Diamond-based polishing composition with improved silicon carbide removal rate

Abstract

Provided is a polishing composition for polishing the surface of a semiconductor wafer, comprising: surface-modified single-crystal diamond having a D(50) particle size in the range of approximately 0.10 μm to approximately 1 μm; a vehicle selected from the group consisting of an aqueous vehicle, a glycol-based vehicle, an oil-based vehicle, and a hydrocarbon-based vehicle; and one or more additives optionally selected. Further provided are related methods for polishing the surface of a semiconductor wafer.

Description

[Technical Field]

[0001] This disclosure relates to a diamond-based slurry composition for polishing the surface of a semiconductor wafer, and related methods for polishing the surface of a semiconductor wafer. [Background technology]

[0002] To achieve a significant reduction in power consumption, there is a strong demand for semiconductor wafers that can operate more efficiently. One industrial area being studied is the polishing of semiconductor wafer surfaces by a process known as chemical mechanical polishing (CMP) in the electronics industry, in which a slurry acts both mechanically and chemically to remove interfering deposited materials and particles from the semiconductor wafer surface.

[0003] In summary, the semiconductor manufacturing process centers on polishing the semiconductor wafer surface to achieve an attractive, smooth surface and obtaining precise dimensions relative to the semiconductor wafer surface.

[0004] The manufacturing process for semiconductor wafers includes a CMP (Chemical Polishing) process as the final step. This process yields a semiconductor wafer surface from which surface defects introduced in previous grinding cycles have been substantially removed, and furthermore, a semiconductor wafer surface that can be used immediately by end users. However, this process has inherent problems that cannot be ignored, namely, the fact that it primarily uses slurries, which are expensive, environmentally harmful, and result in unfavorable low material removal rates. Moreover, since the CMP process takes several hours to complete, there is another drawback: it consumes large quantities of expensive and environmentally harmful slurries.

[0005] Current common methods for manufacturing semiconductor wafers typically incorporate a CMP (Chemical Polishing) process after the fine grinding process or during the final lapping process. At the end of these two processes, the surface roughness of the semiconductor wafer is typically in the range of approximately 1.5 nm to 3 nm. The CMP process is then used to reduce the surface roughness to approximately 0.5 nm, or sometimes even less. In short, polishing processes using currently available CMP slurries formulated specifically for semiconductor wafers have the drawback of taking several hours to complete. CMP slurries are expensive, and the use of associated harsh chemicals that affect the removal speed and surface quality of the semiconductor wafer naturally imposes significant constraints on their use. Therefore, the electronics industry desires the introduction of optimized polishing solutions and processes. With this in mind, the electronics sector is continuously exploring adaptable polishing processes and compositions that will allow end-users to either completely eliminate the CMP process or significantly reduce the time and typically required CMP slurry consumption. This will ultimately lead to lower process costs, optimized lower cycle times, and improved throughput.

[0006] In light of the above, there is a need for a polishing composition and polishing process that is not complicated, does not require much time or cost, does not contain harsh chemicals to optimize the polishing cycle of the semiconductor wafer surface, achieves a high material removal rate from the semiconductor wafer surface, and simultaneously reduces the surface roughness of the semiconductor wafer to a level equivalent to CMP quality. [Overview of the Initiative]

[0007] The provided product is a polishing composition for polishing the surface of a semiconductor wafer, comprising: surface-modified single-crystal diamond having a D(50) particle size in the range of approximately 0.10 μm to approximately 1 μm; a vehicle selected from the group consisting of an aqueous vehicle, a glycol-based vehicle, an oil-based vehicle, and a hydrocarbon-based vehicle; and one or more additives optionally.

[0008] Selectively, the D(50) particle size of surface-modified single-crystal diamond is in the range of approximately 0.25 μm to approximately 0.50 μm.

[0009] Selectively, the D(50) particle size of surface-modified single-crystal diamond ranges from approximately 0.25 μm to approximately 0.75 μm.

[0010] Selectively, the D(50) particle size of surface-modified single-crystal diamond ranges from approximately 0.50 μm to approximately 0.75 μm.

[0011] Selectively, the D(50) particle size of surface-modified single-crystal diamond ranges from approximately 0.75 μm to approximately 1 μm.

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

[0013] Selectively, the material removal rate of silicon carbide (SiC) ranges from approximately 1.3 μm / hr to approximately 8.2 μm / hr.

[0014] Selectively, the material removal rate of SiC ranges from approximately 1.3 μm / hr to approximately 7.2 μm / hr.

[0015] Selectively, the material removal rate of SiC ranges from approximately 1.3 μm / hr to approximately 3.3 μm / hr.

[0016] Selectively, the material removal rate of SiC ranges from approximately 3.3 μm / hr to approximately 7.2 μm / hr.

[0017] Selectively, the material removal rate of SiC ranges from approximately 3.3 μm / hr to approximately 8.2 μm / hr.

[0018] Selectively, the material removal rate of SiC ranges from approximately 7.2 μm / hr to approximately 8.2 μm / hr.

[0019] Optionally, the material removal rate of SiC is increased in the range of about 185% to about 245% compared to a polishing composition containing single crystal diamond particles or polycrystalline diamond particles.

[0020] Optionally, when the D(50) particle size of the surface-modified single crystal diamond is in the range of about 0.25 μm to about 1 μm, the surface roughness of the SiC wafer is substantially the same as or lower than the surface roughness 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 in a weight of about 0.5 weight percent (wt%) to about 5 wt% based on the total weight of the polishing composition.

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

[0023] Optionally, the vehicle is present in a volume of about 10 volume percent (vol%) to about 70 vol% 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 includes one or more spikes and one or more pits.

[0026] Optionally, the semiconductor wafer polishing composition does not contain potassium permanganate.

[0027] Further provided is a method for polishing the surface of a semiconductor wafer, including contacting the surface of the semiconductor wafer with a polishing pad coated with the aforementioned polishing composition. The polishing pad coated with the polishing composition is then moved relative to the semiconductor wafer. Finally, at least a portion of the semiconductor wafer is worn away and the semiconductor wafer is polished.

[0028] Other systems, methods, features, and advantages will be apparent or will become apparent to those of ordinary skill in the art upon examination of the following drawings and detailed description. All such additional systems, methods, features, and advantages are included within this specification, are within the scope of the present disclosure, and are intended to be protected by the following claims. Any content of this section should not be construed as limiting these claims. Further aspects and advantages will be considered below in conjunction with embodiments of the present disclosure. It should be understood that both the foregoing general description of the present disclosure and the following detailed description are exemplary and explanatory and are intended to further explain the disclosure as claimed.

Brief Description of the Drawings

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

[0030] [Figure 1A] FIG. 1A shows an exemplary microstructure of a surface-modified single-crystal diamond crystal according to an exemplary embodiment of the subject matter.

[0031] [Figure 1B] FIG. 1B shows an exemplary microstructure of a single-crystal diamond crystal according to an exemplary embodiment of the subject matter.

[0032] [Figure 2] FIG. 2 is a flowchart showing individual process steps for polishing the surface of a semiconductor wafer according to an exemplary embodiment of the subject matter.

[0033] [Figure 3]Figure 3 shows, according to exemplary embodiments of this subject, the following polishing compositions are used: (I) a polishing composition using surface-modified single-crystal diamond (Smmd) having a D(50) particle size in the range of approximately 0.25 μm to approximately 1 μm; (II) a polishing composition using single-crystal diamond having a D(50) particle size in the range of approximately 0.25 μm to approximately 1 μm; or (III) a polishing composition using polycrystalline diamond having a D(50) particle size in the range of approximately 0.25 μm to approximately 1 μm: (i) the material removal rate of silicon carbide from the silicon carbide wafer (vertical bar) on the left y-axis and (ii) the surface roughness (black filled dot) on the right y-axis. [Modes for carrying out the invention]

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art in the field relating to the subject matter described herein.

[0035] Where a range of values ​​is indicated, such as a concentration range, percentage range, or ratio range, unless otherwise explicitly stated in the context, each intermediate value between the upper and lower limits of that range and any other stated or intermediate values ​​within that range is understood to be included in the stated subject, up to one-tenth of the lower limit. The upper and lower limits of these narrower ranges may independently be included in even narrower ranges, and such embodiments are also included in the stated subject, except for limits that are specifically excluded within the stated range. If a stated range includes one or both limits, the range that excludes either or both of those limits is also included in the stated subject.

[0036] The following definitions describe the parameters of the subject matter described.

[0037] As used in this disclosure, the term “diamond particle” refers to a discrete material made of diamond. As used in this disclosure, the term “diamond particle” may also be interpreted as a diamond crystal or diamond grain.

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

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

[0040] Where used in this disclosure, the term “material removal” refers to the weight of the workpiece removed over a given period of time, reported in milligrams, grams, etc.

[0041] Where used in this disclosure, the term “material removal rate” refers to the amount of material removed divided by a time interval, for example, the amount of material removed from the surface of a semiconductor wafer, reported in microns / hour, milligrams / minute, or grams / hour.

[0042] As used in this disclosure, the term “single-crystal diamond” refers to diamond having an overall flat structural surface formed by high-pressure, high-temperature (HPHT) compaction operations, or naturally formed diamond. Fracture of single-crystal diamond proceeds along the atomic cleavage planes. Single-crystal diamond particles are relatively easily fractured along the cleavage planes.

[0043] As used in this disclosure, the term “polycrystalline diamond” refers to diamond formed by explosive synthesis, resulting in a polycrystalline grain structure. Each polycrystalline diamond grain may contain numerous microcrystals less than approximately 100 angstroms in size. Polycrystalline diamond grains have no cleavage planes.

[0044] Where used in this disclosure, the terms “superabrasive superhard material” or simply “superabrasive” refer to an abrasive material exhibiting superior hardness and wear resistance, typically exhibiting a Knoop-pressure hardness greater than 2000, and are found in, but are not limited to, crystalline diamond, polycrystalline diamond (PCD), thermally stable polycrystalline diamond, chemically vapor-deposited (CVD) diamond, metal matrix diamond composites, ceramic matrix diamond composites, nanodiamond, cubic boron nitride (cBN), polycrystalline cubic boron nitride (PcBN), or any combination thereof. Where used herein, the term “abrasive” refers to any material used to abrade softer materials.

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

[0046] As used in this disclosure, the term “surface-modified single-crystal diamond” typically refers to diamond made from a unique, chemically artificially manufactured or synthesized diamond crystal that provides improved performance in terms of material removal rate from the semiconductor wafer surface during polishing compared to, for example, single-crystal or polycrystalline diamond. The unique irregular surface properties of the surface-modified single-crystal diamonds disclosed herein suitably result in a remarkable material removal rate from the semiconductor wafer surface. Furthermore, they encompass the additional advantage of imparting a superior surface finish to the semiconductor wafer surface due to their unique characteristic polyhedral diamond surface. This unique irregular surface provides multiple small spikes and pits, reducing the surface roughness of the polished semiconductor wafer.

