Chemical mechanical polishing composition

Abstract

The present invention relates to a chemical mechanical polishing (CMP) composition comprising inorganic particles, at least one organic compound comprising an amino group and / or at least one acid group (Y), potassium persulfate, at least one corrosion inhibitor, and an aqueous medium for polishing substrates in the semiconductor industry, the substrates comprising cobalt and / or cobalt alloys and TiN and / or TaN.

Description

[0001] The present invention relates to a chemical mechanical polishing (CMP) composition comprising inorganic particles, at least one organic compound comprising an amino group and / or at least one acid group (Y), potassium persulfate, at least one corrosion inhibitor, and an aqueous medium for polishing substrates in the semiconductor industry, the substrates comprising cobalt and / or cobalt alloys and TiN and / or TaN.

[0002] In the semiconductor industry, chemical mechanical polishing (CMP) is a well-known technique used in the manufacture of advanced photonic, microelectromechanical, and microelectronic materials and devices, such as semiconductor wafers.

[0003] CMP (Chemical Motion Processing) is used to planarize metal and / or oxide surfaces during the manufacture of materials and devices for the semiconductor industry. CMP utilizes the interaction of chemical and mechanical actions to achieve flatness of the surface to be polished. The chemical action is provided by a chemical composition (also known as a CMP composition or CMP slurry). The mechanical action is typically performed by a polishing pad, which is pressed onto the surface to be polished and mounted on a moving platen. The movement of the platen is typically linear, rotary, or track-based.

[0004] In a typical CMP process step, a rotating wafer holder brings the wafer to be polished into contact with a polishing pad. The CMP composition is typically applied between the wafer and the polishing pad.

[0005] As feature sizes continue to shrink in ultra-large scale integrated circuit (ULSI) technology, the dimensions of copper interconnect structures are becoming increasingly smaller. To reduce RC delay, the thickness of the barriers or adhesive layers in copper interconnect structures is becoming thinner. Traditional copper barrier / adhesive layer stacks like Ta / TaN are no longer suitable because Ta has relatively high resistivity, and copper cannot be directly plated onto Ta. Compared to Ta, cobalt has lower resistivity and is cheaper. Cu and Co have good adhesion. Cu readily nucleates on Co, and copper can also be directly plated onto cobalt.

[0006] In integrated circuits, Co is used as an adhesive layer or barrier layer for copper interconnects. Co can also be used as nanocrystalline Co in memory devices and as a metal gate in MOSFETs.

[0007] Porous low-k dielectric materials are currently used in interconnect structures. However, low-k materials are reportedly susceptible to damage from plasma or polishing slurries. In current chemical mechanical polishing (CMP) processes, most current slurries used for copper and barriers are acidic to minimize damage to low-k dielectrics. However, it has been observed that copper and cobalt readily dissolve in acidic solutions containing oxidants (e.g., hydrogen peroxide). This leads to excessively high polishing rates for copper and cobalt, which can induce copper wire delamination. Furthermore, the dissolution of the cobalt adhesion layer on the sidewalls of the copper interconnect structure can cause copper wire delamination and lead to reliability issues.

[0008] Another application of cobalt in semiconductor chip manufacturing is the deposition of cobalt into trenches or vias using CVD or PVD methods. The dielectric layer is covered by an inner liner to ensure that Co does not delaminate or diffuse into the dielectric layer. Ti / TiN and / or Ta / TaN layers can be used as liner and / or barrier layers.

[0009] For CMP décor assembly of materials such as Co-coated wafers, it is advantageous to remove both Co and the liner in a single step. Therefore, high removal rates for Co, as well as Ti / TiN and / or Ta / TaN, are desirable. On the other hand, the dielectric layer should not be damaged, thus requiring low removal rates for this type of material.

[0010] Depending on the integration scheme used in ultra-large-scale integrated circuit (ULSI) technology, the coexistence of Co, Cu, low-k dielectric materials, Ti / TiN and / or Ta / TaN in different amounts and layer thicknesses poses several challenges to chemical mechanical polishing compositions used in semiconductor device manufacturing in terms of selectivity, etching, removal rate and surface quality.

[0011] CMP compositions (comprising inorganic particles, at least one organic compound comprising an amino group and at least one acid group (Y), an oxidant, and an aqueous medium) for polishing semiconductor industrial substrates containing metals and Ti / TiN and / or Ta / TaN are known and described, for example, in the following documents.

[0012] US 6,840,971B2 discloses chemical mechanical polishing compositions and slurries containing α-amino acids, which can be used for polishing substrates including multilayer metals or metal and dielectric substrates such as Cu / TiN / Ti and Cu / TaN / Ta multilayer substrates. In addition to α-amino acids, the slurry includes abrasive particles, an oxidant, and optional further components including passivation film forming agents, dispersants, surfactants, polishing-stopping compounds, and stabilizers. It is particularly suitable for polishing substrates including copper, titanium, titanium nitride, tantalum, tantalum nitride, tungsten, and tungsten nitride layers at good rates under controlled conditions.

[0013] The use of CMP compositions for chemical mechanical polishing of substrates containing cobalt and / or cobalt alloys and TiN and / or TaN is disclosed in PCT / EP2016 / 068964. The CMP compositions used have a pH value greater than 6 and less than 9. Typical components of the CMP compositions used are colloidal silica particles, organic compounds containing amino and acid groups, hydrogen peroxide as an oxidant, and an aqueous medium. The CMP compositions used also further include corrosion inhibitors and nonionic surfactants.

[0014] However, existing CMP compositions do not provide control over the material removal rate (MRR) of Co, Ti / TiN, and / or Ta / TaN. Furthermore, these CMP compositions fail to provide a narrower TiN:TaN MRR ratio to cater to a wide range of applications in the semiconductor and other related industries. In addition, prior art CMP compositions also lead to substrate corrosion and material degradation due to their acidic pH.

[0015] Therefore, the purpose of the subject matter currently claimed is to provide a CMP composition that avoids corrosion of the substrate and material deterioration and provides better control over the MRR of Co, Ti / TiN and / or Ta / TaN, wherein the MRR ratio of TiN:TaN is in the range of ≥0.5 to ≤2.0.

[0016] Overview

[0017] Surprisingly, CMP compositions containing potassium persulfate as an oxidant and with a pH range of ≥8.5 to ≤11.0 have been found to provide better MRR control for Co, Ti / TiN, and / or Ta / TaN with minimal corrosion and material degradation of the substrate. A controlled TiN:TaN MRR ratio in the range of ≥0.5 to ≤2.0 prevents TiN or TaN from pitting or protruding in the CMP compositions.

[0018] Therefore, in one embodiment, the currently claimed subject matter relates to a chemical mechanical polishing composition comprising the following

[0019] (A) Inorganic particles ≥0.10 wt% to ≤4.00 wt%,

[0020] (B) ≥0.10% by weight to ≤0.90% by weight of at least one organic compound containing an amino group and / or at least one acid group (Y),

[0021] (C) Potassium persulfate ≥0.20% to ≤0.90% by weight,

[0022] (D) ≥95.00% by weight to ≤99.58% by weight of aqueous media,

[0023] (E) at least one corrosion inhibitor ranging from ≥0.01% by weight to ≤0.50% by weight, and

[0024] (K) at least one additive from ≥0.01% by weight to ≤1.50% by weight,

[0025] The pH of the composition is ≥8.5 to ≤11.0, and

[0026] The weight percentages are based on the total weight of the composition, and the sum of the weight percentages of components (A), (B), (C), (D), (E) and (K) is 100% by weight.

[0027] In another embodiment of the subject matter currently claimed, the above composition is characterized in that the pH of the composition is ≥8.5 to ≤10.0.

[0028] In another embodiment of the subject matter currently claimed, the above composition is characterized in that the amount of potassium persulfate is ≥0.30% by weight to ≤0.70% by weight.

[0029] In another embodiment of the subject matter currently claimed, the above composition is characterized in that the inorganic particles (A) are colloidal inorganic particles.

[0030] In another embodiment of the subject matter currently claimed, the above composition is characterized in that the colloidal inorganic particles are colloidal silica particles.

[0031] In another embodiment of the subject matter currently claimed, the above composition is characterized in that at least one organic compound (B) is a non-polymeric compound with a molecular weight of less than 600 g / mol.

[0032] In another embodiment of the subject matter currently claimed, the above composition is characterized in that the acid group (Y) in the organic compound (B) is selected from carboxylic acids, sulfonic acids, and phosphoric acids.

[0033] In another embodiment of the subject matter currently claimed, the above composition is characterized in that the organic compound (B) is selected from amino acids, substituted ethylenediamines, and polycarboxylic acids.

[0034] In another embodiment of the subject matter currently claimed, the above composition is characterized in that the organic compound (B) is selected from: glycine, glutamic acid, aspartic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, sulfoalanine, aminotris(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), malonic acid, citric acid, and tartaric acid.

[0035] In another embodiment of the subject matter currently claimed, the above composition is characterized in that the aqueous medium is deionized water.

[0036] In another embodiment of the currently claimed subject matter, the above composition is characterized in that the corrosion inhibitor (E) is selected from: imidazole, benzimidazole, benzotriazole, 4-(dimethylamino)benzoic acid, terephthalic acid, isophthalic acid, 6,6',6”-(1,3,5-triazine-2,4,6-triyltriimino)trihexanoic acid, phenyltetrazole, N-lauroyl sarcosine, 4-dodecylbenzenesulfonic acid, C6-C phosphate. 10 Alkyl esters, polyaspartic acid and mixtures thereof, and salts thereof.

[0037] In another embodiment of the subject matter currently claimed, the above composition is characterized in that at least one additive is selected from: surfactants (F), biocides (H), pH adjusters, buffers, stabilizers, and friction reducers.

[0038] In another aspect of the subject matter currently claimed, the above composition is used to chemically and mechanically polish a substrate comprising (i) cobalt and / or (ii) cobalt alloys and (iii) TiN and / or TaN.

[0039] In another aspect of the currently claimed subject matter, a method of manufacturing a semiconductor device includes chemically mechanically polishing a substrate used in the semiconductor industry, wherein the substrate contains, in the presence of the above-described composition,

[0040] (i) cobalt, and / or

[0041] (ii) Cobalt alloys, and

[0042] (iii) TiN and / or TaN.

[0043] In one embodiment of the subject matter currently claimed, the above method is characterized in that the TiN:TaN material removal rate ratio is in the range of ≥0.5 to ≤2.0.

[0044] Detailed Explanation

[0045] The chemical mechanical polishing composition of the present invention comprises

[0046] (A) Inorganic particles ≥0.10 wt% to ≤4.00 wt%,

[0047] (B) ≥0.10% by weight to ≤0.90% by weight of at least one organic compound containing an amino group and / or at least one acid group (Y),

[0048] (C) Potassium persulfate ≥0.20% to ≤0.90% by weight,

[0049] (D) ≥95.00% by weight to ≤99.58% by weight of aqueous media,

[0050] (E) at least one corrosion inhibitor ranging from ≥0.01% by weight to ≤0.50% by weight, and

[0051] (K) at least one additive from ≥0.01% by weight to ≤1.50% by weight,

[0052] The pH of the composition is ≥8.5 to ≤11.0, and

[0053] The weight percentages are based on the total weight of the composition, and the sum of the weight percentages of components (A), (B), (C), (D), (E) and (K) is 100% by weight.

