Diamond-based polishing composition with improved silicon carbide removal rate

Abstract

There is provided a polishing composition for polishing a surface of a semiconductor wafer, comprising: a surface-modified single crystal diamond having a D (50) particle size range of from about 0.10 m to about 1 m; a carrier selected from the group consisting of an aqueous carrier, a glycol-based carrier, an oil-based carrier, and a hydrocarbon-based carrier; and optionally more than one additive. Related methods of polishing a surface of a semiconductor wafer are also described.

Description

Technical Field

[0001] This disclosure relates to diamond-based slurry compositions for polishing semiconductor wafer surfaces and related methods for polishing semiconductor wafer surfaces. Background Technology

[0002] Semiconductor wafers with the ability to operate more efficiently to achieve significant reductions in power consumption are highly desirable. One industry sector studied involves polishing the surfaces of semiconductor wafers in the electronics industry using a process known as chemical mechanical polishing (CMP), in which the slurry is both mechanically and chemically active to remove interfering deposited materials and particles from the semiconductor wafer surface.

[0003] In summary, the core idea of ​​semiconductor manufacturing processes is to polish the surface of semiconductor wafers to provide an attractive, smooth surface and obtain precise dimensions of the semiconductor wafer surface.

[0004] As the final step in the manufacturing process of semiconductor wafers, CMP (Chemical Motion Processing) is involved. This step provides a semiconductor wafer surface that is essentially free of surface defects acquired from previous grinding cycles, and also produces a semiconductor wafer surface ready for use by the end user. However, an inherent problem that cannot be ignored is that the pastes primarily used in this process are, first and foremost, expensive and environmentally harmful, and adversely result in low material removal rates. Furthermore, another drawback is that the CMP process takes several hours to complete, thus consuming large quantities of expensive and environmentally harmful pastes.

[0005] Current common practice in semiconductor wafer manufacturing typically includes a CMP (Continuous Polishing) step after a fine grinding step or during a final polishing step. At the end of these two steps, the surface roughness of the semiconductor wafer is typically in the range of approximately 1.5 nm to approximately 3 nm. A CMP process is then employed to reduce the surface roughness to approximately 0.5 nm, or in some cases even lower. Simply put, polishing processes using currently available CMP slurries specifically formulated for semiconductor wafers can take several hours to complete, which is disadvantageous. Given the high cost of CMP slurries and the view that the accompanying harsh chemicals can affect the removal rate and surface quality of semiconductor wafers, these characteristics naturally impose strict limitations on their use. Therefore, the electronics industry seeks optimized polishing solutions and processes. With this in mind, the electronics industry is constantly seeking adaptable polishing processes and compositions that allow end users to completely eliminate the CMP step or significantly reduce the typically required time and CMP slurry consumption. This ultimately leads to lower process costs, optimized shorter cycle times, and increased throughput.

[0006] In view of the above, there is a need for polishing compositions and processes that can achieve high material removal rates from the surface of semiconductor wafers while reducing the surface roughness of semiconductor wafers to CMP quality. These polishing compositions and processes are neither cumbersome, time-consuming, nor expensive, and are free of irritating chemicals to optimize the polishing cycle of semiconductor wafer surfaces. Summary of the Invention

[0007] A polishing composition for polishing the surface of a semiconductor wafer is provided, comprising: surface-modified single-crystal diamond having a D(50) particle size ranging from about 0.10 µm to about 1 µm; a carrier selected from the group consisting of aqueous carriers, glycol carriers, oil carriers and hydrocarbon carriers; and optionally one or more additives.

[0008] Optionally, the surface-modified single-crystal diamond has a D(50) particle size range of about 0.25 µm to about 0.50 µm.

[0009] Optionally, the surface-modified single-crystal diamond has a D(50) particle size ranging from about 0.25 µm to about 0.75 µm.

[0010] Optionally, the surface-modified single-crystal diamond has a D(50) particle size range of about 0.50 µm to about 0.75 µm.

[0011] Optionally, the surface-modified single-crystal diamond has a D(50) particle size range of about 0.75 µm to about 1 µm.

[0012] Optionally, the one or more additives are selected from the group consisting of dispersants, pH adjusters, pH buffers, surfactants, polymers, complexing agents, rheology modifiers, chelating agents, defoamers, wetting agents, oxidants, and biocides.

[0013] Optionally, the material removal rate of silicon carbide (SiC) ranges from about 1.3 µm / hour to about 8.2 µm / hour.

[0014] Optionally, the material removal rate of the SiC ranges from about 1.3 µm / hour to about 7.2 µm / hour.

[0015] Optionally, the material removal rate of the SiC ranges from about 1.3 µm / hour to about 3.3 µm / hour.

[0016] Optionally, the material removal rate of the SiC ranges from about 3.3 µm / hour to about 7.2 µm / hour.

[0017] Optionally, the material removal rate of the SiC ranges from about 3.3 µm / hour to about 8.2 µm / hour.

[0018] Optionally, the material removal rate of the SiC ranges from about 7.2 µm / hour to about 8.2 µm / hour.

[0019] Optionally, the SiC improves the material removal rate by about 185% to about 245% compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles.

[0020] Optionally, when the D(50) particle size range of the surface-modified single-crystal diamond is from about 0.25 µm to about 1 µm, the surface roughness of the SiC wafer is substantially similar to or lower than that of a SiC wafer polished with a polishing composition containing single-crystal diamond particles or polycrystalline diamond particles.

[0021] Optionally, the surface-modified single-crystal diamond is present at a weight of about 0.5% by weight (wt.%) to about 5% by weight, based on the total weight of the polishing composition.

[0022] Optionally, the surface-modified single-crystal diamond is present at a weight of about 0.5% to about 2.5% based on the total weight of the polishing composition.

[0023] Optionally, the carrier is present in a volume of about 10% to about 70% based on the total volume of the polishing composition.

[0024] Optionally, the SiC is single-crystal silicon carbide.

[0025] Optionally, the surface-modified single-crystal diamond comprises one or more spikes and one or more pits.

[0026] Optionally, the semiconductor wafer polishing composition is free of potassium permanganate.

[0027] A method for polishing the surface of a semiconductor wafer is also provided, comprising bringing the surface of the semiconductor wafer into contact with a polishing pad on which the polishing composition is applied. Next, the polishing pad on which the polishing composition is applied is moved relative to the semiconductor wafer. Finally, at least a portion of the semiconductor wafer is abraded, thereby polishing the semiconductor wafer.

[0028] Other systems, methods, features, and advantages will or will become apparent to those skilled in the art upon viewing the following figures and detailed description. It is intended that all such additional systems, methods, features, and advantages are encompassed within this specification, within the scope of this disclosure, and protected by the following claims. Nothing in this section should be construed as limiting these claims. Further aspects and advantages are discussed below in conjunction with embodiments of this disclosure. It should be understood that the foregoing general description and the following detailed description of this disclosure are exemplary and illustrative, intended to provide further explanation of the claimed disclosure. Attached Figure Description

[0029] The accompanying drawings, which are included to provide a further understanding of the subject matter and are incorporated in and constitute a part of this specification, illustrate how the subject matter is implemented and, together with the specification, serve to explain the principles of this disclosure.

[0030] Figure 1A An exemplary microstructure of a surface-modified single-crystal diamond crystal is shown according to an exemplary embodiment of this subject matter.

[0031] Figure 1B An exemplary microstructure of a single-crystal diamond crystal according to an exemplary embodiment of this subject matter is shown.

[0032] Figure 2 A flowchart of the various process steps for polishing the surface of a semiconductor wafer according to an exemplary embodiment of this subject matter is shown.

[0033] Figure 3 The following figures illustrate the removal rate of silicon carbide material from the silicon carbide wafer (vertical bars) observed on the left y-axis and the surface roughness (black solid dots) observed on the right y-axis when using (I) a polishing composition employing surface-modified single-crystal diamond (Smmd) with a D(50) particle size range of about 0.25 µm to about 1 µm, (II) a polishing composition employing single-crystal diamond with a D(50) particle size range of about 0.25 µm to about 1 µm, or (III) a polishing composition employing polycrystalline diamond with a D(50) particle size range of about 0.25 µm to about 1 µm, according to an exemplary embodiment of this subject matter. Detailed Implementation

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter described herein belongs.

[0035] Where a range of values ​​is provided, such as a concentration range, percentage range, or ratio range, it should be understood that, unless the context explicitly specifies otherwise, every intermediate value between the upper and lower limits of the range (to one-tenth of the unit of the lower limit), as well as any other values ​​or intermediate values ​​within that range, is encompassed within the described subject matter. The upper and lower limits of these smaller ranges may be independently included within the smaller ranges, and such implementations are also encompassed within the described subject matter (subject to any specific exclusions within the stated ranges). Where a stated range includes one or both of the included limitations, ranges excluding one or both of those included limitations are also included within the subject matter.

[0036] The following definitions describe the parameters of the topic.

[0037] As used in this disclosure, the term "diamond particle" refers to one or more discrete bodies made of diamond. As used in this disclosure, the term "diamond particle" is also considered to be a diamond crystal or diamond grain.

[0038] As used in this disclosure, the terms “weight%” and “volume%” refer to the percentage by weight and the percentage by volume, respectively, based on the total weight or total volume of the polishing composition used to polish the surface of a semiconductor wafer.

[0039] As used in this disclosure, the term "diamond abrasive" refers to a diamond material used to grind away materials that are softer than the diamond abrasive itself.

[0040] As used in this disclosure, the term "material removal" refers to the weight (reported in milligrams, grams, etc.) of workpiece removed within a given time period.

[0041] As used in this disclosure, the term "material removal rate" refers to the amount of material removed divided by a time interval, and is reported, for example, as the amount of material removed from the surface of a semiconductor wafer (in micrometers per hour, milligrams per minute, or grams per hour).

[0042] As used herein, the term "single-crystal diamond" refers to diamond having a monolithically flat surface structure formed through a high-pressure, high-temperature (HPHT) consolidation operation, or to naturally occurring diamond. Fracture in single-crystal diamond occurs along atomic cleavage planes. Single-crystal diamond particles fracture relatively easily at cleavage planes.

[0043] As used in this disclosure, the term "polycrystalline diamond" refers to diamond formed through explosive synthesis, resulting in a polycrystalline particle structure. Each polycrystalline diamond particle may contain a large number of microcrystals smaller than about 100 angstroms. Polycrystalline diamond particles have no cleavage planes.

[0044] As used herein, the term "superhard abrasive" or simply "superhard abrasive material" refers to abrasive materials exhibiting superior hardness and wear resistance (typically exhibiting Knoop indentation hardness exceeding 2000), as listed below, but not limited to crystalline diamond, polycrystalline diamond (PCD), thermally stable polycrystalline diamond, chemical vapor deposition (CVD) diamond, metal-matrix diamond composites, ceramic-matrix diamond composites, nanodiamond, cubic boron nitride (cBN), polycrystalline cubic boron nitride (PcBN), or any combination thereof. As used herein, the term "abrasive" refers to any material used to grind away softer materials.

[0045] As used in this disclosure, the term "workpiece" means a part or object from which material has been removed by polishing, grinding or other material removal methods.

[0046] As used herein, the term "surface-modified single-crystal diamond" refers to diamond made from unique, chemically synthesized, or synthetic diamond crystals that typically offer improved performance in terms of material removal rate from semiconductor wafer surfaces compared to, for example, single-crystal or polycrystalline diamonds, when polished. The unique irregular surface characteristics of the surface-modified single-crystal diamonds disclosed herein advantageously result in significantly improved material removal rates from semiconductor wafer surfaces. Due to their inherently distinctive multifaceted diamond surfaces, they also offer the added benefit of superior surface finish imparted to semiconductor wafer surfaces. This distinctive irregular surface provides multiple small spikes and pits to reduce the surface roughness of polished semiconductor wafers.

[0047] As used in this disclosure, the term "multifaceted" refers to multiple edges located around a plane.