[0047] As used in this disclosure, the term “polyhedron” refers to a set of edges located around a flat face.

[0048] As used in this disclosure, the term “surface roughness” refers to a two-dimensional image measurement that quantifies the extent or degree of pits and spikes on the surface, edges, and boundaries of an object, as described in the CLEMEX Image Analysis System, Clemex Vision User's Guide PE3.5, 2001. Surface roughness is determined by the ratio of the perimeter of the protrusions to the perimeter.

[0049] Surface roughness = Circumference of protrusion / Circumference

[0050] As the degree of pitting and spikes increases, the surface roughness coefficient decreases.

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

[0052] Sphericity=4πA / p 2

[0053] The surface roughness of a semiconductor is an important factor when considering the electrical properties of a semiconductor wafer. The electron mobility in a semiconductor wafer is partially influenced by the thickness of the semiconductor wafer surface and the size and shape of its surface edges. Polishing the semiconductor wafer surface has the advantage of transforming an inherently dull, rough surface into a surface that is substantially flat, smooth, and mirror-like, with virtually no particles that would adversely affect the overall electronic behavior 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 boundaries of a two-dimensional image.

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

[0056] As used in this disclosure, the term “pit” refers to a recess or gap in a particle, a recess or gap in a two-dimensional image, or a recess or gap in an object.

[0057] As used in this disclosure, the term “spike” refers to a sharp projection or protrusion that points outward from the center of mass of a particle, a sharp projection or protrusion that points outward from the center of mass of a two-dimensional image, or a sharp projection or protrusion that points outward from an object.

[0058] As used in this disclosure, the term “surface area” refers to the outer surface of a particle. When used for multiple particles, i.e., a powder, the term “specific surface area” is used and reported as the surface area per gram of powder.

[0059] Where used in this disclosure, the term “about” means plus or minus 5% of the numerical values ​​in the claims and in this disclosure. Thus, “about” can be used to give flexibility to the endpoints of a numerical range, and a given value may be “above” or “below” that given value. For example, the value 50% could be, for example, 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%~51.75%, 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%~51.5%, 4 8.25%~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 It may be intended to encompass ranges that can be defined as 0.25%, 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%, etc.

[0060] As used in this disclosure, the term "D(50)" refers to the particle size that corresponds to the case where 50% of the volume of the collected particles is less than the stated D(50) value and 50% of the volume of the collected particles is greater than the stated D(50) value.

[0061] As used in this disclosure, the term "D(99)" refers to the particle size that corresponds to the case where 99% of the volume of the collected particles is less than the stated D(99) value, and 1% of the volume of the collected particles is greater than the stated D(99) value.

[0062] When used throughout this disclosure, the term “generally” means “typically,” “approximately,” or “nearby or within the scope.”

[0063] Where used in this disclosure, the term “substantially” means the full or near full range or extent of the action, characteristic, nature, state, structure, item, or result. This means including plus or minus 6.25% of the numerical values ​​used in the claims and other parts of this disclosure.

[0064] As used in this disclosure, 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 understand that surfactants may generally include, but are not limited to, a class of chemical components such as 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 “rheological modifier” refers to a compound added to an abrasive composition forming a diamond slurry to increase its viscosity and control its fluidity.

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

[0069] As used in this disclosure, “chemical vapor deposition (CVD)” refers to a method of exposing a substrate to one or more volatile precursors, which react and / or decompose on the substrate surface to produce a desired deposit. Often, volatile byproducts are also produced, which are removed by a gas flow through the reaction chamber.

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

[0071] This disclosure is based on the premise of presenting a polishing composition containing 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 a favorably high rate of material removal from the semiconductor wafer surface and the additional advantage of reducing the surface roughness of the semiconductor wafer to a quality equivalent to chemical mechanical polishing (CMP) in a shorter time. Furthermore, the manufacturing of the semiconductor polishing composition is inexpensive, and even more favorably, the polishing composition does not contain any harmful chemicals, thus optimizing the entire post-formation polishing cycle of the semiconductor wafer.

[0072] The abrasive composition may typically contain surface-modified single-crystal diamond having a D(50) particle size in the range of about 0.10 μm to about 1 μm. In some examples, the abrasive composition contains surface-modified single-crystal diamond having a D(50) particle size in the range of about 0.25 μm to about 1 μm. In other examples, the abrasive composition contains surface-modified single-crystal diamond having a D(50) particle size in the range of about 0.35 μm to about 1 μm. In yet another example, the abrasive composition contains surface-modified single-crystal diamond having a D(50) particle size in the range of about 0.45 μm to about 1 μm. In yet another example, the abrasive composition contains surface-modified single-crystal diamond having a D(50) particle size in the range of about 0.55 μm to about 1 μm. In yet another example, the abrasive composition contains surface-modified single-crystal diamond having a D(50) particle size in the range of about 0.65 μm to about 1 μm. In yet another example, the abrasive composition comprises surface-modified single-crystal diamond having a D(50) particle size in the range of about 0.75 μm to about 1 μm. In yet another example, the abrasive composition comprises surface-modified single-crystal diamond having a D(50) particle size in the range of about 0.85 μm to about 1 μm. In yet yet another example, the abrasive composition comprises surface-modified single-crystal diamond having a D(50) particle size in the range of about 0.95 μm to about 1 μm.

[0073] The abrasive composition is available in the following ranges: approximately 0.10 μm to approximately 0.25 μm, approximately 0.25 μm to approximately 0.35 μm, approximately 0.10 μm to approximately 0.35 μm, approximately 0.35 μm to approximately 0.45 μm, approximately 0.45 μm to approximately 0.55 μm, approximately 0.25 μm to approximately 0.45 μm, approximately 0.25 μm to approximately 0.55 μm, approximately 0.35 μm to approximately 0.55 μm, approximately 0.55 μm to approximately 0.65 μm, approximately 0.65 μm to approximately 0.75 μm, approximately 0.75 μm to approximately 0.85 μm, and approximately 0.25 μm to approximately 0.85 μm. The ranges are approximately 0.30 μm to 0.85 μm, 0.35 μm to 0.85 μm, 0.40 μm to 0.85 μm, 0.45 μm to 0.85 μm, 0.50 μm to 0.85 μm, 0.55 μm to 0.85 μm, 0.60 μm to 0.85 μm, 0.65 μm to 0.85 μm, 0.70 μm to 0.85 μm, 0.80 μm to 0.85 μm, 0.25 μm to 0.90 μm, 0.30 μm to 0.90 μm, and approximately 0. The ranges are approximately 35 μm to 0.90 μm, approximately 0.40 μm to 0.90 μm, approximately 0.45 μm to 0.90 μm, approximately 0.50 μm to 0.90 μm, approximately 0.55 μm to 0.90 μm, approximately 0.60 μm to 0.90 μm, approximately 0.65 μm to 0.90 μm, approximately 0.70 μm to 0.90 μm, approximately 0.75 μm to 0.90 μm, approximately 0.80 μm to 0.90 μm, approximately 0.85 μm to 0.90 μm, approximately 0.25 μm to 0.95 μm, and approximately 0.30 μm. The ranges are approximately 0.95 μm, 0.35 μm to 0.95 μm, 0.40 μm to 0.95 μm, 0.45 μm to 0.95 μm, 0.50 μm to 0.95 μm, 0.55 μm to 0.95 μm, 0.60 μm to 0.95 μm, 0.65 μm to 0.95 μm, 0.70 μm to 0.95 μm, 0.75 μm to 0.95 μm, 0.80 μm to 0.95 μm, 0.85 μm to 0.95 μm, or 0.90 μm to 0.It may also include surface-modified single-crystal diamond having a D(50) particle size in the range of 95 μm.

[0074] To determine a specific diamond particle size, those skilled in the art can typically use one of the following methods: dynamic digital image analysis (DIA), static laser scattering (SLS), also known as laser diffraction, or visual measurement using an electron microscope, a technique known as image analysis and light shielding. Each method covers a specific size range that can be measured. These ranges partially overlap. However, the results of measuring the same sample may all be different depending on the specific method used. A skilled technician wishing to determine the particle size distribution will readily understand how each of the above methods is generally implemented and put into practice. Readers can gain further insight into each procedure and methodology by referring, for example, (i) "Comparison of Methods: Dynamic Digital Image Analysis, Laser Diffraction, Sieve Analysis," Retsch Technology, and (ii) the scientific publication by Kelly et al., "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, all of which are incorporated herein by reference with proper attribution.

[0075] The polishing composition may generally contain surface-modified single-crystal diamond present in an amount of about 0.5% by weight (wt%) to about 5% by weight based on the total weight of the polishing composition. In some examples, the surface-modified single-crystal diamond present in an amount of about 1% by weight to about 5% by weight based on the total weight of the polishing composition. In other examples, the surface-modified single-crystal diamond present in an amount of about 1.5% by weight to about 5% by weight based on the total weight of the polishing composition. In yet another example, the surface-modified single-crystal diamond present in an amount of about 2% by weight to about 5% by weight based on the total weight of the polishing composition. In yet another example, the surface-modified single-crystal diamond present in an amount of about 2.5% by weight to about 5% by weight based on the total weight of the polishing composition. In yet another example, the surface-modified single-crystal diamond present in an amount of about 3% by weight to about 5% by weight based on the total weight of the polishing composition. In yet another example, the surface-modified single-crystal diamond present in an amount of about 3.5% by weight to about 5% by weight based on the total weight of the polishing composition. In yet another embodiment, the surface-modified single-crystal diamond is present in an amount of about 4% to about 5% by weight based on the total weight of the polishing composition. In yet another embodiment, the surface-modified single-crystal diamond is present in an amount of about 4.5% to about 5% by weight based on the total weight of the polishing composition.

[0076] The abrasive composition is available in approximately 0.5% to 1% by weight, approximately 1% to 1.5% by weight, approximately 1.5% to 2% by weight, approximately 0.5% to 1.5% by weight, approximately 0.5% to 2% by weight, approximately 1% to 2% by weight, approximately 1% to 2.5% by weight, approximately 1.5% to 2.5% by weight, approximately 1% to 3% by weight, approximately 1.5% to 3% by weight, and approximately 2% by weight. It may also include surface-modified single-crystal diamond present in weights of approximately 2.5% to 2.5% by weight, approximately 2.5% to 3% by weight, approximately 3% to 3.5% by weight, approximately 2% to 3% by weight, approximately 2% to 3.5% by weight, approximately 2% to 4% by weight, approximately 2.5% to 4% by weight, approximately 3% to 4% by weight, approximately 3.5% to 4% by weight, or approximately 3.5% to 4.5% by weight.