[0054] Generally, the chemical properties of the inorganic particles (A) are not specifically limited. (A) may have the same chemical properties or be a mixture of particles with different chemical properties. Typically, particles (A) with the same chemical properties are preferred.

[0055] (A) can be inorganic particles, such as metals, metal oxides, or carbides, including metalloids, metalloid oxides, or carbides, or

[0056] - A mixture of inorganic particles.

[0057] Generally speaking, (A) can be

[0058] - A type of colloidal inorganic particle

[0059] - A type of smoke-like inorganic particles

[0060] - A mixture of different types of colloidal and / or fumed inorganic particles.

[0061] Generally, colloidal inorganic particles are inorganic particles prepared using wet precipitation methods; smoky inorganic particles are prepared by, for example, using... The method involves preparing precursors, such as metal chlorides, by high-temperature flame hydrolysis with hydrogen in the presence of oxygen.

[0062] Preferably, the inorganic particles (A) are colloidal or fumigated inorganic particles or mixtures thereof. Oxides and carbides of metals or metalloids are preferred. More preferably, particles (A) are aluminum oxide, cerium oxide, copper oxide, iron oxide, nickel oxide, manganese oxide, silicon dioxide, silicon nitride, silicon carbide, tin oxide, titanium dioxide, titanium carbide, tungsten oxide, yttrium oxide, zirconium oxide, or mixtures or composites thereof. Most preferably, particles (A) are aluminum oxide, cerium oxide, silicon dioxide, titanium dioxide, zirconium oxide, or mixtures or composites thereof. Specifically, (A) is silicon dioxide particles. In one embodiment, (A) is colloidal silicon dioxide particles.

[0063] As used herein, the term "colloidal silica" refers to silica prepared by the condensation polymerization of Si(OH)4. The precursor Si(OH)4 can be obtained, for example, by hydrolyzing a high-purity alkoxysilane or by acidifying an aqueous silicate solution. This colloidal silica can be prepared according to U.S. Patent No. 5,230,833, or can be obtained in any of the forms of various commercially available products, such as Fuso PL-1, PL-2, and PL-3, and Nalco 1050, 2327, and 2329, as well as other similar products purchased from DuPont, Bayer, Applied Research, Nissan Chemical, Nyacol, and Clariant.

[0064] According to the subject matter of the invention, the amount of inorganic particles (A) in the CMP composition is ≥0.10 wt% to ≤4.00 wt% based on the total weight of the CMP composition. Preferably, the amount of (A) in the CMP composition is ≥0.15 wt% to ≤4.00 wt%. More preferably, the amount of (A) in the CMP composition is ≥0.20 wt% to ≤4.00 wt%, and even more preferably, the amount of (A) in the CMP composition is ≥0.25 wt% to ≤4.00 wt%, or ≥0.30 wt% to ≤4.00 wt%, or ≥0.35 wt% to ≤4.00 wt%. Most preferably, the amount of (A) in the CMP composition is ≥0.40 wt% to ≤4.00 wt%, or ≥0.45 wt% to ≤4.00 wt%. In each case, the amount of (A) is based on the total weight of the CMP composition. In one embodiment, the amount of (A) in the CMP composition is ≥0.50% by weight to ≤4.00% by weight, based on the total weight of the CMP composition.

[0065] Generally, particles (A) can be contained in the CMP composition with various particle size distributions. The particle size distribution of particles (A) can be unimodal or multimodal. In the case of multimodal particle size distributions, bimodal is generally preferred. For reproducible properties and conditions during the CMP method of the subject matter of this invention, a unimodal particle size distribution is preferred for particles (A). Particles (A) often most preferably have a unimodal particle size distribution. Generally, the particle size distribution that particles (A) can have is not particularly limited.

[0066] The average particle size of particle (A) can vary over a wide range. The average particle size is d of the particle size distribution of particle (A) in the aqueous medium (E). 50The value can be measured, for example, using dynamic light scattering (DLS) or static light scattering (SLS) methods. Such and other methods are well known in this art; see, for example, Kuntzsch, Timo; Witnik, Ulrike; Hollatz, Michael Stintz; Ripperger, Siegfried; Characterization of Slurries Used for Chemical-Mechanical Polishing (CMP) in the Semiconductor Industry; Chem. Eng. Technol; 26 (2003), Vol. 12, p. 1235.

[0067] For DLS, the Horiba LB-550V (DLS, Dynamic Light Scattering Measurement according to the manual) or any other such instrument is typically used. This technique measures the hydrodynamic diameter of particles as they scatter a laser source (λ = 650 nm), detected at angles of 90° or 173° to the incident light. Variations in the intensity of the scattered light are attributed to the random Brownian motion of the particles as they move through the incident beam, and their change over time is monitored. The decay constant is extracted using an autocorrelation function performed by the instrument as a function of the delay time; smaller particles move through the incident beam at higher speeds and correspond to faster decay.

[0068] Decay constant and particle diffusion coefficient D t Proportional and used to calculate particle size according to the Stokes-Einstein equation:

[0069]

[0070] It is assumed that the suspended particles (1) have a spherical morphology and (2) are uniformly dispersed (i.e., do not aggregate) throughout the aqueous medium (E). This relationship is expected to hold for particle dispersions containing less than 1% by weight of solids, since the viscosity of the aqueous dispersant (E) is not significantly deviated, where η = 0.96 mPa·s (at T = 22 °C). The particle size distribution of atomized or colloidal inorganic particle dispersions (A) is typically measured in a plastic photocell at a solids concentration of 0.1% to 1.0%, and diluted with a dispersion medium or ultrapure water if necessary.

[0071] Preferably, when measured using dynamic light scattering techniques with instruments such as a High Performance Particle Sizer (HPPS; from Malvern Instruments Ltd.) or a Horiba LB550, the average particle size of particle (A) is in the range of 20 to 200 nm, more preferably in the range of 25 to 180 nm, most preferably in the range of 30 to 170 nm, particularly preferably in the range of 40 to 160 nm, and especially in the range of 45 to 150 nm.

[0072] The BET surface of particle (A), as determined according to DIN ISO 9277:2010-09, can vary over a wide range. Preferably, the BET surface of particle (A) is between 1 and 500 μm. 2 Within the range of / g, more preferably 5 to 250m 2 Within the range of / g, the optimal value is between 10 and 100m. 2 Within the range of / g, especially in the range of 20 to 95m 2 Within the range of / g, for example, from 25 to 92m 2 Within the range of / g.

[0073] Particle (A) can have various shapes. Thus, particle (A) can have one or essentially only one type of shape. However, particle (A) can also have different shapes. For example, two types of particles (A) with different shapes can exist. For example, (A) can have the following shapes: aggregates, cubes, cubes with slanted edges, octahedrons, icosahedrons, cocoons, nodules, and spheres, with or without protrusions or indentations. Preferably, it is essentially spherical, thereby these particles (A) typically have protrusions or indentations.

[0074] Preferably, the inorganic particles (A) are cocoon-shaped. The cocoons may or may not have protrusions or indentations. The cocoon-shaped particles are particles with a minor axis of 10 to 200 nm and a major axis / minor axis ratio of 1.4 to 2.2, more preferably 1.6 to 2.0. Preferably, their average shape factor is 0.7 to 0.97, more preferably 0.77 to 0.92, their average sphericity is 0.4 to 0.9, more preferably 0.5 to 0.7, and their average equivalent circle diameter is 41 to 66 nm, more preferably 48 to 60 nm, which can be determined by transmission electron microscopy and scanning electron microscopy.

[0075] The following section explains the determination of the shape factor, sphericity, and equivalent circle diameter of cocoon-like particles.

[0076] The shape factor provides information about the shape and indentation of individual particles and can be calculated using the following formula:

[0077] Shape factor = 4π (area / perimeter)2 )

[0078] The shape factor of a spherical particle without dents is 1. As the number of dents increases, the value of the shape factor decreases.

[0079] Sphericity uses the moment about the mean to provide information about the elongation of individual particles, and can be calculated using the following formula, where M is the centroid of the corresponding particle:

[0080]

[0081] Elongation = (1 / sphericity) 0.5

[0082] in

[0083] M xx =Σ(xx) 平均 ) 2 / N

[0084] M yy =Σ(yy) 平均 ) 2 / N

[0085] M xy =Σ[(xx 平均 )×(yy 平均 )] / N

[0086] N is the number of pixels that form the image of an individual particle.

[0087] x, y are the coordinates of pixels.

[0088] x 平均 The mean of the x-coordinates of the N pixels that form the particle image

[0089] y 平均 The mean of the y-coordinates of the N pixels that form the particle image

[0090] A spherical particle has a sphericity of 1. The sphericity value decreases when the particle is stretched.

[0091] The equivalent circle diameter (ECD) of an individual non-circular particle provides information about the diameter of a circle with the same area as the individual non-circular particle.

[0092] The mean shape factor, mean sphericity, and mean ECD are the arithmetic mean of the individual properties related to the number of particles analyzed.

[0093] For particle shape characterization, an aqueous cocoon-like silica particle dispersion with a weight solids content of 20% was dispersed on a carbon foil and dried. The dried dispersion was analyzed using energy-filtered transmission electron microscopy (EF-TEM) (120 kV) and scanning electron microscopy secondary electron image (SEM-SE) (5 kV). EF-TEM images with a resolution of 2 kΩ, 16 bits, and 0.6851 nm / pixel were used for this analysis. The images were binary encoded using threshold values ​​after noise suppression. The particles were then manually separated. Overlying and edge particles were identified and excluded from the analysis. ECD, shape factor, and sphericity were calculated and statistically classified as previously defined.

[0094] The CMP composition also contains at least one organic compound (B) that contains an amino group and / or at least one acid group (Y).

[0095] At least one acid group (Y) is defined as (Y) itself and its deprotonated form. The acid group (Y) contained in the organic compound (B) is preferably any acid group, such that…

[0096] reaction or

[0097] reaction

[0098] The pKa value (logarithmic measurement of acid dissociation constant) is not greater than 7, more preferably not greater than 6, most preferably not greater than 5.5, and particularly preferably not greater than 5, and is measured in deionized water at 25°C and atmospheric pressure.

[0099] The acid group (Y) contained in the organic compound (B) is preferably a carboxylic acid (–COOH), carbonic acid (–O–COOH), sulfonic acid (–SO3H), sulfuric acid (–O–SO3H), phosphonic acid (–P(=O)(OH)2), phosphoric acid (–O–P(=O)(OH)2) moiety or its deprotonated form. More preferably, the acid group (Y) is a carboxylic acid (–COOH), sulfonic acid (–SO3H), sulfuric acid (–O–SO3H), or phosphonic acid (–P(=O)(OH)2) moiety or its deprotonated form. Most preferably, the acid group (Y) is a carboxylic acid (–COOH), sulfonic acid (–SO3H), or phosphonic acid (–P(=O)(OH)2) moiety or its deprotonated form.

