concepts that are further described below in the Detailed Description. This Summary is not intended to identify key 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.
[0007] As defined herein, unless otherwise specified, all percentages expressed should be understood to be weight percent based on the total weight of the chemical-mechanical polishing composition.
[0008] In one aspect, embodiments disclosed herein relate to a polishing composition comprising an abrasive, an optional pH adjuster, a barrier film removal rate enhancer, a TEOS removal rate suppressor, a cobalt removal rate enhancer, an azole-containing corrosion inhibitor, and a cobalt corrosion inhibitor, wherein the barrier film removal rate enhancer is different from the cobalt removal rate enhancer.
[0009] In another aspect, embodiments disclosed herein relate to a polishing composition comprising an abrasive, an optional pH adjuster, an organic acid or its salt, an amino acid, an alkanolamine or a cationic polymer, an azole-containing corrosion inhibitor, and an anionic surfactant, wherein the organic acid is different from the amino acid.
[0010] In yet another aspect, embodiments disclosed herein relate to a method of polishing a substrate, comprising applying a polishing composition described herein to a surface of a substrate, wherein the surface comprises cobalt; and contacting a pad with the surface of the substrate and moving the pad relative to the substrate.
[0011] Other aspects and advantages of the claimed subject matter will become apparent from the following description and appended claims. DETAILED DESCRIPTION OF THE INVENTION
[0012] Embodiments disclosed herein generally relate to compositions and methods of using the compositions to polish substrates that include at least a cobalt portion, and more specifically, that include at least a cobalt and dielectric (such as TEOS, SiN, low-k, etc.) portion. The compositions disclosed herein can be alkaline in nature and can be non-selective cobalt buffing slurries (i.e., exhibiting a dielectric / cobalt polishing selectivity of 1:1).
[0013] With the introduction of cobalt (Co) as a barrier layer, conductive layer, and / or W replacement, there is a need in the market for CMP slurries that can polish Co at effective material removal rates without experiencing significant Co corrosion (i.e., at moderate Co removal rates) and have various selectivities in the polishing rates of other metals and metal nitrides or oxides (Cu, Ti, TiN, Ta, TaN, Ta2O5, TiO2, Ru, ZrO2, HfO2, etc.) and dielectric films (SiN, silicon oxide, polysilicon, low-k dielectrics (e.g., carbon-doped silicon oxide), etc.). For example, after an aggressive bulk polishing step in which a large amount of material is removed, it is often desirable to perform a buffing step to obtain a desired surface topography. In some embodiments, the composition used for buffing removes dielectric materials and metals (e.g., TEOS, SiN, and Co) at a rate lower than that occurring during the bulk polishing step, or at approximately the same removal rate for each component (e.g., within 10% or 5%), to obtain the desired surface topography. Co corrosion prevention is a significant challenge in advanced node slurry design because Co is more chemically reactive than Cu and other precious metals. Current metal polishing slurries are not prepared for polishing Co-containing surfaces due to Co corrosion issues during the CMP process. Furthermore, it is generally desirable to remove a certain amount of Co during polishing to create a smooth surface on patterned semiconductor substrates for subsequent fabrication processes.
[0014] In one or more embodiments, the polishing composition of the present disclosure comprises an abrasive, a pH adjuster, a barrier film removal rate enhancer, a TEOS removal rate inhibitor, a cobalt removal rate enhancer, an azole-containing corrosion inhibitor, and a cobalt corrosion inhibitor.
[0015] In one or more embodiments, the polishing composition according to the present disclosure can comprise about 0.1 wt % to about 25 wt % abrasive, 0 wt % to about 10 wt % pH adjuster, about 0.01 wt % to about 3 wt % barrier film removal rate enhancer, about 0.001 wt % to about 15 wt % TEOS removal rate inhibitor, about 0.01 wt % to about 5 wt % cobalt removal rate enhancer, about 0.001 wt % to about 3 wt % azole-containing corrosion inhibitor, about 0.001 wt % to about 1 wt % cobalt corrosion inhibitor, and the remaining percentage (e.g., about 20 to 99 wt %) is a solvent (e.g., deionized water).
[0016] In one or more embodiments, the present disclosure provides a concentrated polishing slurry that can be diluted with water up to 2 times, 3 times, 4 times, 6 times, 8 times, or 10 times prior to use. In other embodiments, the present disclosure provides a ready-to-use polishing slurry for use on cobalt substrates, comprising the above-described polishing slurry, water, and optionally an oxidizing agent.
[0017] In one or more embodiments, the in-use polishing slurry can include about 0.1 wt % to about 12 wt % abrasive, 0 wt % to about 3 wt % pH adjuster, about 0.01 wt % to about 1 wt % barrier film removal rate enhancer, about 0.001 wt % to about 10 wt % TEOS removal rate inhibitor, about 0.01 wt % to about 2 wt % cobalt removal rate enhancer, about 0.001 wt % to about 0.5 wt % azole-containing corrosion inhibitor, about 0.001 wt % to about 0.5 wt % cobalt corrosion inhibitor, optionally about 0.1 wt % to about 5 wt % oxidizer, and about 75 wt % to about 99 wt % solvent (e.g., deionized water).
[0018] In one or more embodiments, the concentrated polishing slurry can include about 1 wt % to about 25 wt % abrasive, 0 wt % to about 10 wt % pH adjuster, about 0.1 wt % to about 3 wt % barrier film removal rate enhancer, about 0.01 wt % to about 15 wt % TEOS removal rate inhibitor, about 0.1 wt % to about 5 wt % cobalt removal rate enhancer, about 0.01 wt % to about 3 wt % azole-containing corrosion inhibitor, about 0.01 wt % to about 1 wt % cobalt corrosion inhibitor, and the remaining weight (e.g., about 20 wt % to about 98.5 wt %) of solvent (e.g., deionized water).
