WO2017014311A1 - 単結晶ダイヤモンド材、単結晶ダイヤモンドチップおよび穿孔工具 - Google Patents
単結晶ダイヤモンド材、単結晶ダイヤモンドチップおよび穿孔工具 Download PDFInfo
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- WO2017014311A1 WO2017014311A1 PCT/JP2016/071603 JP2016071603W WO2017014311A1 WO 2017014311 A1 WO2017014311 A1 WO 2017014311A1 JP 2016071603 W JP2016071603 W JP 2016071603W WO 2017014311 A1 WO2017014311 A1 WO 2017014311A1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/04—Diamond
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C3/00—Profiling tools for metal drawing; Combinations of dies and mandrels
- B21C3/02—Dies; Selection of material therefor; Cleaning thereof
- B21C3/025—Dies; Selection of material therefor; Cleaning thereof comprising diamond parts
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/274—Diamond only using microwave discharges
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/10—Heating of the reaction chamber or the substrate
- C30B25/105—Heating of the reaction chamber or the substrate by irradiation or electric discharge
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/20—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2226/00—Materials of tools or workpieces not comprising a metal
- B23B2226/31—Diamond
Definitions
- the present invention relates to a single crystal diamond material, a single crystal diamond tip and a drilling tool.
- This application claims priority based on Japanese Patent Application No. 2015-145025 filed on Jul. 22, 2015, and incorporates all the description content described in the above Japanese application.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2000-288804
- Patent Document 2 Japanese Translation of PCT International Publication No. 2000-515818
- Patent Document 3 Japanese Patent Application Laid-Open No. 2002-102817
- Patent Document 3 includes an insert main body and a die main body, A tool insert and a wire drawing die having a grinding wheel tip made of natural or man-made diamond are disclosed.
- single crystal diamond is overwhelmingly hard compared to other materials, it can be used almost equally as a drilling tool, anti-abrasion tool or cutting tool, with almost no wear on any diamond. It has been. In fact, it is true that it is used without any particular problems.
- the single crystal diamond material according to an aspect of the present disclosure has a non-substituted nitrogen atom concentration of 200 ppm or less, a non-substituted nitrogen atom concentration lower than the non-substituted nitrogen atom concentration, and a crystal growth main surface.
- the off angle is 20 ° or less.
- a single crystal diamond tip according to another aspect of the present disclosure has a concentration of unsubstituted nitrogen atoms of 200 ppm or less, a concentration of substituted nitrogen atoms lower than the concentration of unsubstituted nitrogen atoms, and a single crystal diamond tip
- the off-angle of the main surface is 20 ° or less.
- the concentration of the unsubstituted nitrogen atom in the single crystal diamond die is 200 ppm or less, the concentration of the substituted nitrogen atom is lower than the concentration of the unsubstituted nitrogen atom, and It includes a single crystal diamond die having an off angle of a normal of a low index plane expressed by an integer of ⁇ 5 or more and 5 or less with respect to the orientation of the hole for drawing.
- FIG. 1 is a schematic view showing an example of an X-ray topography image of a crystal growth main surface of a single crystal diamond material according to an embodiment of the present invention.
- FIG. 2 is a schematic cross-sectional view showing an example of a cross section perpendicular to the crystal growth main surface of a single crystal diamond material according to an aspect of the present invention.
- FIG. 3 is a schematic cross-sectional view showing another example of a cross section perpendicular to the crystal growth main surface of a single crystal diamond material according to an aspect of the present invention.
- FIG. 4 is a schematic cross-sectional view showing a method for producing a single crystal diamond material according to an embodiment of the present invention.
- an object is to provide a single crystal diamond material, a single crystal diamond tip, and a drilling tool in which the occurrence of large defects is suppressed and the variation in wear rate is small.
- a single crystal diamond material according to an embodiment of the present invention has a concentration of unsubstituted nitrogen atoms of 200 ppm or less, a concentration of substituted nitrogen atoms lower than the concentration of unsubstituted nitrogen atoms, and a crystal The off-angle of the growth main surface is 20 ° or less.
- Such single crystal diamond material suppresses the occurrence of large defects and has a small variation in wear rate.
- the off-angle of the crystal growth main surface can be less than 7 °.
- Such single crystal diamond material suppresses the occurrence of large defects and has a smaller variation in wear rate.
- the single crystal diamond material of the present embodiment can further have a substitutional nitrogen atom concentration of less than 80 ppm. Such single crystal diamond material suppresses the occurrence of large defects and has a smaller variation in wear rate.
- the concentration of all nitrogen atoms, which are the entire non-substituted nitrogen atoms and substituted nitrogen atoms, can be 0.1 ppm or more.
- Such single crystal diamond material suppresses the occurrence of large defects and has a smaller variation in wear rate.
- the deviation angle from the parallel between the main surface opposite to the crystal growth main surface and the crystal growth main surface is less than 2 °, and the opposite side to the crystal growth main surface In the main surface, the maximum height difference Dm of the swell can be set to 10 ⁇ m / mm or less, and the arithmetic average roughness Ra can be set to 0.1 ⁇ m or less.
- Such a single crystal diamond material can easily control the off-angle of the main surface of the chip cut out therefrom.
- the single crystal diamond material of the present embodiment is a point at the tip where a crystal defect line showing a line where a crystal defect exists in an X-ray topography image of the crystal growth main surface reaches the crystal growth main surface. A group of crystal defect points can exist together. Such single crystal diamond material further suppresses the occurrence of large defects.
- the single crystal diamond material of this embodiment can further have a density of crystal defect points larger than 2 mm ⁇ 2 . Such single crystal diamond material further suppresses the occurrence of large defects.
- the single crystal diamond material of the present embodiment further includes a point at the tip where a composite dislocation in which at least one of a plurality of edge dislocations and a plurality of screw dislocations is combined among crystal defect points reaches the crystal growth main surface.
- the density of complex dislocation points can be greater than 2 mm ⁇ 2 .
- Such single crystal diamond material further suppresses the occurrence of large defects.
- the single crystal diamond material of the present embodiment can further include a plurality of single crystal diamond layers. Such single crystal diamond material further suppresses the occurrence of large defects.
- a crystal defect line is newly generated or branched at the interface of each single crystal diamond layer, and the density of crystal defect points on the crystal growth principal surface is the crystal growth principal. It can be made higher than the density of crystal defect points on the main surface opposite to the surface. Such single crystal diamond material further suppresses the occurrence of large defects.
- a plurality of crystal defect linear aggregate regions extending in a linear shape by gathering a group of crystal defect points can exist in parallel.
- Such single crystal diamond material further suppresses the occurrence of large defects.
- the concentration of the unsubstituted nitrogen atom can be further set to 1 ppm or more. Such single crystal diamond material further suppresses the occurrence of large defects.
- the transmittance of light having a wavelength of 400 nm can be 60% or less when the thickness of the single crystal diamond material is 500 ⁇ m. Such single crystal diamond material further suppresses the occurrence of large defects.
- the concentration of the unsubstituted nitrogen atom is 200 ppm or less
- the concentration of the substituted nitrogen atom is lower than the concentration of the unsubstituted nitrogen atom
- the main surface of the single crystal diamond tip has an off angle of 20 ° or less.
- a single crystal diamond tip according to another embodiment of the present invention is cut from the single crystal diamond material of the above embodiment.
- Such single crystal diamond tips suppress the occurrence of large defects and have a small variation in wear rate.
- the main surface of the single crystal diamond chip can be a low index surface represented by an integer having a mirror index of ⁇ 5 or more and 5 or less.
- Such single crystal diamond tips suppress the occurrence of large defects and have a small variation in wear rate.
- the single crystal diamond tip of the present embodiment further includes a line having a crystal defect in an X-ray topography image of either the crystal growth main surface or a main surface parallel to the crystal growth main surface.
- a group of crystal defect points which is the point of the tip where the crystal defect line shown in the figure reaches the main surface of the crystal growth main surface or the main surface parallel to the crystal growth main surface, Can be larger than 2 mm -2 . In such a single crystal diamond tip, the occurrence of large defects is further suppressed.
- the concentration of the unsubstituted nitrogen atom in the single crystal diamond die is 200 ppm or less, and the concentration of the substituted nitrogen atom is higher than the concentration of the unsubstituted nitrogen atom.
- the off-angle of the perpendicular of the low index plane, which is low and the Miller index of the single crystal die with respect to the orientation of the drawing hole is represented by an integer of ⁇ 5 or more and 5 or less, is 20 ° or less.
- a drilling tool includes a single crystal diamond die formed from the single crystal diamond tip of the above embodiment. Such a drilling tool suppresses the occurrence of large defects in the single crystal diamond die and has a small variation in wear rate.
- the crystal defect line indicating the line where the crystal defect exists in the X-ray topography image of the crystal growth main surface of the single crystal diamond die is further provided at the tip where the crystal defect main surface reaches the crystal growth main surface.
- the drilling tool of the present embodiment is further a point at the tip where a composite dislocation in which at least one of a plurality of edge dislocations and a plurality of helical dislocations is combined among crystal defect points reaches the crystal growth main surface.
- the density of complex dislocation points can be made larger than 2 mm ⁇ 2 . Such a drilling tool further suppresses the occurrence of large defects in the single crystal diamond die.
- the single crystal diamond die further includes a plurality of single crystal diamond layers, and crystal defect lines are newly generated or branched at the interface of each single crystal diamond layer to grow crystals.
- the density of crystal defect points on the main surface can be made higher than the density of crystal defect points on the main surface opposite to the crystal growth main surface.
- the single crystal diamond die may further include a plurality of crystal defect linear aggregate regions extending in a line in a group of crystal defect points. Such a drilling tool further suppresses the occurrence of large defects in the single crystal diamond die.