[0100] At least one organic compound (B) comprising an amino group and / or at least one acid group (Y) is preferably an amino acid, a substituted ethylenediamine, or a polycarboxylic acid. The term "polycarboxylic acid" refers to dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and pentacarboxylic acids. Preferably, the polycarboxylic acid is selected from dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids. More preferably, the polycarboxylic acid is selected from dicarboxylic acids and tricarboxylic acids. In one embodiment, the organic compound (B) is selected from: amino acids, substituted ethylenediamine, dicarboxylic acids, and tricarboxylic acids.

[0101] At least one organic compound (B) is a non-polymeric compound, preferably having a molecular weight of less than 600 g / mol. More preferably, it has a molecular weight of less than 400 g / mol. Most preferably, it has a molecular weight of less than 300 g / mol.

[0102] Generally, any organic compound having both an amino group and an acid group is called an amino acid. For the purposes of this invention, all individual stereoisomers and their racemic mixtures are also considered amino acids. Preferably, both the amino group and the acid group are attached to a carbon atom (called α-aminocarboxylic acid), used as a chemical additive in CMP slurries. Many α-aminocarboxylic acids are known, and there are twenty “natural” amino acids that are the basic building blocks of proteins in living organisms. Depending on the side chain present in the aqueous carrier, the amino acid can be acidic, neutral, or basic. If the side chain of an α-amino acid contains an additional proton-donating group (acidic), such as a carboxylic acid group, the amino acid is an acidic amino acid.

[0103] To be understood, the subject matter of this invention is entirely substituted by a group comprising at least one carbon atom covalently bonded to at least one nitrogen atom of an ethylenediamine or diethylenetriamine structure (if present in organic compound (B)). The group comprising the carbon atom serves as a linking group between the nitrogen-containing ethylenediamine or diethylenetriamine structure and the acid group (Y), as a whole, in compound (B).

[0104] The group containing carbon atoms is preferably a CH2, CH2CH2, CH2CH2CH2 or CH2CH2CH2CH2 group, more preferably a CH2, CH2CH2 or CH2CH2CH2 group, and most preferably a CH2 group.

[0105] At least one organic compound (B) is selected from: glycine, glutamic acid, aspartic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, sulfonylalanine, aminotris(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), malonic acid, citric acid, and tartaric acid. Preferably, organic compound (B) is selected from: glycine, ethylenediaminetetraacetic acid, aminotris(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), malonic acid, citric acid, and tartaric acid.

[0106] More preferably, the organic compound (B) is selected from: glycine, ethylenediaminetetraacetic acid, aminotris(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), malonic acid, citric acid and tartaric acid.

[0107] Most preferably, the organic compound (B) is selected from: glycine, ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid), malonic acid, citric acid, and tartaric acid. In one embodiment, the organic compound (B) is selected from: glycine, ethylenediaminetetraacetic acid, malonic acid, citric acid, and tartaric acid.

[0108] According to the subject matter of the invention, the amount of at least one organic compound (B) comprising an amino group and / or at least one acid group (Y) in the CMP composition is ≥0.10 wt% to ≤0.90 wt%. Preferably, the amount of (B) in the CMP composition is ≥0.10 wt% to ≤0.88 wt%. More preferably, the amount of (A) in the CMP composition is ≥0.10 wt% to ≤0.86 wt%, and even more preferably, the amount of (A) in the CMP composition is ≥0.10 wt% to ≤0.84 wt%. Most preferably, the amount of (A) in the CMP composition is ≥0.10 wt% to ≤0.82 wt%. In each case, the amount of (B) is based on the total weight of the CMP composition. In one embodiment, the amount of (B) in the CMP composition is ≥0.10 wt% to ≤0.81 wt% based on the total weight of the CMP composition.

[0109] Adding an organic compound (B) containing an amino group and / or at least one acid group (Y) as a polishing additive can improve the material removal rate of all metals (i.e., cobalt and / or cobalt alloys and TiN and / or TaN).

[0110] The CMP composition according to the present invention comprises potassium persulfate (C) as an oxidant. Typically, an oxidant is a compound capable of oxidizing the substrate to be polished or one of the layers of the substrate. In the prior art, such oxides are present in the form of peroxides, persulfates, perchlorates, perbromates, periodates, permanganates, or derivatives thereof. However, extensive research has not been conducted on using persulfates as oxidants, and more preferably potassium persulfate (K₂S₂O₈). One advantage gained from this selection is the control of the MRR of TiN and TaN. The selective oxidant, namely potassium persulfate (C), helps to achieve a TiN:TaN MRR ratio in the range of ≥0.5 to ≤2.0.

[0111] Therefore, the amount of potassium persulfate (C) is ≥0.20 wt% to ≤0.90 wt% based on the total weight of the CMP composition. Preferably, the amount of (C) is ≥0.20 wt% to ≤0.85 wt%. More preferably, the amount of (C) is ≥0.25 wt% to ≤0.85 wt%, and even more preferably, the amount of (C) is ≥0.30 wt% to ≤0.70 wt%, or ≥0.30 wt% to ≤0.65 wt%, or ≥0.35 wt% to ≤0.65 wt%. Most preferably, the amount of (C) is ≥0.40 wt% to ≤0.65 wt%, or ≥0.45 wt% to ≤0.65 wt%, or ≥0.45 wt% to ≤0.60 wt%. In each case, the amount of (C) is based on the total weight of the CMP composition. In one embodiment, the amount of (C) in the CMP composition is ≥0.45% by weight to ≤0.55% by weight, based on the total weight of the CMP composition.

[0112] During substrate polishing, metal ions from the polishing surface enter the polishing solution. These metal ions can form complexes with the CMP composition, resulting in inefficient substrate polishing. Therefore, a corrosion inhibitor is added to the CMP composition, which acts as a classic complexing / chelating agent in the formation of metal complexes by reacting with the substrate rather than by reacting with metal ions in solution. The CMP composition according to the subject matter of the invention comprises at least one corrosion inhibitor (E).

