Polishing compositions and methods of use thereof

Abstract

To provide polishing compositions which can avoid or minimize deleterious effects of high corrosion inhibitor levels (i.e., poor copper clearance rates and / or residue defects).SOLUTION: This disclosure features a polishing composition that includes: at least one abrasive; at least one first corrosion inhibitor that includes a phosphate group or a phosphonate group; at least one complexing agent; at least one second corrosion inhibitor that is at least one azole compound; and optionally a pH adjuster.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims priority to U.S. Provisional Application No. 63 / 002,537, filed March 31, 2020, the contents of which are incorporated herein by reference in their entirety. [Background technology]

[0002] A process known as chemical-mechanical polishing (CMP) involves polishing various metallic or non-metallic layers on a semiconductor wafer using a polishing pad and polishing composition. Copper is a material commonly used to form interconnects in semiconductor manufacturing. When copper inlaid structures are formed, for example, by a damascene process, the isolated copper wiring is exposed by a polishing process that removes the barrier metal between the copper and the inlaid wiring. Copper bulk layer and copper barrier layer CMP involves polishing the copper layer and the barrier layer. It is desirable to perform polishing at a high material removal rate to increase throughput while maintaining good wafer characteristics, such as a low overall defect count.

[0003] A typical copper bulk CMP process generally involves two process steps: an initial Cu bulk step, which rapidly removes most of the Cu overburden, and a subsequent, less aggressive clearing step, which removes the remainder of the Cu overburden and stops on the barrier layer. In the initial Cu bulk polishing step, the electroplated copper overburden (up to 2 μm thick, depending on the technology node) is rapidly polished with a relatively large downforce until the deposition topography is substantially planarized, but some copper overburden remains. Subsequently, the copper overburden remaining from the first step is polished with a smaller downforce, and polishing stops on the barrier layer. The overall goal is to remove all copper from the barrier material with high throughput and planarization efficiency while minimizing defects (e.g., copper dishing, scratching, organic residues, etc.).

[0004] During the second polishing step, a phenomenon called dishing occurs, resulting in a lowering of the level of the top surface of the interconnect material (e.g., copper). This is believed to be due to excessive removal of the Cu interconnect material during the polishing process performed toward the end of the second polishing step (i.e., stopping on the barrier layer). Overpolishing removes all Cu residues from the entire wafer surface. Two factors influence the final degree of dishing during overpolishing. The first factor is the continuous mechanical attack on the Cu lines. This occurs when the polishing pad mechanically contacts the recessed Cu lines, conforming to the periphery of the feature, and then further polishes them during overpolishing. The second factor is the continuous chemical etching of the Cu lines due to their continued contact with the polishing composition during overpolishing. Dishing reduces the cross-sectional area of ​​the interconnect, thereby causing an undesirable increase in interconnect resistance. Dishing also impairs the planarity of the semiconductor device surface. This places a burden on subsequent copper barrier CMP steps to correct the topographical imbalance before multi-filmed interconnect formation in semiconductor devices is possible. Summary of the Invention

[0005] This Summary is provided to introduce a selection of concepts that are further described below in the Detailed Description. This Summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0006] In one aspect, the disclosure features a polishing composition that includes at least one abrasive, at least one first corrosion inhibitor including a phosphate or phosphonate group, at least one complexing agent, at least one second corrosion inhibitor including at least one azole compound, and optionally at least one pH adjuster, wherein the amount of the at least one first corrosion inhibitor in the polishing composition is such that the polishing composition dissolves about 3 wt. % to 10 wt. % of CuO from the solid CuO powder, when the polishing composition is immersed in a weight ratio of CuO:polishing composition of about 1:2500 at 25° C. for 2 minutes to form a mixture, the mixture is centrifuged to form a supernatant, and the amount of Cu ions dissolved in the supernatant is measured by ICP-MS.

[0007] In another aspect, the disclosure features a polishing composition that includes at least one abrasive, at least one first corrosion inhibitor including a phosphate group or a phosphonate group, at least one complexing agent, and at least one second corrosion inhibitor including at least one azole compound, wherein the amount of the at least one first corrosion inhibitor in the polishing composition is such that, when a 4 cm × 4 cm copper-containing patterned coupon is immersed in 50 g of the polishing composition at 45° C. for 5 minutes to form a mixture, the amount of Cu species in the mixture is measured by ICP-MS to determine whether the amount of Cu species is about 1 ppm to about 10 ppm.

[0008] In another aspect, the disclosure features a method of polishing a substrate, including contacting copper on a surface of the substrate with a polishing composition described herein.

[0009] Other aspects and advantages of the claimed subject matter will become apparent from the following description and appended claims. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a plot showing the dissolution of Cu 2 O by polishing compositions each containing four different primary corrosion inhibitors at various POU concentrations. [Figure 2] FIG. 2 is a plot showing the dissolution of CuO by polishing compositions each containing four different primary corrosion inhibitors at various POU concentrations. [Figure 3] FIG. 3 is a plot showing Cu ion concentrations in liquid samples collected and measured by ICP after treating CuTaTaNBD pattern coupons with a polishing composition containing a first corrosion inhibitor. DETAILED DESCRIPTION OF THE INVENTION

[0011] As defined herein, all percentages expressed should be understood to be weight percent based on the total weight of the composition unless otherwise specified. The term "solvent" referred to herein refers to a single solvent or a combination of two or more (e.g., three or four) solvents unless otherwise specified. In this disclosure, "ppm" means "parts per million" based on the total weight of the composition, and "ppb" means "parts per billion" based on the total weight of the composition.

[0012] The goal of the CMP process is to remove all copper from the barrier layer while significantly reducing dishing of the inlaid copper interconnects, resulting in a nearly defect-free, low surface roughness. Therefore, the polishing composition must strike a careful balance between facilitating copper removal but not removing enough copper to cause undesirable severe dishing and / or corrosion (e.g., galvanic corrosion). To this end, compounds that function as corrosion inhibitors have been added to CMP compositions. While this approach has met with some success, copper residues left on the wafer can become problematic if too high a concentration of corrosion inhibitor is used.