[0048] As used herein, the term "surface roughness" refers to a measurement of a two-dimensional image that quantifies the extent or degree of pits and protrusions on the surface, edges, and boundaries of an object, as described in the CLEMEX Image Analyzer, CLEMEXVision User Guide PE 3.5, 2001. Surface roughness is determined by the ratio of the convex perimeter to the circumference.

[0049] Surface roughness = convex perimeter / perimeter.

[0050] As the degree of pits and protrusions increases, the surface roughness coefficient decreases.

[0051] As used in this disclosure, the term "sphericity" refers to the enclosed area (4πA) of a two-dimensional image or object divided by the square of its perimeter (p). 2 The estimated value of ).

[0052] Sphericity = 4πA / p 2 .

[0053] Surface roughness is an important factor to consider when evaluating the electrical performance of semiconductor wafers. The electron mobility in a semiconductor wafer is partly influenced by the thickness of the wafer surface and the size and shape of its edges. Polishing the semiconductor wafer surface advantageously transforms otherwise dull and rough surfaces into substantially flat and smooth surfaces with mirror-like properties, and is essentially free of particles that negatively impact the overall electronic operation of the semiconductor wafer.

[0054] As used in this disclosure, the term “perimeter” refers to the boundary of a closed planar figure, or the sum of all the boundaries of a two-dimensional image.

[0055] As used in this disclosure, the term "convex perimeter" refers to the line connecting the Feret tangent points, where Feret is the distance between two parallel tangents on each side of the boundary of a two-dimensional image or object.

[0056] As used in this disclosure, the term "dent" refers to a dent or crack in a particle, i.e., a dent or crack in a two-dimensional image, or a dent or crack in an object.

[0057] As used in this disclosure, the term "sharp protrusion" refers to a sharp protrusion or bulge pointing outward from the centroid of a particle, that is, a sharp protrusion or bulge pointing outward from the centroid of a two-dimensional image, or a sharp protrusion or bulge pointing outward from an object.

[0058] As used herein, the term "surface area" refers to the outer surface area of ​​a particle. When used with multiple particles (i.e., powder), the term specific surface area is used and reported as the surface area per gram of powder.

[0059] As used herein, the term “about” is intended to mean a numerical value plus or minus 5%, and thus it is used in the claims and in this disclosure. Therefore, “about” can be used to provide flexibility for the endpoints of a numerical range, where a given value can be “above” or “below” a given value. Thus, for example, a value of 50% can be intended to cover a range that can be defined by, for example, the following ranges: 47.5%-52.25%, 47.5%-52.5%, 47.75%-50%, 50%-52.5%, 48%-48.5%, 48%-48.75%, 48%-49%, 48%-49.5%, 48%-49.75%, 48%-50%, 48%-50.25%, 48%-50.5%, 48%-50.75%, 48%-51%, 48%-51.5%, 48%-51.5%, 48%-50.25%, 48%-50.5%, 48%-50.75%, 48%-51 ...%-50%-50%-50%-50%-50%-50%-50%-50%-50%-50%-50%-50%-50%-50%-50%-50%-50%-51%, 48%-50%-50%-50%-50%-50%-50%-50%-50%-50%-50%-50%-50%-50% %-51.75%, 48%-52%, 48%-52.25%, 48%-52.5%, 48.25%-48.5%, 48.25%-48.75%, 48.25%-49%, 48.25%-49.5%, 48.25%-49.75%, 48.25%-50%, 48.25%-50.25%, 48.25%-50.5%, 48.25%-50.75%, 48.25%-51%, 48.25%-51.35%, 48.25%-5 1.5%, 48.25%-51.75%, 48.25%-52%, 48.25%-52.25%, 48.25%-52.5%, 48.5%-48.75%, 48.5%-49%, 48.5%-49.5%, 48.5%-49.75%, 48.5%-50%, 48.5%-50.25%, 48.5%-50.5%, 48.5%-50.75%, 48.5%-51%, 48.5%-51.35%, 48.5%-51.5%. 48.5%-51.75%, 48.5%-52%, 48.5%-52.25%, 48.5%-52.5%, 49%-49.25%, 49%-49.5%, 49%-49.75%, 49%-50%, 49%-50.25%, 49%-50.5%, 49%-50.75%, 49%-51%, 49%-51.35%, 49%-51.5%, 49%-51.75%, 49%-52%, 49%-52.25%, 49%-52.5% 49.5%-49.75%, 49.5%-50%, 49.5%-50.25%, 49.5%-50.5%, 49.5%-50.75%, 49.5%-51%, 49.5%-51.5%, 49.5%-51.75%, 49.5%-52%, 49.5%-52.25%, 49.5%-52.5%, 49.75%-50%, 49.75%-50%.25%, 49.75%-50.5%, 49.75%-50.75%, 49.75%-51%, 49.75%-51.35%, 49.75%-51.5%, 49.75%-51.75%, 49.75%-52%, 49.75%-52.25%, 49.75%-52.5%, 50%-50.25%, 50%-50.5%, 50%-50.75%, 50%-51%, 50%-51.35%, 50%-51.5%, 50%-52%, 50%-52.25%, 50%-52.5%.

[0060] As used in this disclosure, the term “D(50)” means a particle size in which 50% of the volume of the sampled particles is less than the stated D(50) value and 50% of the volume of the sampled particles is greater than the stated D(50) value.

[0061] As used in this disclosure, the term “D(99)” means a particle size in which 99% of the volume of the sampled particles is less than the stated D(99) value and 1% of the volume of the sampled particles is greater than the stated D(99) value.

[0062] Throughout the publication, wherever it is used, the term “general” means “usually”, “near”, or “in the vicinity or range of”.

[0063] As used in this disclosure, the term "substantially" means the complete or near-complete extent or degree of an action, feature, characteristic, state, structure, item, or result. It is intended to encompass a numerical value of plus or minus 6.25%, and is thus used in the claims and other parts of this disclosure.

[0064] As used herein, the term "surfactant" refers to a compound that reduces surface tension, for example, between two liquids, between a gas and a liquid, or between a liquid and a solid. Those skilled in the art will appreciate that surfactants typically include, but are not limited to, chemical components belonging to, for example, the following categories: detergents, wetting agents, emulsifiers, foaming agents, and dispersants.

[0065] As used in this disclosure, the term "surface tension" refers to the tendency of a liquid surface to contract to the smallest possible surface area when at rest.

[0066] As used in this disclosure, the term "amphoteric" refers to a compound that can react as both a base and an acid.

[0067] As used in this disclosure, the term "rheology modifier" refers to a compound added to polishing compositions that form diamond slurries to increase their viscosity and control the flow properties of the diamond slurries.

[0068] As used in this disclosure, “physical vapor deposition (PVD)” refers to various vacuum deposition methods that can be used to fabricate thin films and coatings. PVD is characterized by processes in which the deposited material is transformed from a condensed phase to a gaseous phase and then back to the condensed phase of the thin film. The most common PVD processes are sputtering and evaporation.

[0069] As used herein, “chemical vapor deposition (CVD)” refers to a method in which a substrate is exposed to one or more volatile precursors that react and / or decompose on the substrate surface to produce the desired deposit. Often, volatile byproducts are also generated, which are removed by an airflow passing through the reaction chamber.

[0070] Diamond-based polishing compositions for polishing the surface of semiconductor wafers

[0071] This disclosure is based on the premise of providing a polishing composition comprising surface-modified single-crystal diamond for polishing the surface of virtually any semiconductor wafer. Key features of the polishing composition of this subject matter include an advantageously high material removal rate from the semiconductor wafer surface, and the additional benefit of reducing the surface roughness of the semiconductor wafer to a level equivalent to chemical mechanical polishing (CMP) quality in a shorter time. Furthermore, the semiconductor polishing composition is inexpensive to manufacture, and advantageously, it is free of any irritating chemicals, thus optimizing the overall post-forming polishing cycle of the semiconductor wafer.

[0072] The polishing composition typically comprises surface-modified single-crystal diamond with a D(50) particle size ranging from about 0.10 µm to about 1 µm. In some examples, the polishing composition comprises surface-modified single-crystal diamond with a D(50) particle size ranging from about 0.25 µm to about 1 µm. In other examples, the polishing composition comprises surface-modified single-crystal diamond with a D(50) particle size ranging from about 0.35 µm to about 1 µm. In still other examples, the polishing composition comprises surface-modified single-crystal diamond with a D(50) particle size ranging from about 0.45 µm to about 1 µm. In yet still other examples, the polishing composition comprises surface-modified single-crystal diamond with a D(50) particle size ranging from about 0.55 µm to about 1 µm. In even more other examples, the polishing composition comprises surface-modified single-crystal diamond with a D(50) particle size ranging from about 0.65 µm to about 1 µm. In other examples, the polishing composition comprises surface-modified single-crystal diamond with a D(50) particle size ranging from about 0.75 µm to about 1 µm. In even further examples, the polishing composition comprises surface-modified single-crystal diamond with a D(50) particle size ranging from about 0.85 µm to about 1 µm. In even further still examples, the polishing composition comprises surface-modified single-crystal diamond with a D(50) particle size ranging from about 0.95 µm to about 1 µm.

[0073] The polishing composition may further comprise surface-modified single-crystal diamond having the following D(50) particle sizes: ranging from 0.10 µm to about 0.25 µm, ranging from about 0.25 µm to about 0.35 µm, ranging from about 0.10 µm to about 0.35 µm, ranging from about 0.35 µm to about 0.45 µm, ranging from about 0.45 µm to about 0.55 µm, ranging from about 0.25 µm to about 0.45 µm, ranging from about 0.25 µm to about 0.55 µm, ranging from about 0.35 µm to about 0.55 µm, ranging from about 0.55 µm to about 0.65 µm, ranging from about 0.65 µm to about 0.75 µm, ranging from about 0.75 µm to about 0.85 µm, ranging from about 0.25 µm to about 0.85 µm, and ranging from about 0.30 µm to about 0.85 µm. µm, ranging from about 0.35 µm to about 0.85 µm, ranging from about 0.40 µm to about 0.85 µm, ranging from about 0.45 µm to about 0.85 µm, ranging from about 0.50 µm to about 0.85 µm, ranging from about 0.55 µm to about 0.85 µm, ranging from about 0.60 µm to about 0.85 µm, ranging from about 0.65 µm to about 0.85 µm, ranging from about 0.70 µm to about 0.85 µm, ranging from about 0.80 µm to about 0.85 µm, ranging from about 0.25 µm to about 0.90 µm, ranging from about 0.30 µm to about 0.90 µm, ranging from about 0.35 µm to about 0.90 µm, ranging from about 0.40 µm to about 0.90 µm, ranging from about 0.45 µm to about 0.90 µm. µm, ranging from about 0.50 µm to about 0.90 µm, ranging from about 0.55 µm to about 0.90 µm, ranging from about 0.60 µm to about 0.90 µm, ranging from about 0.65 µm to about 0.90 µm, ranging from about 0.70 µm to about 0.90 µm, ranging from about 0.75 µm to about 0.90 µm, ranging from about 0.80 µm to about 0.90 µm, ranging from about 0.85 µm to about 0.90 µm, ranging from about 0.25 µm to about 0.95 µm, ranging from about 0.30 µm to about 0.95 µm, ranging from about 0.35 µm to about 0.95 µm, ranging from about 0.40 µm to about 0.95 µm, ranging from about 0.45 µm to about 0.95 µm, ranging from about 0.50 µm to about 0.95 µm. µm, ranging from about 0.55 µm to about 0.95 µm, ranging from about 0.60 µm to about 0.95 µm, ranging from about 0.65 µm to about 0.95 µm, ranging from about 0.70 µm to about 0.95 µm, and ranging from about 0.75 µm to about 0.95 µm, ranging from about 0.80 µm to about 0.95 µm, ranging from about 0.85 µm to about 0.95 µm, or ranging from about 0.90 µm to about 0.95 µm.

