Abrasive composition and method of using the same

Abstract

The polishing composition comprises an abrasive, a pH adjuster, a barrier film removal rate enhancer, a low-k removal rate suppressor, an azole-containing corrosion inhibitor, and a ruthenium removal rate enhancer. A method for polishing a substrate comprises applying the polishing composition described herein to a surface of a substrate, wherein the surface comprises ruthenium or a hard mask material; and contacting a pad with the surface of the substrate and moving the pad relative to the substrate.

Description

Technical Field

[0001] Cross - References to Related Applications This application claims priority from U.S. Provisional Application No. 62 / 975,829, filed on February 13, 2020, the content of which is hereby incorporated by reference in its entirety.

Background Art

[0002] The semiconductor industry is constantly pressured to improve chip performance through further miniaturization of devices by means of innovations in processes, materials, and integration. Previous material innovations include the introduction of copper, the replacement of aluminum as a conductive material in interconnect structures, and the use of tantalum (Ta) / tantalum nitride (TaN) as a diffusion barrier to isolate the Cu conductive material from non - conductive / insulating dielectric materials. Copper (Cu) was selected as an interconnect material due to its low resistivity and excellent resistance to electron migration.

[0003] However, as the features of more advanced - generation chips shrink, in order to maintain effective interconnect resistance in the Back End of Line (BEOL), the multi - layer Cu / barrier / dielectric stack must be thinner and less conformal. Thinner Cu and Ta / TaN barrier film schemes have problems with resistance and flexibility in deposition. For example, at smaller dimensions and advanced manufacturing nodes, the resistivity deteriorates rapidly, and the improvement in transistor circuit speed (in the Front End of Line (FEOL)) is halved due to the delay from the conductive Cu / barrier wiring (BEOL). Ruthenium (Ru) has emerged as a major candidate for use as a liner material, barrier layer, and conductive layer. Ruthenium has excellent anti - Cu diffusivity with respect to dielectric layers and can also facilitate the electro - filling of copper directly into small - dimension trenches without using a copper seed layer. Furthermore, ruthenium is also being studied as a material for vias to replace conventional tungsten (W) metal.

Summary of the Invention

[0004] This general description is provided to introduce a selection of concepts that will be further described in the detailed description that follows. This general description is not intended to identify key features or essential features of the subject matter recited in the claims, nor is it intended to be used as an aid in limiting the scope of the subject matter recited in the claims.

[0005] As defined in the present disclosure, unless otherwise noted, all percent values recited are to be understood as weight percent based on the total weight of the polishing composition.

[0006] In one aspect, embodiments described in the present disclosure relate to a polishing composition comprising an abrasive; a pH adjuster; an agent for increasing the barrier film removal rate; a low-k removal rate inhibitor; an azole-containing corrosion inhibitor; and an agent for increasing the ruthenium removal rate.

[0007] In another aspect, embodiments described in the present disclosure relate to a polishing composition comprising an abrasive; a pH adjuster; an organic acid or its salt; a nonionic surfactant; an azole-containing corrosion inhibitor; and a compound selected from the group consisting of ammonium salts, thiocyanates, halide salts, nitrates, nitric acid, and mixtures thereof.

[0008] In yet another aspect, embodiments described in the present disclosure relate to a method of polishing a substrate (e.g., a substrate containing ruthenium), the method comprising the steps of applying the polishing composition described in the present disclosure to a surface of the substrate, wherein the surface contains ruthenium or a hard mask material; and contacting a pad with the surface of the substrate and moving the pad relative to the substrate.

[0009] Other aspects and advantages of the subject matter recited in the claims will become apparent from the following description and the appended claims. **Mode for Carrying Out the Invention**

[0010] Embodiments described in the present disclosure generally relate to a composition, and a method of using the composition to polish a substrate comprising at least a ruthenium portion and / or a hard mask portion (e.g., tungsten, carbide, nitride ceramic (e.g., TiN) and doped derivatives thereof), and more specifically a substrate that may comprise at least a ruthenium portion, a hard mask portion, and a copper portion. The compositions described in the present disclosure are capable of effectively removing ruthenium and / or hard mask materials while minimizing copper corrosion (e.g., minimizing surface roughness). For example, the compositions described in the present disclosure can be used to polish films of advanced nodes that include copper, ruthenium liners, hard mask materials (e.g., titanium and doped derivatives thereof, tungsten and doped derivatives thereof (e.g., WB4), carbides (e.g., BC, B4C, TiC, SiC, and WC), boron-containing materials (e.g., B6O, BC2N, and AlMgB 14 )), nitride ceramic materials (e.g., SiN, TiN, BN), barrier materials (e.g., Ta, TaN), and dielectric materials (e.g., TEOS, low-k, ultra low-k, etc.).

