Polishing composition and method of use thereof

Abstract

The polishing composition includes an abrasive, a pH adjuster, a barrier film removal rate enhancer, a first low-k removal rate inhibitor, a second low-k removal rate inhibitor, an azole-containing corrosion inhibitor, and a cobalt corrosion inhibitor. The present disclosure also relates to a method for polishing a substrate containing cobalt using the polishing composition described herein.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority from U.S. Provisional Application No. 62 / 904,857, filed September 24, 2019, 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 by further miniaturization of devices through innovations in processes, materials, and integration. Previous material innovations include the introduction of copper, replacing aluminum as the conductive material in interconnect structures, and the use of tantalum (Ta) / tantalum nitride (TaN) as a dispersion barrier to isolate the Cu conductive material from non-conductive / insulating dielectric materials. Copper (Cu) was selected as the interconnect material due to its low resistivity and good resistance to electromigration.

[0003] However, to maintain effective interconnect resistance in the Back End of Line (BEOL), multilayer Cu / barrier / dielectric stacks must become thinner and more conformal as newer chip features shrink. Schemes to make Cu and Ta / TaN barrier films thinner create problems with resistivity and deposition flexibility. For example, resistivity is exponentially worsening with smaller dimensions and advanced manufacturing nodes, and transistor circuit speed improvements (at the Front End of Line (FEOL)) are halved due to delays caused by 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 currently being investigated as a replacement for tungsten (W) in various applications such as W metal contacts, plugs, vias, and gate materials.

[0004] Many currently available CMP slurries were specifically designed to remove materials that were more common in older chip designs, such as the aforementioned copper and tungsten. Because cobalt is more susceptible to chemical attack, certain components in these older CMP slurries can cause harmful and unacceptable defects in the cobalt. As a result, the use of 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 metallic component in semiconductor manufacturing, there is a market need for CMP slurries that can efficiently polish dielectric or barrier components on Co-containing surfaces without significant Co corrosion. Summary of the Invention [Means for solving the problem]

[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] For purposes of definition in this disclosure, unless otherwise specified, all percentages listed should be understood to be weight percent based on the total weight of the chemical-mechanical polishing composition.

[0008] In one aspect, an embodiment described herein relates to a polishing composition comprising an abrasive; a pH adjuster; a barrier film removal rate enhancing agent; a first low-k removal rate inhibitor; a second low-k removal rate inhibitor different from the first low-k removal rate inhibitor; an azole-containing rust inhibitor; and a cobalt rust inhibitor.

[0009] In another aspect, embodiments described herein relate to a polishing composition comprising an abrasive; a pH adjuster; an organic acid or its salt; a nonionic surfactant; an amphiphilic copolymer; an azole-containing rust inhibitor; and an anionic surfactant.

[0010] In yet another aspect, embodiments described herein relate to a method of polishing a substrate, comprising applying the polishing composition of claim 1 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 the appended claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The embodiments described herein generally relate to compositions and methods of using the compositions to polish substrates that include at least a cobalt portion, and more specifically, substrates that may include at least a cobalt portion and a copper portion. The compositions described herein can effectively suppress low-k removal rates, minimize cobalt liner loss, and reduce defects observed on the polished copper surface, while still effectively removing barrier films (e.g., Ta or TaN films). For example, the compositions described herein can be particularly useful for polishing advanced node films that include copper, cobalt liners, barriers (Ta, TaN), and dielectric materials (TEOS, low-k, ultra low-k, etc.).

[0013] With the introduction of cobalt (Co) as a barrier layer, conductive layer, and / or to replace W, there is a market need for a CMP slurry that can polish Co at an effective material removal rate without significant Co corrosion and has a range of options for polishing rates of other metals and metal oxides (Cu, Ti, Ta2O5, TiO2, RuO2, etc.) and dielectric films (SiN, silicon oxide, poly-Si, low k dielectrics (e.g., carbon-doped silicon oxide), etc.). Co corrosion prevention is very challenging in slurry design for advanced nodes, since Co is chemically more reactive than Cu and other precious metals. Current metal polishing slurries are ill-equipped to polish Co-containing surfaces, since they suffer from Co corrosion issues in the CMP process. In addition, it is generally desirable to remove some amount of Co during polishing to produce a smooth surface on the patterned semiconductor substrate for subsequent manufacturing processes. For example, in some fabrication processes, there is often a significant amount of dishing in the copper and cobalt portions after removing excess copper deposition. For this reason, the polishing composition of the present disclosure can be formulated to polish the barrier material (Ta or TaN) at a faster rate than it removes copper metal and removes cobalt from the liner, so that in a subsequent barrier polishing step, the previous dishing can be corrected so that the polished film can have a smooth topography. Therefore, one of the goals of the polishing composition of the present disclosure is to have an adequate Co removal rate while effectively removing a specific target material (e.g., Ta or TaN).

[0014] In one or more embodiments, the polishing composition includes an abrasive, a pH adjuster, a barrier film removal rate enhancing agent, a first low-k removal rate inhibitor, a second low-k removal rate inhibitor, an azole-containing rust inhibitor, and a cobalt rust inhibitor. In one or more embodiments, the polishing composition may also include a chelating agent. In one or more embodiments, the polishing composition according to the present disclosure may include about 0.1 wt% to about 50 wt% of an abrasive, about 0.05 wt% to about 10 wt% of a pH adjuster, about 0.02 wt% to about 4 wt% of a barrier film removal rate increasing agent, about 0.005 wt% to about 5 wt% of a first low-k removal rate inhibitor, about 0.005 wt% to about 5 wt% of a second low-k removal rate inhibitor, about 0.0001 wt% to about 1 wt% of an azole-containing rust inhibitor, about 0.0001 wt% to about 1 wt% of a cobalt rust inhibitor, and the remaining weight percent (e.g., about 20 wt% to about 99 wt%) of a solvent (e.g., deionized water). In one or more embodiments, the polishing composition may further include about 0.001 wt% to about 1 wt% of a chelating agent.

