Chemical mechanical polishing of substrates containing copper and ruthenium

Abstract

The present invention relates to a chemical mechanical polishing (CMP) composition and a chemical mechanical polishing (CMP) method. The present invention particularly relates to a composition and method for chemical mechanical polishing of substrates containing copper and ruthenium, in particular semiconductor substrates containing copper and ruthenium.

Description

Technical Field

[0001] This invention relates to a chemical mechanical polishing (CMP) composition and a chemical mechanical polishing (CMP) method. More particularly, this invention relates to a composition and method for chemically mechanically polishing copper- and ruthenium-containing substrates, specifically a semiconductor substrate containing copper and ruthenium.

[0002] background

[0003] In the semiconductor industry, chemical mechanical polishing (CMP) is a well-known technique used to manufacture advanced photonic, microelectromechanical, and microelectronic materials and devices, such as semiconductor wafers.

[0004] CMP (Chemical Molecular Polishing) is used to planarize surfaces in the manufacturing of materials and devices used in the semiconductor industry. CMP achieves the smoothness of the surface to be polished through the interaction of chemical and mechanical actions. 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 that is usually pressed against the surface to be polished and mounted on a moving stage. The movement of the stage is typically linear, rotary, or track-like.

[0005] In a typical CMP process step, a rotating wafer chuck brings the wafer to be polished into contact with a polishing pad. A CMP composition is typically applied between the wafer and the polishing pad.

[0006] Tantalum (Ta) and tantalum nitride (TaN) are commonly used as barrier layer materials to prevent device contamination caused by copper diffusing through the dielectric layer. However, due to tantalum's high resistivity, it is difficult to effectively deposit copper onto the barrier layer. Recently, ruthenium (Ru) has been identified as a promising barrier layer material to replace existing tantalum barrier layers and copper (Cu) seed layers. The insolubility of copper in ruthenium makes ruthenium an attractive barrier layer material, and due to ruthenium's lower resistivity, copper can also be deposited directly onto the ruthenium layer.

[0007] In the prior art, CMP methods for chemically mechanically polishing substrates containing copper and ruthenium in the presence of CMP compositions comprising surfactants and aromatic compounds are known and are described, for example, in the following references.

[0008] US6,869,336 B1 describes a composition for removing ruthenium from a substrate using low-contact-pressure chemical mechanical polishing, wherein the composition comprises a dispersion medium, abrasive particles, and has a pH in the range of 8-12.

[0009] US7,265,055B2 describes a method for chemical mechanical polishing of a substrate comprising copper, ruthenium, tantalum, and a dielectric layer. The method uses a polishing pad and a CMP composition or reagent comprising α-alumina abrasive particles treated with a negatively charged polymer or copolymer.

[0010] US 2008 / 0105652 A1 discloses a chemical mechanical polishing composition comprising an abrasive, an oxidant, an amphiphilic nonionic surfactant, calcium or magnesium ions, a copper corrosion inhibitor, and water, having a pH in the range of about 6-12.

[0011] US 20130005149 A1 discloses a chemical mechanical polishing composition comprising (a) at least one type of abrasive particles, (b) at least two oxidants, (c) at least one pH adjuster, and (d) deionized water, (e) optionally comprising at least one antioxidant, and a method for chemically mechanically planarizing a substrate containing at least one copper layer, at least one ruthenium layer, and at least one tantalum layer.

[0012] US 6852009 B2 discloses a polishing composition comprising silicon dioxide, at least one alkaline substance selected from alkali metal inorganic salts, ammonium salts, piperazine, and ethylenediamine, at least one chelating agent, and water. This alkaline substance is used for wafer polishing to inhibit metal contamination and diffusion into the wafer.

[0013] The methods and compositions disclosed in the prior art have limitations. In the methods and compositions disclosed in the prior art for chemical mechanical polishing (CMP), polishing of metals such as copper and ruthenium produces residues, which can be removed from the polishing environment by simple rinsing or by adsorption onto different surfaces such as wafer surfaces or polishing pad surfaces. However, both of these situations are undesirable in CMP methods. Furthermore, residues adsorbed or accumulated on the polishing pad may introduce defects on the wafer, leading to undesirable additional defects. Therefore, there is a need for improved CMP compositions and methods for chemical mechanical polishing of substrates containing copper (Cu), tantalum (Ta), and ruthenium (Ru).

[0014] Therefore, the object of the present invention is to provide improved CMP compositions and methods for substrates used in the chemical mechanical polishing semiconductor industry, particularly substrates comprising at least one copper (Cu) layer and / or at least one ruthenium (Ru) layer.

[0015] Another object of the present invention is to remove pad contaminants and particles formed by chemical mechanical polishing of substrates used in the semiconductor industry from the wafer surface and polishing pad.

[0016] Overview

[0017] The invention’s CMP composition described below has been found to provide a high material removal rate (MRR) and a clean, mat-polished surface free of metal residue for preferred substrates to be polished.

[0018] Therefore, in one aspect of the present invention, a chemical mechanical polishing (CMP) composition comprising the following components is provided:

[0019] (A) At least one inorganic abrasive particle;

[0020] (B) At least one chelating agent selected from carboxylic acids;

[0021] (C) At least one corrosion inhibitor selected from unsubstituted or substituted triazoles;

[0022] (D) At least one nonionic surfactant containing at least one polyoxyalkylene group;

[0023] (E) A pad cleaner selected from compounds having at least one amino group and at least one acidic group selected from carboxylic acids, phosphonic acids and sulfonic acids;

[0024] (F) At least one carbonate or bicarbonate;

[0025] (G) At least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromate; and

[0026] (H) Aqueous medium.

[0027] In another aspect, the present invention relates to a method of manufacturing a semiconductor device, comprising chemically mechanically polishing a substrate in the presence of a chemical mechanical polishing (CMP) composition described above or below.

[0028] In another aspect, the present invention relates to the use of the chemical mechanical polishing composition (CMP) in substrates used in the chemical mechanical polishing semiconductor industry.

[0029] The present invention has at least one of the following advantages:

[0030] (1) The CMP compositions and CMP methods of the present invention exhibit improved polishing performance for substrates used in the semiconductor industry, particularly those containing copper (Cu) and / or tantalum (Ta), tantalum nitride (TaN), titanium (Ti), titanium nitride (TiN), ruthenium (Ru), cobalt (Co), or alloys thereof.

[0031] (i) Preferably, the substrate to be polished has a high material removal rate (MRR), such as tantalum nitride.

[0032] (ii) Preferably, the substrate to be polished has a high material removal rate (MRR), such as ruthenium.

[0033] (iii) Preferably, the substrate to be polished is copper and / or a low material removal rate (MRR) of low-k materials.

[0034] (iv) The polished surface of the cleaning pad is free of metal residue by adding a pad cleaner to the CMP composition.

[0035] (v) Safe handling and minimization of harmful byproducts, or

[0036] Combinations of (vi)(i), (ii), (iii), (iv) and (v).

[0037] (2) The CMP compositions of the present invention provide stable formulations or dispersions in which no phase separation occurs.

[0038] (3) The CMP method of the present invention is easy to apply and requires as few steps as possible.

[0039] Other objects, advantages and applications of the present invention will become apparent to those skilled in the art from the following detailed description.

[0040] Detailed description

[0041] The following detailed description is merely exemplary and is not intended to limit the invention or its application and uses. Furthermore, it is not intended to be bound by any theories set forth in the foregoing technical field, background, overview, and the following detailed description.

[0042] The term “comprising” as used herein is synonymous with “including” or “containing”, and is either inclusive or open-ended and does not exclude additional unreferenced members, elements, or method steps. It should be understood that the term “comprising” as used herein includes the term “consisting of”.

[0043] Furthermore, the terms “(a)”, “(b)”, “(c)”, “(d)”, etc., used in the specification and claims are used to distinguish similar elements and are not necessarily used to describe a sequential or chronological order. It should be understood that such terms are interchangeable where appropriate and that embodiments of the invention described herein can be operated in orders other than those described or shown herein. Where the terms “(A)”, “(B)”, and “(C)”, or “(a)”, “(b)”, “(c)”, “(d)”, “(i)”, “(ii)”, etc., relate to steps of a method or use or analysis, there is no temporal or time interval coherence between the steps; that is, these steps may be performed simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months, or even years between these steps, unless otherwise specified in this application as described in the context.

[0044] The various aspects of the invention are defined in more detail in the following paragraphs. The aspects thus defined may be combined with any one or more other aspects unless explicitly stated otherwise. Specifically, any feature shown as preferred or advantageous may be combined with any one or more other features shown as preferred or advantageous.

[0045] Throughout this specification, references to "an embodiment," "an embodiment," or "a preferred embodiment" mean that the specific feature, structure, or characteristic described for that embodiment is included in at least one embodiment of the invention. Therefore, the phrases "in an embodiment," "in a preferred embodiment," or "in a preferred embodiment" appearing in various places throughout the specification do not necessarily all refer to the same embodiment, but may do. Furthermore, these features, structures, or characteristics can be combined in any suitable manner in one or more embodiments, as will be apparent to those skilled in the art from this disclosure. Moreover, although some embodiments described herein include, but not others, features included in other embodiments, combinations of features from different embodiments are intended to be within the scope of the subject matter of the invention and form different embodiments, as will be understood by those skilled in the art. For example, in the appended claims, any claimed embodiment can be used in any combination.

[0046] Furthermore, the ranges defined throughout this specification include end values; that is, the range 1-10 implies that both 1 and 10 are included within this range. To avoid any doubt, the applicant should be granted any equivalent in accordance with applicable law.

[0047] For the purposes of this invention, "% by weight" as used herein refers to the total weight of the coating composition. Furthermore, the sum of the weight percentages of all compounds described below in the respective components is 100% by weight.

[0048] For the purposes of this invention, a corrosion inhibitor is defined as a compound that forms a protective molecular layer on a metal surface.

[0049] For the purposes of this invention, a chelating agent is defined as a compound that forms a soluble complex with certain metal ions, thereby deactivating the ions so that they cannot react normally with other elements or ions to produce precipitation or scale.

[0050] For the purposes of this invention, low-k materials are those with a k-value (dielectric constant) of less than 3.5, preferably less than 3.0, and more preferably less than 2.7. Ultra-low-k materials are those with a k-value (dielectric constant) of less than 2.4.

[0051] For the purposes of this invention, colloidal inorganic particles are inorganic particles produced by wet precipitation; and pyrolysis inorganic particles are produced by hydrolyzing, for example, metal chloride precursors in the presence of oxygen using a high-temperature hydrogen flame, for example, using... Particles produced by the method.

[0052] For the purposes of this invention, "colloidal silica" refers to silica prepared by the polycondensation 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 5,230,833 or can be used as any of a variety of commercially available products, such as... Products PL-1, PL-2 and PL-3, Nalco 1050, 2327 and 2329, and other similar products available from DuPont, Bayer, Applied Research, Nissan Chemical, Nyacol and Clariant.

[0053] For the purposes of this invention, the average particle size is defined as the particle size distribution d of the inorganic abrasive particles (A) in the aqueous medium (H). 50 value.

[0054] For the purposes of this invention, the average particle size is measured, for example, using dynamic light scattering (DLS) or static light scattering (SLS) methods. These and other methods are well known in the art; see, for example, Kuntzsch, Timo; Witnik, Ulrike; Hollatz, Michael Stintz; Ripperger, Siegfried; Characterization of slurries for chemical mechanical polishing (CMP) in the semiconductor industry; Chem. Eng. Technol; 26 (2003), Vol. 12, p. 1235.

[0055] For the purposes of this invention, dynamic light scattering (DLS) is typically performed using a Horiba LB-550V (DLS, Dynamic Light Scattering Measurement) or any other instrument of this type. 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 due to the random Brownian motion of the particles as they pass through the incident beam and are monitored as a function of time. The attenuation constant is extracted using an autocorrelation function performed using this instrument as a function of time delay; smaller particles pass through the incident beam at higher velocities and correspond to faster attenuation.

[0056] For the purposes of this invention, the attenuation constant and the diffusion coefficient D of the inorganic abrasive particles are... t Proportional and used to calculate granularity according to the Stokes-Einstein equation:

[0057]

[0058] It is assumed that the suspended particles (1) have a spherical morphology and (2) are uniformly dispersed throughout the aqueous medium (i.e., do not agglomerate). This relationship is expected to apply to particulate dispersions containing less than 1% by weight of solids, since the viscosity of the aqueous dispersant does not deviate significantly, where η = 0.96 mPa·s (at T = 22 °C). The particle size distribution of pyrolytic or colloidal inorganic particulate dispersions is typically measured in plastic test tubes at a solids concentration of 0.1–1.0% and diluted with a dispersion medium or ultrapure water if necessary.

