TWI421931B - Method of passivating chemical mechanical polishing compositions for copper film planarization processes - Google Patents

Description

Passivation method for chemical mechanical polishing composition in copper film planarization process

The present invention relates to a chemical mechanical polishing composition, and to a wafer substrate having copper (e.g., copper interconnect, electrode, or metallization) thereon as part of the structure of a microelectronic device using the composition. method.

Copper is widely used in semiconductor fabrication as a construction material for components of microelectronic device structures (eg, contacts, electrodes, conductive vias, field emitter substrates, etc.) and because of its relative to aluminum and aluminum alloys High conductivity and increased electromigration resistance quickly become the preferred interconnect metal in semiconductor manufacturing.

Typically, the program flow for utilizing copper in semiconductor fabrication involves a damascene method in which features are etched into the dielectric material. In the dual damascene method, a single step is used to form both the plug and the line. Since copper has a tendency to diffuse into the dielectric material, which can cause leakage between the metal lines, a barrier layer (such as Ta or TaN) deposited using various deposition methods is generally used to seal the copper interconnect. After depositing the barrier layer material, a thin copper seed layer is deposited on the barrier material by physical vapor deposition, and then copper is electrodeposited to fill the features. The deposited copper must then be planarized to give it a suitable form suitable for the subsequent method steps of fabricating the finished semiconductor product, and to allow the microcircuits present therein to function satisfactorily. Flattening typically involves the use of chemical mechanical polishing (CMP) formulated to provide a CMP composition for such use.

Due to the difference in chemical reactivity between copper and barrier layer materials (eg, Ta and/or TaN), two chemically different slurries are typically used in copper CMP processes. The step I slurry is used to quickly planarize the surface morphology and remove copper, wherein the step I grinding terminates in the barrier layer material. The Step II slurry removes the barrier layer material at a high removal rate and terminates in the dielectric layer, or terminates in a coating applied to the protective dielectric.

Step I for Copper Flattening and Grinding The chemical mechanical polishing (CMP) composition is typically comprised of a suitable type of abrasive in a solvent medium containing one or more solvent species (eg, water, organic solvents, etc.) For example, a slurry form selected from the group consisting of vermiculite, alumina, and other abrasives of mineral and mineral materials. Typically, the Step I slurry has a high copper removal rate and a removal rate selectivity of the barrier material from greater than 100:1 copper.

One type of CMP composition for planarizing a copper surface includes an aqueous slurry comprising abrasive particles of hydrogen peroxide as the oxidizing component and glycine as the chelating agent. It has been found that glycine reacts with a solution phase Cu ^{+ 2} ion formed by oxidizing Cu metal to form a Cu ^{2 +} -glycine complex. The mismatch of Cu ^{+ 2} ions by the formation of a water-soluble Cu ^{2 +} -glycine tongs helps to remove Cu in the protruding regions through the direct dissolution mechanism, and the Cu ^{2 +} -glycine is wrong The compound decomposes hydrogen peroxide to produce a hydroxyl radical having a higher oxidation potential than hydrogen peroxide itself.

In the step I CMP slurry, a benzotriazole (BTA) compound is usually included as a corrosion inhibitor. In theory, BTA ( , FW: 119.13) is misaligned with copper to form an insoluble Cu-BTA complex on the copper surface. The resulting insoluble protective film can promote the planarization of the surface morphology of the fabricated device structure by protecting the depressed regions on the surface of the wafer from being dissolved, and at the same time, the mechanical action of the abrasive species on the protruding regions can be performed. Remove and flatten. In addition, the Cu-BTA complex minimizes corrosion and maintains the copper device structure for its functional integrity for the intended use.

It is known that BTA can also act as a copper corrosion inhibitor in the absence of OH radicals. However, in the copper CMP slurry of step I containing hydrogen peroxide and glycine, since the copper metal is susceptible to oxidation in such a slurry environment, it is unavoidable to generate highly oxidized OH radicals under dynamic CMP conditions. Experiments involving the addition of Cu ^{2 +} to the H ₂ O ₂ /glycine/BTA system show that the presence of Cu ^{2 +} can greatly increase the static etch rate of Cu, and at the same time, the Cu corrosion potential can be shifted to a lower range.

The significance of this discovery is that in the presence of H ₂ O ₂ and glycine, BTA does not effectively protect the low-profile features of the copper wafer surface during the CMP process, thus placing high-density patterned regions on the wafer substrate. Undesirable "dishing" and erosion occur.

The dishing phenomenon occurs when excess copper is removed such that the copper surface is recessed relative to the barrier and/or dielectric surface of the semiconductor wafer. The dishing phenomenon occurs when the removal rates of copper and barrier materials are different. Oxide attack occurs when excess dielectric material is removed.

An alternative to the use of BTA as a corrosion inhibitor in CMP compositions includes 5-aminotetrazole (ATA), which is compatible with H ₂ O ₂ /glycine-based CMP compositions, and when processed in CMP A significant amount of Cu ions are present in the bulk solution and/or near the metal/solution interface, which is effective to passivate the copper surface.

In step I, the overall copper is quickly removed and then "soft landing" or "touchdown", wherein the grinding conditions are changed until the underlying barrier material is exposed, which may use an endpoint detection system such as Determined by an in situ rate monitor (ISRM). Although the end point has been detected, a signal indicating the exposure of the barrier layer material is issued, but the overburden of copper remains, which must be removed, and therefore, an over-grinding step is usually performed. Unfortunately, "soft landing" and over-grinding steps often result in dishing and/or erosion into the copper features, which can result in wafer surface flatness and uniformity loss.

In the step I CMP process, the step I CMP slurry advantageously removes copper quickly. However, in soft landing and/or over-grinding, this rapid copper removal rate can be detrimental due to the formation of various surface defects such as depressions, erosion, dishing, and the like on the surface of the copper layer. The net result of the overly aggressive Step I slurry during soft landing and/or over-grinding is a wafer substrate with a non-uniform flat surface that can render the wafer unusable.

Accordingly, it would be a significant advancement in the art to provide a method that overcomes the prior art's lack of rapid copper removal rates during the soft landing and/or over-grinding steps of the Step I CMP process. In particular, it would be an advancement in the art to provide a method of reducing the static etch rate of copper during the soft landing and/or over-grinding steps of the step I polishing process, and thus reducing copper attack.

The present invention relates to a chemical mechanical polishing composition and a method of using the same for polishing a substrate of a microelectronic device having copper thereon. Furthermore, the invention further relates to a method of slowing the copper removal rate during the soft landing and/or overgrinding step of the step I polishing process.