- the single crystal diamond die can further have a non-substituted nitrogen atom concentration of 1 ppm or more. Such a drilling tool further suppresses the occurrence of large defects in the single crystal diamond die.
- the single crystal diamond die can further have a light transmittance of a wavelength of 400 nm of 60% or less when the thickness of the single crystal diamond die is 500 ⁇ m. Such a drilling tool further suppresses the occurrence of large defects in the single crystal diamond die.
- the single crystal diamond material 20 of this embodiment has a concentration of unsubstituted nitrogen atoms of 200 ppm or less, and the concentration of substituted nitrogen atoms is lower than the concentration of unsubstituted nitrogen atoms. And the off angle of the crystal growth main surface is 20 ° or less.
- the crystal growth main surface 20m of the single crystal diamond material 20 refers to a main surface on the crystal growth side formed by crystal growth in the single crystal diamond material.
- the main surface of the single crystal diamond material means a main surface having physical properties as a single crystal diamond material.
- the main surface of the crystal growth main surface is 20 m, the main surface parallel to the crystal growth main surface, and the opposite side to the crystal growth main surface 20 m.
- the main surface 20n is included. Whether the main surface of the single crystal diamond material is a crystal growth main surface, a main surface parallel to the crystal growth main surface, or a main surface opposite to the crystal growth main surface is as described above. It can be identified by an X-ray topography image in a main surface and / or a cross section intersecting with the main surface.
- wear-resistant tools As a cause of variation in the wear rate of drilling tools, wear-resistant tools, cutting tools (for example, wire drawing dies), the inventors of the present invention, among many factors, are variations in impurities and surface orientation in single crystal diamond materials. The variation was found.
- single-crystal diamond produced by an artificial high-pressure synthesis method when used as the single-crystal diamond material, those having different plane orientations did not coexist, but those that deviate by 10 ° or more are several tenths or more. It was acceptable for the same single crystal diamond material to be mixed, or to be mixed by several percent or more when it deviated by 5 ° or more. Also, there was no 100% probability that the off-angles were less than 3 °, and all of them were used as specific surface orientations. Furthermore, even in the single crystal diamond material obtained by the high pressure synthesis method, nitrogen is naturally mixed, and the concentration of the mixed material is not guaranteed in production and varies in the range of 80 to 250 ppm. Variation in the range of ⁇ 85 ppm was acceptable.
- the wear rate of a single crystal diamond tip or single crystal diamond die formed using such a single crystal diamond material is 50% to 200% (that is, 0.5 times the average value). (To be 2.0 times) Variation in the above range occurs.
- the single crystal diamond material includes the following measures in order to reduce the variation in the wear rate of the single crystal diamond material.
- the single crystal diamond material is formed by a vapor phase synthesis method.
- nitrogen is mixed from the raw carbon material, the solvent metal material, or the atmosphere during synthesis, and cannot be controlled as a molar unit (molecular quantity unit).
- the gas phase synthesis method the molar ratio of each atom of the synthesis gas can be controlled.
- the extra (unexpected) gas in the container is also made much smaller than the raw material gas, so that the single crystal diamond material Since the concentration of nitrogen atoms in the inside can be controlled to be constant, variations in the concentration of nitrogen atoms due to unexpected gas mixing from raw materials, solvents, and synthesis atmospheres can be avoided. However, even in the vapor phase synthesis method, since nitrogen gas in the surrounding atmosphere is mixed in very slightly, it is preferable that all nitrogen atoms in the single crystal diamond material have a certain concentration or more, and it is preferable that it is not zero at all. The concentration of nitrogen atoms in the crystalline diamond material is stable.
- the second strategy is to control the off-angle of the main surface of the diamond seed crystal, which is a seed substrate for forming a single crystal diamond material.
- the off angle of the main surface of the diamond seed crystal affects the mixing of impurities, but is a factor that is difficult to control precisely.
- the reduction of the off-angle of the main surface of the diamond seed crystal can be achieved by cutting with a laser that has a good degree of parallelism with the method of projecting the standard surface of the angle, or by using a laser that calculates and corrects the parallelism. Achieved by the method of cutting.
- the laser is a highly parallel light, but when used for processing, the cut surface has a wedge shape with an angle of several degrees due to the intensity distribution in the radial direction.
- laser processing is destructive processing, it cannot always be processed in the same state, and the maximum height roughness Rz of the surface after processing becomes 10 ⁇ m or more.
- the maximum height roughness Rz refers to the maximum height roughness Rz defined by JIS B0601: 2013.
- something is adhered and processed, but it is not always adhered in the same state, and there is always a tilt of several degrees during the adhesion.
- polishing jig Even during polishing, it is once removed and attached to a polishing jig, but this time also tilts several degrees. Since the polished surface is also rough, the polishing finish is inclined several degrees, and the off-angle of the main surface of the obtained single crystal diamond material varies by 20 ° or more in total.
- the present inventors independently improved an ordinary laser processing machine (changed the depth of focus to a non-standard and maintained the parallelism, etc.) to obtain a laser beam having a parallelism of less than 1 °
- the light intensity is also devised (using a uniquely designed DOE lens, etc.), and the degree of parallelism after processing (in this specification, the deviation angle from parallel. The same applies hereinafter) is also 1 °. Less processing was realized. Even if adjustment is insufficient, if the parallelism after processing is less than 2 °, the correction of the cutting direction to the laser beam axis by ⁇ 1 ° is performed on both sides of the plate processing. The parallelism was successfully reduced to less than 1 °.
- a seed crystal having a flatness of 5 ⁇ m or less with a maximum height roughness Rz of the processed surface can be produced.
- a plate-like seed crystal having flatness and parallelism is produced, a flat surface is formed, so that there is no large variation due to adhesion during polishing, and the main surface has an off angle within 20 ° in total.
- a single crystal diamond material can be formed.
- the off-angle of the single crystal diamond material is preferably not zero. This is because, when the off angle is zero, there are almost no atomic steps, and the uptake of impurities such as nitrogen becomes unstable.
- the third strategy controls the concentration of non-substituted nitrogen atoms and / or substituted nitrogen atoms in the single crystal diamond material. This is because the difference in the concentration of substituted nitrogen atoms and non-substituted nitrogen atoms among the nitrogen atoms entering the single crystal diamond material as impurities is different from the single crystal diamond material due to the entry of impurities. This is because it has been found that the occurrence of a large chipping of the material and the wear rate are affected.
- the concentration of the non-substituted nitrogen atom is set to 200 ppm or less, and the concentration of the substituting nitrogen atom is made lower than the concentration of the non-substituted nitrogen atom. And the variation in the wear rate of the single crystal diamond material is reduced.
- the single crystal diamond material 20 of the present embodiment can suppress the variation in the plane orientation by setting the main surface off angle to 20 ° or less. For this reason, the single crystal diamond material 20 of the present embodiment has a concentration of non-substituted nitrogen atoms of 200 ppm or less, a concentration of substituted nitrogen atoms lower than that of non-substituted nitrogen atoms, and a crystal growth main surface. When the off angle is 20 ° or less, the occurrence of large defects is suppressed and the variation in wear rate is reduced.
- the non-substituted nitrogen atom refers to a material obtained by removing the substituted nitrogen atom from all nitrogen atoms.
- the concentration of unsubstituted nitrogen atoms refers to the concentration of all nitrogen atoms minus the concentration of substituted nitrogen atoms.
- the concentration of all nitrogen atoms is measured by SIMS (secondary ion mass spectrometry), and the concentration of substitutional nitrogen atoms is measured by ESR (electron spin resonance method).
- the single crystal diamond material 20 of the present embodiment is not particularly limited, but is preferably formed by a vapor phase synthesis method. Since the gas phase synthesis method can control the molar ratio of each atom of the synthesis gas, the concentration of nitrogen atoms in the single crystal diamond material 20 can be controlled with higher accuracy than other methods.
- the concentration of unsubstituted nitrogen atoms is 200 ppm or less, preferably 110 ppm or less, and more preferably 55 ppm or less, from the viewpoint of small variation in wear rate.
- the main surface has an off-angle of 20 ° or less, preferably less than 10 °, more preferably less than 7 °, and more preferably less than 5 ° from the viewpoint of small variation in wear rate. More preferably, less than 3 ° is more preferable, and less than 1 ° is particularly preferable. This is because the bond of carbon related to wear resistance becomes weaker at 1 / cos ⁇ with the off angle as ⁇ , and the variation is related to the magnitude of the derivative. The smaller the value, the smaller the variation.
- the impurity incorporation becomes unstable.
- nitrogen impurities are affected by the number of atomic steps (line length) on the surface determined by the off angle. Since the atomic step interval is proportional to 1 / sin ⁇ of the off angle ⁇ , when ⁇ is zero, it becomes extremely long (theoretically infinite), and impurities are hardly taken in, but the off angle is 0.
- the step interval is about 1 ⁇ m, and the impurities are on the order of several ppb as compared with the off angle (several ppm) of 5 °.
- the total nitrogen is contained in an amount of 1 ppb or more from the viewpoint of variation in the wear rate.
- the off angle is preferably 0.005 ° or more, more preferably 0.05 ° or more.
- the off-angle of the main surface refers to an off-angle with respect to an arbitrarily specified crystal plane.
- the crystal plane that is arbitrarily specified is not particularly limited, but from the viewpoint of small variation in the wear rate, a low index plane in which the Miller index is represented by an integer of ⁇ 5 or more and 5 or less is preferable, and ⁇ 100 ⁇ , ⁇ 110 ⁇ , ⁇ 111 ⁇ , ⁇ 211 ⁇ , ⁇ 311 ⁇ and ⁇ 331 ⁇ , more preferably at least one plane orientation plane selected from the group consisting of ⁇ 331 ⁇ .