[0011] Many of the currently available CMP slurries are specifically designed to remove more common materials in older chip designs, such as the aforementioned copper and tungsten. However, in back-end-of-line (BEOL) applications in the semiconductor industry, ruthenium is used as a liner material because it has good conductivity, deposition characteristics, and is resistant to Cu diffusion. Unlike other materials such as cobalt and copper, ruthenium is chemically relatively stable and thus does not degrade during polishing and can be difficult to remove. Additionally, ruthenium is often used together with copper, which is a conductive layer. As described above, copper is a relatively soft material and is easy to remove. Copper is essential for the function of many semiconductor devices, and the use of CMP slurries can easily peel or damage the copper layer or inlay, which can have an adverse effect on the performance of the finished device. Since copper is more susceptible to chemical corrosion, older CMP slurries may not be able to effectively remove ruthenium without causing harmful and unacceptable defects in copper. As a result, less advanced slurries can result in unacceptable corrosion, wafer topography, and / or selectivity of the removal rate for one or more of the components of the multi-component substrate being polished. Additionally, more complex integration schemes may use a hard mask as an etching mask together with the Ru liner and Cu conductive layer, which presents yet another material that the polishing slurry must be able to effectively remove.

[0012] With the increasing use and size reduction of multi-component integration schemes in semiconductor manufacturing, there is a market need for CMP slurries that can effectively polish substrates containing ruthenium, copper, and hard mask materials with a minimum of copper corrosion while achieving favorable removal rates and selectivities for all other components.

[0013] In one or more embodiments, the polishing composition described in the present disclosure includes an abrasive; a pH adjuster; an agent for increasing the barrier film removal rate; a low-k removal rate inhibitor; an azole-containing corrosion inhibitor; and an agent for increasing the ruthenium removal rate. In one or more embodiments, the polishing composition can also include a chelating agent and / or an oxidizing agent. In one or more embodiments, the polishing composition according to the present disclosure includes from about 0.1 wt% to about 50 wt% of an abrasive, from about 0.01 wt% to about 10 wt% of a pH adjuster, from about 0.002 wt% to about 4 wt% of an agent for increasing the barrier film removal rate, from about 0.0005 wt% to about 5 wt% of a low-k removal rate inhibitor, from about 0.0001 wt% to about 1 wt% of an azole-containing corrosion inhibitor, from about 0.0001 wt% to about 5 wt% of an agent for increasing the ruthenium removal rate, and the balance by weight (e.g., from about 20 wt% to about 99 wt%) of a solvent (e.g., deionized water). In one or more embodiments, the polishing composition can further include from about 0.001 wt% to about 1 wt% of a chelating agent and / or from about 0.001 wt% to about 5 wt% of an oxidizing agent.

[0014] 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 before use. In other embodiments, the present disclosure provides a point-of-use (POU) polishing composition for use on a ruthenium-containing substrate, the POU polishing composition including the polishing composition, water, and optionally an oxidizing agent.

[0015] In one or more embodiments, the POU polishing composition can include from about 0.1 wt% to about 12 wt% of an abrasive, from about 0.01 wt% to about 5 wt% of a pH adjuster, from about 0.002 wt% to about 2 wt% of an agent for increasing the barrier film removal rate, from about 0.0005 wt% to about 0.5 wt% of a low-k removal rate inhibitor, from about 0.0001 wt% to about 0.1 wt% of an azole-containing corrosion inhibitor, from about 0.0001 wt% to about 0.5 wt% of an agent for increasing the ruthenium removal rate, optionally from about 0.001 wt% to about 5 wt% of an oxidizing agent, and from about 80 wt% to about 99 wt% of a solvent (e.g., deionized water). In one or more embodiments, the POU polishing composition can further include from 0. 001 wt% to 0.1 wt% of a chelating agent.