[0059] For the purposes of this invention, the BET surface of the inorganic abrasive particles was determined according to DIN ISO 9277:2010-09.

[0060] For the purposes of this invention, a surfactant is defined as a surface-active compound that reduces the surface tension of a liquid, the interfacial tension between two liquids, or the interfacial tension between a liquid and a solid.

[0061] For the purposes of this invention, "water solubility" means that the relevant components or ingredients of the composition can be dissolved in the aqueous phase at the molecular level.

[0062] For the purposes of this invention, "water dispersibility" means that the relevant components or ingredients of the composition can be dispersed in an aqueous phase and form a stable emulsion or suspension.

[0063] For the purposes of this invention, an oxidant is defined as a compound that can oxidize one of the substrates or layers thereof to be polished.

[0064] For the purposes of this invention, a pH adjuster is defined as a compound added to adjust its pH value to a desired value.

[0065] The measurement techniques disclosed herein are well known to those skilled in the art for their purpose and therefore do not limit the scope of the invention.

[0066] Chemical mechanical polishing (CMP) composition (Q)

[0067] In one aspect, the present invention provides a chemical mechanical polishing (CMP) composition comprising the following components:

[0068] (A) At least one inorganic abrasive particle;

[0069] (B) At least one chelating agent selected from carboxylic acids;

[0070] (C) At least one corrosion inhibitor selected from unsubstituted or substituted triazoles;

[0071] (D) At least one nonionic surfactant containing at least one polyoxyalkylene group;

[0072] (E) A pad cleaner selected from compounds having at least one amino group and at least one acidic group selected from carboxylic acids, phosphonic acids and sulfonic acids;

[0073] (F) At least one carbonate or bicarbonate;

[0074] (G) At least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromate; and

[0075] (H) Aqueous medium.

[0076] The CMP composition (Q) comprises components (A), (B), (C), (D), (E), (F), (G), (H) and optionally other components as described below.

[0077] In an embodiment of the present invention, at least one inorganic abrasive particle (A) is selected from metal oxides, metal nitrides, metal carbides, silicides, borides, ceramics, diamond, organic / inorganic mixed particles, and silicon dioxide.

[0078] For the purposes of this invention, the chemical properties of at least one inorganic abrasive particle (A) are not particularly limited. (A) may have the same chemical properties or may be a mixture of particles with different chemical properties. For the purposes of this invention, particles (A) having the same chemical properties are preferred. The inorganic abrasive particle (A) is selected from metal oxides, metal nitrides, metal carbides, including metalloids, metalloid oxides or carbides, silicides, borides, ceramics, diamond, organic / inorganic mixed particles, silica, and any mixture of inorganic particles.

[0079] For the purposes of this invention, at least one inorganic abrasive particle (A) may be:

[0080] • A type of colloidal inorganic particle,

[0081] • A type of pyrolysis-based inorganic particle,

[0082] • A mixture of different types of colloids and / or pyrolytic inorganic particles.

[0083] For the purposes of this invention, at least one inorganic particle (A) is selected from colloidal or pyrolytic inorganic particles or mixtures thereof. Preferably, it is an oxide or carbide of a metal or quasi-metal. For the purposes of this invention, at least one inorganic particle (A) is preferably selected from alumina, cerium dioxide, copper oxide, iron oxide, nickel oxide, magnesium oxide, silicon dioxide, silicon nitride, silicon carbide, tin oxide, titanium dioxide, titanium carbide, tungsten oxide, yttrium oxide, zirconium dioxide, or mixtures or complexes thereof. For the purposes of this invention, at least one inorganic particle (A) is more preferably selected from alumina, cerium dioxide, silicon dioxide, titanium dioxide, zirconium dioxide, or mixtures or complexes thereof. (A) is a silicon dioxide particle. For the purposes of this invention, at least one inorganic particle (A) is most preferably a colloidal silicon dioxide particle.

[0084] In another embodiment of the invention, the concentration of at least one inorganic abrasive particle (A) is in the range of ≥0.01% by weight to ≤10% by weight based on the total weight of the chemical mechanical polishing composition.

[0085] For the purposes of this invention, the concentration of at least one inorganic abrasive particle (A) based on the total weight of the composition (Q) is no more than 10% by weight, preferably no more than 5% by weight, particularly no more than 3% by weight, for example no more than 2% by weight, most preferably no more than 1.8% by weight, particularly no more than 1.5% by weight. For the purposes of this invention, the concentration of at least one inorganic abrasive particle (A) based on the total weight of the composition (Q) is preferably at least 0.01% by weight, more preferably at least 0.1% by weight, most preferably at least 0.2% by weight, particularly at least 0.3% by weight. For the purposes of this invention, the concentration of at least one inorganic abrasive particle (A) based on the total weight of the CMP composition (Q) is more preferably in the range of ≥0.4% by weight to ≤1.2% by weight.

[0086] For the purposes of this invention, at least one inorganic abrasive particle (A) may be contained in the CMP composition (Q) in various particle size distributions. The particle size distribution of the at least one inorganic abrasive particle (A) may be unimodal or multimodal. In the case of a multimodal particle size distribution, bimodal is generally preferred. For the purposes of this invention, a unimodal particle size distribution is preferred for the inorganic abrasive particle (A). The particle size distribution of the inorganic abrasive particle (A) is not particularly limited.

[0087] In a preferred embodiment of the present invention, the average particle size of at least one inorganic abrasive particle (A) is in the range of ≥1 nm to ≤1000 nm as determined by dynamic light scattering technology.

[0088] The median or average particle size of at least one inorganic abrasive particle (A) can vary over a wide range. For the purposes of this invention, the median particle size of at least one inorganic abrasive particle (A) is in the range of ≥1 nm to ≤1000 nm, preferably ≥10 nm to ≤400 nm, more preferably ≥20 nm to ≤200 nm, more preferably ≥25 nm to ≤180 nm, most preferably ≥30 nm to ≤170 nm, particularly preferably ≥40 nm to ≤160 nm, and particularly preferably ≥45 nm to ≤150 nm, in each case measured using an instrument such as a high-efficiency particle size analyzer (HPPS) from Malvern Instruments, Ltd. or dynamic light scattering technology from a Horiba LB550.

[0089] The BET surface of at least one inorganic abrasive particle (A) can vary over a wide range. For the purposes of this invention, the BET surface of at least one inorganic abrasive particle (A) is ≥1 μm. 2 / g to ≤500m 2 / g, more preferably ≥5m 2 / g to ≤250m 2 / g, optimal value ≥10m 2 / g to ≤100m 2 / g, with a preferred concentration of ≥20m 2 / g to ≤95m 2 / g, with a preferred value of ≥25m 2 / g to ≤92m 2 Within the range of / g, determined according to DIN ISO 9277:2010-09 in each case.

[0090] For the purposes of this invention, at least one inorganic abrasive particle (A) can have various shapes. Thus, particle (A) can have one type of shape or essentially only one type of shape. However, it is also possible for particle (A) to have different shapes. For example, two different types of particles (A) can exist. For example, (A) can have the following shapes: agglomerates, cubes, cubes with beveled edges, octahedrons, icosahedrons, cocoons, nodules, or spheres with or without protrusions or depressions. For the purposes of this invention, the inorganic abrasive particle (A) is preferably substantially spherical, wherein these typically have protrusions or depressions.

[0091] For the purposes of this invention, at least one inorganic abrasive particle (A) is preferably cocoon-shaped. The cocoon may or may not have protrusions or depressions. Cocoon-shaped particles are particles with a minor axis ≥10 nm to ≤200 nm, a major axis / minor axis ratio ≥1.4 to ≤2.2, more preferably ≥1.6 to ≤2.0. Preferably, they have an average shape factor ≥0.7 to ≤0.97, more preferably ≥0.77 to ≤0.92, an average sphericity ≥0.4 to ≤0.9, more preferably ≥0.5 to ≤0.7, and an average equivalent circular diameter ≥41 nm to ≤66 nm, more preferably ≥48 nm to ≤60 nm, determined in each case by transmission electron microscopy and scanning electron microscopy.

[0092] For the purposes of this invention, the determination of the shape factor, sphericity, and equivalent circle diameter of the cocoon-shaped particles is explained below. The shape factor provides information about the shape and indentation of individual particles and can be calculated according to the following formula:

[0093] Shape factor = 4π(area / perimeter²)

[0094] The shape factor of a spherical particle without indentations is 1. The shape factor decreases as the number of indentations increases. Sphericity provides information about the elongation of a single particle using its central moment and can be calculated using the following formula, where M is the centroid of the corresponding particle:

[0095] Sphericity=(Mxx-Myy)-[4Mxy2+(Myy-Mxx)2]0.5 / (Mxx-Myy)+[4Mxy2+(Myy-Mxx)2]0.5

[0096] Elongation = (1 / sphericity) × 0.5

[0097] in

[0098] Mxx=Σ(x-xmean) 2 / N

[0099] Myy=Σ(y-ymean) 2 / N

[0100] Mxy=Σ[(x-xmean)*(y-ymean)] / N

[0101] N is the number of pixels in the image that forms the corresponding particles.

[0102] x, y pixel coordinates

[0103] xmean is the average x-coordinate of the N pixels forming the image of the particle.

[0104] ymean is the average y-coordinate of the N pixels in the image that forms the particle.

[0105] The sphericity of spherical particles is 1. The sphericity value decreases as the particles become elongated. The equivalent circle diameter (ECD) of a single non-circular particle provides information about the diameter of a circle with the same area as the corresponding non-circular particle. The mean shape factor, mean sphericity, and mean ECD are the arithmetic mean of the corresponding properties in relation to the number of particles analyzed.

[0106] For the purposes of this invention, the procedure for characterizing particle shape is as follows: Aqueous dispersions of cocoon-shaped silica particles with a solid content of 20 wt% were dispersed on carbon foil and dried. The dried dispersions were analyzed using energy-filtered transmission 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 kbps, 16 bits, and 0.6851 nm / pixel were used for this analysis. The images were encoded using thresholded binary encoding after noise reduction. The particles were then manually separated. Overlying and edge particles were distinguished and not used in this analysis. ECD, shape factor, and sphericity, as defined above, were calculated and statistically classified.

[0107] For the purposes of this invention, representative examples of cocoon-shaped particles include, but are not limited to, those manufactured by Fuso Chemical Corporation with an average primary particle size (d1) of 35 nm and an average secondary particle size (d2) of 70 nm. PL-3.

[0108] In a more preferred embodiment of the present invention, at least one inorganic abrasive particle (A) is a silicon dioxide particle with an average primary particle size (d1) of 35 nm and an average secondary particle size (d2) of 70 nm.

[0109] In the most preferred embodiment of the present invention, at least one inorganic abrasive particle (A) is a colloidal silica particle with an average primary particle size (d1) of 35 nm and an average secondary particle size (d2) of 70 nm.

[0110] In another preferred embodiment of the invention, at least one inorganic abrasive particle (A) is a cocoon-shaped silica particle with an average primary particle size (d1) of 35 nm and an average secondary particle size (d2) of 70 nm.

[0111] The CMP composition (Q) further comprises at least one chelating agent (B). The chelating agent (B) is different from components (A), (C), (D), (E), (F) and (G).

[0112] For the purposes of this invention, at least one chelating agent (B) is a carboxylic acid, more preferably at least one chelating agent (B) is a compound containing at least two carboxylic acid (-COOH) or carboxylate (-COO-) groups.

[0113] In embodiments of the present invention, at least one chelating agent (B) is selected from dicarboxylic acids and tricarboxylic acids.

[0114] For the purposes of this invention, at least one chelating agent (B) is selected from malonic acid, tartaric acid, succinic acid, citric acid, acetic acid, adipic acid, malic acid, maleic acid, butyric acid, glutaric acid, glycolic acid, formic acid, lactic acid, lauric acid, malic acid, maleic acid, myristic acid, fumaric acid, palmitic acid, propionic acid, pyruvic acid, stearic acid, valeric acid, 2-methylbutyric acid, hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylvaleric acid, heptanoic acid, 2-methylhexanoic acid, octanoic acid, 2-ethylhexanoic acid, propane-1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, pentane-1,2,3,4,5-pentacarboxylic acid, trimellitic acid, pyromellitic acid, pyromellitic tetroxide, benzohexaic acid, oligomeric or polymeric polycarboxylic acids, and aromatic compounds containing an acid group (Y).

[0115] In a preferred embodiment of the present invention, at least one chelating agent (B) is selected from malonic acid, tartaric acid, succinic acid, adipic acid, malic acid, maleic acid, oxalic acid, and fumaric acid.

[0116] In the most preferred embodiment of the invention, at least one chelating agent (B) is citric acid.