[0013] Due to the presence of oxidizing agents in polishing compositions, copper oxides typically form on exposed copper surfaces during the polishing process. To effectively polish copper (i.e., at an acceptable rate, with minimal defects, etc.), additives that control the solubility / removability of these copper oxides are crucial. Ultimately, an effective polishing composition generally strikes a desirable balance between controlled chemical passivation film formation (e.g., primarily CuO / CuO passivation films) and mechanical film removal to achieve not only sufficient Cu protection against corrosion but also sufficient Cu removal rates. Corrosion inhibitors in slurries can be useful for adjusting the aggressiveness of the slurry's oxidizing agents and can work in combination with complexing agents to control the properties of surface passivation films (e.g., mechanical integrity, porosity, thickness, and solubility). Different classes of copper corrosion inhibitors have different affinities for copper (e.g., via lone pairs and / or π electrons), different copper protection mechanisms, different diffusion properties and time scales of action, different temperature dependencies, and different wettability and solubility when bound to Cu. Therefore, combining multiple Cu corrosion inhibitors often offers advantages over using a single corrosion inhibitor. In general, corrosion inhibitors facilitate polishing when used in the correct amount, but can have a negative effect on polishing when used in the wrong amount (e.g., too little can lead to excessive corrosion, and too much can result in copper residue and / or unacceptably low Cu polishing rates).

[0014] In one or more embodiments, the polishing compositions described herein can minimize dishing and corrosion (i.e., galvanic corrosion) while using a minimal amount of corrosion inhibitor. This allows the use of compositions of the present disclosure to avoid or minimize the adverse effects of high amounts of corrosion inhibitor (i.e., reduced copper removal rate and / or residue defects).

[0015] In one or more embodiments, the polishing composition described herein can include at least one abrasive, at least one first corrosion inhibitor comprising a phosphate or phosphonate group, at least one complexing agent, at least one second corrosion inhibitor comprising at least one azole compound, and optionally at least one pH adjuster. Optionally, a dynamic surface tension reducing agent can be included in the polishing composition described herein.

[0016] In one or more embodiments, the polishing composition according to the present disclosure can comprise from about 0.01 wt % to about 50 wt % of at least one abrasive, from about 0 wt % to about 1 wt % of at least one pH adjuster, from about 0.0001 wt % to about 0.2 wt % of at least one first corrosion inhibitor, from about 0.01 wt % to about 20 wt % of at least one complexing agent, from about 0.0001 wt % to about 5 wt % of at least one second corrosion inhibitor, and the remaining wt % (e.g., from about 20 wt % to about 99 wt %) of a solvent (e.g., deionized water).

[0017] In one or more embodiments, the present disclosure provides concentrated polishing compositions that can be diluted with water up to 2x, or up to 4x, or up to 6x, or up to 8x, or up to 10x, or up to 15x, or up to 20x before use. In other embodiments, the present disclosure provides point-of-use (POU) polishing compositions for use on copper-containing substrates, comprising the polishing composition described above, water, and optionally an oxidizing agent.

[0018] In one or more embodiments, the POU polishing composition can comprise from about 0.01 wt % to about 25 wt % of at least one abrasive, from about 0 wt % to about 0.5 wt % of at least one pH adjuster, from about 0.0001 wt % to about 0.01 wt % of at least one first corrosion inhibitor, from about 0.01 wt % to about 10 wt % of at least one complexing agent, from about 0.0001 wt % to about 2.5 wt % of at least one second corrosion inhibitor, and the remaining wt % (e.g., from about 50 wt % to about 99 wt %) of a solvent (e.g., deionized water).

[0019] In one or more embodiments, the concentrated polishing composition can comprise from about 0.01 wt % to about 50 wt % of at least one abrasive, from about 0 wt % to about 1 wt % of at least one pH adjuster, from about 0.002 wt % to about 0.2 wt % of at least one first corrosion inhibitor, from about 0.2 wt % to about 20 wt % of at least one complexing agent, from about 0.002 wt % to about 5 wt % of at least one second corrosion inhibitor, and the remaining wt % (e.g., from about 20 wt % to about 99 wt %) of a solvent (e.g., deionized water).

[0020] In one or more embodiments, at least one abrasive (e.g., two or three) is selected from the group consisting of cationic abrasives, substantially neutral abrasives, and anionic abrasives. In one or more embodiments, the at least one abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, co-formed products thereof (i.e., co-formed products of alumina, silica, titania, ceria, or zirconia), coated abrasives, surface-modified abrasives, and mixtures thereof. In some embodiments, the at least one abrasive does not contain ceria. In some embodiments, the at least one abrasive is highly pure and may have less than about 100 ppm alcohol, less than about 100 ppm ammonia, and less than about 100 ppb alkali cations, such as sodium cations. The abrasive can be present in an amount of about 0.01% to about 12% (e.g., about 0.5% to about 10%), or any subrange thereof, based on the total weight of the POU polishing composition.

[0021] In one or more embodiments, the at least one abrasive is present in an amount of at least about 0.01 wt. % (e.g., at least about 0.05 wt. %, at least about 0.1 wt. %, at least about 0.2 wt. %, at least about 0.4 wt. %, at least about 0.5 wt. %, at least about 1 wt. %, at least about 1.2 wt. %, at least about 1.5 wt. %, or at least about 2 wt. %) to up to about 50 wt. % (e.g., up to about 45 wt. %, up to about 40 wt. %, up to about 35 wt. %, up to about 30 wt. %, up to about 25 wt. %, up to about 20 wt. %, up to about 15 wt. %, up to about 12 wt. %, up to about 10 wt. %, or up to about 5 wt. %) of the polishing composition described herein.

[0022] In one or more embodiments, the polishing composition described herein can optionally include at least one (e.g., two or three) pH adjuster to adjust the pH to a desired value as needed. In some embodiments, the at least one pH adjuster is selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, propionic acid, citric acid, malonic acid, hydrobromic acid, hydroiodic acid, perchloric acid, 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.

[0023] In one or more embodiments, the at least one pH adjuster is present in an amount of at least about 0.01 wt % (e.g., at least about 0.02 wt %, at least about 0.03 wt %, at least about 0.04 wt %, at least about 0.05 wt %, at least about 0.06 wt %, at least about 0.07 wt %, at least about 0.08 wt %, at least about 0.09 wt %, or at least about 0.1 wt %) to at most about 1 wt % (e.g., at most about 0.9 wt %, at most about 0.8 wt %, at most about 0.7 wt %, at most about 0.6 wt %, at most about 0.5 wt %, at most about 0.4 wt %, at most about 0.3 wt %, at most about 0.2 wt %, at most about 0.1 wt %, at most about 0.08 wt %, at most about 0.06 wt %, or at most about 0.05 wt %) of the polishing composition described herein.