[0016] In one or more embodiments, the concentrated polishing composition can include from about 1 wt% to about 50 wt% abrasive, from about 0.1 wt% to about 10 wt% pH adjuster, from about 0.02 wt% to about 4 wt% barrier film rate enhancer, from about 0.005 wt% to about 5 wt% low-k removal rate inhibitor, from about 0.001 wt% to about 1 wt% azole-containing corrosion inhibitor, from about 0.001 wt% to about 5 wt% ruthenium removal rate enhancer, and the balance by weight (e.g., from about 20 wt% to about 98.5 wt%) of a solvent (e.g., deionized water). In one or more embodiments, the concentrated polishing composition can further include from about 0.01 wt% to about 1 wt% chelating agent and / or from about 0.001 wt% to about 5 wt% oxidizing agent.

[0017] In one or more embodiments, the polishing composition described herein can include at least one (e.g., two or three) abrasive. In some embodiments, the at least one abrasive is selected from the group consisting of cationic abrasives, substantially neutral abrasives, and anionic abrasives. In one or more embodiments, the at least one abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, their co-formed products (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 is of high purity and can contain less than about 100 ppm alcohol, less than about 100 ppm ammonia, and less than about 100 parts per billion (ppb) of alkali cations such as sodium cations. The abrasive can be present in an amount of from about 0.1% to about 12% (e.g., from about 0.5% to about 10%), or in any sub-range amount thereof, based on the total weight of the POU polishing composition.

[0018] 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) based on the polishing composition described in the present disclosure.

[0019] In one or more embodiments, the polishing composition described in the present disclosure can 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, 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.

[0020] In some embodiments, the at least one pH adjuster is present in an amount of about 0.01 wt% or more (e.g., about 0.05% or more, about 0.1 wt% or more, 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 6 wt% or more, or about 8 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) based on the polishing composition described in the present disclosure.

[0021] In some embodiments, the pH value of the polishing composition can be in the range of 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, a polishing composition having a pH less than 7 would significantly increase the copper removal rate and corrosion, and a polishing composition having a pH greater than 14 may affect the stability of the suspended abrasive, significantly increase the roughness, and degrade the overall quality of the film polished with such a composition. To obtain the desired pH, the relative concentrations of the components in the polishing composition described in the present disclosure can be adjusted.

[0022] In one or more embodiments, the polishing composition described in the present disclosure 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 (e.g., carboxylic acid, amino acid, sulfonic acid, or phosphonic acid) or a salt thereof. In some embodiments, the barrier film removal rate enhancer can be 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, 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, salts thereof, and mixtures thereof. Without wishing to be bound by theory, it is believed that an organic acid or a salt thereof (such as those described above) can be used as an effective barrier film removal rate enhancer in the polishing composition described in the present disclosure to improve the removal rate of a barrier film (e.g., Ta film or TaN film) in a semiconductor substrate.

[0023] In some embodiments, the barrier film removal rate enhancer is present in the polishing composition described in the present disclosure in an amount of about 0.002 wt% or more (e.g., about 0.005 wt% or more, about 0.01 wt% or more, about 0.05 wt% or more, about 0.1 wt% or more, about 0.15 wt% or more, about 0.2 wt% or more, about 0.5 wt% or more, about 1 wt% or more, about 1.5 wt% or more, or 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).

[0024] In one or more embodiments, the polishing composition described in the present disclosure can include at least one (e.g., two or three) low-k removal rate inhibitors. In some embodiments, the at least one 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 500 g / mol or more, or about 1000 g / mol or more, or about 2500 g / mol or more, or about 5000 g / mol or more, or about 7500 g / mol or more, or about 10000 g / mol or more. In one or more embodiments, the nonionic surfactant is a polymer having a number average molecular weight of about 1000000 g / mol or less, or about 750000 g / mol or less, or about 500000 g / mol or less, or about 250000 g / mol or less, or about 100000 g / mol or less. In one or more embodiments, the alkoxylate groups of the alkoxylated nonionic surfactant are ethoxylate groups, propoxylate groups, or a combination of ethoxylate groups and propoxylate groups. 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.

[0025] In some embodiments, the low-k removal rate inhibitor is present in the polishing composition described in the present disclosure in an amount of from about 0.0005 wt% or more (e.g., about 0.001 wt% or more, about 0.005 wt% or more, 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).