[0117] For the purposes of this invention, at least one chelating agent (B) is particularly preferably selected from malonic acid, citric acid, adipic acid, propane-1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, and pentane-1,2,3,4,5-pentacarboxylic acid, as well as aromatic compounds containing an acid group (Y). For the purposes of this invention, at least one chelating agent (B) is particularly preferably containing at least three carboxylic acids (-COOH) or carboxylate groups (-COO). - Compounds with a ) group.

[0118] For the purposes of this invention, at least one chelating agent (B) is particularly preferably selected from malonic acid, citric acid, and aromatic compounds containing an acid group (Y). (B) is particularly an aromatic compound containing an acid group (Y). Aromatic compounds containing an acid group (Y) are hereinafter referred to as (B11). Representative examples include, but are not limited to, phenylcarboxylic acids or their salts containing at least two carboxylic acid (-COOH) groups. For the purposes of this invention, at least one chelating agent (B) is particularly preferably phenyl dicarboxylic acid.

[0119] For the purposes of this invention, the acid group (Y) is defined as (Y) and its deprotonated form. The acid group (Y) contained in the aromatic compound (B11) is preferably any acid group, such that the pKa value (logarithmic measure of the acid dissociation constant) for the following reaction, when measured in deionized water at 25°C and atmospheric pressure, does not exceed 7, more preferably not more than 6, most preferably not more than 5.5, and particularly preferably not more than 5:

[0120] · or

[0121] ·

[0122] For the purposes of this invention, the acid group (Y) is preferably directly covalently bonded to the aromatic ring system of the aromatic compound (B11).

[0123] The preferred aromatic compound (B11) contains at least two acid groups (Y) in each aromatic ring.

[0124] The aromatic compound (B11) comprises at least one, preferably at least two, most preferably 2-6, particularly preferably 2-4, for example 2 acid groups (Y). The aromatic compound (B11) preferably comprises at least one, more preferably at least two, and most preferably 2-4, for example 2 acid groups (Y) per aromatic ring.

[0125] In a preferred embodiment, the aromatic compound (B11) contains at least one benzene ring, and (B11) preferably contains at least one per benzene ring, more preferably at least two, and most preferably 2-4, for example, 2 acid groups (Y).

[0126] In another preferred embodiment of the invention, the aromatic compound (B11) comprises at least one benzene ring, and (B11) preferably comprises at least one, more preferably at least two, and most preferably 2-4, for example, 2 carboxylic acid (-COOH) groups or their deprotonated forms.

[0127] In another preferred embodiment of the invention, the aromatic compound (B11) is a phenylcarboxylic acid or a salt thereof containing at least one, more preferably at least two, and most preferably two to four, such as two carboxylic acid (-COOH) groups.

[0128] In another preferred embodiment of the invention, the aromatic compound (B11) is a benzene carboxylic acid or its salt containing at least one, more preferably at least two, and most preferably two to four, such as two carboxylic acid (-COOH) groups directly covalently bonded to the benzene ring.

[0129] In another preferred embodiment of the invention, the aromatic compound (B11) is most preferably phthalic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,2,3,4-tetracarboxylic acid or its derivatives or salts thereof, particularly terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, benzene-1,2,3,4-tetracarboxylic acid or its derivatives or salts thereof, such as terephthalic acid, isophthalic acid or 5-hydroxyisophthalic acid.

[0130] In embodiments of the invention, at least one chelating agent (B) is present in an amount ranging from ≥0.001% by weight to ≤2.5% by weight based on the total weight of the chemical mechanical polishing composition (Q).

[0131] For the purposes of this invention, the chelating agent (B) is preferably no more than 2.5% by weight, preferably no more than 1% by weight, based on the total weight of the CMP composition (Q). For the purposes of this invention, the amount of (B) is preferably at least 0.001% by weight, more preferably at least 0.01% by weight, and most preferably at least 0.07% by weight, based on the total weight of the CMP composition (Q).

[0132] The CMP composition (Q) further comprises at least one corrosion inhibitor (C). The corrosion inhibitor (C) is different from components (A), (B), (D), (E), (F) and (G).

[0133] For the purposes of this invention, at least one corrosion inhibitor (C) is a triazole.

[0134] In embodiments of the present invention, at least one corrosion inhibitor (C) triazole is selected from unsubstituted benzotriazole, substituted benzotriazole, unsubstituted 1,2,3-triazole, substituted 1,2,3-triazole, unsubstituted 1,2,4-triazole and substituted 1,2,4-triazole.

[0135] In a preferred embodiment of the invention, at least one corrosion inhibitor (C) is a substituted benzotriazole selected from 4-methylbenzotriazole, 5-methylbenzotriazole, 5,6-dimethylbenzotriazole, 5-chlorobenzotriazole, 1-octylbenzotriazole, carboxybenzotriazole, butylbenzotriazole, 6-ethyl-1H-1,2,4-benzotriazole, (1-pyrrolidinylmethyl)benzotriazole, 1-n-butylbenzotriazole, benzotriazole-5-carboxylic acid, 4,5,6,7-tetrahydro-1H-benzotriazole, tolyltriazole, 5-bromo-1H-benzotriazole, 5-tert-butyl-1H-benzotriazole, 5-benzoyl-1H-benzotriazole, 5,6-dibromo-1H-benzotriazole, and 5-sec-butyl-1H-benzotriazole.

[0136] In an embodiment of the invention, the corrosion inhibitor (C) is present in an amount ranging from ≥0.001% by weight to ≤1% by weight based on the total weight of the chemical mechanical polishing composition.

[0137] For the purposes of this invention, at least one corrosion inhibitor (C) is preferably present in an amount not exceeding 10% by weight, more preferably not exceeding 2% by weight, most preferably not exceeding 1% by weight, most preferably not exceeding 0.5% by weight, particularly not exceeding 0.15% by weight, for example not exceeding 0.08% by weight, based on the total weight of the CMP composition (Q). The amount of (C) based on the total weight of the CMP composition (Q) is preferably at least 0.0001% by weight, more preferably at least 0.001% by weight, most preferably at least 0.005% by weight, particularly at least 0.02% by weight, for example at least 0.04% by weight.

[0138] The CMP composition (Q) further comprises at least one nonionic surfactant (D). The nonionic surfactant (D) is different from components (A), (B), (C), (E), (F) and (G).

[0139] For the purposes of this invention, at least one nonionic surfactant (D) is preferably water-soluble and / or water-dispersible, more preferably water-soluble.

[0140] In embodiments of the present invention, at least one nonionic surfactant (D) comprises a polyoxyethylene group.

[0141] For the purposes of this invention, at least one nonionic surfactant (D) is preferably an amphiphilic nonionic surfactant, i.e., a surfactant comprising at least one hydrophobic group (b1) and at least one hydrophilic group (b2). The nonionic surfactant (D) may comprise 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 (D) may comprise more than one hydrophilic group (b2), for example, two, three, or more groups (b2) separated from each other by hydrophobic groups (b1) as described below.

[0142] For the purposes of this invention, at least one nonionic surfactant (D) can have different block-like general structures. Representative examples of block-like structures include, but are not limited to, the following:

[0143] -b1-b2,

[0144] -b1-b2-b1,

[0145] -b2-b1-b2,

[0146] -b2-b1-b2-b1,

[0147] -b1-b2-b1-b2-b1, and

[0148] -b2-b1-b2-b1-b2.

[0149] The hydrophobic group (b1) is preferably an alkyl group, more preferably 4-40, most preferably 5-20, particularly preferably 7-18, especially 10-16, for example, an alkyl group with 11-14 carbon atoms.

[0150] The hydrophilic group (b2) is preferably a polyoxyolefin group. The polyoxyolefin group can be oligomeric or polymeric. More preferably, the hydrophilic group (b2) is selected from polyoxyolefin groups comprising the following monomer units:

[0151] •(b21) Oxide olefin monomer unit, and

[0152] •(b22) Oxide olefin monomer units other than ethylene oxide monomer units,

[0153] The monomer unit (b21) is different from the monomer unit (b22), and the polyoxyethylene groups of (b2) contain monomer units (b21) and (b22) in a random, alternating, gradient and / or block distribution.

[0154] The most preferred hydrophilic group (b2) is selected from polyoxyethylene groups containing the following monomer units:

[0155] • (b21) Ethylene oxide monomer unit, and

[0156] •(b22) Oxide olefin monomer units other than ethylene oxide monomer units,

[0157] (b2) contains monomer units (b21) and (b22) in a random, alternating, gradient and / or block distribution of polyoxyethylene groups.

[0158] For the purposes of this invention, the olefin oxide monomer unit (b22) other than the ethylene oxide monomer unit is preferably a substituted olefin oxide monomer unit, wherein the substituent is selected from alkyl, cycloalkyl, aryl, alkylcycloalkyl, alkylaryl, cycloalkylaryl and alkylcycloalkylaryl.

[0159] Oxide monomer units other than ethylene oxide monomer units (b22):

[0160] More preferably, it is derived from substituted ethylene oxide (X), wherein the substituent is selected from alkyl, cycloalkyl, aryl, alkylcycloalkyl, alkylaryl, cycloalkylaryl, and alkylcycloalkylaryl.

[0161] The most preferred derivative is alkyl-substituted ethylene oxide (X).

[0162] • Particularly preferred are substituted ethylene oxides (X), wherein the substituents are selected from alkyl groups having 1-10 carbon atoms.

[0163] For example, derived from methyl ethylene oxide (propylene oxide) and / or ethyl ethylene oxide (butene oxide).

[0164] For the purposes of this invention, the substituent of the substituted ethylene oxide (X) may also contain inert substituents, i.e., substituents that do not adversely affect the copolymerization of ethylene oxide (X) and the surface activity of the nonionic surfactant (D). Examples of such inert substituents include, but are not limited to, fluorine and chlorine atoms, nitro groups, and nitrile groups. If present, the inert substituents are present in an amount that does not adversely affect the hydrophilic-hydrophobic balance of the nonionic surfactant (D). For the purposes of this invention, the substituent of the substituted ethylene oxide (X) preferably does not contain inert substituents.

[0165] For the purposes of this invention, the substituents of the substituted ethylene oxide (X) are preferably selected from alkyl groups having 1-10 carbon atoms, cycloalkyl groups having 5-10 carbon atoms in a spirocyclic, exocyclic, and / or fused configuration, aryl groups having 6-10 carbon atoms, alkylcycloalkyl groups having 6-20 carbon atoms, alkylaryl groups having 7-20 carbon atoms, cycloalkylaryl groups having 11-20 carbon atoms, and alkylcycloalkylaryl groups having 12-30 carbon atoms. For the purposes of this invention, the substituents of the substituted ethylene oxide (X) are more preferably selected from alkyl groups having 1-10 carbon atoms, and particularly preferably selected from alkyl groups having 1-6 carbon atoms.

[0166] Representative examples of the most preferred substituted ethylene oxide (X) include, but are not limited to, methyl ethylene oxide (propylene oxide) and / or ethyl ethylene oxide (butene oxide), especially methyl ethylene oxide.

[0167] In a preferred embodiment of the invention, the hydrophilic group (b2) is preferably composed of monomer units (b21) and (b22). The hydrophilic group (b2) is preferably polyoxyethylene, polyoxypropylene, or polyoxybutene, and more preferably polyoxyethylene groups.

[0168] In embodiments where the hydrophilic group (b2) comprises monomer units (b21) and (b22) or constitutes thereof, the polyoxyethylene group used as the hydrophilic group (b2) is composed of monomer units (b21) and (b22) distributed randomly, alternately, in a gradient, and / or in a block pattern. For example, the hydrophilic group (b2) may have only one type of distribution:

[0169] -Unregulated: …-b21-b21-b22-b21-b22-b22-b22-b21-b22-…;

[0170] - Alternating: ...-b21-b22-b21-b22-b21-...;

[0171] - Gradient: ...b21-b21-b21-b22-b21-b21-b22-b22-b21-b22-b22-b22-b22-...; or

[0172] -Block-like:…-b21-b21-b21-b21-b22-b22-b22-b22-….

[0173] In another preferred embodiment of the invention, the hydrophilic group (b2) is composed of at least two types of distributions, such as oligomeric or polymeric segments with random distributions and oligomeric or polymeric segments with alternating distributions. Preferably, the hydrophilic group (b2) has only one type of distribution, and most preferably, the distribution is random or blocky.

[0174] In embodiments in which the hydrophilic group (b2) comprises monomer units (b21) and (b22) or constituted therewith, the molar ratio of (b21) to (b22) can be widely varied and thus can be most advantageously tuned to the specific requirements of the compositions, methods, and uses of the present invention. For the purposes of the present invention, the molar ratio (b21):(b22) is preferably 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.

[0175] The degree of polymerization of the oligomers and polymers of the polyoxyethylene groups used as hydrophilic groups (b2) can also vary widely and can therefore be most advantageously tuned to the specific requirements of the compositions, methods, and uses of the present invention. For the purposes of the present invention, the degree of polymerization is preferably in the range of 5-100, more preferably 5-90, and most preferably 5-80.