[0113] Preferably, at least one corrosion inhibitor (E) may be phthalic acid, 4-sulfophthalic acid, 4-hydroxyphthalic acid, 3-aminophthalic acid, 4-aminophthalic acid, 4-methylphthalic acid, 4-methoxyphthalic acid, 3,3,4,4-benzophenone tetracarboxylic acid, 5-aminoisophthalic acid, isophthalic acid, 1,3,5-benzenetricarboxylic acid, 5-hydroxyisophthalic acid, 5-methylisophthalic acid, 1,2,3-benzenetricarboxylic acid hydrate, 4-hydroxyisophthalic acid, 5-methoxyisophthalic acid, 4-methoxyisophthalic acid, (1,1,2,1)-triphenyl-3,5-dicarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, 2-aminophthalic acid, etc. 9,10-Anthracene dicarboxylic acid, phenylpentacarboxylic acid, phenylhexacarboxylic acid, 2,5-dihydroxyterephthalic acid, 2,5-diaminoterephthalic acid, dimethyl 2,5-dimethyl-terephthalate, 5,5-carbonylbis(trimethicone), 3,5-dimethylpyrazole, pyrazole, 5-methyl-1H-pyrazole-3-carboxylic acid, 1-methylpyrazole, 1,3,5-trimethyl-1H-pyrazole-4-carboxylic acid, 3-methyl-1-phenyl-1H-pyrazole, 3,5-dimethyl-1-phenylpyrazole, 5-amino-3-methyl-1-phenylpyrazole, 1-phenyl-1H-pyrazole-5-carboxylic acid, 5-phenyl-1H-pyrazole-3-carboxylic acid, 3,5-diphenylpyrazole, 5-amino-1-methyl-1H-pyrazole, 3- Methylpyrazole, 3-amino-5-phenylpyrazole, 3-pyrazole carboxylic acid, 3-aminopyrazole, 3-amino-5-ethyl-1H-pyrazole, 1-methyl-1H-pyrazole-3-amine, 3(5)-phenyl-1H-pyrazole, 4,6-dihydroxypyrazolo[3,4-d]pyrimidine, 3,5-pyrazole dicarboxylic acid monohydrate, 1,3-dimethyl-1H-pyrazole-5-amine, 5-amino-1-ethylpyrazole, ethyl 3-methyl-1H-pyrazole-5-carboxylic acid, 1,3-diphenyl-1H-pyrazole-5-amine, ethyl 1,5-dimethyl-1H-pyrazole-3-carboxylic acid, 1,3-dimethyl-1H-pyrazole-5-carboxylic acid, 1,5-dimethyl-1H-pyrazole-3-carboxylic acid, pyrazolo[1,5-a]pyrazole Dimethyl pyridine-2,3-dicarboxylic acid, 1-methyl-1H-pyrazole-4-carboxylic acid, 3-amino-5-hydroxypyrazole, 3-amino-4-ethoxycarbonylpyrazole, 4-methylpyrazole, 1-methyl-3-phenyl-1H-pyrazole-5-amine, 1-methyl-5-phenyl-1H-pyrazole-3-carboxylic acid, 1-methyl-3-phenyl-1H-pyrazole-5-carboxylic acid, methyl 1H-pyrazole-3-carboxylic acid, 1-methyl-1H-pyrazole-5-carboxylic acid, ethyl 5-amino-1-phenyl-1H-pyrazole-4-carboxylic acid, pyrazolo[1,5-a]pyridine-3-carboxylic acid, 4-(1H-pyrazole-1-yl)aniline, 5-amino-1-methyl-1H-pyrazole-4-carboxamide, 1-methyl-1H-pyrazole-3-carboxylic acidPyrazolo[1,5-a]pyrimidine-3-carboxylic acid, 3-(4-methoxyphenyl)pyrazole, 1,3,5-trimethyl-1H-pyrazolyl-4-amine, 3-(5-methyl-1H-pyrazolyl-4-yl)propylamine, ethyl 5-amino-1-methylpyrazol-4-carboxylic acid, 3-methyl-1H-pyrazolyl-5-amine, 2-methyl-2H-indazole-3-carboxylic acid, ethyl 3,5-dimethyl-1H-4-pyrazolylcarboxylate, ethyl 4-pyrazolylcarboxylate, diethyl pyrazolyl-3,5-dicarboxylic acid, 4-pyrazolylcarboxylic acid, 6-amino-2-methyl-2H-indazole, 1-ethyl-3-methyl-1H-pyrazolyl-5-carboxylic acid, 4-(3,5-dimethyl-1H-pyrazolyl-1-yl)aniline, 4-[3,5-di(tert-)-pyrazolyl-3-carboxylic acid ... [Butyl]-1H-pyrazolyl-1-yl]aniline, 2-(1H-pyrazolyl-1-yl)benzoic acid, (1,3-dimethyl-1H-pyrazolyl-5-yl)methanol, (3,5-dimethyl-1-phenyl-1H-pyrazolyl-4-yl)methanol, 3,5-dimethyl-1-phenyl-1H-pyrazolyl-4-carboxylic acid, pyrazolo[1,5-a]pyridine-2-carboxylic acid, 5-amino-3-(4-methylphenyl)pyrazole, 4-(3,5-dimethyl-1H-pyrazolyl-1-yl)benzoic acid, 4-ethylhydro-1-methyl-1H-pyrazole-4,5-dicarboxylic acid ester, 3-amino-5-tert-butyl-1H-pyrazole, (1-methyl-1H-pyrazolyl-5-yl)methanol, (1-methyl-1H-pyrazolyl-3-yl)-[1,5-dimethyl-1H-pyrazolyl-3-yl]aniline, 2-(1H-pyrazolyl-1-yl)benzoic acid, (1,3-dimethyl-1H-pyrazolyl-5-yl)methanol, (1-methyl-1H-pyrazolyl-3-yl)-[1,5-dimethyl-1H-pyrazolyl-3-yl]aniline, 2-(1H-pyrazolyl-1-yl)benzoic acid ... 7-Amino-2-methylindazole, 5-methyl-1-phenyl-1H-pyrazole-4-carboxylic acid, 3-(2-furanyl)-1H-pyrazole-5-amine, 1-benzyl-3-(tert-butyl)-1H-pyrazole-5-carboxylic acid, ethyl 3-(2-furanyl)-1-methyl-1H-pyrazole-5-carboxylic acid, 1-methyl-5-phenyl-1H-pyrazole-4-carboxylic acid, 5-(2-furanyl)-1-methyl-1H-pyrazole-3-carboxylic acid, 3,5-dimethyl-1H-pyrazole-4-carboxylic acid, 5-(2-furanyl)-1H-pyrazole-3-carboxylic acid, 1-phenyl-5-propyl-1H-pyrazole-4-carboxylic acid, 3-(tert-butyl)-1-methyl-1H-pyrazole-5-amine, 3-cyclopropyl -1-Methyl-1H-pyrazolyl-5-amine, histamine, caffeine, theophylline, xanthine, L-histidine, guanine, theobromine, imidazole acrylic acid, guanosine, imidazo[1,2-a]pyridine, imidazole, benzimidazole L-carnosine, 5-aminoimidazolium-4-carboxamide, 7-(2,3-dihydroxypropyl)theophylline, 1,1'-carbonyldiimidazolium, 4,5-imidazolium dicarboxylic acid, N-methylimidazolium, 4-phenyl-1H-imidazolium, 2-phenylimidazolium, N-[2-(1H-imidazolium-4-yl)ethyl]acetamide, 2-methylimidazolium, imidazo[1,2-b]pyridazine, 4-methylimidazolium, 2'-deoxyinosine, 2,4-dimethylimidazolium, 2-ethylimidazolium, 1H-imidazolium-4-carboxylic acid, 3-methylxanthine,1,2-Dimethylimidazolium, 1-acetylimidazolium, 5-aminoimidazolium-4-carboxamide-1-β-D-ribonucleoside, dimethyl 4,5-imidazolium dicarboxylate, 1-benzylimidazolium, 1-dodecylimidazolium, N-(3-aminopropyl)imidazolium, imidazo[1,2-a]pyridine-3-carboxylic acid, 1-phenylimidazolium, 4-(imidazol-1-yl)phenol, 1H-imidazol-2-carboxylic acid, methyl 1-methyl-1H-imidazol-4-carboxylic acid, methyl 1-methyl-1H-imidazol-5-carboxylic acid, (1-methyl-1H-imidazol-4-yl)methanol, methyl 4-imidazolium carboxylate, (1-methyl-1H-imidazol-2-yl)methanol, 4-(1H-imidazol-1-yl)benzoic acid, Nα-BOC-L-histidine, 1,1 '-Oxaloyldiimidazole, 3-(1H-imidazol-1-yl)propionic acid, 2-amino-7-ethyl-1,7-dihydro-6H-purine-6-one, 1-methyl-1H-imidazol-2-carboxylic acid, 2-methylimidazo[1,2-a]pyridine-3-carboxylic acid, 2-(1H-imidazol-1-yl)benzylamine, 2-(1H-imidazol-1-yl)aniline, 2-(2-methyl-1H-imidazol-1-yl)aniline, 3-isobutyl-1-methylxanthine, 1-allylimidazol, 2-isopropylimidazol, 1-methyl-1H-imidazol-4-carboxylic acid, 1-methyl-1H-imidazol-5-carboxylic acid, 4-methyl-5-imidazol carboxyethyl ester, 4-(1H-imidazol-1-ylmethyl)aniline, acyclovir (Acyclovir) anosine), imidazo[1,2-a]pyridine-2-carboxylic acid monohydrate, (2-butyl-1H-imidazol-4-yl)methanol, (2-butyl-1H-imidazol-4-yl)methanol, 4-(2-methyl-1H-imidazol-1-yl)aniline, 2-phenyl-1H-imidazol-4-carboxylic acid 1,5-hydrate, imidazo[1,2-a]pyridine-2-ylmethanol, [4-(1H-imidazol-1-yl)phenyl]methanol, [4-(1H-imidazol-1-ylmethyl)phenyl]methanol, imidazo[1,2-a]pyridine-6-carboxylonitrile, 3-(1H-imidazol-1-yl)benzoic acid, N-α-FMOC-N-triyl-L-histamine, 4-(1H-imidazol-1-ylmethyl)benzylnitrile, 3- (1H-imidazol-1-ylmethyl)aniline, 1,2-dimethyl-1H-imidazol-5-carboxylic acid, tetrazolium, 5-phenyltetrazole, 5-aminotetrazole, 5-(aminomethyl)tetrazole, 1-propyl5-aminotetrazole, 1-butyl5-aminotetrazole, 3-(1H-tetrazole-1-yl)propionic acid, (5-amino-1H-tetrazole-1-yl)acetic acid, 4-(1H-tetrazole-1-ylmethyl)benzoic acid, (5-amino-1H-tetrazole-1-yl)ethyl acetate, 1H-tetrazole-5-ethyl acetate, 5-(4-methylphenyl)-1H-tetrazole, 4-(1H-tetrazole-5-ylmethyl)phenol, 4-[(5-methyl-1H-tetrazole-1-yl)methyl]benzoic acid, 4-(1H-tetrazole-5-yloxy)aniline,3-(1H-tetrazol-5-yl)benzyl alcohol, 4-(1H-tetrazol-5-yl)piperidine, 2-(1H-tetrazol-1-yl)aniline, 1-allyl-N-benzyl-1H-tetrazol-5-amine, 2-(1H-tetrazol-5-yl)phenylamine, 3-(1H-tetrazol-1-yl)phenol, pentylenetetrazol, (5-methyl-1H-tetrazol-1-yl)(phenyl)acetic acid, 2-amino-4-(1H-tetrazol-5-yl)benzoic acid, 3-methoxy-5-(1H-tetrazol-1-yl)aniline, 3-phenyl-2-tetrazol-1-yl-propionic acid, 4-(5-methyl-1H-tetrazol-1-yl)aniline, 3-(5-methyl-1H-tetrazol-1-yl)aniline, 3-(1H-tetrazol-1-yl)phenylamine ... 5-(1H-methyl-1H-tetrazol-1-yl)benzoic acid, 4-(5-methyl-1H-tetrazol-1-yl)phenol, 2-hydroxy-5-(1H-tetrazol-1-yl)benzoic acid, 3-(5-methyl-1H-tetrazol-1-yl)phenol, 3-(5-p-tolyl-tetrazol-1-yl)propionic acid, 5-(3-pyridine)-1H-tetrazol, 5-(2-pyridine)-1H-tetrazol, [4-(5-methyl-1H-tetrazol-1-yl)phenyl]acetic acid, 3-(1H-tetrazol-1-yl)-1H-pyrazole-4-carboxylic acid, (5-amino-1H-tetrazol-1-yl)acetic acid, (5-methyl-1H-tetrazol-1-yl)(phenyl)acetic acid, [4-(5-methyl-1H-tetrazol-1-yl)phenyl]acetic acid, 1-allyl-N Benzyl-1H-tetrazole-5-amine, 1H-tetrazole-5-acetic acid, 2-(1H-tetrazole-1-yl)aniline, 2-(1H-tetrazole-5-yl)-phenylamine, 2-amino-4-(1H-tetrazole-5-yl)benzoic acid, 2-hydroxy-5-(1H-tetrazole-1-yl)benzoic acid, 3-(1H-tetrazole-1-yl)-1H-pyrazole-4-carboxylic acid, 3-(1H-tetrazole-1-yl)benzoic acid, 3-(1H-tetrazole-1-yl)phenol, 3-(1H-tetrazole-5-yl)benzyl alcohol, 3-(5-methyl-1H-tetrazole-1-yl)phenol, 3-(5-p-tolyl-tetrazole-1-yl)propionic acid, 3-phenyl-2-tetrazole-1-yl-propionic acid, 4-(1H-tetrazole- 1-(1H-tetrazol-5-yl)benzoic acid, 4-(1H-tetrazol-5-yl)piperidine, 4-(1H-tetrazol-5-ylmethyl)phenol, 4-(5-methyl-1H-tetrazol-1-yl)aniline, 4-(5-methyl-1H-tetrazol-1-yl)phenol, 4-[(5-methyl-1H-tetrazol-1-yl)methyl]benzoic acid, (5-amino-1H-tetrazol-1-yl)ethyl acetate, 1H-tetrazol-5-ethyl acetate, 2-phenyl-3-[4-(1H-1,2,3,4-tetrazol-5-yl)benzyl]-4H-chromen-4-one, 2-phenyl-3-[4-(1H-1,2,3,4-tetrazol-5-yl)benzylidene]chroman-4-one,4-Ethyl-5-(1-phenyl-1H-1,2,3,4-tetrazol-5-yl)pyrimidin-2-amine, 6-phenyl-5,6-dihydrobenzo[f][1,2,3,4]tetrazol[1,5-d][1,4]oxazepine, 4-Ethyl-5-[1-(4-methylphenyl)-1H-1,2,3,4-tetrazol-5-yl]pyrimidin-2-amine, 5-[1-(4-methylphenyl)-1H-1,2,3,4-tetrazol-5-yl]-4-propylpyrimidin-2-amine, 4-methyl-3-[1-(4-methylphenyl)-1H-1,2,3,4-tetrazol-5-yl]quinolone, 4-methyl-3-(1-phenyl-1H-1,2,3,4-tetrazol-5-yl]quinolone, 2,3,4-Tetrazol-5-yl)quinolone, N1-benzyl-2-(1-phenyl-1H-1,2,3,4-tetrazol-5-yl)ethylene-1-en-1-amine, N1,N1-diethyl-2-[1-(4-methylphenyl)-1H-1,2,3,4-tetrazol-5-yl]ethylene-1-en-1-amine, methyl 2-{[2-(1-phenyl-1H-1,2,3,4-tetrazol-5-yl)vinyl]amino}benzoate, 2,4-diphenyl-5-(1-phenyl-1H-1,2,3,4-tetrazol-5-yl)pyrimidine, 5-[1-(4-methylphenyl)-1H-1,2,3,4-tetrazol-5-yl]-2,4-diphenylpyrimidine, 1-[4-(tert-butyl) [Phenyl]-5-phenyl-1H-1,2,3,4-tetrazolium, N2-methyl-4-phenyl-5-(1-phenyl-1H-1,2,3,4-tetrazol-5-yl)pyrimidin-2-amine, 3,5-di(acetyloxy)-2-[(acetyloxy)methyl]-6-(1H-1,2,3,4-tetrazol-5-yl)tetrahydro-2H-pyran-4-ylacetate, 3-{5-[4-(tert-butyl)phenyl]-1H-1,2,3,4-tetrazol-1-yl}pyridine, 7-methyl-5-phenyl[1,2,3,4]tetrazol[1,5-a]pyrimidinium, 5-methyl-N-(1H-1,2,3,4-tetrazol-5-yl)-2-pyrazin carboxamide, 5-methyl-3-[1 -(4-methylphenyl)-1H-1,2,3,4-tetrazol-5-yl]-1H-indole, 3-[1-(4-methoxyphenyl)-1H-1,2,3,4-tetrazol-5-yl]-5-methyl-1H-indole, 2,3-di(acetyloxy)-1-[1,2-di(acetyloxy)ethyl]-3-(1H-1,2,3,4-tetrazol-5-yl)propyl acetate, 2,3-di(acetyloxy)-1-[1,2-di(acetyloxy)ethyl]-3-(1H-1,2,3,4-tetrazol-5-yl)propyl acetate, 3-[1-(4-methylphenyl)-1H-1,2,3,4-tetrazol-5-yl]-1,4-dihydroquinoline-4-one,3-(1-Phenylacetyl-1H-1,2,3,4-tetrazol-5-yl)-1,4-dihydroquinoline-4-one, 3-(dimethylamino)-1-(4-methylphenyl)-2-(1-phenyl-1H-1,2,3,4-tetrazol-5-yl)prop-2-en-1-one, 3-(dimethylamino)-1-(2-methylphenyl)-2-(1-phenyl-1H-1,2,3,4-tetrazol-5-yl)prop-2-en-1-one, ethyl 2-({2-[1-(4-methylphenyl)-1H-1,2,3,4-tetrazol-5-yl]vinyl}amino)benzoate, N-methyl-N-(2-{methyl[2-( 1-Phenylacetyl-1H-1,2,3,4-Tetrazol-5-yl)vinyl]aminoethyl)-N-[2-(1-Phenylacetyl-1H-1,2,3,4-Tetrazol-5-yl)vinyl]amine, 4-Methyl-sulfonylbenzoic acid, 3-Methylaminobenzoic acid, 4-(diethylamino)benzoic acid, 3-dimethylaminobenzoic acid, 2-(benzylamino)benzoic acid, 4-methylaminobenzoic acid, 4-(dimethylamino)benzoic acid, N-Oleoylsarcosine, N-Lauroylsarcosine, N-Cocoylsarcosine, N-Cocoylglutamate, 4-Dodecylbenzenesulfonic acid, Toluenesulfonic acid, Tetrapropylenbenzolsulfonate, hexyl phosphate, alkyl phosphate (C6-C10), ([iminobis(methylene)]bisphosphonic acid, N-coco-alkyl derivative), ([iminobis(methylene)]bisphosphonic acid, N-coco-alkyl derivative)-N-oxide, 6,6',6”-(1,3,5-triazine-2,4,6-triyltriimino)trihexanoic acid, 2,4,6-trimethylmelamine, pentamethylmelamine, {[bis(dimethylamino)-1,3,5-triazine-2- [{[(hydroxymethyl)amino)]-1,3,5-triazin-2-yl}amino)methanol, 2,4-diamino-6-diallylamino-1,3,5-triazine, ({[bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl}(hydroxyl-methyl)amino)methanol, N2,N4-di-tert-butyl-1,3,5-triazin-2,4,6-triamine, N2,N4-bis(prop-2-en-1-yl)-1,3,5-triazin-2,4,6-triamine, polyaspartic acid, and mixtures thereof and their salts.