[0019] In one or more embodiments, the polishing compositions described herein can contain at least one abrasive (e.g., two or three). In some embodiments, the at least one abrasive is selected from the group consisting of cationic abrasives, substantially neutral abrasives, and anionic abrasives. In one or more embodiments, the at least one abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, coformers thereof (i.e., coformers of alumina, silica, titania, ceria, or zirconia), coated abrasives, surface-modified 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 highly pure and can have less than about 100 ppm alcohol, less than about 100 ppm ammonia, and less than about 100 ppb alkali cations, such as sodium cations. The abrasive can be present in an amount of about 0.1% to about 12% (e.g., about 0.5% to about 10%) of the total weight of the polishing composition at the time of use, or any subrange thereof.
[0020] In one or more embodiments, the amount of the at least one abrasive is at least about 0.1 wt. % (e.g., at least about 0.5 wt. %, at least about 1 wt. %, at least about 2 wt. %, at least about 4 wt. %, at least about 5 wt. %, at least about 10 wt. %, at least about 12 wt. %, at least about 15 wt. %, or at least about 20 wt. %) to at most about 25 wt. % (e.g., at most about 20 wt. %, at most about 18 wt. %, at most about 15 wt. %, at most about 12 wt. %, at most about 10 wt. %, or at most about 5 wt. %) of the polishing composition described herein.
[0021] In one or more embodiments, the polishing composition described herein can include at least one (e.g., two or three) optional pH adjuster. In some embodiments, the at least one pH adjuster is selected from the group consisting of 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.
[0022] In one or more embodiments, the amount of at least one pH adjuster, when included in the composition, is at least about 0.01 wt. % (e.g., at least about 0.05 wt. %, at least about 0.1 wt. %, at least about 0.5 wt. %, at least about 1 wt. %, at least about 2 wt. %, at least about 4 wt. %, at least about 5 wt. %, or at least about 8 wt. %) to at most about 10 wt. % (e.g., at most about 9 wt. %, at most about 8 wt. %, at most about 7 wt. %, at most about 6 wt. %, at most about 5 wt. %, at most about 4 wt. %, at most about 3 wt. %, at most about 2 wt. %, at most about 1 wt. %, at most about 0.5 wt. %, at most about 0.2 wt. %, or at most about 0.1 wt. %) of the polishing composition described herein.
[0023] In one or more embodiments, the pH value of the polishing composition can range from at least about 7 (e.g., at least about 7.5, at least about 8, at least about 8.5, at least about 9, at least about 9.5, at least about 10, at least about 10.5, at least about 11, at least about 11.5, or at least about 12) to at most about 14 (e.g., at most about 13.5, at most about 13, at most about 12.5, at most about 12, at most about 11.5, at most about 11, at least about 10.5, at most about 10, at most about 9.5, or at most about 9). Without wishing to be bound by theory, polishing compositions with a pH below 7 significantly increase cobalt removal rates and corrosion, while polishing compositions with a pH above 14 affect the stability of the suspended abrasive, significantly increase the roughness of films polished with such compositions, and reduce the overall quality of the films. The relative concentrations of the components in the polishing compositions described herein can be adjusted to obtain the desired pH.
[0024] In one or more embodiments, the polishing composition described herein can include at least one (e.g., two or three) barrier film removal rate enhancer. In some embodiments, the at least one barrier film removal rate enhancer is an organic acid (such as a carboxylic acid, an amino acid, a sulfonic acid, or a phosphonic acid) or a salt thereof. In some embodiments, the barrier film removal rate enhancer 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 some embodiments, the barrier film removal rate enhancer 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, 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 acid or its salt may be selected from the group consisting of methanesulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyanetholsulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, ethyl phosphate, cyanoethyl phosphate, phenyl phosphate, vinyl phosphate, 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, and salts and mixtures thereof. Without wishing to be bound by theory, it is surprising that organic acids or their salts (such as those described above) can be used as effective barrier removal rate enhancers in the polishing compositions described herein to improve the removal rate of barrier films (e.g., Ta or TaN films) on semiconductor substrates.
[0025] In one or more embodiments, the amount of the barrier film removal rate enhancing agent is at least about 0.01% by weight (e.g., 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, or at least about 1.5% by weight) to at most about 3% by weight (e.g., at most about 2.5% by weight, at most about 2% by weight, at most about 1.5% by weight, at most about 1% by weight, at most about 0.8% by weight, or at most about 0.5% by weight).