In one aspect, the invention relates to a method of polishing copper on a substrate having copper thereon, comprising: (a) subjecting copper on the substrate to chemical mechanical polishing (CMP) conditions and the first CMP composition Contacting for sufficient time and planarizing the overall copper under sufficient contact conditions; (b) diluting the first CMP composition with a solvent to produce a second CMP composition; (c) causing copper on the substrate to be associated with the second CMP composition The CMP conditions are contacted for a sufficient period of time and under sufficient contact conditions to effectively remove the copper overlying layer and expose the barrier material layer.

In another aspect, the present invention is directed to a method of polishing copper on a substrate having copper thereon, comprising: (a) forming copper on the substrate under chemical mechanical polishing (CMP) conditions with a first CMP composition Contacting the substrate for a sufficient period of time and under sufficient contact conditions to planarize the overall copper, wherein the first CMP composition comprises 5-aminotetrazole (ATA) and at least one chelating agent, wherein the chelating agent comprises at least one selected Amino group of free glycine, serine, valine, leucine, alanine, aspartic acid, aspartic acid, glutamic acid, lysine and lysine (b) diluting the first CMP composition with a solvent to produce a second CMP composition; (c) contacting the copper on the substrate with the second CMP composition under CMP conditions for a sufficient time and under sufficient contact conditions The copper over-cover layer is effectively removed and the barrier material layer is exposed.

In another aspect, the present invention is directed to a method of polishing copper on a substrate having copper thereon, comprising: (a) forming copper on the substrate under chemical mechanical polishing (CMP) conditions with a first CMP composition Receiving sufficient time to planarize the overall copper under sufficient contact conditions, wherein the first CMP composition comprises 5-aminotetrazole (ATA), at least one oxidizing agent, at least one chelating agent, and a solvent; (b) Diluting the first CMP composition with a solvent to produce a second CMP composition; (c) contacting the copper on the substrate with the second CMP composition under CMP conditions for a sufficient time and effectively removing the copper under sufficient contact conditions Overlying the cover layer and exposing the barrier material layer.

In still another aspect, the present invention is directed to a method of fabricating a microelectronic device, the method comprising: (a) contacting copper on a substrate with a first CMP composition under CMP conditions for a sufficient time, and sufficient Flattening the overall copper under contact conditions; (b) diluting the first CMP composition with a solvent to produce a second CMP composition; and (c) contacting the copper on the substrate with the second CMP composition under CMP conditions Time and under sufficient contact conditions to effectively remove the copper overburden and expose the barrier material layer.

In still another aspect, the present invention is directed to a method of fabricating a microelectronic device, the method comprising: (a) contacting copper on a substrate with a first CMP composition under CMP conditions for a sufficient time, and sufficient The overall copper is planarized under contact conditions, wherein the first CMP composition comprises 5-aminotetrazole (ATA) and at least one chelating agent, wherein the chelating agent comprises at least one selected from the group consisting of glycine, serine a group of amino acids consisting of lysine, leucine, alanine, aspartic acid, aspartic acid, glutamic acid, lysine and lysine; (b) diluted with solvent The first CMP composition produces a second CMP composition; and (c) contacting the copper on the substrate with the second CMP composition under CMP conditions for a sufficient time and effectively removing the copper under sufficient contact conditions The cover layer and the barrier material layer are exposed.

In still another aspect, the present invention is directed to a method of fabricating a microelectronic device, the method comprising: (a) contacting copper on a substrate with a first CMP composition under CMP conditions for a sufficient time and sufficient Flattening the overall copper under contact conditions, wherein the first CMP composition comprises 5-aminotetrazole (ATA), at least one oxidizing agent, at least one chelating agent, and a solvent; (b) diluting the first CMP composition with a solvent to produce a second CMP composition; and (c) contacting the copper on the substrate with the second CMP composition under CMP conditions for a sufficient time and effectively removing the copper overlying layer and the barrier material under sufficient contact conditions The layer is exposed.

In still another aspect, the present invention is directed to a method of determining a relationship between a static etch rate and a chemical mechanical polishing (CMP) composition dilution, the method comprising: (a) preparing a first CMP composition; b) measuring a first static etch rate of the material to be ground using the first CMP composition; (c) diluting the first CMP composition with a solvent to produce a second CMP composition; (d) measuring the material to be ground using the second CMP composition a second static etch rate; (e) repeating steps (c) and (d) as needed to produce a third CMP composition and measuring a third static etch rate; (f) using a logarithmic scale to form a static etch rate into a CMP composition The dilution ratio is plotted as a function; and (g) the nonlinear regression equation is calculated, wherein the regression equation is the relationship between the static etch rate and the CMP composition dilution.

In another aspect, the present invention is directed to a kit comprising a chemical mechanical polishing (CMP) composition reagent contained in one or more containers, wherein the CMP composition comprises 5-aminotetrazole (ATA) And at least one nipper, wherein the chelating agent comprises at least one selected from the group consisting of glycine, serine, valine, leucine, alanine, aspartic acid, aspartic acid, glutamic acid, An amino acid consisting of a combination of proline and lysine, and wherein the kit is adapted to form a microelectronic device suitable for overcoating a layer of copper thereon to planarize the entire copper and move the copper Except for the CMP composition.

In still another aspect, the present invention is directed to a kit comprising a chemical mechanical polishing (CMP) composition reagent contained in one or more containers, wherein the CMP composition comprises 5-aminotetrazole (ATA At least one oxidizing agent, at least one chelating agent, and a solvent, and wherein the kit is adapted to form a CMP suitable for planarizing and removing copper from a microelectronic device having an overlying layer of copper thereon Composition.

Other aspects, features and specific examples of the invention will be apparent from the appended claims and appended claims.

The basis of the present invention is the discovery of 5-aminotetrazole (ATA, , FW: 85.06) Unexpectedly, BTA can be effectively substituted as a copper corrosion inhibitor in the step I CMP composition for planarizing a copper film. ATA is compatible with CMP compositions containing hydrogen peroxide as the oxidizing agent and glycine as the chelating agent. Even when there are significant amounts of copper ions in the CMP processing (e.g., Cu ^{2 +} cations) present in the entire solution and / or a metal / solution interface, the ATA-containing CMP composition may achieve effective passivation of the copper surface.