[0015] In one or more embodiments, the present disclosure provides a concentrated polishing composition that can be diluted up to 2-fold, or up to 4-fold, or up to 6-fold, or up to 8-fold, or up to 10-fold with water prior to use. In other embodiments, the present disclosure provides a point-of-use (POU) polishing composition for use on a cobalt substrate, comprising the polishing composition, water, and optionally an oxidizing agent.

[0016] In one or more embodiments, the POU polishing composition may include about 0.1 wt % to about 12 wt % abrasive, about 0.05 wt % to about 5 wt % pH adjuster, about 0.02 wt % to about 2 wt % barrier film removal rate enhancing agent, about 0.005 wt % to about 0.5 wt % first low-k removal rate inhibitor, about 0.005 wt % to about 0.5 wt % second low-k removal rate inhibitor, about 0.0001 wt % to about 0.1 wt % azole-containing rust inhibitor, about 0.0001 wt % to about 0.1 wt % cobalt rust inhibitor, optionally about 0.1 wt % to about 5 wt % oxidizer, and about 80 wt % to about 99 wt % solvent (e.g., deionized water). In one or more embodiments, the POU polishing composition may further include about 0.001 wt % to about 0.1 wt % chelating agent.

[0017] In one or more embodiments, the concentrated polishing composition may include about 1 wt % to about 50 wt % of an abrasive, about 0.5 wt % to about 10 wt % of a pH adjuster, about 0.2 wt % to about 4 wt % of a barrier film removal rate increasing agent, about 0.05 wt % to about 5 wt % of a first low-k removal rate inhibitor, about 0.05 wt % to about 5 wt % of a second low-k removal rate inhibitor, about 0.001 wt % to about 1 wt % of an azole-containing rust inhibitor, about 0.001 wt % to about 1 wt % of a cobalt rust inhibitor, and the remaining weight percent (e.g., about 20 wt % to about 98.5 wt %) of a solvent (e.g., deionized water). In one or more embodiments, the concentrated polishing composition may further include about 0.01 wt % to about 1 wt % of a chelating agent.

[0018] In one or more embodiments, the polishing composition described herein may include 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, co-formed products thereof (i.e., co-formed products 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 include ceria. In some embodiments, the at least one abrasive may be of high purity, with less than about 100 ppm alcohol, less than about 100 ppm ammonia, and less than about 100 parts per billion (ppb) alkali cations, such as sodium cations. The abrasive can be present in an amount from about 0.1% to about 12% (eg, from about 0.5% to about 10%), based on the total weight of the POU polishing composition, or any subrange therein.

[0019] In some embodiments, the at least one abrasive is present in an amount of about 0.1 wt % or more (e.g., about 0.5 wt % or more, about 1 wt % or more, about 2 wt % or more, about 4 wt % or more, about 5 wt % or more, about 10 wt % or more, about 12 wt % or more, about 15 wt % or more, or about 20 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, or about 5 wt % or less) of the polishing composition described herein.

[0020] In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) pH adjuster. In some embodiments, the at least one pH adjuster is selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide, cerium 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.

[0021] In some embodiments, the at least one pH adjuster is present in an amount of about 0.05 wt % or more (e.g., 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 0.8 wt % or more, about 1 wt % or more, about 2 wt % or more, about 5 wt % or more, or about 7 wt % or more) to about 10 wt % or less (e.g., about 9 wt % or less, about 8 wt % or less, about 7 wt % or less, about 6 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, about 0.5 wt % or less, about 0.2 wt % or less, or about 0.1 wt % or less).

[0022] In some embodiments, the pH value of the polishing composition may range from about 7 or more (e.g., about 7.5 or more, about 8 or more, about 8.5 or more, about 9 or more, about 9.5 or more, about 10 or more, about 10.5 or more, about 11 or more, about 11.5 or more, or about 12 or more) to about 14 or less (e.g., about 13.5 or less, about 13 or less, about 12.5 or less, about 12 or less, about 11.5 or less, about 11 or less, about 10.5 or less, about 10 or less, about 9.5 or less, or about 9 or less). Without wishing to be bound by theory, polishing compositions having a pH lower than 7 will significantly increase cobalt removal rate and corrosion, and polishing compositions having a pH higher than 14 may affect the stability of the suspended abrasive, significantly increasing the roughness and reducing the overall quality of the film polished by the composition. To obtain the desired pH, the relative concentrations of the components in the polishing compositions described herein may be adjusted.

[0023] In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) barrier film removal rate enhancing agent. In some embodiments, the at least one barrier film removal rate enhancing agent is an organic acid (e.g., 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 enhancing agent 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, and hydroxylamine O-sulfonic acid. , methanesulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyanetholsulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, ethyl phosphoric acid, cyanoethyl phosphoric acid, phenyl phosphoric acid, vinyl phosphoric acid, poly(vinylphosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, nitrile tri(methylphosphonic acid), diethylenetriaminepentakis(methylphosphonic acid), N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, salts thereof, and mixtures thereof. Without wishing to be bound by theory, it is surprising that an organic acid or salt thereof (such as those described above) can be used as an effective barrier film removal rate enhancing agent in the polishing composition described in the present disclosure to enhance the removal rate of a barrier film (e.g., Ta film or TaN film) in a semiconductor substrate.

[0024] In some embodiments, the barrier film removal rate increasing agent is present in an amount of about 0.02 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 1.5 wt % or more, about 2 wt % or more) to about 4 wt % or less (e.g., about 3.5 wt % or less, about 3 wt % or less, about 2.5 wt % or less, about 2 wt % or less, about 1.5 wt % or less, or about 1 wt % or less) relative to the polishing composition described herein.