[0026] In one or more embodiments, the polishing composition described herein can include at least one (e.g., two or three) TEOS removal rate inhibitor. In some embodiments, the at least one TEOS removal rate inhibitor is an amine-containing compound (e.g., a compound selected from an alkanolamine and a cationic polymer). In some embodiments, the alkanolamine can be a secondary and / or tertiary amine. In one or more embodiments, the alkanolamine is selected from the group consisting of dimethylethanolamine, diethylethanolamine, triethanolamine, dimethylisopropanolamine, triisopropanolamine, diisopropylethanolamine, methyldiethanolamine, ethyldiethanolamine, isopropanoldiethanolamine, isopropyldiethanolamine, butyldiethanolamine, cyclohexyldiethanolamine, aminopropyldiethanolamine, aminopropyldiisopropanolamine, diethanolamine, diisopropanolamine, methylethanolamine, di-sec-butanolamine, butylethanolamine, N-acetylethanolamine, and mixtures thereof. In one or more embodiments, the TEOS removal rate inhibitor is a cationic polymer and can be selected from the group consisting of polyethyleneimine, polypropyleneimine, chitosan, poly(diallyldimethylammonium salt), poly(esteramine), poly(amidoamine), polylysine, poly(allylamine), poly(amino-co-ester), polyornithine, poly(2-ethyl-2-oxazoline), polyquaternium, a cationic polymer containing at least one hindered amine-containing group, and mixtures thereof. In one or more embodiments, the hindered amine-containing group is 2,2,6,6-tetramethylpiperidinyl.In one or more embodiments, the cationic polymer has a number average molecular weight in the range of at least about 500 g / mol (e.g., at least about 1,000 g / mol, at least about 1,500 g / mol, at least about 2,000 g / mol, at least about 2,500 g / mol, at least about 3,000 g / mol, at least about 4,000 g / mol, or at least about 5,000 g / mol) to up to about 50,000 g / mol (e.g., up to about 45,000 g / mol, up to about 40,000 g / mol, up to about 35,000 g / mol, up to about 30,000 g / mol, up to about 25,000 g / mol, up to about 20,000 g / mol, up to about 15,000 g / mol, or up to about 10,000 g / mol). Without wishing to be bound by theory, it is surprising that amine-containing compounds (such as those described above) can be used as effective TEOS removal rate inhibitors in the polishing compositions described herein to reduce the removal rate of TEOS films on semiconductor substrates.
[0027] In one or more embodiments, the amount of the TEOS removal rate inhibitor is 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 0.5 wt. %, at least about 1 wt. %, at least about 2 wt. %, or at least about 5 wt. %) to at most about 15 wt. % (e.g., at most about 14 wt. %, at most about 12 wt. %, at most about 10 wt. %, at most about 8 wt. %, at most about 6 wt. %, at most about 5 wt. %, at most about 4 wt. %, at most about 2 wt. %, at most about 1 wt. %, or at most about 0.5 wt. %) of the polishing composition described herein.
[0028] In one or more embodiments, the polishing composition described herein can include at least one (e.g., two or three) cobalt removal rate enhancing agent. In some embodiments, the at least one cobalt removal rate enhancing agent is an organic acid (such as a carboxylic acid or an amino acid) or a salt thereof. In some embodiments, the cobalt removal rate enhancing agent can be an organic acid (e.g., an amino acid) or a salt thereof 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, succinic acid, lactic acid, aminoacetic acid, phenoxyacetic acid, bicine, diglycolic acid, glyceric acid, tricine, alanine, glycine, serine, methionine, leucine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, benzoic acid, and salts and mixtures thereof. Without wishing to be bound by theory, it is surprising that organic acids or salts thereof (such as those described above) can be used as effective cobalt removal rate enhancers in the polishing compositions described herein to enhance the removal rate of cobalt films on semiconductor substrates.
[0029] In one or more embodiments, the amount of the cobalt removal rate enhancing agent is at least about 0.01 wt % (e.g., 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 0.6 wt %, at least about 0.8 wt %, at least about 1 wt %, at least about 1.5 wt %, or at least about 2 wt %) to at most about 5 wt % (e.g., at most about 4.5 wt %, at most about 4 wt %, at most about 3.5 wt %, at most about 3 wt %, at most about 2.5 wt %, at most about 2 wt %, at most about 1.5 wt %, at most about 1 wt %, or at most about 0.5 wt %) of the polishing composition described herein.
[0030] In one or more embodiments, the polishing composition described herein can comprise at least one (e.g., two or three) azole-containing corrosion inhibitor. In some embodiments, the at least one azole-containing corrosion inhibitor can be tetrazole, benzotriazole, tolyltriazole, 5-methylbenzotriazole, ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, dimethylbenzotriazole, chlorobenzotriazole, dichlorobenzotriazole, chloromethylbenzotriazole, chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminobenzotriazole, ... The azole-containing corrosion inhibitor is selected from the group consisting of triazole, 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-thiadazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-methylpyrazole, 4-amino-4H-1,2,4-triazole, and combinations thereof. Without wishing to be bound by theory, it is surprising that azole-containing corrosion inhibitors (such as those described above) can significantly reduce or minimize the copper removal rate on semiconductor substrates.
[0031] In one or more embodiments, the amount of the azole-containing corrosion inhibitor is at least about 0.001 wt. % (e.g., at least about 0.002 wt. %, at least about 0.005 wt. %, at least about 0.01 wt. %, at least about 0.02 wt. %, at least about 0.05 wt. %, at least about 0.1 wt. %, at least about 0.2 wt. %, at least about 0.5 wt. %, at least about 1 wt. %, or at least about 2 wt. %) to at most about 3 wt. % (e.g., at most about 2.8 wt. %, at most about 2.5 wt. %, at most about 2 wt. %, at most about 1.5 wt. %, at most about 1 wt. %, at most about 0.8 wt. %, at most about 0.5 wt. %, at most about 0.1 wt. %, at most about 0.05 wt. %, at most about 0.01 wt. %, or at most about 0.005 wt. %) of the polishing composition described herein.
[0032] In one or more embodiments, the polishing composition described herein can include at least one (e.g., two or three) cobalt corrosion inhibitor. In some embodiments, the at least one cobalt corrosion inhibitor is an anionic surfactant. In one or more embodiments, the anionic surfactant includes one or more phosphate groups and one or more of the following groups: a 6 to 24 carbon alkyl chain, 0 to 18 ethylene oxide groups, or a combination thereof. In one or more embodiments, the alkyl chain can have at least 8 carbons, at least 10 carbons, at least 12 carbons, or at least 14 carbons. In one or more embodiments, the alkyl chain can have up to 22 carbons, up to 20 carbons, or up to 18 carbons. In one or more embodiments, the anionic surfactant may have at least 1 (e.g., at least 2, at least 4, at least 6, at least 8, or at least 10) to a maximum of 18 (e.g., a maximum of 17, a maximum of 16, a maximum of 15, a maximum of 14, a maximum of 13, a maximum of 12, a maximum of 11, or a maximum of 10) ethylene oxide groups. Without wishing to be bound by theory, it is surprising that anionic surfactants (such as those described above) can be used as cobalt corrosion inhibitors in the polishing compositions described herein to reduce or minimize the cobalt removal rate on semiconductor substrates. Furthermore, without wishing to be bound by theory, it is believed that the cobalt corrosion inhibitors in the polishing compositions described herein, together with other components, can adjust the dielectric / cobalt polishing selectivity of the polishing composition to about 1:1.