[0074] To determine a specific diamond grain size, those skilled in the art can typically employ dynamic digital image analysis (DIA), static laser scattering (SLS) (also known as laser diffraction), or visual measurement via electron microscopy (a technique known as image analysis and light masking). Each method covers a range of characteristic sizes within which measurements can be taken. These ranges partially overlap. However, the results of measuring the same sample can vary entirely depending on the specific method used. Those skilled in the art who wish to determine the grain size distribution will readily understand how each of the mentioned methods is typically performed and practiced. Therefore, readers may refer to, for example: (i) “Comparison of Methods. Dynamic Digital Image Analysis, Laser Diffraction, Sieve Analysis”, Retsch Technology, and (ii) Kelly et al.’s scientific publication, “Graphical comparison of image analysis and laser diffraction particle size analysis data obtained from the measurements of particle systems”, AAPS PharmSciTech. 2006 Aug 18;Vol.7(3):69, for further understanding of each procedure and method, all of which are incorporated herein by reference in their entirety.

[0075] The polishing composition may typically contain the surface-modified single-crystal diamond, which is present at a weight of about 0.5 wt.% to about 5 wt% based on the total weight of the polishing composition. In some examples, the surface-modified single-crystal diamond is present at a weight of about 1 wt% to about 5 wt% based on the total weight of the polishing composition. In other examples, the surface-modified single-crystal diamond is present at a weight of about 1.5 wt% to about 5 wt% based on the total weight of the polishing composition. In still other examples, the surface-modified single-crystal diamond is present at a weight of about 2 wt% to about 5 wt% based on the total weight of the polishing composition. In still other examples, the surface-modified single-crystal diamond is present at a weight of about 2.5 wt% to about 5 wt% based on the total weight of the polishing composition. In still other examples, the surface-modified single-crystal diamond is present at a weight of about 3 wt% to about 5 wt% based on the total weight of the polishing composition. In even other examples, the surface-modified single-crystal diamond is present at a weight of about 3.5 wt% to about 5 wt% based on the total weight of the polishing composition. In even further examples, the surface-modified single-crystal diamond is present at a weight of about 4 wt% to about 5 wt% based on the total weight of the polishing composition. In even other embodiments, the surface-modified single-crystal diamond is present at a weight of about 4.5 wt% to about 5 wt% based on the total weight of the polishing composition.

[0076] The polishing composition may further comprise the surface-modified single-crystal diamond in the following weights based on the total weight of the polishing composition: about 0.5 wt% to about 1 wt%, about 1 wt% to about 1.5 wt%, about 1.5 wt% to about 2 wt%, about 0.5 wt% to about 1.5 wt%, about 0.5 wt% to about 2 wt%, about 1 wt% to about 2 wt%, about 1 wt% to about 2.5 wt%, about 1.5 wt% to about 2.5 wt%, about 1 wt% to about 3 wt%, about 1.5 wt% to about 3 wt%, about 2 wt% to about 2.5 wt%, about 2.5 wt% to about 3 wt%, about 3 wt% to about 3.5 wt%, about 2 wt% to about 3 wt%, about 2 wt% to about 3.5 wt%, about 2 wt% to about 4 wt%, about 3 wt% to about 4 wt%, about 3.5 wt% to about 4 wt%, or about 3.5 wt% to about 4.5 wt%.

[0077] The surface-modified single-crystal diamond disclosed herein comprises unique, artificial, or synthetic diamond crystals that typically offer improved performance compared to, for example, conventional single-crystal or polycrystalline diamond. The unique irregular surface characteristics of the surface-modified single-crystal diamond disclosed herein advantageously result in a significant material removal rate from semiconductor wafers. Furthermore, due to its inherently distinctive faceted diamond surface, it also provides the additional benefit of excellent surface finish imparted to the semiconductor wafer surface. This distinctive irregular surface provides small cutting points to reduce the overall surface roughness of the semiconductor wafer.

[0078] Now, let's turn the reader's attention to the accompanying diagram, which... Figure 1A It can be best observed in the middle, Figure 1A An exemplary microstructure of the chemically surface-modified single-crystal diamond 10 disclosed herein is depicted. Figure 1A The number 12 is used to highlight unique, specially designed small protrusions to facilitate optimized material removal. This is similar to... Figure 1B This contrasts sharply with, for example, a conventional single-crystal diamond crystal 14 having a substantially entirely flat structural surface 16. Therefore, at least due to the complete lack of faceted surface features on the surface 16 of the single-crystal diamond crystal 14, it differs from the diamond crystals disclosed herein. Figure 1A Compared to the surface-modified single-crystal diamond crystal 10 shown, the material removal rate when using single-crystal diamond crystal 14 will also be simultaneously limited and severely hindered. For example... Figure 1A As further shown, the surface-modified single-crystal diamond particles 10 essentially exhibit the characteristics of... Figure 1BThe spikes 12 and pits 11 shown are significantly lacking in conventional single-crystal diamond 14. The essential function of the spikes 12 is, in particular, to act as cutting edges when used in free abrasive slurry applications. It has been found that the performance of the surface-modified single-crystal diamond particles 10 is significantly improved when used in free abrasive polishing applications in liquid slurries or suspensions. When the surface-modified single-crystal diamond particles 10 are used in a fixed-bonding system, the pits 11 and spikes 12 help to fix the particles within the bonding system. The length of the spikes 12 and the depth of the pits 11 vary depending on the modification treatment parameters. The average depth of the pits 11 on the diamond particles 10 typically ranges from about 5% to about 70% of the longest length of the surface-modified single-crystal diamond particles 10. The surface-modified single-crystal diamond particles 10 also exhibit unique properties in terms of surface roughness, sphericity, and material removal. The surface-modified single-crystal diamond particles 10 exhibit a surface roughness of less than about 0.95. Surface roughness values ​​of approximately 0.50 to approximately 0.80 and approximately 0.50 to approximately 0.70 were also observed. The surface roughness of the surface-modified single-crystal diamond particles 10 is a function of the size of the metal particles used in the process, the amount of metal particles in contact with the diamond 10, the reaction time, and the temperature. As the surface roughness increases, the ability of the diamond particles 10 to remove material during the polishing process also increases. This may be attributed to the increased number of cutting points imparted to the diamond particles 10 by the surface modification process. Furthermore, the surface-modified single-crystal diamond particles 10 exhibit a sphericity of less than approximately 0.70. Sphericity readings of approximately 0.2 to approximately 0.5 and approximately 0.25 to 0.40 were also observed. Although sphericity is a characteristic independent of surface roughness, there is a positive correlation between the sphericity of the surface-modified single-crystal diamond particles 10 and polishing performance. In addition, there is a positive correlation between the weight loss of the diamond particles 10 and polishing performance. Therefore, as the weight loss of the diamond particles 10 increases, the ability of the diamond particles 10 to remove material from the surface of the semiconductor wafer becomes stronger. The above technical parameters are explained in more detail in at least U.S. Patent Nos. 8,182,562B2, 8,652,226B2, and 8,927,101B2, which are incorporated herein by reference in their entirety.

[0079] The process for forming the surface-modified single-crystal diamond 10 will now be explained.

[0080] In one example, a reactive coating is used to modify the surface of diamond. Such reactive coatings can typically include, but are not limited to, alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium peroxide, potassium dichromate, and potassium nitrate. The reactive coating may also comprise a combination of alkali metal hydroxides.

[0081] Other examples of metals that can be used as said reactive coatings may be selected from those contained in at least Group VIII of the periodic table, their metal compounds, and combinations thereof. Other examples of materials that can be used as said reactive coatings include catalyst metals taught in U.S. Patent No. 2,947,609 and U.S. Patent No. 2,947,610, which are incorporated herein by reference in their entirety.

[0082] In one particular example, a nickel (Ni) metal coating is used as the reactive coating. The metal coating used is typically about 10% to about 90% by weight of Ni, or about 10% to about 60% by weight, with the balance being diamond particles. However, it should be noted that these ratios are a matter of economic efficiency, not technical effectiveness. In one example, the metal coating at least partially covers the diamond particles. Alternatively, the metal coating may uniformly surround each diamond particle. The metal is not necessarily chemically bonded to the diamond. Nickel and / or nickel alloys can be used as a coating for diamond. One method of applying nickel to diamond is using a chemical deposition process. However, methods such as electroplating, physical vapor deposition (PVP), or chemical vapor deposition can also be used to coat diamond particles with a nickel layer.

[0083] In one example, diamond particles are coated with a nickel-phosphorus coating of approximately 10% to approximately 60% by weight. The coating process initially involves placing uncoated diamond particles in a solution of colloidal palladium. The fine palladium particles are uniformly adsorbed onto the diamond surface, thus autocatalyzing the chemical deposition of nickel. In the next stage of the process, activated diamond is placed in a nickel sulfamate solution containing approximately 10 grams of dissolved nickel per liter. While mixing the activated diamond and nickel suspension, sodium dithionite is added to the suspension, and the temperature of the coating bath is maintained at approximately 80°C. Upon addition of the sodium dithionite solution, all dissolved nickel in the solution autocatalytically deposits onto the activated diamond surface.

[0084] Depending on the amount of nickel deposited on the diamond, more nickel can be added by replacing the used nickel / diphosphate solution with fresh solution and repeating the process. If the particles are coated uniformly, multiple cycles may be required to achieve a sufficiently uniform nickel coverage on each diamond particle. The nickel content on the diamond is reproducible by monitoring the number of cycles and controlling coating bath parameters such as temperature, pH, and mixing energy. A certain degree of agglomeration is not uncommon in coated diamonds due to the interaction between the diamond particles and the nickel plating during coating. As long as each diamond particle containing agglomerates contains a certain amount of nickel coating, the presence of diamond agglomerates does not affect the quality of the process, and there is no need to attempt to remove the agglomerates.

[0085] After nickel-coating diamond particles, the coated diamond particles are placed in a furnace and heated to approximately 650°C to approximately 1000°C in a hydrogen atmosphere, a vacuum atmosphere, or an inert gas atmosphere. Temperatures of approximately 700°C to approximately 950°C, or approximately 800°C to 900°C, are also commonly used. The nickel-coated diamond can be heated for any period of time, from approximately five minutes to a maximum of approximately five hours. Typically, a heating period of approximately thirty minutes to a maximum of approximately two hours, or from approximately one to approximately two hours, is used.

[0086] After the heating cycle is complete, the diamond particles are cooled, and the modified diamond particles 10 are recovered by dissolving the nickel-coated, surface-modified single-crystal diamond particles 10 in acid. Commonly used acids may include hydrochloric acid, hydrofluoric acid, nitric acid, or combinations thereof. The acid or combination thereof is added at a volume ratio of 100:1 to up to 1000:1 of the coated diamond. The mixture is then heated to approximately 100°C to approximately 120°C for a period of approximately 6 to approximately 8 hours. The solution is then cooled, the released surface-modified single-crystal diamond particles 10 precipitate, and the solution is decanted. The acid washing and heating steps can be repeated until substantially all of the metal coating is dissolved.

[0087] Subsequently, any converted graphite (i.e., carbon converted from diamond to graphite during the reaction with nickel) is removed from the surface-modified single-crystal diamond particles 10 by any dissolution process known to those skilled in the art. An example of a common dissolution procedure involves oxidizing the graphitic carbon in an acidic solution containing a mixture of HNO3 and H2SO4 by gradually heating in the range of about 150°C to about 180°C.

[0088] Depending on the furnace conditions selected, more or less reaction may occur between the metal and the surface-modified single-crystal diamond particles 10. The more nickel is etched into the surface-modified single-crystal diamond 10, the more graphite is unfavorably formed, and therefore the greater the weight loss of diamond. To completely dissolve the graphite, a larger amount of acid may be used, or additional dissolution treatment may be required. The surface-modified single-crystal diamond particles 10 are then washed in water, such as to remove acid and residues. Subsequently, the surface-modified single-crystal diamond particles 10 are dried in an oven, air-dried, microwave-dried, or by other drying methods known to those skilled in the art.

[0089] Although nickel has been described for the process of surface modification of diamond particles, other metals (such as iron, or alternatively, manganese, chromium or their metal compounds, or any combination thereof) may also be used for this purpose.