[0025] In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) first low-k removal rate inhibitor. In some embodiments, the at least one first low-k removal rate inhibitor is a nonionic surfactant. In one or more embodiments, the nonionic surfactant is selected from the group consisting of alcohol alkoxylates, alkylphenol alkoxylates, tristyrylphenol alkoxylates, sorbitan ester alkoxylates, polyalkoxylates, polyalkylene oxide block copolymers, tetrahydroxy oligomers, alkoxylated diamines, and mixtures thereof. In one or more embodiments, the nonionic surfactant is a polymer having a number average molecular weight of about 1,000 g / mol or more, or about 2,500 g / mol or more, or about 5,000 g / mol or more, or about 7,500 g / mol or more, or about 10,000 g / mol or more. In one or more embodiments, the nonionic surfactant is a polymer having a number average molecular weight of about 1,000,000 g / mol or less, or about 750,000 g / mol or less, or about 500,000 g / mol or less, or about 250,000 g / mol or less, or about 100,000 g / mol or less. In one or more embodiments, the alkoxylate group of the alkoxylated nonionic surfactant is an ethoxylate, a propoxylate, or a combination of an ethoxylate group and a propoxylate group. Without wishing to be bound by theory, it is surprising that a nonionic surfactant (such as those described above) can be used as a low-k removal rate inhibitor in the polishing composition described in the present disclosure to reduce or minimize the removal rate of a low-k film (e.g., a carbon-doped silicon oxide film) in a semiconductor substrate.

[0026] In some embodiments, the first low-k removal rate inhibitor is present in an amount of about 0.005 wt % or more (e.g., about 0.01 wt % or more, about 0.05 wt % or more, about 0.1 wt % or more, about 0.5 wt % or more, about 1 wt % or more, about 1.5 wt % or more, about 2 wt % or more, or about 3 wt % or more) to about 5 wt % or less (e.g., about 4.5 wt % or less, about 4 wt % or less, about 3.5 wt % or less, about 3 wt % or less, about 2.5 wt % or less, about 2 wt % or less, about 1.5 wt % or less, about 1 wt % or less, about 0.5 wt % or less, or about 0.1 wt % or less) of the polishing composition described herein.

[0027] In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) second low-k removal rate inhibitor. In some embodiments, the at least one second low-k removal rate inhibitor is an amphiphilic copolymer. In one or more embodiments, the amphiphilic copolymer is a styrene-maleic anhydride copolymer. In one or more embodiments, the amphiphilic copolymer has a number average molecular weight of about 1,000 g / mol or more (e.g., about 2,500 g / mol or more, about 5,000 g / mol or more, about 7,500 g / mol or more, about 10,000 g / mol or more) to about 200,000 g / mol or less (e.g., about 150,000 g / mol or less, about 100,000 g / mol or less, about 50,000 g / mol or less, or about 25,000 g / mol or less). Without wishing to be bound by theory, it is surprising that amphiphilic copolymers (such as those described above) can be used as low-k removal rate inhibitors in the polishing compositions described herein to reduce or minimize the removal rate of low-k films (e.g., carbon-doped silicon oxide films) in semiconductor substrates.

[0028] In some embodiments, the second low-k removal rate inhibitor is present in an amount of about 0.005 wt % or more (e.g., about 0.01 wt % or more, about 0.05 wt % or more, about 0.1 wt % or more, about 0.5 wt % or more, about 1 wt % or more, about 1.5 wt % or more, about 2 wt % or more, or about 3 wt % or more) to about 5 wt % or less (e.g., about 4.5 wt % or less, about 4 wt % or less, about 3.5 wt % or less, about 3 wt % or less, about 2.5 wt % or less, about 2 wt % or less, about 1.5 wt % or less, about 1 wt % or less, about 0.5 wt % or less, or about 0.1 wt % or less) of the polishing composition described herein.

[0029] Without wishing to be bound by theory, it has surprisingly been discovered that the inclusion of both a nonionic surfactant (i.e., a first low-k removal rate inhibitor) and an amphiphilic copolymer (i.e., a second low-k removal rate inhibitor) in the polishing composition described herein can produce a synergistic effect, reducing the removal rate of a low-k film (e.g., a carbon-doped silicon oxide film) by more than the sum of the removal rate reductions caused by each component when used individually.

[0030] In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) azole-containing rust inhibitor. In some embodiments, the at least one azole-containing rust inhibitor is selected from the group consisting of substituted or unsubstituted triazole, substituted or unsubstituted tetrazole, substituted or unsubstituted benzotriazole, substituted or unsubstituted pyrazole, and substituted or unsubstituted imidazole. In one or more embodiments, the azole-containing rust inhibitor may be selected from the group consisting of triazole, 1,2,4-triazole, tetrazole, benzotriazole, tolyltriazole, ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, dimethylbenzotriazole, chlorobenzotriazole, dichlorobenzotriazole, chloromethylbenzotriazole, chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, aminobenzimidazole, aminotetrazole, and mixtures thereof. Without wishing to be bound by theory, it is believed that azole-containing corrosion inhibitors (such as those described above) can significantly reduce or minimize the removal rate of copper in semiconductor substrates.

[0031] In some embodiments, the azole-containing rust inhibitor is present in an amount of about 0.0001 wt% or more (e.g., about 0.0002 wt% or more, about 0.0005 wt% or more, about 0.001 wt% or more, about 0.002 wt% or more, about 0.005 wt% or more, about 0.01 wt% or more, about 0.02 wt% or more, about 0.05 wt% or more, about 0.1 wt% or more, about 0.2 wt% or more, or about 0.5 wt% or more) to about 1 wt% or less (e.g., about 0.8 wt% or less, about 0.6 wt% or less, about 0.5 wt% or less, about 0.4 wt% or less, about 0.2 wt% or less, about 0.1 wt% or less, about 0.05 wt% or less, about 0.02 wt% or less, about 0.01 wt% or less, or about 0.005 wt% or less).