[0176] For the purposes of this invention, at least one nonionic surfactant (D) is particularly preferably an amphiphilic nonionic polyoxyethylene-polyoxypropylene alkyl ether surfactant, which is a molecular mixture containing an alkyl group having an average of 10-16 carbon atoms and 5-20 ethylene oxide monomer units (b21) and 2-8 propylene oxide monomer units in a random distribution. For example, at least one nonionic surfactant (D) is an amphiphilic nonionic polyoxyethylene-polyoxypropylene alkyl ether surfactant, which is a molecular mixture containing an alkyl group having an average of 11-14 carbon atoms and 12-20 ethylene oxide monomer units and 3-5 propylene oxide monomer units in a random distribution.

[0177] In an embodiment of the invention, at least one nonionic surfactant (D) is present in an amount ranging from ≥0.01% by weight to ≤10% by weight based on the total weight of the CMP composition (Q).

[0178] For the purposes of this invention, the amount of at least one nonionic surfactant (D) based on the total weight of the CMP composition (Q) is no more than 10% by weight, more preferably no more than 3% by weight, most preferably no more than 1% by weight, particularly preferably no more than 0.5% by weight, especially no more than 0.1% by weight, for example no more than 0.05% by weight. For the purposes of this invention, the amount of at least one nonionic surfactant (D) based on the total weight of the CMP composition (Q) is at least 0.00001% by weight, more preferably at least 0.0001% by weight, most preferably at least 0.0008% by weight, particularly preferably at least 0.002% by weight, especially at least 0.005% by weight, for example at least 0.008% by weight.

[0179] For the purposes of this invention, at least one nonionic surfactant (D) has a weight-average molecular weight, as determined by gel permeation chromatography (GPC), in the range of ≥1500 g / mol to ≤400 g / mol, preferably ≥1000 g / mol to ≤500 g / mol, and most preferably ≥900 g / mol to ≤600 g / mol.

[0180] The CMP composition (Q) further comprises at least one pad cleaner (E). The pad cleaner (E) is different from components (A), (B), (C), (D), (F), and (G).

[0181] In embodiments of the present invention, at least one pad cleaner (E) is selected from compounds having at least one amino group and at least one acidic group selected from carboxylic acids, phosphonic acids and sulfonic acids.

[0182] In a preferred embodiment of the invention, at least one pad cleaner (E) is selected from compounds having at least one amino group and at least one acidic group selected from phosphonic acids.

[0183] In another embodiment of the invention, at least one pad cleaner (E) is selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta (methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid, and 4-aminobenzenesulfonic acid.

[0184] In the most preferred embodiment of the invention, at least one pad cleaner (E) is selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta (methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra (methylenephosphonic acid), aminotris (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and di(hexamethylenetriaminepenta (methylenephosphonic acid)).

[0185] In embodiments of the invention, the concentration of at least one pad cleaner (E) is in the range of ≥0.001% by weight to ≤1% by weight based on the total weight of the CMP composition (Q).

[0186] For the purposes of this invention, the concentration of at least one pad cleaner, based on the total weight of the CMP composition (Q), is preferably no more than 5% by weight, more preferably no more than 1% by weight, even more preferably no more than 0.5% by weight, and most preferably no more than 0.1% by weight. For the purposes of this invention, the concentration of at least one pad cleaner, based on the total weight of the CMP composition (Q), is preferably at least 0.0001% by weight, more preferably at least 0.001% by weight, most preferably at least 0.005% by weight, and particularly preferably at least 0.01% by weight.

[0187] The CMP composition (Q) further comprises at least one carbonate or bicarbonate (F). For the purposes of this invention, the carbonate comprises at least one CO32-. 2- Anions and bicarbonates containing at least one HCO3- - Anions.

[0188] For the purposes of this invention, the carbonate or bicarbonate (F) preferably does not contain CO3. 2- or HCO3 - Any anion other than anions.

[0189] In embodiments of the invention, the CMP composition (Q) further comprises at least one carbonate. Preferably, the at least one carbonate does not contain CO3. 2- Any anion other than anions.

[0190] For the purposes of this invention, at least one carbonate or bicarbonate (F) comprises at least one component selected from NH4. + A cation, an organoammonium cation, an N-heterocyclic cation, an alkali metal cation, or an alkaline earth metal cation. More preferably, (F) contains at least one NH4+. +Alkali metal or alkaline earth metal cations. Most preferably, (F) contains at least one alkali metal cation. (F) is particularly preferably an alkali metal carbonate or alkali metal bicarbonate. (F) is particularly more preferably containing at least one sodium or potassium cation. (F) is particularly preferably containing at least one potassium cation. (F) is especially potassium carbonate or potassium bicarbonate. For example, (F) is potassium carbonate.

[0191] Organic ammonium ions are of the formula [NR] 11 R 12 R 13 R 14 ] + Any cation in which R 11 R 12 R 13 Each of the following is independently H, alkyl, aryl, alkylaryl, or arylalkyl, and R 14 It can be alkyl, aryl, alkylaryl, or arylalkyl.

[0192] In embodiments of the present invention, the concentration of at least one carbonate or bicarbonate is in the range of ≥0.001% by weight to ≤1% by weight.

[0193] For the purposes of this invention, the concentration of at least one carbonate or bicarbonate, based on the total weight of the CMP composition (Q), is no more than 10% by weight, more preferably no more than 5% by weight, most preferably no more than 3% by weight, particularly preferably no more than 2% by weight, especially no more than 1% by weight, for example no more than 0.7% by weight. For the purposes of this invention, the concentration of at least one carbonate or bicarbonate, based on the total weight of the CMP composition (Q), is at least 0.001% by weight, more preferably at least 0.01% by weight, most preferably at least 0.05% by weight, particularly preferably at least 0.1% by weight, especially at least 0.2% by weight.

[0194] The CMP composition (Q) of the present invention further comprises at least one oxidizing agent (G). The at least one oxidizing agent (G) is different from components (A), (B), (C), (D), (E) and (F).

[0195] In embodiments of the present invention, at least one oxidant (G) is selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromate. For the purposes of the present invention, at least one oxidant (G) is a peroxide. For example, (G) is hydrogen peroxide.

[0196] For the purposes of this invention, the concentration of at least one oxidant (G) is not more than 10% by weight, more preferably not more than 5% by weight, even more preferably not more than 3.5% by weight, and most preferably not more than 2% by weight, in each case based on the total weight of the CMP composition (Q). For the purposes of this invention, the concentration of at least one oxidant (G) is at least 0.01% by weight, more preferably at least 0.05% by weight, and most preferably at least 0.5% by weight, in each case based on the total weight of the CMP (Q).

[0197] For the purposes of this invention, the concentration of hydrogen peroxide as an oxidant is ≥1% by weight to ≤5% by weight, more preferably ≥2% by weight to ≤3.5% by weight, for example 2.5% by weight, and most preferably ≥1% by weight to ≤2% by weight, based on the total weight of the CMP composition (Q) in each case.

[0198] The CMP composition (Q) of the present invention further comprises an aqueous medium (H). The aqueous medium (H) may be a single type of aqueous medium or a mixture of different types of aqueous media.

[0199] For the purposes of this invention, the aqueous medium (H) can be any medium containing water. Preferably, the aqueous medium (H) is a mixture of water and a water-miscible organic solvent. Representative examples of organic solvents include, but are not limited to, C1-C3 alcohols, alkylene glycols, and alkylene glycol derivatives. More preferably, the aqueous medium (H) is water. Most preferably, the aqueous medium (H) is deionized water.

[0200] For the purposes of this invention, if the total amount of components other than (H) is y% by weight of the CMP composition (Q), then the amount of (H) is (100-y)% by weight of the CMP composition.

[0201] For the purposes of this invention, the amount of the aqueous medium (H) in the CMP composition (Q) is no more than 99.9% by weight, more preferably no more than 99.6% by weight, most preferably no more than 99% by weight, particularly preferably no more than 98% by weight, especially no more than 97% by weight, for example no more than 95% by weight. For the purposes of this invention, the amount of the aqueous medium (H) in the CMP composition (Q) is at least 60% by weight, more preferably at least 70% by weight, most preferably at least 80% by weight, particularly preferably at least 85% by weight, especially at least 90% by weight, for example at least 93% by weight.

[0202] The properties of the CMP composition (Q), such as stability and polishing properties, can depend on the pH of the composition. For the purposes of this invention, the pH of the CMP composition (Q) is preferably not more than 14, more preferably not more than 13, most preferably not more than 12, particularly preferably not more than 11.5, particularly most preferably not more than 11, especially not more than 10.7, for example not more than 10.5. For the purposes of this invention, the pH of the CMP composition (Q) is preferably at least 6, more preferably at least 7, most preferably at least 8, particularly preferably at least 8.5, particularly most preferably at least 9, especially at least 9.5, for example at least 9.7.

[0203] For the purposes of this invention, the pH value of the CMP composition (Q) is preferably in the range of ≥6 to ≤14, more preferably ≥7 to ≤13, more preferably ≥8 to ≤12, most preferably ≥8 to ≤11, particularly preferably ≥9 to ≤11, and particularly most preferably ≥9.25 to ≤10.7.

[0204] In embodiments of the present invention, the pH of the CMP composition is in the range of ≥8 to ≤11.

[0205] In another embodiment of the invention, the pH of the CMP composition is in the range of ≥9.25 to ≤11.

[0206] The CMP composition (Q) of the present invention may optionally further contain at least one pH adjuster (I). The at least one pH adjuster (I) is different from components (A), (B), (C), (D), (E), (F) and (G).

[0207] For the purposes of this invention, at least one pH adjuster (I) is selected from inorganic acids, carboxylic acids, amine bases, alkali metal hydroxides, ammonium hydroxide, including tetraalkylammonium hydroxide. Preferably, at least one pH adjuster (I) is selected from nitric acid, sulfuric acid, ammonia, sodium hydroxide, and potassium hydroxide. For example, the pH adjuster (I) is potassium hydroxide.

[0208] For the purposes of this invention, the amount of at least one pH adjuster (I) based on the total weight of the CMP composition (Q) is preferably no more than 10% by weight, more preferably no more than 2% by weight, most preferably no more than 0.5% by weight, particularly no more than 0.1% by weight, for example no more than 0.05% by weight. For the purposes of this invention, the amount of at least one pH adjuster (I) based on the total weight of the CMP composition (Q) is preferably at least 0.0005% by weight, more preferably at least 0.005% by weight, most preferably at least 0.025% by weight, particularly at least 0.1% by weight, for example at least 0.4% by weight.

[0209] For the purposes of this invention, the CMP composition (Q) may optionally contain additives. Representative examples of additives for the purposes of this invention include, but are not limited to, stabilizers. For example, additives commonly used in CMP compositions are used to stabilize the dispersion or improve polishing properties or selectivity between different layers.

[0210] For the purposes of this invention, the concentration of the additive, based on the total weight of the CMP composition (Q), is no more than 10% by weight, more preferably no more than 1% by weight, and most preferably no more than 0.1% by weight, for example, no more than 0.01% by weight. For the purposes of this invention, the concentration of the additive, based on the total weight of the CMP composition (Q), is at least 0.0001% by weight, more preferably at least 0.001% by weight, and most preferably at least 0.01% by weight, for example, at least 0.1% by weight.

[0211] A preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0212] (A) At least one inorganic abrasive particle selected from metal oxides, metal nitrides, metal carbides, silicides, borides, ceramics, diamond, organic mixed particles, inorganic mixed particles and silica;

[0213] (B) At least one chelating agent selected from dicarboxylic acids and tricarboxylic acids;

[0214] (C) At least one corrosion inhibitor selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

[0215] (D) At least one nonionic surfactant containing a polyoxyalkylene group;

[0216] (E) At least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0217] (F) at least one carbonate or bicarbonate selected from alkali metal carbonates or alkali metal bicarbonates; (G) at least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromates; and

[0218] (H) Aqueous medium.

[0219] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0220] (A) At least one inorganic abrasive particle selected from metal oxides, metal nitrides, metal carbides, silicides, borides, ceramics, diamond, organic mixed particles, inorganic mixed particles and silica;

[0221] (B) At least one chelating agent selected from dicarboxylic acids and tricarboxylic acids;

[0222] (C) At least one corrosion inhibitor selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

[0223] (D) At least one nonionic surfactant containing a polyoxyalkylene group;

[0224] (E) At least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0225] (F) At least one carbonate or bicarbonate selected from alkali metal carbonates or alkali metal bicarbonates.

[0226] (G) At least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromate; and

[0227] (H) Aqueous medium,

[0228] The pH of the chemical mechanical polishing (CMP) composition is in the range of ≥8 to ≤11.