[0090] In another specific example of the preparation of surface-modified diamond particles 10, about 10 wt% to about 80 wt% of diamond particles and about 20 wt% to about 90 wt% of iron particles are mixed using any suitable mixing method to achieve a homogeneous mixture. In one example, a weighed portion of the iron and diamond particles is placed in a container, sealed, and immersed in a mixing device such as a Turbula vibratory mixer (Glen Mills, Clifton, NJ, USA) for at least about 1 hour, or alternatively, about 30 minutes to about 1 hour. A binder may optionally be added to the mixture prior to mixing. The binder provides lubricity to the particle surfaces, resulting in a denser buildup and closer contact between the metal powder and the diamond. The binder also helps to hold the pressed body together as a green body.

[0091] The mixture is then compressed to produce a tight mixture of diamond and iron particles. Any method commonly known to those skilled in the art can be used to compress the diamond and iron particles, as long as they form a tight mixture and the particles are in close contact with each other. One method for compressing the mixture is to place it into a fixed die on a press. An example of a suitable press is the Carver pellet mill, manufactured by Carver Corporation (Wabash, Indiana). In a pellet mill, the mixture is subjected to pressures of about 5 psi to about 50,000 psi, about 10,000 psi to about 40,000 psi, or about 15,000 psi to about 30,000 psi to form pellets. While granulation of the mixture is taught, the diamond and iron particle mixture does not necessarily need to strictly form pellets; it is sufficient to compress the particles to form a tight contact with each other. Isostatic pressing or monostatic pressing with deformable tools can also be used to achieve a tight contact.

[0092] Alternatively, the diamond-iron mixture can also be compressed by pressing the mixture into sheets a few millimeters to a few inches thick (i.e., by high-pressure compaction rollers or briquetting rollers). The resulting sheets can then be cut into smaller portions for further processing as described below. Another method of compressing the iron and diamond particle mixture involves mixing and extruding the mixture under pressure. Granulating the diamond-iron particle mixture via a granulator or tumbling the mixture in a tumbling device are also alternative methods for compressing the diamond-iron mixture. The pellets, blocks, or cakes formed by these methods can then be further processed as described below.

[0093] Other methods for compressing the iron and diamond particle mixture may include injection molding, extrusion, pressing the mixture into a container, or casting. Alternatively, the individual diamond particles may be coated with metal particles by ion implantation, sputtering, spray drying, electrolytic coating, chemical coating, or any other suitable method, provided that the iron and diamond particles are in close contact with each other.

[0094] After compressing the mixture of diamond and iron particles, the compressed mixture (which may be pellets, aggregates, or other agglomerated forms) is placed in a furnace and heated to from about 650°C to about 1000°C in a hydrogen atmosphere, a vacuum atmosphere, or an inert gas atmosphere. Temperatures of about 700°C to about 900°C, or about 750°C to about 850°C, are typically used. The compressed mixture can be heated for a period of about five minutes to a maximum of about five hours. A heating period of about thirty minutes to a maximum of about two hours, or about one to two hours, is also typically used.

[0095] After the heating cycle is complete and the compressed mixture is cooled, the surface-modified diamond particles 10 are recovered by dissolving the iron particles in acid. Commonly used acids include hydrochloric acid, hydrofluoric acid, nitric acid, or combinations thereof. The acid or combination thereof is added at a volume ratio of 100:1 to up to 1000:1 of the compressed mixture (i.e., pellets). The mixture is then heated to approximately 100°C to approximately 150°C for a period of approximately 6 to approximately 8 hours. The solution is then cooled, the released surface-modified single-crystal diamond particles 10 precipitate, and the solution is decanted. The acid washing and heating steps can be repeated until substantially all the iron is dissolved.

[0096] Subsequently, any converted graphite (i.e., carbon converted from diamond to graphite during the reaction with iron) is removed from the surface-modified single-crystal diamond particles 10 by any dissolution treatment method known in the art. An example of a common dissolution procedure involves oxidizing the graphitic carbon in an acidic solution containing a mixture of HNO3 and H2SO4 by gradual heating in the range of about 150°C to about 180°C.

[0097] Depending on the furnace conditions selected, more or less reaction may occur between the metal and the surface-modified single-crystal diamond particles 10. The more iron is etched into the surface-modified single-crystal diamond 10, the more graphite is unfavorably formed, and therefore the greater the weight loss of diamond. To completely dissolve the graphite, a larger amount of acid may be used, or additional dissolution treatment may be required. The surface-modified single-crystal diamond particles 10 are then washed in water, such as to remove acid and residues. Subsequently, the surface-modified single-crystal diamond particles 10 are dried in a furnace, air-dried, microwave-dried, or other drying methods conventionally known to those skilled in the art.

[0098] The polishing composition may include a carrier, typically selected from the group consisting of aqueous carriers, glycol-based carriers (e.g., glycol, propylene glycol, or mixtures thereof), oil-based carriers, or hydrocarbon-based carriers, and any desired combinations thereof. The polishing composition may contain any possible combination or volume percentage of the aforementioned carrier elements that is not inconsistent with or incompatible with any purpose of this subject matter, for example, about 10% to about 70% by volume, about 15% to about 70% by volume, about 20% to about 70% by volume, about 25% to about 70% by volume, about 30% to about 70% by volume, about 35% to about 70% by volume, about 40% to about 70% by volume, about 45% to about 70% by volume, about 50% to about 70% by volume. 0% by volume, about 55% by volume to about 70% by volume, about 60% by volume to about 70% by volume, about 65% by volume to about 70% by volume, about 10% by volume to about 15% by volume, about 10% by volume to about 20% by volume, about 10% by volume to about 25% by volume, about 10% by volume to about 30% by volume, about 10% by volume to about 35% by volume, about 10% by volume to about 40% by volume, about 10% by volume to about 45% by volume, about 10% by volume to about 50% by volume, about 10% by volume to about 55% by volume, about 10% by volume to about 60% by volume Per unit volume, about 10% to about 65% per unit volume, about 20% to about 25% per unit volume, about 20% to about 30% per unit volume, about 20% to about 35% per unit volume, about 20% to about 40% per unit volume, about 20% to about 45% per unit volume, about 20% to about 50% per unit volume, about 20% to about 55% per unit volume, about 20% to about 60% per unit volume, or about 20% to about 65% per unit volume, about 30% to about 35% per unit volume, about 30% to about 40% per unit volume, about 30% to about 45% per unit volume %, about 30% to about 50% by volume, about 30% to about 55% by volume, about 30% to about 60% by volume, about 30% to about 65% by volume, about 40% to about 45% by volume, about 40% to about 50% by volume, about 40% to about 55% by volume, about 40% to about 60% by volume, about 40% to about 65% by volume, about 50% to about 55% by volume, about 50% to about 60% by volume, or about 60% to about 65% by volume.

[0099] The polishing composition may optionally contain at least one or more additives, which are typically selected from the group consisting of dispersants, pH adjusters, pH buffers, surfactants, polymers, complexing agents, rheology modifiers, chelating agents, defoamers, wetting agents, oxidants, and biocides. The polishing composition may contain any possible combination or any amount of the above-mentioned elements that is not inconsistent with or incompatible with the purposes of this disclosure.

[0100] In some examples, the optional components described above may be water-soluble, alcohol-soluble, or solvent-soluble. In other examples, the optional components may be water-dispersible, alcohol-dispersible, or solvent-dispersible, and may typically include, but are not limited to, ethanol, methanol, isopropanol, butanol, cyclohexanol, acetone, hexane, heptane, toluene, or any combination thereof. Such combinations may involve mixing, for example, water with an alcohol, water with a solvent, an alcohol with another alcohol, or an alcohol with a solvent.

[0101] In some examples, the polishing compositions disclosed herein can be formed as a slurry. In other examples, the polishing compositions disclosed herein can be formed as a suspension. In still other examples, the polishing compositions disclosed herein can be formed as a dispersion. In yet another set of examples, the polishing compositions disclosed herein can be formed as a paste. However, it should be emphasized that the polishing composition prepared using the surface-modified single-crystal diamond can be formulated in any type or form within the skill range of those skilled in the art, resulting in silicon carbide (SiC) removal rates from the SiC wafer surface ranging from about 1.3 µm / h to about 8.2 µm / h, from about 2.2 µm / h to about 8.2 µm / h, from about 3.2 µm / h to about 8.2 µm / h, from about 4.2 µm / h to about 8.2 µm / h, from about 5.2 µm / h to about 8.2 µm / h, from about 6.2 µm / h to about 8.2 µm / h, from about 7.2 µm / h to about 8.2 µm / h, from about 1.3 µm / h to about 2.2 µm / h, from about 2.2 µm / h to about 3.2 µm / h, and from about 3.2 µm / h to about 4.2 µm / h. µm / hour, ranging from about 1.3 µm / hour to about 4.2 µm / hour, ranging from about 2.2 µm / hour to about 4.2 µm / hour, ranging from about 3.2 µm / hour to about 4.2 µm / hour, ranging from about 4.2 µm / hour to about 5.2 µm / hour, ranging from about 4.2 µm / hour to about 6.2 µm / hour, ranging from about 4.2 µm / hour to about 7.2 µm / hour, ranging from about 5.2 µm / hour to about 6.2 µm / hour, ranging from about 6.2 µm / hour to about 7.2 µm / hour, ranging from about 1.3 µm / hour to about 3.3 µm / hour, ranging from about 1.3 µm / hour to about 7.2 µm / hour, ranging from about 3.3 µm / hour to about 7.2 µm / hour, or ranging from about 3.3 µm / hour to about 8.2 µm / hour.

[0102] The polishing composition may contain surfactants, including, for example, dispersants and wetting agents, such as, but not limited to, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, or any mixtures and combinations thereof. The amount of the surfactant in the polishing composition can typically range from about 0.001 wt% to about 0.05 wt%, about 0.001 wt% to about 0.1 wt%, about 0.001 wt% to about 0.5 wt%, about 0.001 wt% to about 1 wt%, about 0.001 wt% to about 1.5 wt%, about 0.001 wt% to about 2 wt%, about 0.001 wt% to about 2.5 wt%, about 0.001 wt% to about 3 wt%, about 0.0001 wt% to about 1 wt%, about 0.001 wt% to about 0.1 wt%, about 0.001 wt% to about 0.2 wt%, about 0.001 wt% to about 0.3 wt%, about 0.001 wt% to about 0.4 wt%, about 0.001 wt% to about 0.6 wt%, about 0.001 wt% to about 0.7 wt%, about 0. 0.001 wt% to about 0.8 wt%, about 0.001 wt% to about 0.9 wt%, about 0.005 wt% to about 0.1 wt%, about 0.005 wt% to about 0.2 wt%, about 0.005 wt% to about 0.3 wt%, about 0.005 wt% to about 0.4 wt%, about 0.005 wt% to about 0.5 wt%, about 0.005 wt% to about 0.6 wt%, about 0.005 wt% to about 0.7 wt%, about 0.005 wt% to about 0.8 wt%, about 0.005 wt% to about 0.9 wt%, about 0.005 wt% to about 1 wt%, about 0.005 wt% to about 0.05 wt%, about 0.005 wt% to about 0.06 wt%, about 0.005 wt% to about 0.07 wt%, about 0.005 wt% to about 0.08 wt%, or about 0.005 wt% to about 0.09 wt%.