The basis of the present invention is further that it is found that diluting the CMP slurry composition during the soft landing and/or over-grinding step of the CMP process achieves effective passivation of the exposed copper.

The "soft landing" or "landing" as defined herein corresponds to the grinding process of step I to some extent, wherein the downward pressure of the grinder can be reduced and/or the composition of step I can be changed to reduce the copper wiring and connection. The dishing phenomenon and/or erosion of the plug. Soft landing is preferably achieved when the thickness of the copper layer on the barrier material is reduced to a range from about 0.05 microns to about 0.4 microns.

"Excessive grinding" after a soft landing removes the copper overburden from the surface of the barrier material while minimizing the additional dishing or erosion of the copper features.

The "about" used herein is equivalent to ± 5% of the stated value.

The "microelectronic device" used herein is equivalent to a semiconductor substrate, a flat panel display, and a microelectromechanical system (MEMS) manufactured for use in microelectronics, integrated circuits, or computer chip applications. It should be understood that the term "microelectronic device" is not meant to be limiting, and it includes any substrate that will eventually become a microelectronic device or microelectronic assembly.

The barrier layer material as defined herein includes a layer that can be deposited/disposed between the copper interconnect layer and the dielectric material layer to substantially prevent copper ions from leaking into the dielectric material, wherein the barrier material layer comprises a layer selected from the group consisting of Ta a compound of the group consisting of TaN, Ti, TiN, W, WN, a telluride thereof, and combinations thereof.

As used herein, a "microelectronic device" having an overlying cap layer of copper thereon planarizes the overall copper and removes the copper by at least partially removing the copper from the microelectronic device. Preferably, at least 90% of the copper is removed from the microelectronic device using the composition of the present invention, at least 95% of the copper is more preferred, and at least 99% of the copper is most preferred.

The use of "Yu" in the text to flatten the overall copper "after" dilution of the CMP composition corresponds to immediately before the soft landing step, in the soft landing step and in the over-grinding step.

The ATA-containing CMP composition of the present invention broadly comprises ATA, at least one chelating agent, solvent medium, optionally at least one oxidizing agent, optionally at least one additional corrosion inhibitor, optionally abrasive, and optionally Suitable additives, adjuvants, excipients, and the like, such as stabilizers, acids, bases (e.g., amines), surfactants, buffers, and the like. The molar ratio of the tying agent to ATA in the CMP composition ranges from about 1:1 to about 20:1, more preferably from about 3:1 to about 10:1; and the oxidant (when present) is relative to ATA. The ear ratio ranges from about 5:1 to about 30:1, preferably from about 10:1 to about 20:1; and the range of abrasive (when present) relative to ATA is about 0.1:1 to about 10:1, about 1:1 to about 3:1 is better.

The oxidizing agent used in the broad practice of the present invention may be of any suitable type including, for example, hydrogen peroxide (H ₂ O ₂ ), iron nitrate (Fe(NO ₃ ) ₃ ), potassium iodate (KIO ₃ ), Potassium manganate (KMnO ₄ ), nitric acid (HNO ₃ ), ammonium iron (III) oxalate, ammonium iron (III) citrate, ammonium chlorite (NH ₄ ClO ₂ ), ammonium chlorate (NH ₄ ClO ₃ ), ammonium iodate (NH ₄ IO ₃ ), ammonium perborate (NH ₄ BO ₃ ), ammonium perchlorate (NH ₄ ClO ₄ ), ammonium periodate (NH ₄ IO ₃ ), ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), tetramethylammonium chlorite ((N(CH ₃ ) ₄ )ClO ₂ ), tetramethylammonium chlorate ((N(CH ₃ ) ₄ )ClO ₃ ), tetramethyl iodate) ammonium _{((N (CH 3) 4} ) IO 3), tetramethylammonium perborate _{((N (CH 3) 4} ) BO 3), tetramethylammonium perchlorate _{((N (CH 3) 4} ) ClO 4) , tetramethylammonium periodate ((N(CH ₃ ) ₄ ) IO ₄ ), tetramethylammonium persulfate ((N(CH ₃ ) ₄ )S ₂ O ₈ ), urea peroxide ((CO(NH ₂ )) ₂ ) H ₂ O ₂ ), peracetic acid (CH ₃ (CO)OOH), potassium peroxoborate, bromate, benzoquinone, hypochlorite, hypoiodate, oxybromide, percarbonate, Periodate, cerium salt (eg ammonium cerium sulfate), chromate and dichromate compounds, copper (II) cyanide Salt of ferricyanide, iron phenanthroline, pyridine iron, ferrocenium (ferrocinium), amine oxides such as N- methyl -N- porphyrin-N-oxide (NMMO), trimethylamine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide, N-ethyl Polino-N-oxide, N-methylpyrrolidine-N-oxide, N-ethylpyrrolidine-N-oxide; and substituted derivatives or combinations thereof. Preferred oxidizing agents include peracetic acid, urea peroxide, di-tert-butyl peroxide, benzyl peroxide, hydrogen peroxide, and compatible mixtures comprising two or more of such oxidizing agent species. The oxidant includes hydrogen peroxide as the best.

The tying agent in the CMP composition of the present invention may be of any suitable type including, for example, an amino acid such as glycine, serine, valine, leucine, alanine, aspartic acid, and the like. Aspartic acid, glutamic acid, lysine, lysine, etc.; polyamine complexes and salts thereof, including ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, nitrogen triacetic acid , iminodiacetic acid, diethylenetriamine pentaacetic acid, and ethanoldiglycinate; polycarboxylic acid, including capric acid, oxalic acid, malic acid, succinic acid, phenylglycolic acid, and mellitic acid And a compatible mixture comprising two or more of the foregoing species. Preferred chelating agents include amino acids, with glycine being preferred.

The corrosion inhibitor component of the CMP composition of the present invention comprises ATA, and in a specific embodiment of the present invention, other corrosion inhibitor components may be additionally included in combination with ATA. These other corrosion inhibitor ingredients may be of any suitable type including, for example, imidazole, benzotriazole, benzimidazole, amine, imido, carboxyl, sulfhydryl, nitro, alkyl, urea, and thiourea Compounds and derivatives thereof and the like. Preferred inhibitors include tetrazole and its derivatives, and thus, the present invention contemplates providing a separate ATA or in combination with other tetrazole (or other corrosion inhibitor) species as a corrosion inhibitor in the compositions according to the present invention.