[0229] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0230] (A) Silica particles;

[0231] (B) Chelating agents selected from carboxylic acids;

[0232] (C) Corrosion inhibitors selected from triazoles;

[0233] (D) Amphiphilic nonionic surfactants containing polyoxyalkylene groups;

[0234] (E) A pad cleaner selected from compounds having at least one amino group and at least one acidic group selected from carboxylic acids, phosphonic acids and sulfonic acids;

[0235] (F) A carbonate;

[0236] (G) peroxides; and

[0237] (H) Aqueous medium.

[0238] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0239] (A) Silica particles;

[0240] (B) Chelating agents selected from dicarboxylic acids and tricarboxylic acids;

[0241] (C) Corrosion inhibitors selected from triazoles;

[0242] (D) Amphiphilic nonionic surfactants containing polyoxyalkylene groups;

[0243] (E) A pad cleaner selected from compounds having at least one amino group and at least one acidic group selected from phosphonic acids;

[0244] (F) Carbonates or bicarbonates;

[0245] (G) Hydrogen peroxide; and

[0246] (H) Aqueous medium.

[0247] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0248] (A) Silica particles;

[0249] (B) Citric acid;

[0250] (C) is a corrosion inhibitor selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

[0251] (D) Amphiphilic nonionic surfactants containing polyoxyalkylene groups;

[0252] (E) A pad cleaner selected from compounds having at least one amino group and at least one acidic group selected from carboxylic acids, phosphonic acids and sulfonic acids;

[0253] (F) Carbonates or bicarbonates selected from alkali metal carbonates or alkali metal bicarbonates;

[0254] (G) An oxidizing agent selected from organic or inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromates; and

[0255] (H) Aqueous medium.

[0256] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0257] (A) Silica particles;

[0258] (B) Dicarboxylic acids selected from malonic acid, tartaric acid, succinic acid, adipic acid, malic acid, maleic acid, oxalic acid and fumaric acid;

[0259] (C) is a corrosion inhibitor selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

[0260] (D) Amphiphilic nonionic surfactants containing polyoxyalkylene groups;

[0261] (E) A pad cleaner selected from compounds having at least one amino group and at least one acidic group selected from carboxylic acids, phosphonic acids and sulfonic acids;

[0262] (F) Carbonates or bicarbonates selected from alkali metal carbonates or alkali metal bicarbonates;

[0263] (G) An oxidizing agent selected from organic or inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromates; and

[0264] (H) Aqueous medium.

[0265] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0266] (A) Silica particles;

[0267] (B) Dicarboxylic acids selected from malonic acid, tartaric acid, succinic acid, adipic acid, malic acid, maleic acid, oxalic acid and fumaric acid;

[0268] (C) Corrosion inhibitors selected from unsubstituted benzotriazoles and substituted benzotriazoles (C);

[0269] (D) Polyethylene-polypropylene ether;

[0270] (E) A pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0271] (F) Alkali metal carbonates or alkali metal bicarbonates; and

[0272] (H) Aqueous medium.

[0273] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0274] (A) Silica particles;

[0275] (B) Citric acid;

[0276] (C) Corrosion inhibitors selected from unsubstituted benzotriazoles and substituted benzotriazoles (C);

[0277] (D) Polyethylene-polypropylene ether;

[0278] (E) A pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0279] (F) Alkali metal carbonates or alkali metal bicarbonates; and

[0280] (H) Aqueous medium.

[0281] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0282] (A) At least one inorganic abrasive particle selected from metal oxides, metal nitrides, metal carbides, silicides, borides, ceramics, diamond, organic / inorganic mixed particles and silica;

[0283] (B) At least one chelating agent selected from dicarboxylic acids and tricarboxylic acids;

[0284] (C) At least one corrosion inhibitor selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

[0285] (D) At least one nonionic surfactant containing a polyoxyalkylene group;

[0286] (E) At least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0287] (F) At least one carbonate or bicarbonate selected from alkali metal carbonates or alkali metal bicarbonates.

[0288] (G) At least one oxidizing agent selected from organic or inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromates; and

[0289] (H) Aqueous medium.

[0290] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0291] (A) At least one inorganic abrasive particle selected from metal oxides, metal nitrides, metal carbides, silicides, borides, ceramics, diamond, organic / inorganic mixed particles and silica;

[0292] (B) At least one chelating agent selected from dicarboxylic acids and tricarboxylic acids;

[0293] (C) At least one corrosion inhibitor selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

[0294] (D) At least one nonionic surfactant containing a polyoxyalkylene group;

[0295] (E) At least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0296] (F) At least one carbonate or bicarbonate selected from alkali metal carbonates or alkali metal bicarbonates.

[0297] (G) At least one oxidizing agent selected from organic or inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromates; and

[0298] (H) Aqueous medium;

[0299] The pH of the chemical mechanical polishing (CMP) composition is in the range of ≥8 to ≤11.

[0300] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0301] (A) ≥0.01% by weight to ≤5% by weight of at least one inorganic abrasive particle;

[0302] (B) ≥0.001% by weight to ≤2.5% by weight of at least one chelating agent selected from carboxylic acids;

[0303] (C) ≥0.001% by weight to ≤1% by weight of at least one corrosion inhibitor selected from unsubstituted or substituted triazoles;

[0304] (D) ≥0.01% by weight to ≤1% by weight of at least one nonionic surfactant containing at least one polyoxyethylene group;

[0305] (E) ≥0.001% by weight to ≤1% by weight of at least one type of pad cleaner selected from compounds having at least one amino group and at least one acidic group selected from carboxylic acids, phosphonic acids and sulfonic acids;

[0306] (F) ≥0.001% by weight to ≤1% by weight of at least one carbonate or bicarbonate;

[0307] (G) ≥1% to ≤2% by weight of at least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromates; and

[0308] (H) Aqueous medium,

[0309] The weight percentages in each case are based on the total weight of the chemical mechanical polishing (CMP) composition.

[0310] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0311] (A) ≥0.01% by weight to ≤5% by weight of at least one inorganic abrasive particle;

[0312] (B) ≥0.001% by weight to ≤2.5% by weight of at least one chelating agent selected from carboxylic acids;

[0313] (C) ≥0.001% by weight to ≤1% by weight of at least one corrosion inhibitor selected from unsubstituted or substituted triazoles;

[0314] (D) ≥0.01% by weight to ≤1% by weight of at least one nonionic surfactant containing at least one polyoxyethylene group;

[0315] (E) ≥0.001% by weight to ≤1% by weight of at least one type of pad cleaner selected from compounds having at least one amino group and at least one acidic group selected from carboxylic acids, phosphonic acids and sulfonic acids;

[0316] (F) ≥0.001% by weight to ≤1% by weight of at least one carbonate or bicarbonate;

[0317] (G) ≥1% to ≤2% by weight of at least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromates; and

[0318] (H) An aqueous medium, wherein the weight percentage in each case is based on the total weight of the chemical mechanical polishing (CMP) composition; and wherein the pH of the chemical mechanical polishing (CMP) composition is in the range of ≥8 to ≤11.

[0319] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0320] (A) ≥0.01% by weight to ≤5% by weight of at least one inorganic abrasive particle selected from metal oxides, metal nitrides, metal carbides, silicides, borides, ceramics, diamond, organic mixed particles, inorganic mixed particles and silica;

[0321] (B) ≥0.001% by weight to ≤2.5% by weight of at least one chelating agent selected from dicarboxylic acids and tricarboxylic acids;

[0322] (C) ≥0.001% by weight to ≤1% by weight at least one corrosion inhibitor selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

[0323] (D) ≥0.01% by weight to ≤1% by weight of at least one nonionic surfactant containing at least one polyoxyethylene group;

[0324] (E) ≥0.001% by weight to ≤1% by weight of at least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0325] (F) ≥0.001% by weight to ≤1% by weight at least one carbonate or bicarbonate selected from alkali metal carbonates or alkali metal bicarbonates; and

[0326] (G) ≥1% to ≤2% by weight at least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromates, and

[0327] (H) Aqueous medium,

[0328] The weight percentages in each case are based on the total weight of the chemical mechanical polishing (CMP) composition.

[0329] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0330] (A) ≥0.01% by weight to ≤5% by weight colloidal silica;

[0331] (B) ≥0.001% by weight to ≤2.5% by weight of dicarboxylic acids selected from malonic acid, tartaric acid, succinic acid, adipic acid, malic acid, maleic acid, oxalic acid and fumaric acid;

[0332] (C) ≥0.001% by weight to ≤1% by weight of at least one corrosion inhibitor selected from unsubstituted benzotriazoles and substituted benzotriazoles;

[0333] (D) ≥0.01% by weight to ≤1% by weight of at least one nonionic surfactant containing at least one polyoxyethylene group;

[0334] (E) ≥0.001% by weight to ≤1% by weight of at least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0335] (F) ≥0.001% by weight to ≤1% by weight of alkali metal carbonates or alkali metal bicarbonates; and

[0336] (H) Aqueous medium,

[0337] The weight percentages in each case are based on the total weight of the chemical mechanical polishing (CMP) composition.

[0338] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0339] (A) ≥0.01% by weight to ≤5% by weight colloidal silica;

[0340] (B) ≥0.001% by weight to ≤2.5% by weight of citric acid;

[0341] (C) ≥0.001% by weight to ≤1% by weight of at least one corrosion inhibitor selected from unsubstituted benzotriazoles and substituted benzotriazoles;

[0342] (D) ≥0.01% by weight to ≤1% by weight of at least one nonionic surfactant containing at least one polyoxyethylene group;

[0343] (E) ≥0.001% by weight to ≤1% by weight of at least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0344] (F) ≥0.001% by weight to ≤1% by weight of alkali metal carbonates or alkali metal bicarbonates; and

[0345] (H) Aqueous medium, wherein the weight percentage in each case is based on the total weight of the chemical mechanical polishing composition (CMP).

[0346] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0347] (A) ≥0.01% by weight to ≤5% by weight colloidal silica;

[0348] (B) ≥0.001% by weight to ≤2.5% by weight of citric acid;

[0349] (C) ≥0.001% by weight to ≤1% by weight of at least one corrosion inhibitor selected from unsubstituted benzotriazoles and substituted benzotriazoles;

[0350] (D) ≥0.01% by weight to ≤1% by weight of at least one nonionic surfactant containing at least one polyoxyethylene group;

[0351] (E) ≥0.001% by weight to ≤1% by weight of at least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0352] (F) ≥0.001% by weight to ≤1% by weight of alkali metal carbonates or alkali metal bicarbonates; and

[0353] (H) Aqueous medium,

[0354] The weight percentages in each case are based on the total weight of the chemical mechanical polishing (CMP) composition; and

[0355] The pH of the chemical mechanical polishing (CMP) composition is in the range of ≥9.25 to ≤11.

[0356] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0357] (A) ≥0.01% by weight to ≤3% by weight of at least one inorganic abrasive particle selected from metal oxides, metal nitrides, metal carbides, silicides, borides, ceramics, diamond, organic mixed particles, inorganic mixed particles and silica;

[0358] (B) ≥0.01% by weight to ≤1% by weight of at least one chelating agent selected from dicarboxylic acids and tricarboxylic acids;

[0359] (C) ≥0.001% by weight to ≤1% by weight at least one corrosion inhibitor selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

[0360] (D) ≥0.002% by weight to ≤0.5% by weight of at least one nonionic surfactant containing at least one polyoxyethylene group;

[0361] (E) ≥0.001% by weight to ≤0.5% by weight of at least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0362] (F) ≥0.001% by weight to ≤1% by weight at least one carbonate or bicarbonate selected from alkali metal carbonates or alkali metal bicarbonates; and

[0363] (G) ≥1% to ≤2% by weight at least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromates, and

[0364] (H) Aqueous medium,

[0365] The weight percentages in each case are based on the total weight of the chemical mechanical polishing (CMP) composition.

[0366] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0367] (A) ≥0.01% by weight to ≤3% by weight of at least one inorganic abrasive particle selected from metal oxides, metal nitrides, metal carbides, silicides, borides, ceramics, diamond, organic mixed particles, inorganic mixed particles and silica;

[0368] (B) ≥0.01% by weight to ≤1% by weight of at least one chelating agent selected from dicarboxylic acids and tricarboxylic acids;

[0369] (C) ≥0.001% by weight to ≤1% by weight at least one corrosion inhibitor selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

[0370] (D) ≥0.002% by weight to ≤0.5% by weight of at least one nonionic surfactant containing at least one polyoxyethylene group;

[0371] (E) ≥0.001% by weight to ≤0.5% by weight of at least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) and di(hexamethylenetriaminepenta(methylenephosphonic acid));

[0372] (F) ≥0.001% by weight to ≤1% by weight of alkali metal carbonates or alkali metal bicarbonates; and

[0373] (H) Aqueous medium,

[0374] The weight percentages in each case are based on the total weight of the chemical mechanical polishing (CMP) composition.