[0026] In one or more embodiments, the polishing composition described in the present disclosure can include at least one (e.g., two or three) azole-containing corrosion inhibitor. In some embodiments, the at least one azole-containing corrosion inhibitor is selected from the group consisting of substituted or unsubstituted triazoles, substituted or unsubstituted tetrazoles, substituted or unsubstituted benzotriazoles, substituted or unsubstituted pyrazoles, and substituted or unsubstituted imidazoles. In one or more embodiments, the azole-containing corrosion inhibitor can be selected from the group consisting of 1,2,4-triazole, 1,2,3-triazole, tetrazole, benzotriazole, tolyltriazole, ethylbenzotriazole (e.g., 1-methylbenzotriazole, 4-methylbenzotriazole, and 5-methylbenzotriazole), ethylbenzotriazole (e.g., 1-ethylbenzotriazole), propylbenzotriazole (e.g., 1-propylbenzotriazole), butylbenzotriazole (e.g., 1-butylbenzotriazole and 5-butylbenzotriazole), pentylbenzotriazole (e.g., 1-pentylbenzotriazole), hexylbenzotriazole (e.g., 1-hexylbenzotriazole and 5-hexylbenzotriazole), dimethylbenzotriazole (e.g., 5,6-dimethylbenzotriazole), chlorobenzotriazole (e.g., 5-chlorobenzotriazole), dichlorobenzotriazole (e.g., 5,6-dichlorobenzotriazole), chloromethylbenzotriazole (e.g., 1-(chloromethyl)-1-H-benzotriazole), chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, aminobenzimidazole, aminotetrazole, and mixtures thereof. In one or more embodiments, the composition may include benzotriazole and benzotriazole derivatives (e.g., substituted benzotriazole). Without wishing to be bound by theory, it is believed that the azole-containing corrosion inhibitor (e.g., as described above) can significantly reduce or minimize the removal rate of copper in the semiconductor substrate.

[0027] In some embodiments, the azole-containing corrosion inhibitor is present in the polishing composition described in the present disclosure 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).

[0028] In one or more embodiments, the polishing composition described in the present disclosure can include at least one (e.g., two or three) ruthenium removal rate enhancer. In some embodiments, the at least one ruthenium removal rate enhancer can include ammonium salts, thiocyanates, nitric acid or its salts, and halide salts. In some embodiments, the at least one ruthenium removal rate enhancer is selected from the group consisting of ammonium hydroxide, ammonium chloride, ammonium fluoride, ammonium bromide, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium phosphate, ammonium acetate, ammonium thiocyanate, potassium thiocyanate, sodium thiocyanate, nitric acid, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, and mixtures thereof.

[0029] In some embodiments, the ruthenium removal rate enhancer is present in an amount of about 0.0001 wt% to about 5 wt% based on the composition. In one or more embodiments, the ruthenium removal rate enhancer 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 5 wt% or less (e.g., about 4 wt% or less, about 3 wt% or less, about 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, 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) based on the polishing composition described in the present disclosure.

[0030] In one or more embodiments, the polishing composition described in the present disclosure can optionally include at least one (e.g., two or three) chelating agent. In some embodiments, the at least one optional chelating agent can be an amino-containing carboxylic acid (e.g., 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, triethylenetetraaminehexaacetic acid, diaminocyclohexanetetraacetic acid, nitrilotrimethylphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), 1-hydroxylethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and combinations thereof. Without wishing to be bound by theory, it is believed that including 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 a semiconductor substrate (e.g., defects on the surface of a copper wafer).

[0031] 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) based on the polishing composition described in the present disclosure.

[0032] Any oxidizer (or oxidizing agent) can be added when diluting the concentrated slurry to form the POU slurry. The oxidizer can be selected from the group consisting of hydrogen peroxide, ortho-periodic acid, meta-periodic acid, dimeso-periodic acid, diortho-periodic acid, ammonium periodate, potassium periodate, sodium periodate, ammonium persulfate, iodic acid, iodate, perchloric acid, perchlorate, hydroxylamine and hydroxylamine salts, and any combination thereof. In one or more embodiments, the oxidizer can be hydrogen peroxide.

[0033] In some embodiments, the oxidizer is present in an amount of about 0.001 wt% or more (e.g., about 0.002 wt% or more, about 0.004 wt% or more, about 0.005 wt% or more, about 0.01 wt% or more, about 0.025 wt% or more, about 0.05 wt% or more, about 0.075 wt% or more, about 0.1 wt% or more, about 0.5 wt% or more, about 1 wt% or more, or about 2 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) based on the polishing composition described in the present disclosure. In some embodiments, without wishing to be bound by theory, the oxidizer is thought to be able to assist in removing the hard mask material in the hard mask-containing substrate.