[0103] The polishing composition may optionally include a low surface tension defoamer and a defoaming agent. The defoamer may be any suitable antifoaming agent, such as, but not limited to, silicone-based, siloxane, acetylenol-based, insoluble oils such as mineral oil, polymethylsiloxane and other organosilicones, alcohols (such as ethanol, methanol, isopropanol, butanol, cyclohexanol), stearates / salts, hydrophobic polyols, hydrophobic silica, ethylene-bis-stearamide, fatty acids, fatty acid alcohols, and diol defoamers.The concentration of the defoamer in the polishing composition is typically from about 1 ppm (parts per million) to about 10 ppm, from about 1 ppm to about 20 ppm, from about 1 ppm to about 30 ppm, from about 1 ppm to about 40 ppm, from about 1 ppm to about 50 ppm, from about 1 ppm to about 60 ppm, from about 1 ppm to about 70 ppm, from about 1 ppm to about 80 ppm, from about 1 ppm to about 90 ppm, from about 1 ppm to about 100 ppm, from about 1 ppm to about 110 ppm, from about 1 ppm to about 120 ppm, from about 1 ppm to about 130 ppm, from about 1 ppm to about 140 ppm, from about 1 ppm to about 150 ppm, from about 10 ppm to about 150 ppm, from about 20 ppm to about 150 ppm, from about 30 ppm to about 150 ppm, from about 40 ppm to about 150 ppm, from about 50 ppm to about 150 ppm, from about 60 ppm to about 150 ppm, from about 70 ppm... ppm to about 150 ppm, about 80 ppm to about 150 ppm, about 90 ppm to about 150 ppm, about 100 ppm to about 150 ppm, about 110 ppm to about 150 ppm, about 120 ppm to about 150 ppm, about 130 ppm to about 150 ppm, about 140 ppm to about 150 ppm, about 10 ppm to about 20 ppm, about 15 ppm to about 20 ppm, about 20 ppm to about 25 ppm, about 20 ppm to about 30 ppm, about 25 ppm to about 30 ppm, about 30 ppm to about 35 ppm, about 30 ppm to about 40 ppm, about 10 ppm to about 40 ppm, about 15 ppm to about 40 ppm, about 20 ppm to about 40 ppm, about 25 ppm to about 40 ppm, about 40 ppm to about 50 ppm, about 45 ppm to about 50 ppm, about 50 ppm to about 60 ppm ppm, about 55 ppm to about 60 ppm, about 60 ppm to about 70 ppm, about 65 ppm to about 70 ppm, about 40 ppm to about 70 ppm, about 45 ppm to about 70 ppm, about 50 ppm to about 70 ppm, about 55 ppm to about 70 ppm, about 70 ppm to about 80 ppm, about 75 ppm to about 80 ppm, about 80 ppm to about 90 ppm, about 85 ppm to about 90 ppm, about 90 ppm to about 100 ppm, about 70 ppm to about 100 ppm, about 75 ppm to about 100 ppm, or about 80 ppm to about 100 ppm.

[0104] Oxidizing agents may also be optionally used, and may be selected from the group consisting of hydrogen peroxide, potassium bisulfate, cerium ammonium nitrate, periodate, iodate, persulfate, and mixtures thereof. Periodate, iodate, and persulfate may be any periodate, iodate, persulfate, or combination of periodate, iodate, and persulfate, such as, for example, potassium periodate, potassium iodate, ammonium persulfate, potassium persulfate, or sodium persulfate. In some examples, the oxidizing agent is potassium bisulfate or potassium persulfate. The oxidizing agent may be present in the polishing composition in any suitable amount that is inconsistent with and incompatible with the purposes of this subject matter. Typically, the polishing composition may contain more than about 0.001% by weight, for example, more than about 0.005% by weight, more than about 0.01% by weight, more than about 0.05% by weight, or more than about 0.1% by weight of the oxidizing agent. In some examples, the polishing composition may contain less than 20% by weight, such as less than 17% by weight, less than 15% by weight, less than 12% by weight, less than 10% by weight, less than 7% by weight, less than 5% by weight, less than 2% by weight, or less than 0.5% by weight of the oxidant. In other examples, the polishing composition may comprise from about 0.001 wt% to about 20 wt%, for example, from about 0.001 wt% to about 17 wt%, from about 0.001 wt% to about 15 wt%, from about 0.001 wt% to about 12 wt%, from about 0.001 wt% to about 10 wt%, from about 0.001 wt% to about 7 wt%, from about 0.001 wt% to about 5 wt%, from about 0.001 wt% to about 2 wt%, from about 0.005 wt% to about 20 wt%, from about 0.005 wt% to about 17 wt%, from about 0.005 wt% to about 15 wt%, from about 0.005 wt% to about 12 wt%, from about 0.005 wt% to about 10 wt%, from about 0.005 wt% to about 7 wt%, from about 0.0 wt%. 0.05 wt% to about 5 wt%, about 0.005 wt% to about 2 wt%, 0.01 wt% to about 20 wt%, 0.01 wt% to about 17 wt%, about 0.01 wt% to about 15 wt%, about 0.01 wt% to about 12 wt%, about 0.01 wt% to about 10 wt%, about 0.01 wt% to about 7 wt%, about 0.01 wt% to about 5 wt%, 0.01 wt% to about 2 wt%, about 0.05 wt% to about 20 wt%, about 0.05 wt% to about 17 wt%, about 0.05 wt% to about 15 wt%, about 0.05 wt% to about 10 wt%, about 0.05 wt% to about 7 wt%, about 0.05 wt% to about 5 wt%, about 0.05 wt% to about 2 wt%.In some other examples, based on the total weight of the polishing composition, the polishing composition may contain about 0.001 wt% to about 0.05 wt%, about 0.001 wt% to about 0.1 wt%, 0.001 wt% to about 0.2 wt%, 0.001 wt% to about 0.3 wt%, 0.001 wt% to about 0.4 wt%, about 0.001 wt% to about 0.5 wt%, 0.001 wt% to about 0.6 wt%, 0.001 wt% to about 0.7 wt%, 0.001 wt% to about 0.8 wt%, 0.001 wt% to about 0.9 wt%, or about 0.001 wt% to about 1 wt% of the oxidant.

[0105] The polishing compositions disclosed herein may exhibit any suitable pH value that is not inconsistent with or incompatible with the scope of this subject matter. In some examples, the polishing compositions may typically have a pH range of about 3 to about 11. Without wishing to be bound by any particular theory, the polishing rate of the compositions of the present invention may increase as the pH decreases, for example, from 11 to 3. Therefore, in some examples, the polishing composition may have a pH range of about 3 to about 11, about 3 to about 10, about 3 to about 9, about 3 to about 8, about 3 to about 7, about 3 to about 6, about 3 to about 5, about 3 to about 4, or, however, alternatively, a pH range of about 4 to about 11, about 5 to about 11, about 6 to about 11, about 7 to about 11, about 8 to about 11, about 9 to about 11, about 10 to about 11, about 4 to about 10, about 5 to about 10, about 6 to about 10, about 7 to about 10, about 8 to about 10, about 9 to about 10, about 4 to about 9, about 5 to about 9, about 6 to about 9, about 7 to about 9, about 8 to about 9, about 4 to about 8, about 5 to about 8, about 6 to about 8, about 7 to about 8, about 4 to about 7, about 5 to about 7, about 6 to about 7, about 4 to about 6, or about 5 to about 6.

[0106] If necessary, to achieve the above pH level, a pH adjuster, a pH buffer, or a combination thereof can be used. Any suitable pH adjuster can be included in the polishing composition. For example, the pH adjuster can be in the form of one or more of, or any combination thereof, nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid, or in the form of an alkali, such as sodium hydroxide, potassium hydroxide, cesium hydroxide, or ammonium hydroxide, or any combination thereof. The pH buffer can be any suitable buffer, such as phosphates, acetates, borates, sulfonates, carboxylates, ammonium salts, etc., or any combination thereof. Based on the total weight of the polishing composition, the pH adjuster or pH buffer can typically be included in an amount that effectively achieves the desired pH level, such as from about 0.001 wt% to about 20 wt%, for example, from about 0.001 wt% to about 17 wt%, from about 0.001 wt% to about 15 wt%, from about 0.001 wt% to about 12 wt%, from about 0.001 wt% to about 10 wt%, from about 0.001 wt% to about 7 wt%, from about 0.001 wt% to about 5 wt%, from about 0.001 wt% to about 2 wt%. Weight%, about 0.005 wt% to about 20 wt%, about 0.005 wt% to about 17 wt%, about 0.005 wt% to about 15 wt%, about 0.005 wt% to about 12 wt%, about 0.005 wt% to about 10 wt%, about 0.005 wt% to about 7 wt%, about 0.005 wt% to about 5 wt%, about 0.005 wt% to about 2 wt%, 0.01 wt% to about 20 wt%, 0.01 wt% to about 17 wt%, about 0.01 wt% to about 15 wt%, about 0.01 wt% Amount % to about 12 wt%, about 0.01 wt% to about 10 wt%, about 0.01 wt% to about 7 wt%, about 0.01 wt% to about 5 wt%, 0.01 wt% to about 2 wt%, about 0.05 wt% to about 20 wt%, about 0.05 wt% to about 17 wt%, about 0.05 wt% to about 15 wt%, about 0.05 wt% to about 10 wt%, about 0.05 wt% to about 7 wt%, about 0.05 wt% to about 5 wt%, about 0.05 wt% to about 2 wt%, about 0.001 wt% The amounts included are from about 0.05 wt%, about 0.001 wt% to about 0.1 wt%, 0.001 wt% to about 0.2 wt%, 0.001 wt% to about 0.3 wt%, 0.001 wt% to about 0.4 wt%, about 0.001 wt% to about 0.5 wt%, 0.001 wt% to about 0.6 wt%, 0.001 wt% to about 0.7 wt%, 0.001 wt% to about 0.8 wt%, 0.001 wt% to about 0.9 wt%, or about 0.001 wt% to about 1 wt%.

[0107] Ideally, the polishing composition may also comprise polymers, non-limiting examples such as polyvinyl chloride, polyvinyl fluoride, polyvinyl alcohol, polyvinyl acetate, vinyl polymers, polyvinylpyrrolidone, fluorocarbons, polycarbonates, fluoropolymers, polycarbonates, polyesters, polyacrylates, polyethers, polyethylene, polyamides, polyurethanes, polystyrene, polypropylene, polyvinyl fluoride, urethanes, copolymers of nonionic monomers with olefinic unsaturated monomers containing portions such as acryloyl alkyl trialkylammonium salts (e.g., acryloyl ethyl trimethyl ammonium chloride), methacryloyl alkyl trialkylamine salts (e.g., methacryloyl ethyl trimethyl ammonium chloride), acrylamide and methacrylamide alkyl trialkylammonium salts (e.g., acrylamidopropyl trimethyl ammonium chloride and methacrylamidopropyl trimethyl ammonium chloride), and polymers comprising sulfonic acid monomer units (hereinafter referred to as sulfonic acid polymers or copolymers). The sulfonic acid monomer unit may be any suitable sulfonic acid monomer unit containing more than one group of the formula -SO3H. Non-limiting examples of suitable sulfonic acid polymers (homopolymers) include polyvinyl sulfonic acid, polystyrene sulfonic acid (e.g., poly(4-styrene sulfonic acid)), polyallyl sulfonic acid, polyethyl acrylate sulfonic acid, polybutyl acrylate sulfonic acid, polyisoprene sulfonic acid, etc. Suitable sulfonic acid copolymers include copolymers comprising sulfonic acid monomer units and monomers comprising carboxylic acid groups or derivatives of carboxylic acid groups (such as amides).

[0108] The polishing composition may contain more than about 1 ppm, for example, more than about 5 ppm, more than about 10 ppm, more than about 20 ppm, more than about 30 ppm, more than about 40 ppm, or more than about 50 ppm of the polymer. Alternatively or additionally, the polishing composition may contain less than about 500 ppm, for example, less than about 450 ppm, less than about 400 ppm, less than about 350 ppm, less than about 300 ppm, less than about 250 ppm, less than about 200 ppm, less than about 150 ppm, or less than about 100 ppm of the polymer. Therefore, the polishing composition may contain the amount of polymer defined by any two of the above endpoints. For example, the polishing composition may comprise the polymer in amounts of about 1 ppm to about 500 ppm, about 5 ppm to about 450 ppm, about 10 ppm to about 400 ppm, about 10 ppm to about 350 ppm, about 10 ppm to about 300 ppm, about 10 ppm to about 250 ppm, about 10 ppm to about 200 ppm, about 20 ppm to about 300 ppm, about 20 ppm to about 250 ppm, about 20 ppm to about 200 ppm, about 20 ppm to about 150 ppm, about 20 ppm to about 100 ppm, about 10 ppm to about 100 ppm, about 10 ppm to about 90 ppm, about 10 ppm to about 80 ppm, about 10 ppm to about 70 ppm, about 10 ppm to about 60 ppm, about 10 ppm to about 50 ppm, or about 10 ppm to about 40 ppm.