[0114] More preferably, at least one corrosion inhibitor (E) is selected from: imidazole, benzimidazole, benzotriazole, 4-(dimethylamino)benzoic acid, terephthalic acid, isophthalic acid, 6,6',6”-(1,3,5-triazine-2,4,6-triyltriimino)trihexanoic acid, phenyltetrazole, N-lauroyl sarcosine, 4-dodecylbenzenesulfonic acid, C6-C phosphate.10 Alkyl esters, polyaspartic acid and mixtures thereof, and salts thereof.

[0115] Even more preferably, at least one corrosion inhibitor (E) is selected from: benzotriazole, 4-(dimethylamino)benzoic acid, terephthalic acid, isophthalic acid, 6,6',6”-(1,3,5-triazine-2,4,6-triyltriimino)trihexanoic acid, phenyltetrazole, N-lauroyl sarcosine, 4-dodecylbenzenesulfonic acid, C6-C phosphate. 10 Alkyl esters, polyaspartic acid and mixtures thereof, and salts thereof.

[0116] Most preferably, at least one corrosion inhibitor (E) is selected from: benzotriazole, isophthalic acid, 6,6',6”-(1,3,5-triazine-2,4,6-triyltriimino)trihexanoic acid, phenyltetrazole, N-lauroyl sarcosine, 4-dodecylbenzenesulfonic acid, C6-C phosphate. 10 Alkyl esters, polyaspartic acid, mixtures thereof, and salts thereof. In one embodiment, at least one corrosion inhibitor (E) is selected from: benzotriazole, N-lauroyl sarcosine, 4-dodecylbenzenesulfonic acid, polyaspartic acid, mixtures thereof, and salts thereof.

[0117] At least one corrosion inhibitor (E) has a pKa value of less than 8.50, more preferably less than 8.45, and most preferably less than 8.35. In one embodiment, the pKa value of at least one corrosion inhibitor (E) is less than 8.30.

[0118] The amount of at least one corrosion inhibitor (E) in the CMP composition, based on the total weight of the CMP composition, is ≥0.01 wt% to ≤0.50 wt%. Preferably, the amount of (E) is ≥0.01 wt% to ≤0.45 wt%. More preferably, the amount of (E) is ≥0.02 wt% to ≤0.35 wt%, and even more preferably, the amount of (E) is ≥0.02 wt% to ≤0.30 wt%. Most preferably, the amount of (E) is ≥0.02 wt% to ≤0.25 wt%, or ≥0.03 wt% to ≤0.20 wt%, or ≥0.03 wt% to ≤0.15 wt%. In each case, the amount of (E) is based on the total weight of the CMP composition. In one embodiment, the amount of (E) in the CMP composition, based on the total weight of the CMP composition, is ≥0.03 wt% to ≤0.1 wt%.

[0119] The CMP composition may further comprise at least one additive (K) selected from the following: surfactants (F), biocides (H), pH adjusters, buffers, stabilizers, and friction reducers. Such additives are known to those skilled in the art. The amount of at least one additive (K) in the CMP composition is ≥0.01% by weight to ≤1.50% by weight, based on the total weight of the CMP composition. Preferably, the amount of at least one additive (K) is ≥0.01% by weight to ≤1.30% by weight; more preferably, the amount of (K) is ≥0.01% by weight to ≤1.10% by weight; and even more preferably, the amount of (K) is ≥0.01% by weight to ≤1.00% by weight, or ≥0.01% by weight to ≤0.90% by weight, or ≥0.01% by weight to ≤0.70% by weight. Most preferably, the amount of (K) is ≥0.01 wt% to ≤0.50 wt%, or ≥0.01 wt% to ≤0.30 wt%, or ≥0.01 wt% to ≤0.20 wt%. In each case, the amount of (K) is based on the total weight of the CMP composition.

[0120] When the surfactant (F) is selected as at least one additive (K) in the CMP composition, it is a surface-active compound that reduces the surface tension of liquids, the interfacial tension between two liquids, or between a liquid and a solid. Preferably, the surfactant (F) can be any nonionic surfactant (F). Such nonionic surfactants (F) are preferably water-soluble and / or water-dispersible, more preferably water-soluble. The term "water-soluble" means that the relevant components or ingredients of the composition of the subject matter of this invention are soluble in the aqueous phase at the molecular level. The term "water-dispersible" means that the relevant components or ingredients of the composition of the subject matter of this invention can be dispersed in the aqueous phase and form a stable emulsion or suspension.

[0121] The nonionic surfactant (F) is preferably an amphiphilic nonionic surfactant, i.e., a surfactant comprising at least one hydrophobic group (b1) and at least one hydrophilic group (b2). This means that the nonionic surfactant (F) may contain more than one hydrophobic group (b1), for example, two, three or more groups (b1), separated from each other by at least one hydrophilic group (b2), as described below. The nonionic surfactant (F) may also contain more than one hydrophilic group (b2), for example, two, three or more groups (b2), separated from each other by a hydrophobic group (b1), as described below.

[0122] Therefore, nonionic surfactants (F) can have two different universal block structures. Examples of such universal block structures include, but are not limited to:

[0123] -b1-b2,

[0124] -b1-b2-b1,

[0125] -b2-b1-b2,

[0126] -b2-b1-b2-b1,

[0127] -b1-b2-b1-b2-b1, and

[0128] -b2-b1-b2-b1-b2.

[0129] The nonionic surfactant (F) is more preferably an amphiphilic nonionic surfactant containing polyoxyalkylene groups.

[0130] The hydrophobic group (b1) is preferably an alkyl group, more preferably having 4 to 40 carbon atoms, or even more preferably 5 to 20 carbon atoms, or 7 to 18 carbon atoms, or 10 to 16 carbon atoms. The hydrophobic group (b1) is most preferably an alkyl group having 11 to 14 carbon atoms.

[0131] The hydrophilic group (b2) is preferably a polyoxyalkylene group. This polyoxyalkylene group may be oligomerized or polymerized. More preferably, the hydrophilic group (b2) is a hydrophilic group selected from polyoxyalkylene groups comprising the following components.

[0132] (b21) Oxyalkylene monomer units, and

[0133] (b22) Oxyalkylene monomer units other than oxyethylidene monomer units

[0134] The monomer unit (b21) is different from the monomer unit (b22), and the monomer units (b21) and (b22) contained in the polyoxyalkylene group of (b2) are distributed randomly, alternately, in a gradient and / or in blocks.

[0135] Most preferably, the hydrophilic group (b2) is a hydrophilic group selected from polyoxyalkylene groups comprising the following components.