[0033] In one or more embodiments, the amount of cobalt corrosion inhibitor is at least about 0.001 wt % (e.g., at least about 0.002 wt %, at least about 0.005 wt %, at least about 0.01 wt %, at least about 0.02 wt %, at least about 0.05 wt %, at least about 0.1 wt %, at least about 0.2 wt %, at least about 0.5 wt %, or at least about 0.8 wt %) to at most about 1 wt % (e.g., at most about 0.8 wt %, at most about 0.6 wt %, at most about 0.5 wt %, at most about 0.4 wt %, at most about 0.2 wt %, at most about 0.1 wt %, at most about 0.08 wt %, at most about 0.05 wt %, at most about 0.02 wt %, at most about 0.01 wt %, or at most about 0.005 wt %) of the polishing composition described herein.
[0034] An optional oxidizing agent can be added when the concentrated slurry is diluted to form the ready-to-use slurry. The oxidizing agent can be selected from the group consisting of hydrogen peroxide, ammonium persulfate, silver nitrate (AgNO), ferric nitrate or ferric chloride, peracids or salts, ozonated water, potassium ferricyanide, potassium dichromate, potassium iodate, potassium bromate, potassium periodate, periodic acid, vanadium trioxide, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, magnesium hypochlorite, ferric nitrate, potassium permanganate, other inorganic or organic peroxides, and mixtures thereof. In one embodiment, the oxidizing agent is hydrogen peroxide.
[0035] In one or more embodiments, the amount of oxidizing agent is at least about 0.05 wt. % (e.g., 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. %, at least about 1.5 wt. %, at least about 2 wt. %, at least about 2.5 wt. %, at least about 3 wt. %, at least about 3.5 wt. %, at least about 4 wt. %, or at least about 4.5 wt. %) to at most about 5 wt. % (e.g., at most about 4.5 wt. %, at most about 4 wt. %, at most about 3.5 wt. %, at most about 3 wt. %, at most about 2.5 wt. %, at most about 2 wt. %, at most about 1.5 wt. %, at most about 1 wt. %, at most about 0.5 wt. %, or at most about 0.1 wt. %) of the polishing composition described herein. In some embodiments, without wishing to be bound by theory, it is believed that the oxidizing agent helps remove the metal film by forming a metal complex with the chelating agent, so that the metal can be removed during the CMP process. In some embodiments, without wishing to be bound by theory, it is believed that the metal complex formed between the metal film and the oxidizing agent can form a passivation layer that can protect the metal from corrosion. In some embodiments, the oxidizing agent can reduce the shelf life of the polishing composition. In such embodiments, the oxidizing agent can be added to the polishing composition at the point of use just before polishing.
[0036] In one or more embodiments, the polishing composition described herein can include a solvent (e.g., a primary solvent) such as water. In some embodiments, the amount of solvent (e.g., water) is at least about 20% by weight (e.g., at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, at least about 40% by weight, at least about 45% by weight, at least about 50% by weight, at least about 55% by weight, at least about 60% by weight, at least about 65% by weight, at least about 70% by weight, at least about 75% by weight, at least about 80% by weight, at least about 85% by weight, at least about 90% by weight, at least about 92% by weight, at least about 94% by weight, at least about 95% by weight, or at least about 97% by weight) to at most about 99% by weight (e.g., at most about 98% by weight, at most about 96% by weight, at most about 94% by weight, at most about 92% by weight, at most about 90% by weight, at most about 85% by weight, at most about 80% by weight, at most about 75% by weight, at most about 70% by weight, or at most about 65% by weight).
[0037] In one or more embodiments, an optional secondary solvent (e.g., an organic solvent) can be used in the polishing composition (e.g., in-use or concentrated polishing composition) of the present disclosure, which can help dissolve the azole-containing corrosion inhibitor. In one or more embodiments, the secondary solvent can be one or more alcohols, alkylene glycols, or alkylene glycol ethers. In one or more embodiments, the secondary solvent comprises one or more solvents selected from the group consisting of ethanol, 1-propanol, 2-propanol, n-butanol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol propyl ether, and ethylene glycol.
[0038] In one or more embodiments, the amount of secondary solvent is at least about 0.005 wt.% (e.g., at least about 0.01 wt.%, at least about 0.02 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 0.6 wt.%, at least about 0.8 wt.%, at least about 1 wt.%, at least about 3 wt.%, at least about 5 wt.%, or at least about 10 wt.%) to at most about 15 wt.% (e.g., at most about 12 wt.%, at most about 10 wt.%, at most about 5 wt.%, at most about 3 wt.%, at most about 2 wt.%, at most about 1 wt.%, at most about 0.8 wt.%, at most about 0.6 wt.%, at most about 0.5 wt.%, or at most about 0.1 wt.%) of the polishing composition described herein.