[0109] In some examples, biocides known in the art may also be incorporated into the polishing composition. The biocides may be any suitable biocides known to those skilled in the art, and may be present in the polishing composition in any suitable amount that is not inconsistent with or incompatible with the principles of this subject matter. For example, and not as a limitation, suitable biocides may be isothiazolinone biocides, isothiazolinones, or similar biocides, alcohols, aldehydes, chlorine and chlorine-releasing agents (e.g., sodium hypochlorite, chlorhexidine), iodine, peroxides (e.g., hydrogen peroxide, peracetic acid), phenolic compounds, quaternary ammonium compounds (e.g., benzalkonium chloride), bases (e.g., sodium hydroxide, potassium hydroxide), and acids (e.g., inorganic and organic acids). The concentration of the biocidal agent used in the polishing composition can typically be from about 1 ppm to about 60 ppm, from about 1 ppm to about 50 ppm, from about 1 ppm to about 40 ppm, from about 1 ppm to about 30 ppm, from about 1 ppm to about 20 ppm, from about 1 ppm to about 10 ppm, from about 1 ppm to about 5 ppm, from about 10 ppm to about 60 ppm, from about 15 ppm to about 60 ppm, from about 20 ppm to about 60 ppm, from about 25 ppm to about 60 ppm, from about 30 ppm to about 60 ppm, from about 35 ppm to about 60 ppm, from about 40 ppm to about 60 ppm, from about 45 ppm to about 60 ppm, from about 50 ppm to about 60 ppm, or from about 55 ppm to about 60 ppm.

[0110] The polishing composition may also contain conventional rheology modifiers, such as castor oil derivative polymers, cellulose, alkali-acrylic emulsions, hydrophobic ethoxylated urethane resins, polyurea, polyamides, calcium sulfonate, and similar and equivalent rheology modifiers, typically in the range of about 1,000 ppm to about 20,000 ppm. In some examples, the polishing composition contains about 2,500 ppm to about 20,000 ppm of the rheology modifier. In other examples, the polishing composition contains about 5,000 ppm to about 20,000 ppm of the rheology modifier. In still other examples, the polishing composition contains about 7,500 ppm to about 20,000 ppm of the rheology modifier. In yet another example, the polishing composition contains about 10,000 ppm to about 20,000 ppm of the rheology modifier. In still other examples, the polishing composition contains about 12,500 ppm to about 20,000 ppm of the rheology modifier. In even other examples, the polishing composition contains about 15,000 ppm to about 20,000 ppm of the rheology modifier. In even further examples, the polishing composition contains about 17,500 ppm to about 20,000 ppm of the rheology modifier.

[0111] The polishing composition may further contain about 1000 ppm to about 2500 ppm, about 2500 ppm to about 5000 ppm, about 5000 ppm to about 7500 ppm, about 1000 ppm to about 7500 ppm, about 2000 ppm to about 7500 ppm, about 2500 ppm to about 7500 ppm, about 3000 ppm to about 7500 ppm, about 4000 ppm to about 7500 ppm, about 5000 ppm to about 7500 ppm, about 6000 ppm to about 7500 ppm, about 7000 ppm to about 7500 ppm, about 7500 ppm to about 10000 ppm, about 8500 ppm to about 10000 ppm, about 9500 ppm to about 10000 ppm, about 10000 ppm to about 12500 ppm, about 10000 ppm, etc. ppm to about 13,000 ppm, about 11,000 ppm to about 12,500 ppm, about 11,500 ppm to about 12,500 ppm, about 12,000 ppm to about 12,500 ppm, about 12,500 ppm to about 15,000 ppm, about 13,000 ppm to about 15,000 ppm, about 13,500 ppm to about 15,000 ppm, about 14,000 ppm to about 15,000 ppm, about 15,000 ppm to about 17,500 ppm, about 16,000 ppm to about 17,500 ppm, about 16,500 ppm to about 17,500 ppm, about 10,000 ppm to about 15,000 ppm, about 10,500 ppm to about 15,000 ppm, about 11,000 ppm to about 15,000 ppm, about 11,500 ppm to about 15,000 ppm ppm, about 12,000 ppm to about 15,000 ppm, about 10,000 ppm to about 17,500 ppm, about 10,500 ppm to about 17,500 ppm, about 11,000 ppm to about 17,500 ppm, about 11,500 ppm to about 17,500 ppm, about 12,000 ppm to about 17,500 ppm, about 12,500 ppm to about 17,500 ppm, about 13,000 ppm to about 17,500 ppm, about 13,500 ppm to about 17,500 ppm, about 14,000 ppm to about 17,500 ppm, about 14,500 ppm to about 17,500 ppm, about 15,000 ppm to about 17,500 ppm, about 16,000 ppm to about 17,500 ppm ppm, approximately 16,500 ppm to approximately 17,500 ppm, or approximately 17,000 ppm to approximately 17,500 ppmThe rheology modifier is present in ppm.

[0112] The polishing composition may optionally further comprise a chelating agent or a complexing agent. The complexing agent can be any suitable chemical additive that can increase the rate of material removal from the semiconductor wafer surface or remove trace metal contaminants during a polishing cycle. Suitable chelating agents or complexing agents may include, for example, carbonyl compounds (e.g., acetylacetone compounds), simple carboxylates (e.g., acetates, aryl carboxylates, etc.), carboxylates containing one or more hydroxyl groups (e.g., glycolates, lactates, gluconates, gallic acid and their salts or partial salts thereof), dicarboxylates, tricarboxylates and polycarboxylates (e.g., oxalates, oxalic acid, phthalates, citrates, succinates, tartrates, malates, ethylenediaminetetraacetic acid (e.g., dipotassium EDTA), mixtures thereof), carboxylates containing one or more sulfonic acid and / or phosphonic acid groups, etc.Suitable chelating or complexing agents may also include, for example, diols, triols, or polyols (e.g., ethylene glycol, catechol, pyrogallol, tannic acid, etc.), polyphosphonates (such as Dequest 2010, Dequest 2060, or Dequest 2000 (available from Solutia), and amine-containing compounds (e.g., ammonia, amino acids, amino alcohols, diamines, triamines, and polyamines, etc.), wherein the amount of chelating or complexing agent is from about 0.001 wt% to about 20 wt% based on the total weight of the polishing composition, for example, from about 0.001 wt% to about 17 wt%, from about 0.001 wt% to about 15 wt%, from about 0.001 wt% to about 12 wt%, from about 0.001 wt% to about 10 wt%, from about 0.001 wt% to about 7 wt%, from about 0.001 wt% to about 5 wt%. Approximately 0.001 wt% to approximately 2 wt%, approximately 0.005 wt% to approximately 20 wt%, approximately 0.005 wt% to approximately 17 wt%, approximately 0.005 wt% to approximately 15 wt%, approximately 0.005 wt% to approximately 12 wt%, approximately 0.005 wt% to approximately 10 wt%, approximately 0.005 wt% to approximately 7 wt%, approximately 0.005 wt% to approximately 5 wt%, approximately 0.005 wt% to approximately 2 wt%, 0.01 wt% to approximately 20 wt%, 0.01 wt% to approximately 17 wt%, approximately 0.01 wt% to approximately 1 5% by weight, about 0.01% by weight to about 12% by weight, about 0.01% by weight to about 10% by weight, about 0.01% by weight to about 7% by weight, about 0.01% by weight to about 5% by weight, 0.01% by weight to about 2% by weight, about 0.05% by weight to about 20% by weight, about 0.05% by weight to about 17% by weight, about 0.05% by weight to about 15% by weight, about 0.05% by weight to about 10% by weight, about 0.05% by weight to about 7% by weight, about 0.05% by weight to about 5% by weight, about 0.05% by weight to about 2% by weight. About 0.001 wt% to about 0.05 wt%, about 0.001 wt% to about 0.1 wt%, 0.001 wt% to about 0.2 wt%, 0.001 wt% to about 0.3 wt%, 0.001 wt% to about 0.4 wt%, about 0.001 wt% to about 0.5 wt%, 0.001 wt% to about 0.6 wt%, 0.001 wt% to about 0.7 wt%, 0.001 wt% to about 0.8 wt%, 0.001 wt% to about 0.9 wt%, or about 0.001 wt% to about 1 wt%.

[0113] The polishing compositions disclosed herein can be prepared by any suitable technique, many of which are well known to those skilled in the art. The polishing compositions can be prepared using batch, continuous, or combinations thereof.

[0114] It should be understood that, generally, the actual amount of one or more components (e.g., diamond particles, polishing composition components, and water) in the polishing composition according to embodiments of this disclosure can vary depending on the desired level of dilution or concentration. In this regard, some embodiments may be packaged as concentrates, such as 50x, 100x, 200x, etc., in which water may be added, for example, by the end user, to dilute the polishing composition, such as later in use. Alternatively, the polishing composition may be packaged in a diluted form in which water is already contained. For example, in some embodiments, the concentrated form of each component of the polishing composition as a whole can facilitate shipping, distribution, and sales. However, in other embodiments, each component of the polishing composition as a whole may be in a diluted form to, for example, simplify the end-use for the user. Therefore, the weight range of components as described herein may refer to a dilution or concentration range.

[0115] Therefore, each component can be present in a diluted form suitable for end use, or in a concentrated form received and then subsequently diluted for end-user use, for example, concentrated 2x, 5x, 10x, 25x, 40x, 50x, 60x, 70x, 100x, 125x, 150x, 175x, or 200x. When the concentrate is diluted with water, for example with 1 kg, 4 kg, 9 kg, 24 kg, 39 kg, 49 kg, 59 kg, 69 kg, 99 kg, 124 kg, 149 kg, 174 kg, or 199 kg of water respectively, in embodiments of the subject matter, each component of the polishing composition will be present in an amount within the dilution range. Furthermore, as those skilled in the art will understand, the concentrate may contain an appropriate proportion of water present in the final solution. For example, in some applications, the concentrate may contain an appropriate proportion of water present in the final polishing composition, thereby ensuring that the polishing composition components are at least partially or completely dissolved in a concentrated form.

[0116] Methods for polishing the surface of semiconductor wafers

[0117] This disclosure also provides a method for polishing the surface of a semiconductor wafer, in Figure 2 The process is described in the text. Please note... Figure 2The process includes at least the step of contacting the surface of the semiconductor wafer with a polishing pad to which the polishing composition described above is applied in step 20. Next, in step 22, the polishing pad to which the polishing composition is applied is moved relative to the semiconductor wafer. Finally, as shown in step 24, the method concludes by polishing at least a portion of the semiconductor wafer.

[0118] Those skilled in the art will appreciate that this can be routinely performed on, for example, a 15-inch benchtop polisher (LapmasterWolters) in a single-sided polishing configuration typically used on semiconductor wafer surfaces. Alternatively, in other examples, polishing of the semiconductor wafer surface can also be suitably performed using a double-sided polishing configuration.

[0119] Generally, such polishing apparatus includes an impression disk that is in motion during use, with its speed generated by track, linear, or circular motion. The polishing pad is in direct contact with the impression disk, so that when the impression disk is moved, the polishing pad moves with it. A carrier holds the semiconductor wafer to be polished by contacting and moving it relative to the surface of the polishing pad. Polishing of the semiconductor wafer is performed by placing the semiconductor wafer in contact with the polishing pad and the polishing composition (i.e., the polishing composition is disposed between the semiconductor wafer and the polishing pad) while the polishing pad and the impression disk move together relative to the semiconductor wafer in a relative configuration, thereby polishing at least a portion of the semiconductor wafer.