- the concentration of substituted nitrogen atoms is lower than the concentration of non-substituted nitrogen atoms from the viewpoint of suppressing the occurrence of large defects and reducing the variation in wear rate. This is because if the concentration of the substitutional nitrogen atom is higher than the concentration of the non-substitutional nitrogen atom, the amount of wear increases, causing a variation in the wear rate and causing a large defect.
- the concentration of substitutional nitrogen atoms is preferably less than 80 ppm, more preferably less than 20 ppm, even more preferably less than 15 ppm, and more preferably less than 10 ppm from the viewpoint of small variation in wear rate. More preferred is 1 ppm or less, further preferred is 0.5 ppm or less, particularly preferred is 0.3 ppm or less, and most preferred is 0.1 ppm or less.
- the single crystal diamond material 20 of the present embodiment has a concentration of 1 ppb (total nitrogen atoms as non-substituted nitrogen atoms and substituted nitrogen atoms as a whole from the viewpoint of suppressing large defects and reducing wear rate variation. 0.001 ppm) or more is preferable, 0.01 ppm or more is more preferable, 0.1 ppm or more is more preferable, 1 ppm or more is further preferable, and 10 ppm or more is particularly preferable.
- concentration of all nitrogen atoms is less than 0.1 ppb, naturally mixed nitrogen impurities become unstable and the single crystal diamond material becomes brittle.
- the off angle of the main surface of the chip cut out from the single crystal diamond material 20 from the viewpoint of easily growing a single crystal diamond material of an off angle with little variation from the diamond seed crystal.
- the deviation angle from the parallel of the main surface opposite to the crystal growth main surface and the crystal growth main surface is preferably less than 2 °, more preferably less than 0.1 °, 0.05 More preferably less than °.
- the term “deviation angle from the parallel with the crystal growth main surface” strictly means the “deviation angle from the parallel with the main surface of the diamond seed crystal during growth”. The parallelism is transferred as it is to the main surface of crystal growth, so the equivalence is utilized.
- the crystal growth main surface of the single crystal diamond material is within 100 ⁇ m from the main surface of the diamond seed crystal.
- the crystal growth main surface of the initial growth This appears later as growth fringes, so when observed with an optical microscope, SEM (scanning electron microscope), CL (cathode luminescence) or PL (photo luminescence) of the cross section, the crystal growth main surface at the initial growth stage is a stripe pattern.
- the parallel plane can be evaluated.
- the deviation angle from the parallel with the crystal growth main surface at the initial stage of growth is within 200 ⁇ m, preferably within 100 ⁇ m, more preferably within 50 ⁇ m from the main surface opposite to the crystal growth main surface.
- the maximum height difference Dm of the waviness on the main surface opposite to the crystal growth main surface is preferably 10 ⁇ m / mm or less, more preferably 5 ⁇ m / mm or less, and 0.6 ⁇ m / mm or less.
- the arithmetic average roughness Ra is preferably 0.1 ⁇ m or less, more preferably 50 nm or less, further preferably 10 nm or less, further preferably 5 nm or less, and particularly preferably 1 nm or less.
- the deviation angle from the parallel of the main surface opposite to the crystal growth main surface of the single crystal diamond material 20 and the crystal growth main surface (or the crystal growth main surface in the initial stage of growth) causes the single crystal diamond material 20 to grow. This corresponds to a deviation angle between the off angle of the main surface 10 m of the diamond seed crystal 10 and the off angle of the crystal growth main surface 20 m of the single crystal diamond material 20.
- the maximum waviness difference Dm is not the PV value in the range of several hundred ⁇ m, but the difference between the highest value and the lowest value in the gentle surface height over the range of 1 mm, and the actual inclination of the sample ( Except for the inclination of the main surface, it is not a relative value but an absolute value based on the horizontal of the main surface.
- arithmetic mean roughness Ra means arithmetic mean roughness Ra prescribed
- the small deviation angle between the main surface 20n opposite to the crystal growth main surface 20m of the single crystal diamond material 20 and the crystal growth main surface 20m is that the main surface 10m off angle of the diamond seed crystal 10 and the single crystal diamond This proves that the off-angle shift of the main surface 20n on the opposite side to the crystal growth main surface 20m of the material 20 is small.
- the off-angle of the main surface 20n opposite to the crystal growth main surface 20m of the single crystal diamond material 20 grown on the diamond seed crystal 10 is the crystal of the single crystal diamond material 20 separated from the diamond seed crystal 10 after the growth. This is because it does not always coincide with the off-angle of the main surface 20n on the opposite side to the growth main surface 20m.
- the main surface of the single crystal diamond material 20 separated from the diamond seed crystal 10 that is, opposite to the crystal growth main surface.
- the parallel shift angle between the main surface 20n) on the side and the crystal growth main surface 20m of the single crystal diamond material 20 is increased to 2 ° or more. Then, at this point in time, a tool with little variation in the off angle cannot be finally produced. Therefore, a small deviation angle from the parallel of the main surface 20n opposite to the crystal growth main surface and the crystal growth main surface 20m is necessary for producing a tool with little variation in off-angle.
- the small maximum height difference Dm of the undulation of the main surface 20n opposite to the crystal growth main surface is that when the single crystal diamond chip is cut out from the single crystal diamond material, the crystal growth main surface of each single crystal diamond chip is cut. This proves that there is little variation in the off-angle of the opposite main surface.
- Single crystal diamond chips are often smaller than 1 mm square, but if the surface is wavy by 10 ⁇ m or more, the off-angle variation of 1 ° or more including the front and rear is caused. As a result, it is impossible to finally produce a tool with little variation in off-angle.
- the fact that the maximum height difference Dm of the undulation of the main surface 20n opposite to the crystal growth main surface is small is also necessary for producing a tool with little variation in off-angle.
- the single crystal diamond material 20 of the present embodiment has crystal defects in the X-ray topography image of the crystal growth main surface 20m from the viewpoint of suppressing the occurrence of large defects. It is preferable that a group of crystal defect points 20dp, which is a point at the tip where the crystal defect line 20dq indicating a line reaches the crystal growth main surface 20m, is gathered.
- the crystal growth main surface means a main surface on the crystal growth side formed by crystal growth.
- the expression that a group of crystal defect points 20 dp is gathered is a content that has been stepped down as follows in the present invention.
- the crystal defect point 20dp includes a plurality of crystal defect points branched from one starting point or a group of crystal defect points branched from the middle as one group, and those derived from another starting point as another group.
- a group is expressed as a group when an area of one group and an area of another group contact or overlap.
- the existence of the crystal defect point 20dp and the crystal defect line 20dq is shown in the X-ray topography image. That is, since the crystal defect point and the crystal defect line have higher X-ray reflection intensity than other parts of the crystal (parts having fewer defects, that is, parts having higher crystallinity), In the case of a positive image, the presence thereof is indicated as a dark portion, and in the case of a negative image, the presence thereof is indicated as a bright portion.
- the crystal defect line 20dq appears as a dark part or a bright part as a line, and the crystal defect point 20dp appears as an intersection of a main surface such as the crystal growth main surface 20m and the crystal defect line 20dq.
- the crystal defects 20d include various defects such as point defects, dislocations, defects, cracks, and crystal distortions.
- Dislocations include edge dislocations, spiral dislocations, composite dislocations in which at least one of a plurality of edge dislocations and a plurality of spiral dislocations is combined.
- a crystal defect line 20dq composed of these crystal defects 20d or the like is newly generated or stops when the crystal growth main surface 20m is reached.
- the tip of the crystal defect line 20dq reaching the crystal growth principal surface 20m is called a crystal defect point 20dp.
- the density is defined by counting the number of crystal defect points 20 dp per unit area.
- an average value of at least five points in an arbitrary region with a limited range may be taken as follows.
- crystal defects point is 10 / mm 2 or more, an area of 500 ⁇ m angle at 100 / mm 2 or more, and limiting the scope like 100 ⁇ m angle at 1 ⁇ 10 4 pieces / mm 2 or more
- the number of crystal defect points 20dp is counted and converted to mm- 2 units.
- the region where the number of crystal defect points 20dp is counted is always a portion including the crystal defect assembly region.
- the crystal defect gathering region refers to a region where crystal defect points 20 dp are gathered.
- the crystal defect assembly region extending linearly is referred to as a crystal defect linear assembly region 20r.
- the crystal defect line 20dq becomes a crystal defect point 20dp on the crystal growth main surface 20m
- the density of the crystal defect line in the vicinity of the crystal growth main surface 20m is equal to the density of the crystal defect point.
- Crystal defect lines also exist inside the crystal, and there are also intersections with arbitrary surfaces. The density of the intersection points corresponds to the density of crystal defect lines on the surface.
- the arbitrary surface for example, the interface 212i of the single crystal diamond layers 21 and 22 growing in a layer shape shown in FIG. 3 or a surface parallel to the vicinity thereof can be assumed.
- the crystal defect linear assembly region 20r is formed by a crystal defect point 20dp, which is a point at the tip of the crystal defect line 20dq, which is a line where a crystal defect exists, gathers linearly on the crystal growth main surface 20m.
- the crystal defect linear assembly region 20r is suitable in an X-ray topography image measured in a transmission type in a direction parallel to the crystal growth direction of the single crystal diamond material (that is, a direction perpendicular to the crystal growth main surface). Shown in Although it is possible to measure with the reflection type, the X-ray topography image measured with the reflection type is an image in which the crystal defect lines are overlapped with each other, so that the aggregate state of the crystal defect points is difficult to be determined.
- X-rays of emitted light for the X-ray topography image.
- measurement may be performed using a laboratory X-ray diffractometer.
- (111) diffraction may be observed with a Mo source
- (113) diffraction may be observed with a Cu source. It takes a long measurement time.