ATA is used in the CMP composition of the present invention at any suitable concentration. The appropriate ATA concentration in a particular formulation can be readily determined experimentally within the skill set based on the disclosure herein, even if the CMP composition with appropriate copper surface passivation characteristics is provided in a CMP environment containing high copper cation content. Things. In a preferred embodiment of the invention, the amount of ATA in the CMP composition is in the range of from about 0.001 to about 10% by weight based on the total weight of the CMP composition, based on the same total weight. The amount of ATA is preferably in the range of from about 0.01 to about 5% by weight, and the amount of ATA in the range of from about 0.10 to about 1.5% by weight is optimal, although more widely used in the broad scope of the invention Large or smaller percentages for specific applications.

The abrasive can be of any suitable type including, but not limited to, metal oxides, tantalum nitride, carbides, and the like. Clear examples include vermiculite, alumina, tantalum carbide, tantalum nitride, iron oxide, cerium oxide, zirconium oxide, tin oxide, titanium dioxide, and in suitable forms (such as grains, fines, granules, or other divided forms) a mixture of two or more of these components. Alternatively, the abrasive may comprise composite particles formed from two or more materials, for example, NYACOL Alumina colloidal vermiculite (Nyacol Nano Technologies, Inc., Ashland, MA). Alumina is a preferred inorganic abrasive and can be used in the form of boehmite or transitional δ, θ or γ-phase alumina. Organic polymer particles can be utilized, for example, including thermosetting and/or thermoplastic resins, as abrasives. Useful resins in the broad practice of the present invention include epoxies, urethanes, polyesters, polyamides, polycarbonates, polyolefins, polyvinyl chloride, polystyrene, polyolefins, and (A) Base) acrylic resin. A mixture of two or more kinds of organic polymer particles may be used as the grinding medium, and particles containing both inorganic and organic components.

A pH adjustment can be carried out using a base in the composition of the present invention as needed. Illustrative bases include, for example, potassium hydroxide, ammonium hydroxide, and tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methyltris(hydroxyethyl) hydroxide. Ammonium, tetrakis (hydroxyethyl) ammonium hydroxide, and benzyltrimethylammonium hydroxide.

It is also possible to use an acid for pH adjustment in the composition of the present invention. The acid used may be of any suitable type including, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, lactic acid, hydrochloric acid, nitric acid, Phosphoric acid, sulfuric acid, hydrofluoric acid, malic acid, fumaric acid, malonic acid, glutaric acid, glycolic acid, salicylic acid, 1,2,3-benzenetricarboxylic acid, tartaric acid, gluconic acid, citric acid And citric acid, pyroic acid, gallic acid, gallic acid, monodecanoic acid, and mixtures comprising two or more acids of the foregoing or other types.

The amine when present may be of any suitable type including, for example, hydroxylamine, monoethanolamine, diethanolamine, triethanolamine, diglycolamine, N-hydroxyethylpiper , N-methylethanolamine, N,N-dimethylethanolamine, N-ethylethanolamine, N,N-diethylethanolamine, propanolamine, N,N-dimethylpropanolamine, N-ethyl Propylamine, N,N-diethylpropanolamine, 4-(2-hydroxyethyl) Phenanthine And a mixture comprising two or more of the foregoing or other amine species.

Surfactants which may be used in the compositions of the present invention may be of any suitable type, including nonionic, anionic, cationic, and amphoteric surfactants, and polymeric electrolytes including, for example, salts of organic acids; alkane sulfates ( For example, sodium dodecyl sulfate; alkane sulfonate; substituted amine salt (eg, cesium bromide); betaine; polyethylene oxide; polyvinyl alcohol; polyvinyl acetate; polyacrylic acid; Vinyl pyrrolidone; polyethyleneimine; and sorbitan ester, such as commercially available under the registered trademark TWeen And Span The seller, as well as a mixture comprising two or more of the foregoing or other surfactant types.

The pH of the CMP composition of the present invention can be any suitable value that is effective for the particular milling operation used. In one embodiment, the pH of the CMP composition can range from about 2 to about 11, more preferably from about 2 to about 7, and most preferably from about 3 to about 6.

The solvent used in the CMP composition of the present invention may be a single component solvent or a multicomponent solvent depending on the particular application. In one embodiment of the invention, the solvent in the CMP composition is water. In another embodiment, the solvent comprises an organic solvent such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerin or the like. In yet another embodiment, the solvent comprises a water-organic solvent solution. A wide variety of solvent types and specific solvent media can be used in the general practice of the invention to provide a solvate/suspension medium in which the abrasive is dispersed and to which other ingredients are added, while providing a composition of suitable characteristics, for example, as a slurry The form is applied to a press table of the CMP unit to provide a desired degree of grinding of the copper on the wafer substrate.

In a particularly preferred embodiment, the ATA-containing CMP composition comprises ATA and a chelating agent, wherein the chelating agent comprises at least one member selected from the group consisting of glycine, serine, valine, leucine, alanine, and aspartic acid. A group of amino acids consisting of proline, aspartic acid, glutamic acid, lysine and lysine. The molar ratio of the chelating agent to the ATA in the CMP composition is from about 1:1 to about 20:1, more preferably from about 3:1 to about 10:1.

In another preferred embodiment, the ATA-containing CMP composition comprises ATA and glycine.

In yet another preferred embodiment, the present invention provides a step I CMP composition suitable for chemical mechanical polishing of a substrate having copper (e.g., copper interconnects, metallization, device structural components, etc.) thereon, wherein The composition contains hydrogen peroxide, glycine, ATA, and a solvent.

In yet another preferred embodiment, the present invention provides a step I CMP composition suitable for chemical mechanical polishing of a substrate having copper (e.g., copper interconnects, metallization, device structural components, etc.) thereon, wherein The composition comprises hydrogen peroxide, glycine, ATA, an abrasive, and a solvent.

In another embodiment, the CMP composition of the present invention is an aqueous abrasive composition comprising an aqueous medium, an abrasive, ATA, H ₂ O ₂ and glycine, wherein ATA, H ₂ O ₂ and glycine have The following composition by weight based on the total weight of the composition: ATA 0.001-10% by weight H ₂ O ₂ 0.1-30% by weight glycine 0.1-25% by weight water 35-99% by weight

In yet another specific illustrative embodiment, the CMP composition comprises the following composition by weight based on the total weight of the composition: ATA 0.001-10% by weight H ₂ O ₂ 0.1-30% by weight glycine 0.1-25 weight % abrasive 0.1-30% by weight water 5-99% by weight

The total weight % of all the components in the composition was 100% by weight.