[0120] The degree of polishing endpoint is determined by monitoring the weight of the semiconductor wafer (which is used to calculate the amount of material removed from the semiconductor wafer by polishing). Such techniques are conventionally well known to those skilled in the art.

[0121] Polishing refers to removing at least a portion of the surface of a semiconductor wafer to polish the surface. Polishing can be performed by removing, for example, gouges, dents, pits, etc., thereby providing a semiconductor wafer surface with reduced surface roughness when polishing is complete. However, alternatively, polishing can also be performed to introduce or restore a surface geometry characterized by the intersection of planar segments.

[0122] Ideally, the polishing pad can be made of any suitable material or construction, many of which are readily known to those skilled in the art. Suitable polishing pads can be, for example, including but not limited to woven and nonwoven polishing pads. Furthermore, suitable polishing pads can be made of any suitable polymer with varying densities, hardness, thickness, compressibility, resilience after compression, and compressive modulus. Such suitable polymers typically include, for example, but not limited to, the following: polyvinyl chloride, polyvinyl fluoride, nylon, fluorocarbons, polycarbonate, polyester, polyacrylate, polyether, polyethylene, polyamide, polyurethane, polystyrene, polypropylene, their co-formed products, and any mixtures or combinations thereof.

[0123] The polishing pad can typically be of any suitable construction to effectively polish the surface of the semiconductor wafer. For example, the polishing pad can be circular and, in use, can typically rotate about an axis perpendicular to the plane defined by the pad surface. The polishing pad can be cylindrical, with its surface acting as the polishing surface, and, in use, can typically rotate about the central axis of the cylinder. The polishing pad can be in the form of annular strips, which, in use, typically exhibit linear motion relative to the cutting edge being polished. The polishing pad can readily adopt any suitable shape and, in use, can reciprocate or orbit along a plane or semicircle. Many other variations and constructions will be apparent and available to those skilled in the art and are therefore also intended to be incorporated into and covered within the scope of this disclosure.

[0124] It should be emphasized that the methods of this subject matter can be conventionally used to polish any suitable semiconductor wafer surface. In some examples, this may specifically involve polishing at least one layer of silicon carbide (SiC) from, for example, a SiC wafer surface using a polishing composition having surface-modified single-crystal diamond, according to the core principles of this subject matter. In some examples, the SiC may be single-crystal SiC. The SiC can be removed from the surface at any suitable rate to ultimately achieve polishing of the SiC wafer surface. For example, the SiC can be removed at a rate ranging from about 1.3 µm / hour to about 8.2 µm / hour. In some examples, the SiC is removed at a rate ranging from about 2.2 µm / hour to about 8.2 µm / hour. In other examples, the SiC is removed at a rate ranging from about 3.2 µm / hour to about 8.2 µm / hour. In still some other examples, the SiC is removed at a rate ranging from about 4.2 µm / hour to about 8.2 µm / hour. In some other examples, the SiC is removed at a rate ranging from about 5.2 µm / hour to about 8.2 µm / hour. In even more other examples, the SiC is removed at a rate ranging from about 6.2 µm / hour to about 8.2 µm / hour. In still more and even more other examples, the SiC is removed at a rate ranging from about 7.2 µm / hour to about 8.2 µm / hour.

[0125] It can also be in the range of about 1.3 µm / hour to about 2.2 µm / hour, about 2.2 µm / hour to about 3.2 µm / hour, about 3.2 µm / hour to about 4.2 µm / hour, about 1.3 µm / hour to about 4.2 µm / hour, about 2.2 µm / hour to about 4.2 µm / hour, about 3.2 µm / hour to about 4.2 µm / hour, about 4.2 µm / hour to about 5.2 µm / hour, about 4.2 µm / hour to about 6.2 µm / hour, about 4.2 µm / hour to about 7.2 µm / hour, about 5.2 µm / hour to about 6.2 µm / hour, about 6.2 µm / hour to about 7.2 µm / hour, about 1.3 µm / hour to about 3.3 µm / hour, about 1.3 µm / hour to about 7.2 µm / hour, about 3.3 µm / hour. The SiC is removed at a rate ranging from approximately µm / hour to approximately 7.2 µm / hour, or from approximately 3.3 µm / hour to approximately 8.2 µm / hour.

[0126] When compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles, the polishing composition having the surface-modified single-crystal diamond 10 can increase the material removal rate of SiC by about 185% to about 245%. In some examples, when compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles, the polishing composition having the surface-modified single-crystal diamond 10 increases the material removal rate of SiC by about 190% to about 245%. In still other examples, when compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles, the polishing composition having the surface-modified single-crystal diamond 10 increases the material removal rate of SiC by about 200% to about 245%. In even further examples, when compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles, the polishing composition having the surface-modified single-crystal diamond 10 increases the material removal rate of the SiC by about 210% to about 245%. In even further examples, when compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles, the polishing composition having the surface-modified single-crystal diamond 10 increases the material removal rate of the SiC by about 220% to about 245%. In even even further examples, when compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles, the polishing composition having the surface-modified single-crystal diamond 10 increases the material removal rate of the SiC by about 230% to about 245%.

[0127] Compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles, the polishing composition having the surface-modified single-crystal diamond 10 can further increase the material removal rate of SiC by approximately 185% to approximately 190%, approximately 190% to approximately 195%, approximately 185% to approximately 195%, approximately 185% to approximately 200%, approximately 185% to approximately 205%, approximately 185% to approximately 210%, approximately 185% to approximately 215%, approximately 185% to approximately 220%, approximately 185% to approximately 225%, and approximately 185% to approximately 230%, about 185% to about 235%, about 185% to about 240%, about 190% to about 200%, about 190% to about 205%, about 190% to about 210%, about 190% to about 215%, about 190% to about 220%, about 190% to about 225%, about 190% to about 230%, about 190% to about 235%, about 190% to about 240%, about 195% to about 200%, about 195% to about 205%, about 195% to about 210%, about 195% to about 215%, about 195% to Approximately 220%, approximately 195% to approximately 225%, approximately 195% to approximately 230%, approximately 195% to approximately 235%, approximately 195% to approximately 240%, approximately 195% to approximately 245%, approximately 200% to approximately 205%, approximately 200% to approximately 210%, approximately 200% to approximately 215%, approximately 210% to approximately 220%, approximately 210% to approximately 225%, approximately 210% to approximately 230%, approximately 210% to approximately 235%, approximately 210% to approximately 240%, approximately 200% to approximately 220%, approximately 200% to approximately 225%, approximately 200% The range is approximately 230%, approximately 200% to approximately 235%, approximately 215% to approximately 220%, approximately 220% to approximately 225%, approximately 220% to approximately 230%, approximately 220% to approximately 235%, approximately 220% to approximately 240%, approximately 225% to approximately 230%, approximately 220% to approximately 235%, approximately 225% to approximately 235%, approximately 225% to approximately 240%, approximately 230% to approximately 240%, approximately 225% to approximately 245%, approximately 235% to approximately 240%, approximately 235% to approximately 245%, or approximately 240% to approximately 245%.

[0128] Example

[0129] The following embodiments are provided to offer a complete disclosure and description of how to make and use the described subject matter to those skilled in the art, and are not intended to limit the scope of the disclosure as the inventors believe, nor to represent that the following experiments are all or only those conducted. Efforts have been made to ensure the accuracy of the figures used, but some experimental errors and biases should be taken into account.

[0130] Example 1

[0131] When compared with polishing compositions containing monocrystalline diamond particles or polycrystalline diamond particles, polishing compositions containing surface-modified monocrystalline diamond exhibit improved silicon carbide (SiC) removal rates from SiC wafer surfaces.

[0132] According to an exemplary embodiment of this subject matter, the removal rate and surface roughness of silicon carbide (SiC) material from the surface of a 4-inch diameter silicon carbide wafer are tested using the following methods: (I) a polishing composition using surface-modified single-crystal diamond (Smmd* in Table 1) with a D(50) grain size characterized as 0.25 µm, 0.5 µm, 0.75 µm, or 1 µm; (II) a polishing composition using single-crystal diamond (Mono in Table 1) with a D(50) grain size characterized as 0.25 µm, 0.5 µm, 0.75 µm, or 1 µm; or (III) a polishing composition using polycrystalline diamond (Poly in Table 1) with a D(50) grain size characterized as 0.25 µm, 0.5 µm, 0.75 µm, or 1 µm. All the chemical compositions of the polishing compositions (I), (II), and (III) are identical, differing only in the specific type of diamond used.

[0133] Table 1 shows the diamond grit size used in the polishing composition in column 1, the specific diamond type used in the polishing composition in column 2, the results obtained for the SiC material removal rate from the SiC wafer surface in column 3, the surface roughness of the SiC wafer in column 4, the average volume distribution in column 5, the D(50) grit size distribution in column 6, and the D(99) grit size distribution in column 7. All polishing data shown in Table 1 were obtained on a 15-inch benchtop polisher (LapmasterWolters) using a 15-inch polishing pad made of polyurethane. The imprinting disk of the 15-inch benchtop polisher was made to rotate in a circular motion defined by 60 revolutions per minute (RPM), and diamond slurry was applied at a slurry flow rate of 10 mL / min under a downward force of 3.2 psi. In the polishing compositions (I), (II), and (III), diamond particles were used as an aqueous slurry suspended in distilled water (DIW) at a concentration of 80 carats / gallon. The results obtained are as follows.

[0134] Essentially, when compared to the polishing compositions containing monocrystalline diamond particles (Mono in Table 1) or polycrystalline diamond particles (Poly in Table 1), the polishing compositions containing the surface-modified monocrystalline diamond (Smmd* in Table 1) exhibit an improvement in the rate of SiC material removal from the SiC wafer surface by approximately 185% to approximately 245%.

[0135] To obtain the above results, the calculated average material removal rate in column 3 for each particle size of 0.25 µm, 0.5 µm, 0.75 µm, or 1 µm for both monocrystalline diamond (Mono in Table 1) and polycrystalline diamond (Poly in Table 1) was compared with the corresponding values ​​for each surface-modified monocrystalline diamond (Smmd* in Table 1) used at the same diamond particle size. In other words, the average calculated material removal rate in column 3 for Mono 0.25 µm and Poly 0.25 µm was compared with the material removal rate value for the surface-modified monocrystalline diamond (Smmd) 0.25 µm*. The average calculated material removal rate in column 3 for Mono 0.50 µm and Poly 0.50 µm was compared with the material removal rate value for the surface-modified monocrystalline diamond (Smmd) 0.50 µm*. The average calculated material removal rates in column 3 for Mono 0.75µm and Poly 0.75µm were compared with the material removal rate value for the surface-modified single-crystal diamond (Smmd) 0.75µm*. The average calculated material removal rates in column 3 for Mono 1µm and Poly 1µm were compared with the material removal rate value for the surface-modified single-crystal diamond (Smmd) 1µm*.

[0136] The results in Table 1 are... Figure 3 This is further illustrated graphically. Importantly, it is noteworthy that when polished with the surface-modified single-crystal diamond (Smmd* in Table 1), the measured surface roughness is substantially similar to or improved compared to single-crystal diamond (Mono in Table 1) or polycrystalline diamond (Poly in Table 2), as shown in… Figure 3 The surface roughness value obtained by observing it on the right y-axis is illustrated with solid black dots.

[0137]

[0138] Although the present disclosure has been described in conjunction with embodiments thereof, those skilled in the art will understand that additions, deletions, modifications and substitutions not specifically described may be made without departing from the spirit and scope of the present disclosure as defined in the appended claims.

[0139] Regarding the use of virtually any plural and / or singular terms in this document, those skilled in the art may translate plural to singular and / or singular to plural depending on the context and / or the requirements of the application. For clarity, various singular / plural arrangements are not explicitly described herein.