[0077] The surface-modified single-crystal diamonds disclosed herein include unique artificial or synthetic diamond crystals that typically offer improved performance compared to, for example, common single-crystal or polycrystalline diamonds. The unique irregular surface properties of the surface-modified single-crystal diamonds disclosed herein suitably enable a remarkable material removal rate from semiconductor wafers, and additionally, the unique characteristic multifaceted diamond surface provides the advantage of excellent surface finish on the semiconductor wafer surface. This unique irregular surface provides small cutting points, reducing the overall surface roughness of the semiconductor wafer.

[0078] Now, directing the reader's attention to the drawings, this is best observed in Figure 1A, which shows the exemplary microstructure of the chemically surface-modified single-crystal diamond 10 disclosed herein. Unique small spikes, specifically tuned to facilitate optimized material removal, are indicated by reference numeral 12 in Figure 1A. This is in striking contrast to a typical single-crystal diamond crystal 14, which has a substantially flat structural surface 16, for example, as shown in Figure 1B. Thus, at least due to the multifaceted surface signature that is completely absent on the surface 16 of the single-crystal diamond crystal 14, the material removal rate when using the single-crystal diamond crystal 14 is also simultaneously limited and significantly inhibited compared to the surface-modified single-crystal diamond crystal 10 disclosed herein and shown in Figure 1A. Furthermore, as shown in Figure 1A, the surface-modified single-crystal diamond particles 10 inherently exhibit spikes 12 and pits 11, which are clearly absent in the typical single-crystal diamond 14 shown in Figure 1B. The essential function of the spikes 12 is, in particular, that they act as cutting edges when used in free abrasive slurry applications. Surface-modified single-crystal diamond particles 10 have been found to exhibit significantly improved performance when used in free abrasive lapping applications in liquid slurries or suspensions. When 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 parameters. The average depth of the pits 11 on the diamond particles 10 is typically in the range of approximately 5% to 70% of the longest length of the surface-modified single-crystal diamond particles 10. Surface-modified single-crystal diamond particles 10 also exhibit unique properties in surface roughness, sphericity, and material removal. Surface-modified single-crystal diamond particles 10 exhibit a surface roughness of less than approximately 0.95. Surface roughness of approximately 0.50 to 0.80 and approximately 0.50 to 0.70 are also observed. The surface roughness of the surface-modified single-crystal diamond particles 10 is a function of the size of the metal particles, the amount of metal particles in contact with the diamond 10, the reaction time, and the temperature used in the process.As surface roughness increases, the material removal capability of the diamond particles 10 in the lapping process also increases. This is likely due to the increased number of cutting points that the surface modification process imparts to the diamond particles 10. Furthermore, the surface-modified single-crystal diamond particles 10 exhibit a sphericity of less than approximately 0.70. Sphericity values ​​of approximately 0.2 to 0.5 and approximately 0.25 to 0.40 are also observed. Although sphericity is a property independent of surface roughness, there is a positive correlation between the sphericity of the surface-modified single-crystal diamond particles 10 and the lapping performance. Furthermore, there is a positive correlation between the weight loss of the diamond particles 10 and the lapping performance. Therefore, as the weight loss of the diamond particles 10 increases, their ability to remove material from the surface of the semiconductor wafer becomes stronger. The aforementioned technical parameters are described in more detail in at least U.S. Patent Nos. 8182562B2; 8652226B2; and 8927101B2, which are incorporated herein by reference.

[0079] Next, we will describe the process for forming the surface-modified single-crystal diamond 10.

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

[0081] Further examples of metals that can be used as reactive coatings may be selected from metals, metal compounds, and combinations thereof that are at least in Group VIII of the periodic table. Other examples of materials that can be used as reactive coatings may include catalytic metals taught in U.S. Patent No. 2,947609 and U.S. Patent No. 2,947610, which are incorporated herein by reference in their entirety with due attribution.

[0082] In certain applications, nickel (Ni) metal coatings are used as reactive coatings. The metal coatings used typically consist of approximately 10% to 90% Ni by weight, or approximately 10% to 60% Ni by weight, with the remainder being diamond particles. However, it should be noted that these ratios are a matter of economic efficiency, not technical effectiveness. In some applications, the metal coating at least partially covers the diamond particles. Alternatively, the metal coating can uniformly surround each diamond particle. The metal does not need to be chemically bonded to the diamond. Nickel and / or nickel alloys may be used as the diamond coating. One method for applying nickel to diamond is electrolytic deposition. However, methods such as electroplating, physical vapor deposition (PVP), and chemical vapor deposition (CVD) can also be equally 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 60% by weight. In the coating process, uncoated diamond particles are first exposed to a colloidal palladium solution. Fine palladium particles are uniformly adsorbed onto the diamond surface, making the surface autocatalytically precipitation of nickel. In the next step of the process, the activated diamond is placed in a nickel sulfamate solution containing approximately 10 grams / liter of dissolved nickel. While mixing the activated diamond and nickel suspension, sodium subphosphate is added to the suspension, and the temperature of the coating bath is maintained at approximately 80°C. Upon addition of the sodium subphosphate solution, all of the dissolved nickel in the solution autocatalytically precipitates 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 / subphosphoric acid solution with a new solution and repeating this process. When uniformly coating particles, several cycles may be required to ensure sufficient and uniform nickel coverage on each diamond particle. By monitoring the number of cycles and controlling coating bath parameters such as temperature, pH, and mixing energy, the nickel content on the diamond can be reproduced. It is not uncommon for some degree of aggregation to occur on the coated diamond as a result of the interaction between the diamond particles and the nickel plating during coating. As long as the individual diamond particles containing aggregates contain a certain amount of nickel coating, the presence of diamond aggregates does not affect the quality of the process, and attempts to remove the aggregates are not necessary.

[0085] After coating diamond particles with nickel, the coated diamond particles are placed in a furnace and heated to approximately 650°C to 1000°C in a hydrogen atmosphere, vacuum atmosphere, or inert gas atmosphere. Temperatures of approximately 700°C to 950°C, or approximately 800°C to 900°C, can be commonly used. Nickel-coated diamonds can be heated for a period of time ranging from approximately 5 minutes to approximately 5 hours. Typically, periods ranging from approximately 30 minutes to approximately 2 hours, or approximately 1 hour to approximately 2 hours, can be used.

[0086] After the heating cycle is complete and the diamond particles have cooled, the nickel-coated surface-modified single-crystal diamond particles 10 are recovered by dissolving them in an acid. Typical acids that can be used may include hydrochloric acid, hydrofluoric acid, nitric acid, or a combination thereof. The acid, or a combination thereof, is added in a volume ratio of acid to coated diamond of 100:1 to 1000:1. The mixture is then heated to about 100°C to about 120°C for a period of about 6 to 8 hours. The solution is then cooled to precipitate the free surface-modified single-crystal diamond particles 10 and decant the solution. The acid washing and heating process can be repeated until substantially all of the metal coating has been decomposed.

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

[0088] Depending on the conditions of the selected furnace, a reaction may occur between the metal and the surface-modified single-crystal diamond particles 10 to a greater or lesser extent. The more nickel is etched into the surface-modified single-crystal diamond 10, the more graphite is undesirably formed, and therefore the weight loss of diamond increases. To completely dissolve the graphite, it may be necessary to use a larger amount of acid or to perform an additional dissolution treatment. Next, the surface-modified single-crystal diamond particles 10 are cleaned of acid and residue, for example, by washing in water. Subsequently, the surface-modified single-crystal diamond particles 10 are dried by oven drying, air drying, microwave drying, or other drying methods commonly known to those skilled in the art.

[0089] While nickel has been described as being used in the process of modifying the surface of diamond particles, other metals such as iron, or manganese, chromium, or their metallic compounds, or any combination thereof, can also be used for this purpose.

[0090] In another specified example of producing surface-modified diamond particles 10, approximately 10% to approximately 80% by weight of diamond particles and approximately 20% to approximately 90% by weight of iron particles are mixed using any suitable mixing method to achieve a homogeneous mixture. In one example, the weighed iron particles and diamond particles are placed in a jar, sealed, and placed in a mixing device such as a Turbula shaker mixer (Glen Mills, Inc., Clifton, NJ, USA) for at least approximately 1 hour, or approximately 30 minutes to approximately 1 hour. Before mixing, a binder may optionally be added to the mixture. The binder provides lubrication to the particle surface, increases the packing density between the metal powder and diamond, and allows for closer contact. The binder also helps to unify the molded body as a green body.

[0091] Next, the mixture is compressed to produce a dense mixture of diamond and iron particles. These particles can be compressed using any method well known to those skilled in the art, as long as they form a dense mixture and the particles are in close contact with each other. One method used to compress the mixture is to place it on a fixed die set on a press. An example of a suitable press is the Carver pellet press manufactured by Carver (Wabash, Ind.). In the die press, the mixture is subjected to pressures of approximately 5 psi to 50,000 psi, 10,000 psi to 40,000 psi, or 15,000 psi to 30,000 psi to form pellets. While pelletization of the mixture is taught, the mixture of diamond and iron particles does not need to be strictly pelletized; it is sufficient that the particles are compressed so that they are in close contact with each other. To achieve this tightness, isostatic or monostatic presses using deformable tools can also be used.

[0092] Alternatively, the diamond-iron mixture can be compressed into thin sheets several millimeters to several inches thick, i.e., by pressing them with high-pressure compression rolls or briquetting rolls. The formed sheets can then be cut into smaller pieces for further processing, as will be discussed below. Another method for compressing the iron-iron and diamond particle mixture involves mixing the mixture under pressure and then extruding it. Pelleting the diamond-iron and diamond particle mixture in a pelletizer or tumbling the mixture in a tumbling device are also alternative methods that can be used to compress the diamond-iron mixture. The pellets, bricks, or cakes formed by these methods can then be further processed, as will be discussed below.

[0093] Additional methods for compressing the mixture of iron and diamond particles may include injection molding, extrusion molding, press-fitting of the mixture into a container, or tape casting. Alternatively, individual diamond particles may be coated with metal particles by ion implantation, sputtering, spray drying, electrolytic coating, electroless coating, or any other applicable method, as long as the iron and diamond particles are in close contact with each other.

[0094] After compressing a mixture of diamond and iron particles, the compressed mixture, which may be in the form of pellets, aggregates, or other condensed forms, is placed in a furnace and heated to about 650°C to about 1000°C in a hydrogen atmosphere, vacuum atmosphere, or inert gas atmosphere. Typically, temperatures of about 700°C to about 900°C, or about 750°C to about 850°C can be used. The compressed mixture can be heated for a time of about 5 minutes to about 5 hours. Generally, times ranging from about 30 minutes to about 2 hours, or about 1 hour to about 2 hours can be used.