- a CCD camera can be used for the measurement, it is desirable to use a nuclear plate to increase the resolution. It is desirable to store, develop and fix the nuclear plate in a cooling environment of 10 ° C. or less. After development, an image is captured with an optical microscope, and the crystal defect point 20dp and the crystal defect line 20dq are quantified.
- birefringence Birefringence method
- dislocations that do not appear in the birefringence image, and conversely point defects that are not structural defects may appear in the birefringence image. Therefore, X-ray topography is preferable to the birefringence method.
- the density of crystal defect points 20 dp is preferably greater than 2 mm ⁇ 2, more preferably greater than 20 mm ⁇ 2 , still more preferably greater than 300 mm ⁇ 2 , and 1000 mm ⁇ . more preferably greater than 2, and particularly preferably greater than 1 ⁇ 10 4 mm -2.
- the density of the crystal defect points 20 dp is larger than 2 mm ⁇ 2 , generation of large defects is suppressed by stress relaxation due to the high density crystal defect lines corresponding to the high density crystal defect points.
- the defect resistance is particularly excellent.
- the single crystal diamond material 20 of the present embodiment is a composite in which a composite dislocation in which at least one of a plurality of edge dislocations and a plurality of helical dislocations is combined out of crystal defect points 20 dp is a point at the tip where the crystal growth main surface is reached.
- the density of dislocation points is preferably greater than 2 mm ⁇ 2, more preferably greater than 30 mm ⁇ 2 , further preferably greater than 300 mm ⁇ 2 , and particularly preferably greater than 3000 mm ⁇ 2 .
- the density of the composite dislocation point which is the point at which the composite dislocation reaches the crystal growth main surface, is larger than 20 mm ⁇ 2 , and the effect of stress relaxation by the composite dislocation is large, Generation is further suppressed.
- the density of complex dislocation points is larger than 300 mm ⁇ 2 , the fracture resistance is particularly excellent.
- the composite dislocation can be observed by changing the X-ray diffraction direction (g vector) in the X-ray topography.
- g vector X-ray diffraction direction
- the (001) plane which is a crystal plane of a diamond single crystal
- it can be observed with a g vector in the [4-40] direction orthogonal to the g vector.
- it is not observable, it is an edge dislocation, but when it is observable with a plurality of g vectors orthogonal to each other such as [440] direction and [4-40] direction, it is a composite dislocation.
- the single crystal diamond material 20 of the present embodiment preferably includes a plurality of single crystal diamond layers 21 and 22. Since such a single crystal diamond material includes a plurality of single crystal diamond layers 21 and 22, generation of large defects is further suppressed.
- CVD chemical vapor phase
- main surface 10m of diamond seed crystal 10 having a seed crystal defect linear assembly region in which a group of seed crystal defect points 10dp gathers on main surface 10m and extends linearly.
- a crystal defect line 21dq that inherits the defect of the seed crystal defect point 10dp on the main surface 10m extends in the crystal growth direction.
- the crystal defect line 22dq that inherits the defect of the crystal defect line 21dq extends in the crystal growth direction, and the single crystal diamond material The tip of the 20 crystal growth main surface 20m becomes a crystal defect point 20dp.
- a plurality of crystal defect lines 21 dq are inherited from one seed crystal defect point 10 dp of the diamond seed crystal 10, and in the second single crystal diamond layer 22. Since a plurality of crystal defect lines 22dq are inherited from one crystal defect line 21dq of the first single crystal diamond layer 21, the crystal defect point 20dp of the single crystal diamond material 20 increases as the number of single crystal diamond layers 21 and 22 increases. Will be more. As a result, as the number of single crystal diamond layers 21 and 22 increases, the crystal defect lines 21dq and 22dq increase from the main surface 20n opposite to the crystal growth main surface 20m toward the crystal growth main surface 20m. As a result, crystals with higher fracture resistance can be obtained.
- the crystal defect lines 21dq and 22dq are newly generated or branched at the interface 212i between the single crystal diamond layers 21 and 22, and the density of the crystal defect points 20dp on the crystal growth main surface 20m.
- the density is preferably higher than the density of crystal defect points on the main surface 20n opposite to the crystal growth main surface 20m.
- Such single crystal diamond material further suppresses the occurrence of large defects.
- the single crystal diamond material 20 of the embodiment has a crystal defect line 20dq indicating a line in which a crystal defect 20d exists in an X-ray topography image of a certain main surface (for example, a crystal growth main surface 20m).
- a plurality of crystal defect linear collective regions 20r extending in a line from a group of crystal defect points 20dp, which is a tip point reaching at least one surface (for example, crystal growth main surface 20m) of single crystal diamond material 20, are arranged in parallel. Preferably present.
- Such single crystal diamond material suppresses the occurrence of large defects.
- linear refers to an angle ⁇ (for example, not less than 10 ° and not more than 90 °) from the fixed linear shape having a certain width and the existence probability of a crystal defect point located in one fixed linear shape. Can be determined by a sharp decrease in the existence probability of the crystal defect point 20dp. That is, if at least five lines are extracted and the crystal defect points that fall into the angle and the line shape are graphed, a peak appears around the fixed line shape, so that it can be determined.
- ⁇ for example, not less than 10 ° and not more than 90 °
- the crystal defect linear gathering region 20r has a length L and a distance D in the linearly extending direction.
- a plurality of crystal defect linear assembly regions 20r exist in parallel at a pitch P.
- the length L of the crystal defect linear assembly region 20r is preferably as large as possible, preferably 300 ⁇ m or more, and more preferably 500 ⁇ m or more.
- the interval D of the crystal defect linear assembly region 20r is preferably as small as possible, preferably 500 ⁇ m or less, and more preferably 250 ⁇ m or less.
- the pitch P between the crystal defect linear aggregate regions 20r is preferably as small as possible, preferably 500 ⁇ m or less, and more preferably 250 ⁇ m or less. Further, the pitch P may not be constant.
- the direction in which the crystal defect linear assembly region 20r extends linearly refers to the average direction of the directions in which the plurality of crystal defect linear assembly regions 20r extend linearly, and each crystal defect linear assembly region 20r is linear.
- the angle ⁇ formed by the direction extending in the direction with the average direction is preferably 30 ° or less.
- the concentration of the unsubstituted nitrogen atom is preferably 1 ppm or more, more preferably 3 ppm or more, further preferably 5 ppm or more, further preferably 8 ppm or more, further preferably 10 ppm or more, 30 ppm.
- the above is particularly preferable. Since the non-substituted nitrogen atoms in the single crystal diamond material 20 are fused with the crystal defect line 20dq, the single crystal diamond material 20 is prevented from generating large defects and has increased resistance to defects. In particular, when the concentration of the unsubstituted nitrogen atom is 10 ppm or more, excellent defect resistance is exhibited.
- non-substituted nitrogen is likely to be formed in diamond with a high defect resistance and more likely to be contained.
- concentration of the unsubstituted nitrogen atom is calculated by subtracting the concentration of the substituted nitrogen atom measured by ESR (electron spin resonance) from the concentration of all nitrogen atoms measured by SIMS (secondary ion mass spectrometry). Is done.
- the light transmittance at a wavelength of 400 nm when the thickness of the single crystal diamond material 20 is 500 ⁇ m is preferably 60% or less, more preferably 30% or less, and more preferably 10% or less. Is more preferable, and 5% or less is particularly preferable. Further, the transmittance of light having a wavelength of 600 nm when the thickness of the single crystal diamond material 20 is 500 ⁇ m is preferably 60% or less, more preferably 30% or less, further preferably 10% or less, and more preferably 5% or less. Particularly preferred.
- the light transmittance at a wavelength of 400 nm is small, there are many crystal defect lines of the single crystal diamond material of the present embodiment, and there are also many non-substituted nitrogens of the single crystal diamond material of the present embodiment, resulting in suppressing cracks, It shows defect resistance.
- the transmittance of light having a longer wavelength of 600 nm is small, there are many crystal defect lines of the single crystal diamond material of this embodiment, and there are also many non-substituted nitrogens of the single crystal diamond material of this embodiment, resulting in cracks. Is suppressed, and fracture resistance is exhibited.
- the light transmittance does not have a large effect if there are only a large number of crystal defect lines.
- the non-substituted nitrogen and the crystal defect lines are mutually connected (the non-substituted nitrogen enters the gap between the crystal defect lines and the crystal defect lines.
- the non-substituted nitrogen and the crystal defect line increase in a synergistic effect, and the sp2 component of the surrounding carbon also increases by a small amount, affecting the light transmittance and entangled. Since the crystal defect line and the non-substitutional nitrogen affect the prevention of the expansion of cracks and chips, the light transmittance in that case is a good index for defect resistance.
- the light transmittance is a substantial transmittance with respect to incident light, and is not a transmittance only within the interior excluding the reflectance. Accordingly, even when there is no absorption or scattering, the maximum transmittance is about 71%.
- the conversion value of the transmittance with different plate thicknesses can be performed by using a generally known formula considering multiple reflection inside the plate.
- the light transmittance when the thickness of the single crystal diamond material is 500 ⁇ m is the light transmittance measured when the thickness is 500 ⁇ m, or measured when the thickness is other than 500 ⁇ m. It refers to the light transmittance converted when the light transmittance is measured and the thickness is 500 ⁇ m.
- the single crystal diamond tip according to this embodiment has a concentration of non-substituted nitrogen atoms of 200 ppm or less, the concentration of substituted nitrogen atoms is lower than the concentration of non-substituted nitrogen atoms, and the main surface of the single crystal diamond tip The off angle is 20 ° or less.
- Such single crystal diamond tips have a small variation in wear rate. In general, it is advantageous in terms of manufacturing method that a single crystal diamond chip is cut from a single crystal diamond material perpendicularly to its main surface, and the numerical values of both off angles are the same.