[0375] Another preferred embodiment of the present invention relates to a chemical mechanical polishing (CMP) composition comprising the following components:

[0376] (A) ≥0.01 wt% to ≤1.8 wt% colloidal silica;

[0377] (B) ≥0.01% by weight to ≤1% by weight of at least one chelating agent selected from dicarboxylic acids and tricarboxylic acids;

[0378] (C) ≥0.001% by weight to ≤1% by weight of at least one corrosion inhibitor selected from unsubstituted or substituted benzotriazoles;

[0379] (D) ≥0.002% by weight to ≤0.5% by weight of at least one nonionic surfactant containing at least one polyoxyethylene group;

[0380] (E) ≥0.001% by weight to ≤0.5% by weight of at least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0381] (F) ≥0.001% by weight to ≤1% by weight at least one carbonate or bicarbonate selected from alkali metal carbonates or alkali metal bicarbonates; and

[0382] (G) ≥1% to ≤2% by weight at least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromates, and

[0383] (H) an aqueous medium, wherein the weight percentage in each case is based on the total weight of the chemical mechanical polishing (CMP) composition; and wherein the pH of the chemical mechanical polishing (CMP) composition is in the range of ≥9.25 to ≤11.

[0384] Methods for preparing CMP compositions are generally known. These methods can be used to prepare the CMP compositions of the present invention. This can be done by dispersing or dissolving the components (A), (B), (C), (D), (E), (F), (G) and other optional components as described above in an aqueous medium (H), preferably water, and optionally by adjusting the pH value by adding an acid, base, buffer, or pH adjuster. For this purpose, conventional and standard mixing methods and mixing equipment such as stirred tanks, high-shear impellers, ultrasonic mixers, homogenizer nozzles, or countercurrent mixers can be used.

[0385] Polishing methods are generally known and can be performed using methods and apparatus commonly used in CMP for manufacturing wafers for integrated circuits. There are no limitations on the equipment used to perform the polishing methods. As is known in the art, typical CMP apparatus consists of a rotating stage covered with a polishing pad. Orbital polishers can also be used. The wafer is mounted on a holder or chuck. The surface of the wafer to be processed faces the polishing pad (single-sided polishing method). Clamps hold the wafer in a horizontal position.

[0386] Below this support, a larger diameter stage is typically placed horizontally and provides a surface parallel to the wafer surface to be polished. Polishing pads on the stage contact the wafer surface during planarization.

[0387] To induce material loss, the wafer is pressed onto a polishing pad. Typically, both the support and the stage are rotated about their respective axes extending perpendicularly from them. The axis of rotation of the support can remain fixed relative to the rotating stage or can oscillate horizontally relative to the stage. The direction of rotation of the support is typically—but not necessarily—the same as that of the stage. The rotational speeds of the support and the stage are typically—but not necessarily—set to different values. In the CMP method of this invention, the CMP composition of this invention is typically applied to the polishing pad as a continuous stream or by dropwise application. The temperature of the stage is typically set to 10-70°C.

[0388] Loading on the wafer can be applied, for example, by a steel plate covered with a soft pad, commonly known as a backsheet. With more advanced equipment, a flexible membrane pressurized with air or nitrogen presses the wafer onto the pad. This membrane support is preferred for low-pressure methods when using hard polishing pads because the pressure distribution on the wafer is more uniform compared to supports with a hard plate design. Supports can also be used according to the invention to control the pressure distribution on the wafer. They are typically designed with several different chambers that can be independently loaded to varying degrees.

[0389] Downforce or downward pressure is typically the downward pressure or force applied to the wafer by the support pad, which presses the wafer against the pad during CMP. Downforce or downward pressure can be measured, for example, in pounds per square inch (psi).

[0390] According to the method of the invention, the downforce is 2 psi or lower. Preferably, the downforce is in the range of 0.1-1.9 psi, more preferably 0.3-1.8 psi, most preferably 0.4-1.7 psi, particularly preferably in the range of 0.8-1.6 psi, for example 1.5 psi.

[0391] One aspect of the present invention relates to a method of manufacturing a semiconductor device, comprising chemically mechanically polishing a substrate in the presence of a chemical mechanical polishing composition (Q) as described above and below.

[0392] According to the present invention, a method for manufacturing a semiconductor device includes CMP of a substrate comprising a surface region containing at least one copper layer and / or at least one ruthenium layer or an alloy thereof or thereof.

[0393] In a preferred embodiment of the present invention, the substrate comprises at least one copper layer and / or at least one ruthenium layer or an alloy thereof.

[0394] The semiconductor devices that can be manufactured by the method of the present invention are not particularly limited. Semiconductor devices can be electronic components comprising semiconductor materials, such as silicon, germanium, and III-V materials. Semiconductor devices can be those manufactured as a single discrete device or as an integrated circuit (IC) consisting of several devices fabricated and interconnected on a wafer. Semiconductor devices can be two-terminal devices such as diodes, three-terminal devices such as bipolar transistors, four-terminal devices such as Hall effect sensors, or multi-terminal devices. Preferred semiconductor devices are multi-terminal devices. Multi-terminal devices can be logic devices such as integrated circuits, as well as microprocessors or memory devices such as random access memory (RAM), read-only memory (ROM), and phase-change random access memory (PCRAM). Preferred semiconductor devices are multi-terminal logic devices. Semiconductor devices are particularly integrated circuits or microprocessors.

[0395] In integrated circuits, ruthenium (Ru) is commonly used as an adhesion or barrier layer for copper interconnects. Ruthenium is incorporated, for example, in memory devices in nanocrystalline form and as a metal gate in MOSFETs. Ruthenium can also be used as a seed to facilitate copper plating by electrodeposition. Ruthenium and ruthenium alloys can also be used as one or more layers of conductors instead of copper. For example, capacitors (CAPs) can be formed at the same level from metals, insulators, continuous metal layers (MIMs), and thin-film resistors. Circuit designers can now route TaN thin-film resistors at a minimum metal level, reducing interference and allowing for more efficient use of existing wiring levels. Excess copper and / or ruthenium can be removed by the chemical mechanical polishing method of this invention and incorporated as an adhesion / barrier layer on the dielectric layer, for example, in the form of metal nitrides or metal carbonitrides, such as Ru / TaN, Ru / TiN, Ru / TaCN, Ru / TiCN, or, for example, as a single ruthenium alloy layer, such as RuMo, RuTa, RuTi, and RuW.

[0396] Ruthenium and / or ruthenium alloys can typically be produced or obtained in various ways. Ruthenium and ruthenium alloys can be produced by ALD, PVD, or CVD methods. It is possible to deposit ruthenium or ruthenium alloys onto a barrier material. Suitable materials for barrier applications are well known in the art. The barrier layer prevents metal atoms or ions such as ruthenium or copper from diffusing into the dielectric layer and improves the adhesion properties of the conductive layer. Ta / TaN and Ti / TiN can be used.

[0397] Ruthenium and / or ruthenium alloys can generally be of any type, form, or shape. Ruthenium and / or ruthenium alloys preferably have a layered and / or overgrowth shape. If the ruthenium and / or ruthenium alloy has a layered and / or overgrowth shape, the ruthenium and / or ruthenium alloy content is preferably greater than 90% by weight of the corresponding layer and / or overgrowth, more preferably greater than 95% by weight, most preferably greater than 98% by weight, particularly greater than 99% by weight, for example greater than 99.9% by weight. Ruthenium and / or ruthenium alloys are preferably already filled or grown in trenches or pillars between other substrates, more preferably in trenches or pillars in dielectric materials such as SiO2, silicon, low-k (BD1, BD2) or ultra-low-k materials, or other isolation and semiconductor materials used in the semiconductor industry. For example, in the intermediate process of through-silicon vias (TSVs), insulating materials such as polymers, photoresists, and / or polyimides can be used as insulating materials between subsequent processing steps such as wet etching and CMP to provide insulation / isolation performance after the TSV is exposed from the back side of the wafer. A thin layer of barrier material can be present between the copper-containing material and the dielectric material. The barrier material, which prevents metal ions from diffusing into the dielectric material, can typically be, for example, Ti / TiN, Ta / TaN, Ru or Ru alloys, Co or Co alloys.

[0398] With regard to the presence of a barrier layer and low-k or ultra-low-k material in the semiconductor substrate used, the CMP composition of the present invention preferably removes the barrier layer while maintaining the integrity of the low-k and ultra-low-k material, i.e., provides a particularly high selectivity for the barrier layer in terms of material removal rate (MRR) compared to the low-k or ultra-low-k material. In particular, with regard to the presence of a copper layer, a barrier layer, and low-k or ultra-low-k material in the substrate to be polished, the CMP composition of the present invention provides at least one of the following properties: (a) high MRR of the barrier layer, (b) low MRR of the copper layer, (c) low MRR of the low-k or ultra-low-k material, (d) high selectivity of the barrier layer compared to the copper layer in terms of MRR, and (e) high selectivity of the barrier layer compared to the low-k and ultra-low-k material in terms of MRR. Most notably, regarding the presence of a copper layer, a ruthenium, cobalt, tantalum, or tantalum nitride layer, and a low-k or ultra-low-k material in the substrate to be polished, the CMP composition of the present invention provides at least one of the following properties: (a') high MRR of tantalum or tantalum nitride, (b') low MRR of the copper layer, (c') low MRR of the low-k or ultra-low-k material, (d') high selectivity of ruthenium, tantalum, or tantalum nitride compared to copper in terms of MRR, and (e') high selectivity of tantalum nitride or ruthenium compared to low-k or ultra-low-k material in terms of MRR. Furthermore, the CMP composition of the present invention provides a long shelf life while maintaining a high MRR of the barrier layer.

[0399] For the purposes of this invention, the selectivity of ruthenium relative to copper in terms of material removal rate is preferably higher than 0.05, more preferably higher than 0.2, most preferably higher than 1, particularly higher than 2.5, especially higher than 20, for example higher than 40. The selectivity can be advantageously adjusted by a combination of the high material removal rate (MRR) of ruthenium and the low MRR of copper, or vice versa.

[0400] The CMP compositions of the present invention can be used as ready-to-use slurries in the CMP process. They have a long shelf life and exhibit a stable particle size distribution over extended periods. Therefore, they are easy to handle and store. They exhibit excellent polishing properties, particularly in terms of: (a') high MRR of tantalum nitride, (b') high MRR of ruthenium, (c') low MRR of copper layers, (d') low MRR of low-k or ultra-low-k materials, (e') high selectivity of tantalum nitride or ruthenium compared to copper in terms of MRR, and (e') high selectivity of tantalum nitride or ruthenium compared to low-k or ultra-low-k materials in terms of MRR. Furthermore, the CMP compositions of the present invention exhibit a longer shelf life, preventing agglomeration within the CMP compositions while maintaining a high MRR of the barrier layer. Because the amounts of their components are kept to a minimum, the CMP compositions (Q) and CMP methods of the present invention can be used or applied in a cost-effective manner.

[0401] One aspect of this invention relates to the use of the chemical mechanical polishing composition of this invention in substrates used in the chemical mechanical polishing semiconductor industry.

[0402] In an embodiment of the present invention, the use of the chemical mechanical polishing composition of the present invention in a chemical mechanical polishing substrate, the substrate comprising:

[0403] (i) copper, and / or

[0404] (ii) Tantalum, tantalum nitride, titanium, titanium nitride, ruthenium, cobalt or alloys thereof.

[0405] In another embodiment of the invention, the use of the chemical mechanical polishing composition of the invention in a chemical mechanical polishing substrate, the substrate comprising:

[0406] (i) copper, and / or

[0407] (ii) Tantalum, tantalum nitride, titanium, titanium nitride, ruthenium or ruthenium alloys thereof.

[0408] The chemical mechanical polishing composition of the present invention has at least one of the following advantages:

[0409] (i) Preferably, the substrate to be polished has a high material removal rate (MRR), such as tantalum or tantalum nitride or its alloys.

[0410] (ii) Preferably, the substrate to be polished has a high material removal rate (MRR), such as ruthenium or its alloys.

[0411] (iii) Preferably, the substrate to be polished is copper and / or a low material removal rate (MRR) of low-k materials.

[0412] (iv) The polished surface of the cleaning pad is free of metal residue by adding a pad cleaner to the CMP composition.

[0413] Implementation Plan

[0414] The following list of implementation schemes is provided to further illustrate this disclosure, but is not intended to limit this disclosure to the specific implementation schemes listed below.