[0032] In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) cobalt rust inhibitor. In some embodiments, the at least one cobalt rust 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: an alkyl chain having 6 to 24 carbon atoms, 0 to 18 ethylene oxide groups, or a combination thereof. In one or more embodiments, the alkyl chain may have 8 or more carbon atoms, 10 or more carbon atoms, 12 or more carbon atoms, or 14 or more carbon atoms. In one or more embodiments, the alkyl chain may have 22 or fewer carbon atoms, 20 or fewer carbon atoms, or 18 or fewer carbon atoms. Without wishing to be bound by theory, it is surprising that anionic surfactants (such as those described above) can be used as cobalt rust inhibitors in the polishing composition described herein to reduce or minimize the removal rate of cobalt in a semiconductor substrate.

[0033] In some embodiments, the cobalt rust inhibitor is present in an amount of about 0.0001 wt% or more (e.g., about 0.0002 wt% or more, about 0.0005 wt% or more, about 0.001 wt% or more, about 0.002 wt% or more, about 0.005 wt% or more, about 0.01 wt% or more, about 0.02 wt% or more, about 0.05 wt% or more, about 0.1 wt% or more, about 0.2 wt% or more, or about 0.5 wt% or more) to about 1 wt% or less (e.g., about 0.8 wt% or less, about 0.6 wt% or less, about 0.5 wt% or less, about 0.4 wt% or less, about 0.2 wt% or less, about 0.1 wt% or less, about 0.05 wt% or less, about 0.02 wt% or less, about 0.01 wt% or less, or about 0.005 wt% or less).

[0034] In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) optional chelating agent. In some embodiments, the at least one optional chelating agent may be an amino-containing carboxylic acid (e.g., a polyaminopolycarboxylic acid) or a phosphonic acid. In some embodiments, the chelating agent is selected from the group consisting of ethylenediaminetetraacetic acid, iminodiacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraminehexaacetic acid, diaminocyclohexanetetraacetic acid, nitrilotrimethylphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and combinations thereof. Without wishing to be bound by theory, it is believed to be surprising that the inclusion of a chelating agent (e.g., those described above) in the polishing composition described in the present disclosure can significantly reduce or minimize defects observed on semiconductor substrates (e.g., copper wafers).

[0035] In some embodiments, the chelating agent is present in an amount of about 0.001 wt % or more (e.g., about 0.002 wt % or more, about 0.005 wt % or more, about 0.01 wt % or more, about 0.02 wt % or more, about 0.05 wt % or more, about 0.1 wt % or more, about 0.2 wt % or more, or about 0.5 wt % or more) to about 1 wt % or less (e.g., about 0.8 wt % or less, about 0.6 wt % or less, about 0.5 wt % or less, about 0.4 wt % or less, about 0.2 wt % or less, about 0.1 wt % or less, about 0.05 wt % or less, about 0.02 wt % or less, about 0.01 wt % or less, or about 0.005 wt % or less) of the polishing composition described herein.

[0036] An optional oxidizing agent may be added when diluting the concentrated slurry to form the POU slurry. The oxidizing agent may be selected from the group consisting of hydrogen peroxide, ammonium persulfate, silver nitrate (AgNO3), iron(III) nitrate or chloride, peracid or per salt, 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, iron(III) nitrate, potassium permanganate, other inorganic or organic peroxides, and mixtures thereof. In one embodiment, the oxidizing agent is hydrogen peroxide.

[0037] In some embodiments, the oxidizing agent is present in an amount of about 0.05 wt% or more (e.g., 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 1 wt% or more, about 1.5 wt% or more, about 2 wt% or more, about 2.5 wt% or more, about 3 wt% or more, about 3.5 wt% or more, about 4 wt% or more, or about 4.5 wt% or more) to about 5 wt% or less (e.g., about 4.5 wt% or less, about 4 wt% or less, about 3.5 wt% or less, about 3 wt% or less, about 2.5 wt% or less, about 2 wt% or less, about 1.5 wt% or less, about 1 wt% or less, about 0.5 wt% or less, or about 0.1 wt% or less) relative to the polishing composition described herein. In some embodiments, without wishing to be bound by theory, it is believed that the oxidizing agent can aid in the removal of the metal film by forming a metal complex with a 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 metal complexes 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 prior to polishing.

[0038] In some embodiments, the polishing compositions described herein can include a solvent (eg, a primary solvent) such as water. In some embodiments, the solvent (e.g., water) may be present in an amount of about 20 wt% or more (e.g., about 25 wt% or more, about 30 wt% or more, about 35 wt% or more, about 40 wt% or more, about 45 wt% or more, about 50 wt% or more, about 55 wt% or more, about 60 wt% or more, about 65 wt% or more, about 70 wt% or more, about 75 wt% or more, about 80 wt% or more, about 85 wt% or more, about 90 wt% or more, about 92 wt% or more, about 94 wt% or more, about 95 wt% or more, or about 97 wt% or more) to about 99 wt% or less (e.g., about 98 wt% or less, about 96 wt% or less, about 94 wt% or less, about 92 wt% or less, about 90 wt% or less, about 85 wt% or less, about 80 wt% or less, about 75 wt% or less, about 70 wt% or less, or about 65 wt% or less).

[0039] In one or more embodiments, an optional secondary solvent (e.g., an organic solvent) can be used in the polishing composition (e.g., POU polishing composition or concentrated polishing composition) of the present disclosure, and the use of the secondary solvent can help dissolve the azole-containing rust 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 includes one or more solvents selected from the group consisting of ethanol, 1-propanol, 2-propanol, n-butanol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol propyl ether, and ethylene glycol.