[0039] In one or more embodiments, the polishing composition described herein can contain any of a variety of compounds, including but not limited to, organic solvents, pH adjusters, quaternary ammonium compounds (e.g., salts or hydroxides), amines, alkali bases (such as alkali hydroxides), fluoride-containing compounds, silanes (e.g., alkoxysilanes), imines (e.g., amidines such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN)), salts (e.g., halide salts), The polishing composition may be substantially free of one or more specific components, such as: inorganic or inorganic salts (e.g., metal salts), polymers (e.g., cationic or anionic polymers), surfactants (e.g., cationic surfactants, anionic surfactants, or nonionic surfactants), plasticizers, oxidizers (e.g., HO), corrosion inhibitors (e.g., azole or non-azole corrosion inhibitors), and / or certain abrasives (e.g., ceria abrasives, nonionic abrasives, surface-modified abrasives, or negatively / positively charged abrasives). Halide salts that can be excluded from the polishing composition include alkali metal halides (e.g., sodium or potassium halides) or ammonium halides (e.g., ammonium chloride), which may be chlorides, bromides, or iodides. As used herein, a component that is "substantially free" from the polishing composition refers to a component that is not intentionally added to the polishing composition. In some embodiments, the polishing compositions described herein can have up to about 1000 ppm (e.g., up to about 500 ppm, up to about 250 ppm, up to about 100 ppm, up to about 50 ppm, up to about 10 ppm, or up to about 1 ppm) of one or more of the above components that are substantially absent from the polishing composition. In some embodiments, the polishing compositions described herein can be completely free of one or more of the above components.
[0040] In one or more embodiments, the polishing compositions described herein may have a ratio (i.e., removal rate selectivity) of the removal rate of silicon oxide (e.g., TEOS), silicon nitride (e.g., SiN), or barrier material (e.g., Ta, TaN) to the removal rate of Cu, Co, or low-k dielectric material in a range of at least about 1:10 (e.g., at least about 1:8, at least about 1:6, at least about 1:5, at least about 1:4, at least about 1:2, at least about 1:1.5, at least about 1:1.2, at least about 1:1.1, or at least about 1:1) to at most about 10:1 (e.g., at most about 8:1, at most about 6:1, at most about 5:1, at most about 4:1, at most about 2:1, at most about 1.5:1, at most about 1.2:1, at most about 1.1:1, or at most about 1:1). In one or more embodiments, the above ratios are applicable when measuring removal rates for polishing either blanket wafers or patterned wafers (e.g., wafers including conductive, barrier, and / or dielectric layers).
[0041] The present disclosure also contemplates a method of using any of the above-described polishing compositions (e.g., concentrates or ready-to-use slurries). When using a concentrate, the method can include diluting the concentrate (e.g., at least two-fold) to form a ready-to-use slurry, and then contacting a surface at least partially comprising cobalt with the ready-to-use slurry. In some embodiments, an oxidizing agent can be added to the slurry before or after dilution. When using a ready-to-use slurry, the method can include contacting a surface at least partially comprising cobalt with the slurry.
[0042] In one or more embodiments, the present disclosure features a polishing method that can include applying a polishing composition according to the present disclosure to a substrate (e.g., a wafer) having at least cobalt on its surface, contacting a pad with the surface of the substrate, and moving the pad relative to the substrate. In some embodiments, when the substrate contains at least one or more silicon oxides (e.g., TEOS), silicon nitrides (e.g., SiN), and / or barrier materials (e.g., Ta, TaN, Ti, or TiN), the method can remove at least a portion of these materials at approximately the same rate as removing cobalt. For example, in one or more embodiments, the polishing composition of the present disclosure has a difference in polishing rate between TEOS / SiN and Co of less than about 20%, less than about 15%, less than about 10%, or less than about 5%. It should be noted that the term "silicon oxide" as used herein is intended to include both undoped and doped versions of silicon oxide. For example, in one or more embodiments, the silicon oxide can be doped with at least one dopant selected from carbon, nitrogen, oxygen, hydrogen, or any other known dopant for silicon oxide. Examples of silicon oxide film types include TEOS (tetraethyl orthosilicate), SiOC, SiOCN, SiOCH, SiOH, SiON, etc.
[0043] In some embodiments, the method of using the polishing composition described herein can further include manufacturing a semiconductor device from a substrate treated with the polishing composition through one or more processes. For example, semiconductor devices can be manufactured from a substrate treated with the polishing composition described herein using photolithography, ion implantation, dry / wet etching, plasma ashing, deposition (PVD, CVD, ALD, ECD, etc.), wafer mounting, die cutting, packaging, and testing.
[0044] The following specific examples are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. Without further elaboration, it is believed that one skilled in the art can, based on the description herein, utilize the present invention to its fullest extent. [Example]
[0045] In these examples, polishing was performed on 300 mm wafers using an AMAT Reflexion LK CMP polisher, a Fujibo H804 pad, a downforce pressure of 1.5 psi, a platen head speed of 101 / 95 rpm, and a slurry flow rate of 300 mL / min.
[0046] The general compositions used in the following examples are set forth below in Table 1. Specific details regarding the different compositions tested are explained in more detail when discussing each example.
[0047] [Table 1]
[0048] Example 1
[0049] Table 2 below shows the removal rates of TEOS, SiN, and Co blanket wafers when polished with Compositions 1-5. Compositions 1-5 contained the same components at the same concentrations, except for the differences noted below and in Table 2. Composition 1 was a control that did not contain a TEOS removal rate inhibitor (TEOS RRI). Compositions 2-5 contained an alkanolamine as the TEOS RRI-1 at various concentrations.
[0050] The results showed that alkanolamines could reduce the TEOS removal rate and had no significant effect (or only a slight effect) on the SiN and Co removal rates. This indicates that alkanolamines can be used as TEOS removal rate inhibitors. Furthermore, the TEOS removal rate gradually decreased as the concentration of alkanolamine increased.