[0136] (b21) Oxyethylidene monomer unit, and

[0137] (b22) Oxyalkylene monomer units other than oxyethylidene monomer units

[0138] The monomer units (b21) and (b22) of the polyoxyalkylene group in (b2) are distributed randomly, alternately, in a gradient and / or in blocks.

[0139] Preferably, the alkylene monomer unit (b22) other than the oxyethylidene monomer unit is a substituted alkylene monomer unit, wherein the substituent is selected from: alkyl, cycloalkyl, aryl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl, and alkyl-cycloalkyl-aryl. The alkylene monomer unit (b22) other than the oxyethylidene monomer unit is...

[0140] -More preferably derived from substituted ethylene oxide (X), wherein the substituent is selected from: alkyl, cycloalkyl, aryl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl, and alkyl-cycloalkyl-aryl.

[0141] - The most preferred derivative is alkyl-substituted ethylene oxide (X).

[0142] - Particularly preferred are derivatives derived from substituted ethylene oxide (X), wherein the substituents are selected from alkyl groups having 1 to 10 carbon atoms.

[0143] In one embodiment, the oxyalkylene monomer unit (b22) other than the oxyethylene monomer unit is derived from methyl ethylene oxide (propylene oxide) and / or ethyl ethylene oxide (butane oxide).

[0144] The substituent of the substituted ethylene oxide (X) may also contain inert substituents, i.e., substituents that do not negatively affect the copolymerization of ethylene oxide (X) and the surface activity of the nonionic surfactant (F). Examples of such inert substituents are fluorine and chlorine atoms, nitrogen groups, and nitrile groups. If such inert substituents are present, their amount is such that they do not negatively affect the hydrophilic-hydrophobic balance of the nonionic surfactant (F). Preferably, the substituted ethylene oxide (X) substituents do not contain such inert substituents.

[0145] The substituents of the substituted ethylene oxide (X) are preferably selected from the following: alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms in a spirocyclic, exocyclic, and / or annealed configuration, and / or aryl groups having 6 to 10 carbon atoms, alkyl-cycloalkyl groups having 6 to 20 carbon atoms, alkyl-aryl groups having 7 to 20 carbon atoms, cycloalkyl-aryl groups having 11 to 20 carbon atoms, and alkyl-cycloalkyl-aryl groups having 12 to 30 carbon atoms. Most preferably, the substituents of the substituted ethylene oxide (X) are selected from alkyl groups having 1 to 10 carbon atoms. In particular, the substituents of the substituted ethylene oxide (X) are selected from alkyl groups having 1 to 6 carbon atoms.

[0146] In one embodiment, the most preferred substituted ethylene oxide (X) is methyl ethylene oxide (propylene oxide) and / or ethyl ethylene oxide (butane oxide), particularly methyl ethylene oxide.

[0147] The preferred option is that the hydrophilic group (b2) is composed of monomer units (b21) and (b22).

[0148] In another specific embodiment, the hydrophilic group (b2) is preferably polyoxyethylene, polyoxypropylene, or polyoxybutylene, more preferably polyoxyethylene.

[0149] When the hydrophilic group (b2) comprises or is composed of monomer units (b21) and (b22), the polyoxyalkylene group (b2) comprises monomer units (b21) and (b22) distributed randomly, alternately, in a gradient, and / or in a block distribution. This means that a hydrophilic group (b2) may have only one distribution type, i.e.

[0150] -Unregulated: …-b21-b21-b22-b21-b22-b22-b22-b21-b22-…;

[0151] - Alternating: ...-b21-b22-b21-b22-b21-...;

[0152] - Gradient: ...b21-b21-b21-b22-b21-b21-b22-b22-b21-b22-b22-b22-b22-...; or

[0153] - Segment: …-b21-b21-b21-b21-b22-b22-b22-b22-….

[0154] Alternatively, the hydrophilic group (b2) may also contain at least two distribution types, for example, having randomly distributed oligomeric or polymeric segments and having alternatingly distributed oligomeric or polymeric segments. Most preferably, the hydrophilic group (b2) preferably has only one distribution type, and most preferably, the distribution is random or block.

[0155] In specific embodiments, the hydrophilic group (b2) comprises or is composed of monomer units (b21) and (b22), and the molar ratio of (b21) to (b22) varies widely, thus allowing for most advantageous adjustments to suit the specific needs of the compositions, methods, and uses of the subject matter of this invention. Preferably, the molar ratio of (b21):(b22) is 100:1 to 1:1, more preferably, 60:1 to 1.5:1, most preferably 50:1 to 1.5:1, particularly preferably, 25:1 to 1.5:1, especially 15:1 to 2:1, for example, 9:1 to 2:1.

[0156] Furthermore, the degree of polymerization of oligomeric and polymeric polyoxyalkylene groups (b2) varies widely, thus allowing for most advantageous adjustments to suit the specific needs of the compositions, methods, and applications of the present invention. Preferably, the degree of polymerization is in the range of 5 to 100, more preferably 5 to 90, and most preferably 5 to 80.

[0157] Specifically, the nonionic surfactant (F) is an amphiphilic nonionic polyoxyethylene-polyoxypropylene alkyl ether surfactant, which is a molecular mixture comprising 5 to 20 oxyethylene monomer units (b21) having an average of 10 to 16 carbon atoms in a random distribution and 2 to 8 oxypropylene monomer units. In one embodiment, the nonionic surfactant (F) is an amphiphilic nonionic polyoxyethylene-polyoxypropylene alkyl ether surfactant, which is a molecular mixture comprising 12 to 20 oxyethylene monomer units having an average of 11 to 14 carbon atoms in a random distribution and 3 to 5 oxypropylene monomer units.

[0158] If present, the amount of nonionic surfactant (F) may be ≥0.01 wt% to ≤1.30 wt%, more preferably, the amount of (F) is ≥0.01 wt% to ≤1.10 wt%, and even more preferably, the amount of (F) is ≥0.01 wt% to ≤1.00 wt%, or ≥0.01 wt% to ≤0.90 wt%, or ≥0.01 wt% to ≤0.70 wt%. Most preferably, the amount of (F) is ≥0.01 wt% to ≤0.50 wt%, or ≥0.01 wt% to ≤0.30 wt%, or ≥0.01 wt% to ≤0.20 wt%, or ≥0.01 wt% to ≤0.10 wt%, or ≥0.01 wt% to ≤0.08 wt%, or ≥0.01 wt% to ≤0.05 wt%. In each case, the amount of (F) is based on the total weight of the CMP composition. In one embodiment, the amount of nonionic surfactant (F) in the CMP composition is ≥0.01% by weight to ≤0.03% by weight, based on the total weight of the CMP composition.

[0159] Nonionic surfactants (F) can have different weight-average molecular weights. The weight-average molecular weight (F) is preferably at least 300, more preferably at least 500, most preferably at least 700, especially at least 800, for example at least 900. The weight-average molecular weight (F) is preferably not greater than 15,000, more preferably not greater than 6,000, most preferably not greater than 3,000, especially not greater than 2,000, for example not greater than 1,400 [g / mol], determined by gel permeation chromatography (GPC). In particular, the weight-average molecular weight (F) is from 900 to 1,400 [g / mol], determined by GPC. This GPC is a standard GPC technique known to those skilled in the art.

[0160] The solubility of nonionic surfactant (F) in aqueous media varies widely. The solubility of (F) in water at pH 7 at atmospheric pressure and 25°C is preferably at least 1 g / L, more preferably at least 5 g / L, most preferably at least 20 g / L, and even more preferably at least 50 g / L or 150 g / L.

[0161] If present as at least one additive (K), the biocide (H) may be at least one biocide (H). A biocide is a compound that, by means of chemical or biological methods, prevents any harmful organism from becoming harmless, or exerts a controlling effect on any harmful organism. Preferably, (H) is a quaternary ammonium compound, an isothiazolinone-based compound, an N-substituted diazepine dioxide, or an N'-hydroxy-diazepine dioxide salt. More preferably, (H) is an N-substituted diazepine dioxide or an N'-hydroxy-diazepine dioxide salt.

[0162] The amount of biocide (H) in the CMP composition may be ≥0.00 wt% to ≤1.30 wt%, more preferably, the amount of (H) is ≥0.00 wt% to ≤1.10 wt%, even more preferably, the amount of (H) is ≥0.00 wt% to ≤1.00 wt%, or ≥0.00 wt% to ≤0.90 wt%, or ≥0.00 wt% to ≤0.70 wt%. Most preferably, the amount of (H) is ≥0.00 wt% to ≤0.50 wt%, or ≥0.00 wt% to ≤0.30 wt%, or ≥0.00 wt% to ≤0.20 wt%, or ≥0.00 wt% to ≤0.10 wt%, or ≥0.00 wt% to ≤0.08 wt%, or ≥0.00 wt% to ≤0.05 wt%. In each case, the amount of (H) is based on the total weight of the CMP composition.

[0163] Optional additives present as at least one additive (K) may be pH adjusters, buffers, stabilizers, and friction reducers. Such additives are known to those skilled in the art. The amount of these additives in the CMP composition may be ≥0.00 wt% to ≤1.00 wt%, more preferably ≥0.00 wt% to ≤0.90 wt% or ≥0.00 wt% to ≤0.70 wt%. Most preferably, the amount is ≥0.00 wt% to ≤0.50 wt%, ≥0.00 wt% to ≤0.30 wt%, ≥0.00 wt% to ≤0.20 wt%, ≥0.00 wt% to ≤0.10 wt%, ≥0.00 wt% to ≤0.08 wt%, or ≥0.00 wt% to ≤0.05 wt%. In each case, the amount of other additives as at least one additive (K) is based on the total weight of the CMP composition.

[0164] The main component of the CMP composition of this invention is an aqueous medium (D). The aqueous medium (D) can be one type or a mixture of different types of aqueous media. Generally, the aqueous medium (D) can be any medium containing water. Preferably, the aqueous medium (D) is a mixture of water and a water-miscible organic solvent, such as an alcohol, preferably a C1-C3 alcohol or an alkylene glycol derivative. More preferably, the aqueous medium (D) is water. Most preferably, the aqueous medium (D) is deionized water.

[0165] If the total amount of components other than (D) is 'x' wt% based on the total weight of the CMP composition, then the amount of (D) is '(100-x)' wt% based on the total weight of the CMP composition. In one embodiment, the amount of aqueous medium (D) in the CMP composition may be ≥95.00 wt% to ≤99.58 wt% based on the total weight of the CMP composition.

[0166] For different materials, such as metals versus silica, the properties of a CMP composition, such as its stability, polishing performance, and etching characteristics, may depend on the pH of the composition. The pH of a CMP composition can be adjusted in any suitable manner by adding a pH adjuster to the composition. Suitable pH adjusters may include, for example, but not limited to, potassium hydroxide, ammonium hydroxide, sodium carbonate, and mixtures thereof.