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

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

[0097] Depending on the conditions of the selected furnace, a reaction may occur between the metal and the surface-modified single-crystal diamond particles 10 to a greater or lesser extent. The more iron is etched into the surface-modified single-crystal diamond particles 10, the more graphite is formed, and thus the weight loss of diamond increases. To completely dissolve the graphite, more acid may be used, or additional dissolution treatment may be required. Next, the surface-modified single-crystal diamond particles 10 are washed to remove the acid and residue, for example, in water. The surface-modified single-crystal diamond particles 10 are then dried in the furnace, air-dried, microwave-dried, or subjected to other drying methods well known to those skilled in the art.

[0098] Abrasive compositions may typically include a vehicle selected from the group consisting of an aqueous vehicle, a glycol vehicle, such as ethylene glycol, propylene glycol, or a mixture thereof, an oil vehicle, or a hydrocarbon vehicle, and any desired combination thereof. The abrasive composition may include the aforementioned vehicle elements in any possible combination that is not inconsistent with or incompatible with any purpose of this subject, or in volume percent, for example, based on the total volume of the abrasive composition, about 10 to about 70 volume percent, about 15 to about 70 volume percent, about 20 to about 70 volume percent, about 25 to about 70 wt%, about 30 to about 70 volume percent, about 35 to about 70 volume percent, about 40 to about 70 volume percent, about 45 to about 70 volume percent, and about 50 wt%, respectively. From volume % to approximately 70 volume%, from approximately 55 volume% to approximately 70 volume%, from approximately 60 volume% to approximately 70 weight%, from approximately 65 volume% to approximately 70 volume%, from approximately 10 volume% to approximately 15 volume%, from approximately 10 volume% to approximately 20 volume%, from approximately 10 volume% to approximately 25 volume%, from approximately 10 volume% to approximately 30 volume%, from approximately 10 volume% to approximately 35 volume%, from approximately 10 volume% to approximately 40 volume%, from approximately 10 volume% to approximately 45 volume%, from approximately 10 volume% to approximately 50 volume%, from approximately 10 volume% to approximately 55 volume%, from approximately 10 volume% to approximately 60 Volume%, approximately 10 to 65 volumes, approximately 20 to 25 volumes, approximately 20 to 30 volumes, approximately 20 to 35 volumes, approximately 20 to 40 volumes, approximately 20 to 45 volumes, approximately 20 to 50 volumes, approximately 20 to 55 volumes, approximately 20 to 60 volumes, or approximately 20 to 65 volumes, approximately 30 to 35 volumes, approximately 30 to 40 volumes, approximately 30 to 45 volumes, It may contain approximately 30% to 50% by volume, approximately 30% to 55% by volume, approximately 30% to 60% by volume, approximately 30% to 65% by volume, approximately 40% to 45% by volume, approximately 40% to 50% by volume, approximately 40% to 55% by volume, approximately 40% to 60% by volume, approximately 40% to 65% by volume, approximately 50% to 55% by volume, approximately 50% to 60% by volume, approximately 50% to 65% by volume, or approximately 60% to 65% by volume.

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

[0100] In some examples, the aforementioned optional components may be water-soluble, alcohol-soluble, or solvent-soluble. In other examples, the aforementioned optional components may be water-dispersible, alcohol-dispersible, or solvent-dispersible, which typically include, but are not limited to, the following alcohols and solvents: ethanol, methanol, isopropanol, butanol, cyclohexanol, acetone, hexane, heptane, toluene, or any combination thereof. Such combinations may include, for example, water and alcohol, water and solvent, alcohol and yet another alcohol, or mixtures of alcohol and solvent.

[0101] In some examples, the abrasive compositions disclosed herein may be formed as a slurry. In other examples, the abrasive compositions disclosed herein may be formed as a suspension. In yet another example, the abrasive compositions disclosed herein may be formed as a dispersion. In yet another example, the abrasive compositions disclosed herein may be formed as a paste. However, polishing compositions prepared using surface-modified single-crystal diamond can be formulated in any type or form within the scope of the skill of those skilled in the art, resulting in silicon carbide (SiC) removal rates from the SiC wafer surface ranging from approximately 1.3 μm / hr to approximately 8.2 μm / hr, approximately 2.2 μm / hr to approximately 8.2 μm / hr, approximately 3.2 μm / hr to approximately 8.2 μm / hr, approximately 4.2 μm / hr to approximately 8.2 μm / hr, approximately 5.2 μm / hr to approximately 8.2 μm / hr, approximately 6.2 μm / hr to approximately 8.2 μm / hr, approximately 7.2 μm / hr to approximately 8.2 μm / hr, approximately 1.3 μm / hr to approximately 2.2 μm / hr, approximately 2.2 μm / hr to approximately 3.2 μm / hr, and approximately 3.2 μm / hr. The ranges are m / hr to approximately 4.2 μm / hr, approximately 1.3 μm / hr to approximately 4.2 μm / hr, approximately 2.2 μm / hr to approximately 4.2 μm / hr, approximately 3.2 μm / hr to approximately 4.2 μm / hr, approximately 4.2 μm / hr to approximately 5.2 μm / hr, approximately 4.2 μm / hr to approximately 6.2 μm / hr, and approximately 4.2 μm / hr to approximately 7.2 μm / hr. It should be emphasized that the ranges are approximately 5.2 μm / hr to 6.2 μm / hr, 6.2 μm / hr to 7.2 μm / hr, 1.3 μm / hr to 3.3 μm / hr, 1.3 μm / hr to 7.2 μm / hr, 3.3 μm / hr to 7.2 μm / hr, or 3.3 μm / hr to 8.2 μm / hr.

[0102] The abrasive composition may include, for example, a surfactant containing a dispersant and a wetting agent, for example, but not limited to, the following components: cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, or any mixtures and combinations thereof. The amount of surfactant in the abrasive composition is typically, based on the total weight of the abrasive composition, about 0.001% to about 0.05% by weight, about 0.001% to about 0.1% by weight, about 0.001% to about 0.5% by weight, about 0.001% to about 1% by weight, about 0.001% to about 1.5% by weight, about 0.001% to about 2% by weight, and about 0.001% to about 2.5% by weight. Weight %, approximately 0.001% to approximately 3% weight, approximately 0.0001% to approximately 1% weight, approximately 0.001% to approximately 0.1% weight, approximately 0.001% to approximately 0.2% weight, approximately 0.001% to approximately 0.3% weight, approximately 0.001% to approximately 0.4% weight, approximately 0.001% to approximately 0.6% weight, approximately 0.001% to approximately 0.7% weight, approximately 0.001% weight From approximately 0.8% by weight, from approximately 0.001% to approximately 0.9% by weight, from approximately 0.005% to approximately 0.1% by weight, from approximately 0.005% to approximately 0.2% by weight, from approximately 0.005% to approximately 0.3% by weight, from approximately 0.005% to approximately 0.4% by weight, from approximately 0.005% to approximately 0.5% by weight, from approximately 0.005% to approximately 0.6% by weight, from approximately 0.005% to approximately 0.7% by weight, approximately 0 It may range from 0.005% by weight to approximately 0.8% by weight, from approximately 0.005% by weight to approximately 0.9% by weight, from approximately 0.005% by weight to approximately 1% by weight, from approximately 0.005% by weight to approximately 0.05% by weight, from approximately 0.005% by weight to approximately 0.06% by weight, from approximately 0.005% by weight to approximately 0.07% by weight, from approximately 0.005% by weight to approximately 0.08% by weight, or from approximately 0.005% by weight to approximately 0.09% by weight.

[0103] The abrasive composition may further optionally include a low surface tension defoaming agent and a degassing agent. The defoaming agent may be any suitable defoaming agent, such as, but not limited to, silicone-based, siloxane, acetylenediol-based, mineral oil-based or other insoluble oils, polymethylsiloxane and other silicones, alcohols such as ethanol, methanol, isopropanol, butanol, cyclohexanol, stearate, hydrophobic polyol, hydrophobic silica, ethylenebisstearamide, fatty acids, fatty acid alcohols, glycol-based defoaming agents, etc.The concentration of the defoaming agent in the abrasive composition is typically about parts per million (ppm) to about 10 ppm, about 1 ppm to about 20 ppm, about 1 ppm to about 30 ppm, about 1 ppm to about 40 ppm, about 1 ppm to about 50 ppm, about 1 ppm to about 60 ppm, about 1 ppm to about 70 ppm, about 1 ppm to about 80 ppm, about 1 ppm to about 90 ppm, about 1 ppm to about 100 ppm, about 1 ppm to about 110 ppm, about 1 ppm to about 120 ppm, about 1 ppm to about 130 ppm, about 1 ppm to about 140 ppm, and about 1 ppm to approximately 150 ppm, approximately 10 ppm to approximately 150 ppm, approximately 20 ppm to approximately 150 ppm, approximately 30 ppm to approximately 150 ppm, approximately 40 ppm to approximately 150 ppm, approximately 50 ppm to approximately 150 ppm, approximately 60 ppm to approximately 150 ppm, approximately 70 ppm to approximately 150 ppm, approximately 80 ppm to approximately 150 ppm, approximately 90 ppm to approximately 150 ppm, approximately 100 ppm to approximately 150 ppm, approximately 110 ppm to approximately 150 ppm, approximately 120 ppm to approximately 150 ppm, approximately 130 ppm to approximately 150 ppm, approximately 14 0 ppm to approximately 150 ppm, approximately 10 ppm to approximately 20 ppm, approximately 15 ppm to approximately 20 ppm, approximately 20 ppm to approximately 25 ppm, approximately 20 ppm to approximately 30 ppm, approximately 25 ppm to approximately 30 ppm, approximately 30 ppm to approximately 35 ppm, approximately 30 ppm to approximately 40 ppm, approximately 10 ppm to approximately 40 ppm, approximately 15 ppm to approximately 40 ppm, approximately 20 ppm to approximately 40 ppm, approximately 25 ppm to approximately 40 ppm, approximately 40 ppm to approximately 50 ppm, approximately 45 ppm to approximately 50 ppm, approximately 50 ppm to approximately 60 ppm, approximately 55 ppm The concentrations range from m to approximately 60 ppm, from approximately 60 ppm to approximately 70 ppm, from approximately 65 ppm to approximately 70 ppm, from approximately 40 ppm to approximately 70 ppm, from approximately 45 ppm to approximately 70 ppm, from approximately 50 ppm to approximately 70 ppm, from approximately 55 ppm to approximately 70 ppm, from approximately 70 ppm to approximately 80 ppm, from approximately 75 ppm to approximately 80 ppm, from approximately 80 ppm to approximately 90 ppm, from approximately 85 ppm to approximately 90 ppm, from approximately 90 ppm to approximately 100 ppm, from approximately 70 ppm to approximately 100 ppm, from approximately 75 ppm to approximately 100 ppm, or from approximately 80 ppm to approximately 100 ppm.