[0034] In some embodiments, the polishing composition described in the present disclosure can include a solvent such as water (e.g., a primary solvent). In some embodiments, the solvent (e.g., water) is 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) based on the polishing composition described in the present disclosure.

[0035] In one or more embodiments, an optional secondary solvent (e.g., an organic solvent) can be used in the polishing composition of the present disclosure (e.g., a POU or concentrated polishing composition), 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 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, dimethyl sulfoxide, and ethylene glycol.

[0036] In some embodiments, the secondary solvent is 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 5 wt% or less (e.g., about 4 wt% or less, about 3 wt% or less, about 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) based on the polishing composition described in the present disclosure.

[0037] In one or more embodiments, the polishing composition described in the present disclosure is substantially free of one or more specific components such as, for example, an organic solvent, a pH adjuster, a quaternary ammonium compound (e.g., a salt or a hydroxide), an amine, an alkali base (e.g., an alkali hydroxide), a fluorine-containing compound, a silicon-containing compound such as 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]nona-5-ene (DBN)), a salt (e.g., a halide salt or a metal salt), a polymer (e.g., a cationic polymer or an anionic polymer), a surfactant (e.g., a cationic surfactant, anionic surfactant, or nonionic surfactant), a plasticizer, an oxidizing agent (e.g., periodic acid), a corrosion inhibitor (e.g., an azole corrosion inhibitor or a non-azole corrosion inhibitor), and / or a specific abrasive (e.g., a ceria abrasive, a nonionic abrasive, a surface-modified abrasive, or a negatively / positively charged abrasive). Halide salts that can 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 can be fluoride, chloride, bromide, or iodide. As used in the present disclosure, a component that is "substantially absent" from the polishing composition refers to a component that is not intentionally added to the polishing composition. In some embodiments, the polishing composition described in the present disclosure may have one or more of the above components that are substantially absent from the polishing composition at about 1000 ppm or less (e.g., about 500 ppm or less, about 250 ppm or less, about 100 ppm or less, about 50 ppm or less, about 10 ppm or less, or about 1 ppm or less). In some embodiments, the polishing composition described in the present disclosure may not completely contain one or more of the above components.

[0038] The present disclosure also contemplates methods of using any of the above polishing compositions (e.g., concentrates or POU slurries). For a concentrate, the method can include diluting the concentrate (e.g., by a factor of two or more) to form a POU slurry, and then contacting a surface that at least partially includes ruthenium and / or a hard mask material with the POU slurry. In some embodiments, an oxidizing agent can be added to the slurry before, after, or during the dilution. For a POU slurry, the method includes contacting the surface that at least partially includes ruthenium and / or a hard mask material with the slurry.

[0039] In one or more embodiments, the present disclosure provides for applying a polishing composition according to the present disclosure to a substrate (e.g., a wafer) having at least ruthenium and / or a hard mask material on its surface; and contacting a pad with the surface of the substrate and moving the pad relative to the substrate, which can include a polishing method. In some embodiments, when the substrate includes at least one or more types of silicon oxides, ruthenium, copper, a hard mask material, and / or a barrier material (e.g., Ta, TaN), the method can effectively polish the substrate without significant corrosion or undesirable removal rate selectivity. In one or more embodiments, the copper removal rate is less than about 500 Å / min, or less than about 400 Å / min, or less than about 300 Å / min, or less than about 200 Å / min, or less than about 150 Å / min, or less than about 125 Å / min, or less than about 100 Å / min, or less than about 90 Å / min, or less than about 80 Å / min, or less than about 70 Å / min. In one or more embodiments, the static etch rate (SER) of a 2 cm × 2 cm copper test piece incubated at 45°C for 5 minutes with the polishing composition according to the present disclosure is less than about 10 Å / min, or less than about 8 Å / min, or less than about 6 Å / min, or less than about 5 Å / min, or less than about 4 Å / min, or less than about 3.5 Å / min, or less than about 2 Å / min, or less than about 2.5 Å / min. In one or more embodiments, the ruthenium removal rate is at least about 3 Å / min, or at least about 5 Å / min, or at least about 15 Å / min, or at least about 25 Å / min, or at least about 35 Å / min, or at least about 45 Å / min, or at least about 55 Å / min. In one or more embodiments, the ratio of the copper polishing rate to the ruthenium polishing rate (Cu:Ru) is less than or equal to a ratio of about 35:1, or less than or equal to a ratio of about 30:1, or less than or equal to a ratio of about 25:1, or less than or equal to a ratio of about 20:1, or less than or equal to a ratio of about 15:1, or less than or equal to a ratio of about 10:1, or less than or equal to a ratio of about 5:1, or less than or equal to a ratio of about   4:1, or less than or equal to a ratio of about 3:1, or less than or equal to a ratio of about 2.5:1, or less than or equal to a ratio of about 2:1, or less than or equal to a ratio of about 1.5:1, or less than or equal to a ratio of about 1:1.