[0024] In one or more embodiments, the pH value of the polishing compositions described herein can range from at least about 6 (e.g., at least about 6.5, at least about 7, at least about 7.5, at least about 8, at least about 8.5, at least about 9, at least about 9.5, at least about 10, at least about 10.5, at least about 11, at least about 11.5, or at least about 12) to up to about 14 (e.g., up to about 13.5, up to about 13, up to about 12.5, up to about 12, up to about 11.5, up to about 11, at least about 10.5, up to about 10, up to about 9.5, up to about 9, up to about 8.5, or up to about 8). Without wishing to be bound by theory, it is believed that polishing compositions with a pH below 6 can significantly increase copper removal rate and corrosion, while polishing compositions with a pH above 14 can affect the stability of suspended abrasives, significantly increase roughness, and significantly reduce the overall quality of films polished with such compositions. The relative concentrations of each component in the polishing composition described herein may be adjusted to obtain the desired pH.

[0025] In one or more embodiments, at least one (for example, two or three) first corrosion inhibitors comprise a phosphate group or a phosphonate group. It is believed that the first corrosion inhibitors comprising a phosphate group or a phosphonate group can passivate the copper surface and form a passivation film (for example, a CuO film or a CuO film) that is less permeable to the polishing slurry, thereby protecting copper from potential dishing and corrosion caused by interaction with the corrosive components in the polishing slurry, but without being bound by theory. However, the inventors have unexpectedly found that the corrosion inhibitors comprising a phosphate group or a phosphonate group not only have a large variability in their ability to effectively passivate and insolubilize copper oxide, but also have a large variability in their ability to function as corrosion inhibitors during the polishing process. For example, if the organic group bonded to the phosphate or phosphonate group in the corrosion inhibitor is large, unless the amount of corrosion inhibitor used in the polishing composition is kept to a minimum, the use of the corrosion inhibitor generally leads to an undesirable, highly insoluble copper surface passivation layer, resulting in a low copper removal rate and unacceptable copper and / or organic residues remaining on the polished surface, although it is believed, without wishing to be bound by theory. In contrast, it is believed that corrosion inhibitors with relatively small organic groups bonded to the phosphate or phosphonate group are less effective at preventing copper corrosion, and when used in small amounts, copper removal from the surface may be uncontrollable, although it is not wishing to be bound by theory. In other words, these corrosion inhibitors may not provide sufficient corrosion protection (i.e., prevention of dishing and galvanic corrosion) unless used in large amounts so as not to saturate the copper surface and compete with other corrosion inhibitors present in the slurry for available copper surface sites. The required large amount of corrosion inhibitor may affect the stability of the polishing composition and increase the overall cost of the polishing composition. Based on a careful balance of the above considerations, an effective amount of a particular phosphate- or phosphonate-containing corrosion inhibitor can be tailored to provide dishing prevention and galvanic corrosion prevention without leaving copper and / or organic residues on the polished surface.

[0026] In one or more embodiments, the solubility of copper oxides (e.g., CuO or CuO) in a polishing composition can be a surrogate measure of the effectiveness of the polishing composition in polishing copper-containing substrate surfaces. For example, in some embodiments, a polishing composition is said to be effective in polishing copper-containing substrate surfaces if the total CuO dissolved in the polishing composition after an incubation period is about 3 wt.% to about 10 wt.% when a weight ratio of CuO:polishing composition of about 1:2500 is used. In some embodiments, a polishing composition is said to be effective in polishing copper-containing substrate surfaces if the total CuO dissolved in the polishing slurry composition after an incubation period is about 0.25 wt.% to about 1.75 wt.% when a weight ratio of CuO:polishing composition of about 1:5000 is used.

[0027] In one or more embodiments, dissolved CuO or dissolved CuO can be measured by (1) dispersing or immersing copper oxide (e.g., CuO or CuO) powder in a polishing composition sample with stirring at 25°C to form a mixture, (2) centrifuging the mixture (e.g., at 10,000 RPM for 40 minutes), and (3) measuring the concentration of Cu ions in the supernatant, for example, by using inductively coupled plasma mass spectrometry (ICP-MS). In one or more embodiments, the copper oxide powder can have an average particle size of at least about 0.01 micron (e.g., at least about 0.05 micron, at least about 0.1 micron, at least about 0.5 micron, and at least about 1 micron) and up to about 500 microns (e.g., up to about 250 microns, up to about 100 microns, up to about 50 microns, up to about 25 microns, or up to about 10 microns), and any subrange therebetween. In one or more embodiments, dispersing or immersing copper oxide (e.g., CuO or CuO) in the polishing composition may include agitating a container containing the mixed slurry (e.g., CuO powder and polishing composition) for a period of time. For example, agitation may be performed by immersing the container containing the mixed slurry in an ultrasonic bath, using a vortex mixer, using a stir plate, using a laboratory rotator, or any other known equivalent method. In one or more embodiments, the container containing the mixed slurry may be agitated for about 2 to 5 minutes.

[0028] In some embodiments, a static etching test can be performed by incubating a patterned coupon in a polishing composition and measuring the dissolved and dispersed copper by ICP-MS after incubation. In some embodiments, a solubility test can involve placing a 4 cm × 4 cm copper-containing patterned coupon in 50 g of the polishing composition at 45° C. for 5 minutes and then measuring the copper dissolved and dispersed in the polishing composition. In one or more embodiments, the copper-containing patterned coupon can be at least one selected from the group consisting of CuTaTaNBD and CuRuTaNTEOS MIT 854 mask 200 mm patterned wafers that have undergone an initial Cu bulk polishing step and have had the copper overburden substantially removed by completion of the clearing, endpoint, and overpolishing portions of the Cu bulk polishing step, but before any barrier polishing step (i.e., the Ta / TaN and Ru / TaN barrier layers are still intact and have not been removed except for incidental erosion as part of the Cu bulk polishing process). In one or more embodiments, the amount of copper dissolved and dispersed in a solubility test of a patterned coupon can be at least about 1 ppm (e.g., at least about 2 ppm, at least about 3 ppm, at least about 4 ppm, at least about 5 ppm) and at most about 10 ppm (e.g., at most about 9 ppm, at most about 8 ppm, at most about 7 ppm, at most about 6 ppm) of the polishing composition.