[0104] An oxidizing agent may also be used optionally, and the oxidizing agent may be selected from the group consisting of hydrogen peroxide, oxone, cerium ammonium nitrate, periodates, iodates, persulfates, and mixtures thereof. Periodates, iodates, and persulfates may be any periodate, iodate, persulfate, or combination of periodates, iodates, and persulfates, for example, potassium periodate, potassium iodate, ammonium persulfate, potassium persulfate, or sodium persulfate. In some examples, the oxidizing agent is oxone or potassium persulfate. The oxidizing agent may be present in the abrasive composition in any appropriate amount that is not inconsistent with and unsuitable for the purposes of this subject. Typically, the abrasive composition may contain about 0.001% by weight or more, for example, about 0.005% by weight or more, about 0.01% by weight or more, about 0.05% by weight or more, or about 0.1% by weight or more of the oxidizing agent. In some examples, the abrasive composition may contain an oxidizing agent in an amount of about 20% by weight or less, for example, about 17% by weight or less, about 15% by weight or less, about 12% by weight or less, about 10% by weight or less, about 7% by weight or less, about 5% by weight or less, about 2% by weight or less, or about 0.5% by weight or less.In other examples, the abrasive composition is approximately 0.001% by weight to approximately 20% by weight, for example, approximately 0.001% by weight to approximately 17% by weight, approximately 0.001% by weight to approximately 15% by weight, approximately 0.001% by weight to approximately 12% by weight, approximately 0.001% by weight to approximately 10% by weight, approximately 0.001% by weight to approximately 7% by weight, approximately 0.001% by weight to approximately 5% by weight, approximately 0.001% by weight to approximately 2% by weight, approximately 0.005% by weight to approximately 20% by weight, approximately 0.005% by weight to approximately 17% by weight, approximately 0.005% by weight to approximately 15% by weight, approximately 0.005% by weight to approximately 12% by weight, approximately 0.005% by weight to approximately 10% by weight, approximately 0.005% by weight to approximately 7% by weight, and approximately 0.005% by weight to It may contain an oxidizing agent in amounts of approximately 5% by weight, approximately 0.005% to approximately 2% by weight, 0.01% to approximately 20% by weight, 0.01% to approximately 17% by weight, approximately 0.01% to approximately 15% by weight, approximately 0.01% to approximately 12% by weight, approximately 0.01% to approximately 10% by weight, approximately 0.01% to approximately 7% by weight, approximately 0.01% to approximately 5% by weight, 0.01% to approximately 2% by weight, approximately 0.05% to approximately 20% by weight, approximately 0.05% to approximately 17% by weight, approximately 0.05% to approximately 15% by weight, approximately 0.05% to approximately 10% by weight, approximately 0.05% to approximately 7% by weight, approximately 0.05% to approximately 5% by weight, and approximately 0.05% to approximately 2% by weight. In further examples, the abrasive composition may contain, based on the total weight of the abrasive composition, an oxidizing agent in amounts ranging from about 0.001% to about 0.05% by weight, from about 0.001% to about 0.1% by weight, from 0.001% to about 0.2% by weight, from 0.001% to about 0.3% by weight, from 0.001% to about 0.4% by weight, from about 0.001% to about 0.5% by weight, from 0.001% to about 0.6% by weight, from 0.001% to about 0.7% by weight, from 0.001% to about 0.8% by weight, from 0.001% to about 0.9% by weight, or from about 0.001% to about 1% by weight.

[0105] The abrasive compositions disclosed herein may exhibit any suitable pH that is not inconsistent with or incompatible with the scope of this subject matter. In some examples, the abrasive compositions may typically have a pH ranging from about 3 to about 11. While we do not wish to be bound by any particular theory, the abrasive rate of the compositions of the present invention may increase as the pH decreases, for example, from 11 to 3. Thus, in some examples, the abrasive compositions may have a pH ranging from 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, and about 3 to about 4, or however, the pH may be 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, and about 10 to about 1 1. It spans the range of approximately 4 to 10, approximately 5 to 10, approximately 6 to 10, approximately 7 to 10, approximately 8 to 10, approximately 9 to 10, approximately 4 to 9, approximately 5 to 9, approximately 6 to 9, approximately 7 to 9, approximately 8 to 9, approximately 4 to 8, approximately 5 to 8, approximately 6 to 8, approximately 7 to 8, approximately 4 to 7, approximately 5 to 7, approximately 6 to 7, approximately 4 to 6, or approximately 5 to 6.

[0106] If desired, pH adjusters, pH buffers, or combinations thereof may be used to achieve the aforementioned pH level. The abrasive composition may include any suitable pH adjuster. For example, the pH adjuster may be in the form of one or more of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, or any combination thereof, or in the form of a base such as sodium hydroxide, potassium hydroxide, cesium hydroxide, or ammonium hydroxide, or any combination thereof. The pH buffer may be any suitable buffer, such as phosphates, acetates, borates, sulfonates, carboxylates, ammonium salts, or any combination thereof.pH adjusters or pH buffers are typically present in an amount effective to achieve the desired pH level, for example, about 0.001% to about 20% by weight based on the total weight of the abrasive composition, for example, about 0.001% to about 17% by weight, about 0.001% to about 15% by weight, about 0.001% to about 12% by weight, about 0.001% to about 10% by weight, about 0.001% to about 7% by weight, about 0.001% to about 5% by weight, and about 0.001% to about 2% by weight. Weight %, approximately 0.005% to approximately 20% weight, approximately 0.005% to approximately 17% weight, approximately 0.005% to approximately 15% weight, approximately 0.005% to approximately 12% weight, approximately 0.005% to approximately 10% weight, approximately 0.005% to approximately 7% weight, approximately 0.005% to approximately 5% weight, approximately 0.005% to approximately 2% weight, approximately 0.01% to approximately 20% weight, approximately 0.01% to approximately 17% weight, approximately 0.01% to approximately 15% weight, approximately 0.01 weight From % to approximately 12% by weight, from approximately 0.01% by weight to approximately 10% by weight, from approximately 0.01% by weight to approximately 7% by weight, from approximately 0.01% by weight to approximately 5% by weight, from 0.01% by weight to approximately 2% by weight, from approximately 0.05% by weight to approximately 20% by weight, from approximately 0.05% by weight to approximately 17% by weight, from approximately 0.05% by weight to approximately 15% by weight, from approximately 0.05% by weight to approximately 10% by weight, from approximately 0.05% by weight to approximately 7% by weight, from approximately 0.05% by weight to approximately 5% by weight, from approximately 0.05% by weight to approximately 2% by weight, and from approximately 0.001% by weight. It may be included in amounts of approximately 0.05% by weight, approximately 0.001% to approximately 0.1% by weight, 0.001% to approximately 0.2% by weight, 0.001% to approximately 0.3% by weight, 0.001% to approximately 0.4% by weight, approximately 0.001% to approximately 0.5% by weight, 0.001% to approximately 0.6% by weight, 0.001% to approximately 0.7% by weight, 0.001% to approximately 0.8% by weight, 0.001% to approximately 0.9% by weight, or approximately 0.001% to approximately 1% by weight.

[0107] The abrasive composition may ideally further include polymers of 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, nonionic monomers and ethylenically unsaturated monomers including portions such as acryloylalkyltrialkylammonium salts (e.g., acryloylethyltrimethylammonium chloride), methacryloylalkyltrialkylammonium salts (e.g., methacryloylethyltrimethylammonium chloride), acrylamide- and methacrylamidoalkyltrialkylammonium salts (e.g., acrylamidopropyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride), and polymers containing sulfonic acid monomer units, hereafter referred to as sulfonic acid polymers or copolymers. A sulfonic acid monomer unit can be any suitable sulfonic acid monomer unit containing one or more groups of the formula :-SO3H. Non-limiting examples of suitable sulfonic acid (homo)polymers 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, and polyisoprene sulfonic acid. Suitable sulfonic acid copolymers include copolymers containing a sulfonic acid monomer unit and a monomer containing a carboxylic acid group, or a derivative of a carboxylic acid group such as an amide.

[0108] The abrasive composition may contain polymers in amounts of approximately 1 ppm or more, for example, approximately 5 ppm or more, approximately 10 ppm or more, approximately 20 ppm or more, approximately 30 ppm or more, approximately 40 ppm or more, or approximately 50 ppm or more. Alternatively, or in addition, the abrasive composition may contain polymers in amounts of approximately 500 ppm or less, for example, approximately 450 ppm or less, approximately 400 ppm or less, approximately 350 ppm or less, approximately 300 ppm or less, approximately 250 ppm or less, approximately 200 ppm or less, approximately 150 ppm or less, or approximately 100 ppm or less. Thus, the abrasive composition may contain polymers in amounts that are bounded by any two of the aforementioned endpoints. For example, abrasive compositions can be found in concentrations of approximately 1 ppm to 500 ppm, 5 ppm to 450 ppm, 10 ppm to 400 ppm, 10 ppm to 350 ppm, 10 ppm to 300 ppm, 10 ppm to 250 ppm, 10 ppm to 200 ppm, 20 ppm to 300 ppm, 20 ppm to 250 ppm, and 20 ppm. It may contain polymers in amounts ranging from approximately 200 ppm to approximately 20 ppm, approximately 20 ppm to approximately 150 ppm, approximately 20 ppm to approximately 100 ppm, approximately 10 ppm to approximately 100 ppm, approximately 10 ppm to approximately 90 ppm, approximately 10 ppm to approximately 80 ppm, approximately 10 ppm to approximately 70 ppm, approximately 10 ppm to approximately 60 ppm, approximately 10 ppm to approximately 50 ppm, or approximately 10 ppm to approximately 40 ppm.

[0109] Biocides known in the art can also be incorporated into the abrasive composition in some examples. The biocides can be any suitable biocides known to those skilled in the art and can be present in the abrasive composition in any suitable amount that is not inconsistent with or incompatible with the principles of this subject. Suitable biocides, to the extent that they are not limited, may include isothiazolinone biocides, isothiazolinone, or similar biocides, alcohols, aldehydes, chlorine, and chlorine-releasing agents, such as sodium hypochlorite, chlorhexidine, iodine, peroxygen compounds, such as hydrogen peroxide, peracetic acid, phenolic compounds, quaternary ammonium compounds, such as benzalkonium chloride, bases, such as sodium hydroxide, potassium hydroxide, and acids, such as mineral acids and organic acids. The concentration of biocides used in the abrasive composition can typically be about 1 ppm to about 60 ppm, about 1 ppm to about 50 ppm, about 1 ppm to about 40 ppm, about 1 ppm to about 30 ppm, about 1 ppm to about 20 ppm, about 1 ppm to about 10 ppm, about 1 ppm to about 5 ppm, about 10 ppm to about 60 ppm, about 15 ppm to about 60 ppm, about 20 ppm to about 60 ppm, about 25 ppm to about 60 ppm, about 30 ppm to about 60 ppm, about 35 ppm to about 60 ppm, about 40 ppm to about 60 ppm, about 45 ppm to about 60 ppm, about 50 ppm to about 60 ppm, or about 55 ppm to about 60 ppm.