[0051] [Table 2]
[0052] Example 2
[0053] Table 3 below shows the removal rates of TEOS, SiN, and Co blanket wafers polished with Compositions 6-11. Compositions 6-11 contained the same components at the same concentrations, except for the differences noted below and in Table 3. Compositions 6-11 did not contain TEOS RRI. The aspect of the composition that varied in this example was the size of the colloidal silica abrasive used in the polishing compositions. Abrasives 1-6 were colloidal silica abrasives with average diameters of 40 nm, 40 nm, 25 nm, 25 nm, 25 nm, and 18 nm, respectively. Abrasives 1 and 2 differed only in that Abrasive 2 had a lower density of silanol groups on its surface. Abrasives 3 and 4 differed only in that Abrasive 3 had a lower density of silanol groups on its surface. Abrasives 5 and 6 were colloidal silicas chemically modified to be negatively charged across all pH ranges.
[0054] The results in Table 3 demonstrate that abrasive size can affect the polishing selectivity between TEOS and SiN. Specifically, a TEOS:SiN selectivity of approximately 1:1 can be achieved using smaller abrasives (i.e., particle sizes less than 30 nm). In contrast, the larger abrasives used in Compositions 6 and 7 resulted in compositions that polished TEOS faster than SiN.
[0055] [Table 3]
[0056] Example 3
[0057] Table 4 below shows the removal rates of TEOS, SiN, and Co blanket wafers when polished with Compositions 12-14. Compositions 12-14 contained the same components at the same concentrations, except for the differences identified below and in Table 4. Specifically, Compositions 12-14 contained a phosphate-based anionic surfactant as a cobalt corrosion inhibitor (Co CI-1) at different concentrations.
[0058] The results in Table 4 show that the phosphate-based anionic surfactant has a clear effect on the Co polishing rate and can achieve a selectivity of approximately 1:1:1 for TEOS:SiN:Co by varying the concentration.
[0059] [Table 4]
[0060] Example 4
[0061] Table 5 below shows the removal rates of TEOS, SiN, and Co blanket wafers polished with Compositions 15-19. Compositions 15-19 contained the same components at the same concentrations, except for the differences noted below and in Table 5. Composition 15 was a control without a TEOS removal rate inhibitor. Compositions 16-19 contained a cationic polymer containing at least one hindered amine group as a TEOS removal rate inhibitor (TEOS RRI-2). Additionally, Compositions 15-19 all contained a phosphate-based anionic surfactant as a cobalt corrosion inhibitor (Co CI-1) at different concentrations.
[0062] As shown in Table 5, the results obtained from compositions 15 and 16 indicate that the inclusion of the above cationic polymer can effectively minimize the difference in removal rate between TEOS and SiN, resulting in a TEOS:SiN removal rate ratio of approximately 1:1. Furthermore, the CoCl-1 concentration can be used to adjust the cobalt removal rate.
[0063] [Table 5]
[0064] Example 5
[0065] Table 6 below shows the removal rates of TEOS, SiN, and Co blanket wafers when polished with Compositions 20-22. Compositions 20-22 contained the same components at the same concentrations, except for the differences noted below and in Table 6. Specifically, Composition 20 contained a primary amine alkanolamine as TEOS RRI-3, Composition 21 contained a secondary amine alkanolamine as TEOS RRI-4, and Composition 22 contained a tertiary amine alkanolamine as TEOS RRI-5.
[0066] As shown in Table 6, polishing compositions containing a TEOS RRI that is a secondary or tertiary amine (i.e., compositions 21 and 22) surprisingly suppressed the TEOS removal rate to a greater extent than the polishing composition containing a TEOS RRI that is a primary amine (i.e., composition 20). Furthermore, compositions 21 and 22 substantially eliminated the difference in removal rate between TEOS and SiN.
[0067] [Table 6]
[0068] While only a few examples have been described in detail above, those skilled in the art will readily appreciate that many variations in the examples are possible without substantially departing from the invention, and all such variations are intended to be included within the scope of the present disclosure as defined in the following claims. The present invention may include the following embodiments. <1> Abrasives and Optionally, a pH adjuster; and a barrier film removal rate enhancer; a TEOS removal rate inhibitor; a cobalt removal rate enhancer; an azole-containing corrosion inhibitor; a cobalt corrosion inhibitor; Including, the barrier film removal rate enhancer is different from the cobalt removal rate enhancer; Polishing composition. <2> the abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, coformers of alumina, silica, titania, ceria, or zirconia, coated abrasives, surface-modified abrasives, and mixtures thereof; <1> The polishing composition according to claim 1. <3> The amount of the abrasive is about 0.1% to about 25% by weight of the composition. <1> The polishing composition according to claim 1. <4> the composition comprises the pH adjuster, wherein the pH adjuster is selected from the group consisting of 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; <1> The polishing composition according to claim 1. <5> The amount of the pH adjuster is about 0.01% to about 10% by weight of the composition. <1> The polishing composition according to claim 1. <6> the barrier film removal rate enhancer is an organic acid or a salt thereof 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, succinic acid, lactic acid, aminoacetic acid, phenoxyacetic acid, bicine, phosphoric acid, diglycolic acid, glyceric acid, tricine, benzoic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, pentetic acid, diaminocyclohexanetetraacetic acid, ethyl phosphate, cyanoethyl phosphate, phenyl phosphate, vinyl phosphate, 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, and salts and mixtures thereof; <1> The polishing composition according to claim 1. <7> the amount of the barrier film removal rate enhancer is about 0.01% by weight to about 3% by weight of the composition; <1> The polishing composition according to claim 1. <8> The TEOS removal rate inhibitor comprises an alkanolamine and a cationic polymer. The amine-containing compound is selected from the group consisting of <1> The polishing composition according to claim 1. <9> The alkanolamine is a secondary or