In still another preferred embodiment, the ATA-containing CMP composition comprises ATA, at least one metal chelating agent, solvent, CMP residual material, optionally at least one oxidizing agent, and optionally an abrasive, wherein the CMP residual material comprises Abrasive slurry, carbon-rich particles, abrasive pad particles, brushed falling particles, particles of equipment construction materials, copper, copper oxides, and any other material that is a by-product of the CMP process.

The CMP compositions of the present invention can be provided in a single package formulation or as a plurality of formulations that are mixed during use or mixed in a reservoir upstream of the tool. The advantage of multiple formulations is their extended shelf life relative to a single package formulation. Due to the presence of oxidizing agents in a single packaged CMP composition, single package formulations are more susceptible to decomposition and their properties over time relative to multiple formulations. In the broad practice of the invention, the concentration of individual packages of a single package or multiple formulations may vary widely within a particular multiple, ie, more dilute or more concentrated, and when it is apparent that the CMP composition of the present invention may vary and alternatively Any combination of ingredients that are consistent with the disclosure herein, consists of, or consists essentially of, a combination thereof.

In one embodiment, the individual components of the CMP composition are individually transferred to a polishing station for bonding to the mesa to form a CMP composition for use. In another embodiment, the CMP composition is formulated as a two-part composition, wherein the first portion comprises an abrasive and a corrosion inhibitor in an aqueous medium, and the second portion comprises an oxidizing agent and a chelating agent. In yet another embodiment, the CMP composition is formulated as a two-part composition, wherein the first portion comprises an abrasive, a corrosion inhibitor, and a chelating agent in an aqueous medium, and the second portion comprises an oxidizing agent. In all of these various specific examples, the ingredients or portions are mixed to form a final composition which, when used, is mixed on a polishing table, a polishing belt, in a transfer line, or the like, shortly before reaching the polishing table. In a suitable container, or at the CMP composition manufacturer and / or supplier.

Accordingly, another aspect of the invention is directed to a kit comprising an ingredient contained in one or more containers suitable for forming a composition of the invention as described above. The kit includes at least one corrosion inhibitor and at least one chelating agent contained in one or more containers for bonding with the at least one oxidant at the point of manufacture. According to another embodiment, the kit includes at least one corrosion inhibitor, abrasive, and at least one chelating agent for combining at least one oxidant at the point of manufacture. According to yet another embodiment, the kit includes at least ATA, abrasive, and glycine for binding to at least one oxidant at the point of manufacture. The container of the kit must be suitable for storing and transporting the components of the CMP composition, for example, NOWPak Container (Advanced Technology Materials, Inc., Danbury, Conn., USA).

The copper CMP composition of the present invention can be utilized in CMP operations in a conventional manner by applying the CMP composition to the copper surface on the substrate of the microelectronic device in a conventional manner, and conventional abrasive elements such as polishing pads can be used. Grinding tape, or the like, for grinding the copper surface.

The CMP composition of the present invention can be advantageously used to polish the surface of a copper component on a substrate of a microelectronic device without causing dishing or other unfavorable planarization defects in the ground copper, even when in CMP processing. the overall CMP slurry composition and / or in the presence of significant amounts of copper / copper interface CMP slurries ions (e.g., Cu ^{2 +} ions) EVEN.

Step I The CMP slurry advantageously removes copper rapidly in the Step I CMP process. However, when the step I process enters a soft landing and/or over-grinding period, this rapid copper removal rate can be detrimental due to the formation of various surface defects such as recesses, erosion, dishing, etc. on the surface of the copper layer. .

To limit the overly aggressive CMP slurry composition during the soft landing and/or over-grinding step of the step I milling step, the step I CMP slurry of the present invention can be diluted in a continuous manner. Accordingly, another embodiment of the present invention is directed to a method of planarizing a copper-containing microelectronic device substrate efficiently and uniformly using a CMP composition. After the entire copper layer is quickly removed using a more concentrated CMP composition, the CMP composition is diluted by in-line mixing or directly on the platen to form a process for the soft landing and over-grinding steps. Dilute CMP composition. The diluent medium preferably comprises a solvent of the step I CMP composition and may or may not further comprise at least one pH adjusting agent to alter the pH of the diluted CMP composition, or an additional corrosion inhibitor to improve the soft landing. Additional oxidizing agents or selective reinforcing agents such as rheological agents that minimize Ta removal rates may also be included to promote passivation.

To confirm the effect of dilution on the corrosion rate of copper, the step I CMP composition was diluted twice in a stepwise manner and the Cu corrosion rate was determined electrochemically. The "Cu corrosion rate" defined in the text is equivalent to the "static etch rate". For example, the initial Step I CMP composition comprises 5% by weight H ₂ O ₂ , 6% by weight glycine, 1% by weight abrasive, different concentrations of ATA, and the balance of water. In order to simulate the accelerating effect of corrosive copper ions in the solution, a Cu ^{2 +} -glycine complex which decomposes H ₂ O ₂ to form a highly oxidizing OH radical is formed, which is 0.5% by weight of CuSO ₄ . 5 H ₂ O was added to the initial step I CMP composition. In each case, step I CMP composition comprising ATA and step I CMP comprising 5% by weight of H ₂ O ₂ , 6% by weight of glycine, 1% by weight of abrasive, 0.1% by weight of BTA, and the balance of water For comparison of the composition, the BTA-containing solution also contained 0.5% by weight of CuSO ₄ . 5 H ₂ O.

The two-step I CMP composition (hereinafter referred to as slurry 1) is gradually diluted with water to produce a second CMP slurry (1 part slurry 1 to 5 parts water; hereinafter referred to as slurry 2) and a third CMP slurry (1 part slurry 1 pair) 50 parts of water; hereinafter referred to as slurry 3). The blanketed copper wafer was immersed in each of the separate slurries and the Cu corrosion rate in angstroms per minute was measured. The average Cu corrosion rate was plotted as a function of CMP slurry dilution using linear and logarithmic scales.

It should be noted that the number of consecutive dilutions of the slurry 1 (i.e., the most concentrated CMP slurry) is not limited to the two dilutions described above. The number of dilutions depends on the final desired result of the step I CMP milling, and it can vary from one stepwise dilution to ten or more stepwise dilutions. Alternatively, the dilution can be achieved in a continuous manner wherein the diluent solvent is continuously added to the CMP slurry in a soft landing and/or over-grinding step. In yet another alternative, the slurry 1 itself is not diluted, but a diluted CMP composition is prepared to deliver a clean, diluted chemical to the tool after grinding with the slurry 1.