[0110] The abrasive composition may also contain common rheological modifiers such as castor oil derivative polymers, cellulose, alkali acrylic emulsions, hydrophobic ethoxylated urethane resins, polyureas, polyamides, calcium sulfonates, and similar or equivalent rheological modifiers, generally in concentrations ranging from about 1,000 ppm to about 20,000 ppm. In some examples, the abrasive composition contains about 2,500 ppm to about 20,000 ppm of rheological modifiers. In other examples, the abrasive composition contains about 5,000 ppm to about 20,000 ppm of rheological modifiers. In yet another example, the abrasive composition contains about 7,500 ppm to about 20,000 ppm of rheological modifiers. In yet another example, the abrasive composition contains about 10,000 ppm to about 20,000 ppm of rheological modifiers. In yet another example, the abrasive composition contains about 12,500 ppm to about 20,000 ppm of rheological modifiers. In yet another example, the abrasive composition contains approximately 15,000 ppm to approximately 20,000 ppm of rheological modifier. In yet another example, the abrasive composition contains approximately 17,500 ppm to approximately 20,000 ppm of rheological modifier.

[0111] The abrasive compositions are available in concentrations of approximately 1000 ppm to 2500 ppm, 2500 ppm to 5000 ppm, 5000 ppm to 7500 ppm, 1000 ppm to 7500 ppm, 2000 ppm to 7500 ppm, 2500 ppm to 7500 ppm, 3000 ppm to 7500 ppm, 4000 ppm to 7500 ppm, 5000 ppm to 7500 ppm, 6000 ppm to 7500 ppm, 7000 ppm to 7500 ppm, 7500 ppm to 10000 ppm, and 8500 ppm. ppm to approximately 10,000 ppm, approximately 9,500 ppm to approximately 10,000 ppm, approximately 10,000 ppm to approximately 12,500 ppm, approximately 10,000 ppm to approximately 13,000 ppm, approximately 11,000 ppm to approximately 12,500 ppm, approximately 11,500 ppm to approximately 12,500 ppm, approximately 12,000 ppm to approximately 12,500 ppm, approximately 12,500 ppm to approximately 15,000 ppm, approximately 13,000 ppm to approximately 15,000 ppm, approximately 13,500 ppm to approximately 15,000 ppm, approximately 14,000 ppm to approximately 15,000 ppm, approximately 15,000 ppm to approximately 17,500 ppm pm, approximately 16000 ppm to approximately 17500 ppm, approximately 16500 ppm to approximately 17500 ppm, approximately 10000 ppm to approximately 15000 ppm, approximately 10500 ppm to approximately 15000 ppm, approximately 11000 ppm to approximately 15000 ppm, approximately 11500 ppm to approximately 15000 ppm, approximately 12000 ppm to approximately 15000 ppm, approximately 10000 ppm to approximately 17500 ppm, approximately 10500 ppm to approximately 17500 ppm, approximately 11000 ppm to approximately 17500 ppm, approximately 11500 ppm to approximately 17500 ppm, approximately 12000 ppm It may also contain rheology modifiers ranging from approximately 17,500 ppm to 17,500 ppm, from approximately 12,500 ppm to 17,500 ppm, from approximately 13,000 ppm to 17,500 ppm, from approximately 13,500 ppm to 17,500 ppm, from approximately 14,000 ppm to 17,500 ppm, from approximately 14,500 ppm to 17,500 ppm, from approximately 15,000 ppm to 17,500 ppm, from approximately 15,500 ppm to 17,500 ppm, from approximately 16,000 ppm to 17,500 ppm, from approximately 16,500 ppm to 17,500 ppm, or from approximately 17,000 ppm to 17,500 ppm.

[0112] The polishing composition may optionally further contain a chelating agent or a complexing agent. The complexing agent may be any suitable chemical additive that improves the rate of material removal from the semiconductor wafer surface or removes trace metal contaminants during the polishing cycle. Suitable chelating agents or complexing agents include, for example, carbonyl compounds such as acetylacetonate, simple carboxylates such as acetate and aryl carboxylates, carboxylates containing one or more hydroxyl groups such as glucolate, lactate, gluconate, gallic acid and its salts, or partial salts thereof, di-, tri-, and polycarboxylates such as oxalate, oxalic acid, phthalate, citrate, succinate, tartrate, malate, edetate, such as dipotassium EDTA, mixtures thereof, and carboxylates containing one or more sulfonic acid groups and / or phosphonic acid groups.Suitable chelating or complexing agents include, for example, di-, tri-, or polyalcohols, such as ethylene glycol, pyrocatechol, pyrogallol, and tannic acid; polyphosphonates, such as Dequest 2010, Dequest 2060, or Dequest 2000 (available from Solutia Corp.); and amine-containing compounds, such as ammonia, amino acids, amino alcohols, di-, tri-, and polyamines, in amounts ranging from about 0.001% to about 20% by weight, based on the total weight of the abrasive composition, for example, about 0.001% to about 17% by weight, about 0.001% to about 15% by weight, about 0.001% to about 12% by weight, about 0.001% to about 10% by weight, about 0.001% to about 7% by weight, and about 0.001% to about 5% by weight. Weight %, approximately 0.001% to approximately 2% by weight, approximately 0.005% to approximately 20% by weight, approximately 0.005% to approximately 17% by weight, approximately 0.005% to approximately 15% by weight, approximately 0.005% to approximately 12% by weight, approximately 0.005% to approximately 10% by weight, approximately 0.005% to approximately 7% by weight, approximately 0.005% to approximately 5% by weight, approximately 0.005% to approximately 2% by weight, approximately 0.01% to approximately 20% by weight, approximately 0.01% to approximately 17% by weight, approximately 0.01% to approximately 15% by weight Weight %, approximately 0.01% to approximately 12% weight, approximately 0.01% to approximately 10% weight, approximately 0.01% to approximately 7% weight, approximately 0.01% to approximately 5% weight, approximately 0.01% to approximately 2% weight, approximately 0.05% to approximately 20% weight, approximately 0.05% to approximately 17% weight, approximately 0.05% to approximately 15% weight, approximately 0.05% to approximately 10% weight, approximately 0.05% to approximately 7% weight, approximately 0.05% to approximately 5% weight, approximately 0.05% to approximately 2% weight, approximately 0.00 It may also be contained in amounts ranging from 1% by weight to about 0.05% by weight, from about 0.001% by weight to about 0.1% by weight, from 0.001% by weight to about 0.2% by weight, from 0.001% by weight to about 0.3% by weight, from 0.001% by weight to about 0.4% by weight, from about 0.001% by weight to about 0.5% by weight, from 0.001% by weight to about 0.6% by weight, from 0.001% by weight to about 0.7% by weight, from 0.001% by weight to about 0.8% by weight, from 0.001% by weight to about 0.9% by weight, or from about 0.001% by weight to about 1% by weight.

[0113] The abrasive compositions disclosed herein can be prepared by any suitable technique readily known to those skilled in the art. The abrasive compositions can be prepared in batches, by continuous processes, or in combination thereof.

[0114] In general, it will be understood that the actual amounts of one or more components in the abrasive compositions according to embodiments of this disclosure, such as diamond particles, abrasive composition components, and water, may vary depending on the desired dilution or concentration. In this embodiment, some embodiments may be packaged in the form of concentrates, such as 50-fold, 100-fold, or 200-fold concentrates, in which case water may be added later, for example, at the time of use by the end user, to dilute the abrasive composition. Alternatively, the abrasive composition may be packaged in a diluted form that already contains water. For example, in some embodiments, the components of the abrasive composition as a whole may be in a concentrated form to facilitate transportation, distribution, and sale. However, in other embodiments, the components of the abrasive composition may be in a diluted form as a whole, for example, to simplify the end use by the user. Accordingly, the weight ranges of the components described herein may refer to either the diluted range or the concentrated range.

[0115] Accordingly, each component may exist in a diluted form suitable for final use, or it may exist in a form that is concentrated upon receipt and then diluted upon use by the final user, for example, in the form of 2x concentrate, 5x concentrate, 10x concentrate, 25x concentrate, 40x concentrate, 50x concentrate, 60x concentrate, 70x concentrate, 100x concentrate, 125x concentrate, 150x concentrate, 175x concentrate, 200x concentrate, etc. When the concentrate is diluted with water, for example, 1 wt of water, 4 wt of water, 9 wt of water, 24 wt of water, 39 wt of water, 49 wt of water, 59 wt of water, 69 wt of water, 99 wt of water, 124 wt of water, 149 wt of water, 174 wt of water, and 199 wt of water respectively, each component of the abrasive composition exists in amounts within the dilution range in this embodiment. Furthermore, as will be understood by those skilled in the art, 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 to ensure that the components of the polishing composition are at least partially or completely dissolved in the concentrated form.

[0116] [Method for polishing the surface of semiconductor wafers]

[0117] The subject matter of this disclosure also provides a method for polishing the surface of a semiconductor wafer, the process of which is shown in Figure 2. Turning the reader's attention to Figure 2, the process includes at least a step 20 in which the surface of a semiconductor wafer is brought into contact with a polishing pad coated with the aforementioned polishing composition. Next, in step 22, the polishing pad coated with the aforementioned polishing composition is moved relative to the semiconductor wafer. Finally, the method is completed by polishing the semiconductor wafer by abrading at least a portion of the semiconductor wafer, as shown in step 24.

[0118] Those skilled in the art will see that this can be routinely performed, for example, using a 15-inch benchtop lapping machine (Lapmaster Wolters), typically applied to a semiconductor wafer surface in a single-sided polishing configuration. Alternatively, in other examples, polishing of the semiconductor wafer surface can also be suitably performed using a double-sided polishing configuration.

[0119] Generally speaking, such a lapping and polishing apparatus includes a platen, which is in motion during use and has a velocity resulting from orbital, linear, or circular motion. The polishing pad is in direct contact with the platen and therefore moves with the platen when the platen moves. A carrier holds the semiconductor wafer to be polished by contacting the semiconductor wafer and moving it relative to the surface of the polishing pad. Polishing of the semiconductor wafer is carried out by bringing the semiconductor wafer into contact with the polishing pad and polishing composition (i.e., the polishing composition placed between the semiconductor wafer and the polishing pad) and moving the polishing pad and platen together in a configuration relative to the semiconductor wafer to wear away 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 worn down and thus removed from the semiconductor wafer. Such techniques are well known to those skilled in the art.