[0029] In one or more embodiments, the first corrosion inhibitor containing a phosphate group is selected from at least one of alkyl phosphate, aromatic phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene aryl alkyl ether phosphate, polyoxyethylene nonyl aryl ether phosphate, and polyoxyethylene nonyl phenyl ether phosphate. In one or more embodiments, the first corrosion inhibitor containing a phosphate group contains an alkyl chain (e.g., linear, branched, or cyclic) having at least 8 (e.g., at least 10, at least 12, at least 14, at least 16, at least 18, or at least 20) to at most 22 (e.g., at most 20, at most 18, at most 16, at most 14, at most 12, or at most 10) carbons. In one or more embodiments, the alkyl chain can be separated from the phosphate group by at least 0 (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, or at least 12) to up to 16 (e.g., up to 14, up to 12, up to 10, up to 8, up to 6, or up to 4) ethylene oxide groups. In one or more embodiments, the first corrosion inhibitor comprising a phosphate group comprises an alkyl chain having 8 to 22 carbons directly bonded to the phosphate group (i.e., no ethylene oxide groups). In one or more embodiments, the first corrosion inhibitor comprises a phosphonate group. In one or more embodiments, the first corrosion inhibitor comprising a phosphonate group comprises an alkyl phosphonate (e.g., a linear or branched C1-C 10 Alkyl or cyclic C3-C 10 alkyl group), aromatic phosphonates (e.g., benzyl phosphonate and phenyl phosphonate), polyoxyethylene alkyl ether phosphonates, polyoxyethylene aryl alkyl ether phosphonates, polyoxyethylene nonyl aryl ether phosphonates, and polyoxyethylene nonyl phenyl ether phosphonates, and substituted versions thereof.

[0030] In one or more embodiments, the amount of the first corrosion inhibitor is at least about 0.0001 wt. % or 1 ppm (e.g., at least about 0.00025 wt. % or 2.5 ppm, at least about 0.0005 wt. % or 5 ppm, at least about 0.001 wt. % or 10 ppm, at least about 0.0025 wt. % or 25 ppm, at least about 0.005 wt. % or 50 ppm, or at least about 0.01 wt. % or 100 ppm) to up to about 0.2 wt. % or 2000 ppm (e.g., For example, up to about 0.15% or 1500 ppm by weight, up to about 0.1% or 1000 ppm, up to about 0.05% or 500 ppm by weight, up to about 0.02% or 200 ppm by weight, up to about 0.01% or 100 ppm, up to about 0.0075% or 75 ppm by weight, up to about 0.005% or 50 ppm by weight, up to about 0.0025% or 25 ppm by weight, up to about 0.001% or 10 ppm, up to about 0.00075% or 7.5 ppm by weight, or up to about 0.0005% or 5 ppm by weight).

[0031] In one or more embodiments, the first corrosion inhibitor has a molecular weight of at least about 150 g / mol (e.g., at least about 200 g / mol, at least about 250 g / mol, at least about 300 g / mol, at least about 350 g / mol, at least about 400 g / mol, at least about 450 g / mol, at least about 500 g / mol, or at least about 550 g / mol) to up to about 1100 g / mol (e.g., up to about 1050 g / mol, up to about 1000 g / mol, up to about 950 g / mol, up to about 900 g / mol, up to about 850 g / mol, up to about 800 g / mol, up to about 750 g / mol, up to about 700 g / mol, up to about 650 g / mol, or up to about 600 g / mol).

[0032] In one or more embodiments, the at least one (e.g., two or three) complexing agent is selected from the group consisting of organic acids, amines (e.g., polyamines), ammonia, quaternary ammonium compounds, inorganic acids, salts thereof, and mixtures thereof. In one or more embodiments, the organic acid may be selected from the group consisting of amino acids, carboxylic acids, organic sulfonic acids, and organic phosphonic acids.

[0033] In one or more embodiments, the at least one complexing agent is selected from the group consisting of gluconic acid, lactic acid, citric acid, tartaric acid, malic acid, glycolic acid, malonic acid, formic acid, oxalic acid, acetic acid, propionic acid, peracetic acid, succinic acid, lactic acid, aminoacetic acid, phenoxyacetic acid, bicine, diglycolic acid, glyceric acid, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, benzoic acid, ammonia, 1, The sulfonic acid may be selected from the group consisting of 2-ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, hydroxylamine-O-sulfonic acid, methanesulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyantholsulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, salts thereof, and mixtures thereof.

[0034] In one or more embodiments, the at least one complexing agent is present in an amount of at least about 0.01 wt % (e.g., at least about 0.05 wt %, at least about 0.1 wt %, at least about 0.5 wt %, at least about 1 wt %, at least about 2 wt %, at least about 4 wt %, at least about 5 wt %, at least about 6 wt %, at least about 8 wt %, at least about 10 wt %, or at least about 15 wt %) to up to 20 wt % (e.g., up to about 18 wt %, up to about 16 wt %, up to about 15 wt %, up to about 14 wt %, up to about 12 wt %, up to about 10 wt %, up to about 8 wt %, up to about 6 wt %, up to about 5 wt %, up to about 4 wt %, up to about 2 wt %, or up to about 1 wt %) of the polishing composition described herein.

[0035] In one or more embodiments, the at least one (e.g., two or three) second corrosion inhibitors can include at least one azole compound, such as a substituted or unsubstituted triazole (e.g., benzotriazole), a substituted or unsubstituted tetrazole, a substituted or unsubstituted imidazole (e.g., purine), a substituted or unsubstituted thiadiazole, or a substituted or unsubstituted pyrazole. For example, the at least one second corrosion inhibitor may be selected from the group consisting of tetrazole, benzotriazole, tolyltriazole, methylbenzotriazole (such as 1-methylbenzotriazole, 4-methylbenzotriazole, and 5-methylbenzotriazole), ethylbenzotriazole (such as 1-ethylbenzotriazole), propylbenzotriazole (such as 1-propylbenzotriazole), butylbenzotriazole (such as 1-butylbenzotriazole and 5-butylbenzotriazole), pentylbenzotriazole (such as 1-pentylbenzotriazole), hexylbenzotriazole (such as 1-butylbenzotriazole and 5-butylbenzotriazole), dimethylbenzotriazole (such as 5,6-dimethylbenzotriazole), chlorobenzotriazole (such as 5-chlorobenzotriazole), dichlorobenzotriazole, and the like. The benzotriazole may be selected from the group consisting of benzotriazole (such as 5,6-dichlorobenzotriazole), chloromethylbenzotriazole (such as 1-(chloromethyl)-1-H-benzotriazole), chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, aminobenzimidazole, pyrazole, imidazole, aminotetrazole, adenine, benzimidazole, thiabendazole, 1,2,3-triazole, 1,2,4-triazole, 1-hydroxybenzotriazole, 2-methylbenzothiazole, 2-aminobenzimidazole, 2-amino-5-ethyl-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-methylpyrazole, 4-amino-4H-1,2,4-triazole, and combinations thereof.