[0140] The topics described herein sometimes illustrate different components contained within or connected to different other components. It should be understood that such depicted architectures are merely exemplary, and in fact, many other architectures can be implemented to achieve the same functionality. In a conceptual sense, any arrangement of components achieving the same function is effectively “associated” to achieve the desired functionality. Therefore, any two components combined herein to achieve a particular function can be considered “associated” with each other to achieve the desired functionality, regardless of the architecture or intermediate components. Similarly, any two such associated components can also be considered “operably connected” or “operably linked” with each other to achieve the desired functionality, and any two components that can be suchly associated can also be considered “operably linked” with each other to achieve the desired functionality. Specific examples of operable linkage include, but are not limited to, physically matchable and / or physically interacting components, and / or wirelessly interactive and / or wirelessly interacting components, and / or logically interacting and / or logically interactive components.

[0141] In some cases, more than one component may be referred to herein as “constructed as,” “constructed by,” “constructible as,” “operable / runnable to,” “adaptable / adaptable,” “capable of,” “compliant / compliant,” etc. Those skilled in the art will recognize that, unless the context otherwise requires, such terms (e.g., “constructed as”) can generally cover components in an active state and / or components in an inactive state and / or components in a standby state.

[0142] While specific aspects of the subject matter described herein have been shown and described, it will be apparent to those skilled in the art that, based on the teachings herein, changes and modifications can be made without departing from the subject matter and its broader aspects, and therefore the appended claims are intended to cover within their scope all such changes and modifications that fall within the true spirit and scope of the subject matter described herein. It will be understood by those skilled in the art that, in general, the terminology used herein, particularly in the appended claims (e.g., the terms used in the appended claims), is generally intended as “open” terms (e.g., the term “comprising” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “at least having,” the term “including” should be interpreted as “including but not limited to,” etc.).

[0143] Those skilled in the art will further understand that if a particular number of claims is intended to be included, this intention will be explicitly stated in the claims, and the absence of such a statement indicates the absence of such intention. For example, to aid understanding, the appended claims may contain the use of the introductory phrases “at least one” and “more than one” to introduce the claims. However, the use of such phrases should not be construed as implying that introducing a claim with the indefinite article “a” or “an” limits any particular claim containing such an introduction to a claim containing only one such claim, even when the same claim contains the introductory phrases “more than one” or “at least one” and indefinite articles such as “a” and “an” (e.g., “a” and / or “an” should generally be interpreted as meaning “at least one” or “more than one”); the same applies to the use of definite articles used to introduce the claims.

[0144] Furthermore, even if a specific number is explicitly stated in the introduced claims, those skilled in the art will recognize that such a statement should generally be interpreted as meaning at least the number stated (e.g., in the absence of other modifiers, simply stating "two statements" generally means at least two statements, or more than two statements).

[0145] Furthermore, in cases where conventions such as "at least one of A, B, and C" are used, this construction is generally intended in the sense that a person skilled in the art would understand from that convention (e.g., "a system having at least one of A, B, and C" includes, but is not limited to, systems having only A, only B, only C, both A and B, both A and C, both B and C, and / or systems having A, B, and C, etc.). In cases where conventions such as "at least one of A, B, or C" are used, this construction is generally intended in the sense that a person skilled in the art would understand from that convention (e.g., "a system having at least one of A, B, and C" includes, but is not limited to, systems having only A, only B, only C, both A and B, both A and C, both B and C, and / or systems having A, B, and C, etc.). A person skilled in the art will further understand that, generally, whether in the specification, claims, or drawings, the presentation of separate words and / or phrases containing two or more alternative terms should be understood to consider the possibility of including one, any one, or both of the terms, unless the context otherwise requires. For example, the phrase “A or B” is often understood to include the possibility of “A” or “B” or “A and B”.

[0146] Regarding the appended claims, those skilled in the art will understand that the operations described herein can generally be performed in any order. Furthermore, although the various operational flows are presented in one or more orders, it should be understood that the various operations can be performed in a different order than those shown, or can be performed simultaneously. Unless the context otherwise specifies, examples of such alternating ordering can include overlapping, interleaving, interrupting, rearranging, incremental, preparatory, supplementary, simultaneous, reverse, or other variations of ordering. Furthermore, unless the context otherwise specifies, terms such as "in response to," "related to," or other past tense adjectives generally do not exclude such variations.

[0147] Those skilled in the art will understand that the specific exemplary processes and / or equipment and / or techniques described above represent more general processes and / or equipment and / or techniques taught elsewhere herein (such as in the claims filed herein and / or other parts of this application).

[0148] While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for illustrative purposes only and are not intended to be limiting, wherein the true scope and spirit are indicated by the appended claims.

[0149] The illustrative embodiments described in the detailed specifications, drawings, and claims are not intended to be limiting. Other embodiments and modifications may be used without departing from the spirit or scope of the subject matter presented herein.

[0150] Where a range of values ​​is provided, unless the context explicitly specifies otherwise, every intermediate value between the upper and lower limits of that range (to one-tenth of the unit of the lower limit), as well as any other values ​​or intermediate values ​​within that range, is included in the disclosure. The upper and lower limits of these smaller ranges may be independently included within those smaller ranges, which are also included in the disclosure (subject to any specific exclusions within the stated range). Where the stated range includes one or both of the included limitations, the range excluding one or both of those included limitations is also included in the disclosure.

[0151] Those skilled in the art will recognize that, for clarity of concept, the components (e.g., operations), devices, objects, and accompanying discussions described herein are used as examples, and various construction modifications are contemplated. Therefore, as used herein, the specific examples and accompanying discussions are intended to represent their more general categories. In general, the use of any specific example intended to represent its category, and the omission of specific components (e.g., operations), devices, and objects, should not be considered limiting.

[0152] Furthermore, for example, any one or more orders and / or chronological order of the systems and methods described herein are illustrative and should not be construed as inherently limiting. Therefore, it should be understood that process steps may be shown and described in order or chronological sequence, but they are not necessarily limited to being performed in any particular order or sequence. For example, steps in such processes or methods can often be performed in a variety of different orders and sequences while still falling within the scope of this disclosure.

[0153] Finally, the publications and / or patents discussed herein are provided only for their disclosures prior to the application date of the disclosed content. Nothing in this document should be construed as an admission that the disclosed content was not entitled to precede that publication by virtue of prior disclosure.

Claims

1. A semiconductor wafer polishing composition, comprising: Surface-modified single-crystal diamond, wherein the D(50) particle size ranges from about 0.10 µm to about 1 µm; The carrier, selected from the group consisting of aqueous carriers, glycol carriers, oil carriers, and hydrocarbon carriers; and Choose one or more additives.

2. The semiconductor wafer polishing composition according to claim 1, wherein the surface-modified single-crystal diamond has a D(50) particle size ranging from about 0.25 µm to about 0.50 µm.

3. The semiconductor wafer polishing composition according to claim 1, wherein the surface-modified single-crystal diamond has a D(50) particle size ranging from about 0.25 µm to about 0.75 µm.

4. The semiconductor wafer polishing composition according to claim 3, wherein the surface-modified single-crystal diamond has a D(50) particle size ranging from about 0.50 µm to about 0.75 µm.

5. The semiconductor wafer polishing composition according to claim 1, wherein the surface-modified single-crystal diamond has a D(50) particle size ranging from about 0.75 µm to about 1 µm.

6. The semiconductor wafer polishing composition according to claim 1, wherein the one or more additives are selected from the group consisting of dispersants, pH adjusters, pH buffers, surfactants, polymers, complexing agents, rheology modifiers, chelating agents, defoamers, wetting agents, oxidants, and biocides.

7. The semiconductor wafer polishing composition according to claim 1, wherein the silicon carbide (SiC) material removal rate ranges from about 1.3 µm / hour to about 8.2 µm / hour.

8. The semiconductor wafer polishing composition of claim 7, wherein the SiC material removal rate ranges from about 1.3 µm / h to about 7.2 µm / h.

9. The semiconductor wafer polishing composition of claim 8, wherein the SiC material removal rate ranges from about 1.3 µm / hour to about 3.3 µm / hour.

10. The semiconductor wafer polishing composition of claim 8, wherein the SiC material removal rate ranges from about 3.3 µm / h to about 7.2 µm / h.

11. The semiconductor wafer polishing composition of claim 7, wherein the SiC material removal rate ranges from about 3.3 µm / h to about 8.2 µm / h.

12. The semiconductor wafer polishing composition of claim 11, wherein the SiC material removal rate ranges from about 7.2 µm / h to about 8.2 µm / h.

13. The semiconductor wafer polishing composition of claim 7, wherein the material removal rate of the SiC is increased by about 185% to about 245% compared to a polishing composition comprising single-crystal diamond particles or polycrystalline diamond particles.

14. The semiconductor wafer polishing composition according to claim 1, wherein when the D(50) particle size range of the surface-modified single-crystal diamond is from about 0.25 µm to about 1 µm, the surface roughness of the SiC wafer is substantially similar to or lower than that of a SiC wafer polished with a polishing composition comprising single-crystal diamond particles or polycrystalline diamond particles.

15. The semiconductor wafer polishing composition of claim 1, wherein the surface-modified single-crystal diamond is present at a weight of about 0.5% by weight (wt.%) to about 5% by weight, based on the total weight of the polishing composition.

16. The semiconductor wafer polishing composition of claim 15, wherein the surface-modified single-crystal diamond is present at a weight of about 0.5% to about 2.5% based on the total weight of the polishing composition.

17. The semiconductor wafer polishing composition of claim 1, wherein the carrier is present in a volume of about 10% to about 70% based on the total volume of the polishing composition.

18. The semiconductor wafer polishing composition according to claim 7, wherein the SiC is single-crystal SiC.

19. The semiconductor wafer polishing composition of claim 1, wherein the surface-modified single-crystal diamond comprises one or more spikes and one or more pits.

20. The semiconductor wafer polishing composition according to claim 1, wherein the semiconductor wafer polishing composition is free of potassium permanganate.

21. A method for polishing the surface of a semiconductor wafer, comprising: The surface of the semiconductor wafer is brought into contact with a polishing pad to which a polishing composition is applied, the polishing composition comprising: Surface-modified single-crystal diamond, wherein the surface-modified single-crystal diamond has a D(50) particle size range of about 0.10 µm to about 1 µm; a support selected from the group consisting of aqueous supports, glycol supports, oil supports and hydrocarbon supports; and one or more optional additives; The polishing pad on which the polishing composition is applied is moved relative to the semiconductor wafer; and At least a portion of the semiconductor wafer is ground to polish the semiconductor wafer.

22. The method for polishing the surface of a semiconductor wafer according to claim 21, wherein the silicon carbide (SiC) material removal rate ranges from about 1.3 µm / hour to about 8.2 µm / hour.

23. The method for polishing the surface of a semiconductor wafer according to claim 22, wherein the material removal rate of the SiC ranges from about 1.3 µm / hour to about 7.2 µm / hour.

24. The method for polishing the surface of a semiconductor wafer according to claim 23, wherein the material removal rate of the SiC ranges from about 1.3 µm / hour to about 3.3 µm / hour.

25. The method for polishing the surface of a semiconductor wafer according to claim 23, wherein the material removal rate of the SiC ranges from about 3.3 µm / hour to about 7.2 µm / hour.

26. The method for polishing the surface of a semiconductor wafer according to claim 22, wherein the material removal rate of the SiC ranges from about 3.3 µm / hour to about 8.2 µm / hour.

27. The method for polishing the surface of a semiconductor wafer according to claim 26, wherein the material removal rate of the SiC ranges from about 7.2 µm / hour to about 8.2 µm / hour.

28. The method for polishing the surface of a semiconductor wafer according to claim 22, wherein the material removal rate of the SiC is increased by about 185% to about 245% compared to a polishing composition comprising single-crystal diamond particles or polycrystalline diamond particles.

29. The method for polishing the surface of a semiconductor wafer according to claim 21, wherein when the D(50) particle size range of the surface-modified single-crystal diamond is from about 0.25 µm to about 1 µm, the surface roughness of the SiC wafer is substantially similar to or lower than that of a SiC wafer polished with a polishing composition comprising single-crystal diamond particles or polycrystalline diamond particles.

30. The method for polishing the surface of a semiconductor wafer according to claim 22, wherein the SiC is single-crystal SiC.

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