Figures 1 and 2 are linear and logarithmic plots, respectively, corresponding to the average Cu corrosion rate of the step I CMP slurry having an ATA concentration of 0.1% by weight as a function of CMP slurry dilution. The nonlinear regression for the best-fit line in Figure 2 with the slurry of ATA yields a power relationship between the corrosion rate and the slurry dilution of y = 14.396x ^{- 0 . 4 8 8 1} .

Figures 3 and 4 are linear and logarithmic plots, respectively, corresponding to the average Cu corrosion rate of the step I CMP slurry having a ATA concentration of 0.8% by weight as a function of CMP slurry dilution. The nonlinear regression for the best-fit line in Figure 4 with the slurry of ATA yields a power relationship between the corrosion rate and the slurry dilution of y = 10.306x ^{- 0 . 5 0 2 4} .

Figures 5 and 6 are linear and logarithmic plots, respectively, corresponding to the average Cu corrosion rate of the step I CMP slurry having an ATA concentration of 1.2 wt% as a function of CMP slurry dilution. The non-linear regression of the best-fit line in Figure 6 with the slurry of ATA yields a power relationship between the corrosion rate and the slurry dilution of y = 8.0513x ^{- 0 . 5 5 1 7} .

In each case, the copper corrosion rate decreases as the slurry dilution increases. This confirms that it is beneficial to slow the rate of copper corrosion during the soft landing and over-grinding steps, and to minimize the dishing and erosion of copper lines, channels, and/or plugs. Furthermore, as evidenced by the slope of the regression line, ATA has a lower total corrosion rate and a faster reduction in corrosion with increasing dilution compared to compositions containing BTA.

These power relationships between copper corrosion rate and slurry dilution provide a means of controlling the static etching of Cu during the step I CMP milling. To achieve acceptable planarization of the wafer surface at an efficient etch rate, while having a minimum amount of dishing, prior to soft landing of step I CMP, during soft landing, and/or during over-grinding Slurry 1 is diluted at certain points during the process, which can be readily determined by those skilled in the art. The "integral layer" as defined herein means a copper layer which is quickly removed by the step I CMP composition of the present invention (for example, slurry 1), and the "residual layer" means a copper layer remaining after removing the entire layer. An overcoat layer comprising copper is removed at a slower rate, for example, using Slurry 2, Slurry 3, and the like. By diluting the overly aggressive slurry 1 at the appropriate point in the CMP milling, abrasive burrs such as dishing and erosion can be substantially eliminated.

The diluent solvent (e.g., water) can be delivered to the polishing station at an appropriate time and in an appropriate amount based on a regression equation specific to the selected slurry composition, as readily determined by those skilled in the art. In practice, Slurry 1 can be diluted in a continuous manner and the Cu corrosion rate of each composition can be measured using Tafel or some equivalent measurement. A logarithmic plot of the Cu corrosion rate as a function of slurry dilution can be plotted, and a nonlinear regression equation can be calculated. Using regression equations and knowledge of the wafer to be polished, such as film thickness, removal rate, etc., those skilled in the art can decide to transfer the dilution solvent to the polishing station to slow the static etch rate of copper to such a The appropriate time and appropriate amount of the rate at which the dish phenomenon is minimized.

The CMP composition of the present invention can be diluted in a continuous manner to achieve substantial removal of the residual layer of copper while minimizing the dishing and erosion of the copper lines and plugs, as readily determined by those skilled in the art. "Substantial removal" as defined herein is equivalent to removing at least 80% of the residual layer of copper using the series of steps I CMP, at least 90% is preferred, at least 95% is better, and at least 99% is most good.

The dilution procedure can also be considered here, in which the polishing table can be connected to a programmable logic control (PLC) unit and the regression equation of the selected CMP slurry can be input to the PLC. It can be controlled by the PLC and an appropriate amount of dilution solvent is delivered to the polishing station at the appropriate time.

After the step I CMP procedure is completed, the platen and the substrate are rinsed with a solvent. The solvent is preferably the same as the user (e.g., water) in the step I CMP composition described herein. The rinsing time may range from about 5 seconds to about 30 seconds, preferably from about 10 seconds to about 20 seconds. Thereafter, the wafer substrate can be transferred to another press table to perform the step II polishing thereon.

The features and advantages of the present invention are more fully described by the following non-limiting examples in which all parts and percentages are by weight unless otherwise specified.

(Example 1)

Tool error corrosion studies were performed to demonstrate the effectiveness of dilution to slow the corrosion of the exposed copper surface (ie, the etch rate). The Sematech 854 (TEOS) wafer was ground on the Mirra tool using the step I CMP slurry, and after the step I was polished on the second platen, after removing all copper residual material, but transferring the wafer Before the third press to perform the step II grinding, the tool is manually adjusted to the tool error condition, which positions the wafer on the cleaner between the press tables. The wafer was sprayed with deionized water for 15 minutes during the tool error mode.

After completion of the step I polishing, the wafer surface is comprised of copper features surrounded by the barrier layer material and isolated from the electrically insulating dielectric material. It is reported that the conventional step of containing BTA I CMP slurry is ineffective for eliminating corrosion (i.e., etching) of exposed copper features during incorrect spraying of the tool between the press tables. To this end, the CMP composition of the present invention comprising ATA was used during the grinding of step I, and the corrosion of the exposed copper features was evaluated after the inter-press tool was erroneously sprayed with deionized water.

It was found that wafers ground using the ATA-containing composition of the present invention showed no signs of copper characteristic corrosion after 15 minutes of tool error conditions, even when the ATA-containing composition was subjected to constant dilution. In fact, the number of turns calculated on the tool-error wafer (obtained on the AIT (KLA-Tencor) tool) is actually lower than the control wafer that does not accept the hand tool error condition. The topdown SEM image of the copper features on the wafer surface showed no signs of corrosion, confirming the results of the enthalpy.

The results show that the ATA-containing compositions of the present invention provide better copper corrosion protection than conventional BTA-containing compositions when diluted or extended.

Although the present invention has been described with reference to the specific aspects, features, and description of the present invention, it is understood that the utility of the present invention is not limited thereby, but may be extended to cover many other variations, modifications, and alternative embodiments. It will be readily apparent to those skilled in the art from this disclosure based on the disclosure herein. Accordingly, the invention, which is set forth in the appended claims, is to be construed broadly,

Figure 1 is the copper corrosion rate (unit: angstroms per minute) to 0.1% ATA / H ₂ O ₂ / glycine acid slurry dilution ratio (◆) and 0.1% BTA / H ₂ O ₂ / glycine acid slurry dilution ratio (■ A diagram of the function of ).