[0036] In one or more embodiments, the at least one second corrosion inhibitor is present in an amount of at least about 0.0001 wt % (e.g., at least about 0.0005 wt %, at least about 0.001 wt %, at least about 0.005 wt %, at least about 0.01 wt %, at least about 0.05 wt %, at least about 0.1 wt %, at least about 0.5 wt %, at least about 1 wt %, or at least about 2 wt %) to up to about 5 wt % (e.g., up to about 4 wt %, up to about 3 wt %, up to about 2 wt %, up to about 1 wt %, up to about 0.8 wt %, up to about 0.6 wt %, up to about 0.5 wt %, up to about 0.4 wt %, up to about 0.2 wt %, or up to about 0.1 wt %) of the polishing composition described herein.

[0037] In one or more embodiments, the polishing compositions described herein can include at least one (e.g., two or three) solvent. Suitable solvents include water and organic solvents. In some embodiments, the at least one solvent is present in an amount of at least about 20% by weight (e.g., at least about 30% by weight, at least about 40% by weight, at least about 50% by weight, at least about 60% by weight, at least about 70% by weight, at least about 80% by weight, at least about 90% by weight, at least about 95% by weight, or at least about 98% by weight) to up to about 99% by weight (e.g., up to about 95% by weight, up to about 90% by weight, up to about 85% by weight, up to about 80% by weight, up to about 75% by weight, up to about 70% by weight, up to about 65% by weight, up to about 60% by weight, up to about 55% by weight, or up to about 50% by weight) of the polishing compositions described herein.

[0038] In one or more embodiments, a second solvent (e.g., an organic solvent) may optionally be used in the polishing composition (e.g., POU polishing composition or concentrated polishing composition) of the present disclosure, which can aid in dissolving the azole-containing corrosion inhibitor. In one or more embodiments, the second solvent can be one or more alcohols, one or more alkylene glycols, or one or more alkylene glycol ethers. In one or more embodiments, the second solvent comprises one or more solvents selected from the group consisting of ethanol, 1-propanol, 2-propanol, n-butanol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol propyl ether, dimethyl sulfoxide, and ethylene glycol.

[0039] In one or more embodiments, the second solvent is present in an amount of at least about 0.0025 wt % (e.g., at least about 0.005 wt %, at least about 0.01 wt %, at least about 0.02 wt %, at least about 0.05 wt %, at least about 0.1 wt %, at least about 0.2 wt %, at least about 0.4 wt %, at least about 0.6 wt %, at least about 0.8 wt %, or at least about 1 wt %) to up to about 5 wt % (e.g., up to about 4 wt %, up to about 3 wt %, up to about 2 wt %, up to about 1 wt %, up to about 0.8 wt %, up to about 0.6 wt %, up to about 0.5 wt %, or up to about 0.1 wt %) of the polishing composition described herein.

[0040] In one or more embodiments, the polishing composition can optionally include a dynamic surface tension reducing agent (DSTR). In some embodiments, the DSTR is an acetylene compound. In some embodiments, the DSTR is acetylene glycol or an ethoxylated adduct thereof. In some embodiments, the DSTR is an ethoxylated adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol. In one or more embodiments, the DSTR can be present in an amount of at least about 0.0001 wt.% (e.g., at least about 0.0005 wt.%, at least about 0.001 wt.%, at least about 0.005 wt.%, at least about 0.01 wt.%, at least about 0.05 wt.%, at least about 0.1 wt.%, at least about 0.2 wt.%, at least about 0.4 wt.%, or at least about 0.5 wt.%) to up to about 1 wt.% (e.g., up to about 0.8 wt.%, up to about 0.6 wt.%, up to about 0.5 wt.%, up to about 0.4 wt.%, up to about 0.2 wt.%, up to about 0.1 wt.%, up to about 0.05 wt.%, up to about 0.01 wt.%, up to about 0.005 wt.%, or up to about 0.001 wt.%) of the polishing composition described herein. In one or more embodiments, the POU polishing composition can include about 0.0001 wt.% to 0.005 wt.% DSTR. In one or more embodiments, the concentrated polishing composition can include about 0.001 wt % to 1 wt % DSTR.

[0041] In one or more embodiments, the polishing composition described herein may contain any of a variety of compounds, including but not limited to, organic solvents, pH adjusters, quaternary ammonium compounds (e.g., salts or hydroxides), amines, alkali bases (e.g., alkali hydroxides), fluoride-containing compounds, silanes (e.g., alkoxysilanes), imines (e.g., amidines such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN)), salts (e.g., halide salts or metal salts), The polishing composition may be substantially free of one or more of the following specific components: a polymer (e.g., a cationic polymer or an anionic polymer), a surfactant (e.g., a cationic surfactant, an anionic surfactant, or a nonionic surfactant), a plasticizer, an oxidizer (e.g., HO), 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 the polishing composition may be free of include alkali metal halides (e.g., sodium halide or potassium halide) or ammonium halides (e.g., ammonium chloride), and may be chlorides, bromides, or iodides. As used herein, a component that the polishing composition is "substantially free of" refers to a component that is not intentionally added to the polishing composition. In some embodiments, the polishing compositions described herein can have up to about 1000 ppm (e.g., up to about 500 ppm, up to about 250 ppm, up to about 100 ppm, up to about 50 ppm, up to about 10 ppm, or up to about 1 ppm) of one or more of the above components from which the polishing composition is substantially free. In some embodiments, the polishing compositions described herein can be completely free of one or more of the above components.

[0042] The present disclosure also contemplates methods of using any of the above-described polishing compositions (e.g., concentrates or POU slurries). When a concentrate is used, the method can include diluting the concentrate (e.g., at least two-fold) to form a POU slurry, and then contacting a surface at least partially comprising copper with the POU slurry. In some embodiments, an oxidizer can be added to the slurry before, after, or during dilution. When a POU slurry is used, the method can include contacting a surface at least partially comprising copper with the slurry.