[0167] Therefore, the pH of the CMP composition is ≥8.5 to ≤11.0. Preferably, the pH is ≥9.0 to ≤10.5, more preferably, the pH is ≥9.0 to ≤10.3, and most preferably, the pH is ≥9.0 to ≤10.0.

[0168] The CMP composition of the present invention is used for chemical mechanical polishing of substrates used in the semiconductor industry, wherein the substrate comprises cobalt and / or cobalt alloys as well as TiN and / or TaN.

[0169] Cobalt and / or cobalt alloys can be of any type, form, or shape. Such type, form, or shape of cobalt and / or cobalt alloys is known to those skilled in the art. However, cobalt and / or cobalt alloys preferably have a layered and / or overlay growth shape. If the cobalt and / or cobalt alloy has a layered and / or overlay growth shape, the cobalt and / or cobalt alloy content, based on the weight of the corresponding layer and / or overlay growth, is preferably greater than 90%, more preferably greater than 95%, most preferably greater than 98%, particularly greater than 99%, for example greater than 99.9%. The cobalt and / or cobalt alloy is preferably filled or grown in trenches or plugs between other substrates, more preferably in trenches or plugs in dielectric materials (e.g., SiO2, silicon, low-k (BD1, BD2) or ultra-low-k materials) or other discrete and semiconductor materials used in the semiconductor industry. For example, in the intermediate process of Through Silicon Vias (TSV), after the TSV is displayed from the back side of the wafer, a separating material such as a polymer, photoresist, and / or polyimide can be used as an insulating material between the wet etching subsequent processing step and CMP, depending on its insulating / separating properties. A thin layer of barrier material can be placed between the contained copper and the dielectric material. Generally, barrier materials that prevent metal ions from diffusing into the dielectric material are Ti / TiN, Ta / TaN, or, for example, Ru or Ru alloys, Co or Co alloys. Another application of cobalt in semiconductor chip manufacturing is the deposition of cobalt into trenches or vias vias using CVD or PVD methods. The dielectric layer is covered by an inner liner to ensure that Co does not delaminate or diffuse into the dielectric layer. Ti / TiN and / or Ta / TaN layers can be used as liner and / or barrier layers.

[0170] The CMP composition according to the present invention is used for polishing substrates comprising cobalt and / or cobalt alloys, as well as TiN and / or TaN. The CMP composition provides control over the TiN:TaN material removal rate (MRR) ratio, which can vary in the range of ≥0.5 to ≤2.0. Preferably, the TiN:TaN MRR ratio is in the range of ≥0.5 to ≤1.8. More preferably, this range is ≥0.5 to ≤1.6. Most preferably, this range is ≥0.5 to ≤1.4.

[0171] Therefore, as described above, the MRR of TiN and TaN can be varied to maintain this ratio. This ratio can be varied depending on the desired end use of the polished substrate in the presence of the CMP composition of the subject matter of this invention, and thus the corresponding MRR can vary. However, the MRR of TiN is preferably maintained between ≥50 and ≤700. More preferably, it is ≥50 to ≤650. Optimal selection ≥50 to ≤600 In one implementation, the MRR of TiN is ≥50 to ≤550.

[0172] The removal rates of TaN and TiN materials are related.

[0173] Semiconductor devices can be fabricated by a method comprising chemically mechanically polishing a substrate used in the semiconductor industry in the presence of a CMP composition of the subject matter of this invention. According to the subject matter of this invention, the method comprises chemically mechanically polishing a substrate comprising cobalt and / or cobalt alloys, and TiN and / or TaN.

[0174] Generally, semiconductor devices that can be manufactured using the methods described in this invention are not specifically limited. A semiconductor device can be an electronic component comprising semiconductor materials, such as silicon, germanium, and III-V materials. A semiconductor device can be one manufactured as a single discrete device or as an integrated circuit (IC), which consists of multiple devices fabricated and interconnected on a wafer. A semiconductor device can be a two-terminal device (e.g., a diode), a three-terminal device (e.g., a bipolar transistor), a four-terminal device (e.g., a Hall effect sensor), or a multi-terminal device. Preferably, the semiconductor device is a multi-terminal device. A multi-terminal device can be a logic device, such as an integrated circuit and a microprocessor, or a memory device, such as random access memory (RAM), read-only memory (ROM), and phase-change random access memory (PCRAM). Preferably, the semiconductor device is a multi-terminal logic device. Specifically, the semiconductor device is an integrated circuit or a microprocessor.

[0175] Generally, in integrated circuits, cobalt is used as an adhesive or barrier layer for copper interconnects. In its nanocrystalline form, cobalt is contained in, for example, memory devices and serves as the metal gate in MOSFETs. Cobalt can also be used as a seed crystal to achieve copper plating via electrodeposition. Cobalt or cobalt alloys can also replace copper as one or more layers of interconnects. For example, capacitors (CAPs) can be formed in a continuous layer at the same level using metals, insulators, metal-insulators (MIMs), and thin-film resistors. Circuit designers can now connect to TaN thin-film resistors down to the lowest metal level, reducing parasitic phenomena and allowing for more efficient use of existing interconnect levels. Excess copper and / or cobalt, and adhesive / barrier layers containing Co in the form of, for example, metal nitrides or metal carbon nitrides (such as Co / TaN, Co / TiN, Co / TaCN, Co / TiCN), or single cobalt alloy layers (such as CoMo, CoTa, CoTi, and CoW) above dielectrics, can be removed using chemical mechanical polishing processes according to the subject matter of the invention.

[0176] Generally, cobalt and / or cobalt alloys, as well as TiN and / or TaN, can be prepared or obtained in various ways. Cobalt or cobalt alloys can be prepared by ALD, PVD, or CVD processes. Cobalt or cobalt alloys are deposited onto a barrier material of TiN and / or TaN. Suitable materials for barrier applications are well known in this art. The barrier prevents metal atoms or ions (such as cobalt or copper) from diffusing into the dielectric layer and improves the adhesion properties of the conductive layer.

[0177] Generally, the cobalt and / or cobalt alloy can be of any type, form, or shape. The cobalt and / or cobalt alloy preferably has a layered and / or overlay growth shape. If the cobalt and / or cobalt alloy has a layered and / or overlay growth shape, the cobalt and / or cobalt alloy content, based on the weight of the corresponding layer and / or overlay growth, is preferably greater than 90%, more preferably greater than 95%, most preferably greater than 98%, particularly greater than 99%, for example greater than 99.9%. The cobalt and / or cobalt alloy is preferably filled or grown in trenches or plugs between other substrates, more preferably in trenches or plugs in dielectric materials (e.g., SiO2, silicon, low-k (BD1, BD2) or ultra-low-k materials) or other discrete and semiconductor materials used in the semiconductor industry.

[0178] Generally speaking, downforce or downpressure is the downward pressure or force applied to the wafer by the carrier during CMP to press it against the pad. This downforce or downpressure can be measured, for example, in pounds per square inch (psi).

[0179] For example, the method of the subject matter of this invention can be carried out with a downward pressure of 2 psi or less. The downward pressure is preferably in the range of 0.1 psi to 1.9 psi, more preferably in the range of 0.3 psi to 1.8 psi, most preferably in the range of 0.4 psi to 1.7 psi, and especially preferably in the range of 0.8 psi to 1.6 psi, such as 1.5 psi.

[0180] Methods for preparing CMP compositions are generally known. Such methods can be used to prepare the CMP composition (Q) used in the present invention. This can be achieved by dispersing or dissolving components (A), (B), (C), (E), and (K) in an aqueous medium (D) and adjusting the pH value as described above. To achieve this, conventional and standard mixing methods and equipment, such as stirred tanks, high-shear impellers, ultrasonic mixers, homogenizer nozzles, or countercurrent mixers, can be used.

[0181] Chemical mechanical polishing (CMP) methods are generally known to those skilled in the art and can be performed using such methods and equipment under conditions commonly used in CMP in the fabrication of wafers containing integrated circuits. There are no restrictions on the equipment that can be used to perform the polishing method.

[0182] As is known in this art, typical equipment for CMP methods consists of a rotating pressure plate covered with a polishing pad. Rail-mounted polishers are also used. The wafer is mounted on a carrier or chuck. The processing surface of the wafer faces the polishing pad (single-sided polishing method). A retaining ring holds the wafer in a horizontal position.

[0183] Below the carrier, a larger diameter platen is also typically positioned horizontally and provides a surface parallel to the wafer surface to be polished. Polishing pads on the platen contact the wafer surface during the planarization process.

[0184] To induce material loss, the wafer is pressed onto a polishing pad. Typically, both the carrier and the platen rotate about individual axes extending perpendicularly from themselves. The rotating carrier axis may remain fixed in place relative to the rotating platen, or it may oscillate horizontally relative to the platen. The direction of rotation of the carrier is typically (but not necessarily) the same as that of the platen. The rotational speeds of the carrier and the platen are generally (but not necessarily) set to different values. During the CMP method of the subject matter of this invention, the CMP composition of the subject matter of this invention is typically applied to the polishing pad in a continuous flow or dropwise manner. The platen temperature is typically set to a temperature between 10°C and 70°C.

[0185] A load can be applied to the wafer using, for example, a steel plate covered with a soft pad (commonly referred to as a substrate film). With more advanced equipment, the wafer is pressed onto the pad using a flexible membrane pressurized with air or nitrogen. Because the downward pressure distribution on the wafer is more uniform than that of a carrier with a hard plate design, this membrane carrier is preferred for low downward force processes when using hard polishing pads. According to the subject matter of the invention, a carrier with options for controlling the pressure distribution on the wafer can also be used. These are typically designed to have a number of different chambers, which can be loaded to some extent independently of each other.

[0186] For other details, refer to WO 2004 / 063301 A1, specifically paragraphs

[0036] on page 16 to

[0040] on page 18 and Figure 2.

[0187] By means of the CMP method and / or the CMP composition of the present invention, wafers having integrated circuits comprising cobalt and / or cobalt alloys and TiN and / or TaN can be obtained, which have excellent functionality and can be adapted as needed.

[0188] The CMP compositions of the present invention can be used in CMP processes in ready-to-use slurry form, exhibiting a long shelf life and stable particle size distribution over extended periods. Therefore, they are easy to handle and store. They demonstrate excellent polishing performance and controlled MRR for cobalt and / or cobalt alloys, as well as TiN and / or TaN. Because the amounts of the components in the CMP composition are kept to a minimum, the CMP compositions of the present invention can result in cost-effective chemical mechanical polishing.

[0189] Different MRR values ​​for cobalt, TiN, and / or TaN can be achieved by varying the concentrations of different components in the CMP composition.

[0190] The CMP compositions according to the present invention have several advantages over existing compositions, such as:

[0191] - The material removal rate for Co, TiN, and / or TaN is controlled, and / or

[0192] - By varying the MRR ratio of TiN:TaN within the required range to meet the requirements of the semiconductor industry / users, and / or

[0193] -Using components of the CMP composition in low quantities, thereby providing a cost-effective and relatively economical composition, and / or

[0194] - The alkaline pH of the CMP composition prevents substrate corrosion and material deterioration.