[0040] The term "silicon oxide" as used herein is intended to include both undoped and doped silicon oxides. For example, in one or more embodiments, the silicon oxide may be doped with at least one dopant selected from carbon, nitrogen (for silicon oxide), 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.

[0041] 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 by one or more processes. For example, photolithography, ion implantation, dry / wet etching, plasma etching, deposition (e.g., PVD, CVD, ALD, ECD), wafer mounting, die cutting, packaging, and testing can be used to manufacture a semiconductor device from a substrate treated with the polishing composition described herein.

[0042] 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]

[0043] In these examples, polishing was performed using two polishing systems. The first polishing system used an Ebara CMP polisher with a Fujibo soft pad, a downforce pressure of 105 hPa, and a slurry flow rate of 100 mL / min to 500 mL / min to polish 300 mm wafers. The second polishing system used an AMAT Mirra CMP polisher with a Fujibo soft pad, a downforce pressure of 1.5 psi, and a slurry flow rate of 100 mL / min to 400 mL / min to polish 200 mm wafers.

[0044] The general compositions used in the following examples are shown in Table 1 below. Specific details regarding the differences in the compositions tested will be described in more detail when explaining each example.

[0045]

Table 1

[0046] Example 1 Table 2 below shows the removal rates of Ru, Cu, and black diamond (BD-1) blanket wafers when polished using Compositions 1-6. Compositions 1-6 contained the same components at the same concentration except for the differences shown below and in Table 2. The BD-1 blanket wafer is a low-k dielectric material (i.e., carbon-doped silicon oxide) coated on a silicon wafer.

[0047] Composition 1 contained a Cu removal rate inhibitor (Cu RRI), which was an azole-containing corrosion inhibitor. Each of Compositions 2-5 contained a ruthenium removal rate enhancer (Ru RRE) at different concentrations, as shown in Table 2. Compositions 6 and 7 contained Ru RRE and two Cu removal rate inhibitors (i.e., Cu RRI-1 and Cu RRI-2), both of which were azole-containing corrosion inhibitors. Composition 8 contained only one of Ru RRE and Cu RRI.

[0048] The results surprisingly showed that the addition of Ru RRE increased the Ru removal rate to an acceptable range of about 30 Å / min. Furthermore, the Cu removal rate increased with the addition of Ru RRE but could be appropriately controlled by the addition of the second Cu RRI. In addition, these results showed that the removal rate of BD-1 was not significantly affected by the addition of Ru RRE and Cu-RRI-2.

[0049]