[0043] In one or more embodiments, the present disclosure features a polishing method that can include applying a polishing composition according to the present disclosure to a substrate (e.g., a wafer) having at least copper (e.g., copper in the form of copper wiring and / or copper overburden) on a surface thereof, contacting a pad with the surface of the substrate, and moving the pad relative to the substrate. In some embodiments, when the substrate includes at least one species of copper, the method can effectively polish the substrate (e.g., remove at least the copper overburden without leaving copper residue or causing galvanic corrosion at the interface between the copper and the barrier material (e.g., Ta / TaN)).

[0044] In one or more embodiments, the method of using the polishing composition described herein can further include fabricating a semiconductor device from a substrate treated with the polishing composition through one or more processes, such as photolithography, ion implantation, dry / wet etching, plasma etching, deposition (e.g., PVD, CVD, ALD, ECD), wafer loading, die cutting, packaging, and testing.

[0045] 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.

[0046] Example The slurries tested in the examples had the following general composition: The amount and type of primary corrosion inhibitor was varied as explained in the results discussion and in the accompanying Figures 1-3.

[0047] [Table 1]

[0048] Example 1 - Dissolution of CuO and CuO This example was designed to test the additive's ability to modify the polishing of copper-containing substrates. The test procedure was as follows: Copper oxide powder (e.g., 0.01 g CuO or 0.005 g CuO) was weighed and placed in a centrifuge tube. 25 g of a slurry sample containing each of the above ingredients was added to the centrifuge tube so that the copper oxide powder was immersed in the slurry sample. The centrifuge tube was placed in an ultrasonic bath maintained at 25°C and sonicated for 2 minutes. The mixture in the tube was then centrifuged at 10,000 RPM for 40 minutes. A 10 mL sample of the supernatant was then removed for ICP-MS analysis to determine the copper content in the supernatant. Polishing slurry samples containing four primary corrosion inhibitors were tested: an alkyl phosphate, two different ethoxylated alkyl phosphates, and an aromatic phosphonate. The four primary corrosion inhibitors had molecular weights ranging from about 150 g / mol to about 1,100 g / mol.

[0049] The results for CuO dissolution are shown in Figure 1, and those for CuO dissolution are shown in Figure 2. The results show that corrosion inhibitor 1, even at low dosages, has a very significant effect in inhibiting copper oxide dissolution, effectively stopping copper oxide dissolution in the slurry when added to the slurry at approximately 5 ppm. Corrosion inhibitors 2 and 3 had a more gradual ability to inhibit copper oxide dissolution. Figures 1 and 2 show that corrosion inhibitor 4 first increased copper oxide dissolution at low dosages, and then inhibited dissolution at higher dosages.

[0050] Example 2 - Static etch rate of patterned coupons In this example, a static etch rate test was performed by immersing a patterned coupon in a polishing composition containing corrosion inhibitor 3 and measuring the dissolved copper by ICP-MS. More specifically, a 4 cm x 4 cm copper-containing patterned coupon was placed in 50 g of a polishing composition containing corrosion inhibitor 3 and incubated at 45°C for 5 minutes. The copper dissolved in the polishing composition solution was then measured by ICP-MS. The copper-containing patterned coupon was a piece of a 200 mm patterned wafer with a CuTaTaNBD854 mask that had been initially polished to substantially remove the copper overburden, revealing the copper wiring pattern. Figure 3 shows the results of a static etch rate test for a composition using corrosion inhibitor 3, demonstrating a profile similar to the plot profiles obtained in Figures 1 and 2.

[0051] Example 3 - Copper bulk polishing using patterned wafers In this example, a 200 mm patterned wafer with a CuTaTaNBD854 mask was polished using compositions containing CI-1 through CI-4 and other components in the amounts listed in Table 1 above to complete the copper bulk removal process and stop on the barrier layer. Table 1 describes the resulting wafers based on whether polishing was acceptable (i.e., Cu removal rate was sufficient and no defects were observed) or unacceptable. Acceptable polishing results are indicated in Table 2 with a "●" and unacceptable results with an "x."

[0052] [Table 2]

[0053] Importantly, there is a general need to balance the removal of copper oxide and the suppression of copper oxide removal during the polishing process so that polishing can proceed uniformly and with few corrosion-related defects.The inventors have unexpectedly discovered that in some embodiments, the above-mentioned optimal polishing balance can be achieved by using a polishing slurry that maintains the dissolution percentage of CuO and the dissolution percentage of CuO within the shaded area of ​​the plots shown in Figures 1 and 2 for copper-containing substrates.

[0054] Specifically, the preferred % dissolved CuO range is about 3-10%, and the preferred % dissolved CuO range is about 0.25-1.75%. Figure 3 shows the window of suitable polishing results in the shaded area, which is about 0.5 ppm to about 6 ppm of dissolved Cu in the polishing composition. Furthermore, based on the results of the tests conducted in Example 3, it was generally found that when the concentration of the first corrosion inhibitor exceeds 50 ppm in the polishing slurry, the Cu removal rate becomes unacceptably low. Thus, unexpectedly, each of the tested first corrosion inhibitors has a concentration window suitable for polishing copper-containing substrates, and once outside the concentration window, a polishing composition containing one of the tested first corrosion inhibitors exhibits a low removal rate. It has been discovered that copper-containing substrates may not be polished properly due to numerous defects caused by etch and / or uncontrolled copper corrosion.

[0055] Although Example 3 shows that a polishing composition containing a particular first corrosion inhibitor (e.g., one of four corrosion inhibitors tested) at a particular concentration may have unacceptable polishing results for the particular purpose and conditions described in Example 3, it should be noted that such a first corrosion inhibitor may be used in combination with other components described herein at different concentrations to form a polishing composition with acceptable results, or may form a polishing composition with acceptable results for a different polishing application. Thus, the polishing compositions listed in Example 3 as giving "unacceptable" results are also within the scope of the present disclosure.