[0040] In some embodiments, the secondary solvent may be present in an amount of about 0.0025 wt % or more (e.g., about 0.005 wt % or more, about 0.01 wt % or more, about 0.02 wt % or more, 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 0.6 wt % or more, about 0.8 wt % or more, or about 1 wt % or more) to about 2 wt % or less (e.g., about 1.8 wt % or less, about 1.6 wt % or less, about 1.5 wt % or less, about 1.4 wt % or less, about 1.2 wt % or less, about 1 wt % or less, about 0.8 wt % or less, about 0.6 wt % or less, about 0.5 wt % or less, or about 0.1 wt % or less).

[0041] In one or more embodiments, the polishing composition of the present disclosure can comprise any of a number of additives, such as an organic solvent, a pH adjuster, a quaternary ammonium compound (e.g., a salt or hydroxide), an amine, an alkali base (e.g., an alkali hydroxide), a fluorine-containing compound, a silane (e.g., an alkoxysilane), an imine (e.g., an amidine such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN)), a salt (e.g., a halide salt or a metal salt ... a fluorine-containing compound, a silane (e.g., an alkoxysilane), a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine-containing compound, a fluorine The polishing composition may be substantially free of one or more specific components, such as polymers (e.g., cationic or anionic polymers), surfactants (e.g., cationic surfactants, anionic surfactants, or nonionic surfactants), plasticizers, oxidizers (e.g., H2O2), rust inhibitors (e.g., azole rust inhibitors or non-azole rust inhibitors), and / or specific abrasives (e.g., ceria abrasives, nonionic abrasives, surface-modified abrasives, or negatively / positively charged abrasives). The halide salts that may be excluded from the polishing composition include alkali metal halides (e.g., sodium halide or potassium halide) or ammonium halides (e.g., ammonium chloride), and may be chlorides, bromides, or iodides. As used in this disclosure, 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 may have 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) of one or more of the above components that are substantially absent from the polishing composition. In some embodiments, the polishing compositions described herein may be completely free of one or more of the above components.

[0042] In one or more embodiments, the polishing composition described herein may have a ratio of removal rate for silicon oxide (e.g., TEOS), barrier material (e.g., Ta, TaN) to removal rate for Cu, Co, or low-k dielectric material (i.e., removal rate selectivity) of about 3:1 or more (e.g., 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). In one or more embodiments, the above ratios may be applied when measuring removal rates for polishing blanket wafers or when measuring removal rates for polishing patterned wafers (e.g., wafers including conductive, barrier, and / or dielectric layers).

[0043] In one or more embodiments, the total defect count on a wafer having a diameter of 12 inches (i.e., about 300 mm) (e.g., on the copper surface of the wafer) is 800 or less (e.g., 700 or less, 600 or less, 500 or less, 400 or less, 300 or less, 250 or less, 200 or less, 150 or less, 100 or less, or 50 or less) when the wafer is polished with a polishing composition according to the present disclosure. In one or more embodiments, the defects may result from scratches, organic residues, particulate contamination (e.g., abrasives), and combinations thereof. In general, the defects may be counted using a laser scattering inspection system and analyzed and classified by reviewing images of the polished wafer taken with a scanning electron microscope (SEM). In one or more embodiments, the defects counted are about 100 nm or greater in size.

[0044] The present disclosure also contemplates methods of using any of the above polishing compositions (e.g., concentrates or POU slurries). In the case of a concentrate, the method may include diluting the concentrate (e.g., by 2x or more) to form a POU slurry, and then contacting a surface that at least partially comprises cobalt with the POU slurry. In some embodiments, an oxidizing agent may be added to the slurry before or after the dilution. In the case of a POU slurry, the method may include contacting a surface that at least partially comprises cobalt with the slurry.

[0045] In one or more embodiments, the present disclosure features a polishing method that may include applying a polishing composition according to the present disclosure to a substrate (e.g., a wafer) having at least cobalt on its surface; and moving a pad against the surface of the substrate. In some embodiments, if the substrate includes at least one of silicon oxide and / or barrier materials (e.g., Ta, TaN), the method may remove at least a portion of these materials without substantially removing cobalt. The term "silicon oxide" in the present disclosure is expressly intended to include both undoped silicon oxide and doped silicon oxide. For example, in one or more embodiments, the silicon oxide may be doped with at least one dopant selected from carbon, nitrogen, oxygen, hydrogen, and any other known dopant for silicon oxide. Some examples of types of silicon oxide films include TEOS (tetraethyl orthosilicate), SiOC, SiOCN, SiOCH, SiOH, and SiON.

[0046] In some embodiments, the method of using the polishing composition described herein may further include manufacturing a semiconductor device from a substrate treated with the polishing composition by one or more steps. For example, photolithography, ion implantation, dry / wet etching, plasma ash, deposition (e.g., PVD, CVD, ALD, ECD), wafer mounting, die cutting, packaging, and testing may be used to manufacture a semiconductor device from a substrate treated with the polishing composition described herein.

[0047] 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. EXAMPLES

[0048] In these examples, polishing was performed on 200 mm wafers using an AMAT Mirra CMP polisher, a Fujibo H804 pad, a downforce pressure of 1.5 psi, a platen head speed of 120 / 114 rpm, and a slurry flow rate of 175 mL / min.

[0049] The general compositions used in the following examples are set forth below in Table 1. Details of the differences between the compositions tested are explained in further detail when describing each example.