- the off-angle of the main surface of the single crystal diamond material generally has a large off-angle for the convenience of synthesis such as suppressing polycrystallization. Therefore, even when the off-angle of the main surface is large, the single crystal diamond chip is obliquely cut out from the single crystal diamond material by the off-angle so that the off-angle of the main surface of the single crystal diamond chip is 20 ° or less. This is effective from the viewpoint of less variation in wear rate. From this viewpoint, the off angle of the main surface is preferably less than 10 °, more preferably less than 7 °, further preferably less than 5 °, further preferably less than 3 °, and particularly preferably less than 1 °.
- the variation in the off angle of the single crystal diamond chip depends on the variation in the off angle of the single crystal diamond material, and the smaller the off angle of the single crystal diamond material is, the easier it is to reduce the off angle of the single crystal diamond chip. Further, the above-described explanation is that the difference in the off angle between the crystal growth main surface of the single crystal diamond material (or the crystal growth main surface in the initial stage of growth) and the main surface of the single crystal diamond chip is smaller (for example, 5 ° or less). It is easy to make the variation as follows, but when it exceeds 5 °, it tends to be more than 10 ° off-angle, but the final product is the off-angle of the main surface of the single crystal diamond tip.
- the main surface of the single crystal diamond tip means a surface that plays the main role of functioning as a tool when mounted on a tool regardless of its size, for example, in the case of a drilling tool Means the principal surface assumed to be drilled, and in the case of a cutting tool, the principal surface assumed to be a rake face.
- the main surface of the single crystal diamond tip is not a surface having the maximum area but a surface having higher objectivity. If it is a cylinder, it is a circular surface, and if it is a rectangular parallelepiped or a quadrangular prism, the surface closer to a square is the main surface. If any of the surfaces is close to a square within an error of 8%, it is assumed that the pair of surfaces with higher parallelism is the main surface. In the case of a cube, since the crystal structure of diamond is a face-centered cubic, there is no problem because the off angle is the same regardless of which plane is assumed.
- the single crystal diamond tip according to the present embodiment is cut from the single crystal diamond of the first embodiment. Therefore, the single crystal diamond tip according to the present embodiment has a substantially polygonal column shape (the main surface is a substantially polygonal surface), for example, a substantially quadrangular prism, a substantially regular rectangular column, a substantially rectangular parallelepiped, a substantially cubic shape, Alternatively, it refers to the whole of a substantially cylindrical shape (the main surface is a substantially circular surface) and the like refers to a shape that looks as it is visually, and not to a strictly precise shape. The accuracy is expected to be within ⁇ 10%. Therefore, the off angle of the single crystal diamond material and the off angle of the single crystal diamond chip are not always the same. Moreover, it is preferable from the viewpoint of efficiently using the material that the single crystal diamond tip is basically cut out of translational symmetry from the single crystal diamond material. Such single crystal diamond tips have less wear rate variation.
- the single crystal diamond tip of the present embodiment is manufactured by cutting out a single crystal diamond material, but the off angle and the like that are aligned with the single crystal diamond material vary by simply cutting out. Therefore, it is preferable to cut using a laser having a parallelism of 2 ° or less.
- the parallelism of such a laser is more preferably 1 ° or less, further preferably 0.5 ° or less, and particularly preferably 0.2 ° or less.
- the parallelism requires a device such as improving the optical system at the expense of the depth of focus.
- By utilizing the fact that the laser shows the cutting shape on the wedge it is possible to control a quarter angle (0.05 °) by changing the cutting direction of the opposite sides. With this technique, the off-angle of the main surface of the single crystal diamond tip can be controlled with a small variation.
- the single crystal diamond tip has a highly symmetrical shape such as a cube, it is not good because the surface to be used is difficult to understand.
- a rectangular parallelepiped and shapes having different lengths, widths, and lengths are preferable because the surfaces to be used are easy to understand.
- parallelism can be used regardless of whether they are cut perpendicularly to the surface, obliquely cut, cut perpendicularly to the side, or cut obliquely.
- the main surface of the single crystal diamond tip is preferably a low index surface where the Miller index is represented by an integer of ⁇ 5 or more and 5 or less.
- Such single crystal diamond tips have less wear rate variation.
- at least one plane orientation plane selected from the group consisting of ⁇ 100 ⁇ , ⁇ 110 ⁇ , ⁇ 111 ⁇ , ⁇ 211 ⁇ , ⁇ 311 ⁇ , and ⁇ 331 ⁇ is used as the low index plane. preferable.
- the single crystal diamond chip of the present embodiment has a crystal growth main surface and a main surface parallel to the crystal growth main surface (this main surface is a main surface formed by cutting out from a single crystal diamond material, the same applies hereinafter).
- this main surface is a main surface formed by cutting out from a single crystal diamond material, the same applies hereinafter.
- a crystal defect line showing a line in which a crystal defect is present reaches the principal plane of either the crystal growth principal plane or a principal plane parallel to the crystal growth principal plane. It is preferable that a group of crystal defect points, which are points, exist together and the density of crystal defect points is larger than 2 mm ⁇ 2 . In such a single crystal diamond chip, the occurrence of large defects is suppressed.
- the crystal growth main surface of the single crystal diamond chip and the main surface parallel to the crystal growth main surface are not particularly limited, but from the viewpoint of suppressing the occurrence of large defects in the single crystal diamond chip, It is preferable to be parallel or perpendicular to the main surface.
- the transmittance of light having a wavelength of 400 nm when the thickness of the single crystal diamond tip is 500 ⁇ m is preferably 60% or less, more preferably 30% or less, and further more preferably 10% or less. Preferably, 5% or less is particularly preferable. Further, the transmittance of light having a wavelength of 600 nm when the thickness of the single crystal diamond material 20 is 500 ⁇ m is preferably 60% or less, more preferably 30% or less, further preferably 10% or less, and more preferably 5% or less. Particularly preferred.
- the single crystal diamond tip is made smaller than the single crystal diamond material, it is effective to measure with a general microspectrophotometer. It is preferable that the light incident surface and the light exit surface are polished optically flat so that scattering on the surface is minimized.
- the concentration of the unsubstituted nitrogen atom in the single crystal diamond die is 200 ppm or less
- the concentration of the substituted nitrogen atom is lower than the concentration of the unsubstituted nitrogen atom
- the off-angle of the perpendicular of the low index surface, in which the Miller index of the single crystal die with respect to the hole orientation is expressed by an integer of ⁇ 5 to 5, is 20 ° or less.
- the drilling tool according to the present embodiment includes a single crystal diamond die formed from the single crystal diamond tip of the second embodiment.
- Such drilling tools have small variations in the wear rate of single crystal diamond dies.
- the single crystal diamond die included in the drilling tool of the present embodiment is manufactured from the single crystal diamond chip of the second embodiment. Since the single crystal diamond tip has at least one flat surface, when this drilling tool is used as a reference, a hole for drawing with a certain direction can be formed. (Here, the reference surface is basically the main surface of the single crystal diamond tip, but sometimes the perforation is made on a surface different from the surface defining the main surface of the single crystal diamond tip.) For example, this flat surface and the surface on which the die is placed are matched. If this surface varies, the hole of the drilling tool varies with respect to the surface orientation. Depending on the shape of the rectangular parallelepiped, it is possible to prevent the face from being set by mistake.
- the length, width, and length are all different, but if a rectangular (including a square) or cube (marked by a laser or a graphite layer) is formed, use it if there is no mistake. be able to.
- a single crystal diamond die can be produced from a single crystal diamond chip in which the nitrogen atom concentration and the off-angle of the main surface are controlled.
- the drilling tool of the present embodiment is a crystal defect that is a point at the tip where a crystal defect line showing a crystal defect line in the X-ray topography image of the crystal growth main surface of a single crystal diamond die reaches the crystal growth main surface. It is preferable that a group of points exist and the density of crystal defect points is larger than 2 mm ⁇ 2 . Such a drilling tool suppresses the occurrence of large defects in the single crystal diamond die.
- the crystal growth main surface of the single crystal diamond die is not particularly limited, but it should be parallel or perpendicular to the hole direction of the single crystal diamond die from the viewpoint of suppressing the occurrence of large defects in the single crystal diamond die. Is preferred.
- the drilling tool according to the present embodiment has a density of compound dislocation points, which is a point at a tip where a compound dislocation in which at least one of a plurality of edge dislocations and a plurality of screw dislocations is combined among crystal defect points reaches the crystal growth main surface. Is preferably greater than 2 mm ⁇ 2 . Such a drilling tool suppresses the occurrence of large defects in the single crystal diamond die.
- the single crystal diamond die includes a plurality of single crystal diamond layers, and a crystal defect line is newly generated or branched at the interface of each single crystal diamond layer, so that the crystal defect on the crystal growth main surface It is preferable that the density of points is higher than the density of crystal defect points on the main surface opposite to the crystal growth main surface. Such a drilling tool suppresses the occurrence of large defects in the single crystal diamond die.
- a single crystal diamond die has a plurality of crystal defect linear aggregate regions extending in a line extending from a group of crystal defect points. Such a drilling tool suppresses the occurrence of large defects in the single crystal diamond die.
- the single crystal diamond die preferably has a non-substituted nitrogen atom concentration of 1 ppm or more. Such a drilling tool suppresses the occurrence of large defects in the single crystal diamond die.
- the single crystal diamond die preferably has a light transmittance of a wavelength of 400 nm of 60% or less, more preferably 30% or less when the thickness of the single crystal diamond die is 500 ⁇ m. 10% or less is more preferable, and 5% or less is particularly preferable. Furthermore, the transmittance of light having a wavelength of 600 nm is preferably 60% or less, more preferably 30% or less, further preferably 10% or less, and particularly preferably 5% or less. Such a drilling tool suppresses the occurrence of large defects in the single crystal diamond die.