[0056] While only a few example embodiments have been described in detail above, those skilled in the art will readily appreciate that many modifications can be made in the illustrated embodiments without departing from the invention in its essential form, and all such modifications are intended to be included within the scope of this disclosure as defined in the following claims. Exemplary embodiments of the present invention are described below. <1> at least one abrasive; at least one first corrosion inhibitor containing a phosphate or phosphonate group; at least one complexing agent; at least one second corrosion inhibitor comprising at least one azole compound; optionally at least one pH adjuster; A polishing composition comprising: the amount of the at least one first corrosion inhibitor in the polishing composition is such that the polishing composition dissolves about 3 wt. % to 10 wt. % of the CuO from the solid CuO powder, when a solid CuO powder having an average particle size of about 0.01 microns to about 500 microns is immersed in the polishing composition at a weight ratio of CuO:polishing composition of about 1:2500 with stirring at 25° C. for 2 minutes to form a mixture, the mixture is centrifuged to form a supernatant, and the amount of Cu ions dissolved in the supernatant is measured by ICP-MS; Polishing composition. <2> the at least one abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, co-formed products of alumina, silica, titania, ceria, or zirconia, coated abrasives, surface-modified abrasives, and mixtures thereof; <1> The polishing composition according to claim 1. <3> the at least one abrasive is present in an amount of from about 0.01% to about 50% by weight of the composition; <1> The polishing composition according to claim 1. <4> the at least one first corrosion inhibitor comprises a phosphate group and includes at least one of alkyl phosphate, aromatic phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene aryl alkyl ether phosphate, polyoxyethylene nonyl aryl ether phosphate, and polyoxyethylene nonyl phenyl ether phosphate; <1> The polishing composition according to claim 1. <5> the at least one first corrosion inhibitor comprises an alkyl chain having 8 to 22 carbons separated from the phosphate group by 2 to 16 ethylene oxide groups; <4> The polishing composition according to claim 1. <6> the at least one first corrosion inhibitor comprises a phosphonate group and includes at least one of an alkyl phosphonate, an aromatic phosphonate, a polyoxyethylene alkyl ether phosphonate, a polyoxyethylene aryl alkyl ether phosphonate, a polyoxyethylene nonyl aryl ether phosphonate, and a polyoxyethylene nonyl phenyl ether phosphonate; <1> The polishing composition according to claim 1. <7> the amount of the at least one first corrosion inhibitor is about 1 ppm to 2000 ppm of the composition; <1> The polishing composition according to claim 1. <8> the at least one first corrosion inhibitor has a molecular weight of about 150 g / mol to about 1100 g / mol; <1> The polishing composition according to claim 1. <9> the at least one complexing agent is selected from the group consisting of organic acids, amines, ammonia, quaternary ammonium compounds, inorganic acids, salts thereof, and mixtures thereof; <1> The polishing composition according to claim 1. <10> The at least one complexing agent may be 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, ammonia, 1,2-ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, hydroxylamine-O- ... sulfonic acid, methanesulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyantholsulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, ethyl phosphate, cyanoethyl phosphate, phenyl phosphate, vinyl phosphate, poly(vinylphosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, nitrilotri(methylphosphonic acid), diethylenetriaminepentakis(methylphosphonic acid), N,N,N'N'-ethylenediaminetetrakis(methylenephosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, salts thereof, and mixtures thereof; <1> The polishing composition according to claim 1. <11> the at least one complexing agent is present in an amount of from about 0.01% to about 20% by weight of the composition; <1> The polishing composition according to claim 1. <12> The at least one second corrosion inhibitor is selected from the group consisting of tetrazole, benzotriazole, tolyltriazole, 5-methylbenzotriazole, ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, dimethylbenzotriazole, chlorobenzotriazole, dichlorobenzotriazole, chloromethylbenzotriazole, chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, and benzotriazole. selected from the group consisting of aminobenzimidazole, pyrazole, imidazole, aminotetrazole, adenine, benzimidazole, thiabendazole, 1,2,3-triazole, 1,2,4-triazole, 1-hydroxybenzotriazole, 2-methylbenzothiazole, 2-aminobenzimidazole, 2-amino-5-ethyl-1,3,4-thiadazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-methylpyrazole, 4-amino-4H-1,2,4-triazole, and combinations thereof; <1> The polishing composition according to claim 1. <13> the at least one second corrosion inhibitor is present in an amount of from about 0.0001% to about 5% by weight of the composition; <1> The polishing composition according to claim 1. <14> at least one abrasive; at least one first corrosion inhibitor containing a phosphate or phosphonate group; at least one complexing agent; at least one second corrosion inhibitor comprising at least one azole compound; optionally at least one pH adjuster; A polishing composition comprising: the amount of the at least one first corrosion inhibitor in the polishing composition is such that, when a 4 cm x 4 cm copper-containing patterned coupon is immersed in 50 g of the polishing composition at 45°C for 5 minutes to form a mixture, and the amount of Cu species in the mixture is measured by ICP-MS, the amount of the Cu species is about 1 ppm to about 10 ppm; Polishing composition. <15> The at least one abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, co-formed products of alumina, silica, titania, ceria, or zirconia. t), coated abrasives, surface-modified abrasives, and mixtures thereof; <14> The polishing composition according to claim 1. <16> the at least one abrasive is present in an amount of from about 0.01% to about 50% by weight of the composition; <14> The polishing composition according to claim 1. <17> the at least one first corrosion inhibitor comprises a phosphate group and includes at least one of alkyl phosphate, aromatic phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene aryl alkyl ether phosphate, polyoxyethylene nonyl aryl ether phosphate, and polyoxyethylene nonyl phenyl ether phosphate; <14> The polishing composition according to claim 1. <18> the at least one first corrosion inhibitor comprises an alkyl chain having 8 to 22 carbons separated from the phosphate group by 0 to 16 ethylene oxide groups; <17> The polishing composition according to claim 1. <19> the at least one first corrosion inhibitor comprises a phosphonate group and includes at least one of an alkyl phosphonate, an aromatic phosphonate, a polyoxyethylene alkyl ether phosphonate, a polyoxyethylene aryl alkyl ether phosphonate, a polyoxyethylene nonyl aryl ether phosphonate, and a polyoxyethylene nonyl phenyl ether phosphonate; <14> The polishing composition according to claim 1. <20> the amount of the at least one first corrosion inhibitor is about 1 ppm to 2000 ppm of the composition; <14> The polishing composition according to claim 1. <21> the at least one first corrosion inhibitor has a molecular weight of about 150 g / mol to about 1100 g / mol; <14> The polishing composition according to claim 1. <22> the at least one complexing agent is selected from the group consisting of organic acids, amines, ammonia, quaternary ammonium compounds, inorganic acids, salts thereof, and mixtures thereof; <14> The polishing composition according to claim 1. <23> The at least one complexing agent may be 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, ammonia, 1,2-ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, hydroxylamine-O- ... sulfonic acid, methanesulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyantholsulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, ethyl phosphate, cyanoethyl phosphate, phenyl phosphate, vinyl phosphate, poly(vinylphosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, nitrilotri(methylphosphonic acid), diethylenetriaminepentakis(methylphosphonic acid), N,N,N'N'-ethylenediaminetetrakis(methylenephosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, salts thereof, and mixtures thereof; <14> The polishing composition according to claim 1. <24> the at least one complexing agent is present in an amount of from about 0.01% to about 20% by weight of the composition; <14> The polishing composition according to claim 1. <25> The at least one second corrosion inhibitor is selected from the group consisting of tetrazole, benzotriazole, tolyltriazole, 5-methylbenzotriazole, ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, dimethylbenzotriazole, chlorobenzotriazole, dichlorobenzotriazole, chloromethylbenzotriazole, chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, and benzotriazole. selected from the group consisting of aminobenzimidazole, pyrazole, imidazole, aminotetrazole, adenine, benzimidazole, thiabendazole, 1,2,3-triazole, 1,2,4-triazole, 1-hydroxybenzotriazole, 2-methylbenzothiazole, 2-aminobenzimidazole, 2-amino-5-ethyl-1,3,4-thiadazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-methylpyrazole, 4-amino-4H-1,2,4-triazole, and combinations thereof; <14> The polishing composition according to claim 1. <26> the at least one second corrosion inhibitor is present in an amount of from about 0.0001% to about 5% by weight of the composition; <14> The polishing composition according to claim 1. <27> Copper on the surface of the board <1> 10. A method of polishing a substrate, comprising contacting the substrate with the polishing composition of claim 1.