[0050] [Table 1]

[0051] Example 1 Table 2 below shows the removal rates for TEOS blanket wafers, Ta blanket wafers, Black Diamond 1 (BD-1) blanket wafers, and Black Diamond 2 (BD-2) blanket wafers when polished with compositions 1-6. Compositions 1-6 contained the same components at the same concentrations, except for the differences described below and shown in Table 2. Composition 1 contained one polyalkoxylate low-k removal rate inhibitor (LK RRI; nonionic surfactant) and served as the control. As shown in Table 2, compositions 2-6 each contained a combination of two separate LK RRIs (i.e., alkoxylated diamine nonionic surfactant (LK RRI-1) and amphiphilic copolymer (LK RRI-2)) at various concentrations. BD-1 and BD-2 blanket wafers are low-k dielectric materials (i.e., carbon-doped silicon oxide) coated on silicon wafers.

[0052] The results surprisingly showed that nonionic surfactants and amphiphilic copolymers can be used as low-k removal rate inhibitors, and the combination of these two inhibitors (i.e., LK RRI-1 and LK RRI-2) suppressed the polishing rate more effectively than the comparable LK RRI. Furthermore, the data showed that as the concentration of LK RRI-1 in the combination of LK RRI-1 and LK RRI-2 increased, the removal rates of low-k dielectric materials in BD-1 and BD-2 blanket wafers decreased much more significantly than the TEOS and Ta removal rates, indicating the impact that LK RRI-1 and LK RRI-2 have on the low-k removal rate.

[0053] [Table 2]

[0054] Example 2 Table 3 below shows the removal rates for Cu blanket wafers, TEOS blanket wafers, Ta blanket wafers, and BD-1 blanket wafers when polished with polishing compositions 7-14. Compositions 7-14 contained the same components at the same concentrations, except for the differences described below and shown in Table 3. Composition 7 used LK RRI and benzotriazole as the copper rust inhibitor (CI-1) and served as a control. Compositions 8-14 contained a combination of two separate LK RRIs (LK RRI-1 and LK RRI-2) with copper rust inhibitors selected from CI-1 (benzotriazole) and CI-3-CI-5 (substituted benzotriazoles). Additionally, compositions 8-14 varied the concentration of rust inhibitor from 6x to 25x, as shown in Table 3.

[0055] The combination of two separate LK RRIs (LK RRI-1 and LK RRI-2) with copper rust inhibitors selected from CI-1 and CI-3 to CI-5 showed comparable TEOS and Ta polishing rates to those achieved by composition 7, and better Cu removal rate inhibition performance (see compositions 8 to 14). That is, the results showed that the low-k removal rate inhibitors and copper rust inhibitors did not substantially affect the TEOS and Ta removal rates. On the other hand, the results showed that the inclusion of a substituted benzotriazole significantly reduced the copper removal rate (see compositions 10 to 14).

[0056] [Table 3]

[0057] Example 3 Table 4 below shows the removal rates and defect counts on Cu wafers for Cu blanket wafers, Co blanket wafers, and BD blanket wafers when polished with polishing compositions 15-21. Compositions 15-21 contained the same components at the same concentrations, except for the differences noted below and shown in Table 4. Composition 15 contained a combination of two separate LK RRIs (LK RRI-1 and LK RRI-2) with benzotriazole (CI-1) as the copper rust inhibitor. Composition 16 was compositionally the same as composition 15, but used an alkylbenzotriazole (CI-5) instead of benzotriazole (CI-1) as the copper rust inhibitor. This change resulted in significantly fewer defects being observed on the Cu wafers.

[0058] Composition 17 contained a phosphate-based anionic surfactant as a cobalt rust inhibitor (Co-CI) in addition to the copper rust inhibitor (CI-5). This addition significantly reduced the cobalt polishing rate and, surprisingly, significantly reduced the defects observed on Cu wafers, even though the amount of CI-5 used was half that used in Composition 16.

[0059] Compositions 18-21 surprisingly demonstrated that the addition of a chelating agent (CA) can reduce the cobalt removal rate and defects observed on copper wafers. In particular, the use of high concentrations of the aminopolycarboxylic acid chelating agent CA-1 in composition 19 resulted in a very low cobalt removal rate and a better reduction in defects on copper wafers. Compositions 20 and 21 are analogous to compositions 18 and 19, but use a different, comparative chelating agent (CA-2). CA-2 is a sulfonic acid chelating agent and did not show the same ability to reduce defects on Cu wafers at high concentrations compared to CA-1 used in composition 19.

[0060] [Table 4]

[0061] Example 4 In this example, patterned copper coupons with cobalt liners were immersed in each of polishing compositions 22-24 for 5 minutes at 60° C. Compositions 22-24 contained the same components in the same concentrations (i.e., all of the components shown in Table 1) except for the differences described below and shown in Table 5. After immersion, the resulting slurry was analyzed by ICP-MS to determine the concentration of cobalt ions etched away from the patterned coupons.

[0062] Table 5 below shows that the cobalt ion concentration in the polishing slurry decreased with the addition of Co rust inhibitor (CoCI), indicating the protective ability of the Co rust inhibitor during polishing. See the "60°C SER Co Ion Concentration" column. Table 5 shows electrochemical test data obtained by testing blanket coupons of Cu or Co when measured in a polishing slurry containing all of the components shown in Table 1 (except composition 22 did not contain a cobalt rust inhibitor), and compares the corrosion potential (Ecorr) and the current corresponding to the corrosion potential (Icorr) for cobalt and copper. Generally, a higher value of Ecorr or a lower value of Icorr indicates that the material of interest is better protected / passivated. Thus, it can be seen that composition 24, which contains the highest amount of Co rust inhibitor, had the highest protection / passivation for cobalt. Furthermore, it is shown that the addition of Co rust inhibitor does not significantly affect the corrosion potential of copper.