- the method for manufacturing single crystal diamond material 20 of the present embodiment prepares diamond seed crystal 10 having a seed crystal defect gathering region in which seed crystal defect points 10 dp are gathered on main surface 10 m.
- the seed crystal defect point 10 dp means the seed crystal defect point 10 dp on the main surface 10 m of the diamond seed crystal 10
- the seed crystal defect assembly region is an assembly of crystal defect points on the main surface 10 m of the diamond seed crystal 10. It is the area that is.
- the seed crystal defect gathering region on the main surface 10m of the diamond seed crystal 10 is more preferably a group of seed crystal defect points 10dp, and the seed crystal defect points 10dp are gathered to extend linearly. More preferably, it is a seed crystal defect linear assembly region in which a group of 10 dp seed crystal defect points gather and extend linearly.
- the seed crystal defect point 10 dp, the seed crystal defect assembly region, and the seed crystal defect linear assembly region are transmissive in the direction perpendicular to the main surface 10 m of the diamond seed crystal 10.
- X-ray topography image that is, an X-ray topography image of the main surface 10 m of the diamond seed crystal 10) measured in (1).
- the step of preparing diamond seed crystal 10 having a seed crystal defect gathering region in which seed crystal defect points 10dp are gathered on main surface 10m is not particularly limited. From the viewpoint of efficiently preparing a diamond seed crystal 10 having a seed crystal defect linear assembly region in which a group of seed crystal defect points 10dp is gathered on 10 m and extends linearly, a sub-process of preparing the diamond seed crystal 10; A sub-process for forming a seed crystal defect gathering region in which seed crystal defect points 10 dp are gathered on the main surface 10 m of the diamond seed crystal 10, and implanting ions into the main surface 10 m side of the diamond seed crystal 10. And a sub-process of forming a conductive layer region 10c in which diamond is broken and converted into graphite in the ion-implanted region.
- the diamond seed crystal 10 is an Ib type single crystal diamond or IIa type single crystal diamond grown by an HPHT (high pressure high temperature) method, or an Ib type single crystal diamond or type IIa.
- Single crystal diamond grown by the CVD method using single crystal diamond as a seed crystal is prepared.
- the seed crystal defect point 10 dp includes a seed crystal defect point and a seed crystal dislocation point 10 dd.
- a seed crystal defect point such as edge dislocations, spiral dislocations, composite dislocations in which at least one of a plurality of edge dislocations and a plurality of spiral dislocations is combined
- seed crystal defect point 10 dv seed crystal crack
- Various defect points such as point and seed crystal damage point 10di are included.
- the method for forming the seed crystal defect gathering region is, for example, using a grindstone in which diamond abrasive grains having an average grain size of 9 ⁇ m to 35 ⁇ m are fixed with metal under conditions of a rotational speed of 500 rpm to 3000 rpm and a load of 0.5 kgf to 50 kgf. It is preferable to perform mechanical polishing.
- the load is within a range of 0.5 kgf to 50 kgf, preferably 0.5 kgf or more, more preferably 5 kgf or more, further preferably 10 kf or more, and particularly preferably 20 kgf or more.
- the thickness with respect to the size of the diamond seed crystal is preferably 0.8 mm or more with respect to 4 mm square when the load is 0.5 kgf or more and less than 5 kgf, and 1.6 mm with respect to 4 mm square when the load is 5 kgf or more and less than 20 kgf. Thickness or more is preferable, and when the load is 20 kgf or more, a thickness of 3.2 mm or more is preferable with respect to a 4 mm square.
- RIE reactive ion etching
- microwave plasma etching ion milling, etc. after such mechanical polishing, the density of seed crystal defect point generation can be finely adjusted, and the effect is almost sustained.
- fine cracks can be formed where diamonds that have grown from the left and right are struck by synthesizing diamond so as to fill the grooves using photolithography and etching techniques or lasers.
- the off-angle direction and the groove direction are preferably parallel within a range of ⁇ 10 °. If the off-angle direction and the groove direction are not parallel within the above-mentioned range, the groove is beautifully joined and disappears particularly near the vertical, and a microcrack effective in the present invention cannot be obtained. In this case, the effect of the present invention is eliminated if reactive ion etching, plasma etching, or ion milling is performed up to the formation of the groove.
- the sub-process of forming the conductive layer region 10c on the main surface 10m side of the diamond seed crystal 10 is performed by implanting ions on the main surface 10m side of the diamond seed crystal 10 to form an ion implantation region.
- ions to be implanted carbon, nitrogen, silicon or phosphorus ions are preferably used.
- single crystal diamond material 20 is grown on main surface 10m of diamond seed crystal 10 by a CVD (chemical vapor deposition) method.
- CVD chemical vapor deposition
- a microwave plasma CVD method, a DC plasma CVD method, a hot filament CVD method, or the like is preferably used.
- the gas for single crystal growth hydrogen, methane, argon, nitrogen, oxygen, carbon dioxide, etc. are used, and the concentration of non-substituted nitrogen atoms in the single crystal diamond material (from the total nitrogen atom concentration to the substituted nitrogen atom concentration).
- the subtracted concentration is preferably adjusted to 1 ppm or more, more preferably 3 ppm or more, further preferably 5 ppm or more, further preferably 8 ppm or more, further preferably 10 ppm or more, and particularly preferably 30 ppm or more. Further, a doping gas such as diborane, trimethylboron, phosphine, tertiary butyl phosphorus, or silane may be added.
- the crystal growth principal surface of the single crystal diamond material 20 is preferably in the (100) plane orientation, and at least in the region where the initial crystal growth thickness is 1 ⁇ m to 7 ⁇ m, the growth parameter ( ⁇ ) is 2 or more and the diamond seed crystal 10 It is preferable to grow at a temperature of 1100 ° C. or lower.
- the growth parameter ( ⁇ ) is a value obtained by multiplying the ratio of the crystal growth rate in the ⁇ 100> direction to the crystal growth rate in the ⁇ 111> direction by ⁇ 3.
- the thickness of the single crystal diamond material 20 to be grown is not particularly limited, but is preferably 300 ⁇ m or more, more preferably 500 ⁇ m or more from the viewpoint of suitably forming a cutting tool, polishing tool, optical component, electronic component, semiconductor material, and the like. preferable. From the viewpoint of preventing the occurrence of cracking due to stress with the diamond seed crystal 10, it is preferably 3 mm or less, and more preferably 1.5 mm or less.
- a second single crystal diamond layer 22 is preferably grown as an additional single crystal diamond material 20 on the first single crystal diamond layer 21.
- the first single crystal diamond layer 21 is formed as a single crystal diamond material 20 on the diamond seed crystal 10.
- the second single crystal diamond layer 22 can also be grown continuously.
- the diamond seed crystal 10 is prevented from cracking due to stress due to the increase in the thickness of the single crystal diamond material 20. From this point of view, it is preferable to grow the first single crystal diamond layer 21 having a thickness of 500 ⁇ m or less, then separate the diamond seed crystal, and then add the second single crystal diamond layer 22 to grow.
- the crystal formed in advance in the present invention is used. Defect lines are easily branched, and crystal defect points are increasing.
- the above-mentioned mechanical polishing can also be performed on the crystal growth main surface of the first single crystal diamond layer 21.
- the first single crystal diamond layer 21 is used as a new seed substrate as a diamond shown in FIG.
- the seed crystal 10 grows with an initial starting point.
- the method for manufacturing single crystal diamond material 20 of the present embodiment can further include a step of separating diamond seed crystal 10 from the viewpoint of obtaining single crystal diamond material 20 efficiently. .
- the step of separating the diamond seed crystal 10 is an ion implantation region formed by ion implantation into the diamond seed crystal 10 by electrochemical etching such as electrolytic etching from the viewpoint of efficiently separating the diamond seed crystal 10.
- the diamond seed crystal 10 is preferably separated by decomposing and removing the conductive layer region 10c.
- the method for manufacturing single-crystal diamond material 20 of the present embodiment adds single-crystal diamond material 20 from the viewpoint of obtaining single-crystal diamond material 20 in which the generation of large defects is further suppressed. Then, a step of growing can be further provided.
- a crystal defect line 21dq that inherits the defect of the seed crystal defect point 10dp on the main surface 10m of the diamond seed crystal 10 extends in the crystal growth direction.
- the crystal defect line 22dq that inherits the defect of the crystal defect line 21dq extends in the crystal growth direction, and the single crystal diamond material The tip of the 20 crystal growth main surface 20m becomes a crystal defect point 20dp.
- a plurality of crystal defect lines 21 dq are inherited from one seed crystal defect point 10 dp of the diamond seed crystal 10, and in the second single crystal diamond layer 22. Since a plurality of crystal defect lines 22dq are inherited from one crystal defect line 21dq of the diamond seed crystal 10, as the number of single crystal diamond layers 21 and 22 increases, the number of crystal defect points 20dp of the single crystal diamond material 20 increases. The occurrence of large defects is further suppressed.
- a diamond seed crystal 10 has a main surface grown by the HPHT (high pressure high temperature) method having an off angle of 2 ° in the ⁇ 100> direction from the (001) plane.
- HPHT high pressure high temperature
- An Ib type single crystal diamond having a size of 4 mm ⁇ 4 mm and a thickness shown in Table 1 was prepared.
- the rotational speed is 500 rpm to 3000 rpm, and the load shown in Table 1 (specifically, 10 kgf to 20 kgf or 0.5 kgf to 5 kgf).
- Table 1 specifically, 10 kgf to 20 kgf or 0.5 kgf to 5 kgf.