Table 2

[0050] In the above, a few exemplary embodiments have been described in detail. However, those skilled in the art will readily understand that many modifications are possible in the above exemplary embodiments without substantially departing from the present invention. Therefore, all of those modifications are intended to be included within the scope of the present disclosure as defined in the following claims. (Additional Note) The present disclosure includes the following aspects. Item 1: A polishing agent; A pH adjuster; An agent for increasing the barrier film removal rate; A low-k removal rate inhibitor; An azole-containing anticorrosive agent; and An agent for increasing the ruthenium removal rate A polishing composition comprising the same. Item 2: The polishing composition according to Item 1, wherein the polishing agent is selected from the group consisting of alumina; silica; titania; ceria; zirconia; a co-formed product of alumina, silica, titania, ceria, or zirconia; a coated polishing agent; a surface-modified polishing agent; and mixtures thereof. Item 3: The polishing composition according to Item 1, wherein the polishing agent is present in an amount of about 0.1% by weight to about 50% by weight of the composition. Item 4: The polishing composition according to Item 1, wherein the agent for increasing the barrier film removal rate 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, 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, salts thereof, and mixtures thereof. Item 5: The polishing composition according to Item 1, wherein the agent for increasing the barrier film removal rate is present in an amount of about 0.002% by weight to about 4% by weight of the composition. Item 6: The polishing composition according to Item 1, wherein the low-k removal rate inhibitor is a nonionic surfactant. Item 7: The polishing composition according to Item 6, 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. Item 8: The polishing composition according to Item 1, wherein the low-k removal rate inhibitor is present in an amount of about 0.0005% by weight to about 5% by weight of the composition. Item 9: The polishing composition according to item 1, wherein the azole-containing corrosion inhibitor is selected from the group consisting of triazole, tetrazole, benzotriazole, tolyltriazole, 1,2,4-triazole, ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, dimethylbenzotriazole, chlorobenzotriazole, dichlorobenzotriazole, chloromethylbenzotriazole, chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, aminobenzimidazole, pyrazole, imidazole, aminotetrazole, and mixtures thereof. Item 10: The polishing composition according to item 1, wherein the azole-containing corrosion inhibitor is present in an amount of about 0.0001 wt% to about 1 wt% of the composition. Item 11: The polishing composition according to item 1, 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. Item 12: The polishing composition according to item 1, wherein the pH adjuster is present in an amount of about 0.01 wt% to about 10 wt% of the composition. Item 13: The polishing composition according to claim 1, wherein the ruthenium removal rate enhancer is selected from the group consisting of ammonium hydroxide, ammonium chloride, ammonium fluoride, ammonium bromide, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium phosphate, ammonium acetate, ammonium thiocyanate, potassium thiocyanate, sodium thiocyanate, nitric acid, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, and mixtures thereof. Item 14: The polishing composition according to claim 1, wherein the ruthenium removal rate enhancer is present in an amount of about 0.0001 wt% to about 5 wt% of the composition. Item 15: The polishing composition according to 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, triethylenetetraaminehexaacetic acid, diaminocyclohexanetetraacetic acid, nitrilotrimethylphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), 1-hydroxylethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and combinations thereof. Item 16: The polishing composition according to claim 15, wherein the chelating agent is present in an amount of about 0.001 wt% to about 1 wt% of the composition. Item 17: The polishing composition according to claim 1, further comprising an oxidizing agent selected from the group consisting of hydrogen peroxide, orthoperiodic acid, metaperiodic acid, dimethoperiodic acid, diorthoperiodic acid, ammonium periodate, potassium periodate, sodium periodate, ammonium persulfate, iodic acid, iodate, perchloric acid, perchlorate, hydroxylamine and hydroxylamine salts, and any combinations thereof. Item 18: The composition is the abrasive in an amount of about 0.1 wt% to about 50 wt% of the composition; the pH adjuster in an amount of about 0.01 wt% to about 10 wt% of the composition; the barrier film removal rate enhancer in an amount of about 0.002 wt% to about 4 wt% of the composition; the low-k removal rate inhibitor in an amount of about 0.0005 wt% to about 5 wt% of the composition ; The azole-containing corrosion inhibitor in an amount of about 0.0001% to about 1% by weight of the composition; and The ruthenium removal accelerator in an amount of about 0.0001% to about 5% by weight of the composition The polishing composition according to claim 1, comprising the same. Claim 19: The polishing composition according to claim 1, wherein the pH of the composition is from about 7 to about 14. Claim 20: A polishing agent; A pH adjuster; An organic acid or its salt; A nonionic surfactant; An azole-containing corrosion inhibitor; and A compound selected from the group consisting of ammonium salts, thiocyanates, halide salts, nitrates, nitric acid, and mixtures thereof A polishing composition comprising the same. Claim 21: A step of applying the polishing composition according to claim 1 to the surface of a substrate, wherein the surface contains ruthenium or a hard mask material; and A step of bringing a pad into contact with the surface of the substrate and moving the pad relative to the substrate A method of polishing a substrate, comprising the same.

Claims

1. A polishing agent; a pH adjuster; a low-k removal rate inhibitor; an azole-containing corrosion inhibitor; and a ruthenium removal rate enhancer comprising, wherein the ruthenium removal rate enhancer is selected from the group consisting of ammonium hydroxide, ammonium chloride, ammonium fluoride, ammonium bromide, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium phosphate, ammonium acetate, ammonium thiocyanate, potassium thiocyanate, sodium thiocyanate, nitric acid, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, and mixtures thereof, a polishing composition having a pH of 7 to 14.