[0063] [Table 5]

[0064] Example 5 Table 6 below shows the removal rates for Cu blanket wafers, TEOS blanket wafers, TaN blanket wafers, Black Diamond 1 (BD-1) blanket wafers, and ultra low-k (ULK) blanket wafers when polished with compositions 25-29. Compositions 25-29 contained the same components at the same concentrations, with the exceptions noted below and shown in Table 4. Specifically, composition 25 contained no low-k removal rate inhibitor, composition 26 contained one polyalkoxylate low-k removal rate inhibitor (LK RRI), compositions 27 and 28 contained only one of LK RRI-1 and LK RRI-2, and composition 29 contained a combination of two distinct LK RRIs, i.e., an alkoxylated diamine nonionic surfactant (LK RRI-1) and an amphiphilic copolymer (LK RRI-2).

[0065] The results surprisingly show that nonionic surfactants (LK RRI and LK RRI-1) and amphiphilic copolymer (LK RRI-2) could be used as low-k removal rate inhibitors, and that the combination of both LK RRI-1 and LK RRI-2 suppressed the polishing rate of BD-1 more effectively than either the comparative LK RRI or LK RRI-1 and LK RRI-2 used alone.

[0066] [Table 6]

[0067] Although only a few exemplary embodiments have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without departing from the essence of the invention, all of which are intended to be included within the scope of the present disclosure, as defined in the claims that follow. [1] Abrasives; pH adjuster; Barrier film removal rate enhancer; The first low-k removal rate inhibitor; a second low-k removal rate inhibitor different from the first low-k removal rate inhibitor; Azole-containing rust inhibitors; and Cobalt Rust Inhibitor 1. A polishing composition comprising: [2] The polishing composition according to [1], wherein the abrasive is selected from the group consisting of alumina; silica; titania; ceria; zirconia; co-formed products of alumina, silica, titania, ceria, or zirconia; coated abrasives; surface-modified abrasives; and mixtures thereof. [3] The polishing composition according to [1] above, wherein the abrasive is present in an amount of about 0.1% by weight to about 50% by weight of the composition. [4] The barrier film removal rate increasing agent 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, potassium acetate, potassium citrate, aminoacetic acid, phenoxyacetic acid, bicine, diglycolic acid, glyceric acid, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, benzoic acid, 1,2-ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, hydroxylamine O-sulfonic acid, methanesulfonic acid, benzoic ... The polishing composition according to the above item [1], wherein the organic acid or salt thereof is selected from the group consisting of: phosphonic 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(vinyl phosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, nitrile tri(methylphosphonic acid), diethylenetriaminepentakis(methylphosphonic acid), N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, salts thereof, and mixtures thereof. [5] The polishing composition according to [1] above, wherein the barrier film removal rate increasing agent is present in an amount of about 0.02% by weight to about 4% by weight of the composition. [6] The polishing composition according to [1], wherein the first low-k removal rate inhibitor is a nonionic surfactant. [7] The composition according to [6] above, wherein the nonionic surfactant is selected from the group consisting of alcohol alkoxylates, alkylphenol alkoxylates, tristyrylphenol alkoxylates, sorbitan ester alkoxylates, polyalkoxylates, polyalkylene oxide block copolymers, tetrahydroxy oligomers, alkoxylated diamines, and mixtures thereof. [8] The polishing composition according to [1], wherein the first low-k removal rate inhibitor is present in an amount of about 0.005% by weight to about 5% by weight of the composition. [9] The polishing composition described in [1], wherein the second low-k removal rate inhibitor is an amphiphilic copolymer.

[10] The polishing composition according to [1] above, wherein the amphiphilic copolymer is a styrene-maleic anhydride copolymer.

[11] The polishing composition according to [1], wherein the second low-k removal rate inhibitor is present in an amount of about 0.005% by weight to about 5% by weight of the composition.

[12] The polishing composition according to [1] above, wherein the azole-containing rust inhibitor is selected from the group consisting of triazole, tetrazole, benzotriazole, tolyltriazole, ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, dimethylbenzotriazole, chlorobenzotriazole, dichlorobenzotriazole, chloromethylbenzotriazole, chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, aminobenzimidazole, pyrazole, imidazole, aminotetrazole, and mixtures thereof.

[13] The polishing composition according to [1] above, wherein the azole-containing rust inhibitor is present in an amount of about 0.0001% by weight to about 1% by weight of the composition.

[14] The polishing composition according to [1], wherein the cobalt rust inhibitor is an anionic surfactant.

[15] The anionic surfactant is One or more phosphate groups and one or more of the following groups: an alkyl chain having 6 to 24 carbon atoms, 0 to 18 ethylene oxide groups, or a combination thereof; The polishing composition according to

[14] above,

[16] The polishing composition according to [1], wherein the cobalt rust inhibitor is present in an amount of about 0.0001% by weight to about 1% by weight of the composition.

[17] The polishing composition according to [1] above, wherein the pH adjuster is selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide, cerium 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.

[18] The polishing composition according to [1] above, wherein the pH adjuster is present in an amount of about 0.05% by weight to about 10% by weight of the composition.

[19] The polishing composition according to [1], further comprising a chelating agent selected from the group consisting of ethylenediaminetetraacetic acid, iminodiacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraminehexaacetic acid, diaminocyclohexanetetraacetic acid, nitrilotrimethylphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and combinations thereof.

[20] The polishing composition according to

[19] , wherein the chelating agent is present in an amount of about 0.001% by weight to about 1% by weight of the composition.

[21] The composition, the abrasive in an amount of about 0.1% to about 50% by weight of the composition; the pH adjuster in an amount of about 0.05% to about 10% by weight of the composition; the barrier film removal rate enhancing agent in an amount of about 0.02% to about 4% by weight of the composition; the first low-k removal rate inhibitor in an amount of about 0.005% to about 5% by weight of the composition; the second low-k removal rate inhibitor in an amount of about 0.005% to about 5% by weight of the composition; the azole-containing rust inhibitor in an amount of about 0.0001% to about 1% by weight of the composition; and the cobalt rust inhibitor in an amount of about 0.0001% to about 1% by weight of the composition; The polishing composition according to [1] above,

[22] The polishing composition according to [1] above, wherein the pH of the composition is about 7 to about 14.