[0121] Polishing refers to the process of removing at least a portion of the surface of a semiconductor wafer to achieve a polished surface. Polishing can be performed, for example, by removing grooves, crates, pits, etc., to provide a semiconductor wafer surface with reduced surface roughness upon completion of polishing. Alternatively, polishing can also be performed to introduce or restore surface morphology characterized by the intersection of planar segments.

[0122] Abrasive pads can, ideally, be made from any suitable material or composition, many of which will be readily apparent to those skilled in the art. Suitable abrasive pads include, but are not limited to, woven and nonwoven abrasive pads. Furthermore, suitable abrasive pads can be made from any suitable polymer of varying densities, hardness, thickness, compressibility, compressive rebound, and compressive modulus. Typical suitable polymers include, but are not limited to, polyvinyl chloride, polyvinyl fluoride, nylon, fluorocarbon, polycarbonate, polyester, polyacrylate, polyether, polyethylene, polyamide, polyurethane, polystyrene, polypropylene, co-molded products thereof, and any mixtures or combinations thereof.

[0123] Polishing pads can typically take any suitable shape to provide an effective polishing cycle on the semiconductor wafer surface. For example, a polishing pad may be circular and, in use, typically rotate around an axis perpendicular to the plane defined by the pad's surface. A polishing pad may be cylindrical, with its surface acting as the polishing surface, and, in use, typically rotate around the central axis of the cylinder. A polishing pad may be in the form of an endless belt and, in use, typically move linearly with respect to the cutting edge being polished. A polishing pad can easily take any suitable shape and, in use, move reciprocatingly or circumferentially along a plane or semicircle. Many other variations and configurations are readily apparent and available to those skilled in the art, and are therefore intended to be incorporated and encompassed within the scope of this disclosure as well.

[0124] It should be emphasized that the method described in this subject can be conventionally used to polish any suitable semiconductor wafer surface. In some examples, this may 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 in it, in accordance with the core principles of this subject. In some examples, the SiC may be single-crystal SiC. The SiC can be removed from the surface at any suitable rate in order to ultimately polish the SiC wafer surface. For example, the SiC can be removed at a rate in the range of about 1.3 μm / hr to about 8.2 μm / hr. In some examples, the SiC is removed at a rate in the range of about 2.2 μm / hr to about 8.2 μm / hr. In other examples, the SiC is removed at a rate in the range of about 3.2 μm / hr to about 8.2 μm / hr. In yet another example, the SiC is removed at a rate in the range of about 4.2 μm / hr to about 8.2 μm / hr. In yet another example, SiC is removed at a rate ranging from approximately 5.2 μm / hr to approximately 8.2 μm / hr. In yet another example, SiC is removed at a rate ranging from approximately 6.2 μm / hr to approximately 8.2 μm / hr. In yet another example, SiC is removed at a rate ranging from approximately 7.2 μm / hr to approximately 8.2 μm / hr.

[0125] SiC has a range of approximately 1.3 μm / hr to approximately 2.2 μm / hr, approximately 2.2 μm / hr to approximately 3.2 μm / hr, approximately 3.2 μm / hr to approximately 4.2 μm / hr, approximately 1.3 μm / hr to approximately 4.2 μm / hr, approximately 2.2 μm / hr to approximately 4.2 μm / hr, approximately 3.2 μm / hr to approximately 4.2 μm / hr, approximately 4.2 μm / hr to approximately 5.2 μm / hr, and approximately 4.2 μm / hr to approximately 6.2 μm It can also be removed at a rate in the range of m / hr, approximately 4.2 μm / hr to approximately 7.2 μm / hr, approximately 5.2 μm / hr to approximately 6.2 μm / hr, approximately 6.2 μm / hr to approximately 7.2 μm / hr, approximately 1.3 μm / hr to approximately 3.3 μm / hr, approximately 1.3 μm / hr to approximately 7.2 μm / hr, approximately 3.3 μm / hr to approximately 7.2 μm / hr, or approximately 3.3 μm / hr to approximately 8.2 μm / hr.

[0126] In polishing compositions containing surface-modified single-crystal diamond 10, the material removal rate of SiC can increase by approximately 185% to approximately 245% compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles. In some examples, the material removal rate of SiC in polishing compositions containing surface-modified single-crystal diamond 10 increases by approximately 190% to approximately 245% compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles. In yet another example, the material removal rate of SiC in polishing compositions containing surface-modified single-crystal diamond 10 increases by approximately 200% to approximately 245% compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles. In yet another example, the material removal rate of SiC in polishing compositions containing surface-modified single-crystal diamond 10 increases by approximately 210% to approximately 245% compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles. In yet another example, in a polishing composition containing surface-modified single-crystal diamond 10, the SiC material removal rate increases by approximately 220% to approximately 245% compared to a polishing composition containing single-crystal diamond particles or polycrystalline diamond particles.

[0127] In polishing compositions containing surface-modified single-crystal diamond 10, the SiC material removal rate is 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 2 30%, approximately 185% to approximately 235%, approximately 185% to approximately 240%, approximately 190% to approximately 200%, approximately 190% to approximately 205%, approximately 190% to approximately 210%, approximately 190% to approximately 215%, approximately 190% to approximately 220%, approximately 190% to approximately 225%, approximately 190% to approximately 230%, approximately 190% to approximately 235%, approximately 190% to approximately 240%, approximately 195% to approximately 200%, approximately 195% to approximately 205%, approximately 195% to approximately 210%, approximately 195% to approximately 215%, approximately 195% to approximately 22 0%, 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% to approximately 230 It may also increase within the range of approximately 200% to 235%, approximately 215% to 220%, approximately 220% to 225%, approximately 220% to 230%, approximately 220% to 235%, approximately 220% to 240%, approximately 225% to 230%, approximately 220% to 235%, approximately 225% to 235%, approximately 225% to 240%, approximately 230% to 240%, approximately 225% to 245%, approximately 235% to 240%, approximately 235% to 245%, or approximately 240% to 245%. [Examples]

[0128] The following embodiments are provided to those skilled in the art to provide a complete disclosure and explanation of the manufacturing method and use of the subject matter described herein, and are not intended to limit the scope of what the inventors consider to be such disclosure, nor are they intended to represent that the following experiments are all or only those experiments performed. While efforts have been made to ensure accuracy in the numbers used, some experimental error and deviation should be taken into consideration.

[0129] Example 1 Polishing compositions containing surface-modified single-crystal diamond exhibit an improved silicon carbide (SiC) removal rate from the surface of SiC wafers compared to polishing compositions containing single-crystal diamond particles or polycrystalline diamond particles.

[0130] Surface-modified single-crystal diamond (Smmd in Table 1) having a D(50) particle size, characterized by (I) 0.25 μm, 0.5 μm, 0.75 μm, or 1 μm, which allows for the removal rate of silicon carbide (SiC) material from the surface of a 4-inch diameter silicon carbide wafer and results in a surface roughness. * The tests were conducted using either (I), (II), (III), (III), (III), (I), (II), (III), (III), (III), (I), (II), (II), (III), (III), (III), (IIII), (III), (II), (II), (II), (III), (II), (II), (II), (III), (II), (II), (II), (II), (III), (II), (II), (II), (II), (III), (II), (II), (II), (II), (II), (II), (II), (II), (

[0131] Table 1 shows the particle size of the diamond used in the polishing composition in the first column, the specific type of diamond used in the polishing composition in the second column, the results obtained regarding the material removal rate of SiC from the SiC wafer surface in the third column, the surface roughness of the SiC wafer in the fourth column, the average value by volume distribution in the fifth column, the D(50) particle size distribution in the sixth column, and the D(99) particle size distribution in the seventh column. All demonstrative polishing data shown in Table 1 were obtained using a 15-inch benchtop lapping machine (Lapmaster Wolters) with a 15-inch polyurethane polishing pad. The platen of the 15-inch benchtop lapping machine was subjected to a circular motion specified at 60 revolutions per minute (RPM), and the diamond slurry was applied at a downforce of 3.2 psi and a slurry flow rate of 10 mL / min. Diamond particles were used as an aqueous slurry suspended in distilled water (DIW) at a concentration of 80 carats / gallon in polishing compositions (I), (II), and (III). The results obtained were as follows:

[0132] Essentially, surface-modified single-crystal diamond (Smmd in Table 1) * Polishing compositions containing ) showed a material removal rate of SiC from the SiC wafer surface that increased by approximately 185% to approximately 245% compared to polishing compositions containing either single-crystal diamond particles (Mono in Table 1) or polycrystalline diamond particles (Poly in Table 1).

[0133] To obtain the above results, the calculated average values ​​of the material removal rates in the third column for each particle size of 0.25 μm, 0.5 μm, 0.75 μm, or 1 μm for single-crystal diamond (Mono in Table 1) and polycrystalline diamond (Poly in Table 1), respectively, were used for the corresponding surface-modified single-crystal diamond (Smmd in Table 1) using the same diamond particle size. * The values ​​were compared with those of Mono 0.25μm and Poly 0.25μm. In other words, the average calculated material removal rate in the third column was compared with that of surface-modified single-crystal diamond (Smmd) 0.25μm. *were compared with the material removal rate values. The average calculated material removal rates in the third column for Mono 0.50 μm and Poly 0.50 μm were compared with those of surface modified single crystal diamond (Smmd) 0.50 μm * were compared with the material removal rate values. The average calculated material removal rates in the third column for Mono 0.75 μm and Poly 0.75 μm were compared with those of surface modified single crystal diamond (Smmd) 0.75 μm * were compared with the material removal rate values. The average calculated material removal rates in the third column for Mono 1 μm and Poly 1 μm were compared with those of surface modified single crystal diamond (Smmd) 1 μm * were compared with the material removal rate values.

[0134] The results in Table 1 are further shown graphically in Figure 3. Importantly, the key point to note is that when polished with surface modified single crystal diamond (Smmd in Table 1 * ), the measured surface roughness is substantially the same or improved compared to single crystal diamond (Mono in Table 1) or polycrystalline diamond (Poly in Table 1), as indicated by the black filled dots, where the resulting surface roughness values can be confirmed on the right y-axis of Figure 3.

Table 1

[0135] Although the present disclosure has been described in relation to its embodiments, it will be understood by those skilled in the art that additional, deletion, modification, and substitution not specifically described may be made without departing from the spirit and scope of the present disclosure as defined in the appended claims.