Figure 2 is a logarithmic plot showing the copper corrosion rate in Figure 1 as a function of the ATA/H ₂ O ₂ /glycine slurry dilution ratio and the BTA/H ₂ O ₂ /glycine slurry dilution ratio.

Figure 3 is the copper corrosion rate (unit: angstroms per minute) to 0.8% ATA / H ₂ O ₂ / glycine acid slurry dilution ratio (◆) and 0.1% BTA / H ₂ O ₂ / glycine acid slurry dilution ratio (■ A diagram of the function of ).

Figure 4 is a logarithmic plot showing the copper corrosion rate in Figure 3 as a function of the ATA/H ₂ O ₂ /glycine slurry dilution ratio and the BTA/H ₂ O ₂ /glycine slurry dilution ratio.

Figure 5 is the copper corrosion rate (unit: angstroms per minute) to 1.2% ATA / H ₂ O ₂ / glycine acid slurry dilution ratio (◆) and 0.1% BTA / H ₂ O ₂ / glycine acid slurry dilution ratio (■ A diagram of the function of ).

Figure 6 is a logarithmic plot showing the copper corrosion rate in Figure 5 as a function of the ATA/H ₂ O ₂ /glycine slurry dilution ratio and the BTA/H ₂ O ₂ /glycine slurry dilution ratio.

Claims (56)