- “fixed” means that the single crystal diamond material is fixed and polished so that the polishing disk flows in a direction that is relatively easy to polish (for example, the ⁇ 100> direction with respect to the (100) plane). This is a general polishing method (load is small).
- “Rotation ⁇ fixed” is a procedure in which a substrate that has become relatively flat by a general method is first polished for 2 hours while rotating (rotating), and then fixed and polished for 1 hour. It is easy to introduce defects in a linear shape.
- the load during polishing in Table 1 is the load during “fixed” or “rotation ⁇ fixed”.
- a polishing flaw extending linearly in the ⁇ 100> direction is formed as a seed crystal defect linear aggregate region in which crystal defect points are linearly aggregated.
- polishing scratches with scattered crystal defect points were formed.
- an apparatus having a mechanism for suppressing the vibration of the grindstone so that it gradually increases at a speed of 3 kgf / min or less and does not exceed 110% of the maximum value of the above range of the load. Used.
- the average particle diameter is an average particle diameter designated by a manufacturer that supplies a diamond polishing disk, and here, is an average particle diameter in the specifications of a polishing disk manufactured by International Diamond Corporation.
- Such an average particle size is generally determined by a method of selecting particles by sieving, and an average particle size of 35 ⁇ m to 9 ⁇ m is selected by a sieve of # 600 to # 1500 (600 to 1500 sieves per inch). This corresponds to the particle size.
- Examples 1-2, 1-3, and 1-5 as shown in Table 1, grooves having an aspect ratio of 2, a groove width of 3 ⁇ m, and a groove interval of 200 ⁇ m were obtained by photolithography. After the formation, CVD growth was performed without adding nitrogen.
- microwave plasma CVD chemical vapor
- a single crystal diamond material 20 was grown by a phase deposition method.
- the crystal growth gas hydrogen (H 2 ) gas, methane (CH 4 ) gas, and nitrogen (N 2 ) gas are used, and the concentration of CH 4 gas with respect to H 2 gas is 5 mol% to 20 mol%, CH The concentration of N 2 gas with respect to 4 gases was 0 to 5 mol%.
- the crystal growth pressure was 5 kPa to 15 kPa
- the crystal growth temperature (diamond seed crystal temperature) was 800 ° C. to 1200 ° C.
- each diamond seed crystal 10 from each single-crystal diamond material 20 is electroetched to form a conductive layer region in the diamond seed crystal.
- the sample was sliced using a laser and separated from the diamond seed crystal.
- the maximum height difference Dm and the arithmetic mean roughness Ra of the separated surface (main surface opposite to the crystal growth main surface) of the single crystal diamond material obtained by ion implantation and subsequent electrolytic etching are white scanning type white When measured with an interference microscope (ZYGO manufactured by Canon Inc.), Dm was 1 ⁇ m / mm or less, and Ra was 10 nm or less.
- the maximum height difference Dm of the undulation of the separated surface of the single crystal diamond material is 1 ⁇ m /
- the arithmetic average roughness Ra was 10 nm or less. By setting the arithmetic average roughness Ra to 10 nm or less, it was possible to eliminate the influence of scattering in the transmittance evaluation. In the case of separation using a laser, it is necessary to reduce the parallelism as much as possible and to eliminate the deviation between the growth surface and the separation surface in consideration of the spread angle, and to maintain it after polishing. Realized below 5 °.
- Separation using ion implantation was achieved at 0.02 ° or less. Only Examples 1-4 were separated using a laser, and the other samples were separated using ion implantation and subsequent electrolytic etching. When the precise separation method as described above was not used, a variation of ⁇ 2 ° or more had already occurred at this point. In polishing for optical measurement, the parallelism does not have to be particularly concerned. However, since this is an important point in this embodiment in which the variation in off-angle is controlled to be small, separation using ion implantation is preferable.
- the transmittance of light and the transmittance of light having a wavelength of 600 nm are summarized in Table 1.
- the state of the crystal defect points on the main surface, the parallel number of crystal defect linear aggregate regions, the density of crystal defect points, and the density of complex dislocation points were observed and calculated from an X-ray topography image on the main surface.
- the main surface off-angle was measured and calculated by precise X-ray diffraction.
- the concentration of all nitrogen atoms was measured by SIMS.
- the concentration of substitutional nitrogen atoms was measured by ESR.
- the concentration of unsubstituted nitrogen atoms was calculated from the difference between the concentration of all nitrogen atoms and the concentration of substituted nitrogen atoms.
- the transmittance of light having a wavelength of 400 nm and the transmittance of light having a wavelength of 600 nm were measured with a spectrophotometer.
- the single crystal diamond material 20 was processed into the shape of a cutter blade, and the workpiece was cut to evaluate fracture resistance.
- RF4080R manufactured by Sumitomo Electric Hardmetal Co., Ltd. was used as the cutter, and SNEW1204ADFR-WS was used as the wiper chip.
- the cutting speed was 2000 m / min, the depth of cut was 0.05 mm, and the feed amount was 0.05 mm / blade.
- the workpiece was made of aluminum material A5052, and after cutting the workpiece for 30 km, the fracture resistance evaluation I was performed based on the number of defects (number of defects) of the cutter blade of 5 ⁇ m or more. The results are summarized in Table 1.
- the defect resistance evaluation I when the number of defects was 1 or less, it was judged as a usable product.
- the workpiece under the conditions of a cutting speed of 2000 m / min, a cutting amount of 0.10 mm, and a feeding amount of 0.10 mm / blade, the workpiece was made of aluminum material A5052, and after cutting the workpiece by 30 km, the cutter blade was damaged by 5 ⁇ m or more.
- Fracture resistance evaluation II was performed based on the number (number of defects). The results are summarized in Table 1. In the defect resistance evaluation II, when the number of defects was 4 or less, it was regarded as a usable product.
- the concentration of the unsubstituted nitrogen atom is 200 ppm or less
- the concentration of the substituted nitrogen atom is lower than the concentration of the unsubstituted nitrogen atom
- the crystal growth main surface has an off angle of 20 ° or less
- the crystal growth main surface, which is the main surface has a group of crystal defect points that are linearly gathered.
- the number of defects was low in any of the defect evaluation II.
- the concentration of unsubstituted nitrogen atoms was 200 ppm or less and the off-angle of the main surface was 20 ° or less.
- the concentration of the type nitrogen atom is high and the crystal defect points are not gathered on the main surface of the crystal growth main surface.
- the number of defects was also high.
- the observation of the crystal defect point is a point on the crystal growth main surface which is the outermost surface of the single crystal diamond material, and the main surface on which the off angle was measured was measured on the crystal growth main surface in the initial stage of growth.
- the crystal growth main surface at the initial stage of growth substantially coincided with the average surface of the crystal growth main surface at the center 50% of the single crystal diamond material.
- the crystal growth main surface in the initial stage of growth was calculated by measuring two cut surfaces orthogonal to each other almost perpendicularly with CL (cathode luminescence) at the center 1 mm of the single crystal diamond material, and calculating the direction of inclination.
- CL cathode luminescence
- This single crystal diamond material was obtained by polishing and flattening the main surface of crystal growth, but the evaluation result was the same as before polishing.
- This single crystal diamond material used a technique of performing ion etching and electrolytic etching in a separation step from a diamond seed crystal, but there was no significant difference in evaluation results depending on the method of slicing with a laser. In the method of slicing with a laser, after evaluation, mechanical polishing is performed to form a normal flat surface, and then this plate is cut into a desired size with a laser to form a die die for wire drawing. Was made.
- the light transmittance was measured in the state of the single crystal diamond chip just before dicing, and the light transmittance was almost the same as that of the single crystal diamond material.
- the transmittance of the die was measured with a microscopic visible ultraviolet spectrophotometer.
- the laser was cut strictly perpendicular to the main surface of the single crystal diamond material, and the direction was ⁇ 100>, so the main surface of the single crystal diamond chip was (100).
- the hole of the wire drawing die was processed exactly perpendicular to the main surface of the single crystal diamond tip (Group A), and the hole of the wire drawing die was processed by turning off the hole of the wire drawing die by 2 ° in the direction of 2 ° off ( Group B) was produced. Since the off direction is known in relation to the main surface from the time of synthesis of the single crystal diamond material and the formation of the chip, the direction can be marked and aligned in the same direction.
- the hole axis of the B group is less than 1 ° with respect to the low index plane of the crystal plane (100) (the variation of the hole axis is 0
- the hole axis of group A was less than 3 ° (the variation of the hole axis was less than 0.2 °) with respect to the low index plane of the crystal plane (100).
- Table 2 shows the variation in the concentration of unsubstituted nitrogen atoms in each of the A group and the B group (variation with respect to the average concentration).
- Table 2 shows the variation of the wear rate within each group of the A group and the B group (variation with respect to the average wear rate) and the variation of the wear rate within the whole of the A group and the B group (variation with respect to the average wear rate).
- the variation in the concentration of the unsubstituted nitrogen atom within each group of Group A and Group B is within ⁇ 20%.
- the variation of the wear rate within each group was within ⁇ 3%, and the variation of the wear rate within the entire group A and B was within ⁇ 5%.
- Examples 1-4 and 1-5 since a large defect occurred, it was difficult to measure the variation in wear rate in both groups A and B.
- the variation in the angle of the hole axis was less than 0.2 ° in each of the groups A and B, so that the angle of the hole axis was 1 ° and 3 °. Even though it was different from °, the variation in wear rate was small. However, since the variation of the angle of the hole axis is 3 ° or more in the whole of the A group and the B group as a whole, it has been found that the variation in the overall wear rate also becomes large. This was originally due to variations in the off-angle of the diamond material. Furthermore, it has been found that this variation can be easily suppressed when the off-angle of the diamond material is small. Further, it has been found that if the off angle from the index surface of the main surface of the diamond tip is small, the variation in the angle of the hole axis is small, which is more preferable.