[0415] 1. A chemical mechanical polishing (CMP) composition comprising:

[0416] (A) At least one inorganic abrasive particle;

[0417] (B) At least one chelating agent selected from carboxylic acids;

[0418] (C) At least one corrosion inhibitor selected from unsubstituted or substituted triazoles;

[0419] (D) At least one nonionic surfactant containing at least one polyoxyalkylene group;

[0420] (E) A pad cleaner selected from compounds having at least one amino group and at least one acidic group selected from carboxylic acids, phosphonic acids and sulfonic acids;

[0421] (F) At least one carbonate or bicarbonate;

[0422] (G) At least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromate; and

[0423] (H) Aqueous medium.

[0424] 2. The chemical mechanical polishing (CMP) composition according to embodiment 1, wherein at least one inorganic abrasive particle (A) is selected from metal oxides, metal nitrides, metal carbides, silicides, borides, ceramics, diamond, organic mixed particles, inorganic mixed particles, and silicon dioxide.

[0425] 3. The chemical mechanical polishing (CMP) composition according to embodiment 1, wherein the average particle size of at least one inorganic abrasive particle (A) is in the range of ≥1 nm to ≤1000 nm as determined by dynamic light scattering technique.

[0426] 4. The chemical mechanical polishing (CMP) composition according to embodiment 1, wherein the concentration of at least one inorganic abrasive particle (A) is in the range of ≥0.01% by weight to ≤10% by weight based on the total weight of the chemical mechanical polishing composition.

[0427] 5. A chemical mechanical polishing (CMP) composition according to any one of embodiments 1-4, wherein the carboxylic acid is selected from dicarboxylic acids and tricarboxylic acids.

[0428] 6. The chemical mechanical polishing (CMP) composition according to embodiment 5, wherein the tricarboxylic acid is citric acid.

[0429] 7. The chemical mechanical polishing (CMP) composition according to embodiment 5, wherein the dicarboxylic acid is selected from malonic acid, tartaric acid, succinic acid, adipic acid, malic acid, maleic acid, oxalic acid and fumaric acid.

[0430] 8. A chemical mechanical polishing (CMP) composition according to any one of embodiments 1-7, wherein the concentration of at least one chelating agent (B) is in the range of ≥0.001% by weight to ≤2.5% by weight based on the total weight of the chemical mechanical polishing composition.

[0431] 9. A chemical mechanical polishing (CMP) composition according to any one of embodiments 1-8, wherein the triazole is selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

[0432] 10. The chemical mechanical polishing (CMP) composition according to embodiment 9, wherein the substituted benzotriazole is selected from 4-methylbenzotriazole, 5-methylbenzotriazole, 5,6-dimethylbenzotriazole, 5-chlorobenzotriazole, 1-octylbenzotriazole, carboxybenzotriazole, butylbenzotriazole, 6-ethyl-1H-1,2,4-benzotriazole, (1-pyrrolidinylmethyl)benzotriazole, 1-n-butylbenzotriazole, benzotriazole-5-carboxylic acid, 4,5,6,7-tetrahydro-1H-benzotriazole, tolyltriazole, 5-bromo-1H-benzotriazole, 5-tert-butyl-1H-benzotriazole, 5-benzoyl-1H-benzotriazole, 5,6-dibromo-1H-benzotriazole, and 5-sec-butyl-1H-benzotriazole.

[0433] 11. A chemical mechanical polishing (CMP) composition according to any one of embodiments 1-10, wherein the concentration of at least one corrosion inhibitor (C) is in the range of ≥0.001% by weight to ≤1% by weight of the total weight of the chemical mechanical polishing composition.

[0434] 12. The chemical mechanical polishing (CMP) composition according to embodiment 1, wherein the concentration of a nonionic surfactant (D) comprising at least one polyoxyethylene group is in the range of ≥0.01% by weight to ≤10% by weight based on the total weight of the chemical mechanical polishing composition.

[0435] 13. A chemical mechanical polishing (CMP) composition according to any one of embodiments 1-12, wherein the compound having at least one amino group and at least one acidic group selected from carboxylic acids, phosphonic acids and sulfonic acids is selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta (methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid.

[0436] 14. A chemical mechanical polishing (CMP) composition according to any one of embodiments 1-13, wherein the concentration of the pad cleaner (E) is in the range of ≥0.001% by weight to ≤1% by weight based on the total weight of the chemical mechanical polishing composition.

[0437] 15. A chemical mechanical polishing (CMP) composition according to any one of embodiments 1-14, wherein the pH of the chemical mechanical polishing composition is in the range of 8-11.

[0438] 16. A chemical mechanical polishing (CMP) composition according to any one of embodiments 1-14, wherein the pH of the chemical mechanical polishing composition is in the range of 9.25-11.

[0439] 17. A chemical mechanical polishing (CMP) composition according to any one of embodiments 1-16, comprising:

[0440] (A) ≥0.01% by weight to ≤5% by weight of at least one inorganic abrasive particle;

[0441] (B) ≥0.001% by weight to ≤2.5% by weight of at least one chelating agent selected from carboxylic acids;

[0442] (C) ≥0.001% by weight to ≤1% by weight of at least one corrosion inhibitor selected from unsubstituted or substituted triazoles;

[0443] (D) ≥0.01% by weight to ≤1% by weight of at least one nonionic surfactant containing at least one polyoxyethylene group;

[0444] (E) ≥0.001% by weight to ≤1% by weight of at least one type of pad cleaner selected from compounds having at least one amino group and at least one acidic group selected from carboxylic acids, phosphonic acids and sulfonic acids;

[0445] (F) ≥0.001% by weight to ≤1% by weight of at least one carbonate or bicarbonate;

[0446] (G) ≥1% to ≤2% by weight of at least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromates; and

[0447] (H) Aqueous medium,

[0448] The weight percentages in each case are based on the total weight of the chemical mechanical polishing (CMP) composition.

[0449] 18. A chemical mechanical polishing (CMP) composition according to any one of embodiments 1-17, comprising: (A) at least one selected from metal oxides, metal nitrides, metal carbides, silicides, borosilicates, etc.

[0450] Inorganic abrasive particles, including materials, ceramics, diamond, organic mixed particles, inorganic mixed particles, and silica;

[0451] (B) At least one chelating agent selected from dicarboxylic acids and tricarboxylic acids;

[0452] (C) At least one corrosion inhibitor selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

[0453] (D) At least one nonionic surfactant containing a polyoxyalkylene group;

[0454] (E) At least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0455] (F) At least one carbonate or bicarbonate selected from alkali metal carbonates or alkali metal bicarbonates.

[0456] (G) At least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromate; and

[0457] (H) Aqueous medium.

[0458] 19. A chemical mechanical polishing (CMP) composition according to any one of embodiments 1-18, comprising:

[0459] (A) ≥0.01% by weight to ≤5% by weight of at least one inorganic abrasive particle selected from metal oxides, metal nitrides, metal carbides, silicides, borides, ceramics, diamond, organic mixed particles, inorganic mixed particles and silica;

[0460] (B) ≥0.001% by weight to ≤2.5% by weight of at least one chelating agent selected from dicarboxylic acids and tricarboxylic acids;

[0461] (C) ≥0.001% by weight to ≤1% by weight at least one corrosion inhibitor selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

[0462] (D) ≥0.01% by weight to ≤1% by weight of at least one nonionic surfactant containing at least one polyoxyethylene group;

[0463] (E) ≥0.001% by weight to ≤1% by weight of at least one pad cleaner selected from diethylenetriaminepentaacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, diethylenetriaminepenta(methylphosphonic acid), ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, hexamethylenediaminetetra(methylenephosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), di(hexamethylenetriaminepenta(methylenephosphonic acid)), aminosulfonic acid, 2-aminoethanesulfonic acid, 3-sulfo-L-alanine, 3-aminobenzenesulfonic acid and 4-aminobenzenesulfonic acid;

[0464] (F) ≥0.001% by weight to ≤1% by weight at least one carbonate or bicarbonate selected from alkali metal carbonates or alkali metal bicarbonates; and

[0465] (G) ≥1% to ≤2% by weight at least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromates, and

[0466] (H) Aqueous medium,

[0467] The weight percentages in each case are based on the total weight of the chemical mechanical polishing (CMP) composition.

[0468] 20. A method of manufacturing a semiconductor device, comprising chemically mechanically polishing a substrate in the presence of a chemical mechanical polishing (CMP) composition according to any one of embodiments 1-19.

[0469] 21. The method according to embodiment 20, wherein the substrate comprises at least one copper layer and / or at least one ruthenium layer.

[0470] 22. Use of the chemical mechanical polishing composition according to any one of embodiments 1-19 in a substrate used in the chemical mechanical polishing semiconductor industry.

[0471] 23. According to the use of embodiment 22, the substrate comprises:

[0472] (i) copper, and / or

[0473] (ii) Tantalum, tantalum nitride, titanium, titanium nitride, ruthenium or ruthenium alloys thereof.

[0474] Although the invention has been described with respect to specific embodiments thereof, certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the invention.

[0475] Examples and Comparative Examples

[0476] The present invention will be described in more detail below through the following working embodiments. More specifically, the test methods described below are part of the general disclosure of this application and are not limited to the specific working embodiments.

[0477] The general procedure for CMP testing is as follows.

[0478] Slurry composition:

[0479] A silica-based paste is used to polish copper and / or ruthenium-coated wafers. The paste composition comprises: (A) an inorganic abrasive: (trade name omitted) PL-3 was purchased from Fuso Chemical Corporation.

[0480] Silica particles;

[0481] (B) Chelating agent: Citric acid, purchased from Sigma-Aldrich

[0482] (C) Corrosion inhibitor: Benzotriazole (BTA), purchased from Sigma-Aldrich

[0483] (D) Nonionic surfactant, polyethylene-polypropylene ether ( DF 16), purchased from

[0484] (E) Pad cleaner, hexamethylenediaminetetra(methylenephosphonic acid) (HMDTMPA), purchased from Zschimmer & Schwarz.

[0485] (F) Carbonate, K2CO3, purchased from Sigma-Aldrich.

[0486] (G) Oxidant H2O2, purchased from [unclear] and

[0487] (H) Water.

[0488] Add oxidant (G) (1% H2O2) before using the slurry for chemical mechanical polishing (CMP) (1-15 min).

[0489] method

[0490] Procedure for preparing slurry compositions

[0491] The components of the slurry composition are thoroughly mixed, and all mixing procedures are carried out under stirring. Stock aqueous solutions of each compound (B), (C), (D), (E), (F), and (G) are prepared by dissolving the required amount of the corresponding compound in ultrapure water (UPW). For the stock solutions of each component, KOH is preferably used to support dissolution. The pH of the stock solution is adjusted to approximately pH 9 using KOH. The stock solution of (B) has a corresponding additive concentration of 10% by weight, and the stock solutions of (C), (D), and (E) have a corresponding additive concentration of 1.0% by weight. For (A), a dispersion supplied by the supplier is used, typically with an abrasive concentration of about 20-30% by weight. Oxidant (G) is used as a 30% by weight stock solution.

[0492] To prepare 10,000 g of slurry, the required amount of stock solution (F) is placed in a mixing tank or beaker, and the pH is adjusted by adding KOH while stirring at 350 rpm. Stock solutions (B), (C), (D), and (E) are added to achieve the desired concentration. The solution is maintained at the desired alkaline pH using KOH. Then (A) is added in the required amount. To adjust the final concentration, (H) is added as equilibrium water relative to the required amount of oxidant stock solution. The pH is adjusted to the desired value using KOH. The oxidant is added in the required amount (1% by weight) approximately 60 minutes before chemical mechanical polishing.

[0493] Inorganic particles (A) used in the examples

[0494] The average primary particle size (d1) was 35 nm and the average secondary particle size (d2) was 70 nm (measured using dynamic light scattering technique via a Horiba instrument), and the specific surface area was approximately 46 m². 2 / g of colloidal cocoon-shaped silica particles (Al) (e.g.) PL-3).

[0495] Particle shape characterization procedure

[0496] A cocoon-shaped silica particle aqueous dispersion with a solids content of 20 wt% was dispersed on 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 imaging (SEM-SE) (5 kV). EF-TEM images with a resolution of 2 k, 16 bits, and 0.6851 nm / pixel were used for this analysis. The images were thresholded binary encoded after noise reduction. The particles were then manually separated. Overlying and edge particles were distinguished and not used in this analysis. ECD, shape factor, and sphericity were calculated and statistically classified as defined above.

[0497] The A2 used has a specific surface area of ​​approximately 90 m². 2 / g of agglomerated particles with an average primary particle size (d1) of 35 nm and an average secondary particle size (d2) of 75 nm (measured using dynamic light scattering technique via a Horiba instrument) (e.g. PL-3H).