[23] Abrasives; pH adjuster; Organic acids or their salts; Nonionic surfactants; Amphiphilic copolymers; Azole-containing rust inhibitors; and Anionic Surfactants 1. A polishing composition comprising:

[24] applying the polishing composition of [1] to a surface of a substrate, wherein the surface contains cobalt; and contacting a pad with the surface of the substrate and moving the pad relative to the substrate; 16. A method for polishing a substrate, comprising:

Claims

1. Abrasives; pH adjuster; Barrier film removal rate enhancer; A first low-k removal rate inhibitor; a second low-k removal rate inhibitor different from the first low-k removal rate inhibitor; An azole-containing rust inhibitor; and Cobalt Rust Inhibitor Including, the first low-k removal rate inhibitor is a nonionic surfactant; the second low-k removal rate inhibitor is an amphiphilic copolymer; 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; co-formed products 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 abrasive is present in an amount of 0.1% to 50% by weight of the composition.

4. The barrier film removal rate increasing agent 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, potassium acetate, potassium citrate, aminoacetic acid, phenoxyacetic acid, bicine, diglycolic acid, glyceric acid, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, benzoic acid, 1,2-ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, hydroxylamine O-sulfonic acid, methanesulfonic acid, benzoic ...

2. The polishing composition of claim 1, wherein the organic acid or salt thereof is selected from the group consisting of: sulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyanetholesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, ethyl phosphate, cyanoethyl phosphate, phenyl phosphate, vinyl phosphate, poly(vinyl phosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, nitrile tri(methylphosphonic acid), diethylenetriaminepentakis(methylphosphonic acid), N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, salts thereof, and mixtures thereof.

5. 2. The polishing composition of claim 1, wherein the barrier film removal rate enhancing agent is present in an amount of 0.02% to 4% by weight of the composition.

6. 2. The polishing composition of claim 1, wherein the nonionic surfactant is selected from the group consisting of alcohol alkoxylates, alkylphenol alkoxylates, tristyrylphenol alkoxylates, sorbitan ester alkoxylates, polyalkoxylates, polyalkylene oxide block copolymers, tetrahydroxy oligomers, alkoxylated diamines, and mixtures thereof.

7. 2. The polishing composition of claim 1, wherein the first low-k removal rate inhibitor is present in an amount of 0.005% to 5% by weight of the composition.

8. 2. The polishing composition of claim 1, wherein the amphiphilic copolymer is a styrene-maleic anhydride copolymer.

9. 2. The polishing composition of claim 1, wherein the second low-k removal rate inhibitor is present in an amount of 0.005% to 5% by weight of the composition.

10. 2. The polishing composition of claim 1, wherein the azole-containing rust inhibitor is selected from the group consisting of triazole, tetrazole, benzotriazole, tolyltriazole, ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, dimethylbenzotriazole, chlorobenzotriazole, dichlorobenzotriazole, chloromethylbenzotriazole, chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, aminobenzimidazole, pyrazole, imidazole, aminotetrazole, and mixtures thereof.

11. 2. The polishing composition of claim 1, wherein the azole-containing rust inhibitor is present in an amount of 0.0001% to 1% by weight of the composition.

12. The polishing composition of claim 1 , wherein the cobalt rust inhibitor is an anionic surfactant.

13. The anionic surfactant is one or more phosphate groups and one or more of the following groups: an alkyl chain containing 6 to 24 carbon atoms, 0 to 18 ethylene oxide groups, or a combination thereof; The polishing composition of claim 12 , comprising:

14. 2. The polishing composition of claim 1, wherein the cobalt rust inhibitor is present in an amount of 0.0001% to 1% by weight of the composition.

15. 2. The polishing composition of claim 1, wherein the pH adjuster is selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide, cerium 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.

16. 2. The polishing composition of claim 1, wherein the pH adjuster is present in an amount of 0.05% to 10% by weight of the composition.

17. 2. The polishing composition of claim 1, further comprising a chelating agent selected from the group consisting of ethylenediaminetetraacetic acid, iminodiacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraminehexaacetic acid, diaminocyclohexanetetraacetic acid, nitrilotrimethylphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and combinations thereof.

18. 18. The polishing composition of claim 17, wherein the chelating agent is present in an amount of 0.001% to 1% by weight of the composition.

19. The composition, said abrasive in an amount of 0.1% to 50% by weight of said composition; said pH adjuster in an amount of 0.05% to 10% by weight of said composition; said barrier film removal rate enhancing agent in an amount of 0.02% to 4% by weight of said composition; the first low-k removal rate inhibitor in an amount of 0.005% to 5% by weight of the composition; the second low-k removal rate inhibitor in an amount of 0.005% to 5% by weight of the composition; the azole-containing rust inhibitor in an amount of 0.0001% to 1% by weight of the composition; and said cobalt rust inhibitor in an amount of 0.0001% to 1% by weight of said composition; The polishing composition of claim 1 , comprising:

20. 2. The polishing composition of claim 1, wherein the pH of the composition is from 7 to 14.

21. Abrasives; pH adjuster; Organic acids or salts thereof; Nonionic surfactants; Amphiphilic copolymers; An azole-containing rust inhibitor; and Anionic Surfactants Including, The polishing composition, wherein the amphiphilic copolymer is present in an amount of 0.1% to 5% by weight of the polishing composition.

22. applying the polishing composition of claim 1 to a surface of a substrate, the surface comprising cobalt; and contacting a pad with the surface of the substrate and moving the pad relative to the substrate; 16. A method for polishing a substrate, comprising:

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