2. The polishing composition according to claim 1, wherein the polishing agent is selected from the group consisting of alumina; silica; titania; ceria; zirconia; co-formed products of alumina, silica, titania, ceria, or zirconia; coated polishing agents; surface-modified polishing agents; and mixtures thereof.

3. The polishing composition according to claim 1, wherein the polishing agent is present in an amount of 0.1% to 50% by weight of the polishing composition.

4. The polishing composition according to claim 1, further comprising a barrier film removal rate enhancer.

5. The polishing composition according to claim 4, wherein 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, peracetic acid, succinic 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, salts thereof, and mixtures thereof.

6. The polishing composition according to claim 4, wherein the barrier film removal rate enhancer is present in an amount of 0.002% to 4% by weight of the polishing composition.

7. The polishing composition according to claim 1, wherein the low-k removal rate inhibitor is a nonionic surfactant.

8. The polishing composition according to claim 7, 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.

9. The polishing composition according to claim 1, wherein the low-k removal rate inhibitor is present in an amount of 0.0005 wt% to 5 wt% of the polishing composition.

10. The polishing composition according to claim 1, wherein the azole-containing corrosion inhibitor is selected from the group consisting of triazole, tetrazole, benzotriazole, tolyltriazole, 1,2,4-triazole, ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, dimethylbenzotriazole, chlorobenzotriazole, dichlorobenzotriazole, chloromethylbenzotriazole, chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, aminobenzimidazole, pyrazole, imidazole, aminotetrazole, and mixtures thereof.

11. The polishing composition according to claim 1, wherein the azole-containing corrosion inhibitor is present in an amount of 0.0001 wt% to 1 wt% of the polishing composition.

12. The polishing composition according to claim 1, 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.

13. The polishing composition according to claim 1, wherein the pH adjuster is in an amount of 0.01% to 10% by weight of the polishing composition.

14. The polishing composition according to claim 1, wherein the ruthenium removal rate increasing agent is in an amount of 0.0001% to 5% by weight of the polishing composition.

15. The polishing composition according to 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, triethylenetetraaminehexaacetic acid, diaminocyclohexanetetraacetic acid, nitrilotrimethylphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), 1-hydroxylethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and combinations thereof.

16. The polishing composition according to claim 15, wherein the chelating agent is in an amount of 0.001% to 1% by weight of the polishing composition.

17. The polishing composition according to claim 1, further comprising an oxidizing agent selected from the group consisting of hydrogen peroxide, orthoperiodic acid, metaperiodic acid, dimethyldioxirane, diorthoperiodic acid, ammonium periodate, potassium periodate, sodium periodate, ammonium persulfate, iodic acid, iodates, perchloric acid, perchlorates, hydroxylamine and hydroxylamine salts, and any combinations thereof.

18. The polishing composition is the abrasive in an amount of 0.1% to 50% by weight of the polishing composition; the pH adjuster in an amount of 0.01% to 10% by weight of the polishing composition; the low-k removal rate inhibitor in an amount of 0.0005% to 5% by weight of the polishing composition ； the azole-containing corrosion inhibitor in an amount of 0.0001% to 1% by weight of the polishing composition; and the ruthenium removal rate increasing agent in an amount of 0.0001% to 5% by weight of the polishing composition and includes the polishing composition according to claim 1.

19. The polishing composition according to claim 18, further comprising a barrier film removal rate increasing agent in an amount of 0.002% to 4% by weight of the polishing composition.

20. Abrasive; pH adjuster; Organic acid or its salt; Nonionic surfactant; Azole-containing corrosion inhibitor; and A compound selected from the group consisting of ammonium hydroxide, ammonium chloride, ammonium fluoride, ammonium bromide, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium phosphate, ammonium acetate, ammonium thiocyanate, potassium thiocyanate, sodium thiocyanate, nitric acid, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, and mixtures thereof comprising a polishing composition having a pH of 7 to 14.

21. A step of applying the polishing composition according to claim 1 to the surface of a substrate, wherein the surface contains ruthenium or a hard mask material; and a step of bringing a pad into contact with the surface of the substrate and moving the pad relative to the substrate A method for polishing a substrate, comprising.

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