[0195] Examples and Comparative Examples

[0196] compound

[0197]

[0198]

[0199] Standard CMP method for 200mm Co wafers:

[0200] Tools: Mirra-mesa (applied materials)

[0201]

[0202] Mix the slurry at the local supply station.

[0203] Standard analytical procedures for thin film thickness measurement:

[0204] Cobalt, TiN, and TaN thin films: Resistage RG-120 / RT-80, 4-point probe instrument (NAPSON Corporation)

[0205] TEOS: Opti-Probe 2600 (Therma Wave, KLA-Tencor).

[0206] Film thickness was measured using a 49-point scan before and after CMP (excluding 5 mm at the edges). The material removal rate (MRR) was obtained by averaging the thickness loss and dividing by the polishing time.

[0207] Co-coated wafer: 2000A PVD Co on Ti liner (supplier: AMT);

[0208] TiN and TaN: PVD is performed on TEOS.

[0209] pH values ​​were measured using a pH combination electrode (Schott, blue line 22 pH electrode).

[0210] Standard procedure for slurry preparation:

[0211] All mixing processes are carried out under stirring. Aqueous solutions of each compound (B), (E), and (F) are prepared by dissolving the desired amounts of the individual compounds in ultrapure water (UPW) (D). KOH can be used to support the dissolution of the raw material solutions of (B) and (E). The pH of the raw material solutions is adjusted to 8 using KOH. The raw material solution of (B) contains 10% by weight of the individual additive and 1.0% by weight of (E) and (F). For (A), a dispersion provided by the supplier, typically a grinding agent with a concentration of approximately 20%-30% by weight, is used. The oxidant (C) is used in the form of a 30% by weight raw material solution.

[0212] To prepare 1000 g of slurry, add 600 g of (D) to a mixing tank or beaker. Add the amounts of (B), (E), and (F) feedstock solutions to achieve the desired concentration. Maintain the solution at an alkaline to neutral pH using KOH. Then, add the required amount of (A). To adjust the final concentration, add (D) as equilibrium water relative to the required amount of oxidant feedstock solution. Adjust the pH to the desired value using KOH. Approximately 60 minutes before CMP, add the desired amount of oxidant.

[0213] Inorganic particles (A) used in the embodiments

[0214] The average primary particle size (d1) is 35 nm, the average secondary particle size (d2) is 70 nm (as measured using dynamic light scattering techniques via a Horiba instrument), and the specific surface area is approximately 46 m². 2 / g of colloidal cocoon-shaped silica particles (Al).

[0215] Table 1: Experimental results of particle shape analysis of cocoon-shaped silica particles (A)

[0216] Statistical functions ECD sphericity shape factor unit nm Number of particles 475 475 475 average value 53.67 0.631 0.881 Minimum value 33.68 0.150 0.513 Maximum value 99.78 0.997 0.978 Standard deviation 11.69 0.199 0.083 Median d50 51.32 0.662 0.911 d90 0.955

[0217] Particle shape characterization procedure

[0218] An aqueous dispersion of cocoon-shaped silica particles with a solid content of 20 wt% was dispersed on carbon foil and dried. The dried dispersion was analyzed using energy-filtered-through electron microscopy (EF-TEM) (120 kV) and scanning electron microscopy secondary electron imaging (SEM-SE) (5 kV). EF-TEM images with a resolution of 2 kΩ, 16 bits, and 0.6851 nm / pixel were used for this analysis. After noise suppression, the images were binary encoded using threshold values. The particles were then manually separated. Overlying and edge particles were identified and excluded from this analysis. ECD, shape factor, and sphericity were calculated and statistically classified as previously defined.

[0219] If a surfactant (F) is available, an amphiphilic nonionic polyoxyethylene-polyoxypropylene alkyl ether surfactant is used, which is a molecular mixture comprising an alkyl group having an average of 6 to 12 carbon atoms and 2 to 10 oxyethylene monomer units and 1 to 5 oxypropylene monomer units distributed randomly.

[0220] CMP Composition

[0221] The CMP compositions of the present invention are compared and prepared using H2O2 and K2S2O8 as oxidants, wherein the different components are within the scope specified in the subject matter of the present invention. In all compositions given in Table 2 below, weight % is based on the total weight of the CMP composition. Furthermore, in Table 2, if the total amount of the components other than (D) is y% by weight of the CMP composition, then the amount of (D) is (100-y)% by weight of the CMP composition.

[0222]

[0223] Table 3: Effect of Oxidizing Agent (C)

[0224]

[0225] As is evident from the table above, the control of MRR for TiN and TaN is better when using K₂S₂O₈ instead of H₂O₂ as the oxidant. Furthermore, the MRR of Co obtained using K₂S₂O₈ as the oxidant is slightly higher than that obtained using H₂O₂. This indicates that using persulfate provides better tuning and control of the substrate MRR. Therefore, persulfate was chosen as the oxidant for the CMP compositions in all other experiments.

[0226] Table 4: Effect of pH

[0227]

[0228] Table 5: Effects of organic compound (B)

[0229]

[0230] Table 6: Effects of Inorganic Particles (A)

[0231]

[0232] Table 7: Effect of Corrosion Inhibitor (E)

[0233]

[0234] As is evident from the table described above, the CMP compositions according to the subject matter of the present invention exhibit high cobalt material removal rates (MRR). And the improved polishing performance in terms of the desired TiN:TaN MRR ratio. Furthermore, the wafer polished in the presence of the CMP composition has a glossy surface.

[0235] Furthermore, it can be concluded from the table above that the CMP composition of the present invention provides better control over the material removal rate of different materials on the substrate. These results further illustrate that potassium persulfate (i.e., the oxidant) and pH significantly affect the material removal rate of different materials on the substrate or wafer.

Claims

1. A chemical mechanical polishing composition for use in chemical mechanical polishing of substrates comprising (i) cobalt and / or (ii) cobalt alloys and (iii) TiN and TaN, said chemical mechanical polishing composition comprising: (A) Inorganic particles ≥0.10 wt% to ≤4.00 wt%, (B) ≥0.10% by weight to ≤0.90% by weight of at least one organic compound containing an amino group and / or at least one acid group (Y), (C) Potassium persulfate ≥0.20% to ≤0.90% by weight, (D) ≥95.00% by weight to ≤99.58% by weight of aqueous media, (E) at least one corrosion inhibitor ranging from ≥0.01% by weight to ≤0.50% by weight, and (K) at least one additive from ≥0.01% by weight to ≤1.50% by weight, The pH of the composition is ≥8.5 to ≤11.0, and The weight percentage is based on the total weight of the composition.

2. The use according to claim 1, characterized in that... The pH of the composition is ≥8.5 to ≤10.

0.

3. The use according to claim 1, characterized in that... The amount of potassium persulfate is ≥0.30% by weight to ≤0.70% by weight.

4. The use according to claim 2, characterized in that... The amount of potassium persulfate is ≥0.30% by weight to ≤0.70% by weight.

5. The use according to claim 1, characterized in that... The inorganic particle (A) is a colloidal inorganic particle.

6. The use according to claim 2, characterized in that... The inorganic particle (A) is a colloidal inorganic particle.

7. The use according to claim 3, characterized in that... The inorganic particle (A) is a colloidal inorganic particle.

8. The use according to claim 4, characterized in that... The inorganic particle (A) is a colloidal inorganic particle.

9. The use according to claim 5, characterized in that... The colloidal inorganic particles are colloidal silica particles.

10. The use according to claim 6, characterized in that... The colloidal inorganic particles are colloidal silica particles.

11. The use according to claim 7, characterized in that... The colloidal inorganic particles are colloidal silica particles.

12. The use according to claim 8, characterized in that... The colloidal inorganic particles are colloidal silica particles.

13. The use according to any one of claims 1-12, characterized in that... The at least one organic compound (B) is a non-polymeric compound with a molecular weight of less than 600 g / mol.

14. The use according to any one of claims 1-12, characterized in that... The acid group (Y) in the organic compound (B) is selected from carboxylic acids, sulfonic acids, and phosphonic acids.

15. The use according to claim 13, characterized in that... The acid group (Y) in the organic compound (B) is selected from carboxylic acids, sulfonic acids, and phosphonic acids.

16. The use according to any one of claims 1-12, characterized in that... The organic compound (B) is selected from amino acids, substituted ethylenediamines, and polycarboxylic acids.

17. The use according to claim 15, characterized in that... The organic compound (B) is selected from amino acids, substituted ethylenediamines, and polycarboxylic acids.

18. The use according to any one of claims 1-12, characterized in that... The organic compound (B) is selected from: glycine, glutamic acid, aspartic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, sulfoalanine, aminotris(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), malonic acid, citric acid, and tartaric acid.

19. The use according to claim 17, characterized in that... The organic compound (B) is selected from: glycine, glutamic acid, aspartic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, sulfoalanine, aminotris(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), malonic acid, citric acid, and tartaric acid.

20. The use according to any one of claims 1-12, characterized in that... The aqueous medium is deionized water.

21. The use according to claim 19, characterized in that... The aqueous medium is deionized water.

22. The use according to any one of claims 1-12, characterized in that... The corrosion inhibitor (E) is selected from: imidazole, benzimidazole, benzotriazole, 4-(dimethylamino)benzoic acid, terephthalic acid, isophthalic acid, 6,6',6”-(1,3,5-triazine-2,4,6-triyltriimino)trihexanoic acid, phenyltetrazole, N-lauroyl sarcosine, 4-dodecylbenzenesulfonic acid, C6-C phosphate. 10 Alkyl esters, polyaspartic acid and mixtures thereof, and salts thereof.

23. The use according to claim 21, characterized in that... The corrosion inhibitor (E) is selected from: imidazole, benzimidazole, benzotriazole, 4-(dimethylamino)benzoic acid, terephthalic acid, isophthalic acid, 6,6',6”-(1,3,5-triazine-2,4,6-triyltriimino)trihexanoic acid, phenyltetrazole, N-lauroyl sarcosine, 4-dodecylbenzenesulfonic acid, C6-C phosphate. 10 Alkyl esters, polyaspartic acid and mixtures thereof, and salts thereof.

24. The use according to any one of claims 1-12, characterized in that... The at least one additive (K) is selected from: surfactants (F), biocides (H), pH adjusters, buffers, stabilizers and friction reducers.

25. The use according to claim 23, characterized in that... The at least one additive (K) is selected from: surfactants (F), biocides (H), pH adjusters, buffers, stabilizers and friction reducers.

26. A method of manufacturing a semiconductor device, the method comprising chemically mechanically polishing a substrate used in the semiconductor industry in the presence of a chemical mechanical polishing composition as defined in any one of claims 1-25, wherein the substrate comprises (i) cobalt, and / or (ii) Cobalt alloys, and (iii) TiN and TaN.

27. The method according to claim 26, characterized in that... The material removal rate (MRR) ratio of TiN:TaN is in the range of ≥0.5 to ≤2.0.

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