tertiary amine. <8> The polishing composition according to claim 1. <10> the alkanolamine is selected from the group consisting of dimethylethanolamine, diethylethanolamine, triethanolamine, dimethylisopropanolamine, triisopropanolamine, diisopropylethanolamine, methyldiethanolamine, ethyldiethanolamine, isopropanoldiethanolamine, isopropyldiethanolamine, butyldiethanolamine, cyclohexyldiethanolamine, aminopropyldiethanolamine, aminopropyldiisopropanolamine, diethanolamine, diisopropanolamine, methylethanolamine, di-sec-butanolamine, butylethanolamine, N-acetylethanolamine, and mixtures thereof; <9> The polishing composition according to claim 1. <11> The TEOS removal rate inhibitor is a cationic polymer. <8> The polishing composition according to claim 1. <12> the cationic polymer is selected from the group consisting of polyethyleneimine, polypropyleneimine, chitosan, poly(diallyldimethylammonium salt), poly(esteramine), poly(amidoamine), polylysine, poly(allylamine), poly(amino-co-ester), polyornithine, poly(2-ethyl-2-oxazoline), polyquaternium, cationic polymers containing at least one hindered amine-containing group, and mixtures thereof; <11> The polishing composition according to claim 1. <13> the hindered amine-containing group is 2,2,6,6-tetramethylpiperidinyl; <12> The polishing composition according to <14> the cationic polymer has a number average molecular weight of about 500 g / mole to about 50,000 g / mole; <11> The polishing composition according to claim 1. <15> the amount of the TEOS removal rate inhibitor is from about 0.001% to about 15% by weight of the composition; <1> The polishing composition according to claim 1. <16> the cobalt removal rate enhancing agent is an organic acid or a salt thereof 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, succinic acid, lactic acid, aminoacetic acid, phenoxyacetic acid, bicine, diglycolic acid, glyceric acid, tricine, alanine, glycine, serine, methionine, leucine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, benzoic acid, and salts and mixtures thereof; <1> The polishing composition according to claim 1. <17> the amount of the cobalt removal rate enhancer is from about 0.01% to about 5% by weight of the composition; <1> The polishing composition according to claim 1. <18> The azole-containing corrosion inhibitor may be selected from the group consisting of tetrazole, benzotriazole, tolyltriazole, 5-methylbenzotriazole, ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, dimethylbenzotriazole, chlorobenzotriazole, dichlorobenzotriazole, chloromethylbenzotriazole, chloroethylbenzotriazole, fluoro ... the compound is selected from the group consisting of 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-thiadazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-methylpyrazole, 4-amino-4H-1,2,4-triazole, and combinations thereof; <1> The polishing composition according to claim 1. <19> the amount of the azole-containing corrosion inhibitor is from about 0.001% to about 3% by weight of the composition; <1> The polishing composition according to claim 1. <20> The cobalt corrosion inhibitor is an anionic surfactant. <1> The polishing composition according to claim 1. <21> the anionic surfactant comprises one or more phosphate groups and one or more of the following: <20> The polishing composition according to claim 1, wherein the alkyl chain has 6 to 24 carbon atoms, 0 to 18 ethylene oxide groups, or a combination of an alkyl chain of 6 to 24 carbon atoms and multiple ethylene oxide groups. <22> the amount of the cobalt corrosion inhibitor is from about 0.001% to about 1% by weight of the composition; <1> The polishing composition according to claim 1. <23> the abrasive in an amount of about 0.1% to about 25% by weight of the composition; the pH adjuster in an amount of about 0.01% to about 10% by weight of the composition; the barrier film removal rate enhancer in an amount of about 0.01% to about 3% by weight of the composition; the TEOS removal rate inhibitor in an amount of about 0.001% to about 15% by weight of the composition; the cobalt removal rate enhancer in an amount of about 0.01% to about 5% by weight of the composition; the azole-containing corrosion inhibitor in an amount of about 0.001% to about 3% by weight of the composition; the cobalt corrosion inhibitor in an amount of about 0.001% to about 1% by weight of the composition; The above-mentioned <1> The polishing composition according to claim 1. <24> The pH of the composition is about 7 to about 14. <1> The polishing composition according to claim 1. <25> Abrasives and Optionally, a pH adjuster; and an organic acid or a salt thereof; Amino acids and an alkanolamine or a cationic polymer; an azole-containing corrosion inhibitor; an anionic surfactant; Including, the organic acid is different from the amino acid; Polishing composition. <26> The aforementioned <1> applying the polishing composition of claim 1 to a surface of a substrate, the surface comprising cobalt; contacting a pad with a surface of the substrate and moving the pad relative to the substrate; 1. A method for polishing a substrate, comprising:
Claims
1. Abrasives and Optionally, a pH adjuster; and a Ta or TaN barrier film removal rate enhancer; a TEOS removal rate inhibitor; and a cobalt removal rate enhancer; an azole-containing corrosion inhibitor; a cobalt corrosion inhibitor; Including, the Ta or TaN barrier film removal rate enhancer is different from the cobalt removal rate enhancer; Polishing composition.
2. 2. The polishing composition of claim 1, wherein the abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, coformers of alumina, silica, titania, ceria, or zirconia, coated abrasives, surface-modified abrasives, and mixtures thereof.
3. 10. The polishing composition of claim 1, wherein the amount of the abrasive is 0.1% to 25% by weight of the composition.
4. The composition includes the pH adjuster, and the pH adjuster is selected from the group consisting of 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, and benzyltrimethylammonium hydroxide.
2. The polishing composition of claim 1, wherein the at least one ammonium hydroxide is selected from the group consisting of ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, choline hydroxide, and any combination thereof.
5. 2. The polishing composition of claim 1, wherein the amount of the pH adjuster is 0.01% to 10% by weight of the composition.