Claims

1. 1. A polishing composition comprising: at least one abrasive present in an amount of 0.01 wt. % to 50 wt. % of the polishing composition; at least one first corrosion inhibitor comprising an alkyl phosphate, an aromatic phosphate, an alkyl phosphonate, or an aromatic phosphonate; at least one complexing agent present in an amount of 0.01 wt % to 20 wt % of the polishing composition and selected from the group consisting of organic acids, amines, ammonia, quaternary ammonium compounds, inorganic acids, salts thereof, and mixtures thereof; at least one second corrosion inhibitor present in an amount of 0.0001 wt % to 5 wt % of the polishing composition and comprising at least one azole compound; optionally at least one pH adjuster; Including, the amount of the at least one first corrosion inhibitor in the polishing composition is 1 ppm to 2000 ppm of the polishing composition, Solid Cu having an average particle size of 0.01 microns to 500 microns ２ O powder at a ratio of 1:2500 Cu ２ The polishing composition is immersed in the polishing composition at a weight ratio of 0:1 for 2 minutes at 25°C with stirring to form a mixture, the mixture is centrifuged to form a supernatant, and the amount of Cu ions dissolved in the supernatant is measured by ICP-MS. ２ The Cu derived from O powder ２ Amount that dissolves 3 to 10% by weight of O That is, Polishing composition.

2. 2. The polishing composition of claim 1, wherein the at least one abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, co-formed products of alumina, silica, titania, ceria, or zirconia, coated abrasives, surface-modified abrasives, and mixtures thereof.

3. 10. The polishing composition of claim 1, wherein the at least one abrasive is present in an amount of 0.05% to 45% by weight of the polishing composition.

4. 2. The polishing composition of claim 1, wherein the at least one first corrosion inhibitor comprises a phosphate group and includes at least one of alkyl phosphate, aromatic phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene aryl alkyl ether phosphate, polyoxyethylene nonyl aryl ether phosphate, and polyoxyethylene nonyl phenyl ether phosphate.

5. 5. The polishing composition of claim 4, wherein the at least one first corrosion inhibitor comprises an alkyl chain having 8 to 22 carbons separated from the phosphate group by 2 to 16 ethylene oxide groups.

6. 2. The polishing composition of claim 1, wherein the at least one first corrosion inhibitor contains a phosphonate group and includes at least one of alkyl phosphonates, aromatic phosphonates, polyoxyethylene alkyl ether phosphonates, polyoxyethylene aryl alkyl ether phosphonates, polyoxyethylene nonyl aryl ether phosphonates, and polyoxyethylene nonyl phenyl ether phosphonates.

7. 10. The polishing composition of claim 1, wherein the amount of the at least one first corrosion inhibitor is from 1 ppm to 1000 ppm of the polishing composition.

8. 10. The polishing composition of claim 1, wherein the at least one first corrosion inhibitor has a molecular weight of 150 g / mol to 1100 g / mol.

9. The at least one complexing agent may be 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, ammonia, 1,2-ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, hydroxylamine-O-sulfonic acid, metasulfonic acid, methylparaben ...

2. The polishing composition of claim 1, wherein the polishing agent is selected from the group consisting of dimethylaminomethylphosphonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyantholsulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, ethyl phosphate, cyanoethyl phosphate, phenyl phosphate, vinyl phosphate, poly(vinylphosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, nitrilotri(methylphosphonic acid), diethylenetriaminepentakis(methylphosphonic acid), N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, salts thereof, and mixtures thereof.

10. 10. The polishing composition of claim 1, wherein the at least one complexing agent is present in an amount of 0.05% to 18% by weight of the polishing composition.

11. The at least one second corrosion inhibitor is selected from the group consisting of tetrazole, benzotriazole, tolyltriazole, 5-methylbenzotriazole, ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, dimethylbenzotriazole, chlorobenzotriazole, dichlorobenzotriazole, chloromethylbenzotriazole, chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, and aminobenzimidazole.

2. The polishing composition of claim 1, wherein the compound is selected from the group consisting of thiabendazole, pyrazole, imidazole, aminotetrazole, adenine, benzimidazole, thiabendazole, 1,2,3-triazole, 1,2,4-triazole, 1-hydroxybenzotriazole, 2-methylbenzothiazole, 2-aminobenzimidazole, 2-amino-5-ethyl-1,3,4-thiadazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-methylpyrazole, 4-amino-4H-1,2,4-triazole, and combinations thereof.

12. 10. The polishing composition of claim 1, wherein the at least one second corrosion inhibitor is present in an amount of 0.0005% to 4% by weight of the polishing composition.

13. 10. A method of polishing a substrate comprising contacting copper on a surface of the substrate with the polishing composition of claim 1.

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