[0136] Regarding the use of substantially any plural and / or singular terms herein, those skilled in the art can translate from plural to singular and / or from singular to plural according to the context and / or application. For clarity, various singular / plural permutations are not explicitly described herein.

[0137] The subject matter described herein may include different components contained within or combined with other different components. The architectures presented in this manner are merely illustrative, and it should be understood that many other architectures are actually feasible to achieve the same function. Conceptually, any arrangement of components to achieve the same function is effectively “associated” in such a way that the desired function is achieved. Therefore, any two components combined here to achieve a particular function, regardless of architecture or intermediate components, can be considered “associated” with each other in such a way that the desired function is achieved. Similarly, any two such associated components can be considered “operably coupled” or “operably linked” with each other to achieve the desired function, and any two such associated components can be considered “operably linkable” with each other to achieve the desired function. Specific examples of operable linkability include, but are not limited to, physically matable and / or physically interacting components, and / or wirelessly interactable and / or wirelessly interacting components, and / or logically interacting and / or logically interactable components.

[0138] In some cases, one or more components may be referred to here as "composed of," "composed by," "configurable to," "actable to," "adapted to," "capable of," or "adaptable to." Those skilled in the art will understand that, unless otherwise specified in the context, such terms (e.g., "composed of") generally encompass active components and / or inactive components and / or standby components.

[0139] While specific aspects of the subject matter described herein have been shown and described, modifications and alterations can be made based on the teachings herein without departing from the subject matter and its broader aspects, and it will be apparent to those skilled in the art that the attached claims encompass all such modifications and alterations within their scope, which fall within the true spirit and scope of the subject matter described herein. In general, the terms used herein, and in particular in the attached claims (e.g., the feature section of the attached claims), will be understood by those skilled in the art to be generally intended as “open” terms (for example, the term “including” should be interpreted as “including, but not limited to,” the term “having” should be interpreted as “at least having,” and the term “includes” should be interpreted as “including, but not limited to,” etc.).

[0140] Those skilled in the art will further understand that if a specific number of introduced claims are intended, such intention is explicitly stated in the claim, and if such statement is absent, such intention is not present. For example, to aid understanding, the following appended claims may include the use of the introductory phrases “at least one” and “one or more” to introduce a claim. However, the use of such phrases should not be interpreted as meaning that the introduction of a claim by the indefinite article “a” or “an” limits any particular claim containing such introduced claims to claims containing only one such claim, even if the same claim includes the introductory phrase “one or more” or “at least one” and an indefinite article such as “a” or “an” (for example, “a” and / or “an” should typically be interpreted as meaning “at least one” or “one or more”); the same applies to the use of the definite article used to introduce a claim.

[0141] In addition, even when a claim explicitly states that a specific number has been introduced, a person skilled in the art will recognize that such a statement should typically be interpreted as meaning at least the number stated (for example, the mere statement “two statements” without other modifiers typically means at least two statements, or two or more statements).

[0142] Furthermore, in examples where a conventional phrase similar to "at least one of A, B, and C" is used, such constructions are generally intended to be understood by those skilled in the art (for example, "a system having at least one of A, B, and C" may include, but is not limited to, systems having only A, only B, only C, A and B together, A and C together, B and C together, and / or systems having A, B, and C together). In examples where a conventional phrase similar to "at least one of A, B, or C" is used, such constructions are generally intended to be understood by those skilled in the art (for example, "a system having at least one of A, B, or C" may include, but is not limited to, systems having only A, only B, only C, A and B together, A and C together, B and C together, and / or systems having A, B, and C together). Furthermore, it will be understood by those skilled in the art that, typically in the specification, claims, or drawings, any separating words and / or phrases presenting two or more alternative terms should be understood, unless otherwise specified in the context, as construed to include one of the terms, either of the terms, or both. For example, the phrase "A or B" is typically understood to include the possibilities of "A" or "B," or "A and B."

[0143] With respect to the attached claims, those skilled in the art will understand that the operations described herein may generally be performed in any order. Furthermore, while various operational flows are presented in sequence, it should be understood that the various operations may be performed in an order other than that illustrated, or simultaneously. Examples of such alternative orders may include, unless otherwise specified in the context, overlapping, alternating, interrupted, reordered, incremental, preparatory, supplementary, simultaneous, reversed, or other variant orders. Moreover, terms such as “responding to,” “related to,” or other past tense adjectives do not generally preclude such variations unless otherwise specified in the context.

[0144] Those skilled in the art will understand that the specific exemplary processes and / or apparatus and / or techniques described herein are representative of more general processes and / or apparatus and / or techniques taught elsewhere in this specification, for example, in the claims attached herein and / or elsewhere in this application.

[0145] While various aspects and embodiments have been disclosed herein, other aspects and embodiments will also 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 limit, and the true scope and spirit are set forth by the following claims.

[0146] The exemplary embodiments described in the detailed description, drawings, and claims are not limiting. Other embodiments may be used and other modifications may be made without departing from the spirit or scope of the subject matter presented herein.

[0147] Where a range of values ​​is provided, unless otherwise explicitly stated in the context, each intermediate value between the upper and lower limits of that range and any other stated or intermediate values ​​within that range is understood to be included in the disclosure up to one-tenth of the lower limit. The upper and lower limits of these smaller ranges, which may independently be included in smaller ranges, are also included in this disclosure, except for limits that are specifically excluded within the stated range. If a stated range includes one or both limits, a range that does not include either of those limits is also included in this disclosure.

[0148] Those skilled in the art will understand that the components (e.g., operations), apparatus, objects, and accompanying considerations described herein are used as examples for conceptual clarification and that various configurations are expected. Therefore, when used herein, the specific embodiments and accompanying considerations described are intended to represent a more general class. In general, the use of a particular embodiment is intended to represent that class, and the absence of specific components (e.g., operations), apparatus, and objects should not be interpreted as limiting.

[0149] In addition, any sequences and / or temporal orders of systems and methods described herein are illustrative and should not be interpreted as inherently restrictive. Therefore, process steps may be shown and described in sequence or temporal order, but are not necessarily limited to being performed in a specific sequence or order. For example, steps in such a process or method may generally be performed in a variety of different sequences and orders, while still within the scope of this disclosure.

[0150] Finally, the published patent applications and / or patents considered herein are provided solely for the purpose of disclosure prior to the filing date of the disclosed disclosure. Nothing herein should be construed as acknowledging that the disclosed disclosure does not have prior rights to such disclosure on the grounds of prior disclosure.

Claims

1. Surface-modified single-crystal diamond having D(50) particle sizes ranging from approximately 0.10 μm to approximately 1 μm; A vehicle selected from the group consisting of water-based vehicles, glycol-based vehicles, oil-based vehicles, and hydrocarbon-based vehicles; and Selectively one or more types of additives A semiconductor wafer polishing composition containing [the specified ingredient].

2. The semiconductor wafer polishing composition according to claim 1, wherein the D(50) particle size of the surface-modified single-crystal diamond is in the range of about 0.25 μm to about 0.50 μm.

3. The semiconductor wafer polishing composition according to claim 1, wherein the D(50) particle size of the surface-modified single-crystal diamond is in the range of about 0.25 μm to about 0.75 μm.

4. The semiconductor wafer polishing composition according to claim 3, wherein the D(50) particle size of the surface-modified single-crystal diamond is in the range of about 0.50 μm to about 0.75 μm.

5. The semiconductor wafer polishing composition according to claim 1, wherein the D(50) particle size of the surface-modified single-crystal diamond is in the range of about 0.75 μm to about 1 μm.

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

7. The semiconductor wafer polishing composition according to claim 1, wherein the material removal rate of silicon carbide (SiC) is in the range of about 1.3 μm / hr to about 8.2 μm / hr.

8. The semiconductor wafer polishing composition according to claim 7, wherein the SiC material removal rate is in the range of about 1.3 μm / hr to about 7.2 μm / hr.

9. The semiconductor wafer polishing composition according to claim 8, wherein the SiC material removal rate is in the range of about 1.3 μm / hr to about 3.3 μm / hr.

10. The semiconductor wafer polishing composition according to claim 8, wherein the SiC material removal rate is in the range of about 3.3 μm / hr to about 7.2 μm / hr.

11. The semiconductor wafer polishing composition according to claim 7, wherein the SiC material removal rate is in the range of about 3.3 μm / hr to about 8.2 μm / hr.

12. The semiconductor wafer polishing composition according to claim 11, wherein the SiC material removal rate is in the range of about 7.2 μm / hr to about 8.2 μm / hr.

13. The semiconductor wafer polishing composition according to claim 7, wherein the SiC material removal rate is increased by about 185% to about 245% compared to a polishing composition containing 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 of the surface-modified single-crystal diamond is in the range of about 0.25 μm to about 1 μm, the surface roughness of the SiC wafer is substantially the same as, or lower than, the surface roughness of a SiC wafer polished with a polishing composition containing single-crystal diamond particles or polycrystalline diamond particles.

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

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

17. The semiconductor wafer polishing composition according to claim 1, wherein the vehicle 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 according to 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 does not contain potassium permanganate.

21. A method for polishing the surface of a semiconductor wafer, A step of bringing the surface of a semiconductor wafer into contact with a polishing pad coated with a polishing composition comprising surface-modified single-crystal diamond having a D(50) particle size in the range of approximately 0.10 μm to approximately 1 μm, a vehicle selected from the group consisting of an aqueous vehicle, a glycol-based vehicle, an oil-based vehicle, and a hydrocarbon-based vehicle, and one or more additives optionally; A step of moving a polishing pad coated with a polishing composition relative to a semiconductor wafer; and A process of polishing a semiconductor wafer by wearing down at least a portion of it. Methods that include...

22. A method for polishing the surface of a semiconductor wafer according to claim 21, wherein the silicon carbide (SiC) material removal rate is in the range of about 1.3 μm / hr to about 8.2 μm / hr.

23. A method for polishing the surface of a semiconductor wafer according to claim 22, wherein the SiC material removal rate is in the range of about 1.3 μm / hr to about 7.2 μm / hr.

24. A method for polishing the surface of a semiconductor wafer according to claim 23, wherein the SiC material removal rate is in the range of about 1.3 μm / hr to about 3.3 μm / hr.

25. A method for polishing the surface of a semiconductor wafer according to claim 23, wherein the SiC material removal rate is in the range of about 3.3 μm / hr to about 7.2 μm / hr.

26. A method for polishing the surface of a semiconductor wafer according to claim 22, wherein the SiC material removal rate is in the range of about 3.3 μm / hr to about 8.2 μm / hr.

27. A method for polishing the surface of a semiconductor wafer according to claim 26, wherein the SiC material removal rate is in the range of about 7.2 μm / hr to about 8.2 μm / hr.

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

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

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

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