6. 2. The polishing composition of claim 1, wherein the Ta or TaN barrier film removal rate enhancing agent is an organic acid or a salt thereof 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, succinic acid, lactic acid, aminoacetic acid, phenoxyacetic acid, bicine, phosphoric acid, diglycolic acid, glyceric acid, tricine, benzoic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, pentetic acid, diaminocyclohexanetetraacetic acid, ethyl phosphate, cyanoethyl phosphate, phenyl phosphate, vinyl phosphate, 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, and salts and mixtures thereof.
7. 2. The polishing composition of claim 1, wherein the amount of the Ta or TaN barrier film removal rate enhancer is 0.01% to 3% by weight of the composition.
8. 2. The polishing composition of claim 1, wherein the TEOS removal rate inhibitor is an amine-containing compound selected from the group consisting of alkanolamines and cationic polymers.
9. 9. The polishing composition of claim 8, wherein the alkanolamine is a secondary or tertiary amine.
10. 10. The polishing composition of claim 9, wherein the alkanolamine is selected from the group consisting of dimethylethanolamine, diethylethanolamine, triethanolamine, dimethylisopropanolamine, triisopropanolamine, diisopropylethanolamine, methyldiethanolamine, ethyldiethanolamine, isopropanoldiethanolamine, isopropyldiethanolamine, butyldiethanolamine, cyclohexyldiethanolamine, aminopropyldiethanolamine, aminopropyldiisopropanolamine, diethanolamine, diisopropanolamine, methylethanolamine, di-sec-butanolamine, butylethanolamine, N-acetylethanolamine, and mixtures thereof.
11. The polishing composition of claim 8 , wherein the TEOS removal rate inhibitor is a cationic polymer.
12. 12. The polishing composition of claim 11, wherein the cationic polymer is selected from the group consisting of polyethyleneimine, polypropyleneimine, chitosan, poly(diallyldimethylammonium salt), poly(esteramine), poly(amidoamine), polylysine, poly(allylamine), poly(amino-co-ester), polyornithine, poly(2-ethyl-2-oxazoline), polyquaternium, a cationic polymer containing at least one hindered amine-containing group, and mixtures thereof.
13. 13. The polishing composition of claim 12, wherein the hindered amine-containing group is 2,2,6,6-tetramethylpiperidinyl.
14. 12. The polishing composition of claim 11, wherein the cationic polymer has a number average molecular weight of 500 g / mol to 50,000 g / mol.
15. 2. The polishing composition of claim 1, wherein the amount of the TEOS removal rate inhibitor is 0.001% to 15% by weight of the composition.
16. 2. The polishing composition of claim 1, wherein the cobalt removal rate enhancing agent is an organic acid or a salt thereof 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, succinic acid, lactic acid, aminoacetic acid, phenoxyacetic acid, bicine, diglycolic acid, glyceric acid, tricine, alanine, glycine, serine, methionine, leucine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, benzoic acid, and salts and mixtures thereof.
17. 2. The polishing composition of claim 1, wherein the amount of the cobalt removal rate enhancing agent is 0.01% to 5% by weight of the composition.
18. The azole-containing corrosion inhibitor is selected from the group consisting of tetrazole, benzotriazole, tolyltriazole, 5-methylbenzotriazole, ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, dimethylbenzotriazole, chlorobenzotriazole, dichlorobenzotriazole, chloromethylbenzotriazole, chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, and aminobenzimidazoline.
2. The polishing composition of claim 1, wherein the compound is selected from the group consisting of benzophenone, 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-thiadazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-methylpyrazole, 4-amino-4H-1,2,4-triazole, and combinations thereof.
19. 2. The polishing composition of claim 1, wherein the amount of the azole-containing corrosion inhibitor is 0.001% to 3% by weight of the composition.
20. The polishing composition of claim 1 , wherein the cobalt corrosion inhibitor is an anionic surfactant.
21. 21. The polishing composition of claim 20, wherein the anionic surfactant comprises one or more phosphate groups and one or more of the following: an alkyl chain of 6 to 24 carbons, 0 to 18 ethylene oxide groups, or a combination of an alkyl chain of 6 to 24 carbons and multiple ethylene oxide groups.
22. 2. The polishing composition of claim 1, wherein the amount of the cobalt corrosion inhibitor is 0.001% to 1% by weight of the composition.
23. the abrasive in an amount of 0.1% to 25% by weight of the composition; the pH adjuster in an amount of 0.01% to 10% by weight of the composition; the Ta or TaN barrier film removal rate enhancer in an amount of 0.01% to 3% by weight of the composition; the TEOS removal rate inhibitor in an amount of 0.001% to 15% by weight of the composition; the cobalt removal rate enhancer in an amount of 0.01% to 5% by weight of the composition; the azole-containing corrosion inhibitor in an amount of 0.001% to 3% by weight of the composition; the cobalt corrosion inhibitor in an amount of 0.001% to 1% by weight of the composition; The polishing composition of claim 1 , comprising:
24. 2. The polishing composition of claim 1, wherein the pH of the composition is 7 to 14.
25. Abrasives and Optionally, a pH adjuster; and a Ta or TaN barrier film removal rate enhancer comprising an organic acid or its salt; Amino acids and an alkanolamine or a cationic polymer; an azole-containing corrosion inhibitor; a cobalt corrosion inhibitor comprising an anionic surfactant; A polishing composition comprising: the organic acid is different from the amino acid, the polishing composition does not contain hydrogen peroxide; The polishing composition.
26. applying the polishing composition of claim 1 to a surface of a substrate, the surface comprising cobalt; contacting a pad with a surface of the substrate and moving the pad relative to the substrate; 1. A method for polishing a substrate, comprising:
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