A method of polishing copper on a substrate having copper thereon, comprising: (a) contacting copper on the substrate with a first CMP composition under chemical mechanical polishing (CMP) conditions effective to planarize the overall copper; Diluting the first CMP composition with a solvent to produce a second CMP composition; (c) allowing the copper on the substrate and the second CMP composition to effectively remove copper overburden and expose the barrier material layer Contact under CMP conditions. The method of claim 1, wherein the first CMP composition comprises 5-aminotetrazole (ATA), at least one oxidizing agent, at least one chelating agent, and a solvent. The method of claim 2, wherein the at least one oxidizing agent comprises at least one compound selected from the group consisting of hydrogen peroxide, di-tert-butyl peroxide, benzyl peroxide, nitric acid Iron, potassium iodate, potassium permanganate, ammonium (III) oxalate, ammonium iron (III) citrate, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, Ammonium periodate, ammonium persulfate, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, persulfate Tetramethylammonium, carbamide peroxide, peracetic acid, potassium peroxoborate, bromate, benzoquinone, hypochlorite, hypoiodate, oxybromide, percarbonate, periodate, ammonium sulphate , a chromate compound, a dichromate compound, a copper (II) cyanide salt, a ferricyanide salt, an iron morpholine, an iron pyridine, a ferrocenium, and combinations thereof. The method of claim 2, wherein the at least one chelating agent comprises at least one chelating agent selected from the group consisting of glycine, serine, valine, leucine, alanine, Aspartic acid, aspartic acid, glutamic acid, valine, lysine, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, nitrogen triacetic acid, iminodiamide Acetic acid, diethylenetriamine pentaacetic acid, ethanoldiglycinate, citric acid, oxalic acid, malic acid, succinic acid, phenylglycolic acid, mellitic acid, and combinations thereof. The method of claim 2, wherein the at least one chelating agent comprises glycine. The method of claim 2, wherein the first CMP composition further comprises another corrosion inhibitor in combination with ATA, wherein the another corrosion inhibitor comprises at least one inhibitor selected from the group consisting of: Imidazole, benzotriazole, benzimidazole, tetrazole, tetrazole derivatives, urea compounds, thiourea compounds and derivatives thereof. The method of claim 2, wherein the first CMP composition further comprises an abrasive, wherein the abrasive comprises at least one abrasive selected from the group consisting of vermiculite, alumina, tantalum carbide, tantalum nitride And a mixture of two or more of iron oxide, cerium oxide, zirconium oxide, tin oxide, titanium dioxide, colloidal vermiculite coated with alumina, a thermosetting resin, a thermoplastic resin, and the like in an appropriate form. The method of claim 2, wherein the first CMP composition further comprises a pH adjuster selected from the group consisting of acids and bases. The method of claim 1, wherein the first CMP group The product has a pH in the range of 2 to 11. The method of claim 2, wherein the first CMP composition has a pH in the range of 2 to 11. The method of claim 1, wherein the solvent comprises water. The method of claim 2, wherein the solvent comprises water. The method of claim 1, wherein the first CMP composition is diluted with a solvent in a dilution range of 1:2 to 1:100. The method of claim 1, wherein the first CMP composition is diluted with a solvent in a dilution range of 1:5 to 1:50. The method of claim 1, wherein the static etch rate of copper using the first CMP composition is greater than the static etch rate of copper using the second CMP composition. The method of claim 1, wherein the CMP condition comprises using an abrasive element on the copper, wherein the abrasive element comprises at least one element selected from the group consisting of a polishing pad and a polishing tape. The method of claim 1, further comprising diluting the second CMP composition with a solvent to produce a third CMP composition, and contacting the copper on the substrate with the third CMP composition under CMP conditions for a sufficient time, and The overlying cover layer of copper is substantially removed under sufficient contact conditions and the barrier material layer is exposed. The method of claim 1, wherein the static etching rate of the copper using the first CMP composition is higher than the copper using the second CMP composition. The static etch rate is 2 to 10 times faster. For example, the method of claim 1 of the patent scope, wherein the dilution system is gradually achieved. The method of claim 1, wherein the dilution is continuously achieved. The method of claim 1, wherein the barrier layer material comprises ruthenium. The method of claim 2, wherein the first CMP composition further comprises a surfactant. The method of claim 1, wherein the first CMP composition is diluted by in-line mixing to produce a second CMP composition. The method of claim 1, wherein the first CMP composition is diluted directly to the CMP stage to produce a second CMP composition. The method of claim 1, wherein the first CMP composition is diluted prior to soft-landing to produce a second CMP composition during soft landing or during over-grinding. The method of claim 2, wherein the first CMP composition further comprises an abrasive, and wherein ATA, the at least one oxidizing agent, the at least one chelating agent, and the solvent have the following weight concentrations based on the total weight of the composition : The solvent is 5-99% by weight. The method of claim 1, wherein the solvent comprises a species selected from the group consisting of water, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerin, and combinations thereof. The method of claim 1, wherein the first CMP composition comprises 5-aminotetrazole (ATA). A method of fabricating a semiconductor device, comprising the method of polishing copper on a substrate of claim 1 and further comprising incorporating the substrate into a semiconductor device. The method of claim 1, wherein the first CMP composition comprises at least one oxidizing agent. A method of determining a relationship between a static etch rate and a chemical mechanical polishing (CMP) composition dilution, the method comprising: (a) preparing a first CMP composition; (b) measuring a material to be ground using the first CMP composition a first static etch rate; (c) diluting the first CMP composition with a solvent to produce a second CMP composition; (d) measuring a second static etch rate of the material to be ground using the second CMP composition; (e) as needed Repeating steps (c) and (d) to produce a third CMP composition and measuring a third static etch rate; (f) plotting the static etch rate as a function of the CMP composition dilution ratio using a logarithmic scale; and (g) Calculating a nonlinear regression equation, where the regression equation is static The relationship between the etch rate and the dilution of the CMP composition. The method of claim 31, further comprising repeating step (e) at least once. The method of claim 31, wherein the first CMP composition comprises 5-aminotetrazole (ATA). The method of claim 31, wherein the solvent comprises water. The method of claim 33, wherein the first CMP composition further comprises an abrasive, wherein the abrasive comprises at least one abrasive selected from the group consisting of vermiculite, alumina, tantalum carbide, tantalum nitride And a mixture of two or more of iron oxide, cerium oxide, zirconium oxide, tin oxide, titanium dioxide, colloidal vermiculite coated with alumina, a thermosetting resin, a thermoplastic resin, and the like in an appropriate form. The method of claim 33, wherein the first CMP composition further comprises at least one oxidizing agent, wherein the oxidizing agent comprises at least one compound selected from the group consisting of hydrogen peroxide, di-tert-butyl Peroxide, benzyl peroxide, iron nitrate, potassium iodate, potassium permanganate, ammonium iron (III) oxalate, ammonium iron (III) citrate, ammonium chlorite, ammonium chlorate, iodic acid Ammonium, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethyl perchlorate Ammonium, tetramethylammonium periodate, tetramethylammonium persulfate, urea peroxide, peracetic acid, potassium peroxoborate, bromate, benzoquinone, hypochlorite, hypoiodate, oxybromide salt, Carbonate, periodate, ammonium sulphate, chromate compound, dichromate compound, copper (II) cyanide salt, Ferricyanide salt, iron morpholine, iron pyridine, ferrocenium, and combinations thereof. The method of claim 33, wherein the first CMP composition further comprises at least one chelating agent, wherein the at least one chelating agent comprises at least one chelating agent selected from the group consisting of glycine, silk Aminic acid, valine acid, leucine, alanine, aspartic acid, aspartic acid, glutamic acid, lysine, lysine, ethylenediaminetetraacetic acid, N-hydroxyethyl Diamine triacetic acid, nitrogen triacetic acid, diethylenetriamine pentaacetic acid, ethanolimine diacetate, citric acid, oxalic acid, malic acid, succinic acid, phenylglycolic acid, and mellitic acid. The method of claim 33, wherein the first CMP composition further comprises a solvent, wherein the solvent comprises water. The method of claim 31, wherein the first CMP composition is diluted with a solvent in a dilution range of from about 1:2 to about 1:100. For example, the method of claim 31, wherein the dilution is gradually achieved. The method of claim 31, wherein the dilution is continuously achieved. The method of claim 31, wherein the regression equation is used to control the static etch rate of copper. The method of claim 31, wherein the solvent is delivered to the first CMP composition to slow the static etch rate of the copper. The method of claim 33, wherein the first CMP composition further comprises an abrasive, and wherein ATA, the at least one oxidizing agent, the at least one chelating agent, and the solvent have the following weight concentrations based on the total weight of the composition : The total weight percentage of such components in the composition does not exceed 100% by weight. The method of claim 33, wherein the static etch rate of copper using the first CMP composition is greater than the static etch rate of copper using the second CMP composition. The method of claim 2, wherein the at least one oxidizing agent comprises at least one compound selected from the group consisting of nitric acid, N-methyl porphyrin-N-oxide (NMMO), trimethylamine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide, N-ethyl Porphyrin-N-oxide, N-methylpyrrolidine-N-oxide, N-ethylpyrrolidine-N-oxide, and combinations thereof. The method of claim 1, wherein the barrier layer material comprises a compound selected from the group consisting of titanium, titanium nitride, tungsten, tungsten nitride, telluride thereof, and combinations thereof. The method of claim 1, wherein the first CMP composition comprises at least one chelating agent. The method of claim 1, wherein the first CMP composition comprises a solvent. The method of claim 2, wherein the oxidant package Contains hydrogen peroxide. The method of claim 6, wherein the another corrosion inhibitor comprises at least one inhibitor selected from the group consisting of imidazole, benzotriazole, benzimidazole, tetrazole and tetrazole derivatives . The method of claim 1, wherein the barrier layer material comprises tantalum nitride. The method of claim 30, wherein the at least one oxidizing agent comprises at least one compound selected from the group consisting of hydrogen peroxide, di-tert-butyl peroxide, benzyl peroxide, nitric acid Iron, potassium iodate, potassium permanganate, ammonium (III) oxalate, ammonium iron (III) citrate, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, Ammonium periodate, ammonium persulfate, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, persulfate Tetramethylammonium, carbamide peroxide, peracetic acid, potassium peroxoborate, bromate, benzoquinone, hypochlorite, hypoiodate, oxybromide, percarbonate, periodate, ammonium sulphate , a chromate compound, a dichromate compound, a copper (II) cyanide salt, a ferricyanide salt, an iron phenanthroline, an iron pyridine, a ferrocenium, and combinations thereof. The method of claim 48, wherein the at least one forceps comprises at least one chelating agent selected from the group consisting of glycine, serine, valine, leucine, alanine, Aspartic acid, aspartic acid, glutamic acid, valine, lysine, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, nitrogen triacetic acid, iminodiamide Acetic acid, diethylenetriamine pentaacetic acid, ethanolimine diacetate (ethanoldiglycinate), citric acid, oxalic acid, malic acid, succinic acid, phenylglycolic acid, mellitic acid, and combinations thereof. The method of claim 48, wherein the at least one forceps comprises glycine. The method of claim 1, wherein the first CMP composition further comprises a pH adjuster.