[0498] Standard CMP method for 200mm barrier polishing wafers:

[0499] Equipment: Mirra-mesa (Applied Materials)

[0500] Downforce: 1.5 psi for all substrates, 2 psi for Ru;

[0501] Polishing table / stand speed: 93 / 87 rpm;

[0502] Slurry flow rate: 200 ml / min;

[0503] Polishing time: Ru 60s, Cu 60s, TEOS 60s, TaN 60s, BD2 60s

[0504] Polishing pad: Fujibo H800 NW;

[0505] Adjustment tool: 3M A189L diamond abrasive disc for AMAT CMP machines, adjusted in place with a 5 lbf downward force.

[0506] The slurry is mixed at the local supply station.

[0507] Equipment: GnP (G&P Technology)

[0508] Downforce: 2 psi for wafer samples

[0509] Polishing table / stand speed: 93 / 87 rpm;

[0510] Slurry flow rate: 200 ml / min;

[0511] Polishing time: For primary polishing, Ru 60s, Cu 60s, TEOS 60s, TaN 60s, BD2 60s.

[0512] Polishing pad: Fujibo H800 NW

[0513] Adjustment tool: A189L

[0514] Adjustment type: In-situ oscillation 65 rpm, downward force 5 lbf for main polishing 60 s.

[0515] Standard analytical procedure for thin film thickness measurement:

[0516] Cu and Ru thin films: Resistage RG-120 / RT-80, 4-point probe instrument (NAPSON Corporation)

[0517] TEOS: Opti-Probe 2600 (Therma Wave, KLA-Tencor)

[0518] TaN: Resistage RG-120 / RT-80, 4-point probe instrument (NAPSON Corporation)

[0519] BD1: Opti-Probe 2600 (Therma Wave, KLA-Tencor)

[0520] Film thickness was measured using a 49-point scan (5 mm edge rejection) before and after CMP. The material removal rate (MRR) was obtained by averaging the thickness loss and dividing by the polishing time.

[0521] Ru-coated wafers: Resistage RG-120 / RT-80, 4-point probe instrument (NAPSON Corporation)

[0522] Cu-coated wafers: Resistage RG-120 / RT-80, 4-point probe instrument (NAPSON Corporation)

[0523] TaN: Resistage RG-120 / RT-80, 4-point probe instrument (NAPSON Corporation)

[0524] TEOS: Opti-Probe 2600 (Therma Wave, KLA-Tencor)

[0525] BD2: Opti-Probe 2600 (Therma Wave, KLA-Tencor)

[0526] BD1: Opti-Probe 2600 (Therma Wave, KLA-Tencor)

[0527] pH measurement

[0528] pH values ​​were measured using a pH combination electrode (Schott, blue line 22 pH electrode).

[0529] Pad smudge test on a 200mm Mirra Messa polishing machine

[0530] Chemical mechanical polishing (CMP) typically produces polishing residue, which is undesirable in CMP methods. Furthermore, residue adsorbed or accumulated on the polishing pad can introduce additional defects on the wafer, leading to unwanted additional defects. Therefore, residue adsorption on the pad surface should be prevented. To evaluate the effects of different slurry compositions and parameters, the following test procedure was developed and named the Pad Stain Test. The Pad Stain Test was conducted with and without copper (Cu) ions, producing different residues during polishing. The slurry was prepared as described above.

[0531] Pad smudging test using copper (Cu) ions

[0532] The pad contamination test using copper ions was conducted by adding 50 ppm CuSO4·5H2O to a slurry before polishing on a Fujibo H804 pad. The mixture was then applied to the pad while polishing a ruthenium (Ru) wafer until the coated ruthenium film was completely removed from the wafer surface. The pad was then removed from the polishing machine and allowed to dry completely. Images of the pad were captured and analyzed using imaging software. The test simulates the accumulation of ruthenium and copper residues on the pad. The Fujibo H804 pad was used in these tests for easier analysis of contamination (material accumulation) on the pad, as it is a white pad.

[0533] Pad smudge test without copper (Cu) ions

[0534] For pad contamination tests that do not use copper ions, the paste is applied to the pad while polishing the ruthenium wafer until the coated ruthenium film is completely removed from the wafer surface. The pad is then removed from the polishing machine and allowed to dry completely. Images of the pad are captured and analyzed using imaging software. Fresh pads are used for each test. The tests simulate the accumulation of ruthenium residue on the polishing pad.

[0535] Pad smudge test on a GnP polishing machine:

[0536] Pad smudging test using copper (Cu) ions

[0537] The pad fouling test using copper ions was conducted by adding 50 ppm CuSO4·5H2O to a slurry before polishing on a Fujibo H804 pad. The mixture was then applied to the pad while polishing ruthenium (Ru) samples measuring 30 mm × 30 mm, until the coated ruthenium film was completely removed from the sample surface (Ru samples were cut from 200 mm Ru wafers). After polishing, the pad was removed from the polisher and allowed to dry completely. Circular fouling was observed on the pads containing polished Ru samples. A small piece of the pad was cut and removed for further analysis using imaging software. The pad fouling test simulates the accumulation of Ru and Cu residues on the pad. The Fujibo H804 pad was used in these tests for easier analysis of the fouling (material accumulation) on the pad, as it is a white pad.

[0538] Pad smudge test without copper (Cu) ions

[0539] For the pad contamination test without copper ions, the slurry is applied to the pad while polishing the ruthenium sample until the ruthenium film is completely removed from the sample surface. The pad is then removed from the polishing machine and allowed to dry completely. Images of the pad are taken and analyzed using imaging software. Fresh pads are used for each test. The test simulates the accumulation of ruthenium residue on the polishing pad.

[0540] result

[0541] A quantitative pad fouling test was conducted to compare different slurry compositions.

[0542] After the pad smudge test, the polishing pads were removed from the polishing machine and dried at room temperature. Images of the pads were captured using a digital camera under defined lighting conditions (all pads were identical), and a defined area (500×500 pixels) was cropped using software for grayscale analysis. The software generated values ​​between 0 (black) and 255 (white). To quantitatively analyze the pad images, the average value of the analyzed pixel area was taken.

[0543] The software was used to analyze a new (unused) Fujibo H804 pad and found its grayscale value to be 156, which relates to pad cleanliness. Therefore, the highest obtainable value for pad fouling analysis is 156. To evaluate the pad fouling results, a pad fouling value closer to 156 indicates a cleaner pad surface (free of metal residue).

[0544] Correlation between 200mm Mirra Mesa and GnP polishing pad contamination results

[0545] To confirm the effectiveness of the GnP polisher and establish a correlation between the two polishing platforms, 200mm Mirra Mesa and GnP, a pair of formulations were selected from existing results produced on the 200mm polisher and pad smudge tests were also performed using the GnP polisher. Figure 1 The correlation results of polishing GnP ruthenium samples and 200 mm Mirra Mesa wafers with and without Cu ions are shown. Figure 1 As shown, a reasonable correlation exists between the polishing of GnP ruthenium samples and the polishing of 200mm wafers. It can be concluded that the resulting pad contamination is independent of the size of the ruthenium wafer / sample.

[0546]

[0547]

[0548] Results Discussion

[0549] Tables 1 and 2 show the Material Removal Rate (MRR) for different substrates and pad contamination with and without copper ions. The addition of hexamethylenediaminetetra(methylenephosphonic acid) prevented the adsorption of ruthenium, copper, and ruthenium residues within the provided pH range compared to slurries without these additives. Tables 1 and 2 also illustrate the effects of pad cleaners such as hexamethylenediaminetetra(methylenephosphonic acid) in conjunction with BTA to produce the cleanest pad surface.

[0550] Tables 1 and 2 show the most significant effect of pH on material removal rate. Higher pH values ​​result in cleaner pads (higher ash values). Higher pH values ​​prevent the adsorption of metal residues on the pad surface.

[0551] Regarding the selectivity of ruthenium to copper, the high material removal rate of ruthenium at low abrasive (A) concentrations, the low material removal rate of low-k materials, the low etching behavior, and the high dispersion stability, the CMP compositions of the present invention exhibit improved performance. Pad cleaners such as hexamethylenediaminetetra(methylenephosphonic acid) adsorb onto Cu / Ru residues and make the residues more hydrophilic, which makes it easier to remove the residues from the polishing environment.

Claims

1. A chemical mechanical polishing (CMP) composition comprising: (A) At least one inorganic abrasive particle; (B) At least one chelating agent selected from carboxylic acids, wherein the carboxylic acid is selected from dicarboxylic acids and tricarboxylic acids; (C) At least one corrosion inhibitor selected from unsubstituted or substituted triazoles; (D) At least one nonionic surfactant containing at least one polyoxyalkylene group; (E) At least one pad cleaner, wherein the at least one pad cleaner is hexamethylenediaminetetra(methylenephosphonic acid); (F) At least one carbonate or bicarbonate; (G) At least one oxidizing agent selected from organic peroxides, inorganic peroxides, persulfates, iodates, periodic acid, periodate, permanganate, perchloric acid, perchlorate, bromic acid, and bromate; and (H) Aqueous medium, The concentration of the pad cleaner (E) is in the range of ≥0.001% by weight to ≤0.5% by weight based on the total weight of the chemical mechanical polishing composition; Furthermore, the pH of the chemical mechanical polishing composition is in the range of ≥9 to ≤9.

7.

2. The chemical mechanical polishing (CMP) composition according to claim 1, wherein the at least one inorganic abrasive particle (A) is selected from metal oxides, metal nitrides, metal carbides, silicides, borides, ceramics, diamond, organic mixed particles, inorganic mixed particles, and silicon dioxide.

3. The chemical mechanical polishing (CMP) composition according to claim 1, wherein the concentration of the at least one inorganic abrasive particle (A) is in the range of ≥0.01% by weight to ≤10% by weight based on the total weight of the chemical mechanical polishing composition.

4. The chemical mechanical polishing (CMP) composition according to claim 1, wherein the concentration of the at least one chelating agent (B) is in the range of ≥0.001% by weight to ≤2.5% by weight based on the total weight of the chemical mechanical polishing composition.

5. The chemical mechanical polishing (CMP) composition according to claim 2, wherein the concentration of the at least one chelating agent (B) is in the range of ≥0.001% by weight to ≤2.5% by weight based on the total weight of the chemical mechanical polishing composition.

6. The chemical mechanical polishing (CMP) composition according to claim 3, wherein the concentration of the at least one chelating agent (B) is in the range of ≥0.001% by weight to ≤2.5% by weight based on the total weight of the chemical mechanical polishing composition.

7. The chemical mechanical polishing (CMP) composition according to claim 1, wherein the triazole is selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

8. The chemical mechanical polishing (CMP) composition according to claim 2, wherein the triazole is selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

9. The chemical mechanical polishing (CMP) composition according to claim 3, wherein the triazole is selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

10. The chemical mechanical polishing (CMP) composition of claim 4, wherein the triazole is selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

11. The chemical mechanical polishing (CMP) composition of claim 5, wherein the triazole is selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

12. The chemical mechanical polishing (CMP) composition of claim 6, wherein the triazole is selected from unsubstituted benzotriazoles, substituted benzotriazoles, unsubstituted 1,2,3-triazoles, substituted 1,2,3-triazoles, unsubstituted 1,2,4-triazoles and substituted 1,2,4-triazoles.

13. The chemical mechanical polishing (CMP) composition according to any one of claims 1-12, wherein the concentration of the at least one corrosion inhibitor (C) is in the range of ≥0.001% by weight to ≤1% by weight based on the total weight of the chemical mechanical polishing composition.

14. The chemical mechanical polishing (CMP) composition of claim 1, wherein the concentration of the nonionic surfactant (D) comprising at least one polyoxyethylene group is in the range of ≥0.01% by weight to ≤10% by weight based on the total weight of the chemical mechanical polishing composition.

15. The chemical mechanical polishing (CMP) composition according to any one of claims 1-12, wherein the concentration of the pad cleaner (E) is in the range of ≥0.001% by weight to ≤0.1% by weight based on the total weight of the chemical mechanical polishing composition.

16. The chemical mechanical polishing (CMP) composition of claim 13, wherein the concentration of the pad cleaner (E) is in the range of ≥0.001% by weight to ≤0.1% by weight based on the total weight of the chemical mechanical polishing composition.

17. The chemical mechanical polishing (CMP) composition of claim 14, wherein the concentration of the pad cleaner (E) is in the range of ≥0.001% by weight to ≤0.1% by weight based on the total weight of the chemical mechanical polishing composition.

18. A method of manufacturing a semiconductor device, comprising chemically mechanically polishing a substrate in the presence of a chemical mechanical polishing (CMP) composition according to any one of claims 1-17.

19. The method of claim 18, wherein the substrate comprises at least one copper layer and / or at least one ruthenium layer.

20. Use of the chemical mechanical polishing composition according to any one of claims 1-17 in a substrate used in the chemical mechanical polishing semiconductor industry.

21. The use of claim 20, wherein the substrate comprises: (i) copper, and / or (ii) Tantalum, tantalum nitride, titanium, titanium nitride, ruthenium or ruthenium alloys thereof.

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