- Example 2 Except for the conditions shown in Table 3 and Table 4, the single crystal diamond materials of Examples 2-1 to 2-12 were produced in the same manner as in Example 1, and their fracture resistance evaluation I and fracture resistance evaluation II. Was done. The results are shown in Tables 3 and 4. Here, since the polishing was performed carefully with respect to how to select the polishing direction at the time of polishing in Tables 3 and 4, the distinction was described.
- “rotation ⁇ fixed” is a procedure in which a substrate that has become relatively flat by a general method is first polished (rotated) for 2 hours and then fixed and then polished for 1 hour. That is. It is easy to introduce defects in a linear shape.
- “Fixing ⁇ rotation” is a procedure in which a substrate that has become relatively flat by a general method is first fixed and polished for 1 hour, and then rotated and rotated for 2 hours. It is easy to introduce non-linear assembled defects.
- the loads during polishing in Tables 3 and 4 are loads during “rotation ⁇ fixed” and “fixed ⁇ rotation”. Since the substrate formed by the CVD method has a clean AsGrown surface, it can be grown without polishing. Therefore, a diamond seed crystal without polishing was also tested.
- the concentration of the unsubstituted nitrogen atom is 200 ppm or less and the main surface has an off angle of 20 ° or less. Since a group of crystal defect points existed in a set or a linear form on a certain crystal growth main surface, the number of defects was low in both the defect resistance evaluation I and the defect resistance evaluation II.
- the single crystal diamond material was separated from the diamond seed crystal. In Example 2-11 alone, the single crystal diamond material was not separated from the diamond seed crystal and was evaluated to include the unpolished CVD diamond seed crystal shown in Example 2-11.
- Example 2-12 the single crystal diamond material was separated from the unpolished CVD diamond seed crystal shown in Example 2-12, and the separated single crystal diamond material was evaluated.
- Example 2-12 since the surfaces were separated without being polished, the undulation of the main surface opposite to the crystal growth main surface was large.
- Example 2-13 an attempt was made to synthesize a single crystal diamond material having a non-substituted nitrogen atom concentration of 250 ppm. However, since a diamond material containing 15% or more of non-single crystal diamond and non-diamond was obtained, Table 3 and Evaluation in Table 4 could not be performed. Therefore, it was difficult to produce a drilling tool.
- Example 2-14 an attempt was made to produce a single crystal diamond material under the same conditions as in Example 2-4 except that only the off-angle of the diamond seed crystal was 25 °. %, The evaluation in Tables 3 and 4 could not be performed.
- the observation of the crystal defect point is a point on the crystal growth main surface which is the outermost surface of the single crystal diamond material, but the main surface where the off-angle is measured is the crystal growth main surface in the initial stage of growth.
- the crystal growth main surface at the initial stage of growth substantially coincided with the average surface of the crystal growth main surface at the center 50% of the single crystal diamond material.
- the crystal growth main surface in the initial stage of growth was calculated by measuring two cut surfaces orthogonal to each other almost perpendicularly with CL (cathode luminescence) at the center 1 mm of the single crystal diamond material, and calculating the direction of inclination.
- a group of points means that the areas of points are in contact with each other or overlapped.
- a set of points in a line means that a set of points is elongated and connected in a line.
- a “group of points” refers to a collection of crystal defect points based on crystal defect lines branched from the same starting point.
- the “crystal defect point of the seed crystal” is a combination of the origin of a group of crystal defect lines of a single crystal layer and the origin of a crystal defect line that is not a group.
- “Aggregation” means that 70% of the total number of crystal defect points in a specific range are concentrated in an area of 50% of the total area of the specific range.
- the range of one crystal defect point is a range having a radius to the nearest crystal defect point.
- Dotted refers to a state in which the above definitions are not aggregated.
- Ib type single crystal diamond material and natural Ia type single crystal diamond material produced by the HPHT (high pressure and high temperature) method were used.
- the evaluations in Table 3 and Table 4 were performed. The results are summarized in Table 5.
- Example 3 For the single crystal diamond materials of Examples 2-1 to 2-11 where the number of defects is 1 or less in Fracture Resistance Evaluation I, a diamond tip and a diamond drilling tool were prepared, and variations in off-angle and wear rate were evaluated. did. The results are summarized in Tables 5-7. For comparison, Ib type single crystal diamond material and natural Ia type single crystal diamond material manufactured by HPHT (high pressure and high temperature) method are also prepared with diamond tips and diamond drilling tools, and variation in off-angles. And the variation of wear rate was evaluated. The results are summarized in Tables 6 to 8.
- the hole axis and crystal plane orientation can be confirmed by looking at the outline of multiple holes as seen through the hole axis direction with a microscope (the innermost circle that can be confirmed with the smallest diameter of the outermost circle and hole where the rectangular parallelepiped of the hole and the tip intersects) Evaluation was performed by X-ray diffraction in a state where the chip was fixed to the pedestal so that the direction in which the contours of the circles and the like became concentric was vertical. X-ray evaluation was performed in the same manner as a general method for evaluating fluctuations, off-angles, and pole figures of plate-like single crystal diamond crystals. By making the perpendicular direction of the X-ray diffraction measurement coincide with the direction of the hole axis, the inclination angle of the hole axis could be confirmed by measuring the off-tilt of the crystal plane.
- variation in off-angle within ⁇ 1.0 ° for Examples 3-1 to 3-17, within ⁇ 3.0 ° for Example 3-18
- variation in wear rate Within ⁇ 5.0% for Examples 3-1 to 3-17 and within ⁇ 10% for Example 3-18
- HPHT high pressure and high temperature
- Example 3 From the evaluation of the variation in off angle and the variation in wear rate in Example 3, it was found that a single crystal diamond tip having a small off angle on the main surface has a small variation in wear rate due to wire drawing and is preferable. .
- the off angle of the main surface of the single crystal diamond tip coincided with the off angle from the crystal plane orientation of the hole axis of the wire drawing die. Basically, since a single crystal diamond chip cuts a single crystal diamond material vertically, it is judged that a smaller off angle of the main surface of the single crystal diamond material is better.
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Abstract
Description
しかしながら、注意深く観察すると、同じように使ってきたはずの穿孔工具、耐磨工具や切削工具(たとえば、伸線ダイス、切削バイト)でも、大きな欠損の発生程度や摩耗率に違いがあることが確認できる。これは加工(たとえば、伸線)という行為が非常に複雑なメカニズムで起こっている現象であることから、その違いに対して、特に注意を払ってこなかった。すなわち、まず被加工材自体が全く同じ特性というわけではなく、弾性率、ヤング率、硬さ、強度などにおいて微妙にばらついている。また、機械で加工するのであるが、モーターや被加工材への圧力や張力に微妙なばらつきが伴い、被加工材に押し当てる力や引く力が微妙に違っている。加工をドライ方式で行う場合は、室温、湿度の影響を受けると考えられるが、同じ室温、同じ湿度でいつも加工しているわけではない。また、ウェット方式で行う場合でも、冷却剤や潤滑剤も種類が多く、品質にも若干のムラがある。等々のようにあらゆるパラメータが絡んでいるのであるから、何かが少しずつ違うだけでも、大きく摩耗に影響すると考えられる。このような現象の複雑さがあるために、穿孔工具、耐磨工具や切削工具側の違いもあると認識したとしても、明確に制御の対象として注目はされてこなかった。
上記によれば、大きな欠損の発生が抑制されるとともに摩耗率のばらつきが小さい単結晶ダイヤモンド材、単結晶ダイヤモンドチップおよび穿孔工具が提供できる。
最初に本発明の実施態様を列記して説明する。
<実施形態1:単結晶ダイヤモンド材>
図1~図3を参照して、本実施形態の単結晶ダイヤモンド材20は、非置換型窒素原子の濃度が200ppm以下であり、非置換型窒素原子の濃度より置換型窒素原子の濃度が低く、かつ、結晶成長主面のオフ角が20°以下である。本実施形態の単結晶ダイヤモンド材20は、大きな欠損の発生が抑制されるとともに摩耗率のばらつきが小さい。ここで、単結晶ダイヤモンド材20の結晶成長主面20mとは、単結晶ダイヤモンド材において結晶成長により形成される結晶成長側の主な表面をいう。単結晶ダイヤモンド材の主面とは、単結晶ダイヤモンド材としての物性を有する主な表面をいい、結晶成長主面20m、結晶成長主面に平行な主面および結晶成長主面20mに反対側の主面20nなどを含む。なお、単結晶ダイヤモンド材の主面が、結晶成長主面、結晶成長主面に平行な主面、および結晶成長主面に反対側の主面のいずれであるかは、後述のように、上記主面および/または上記主面と交わる断面におけるX線トポグラフィー像により識別できる。
本実施形態にかかる単結晶ダイヤモンドチップは、非置換型窒素原子の濃度が200ppm以下であり、非置換型窒素原子の濃度より置換型窒素原子の濃度が低く、かつ、単結晶ダイヤモンドチップの主面のオフ角が20°以下である。かかる単結晶ダイヤモンドチップは、摩耗率のばらつきが小さい。一般に単結晶ダイヤモンドチップは単結晶ダイヤモンド材からその主面に垂直に切り出し、双方のオフ角の数値が一致していることが製法上有利である。しかしながら、単結晶ダイヤモンド材の主面のオフ角は、多結晶化を抑制するなどの合成上の都合により、一般的に大きなオフ角を有する。したがって、主面のオフ角が大きい場合も、単結晶ダイヤモンドチップは単結晶ダイヤモンド材からオフ角分だけ斜めに切り出して、単結晶ダイヤモンドチップの主面のオフ角を20°以下にすることが、摩耗率のばらつきがより小さい観点から有効である。かかる観点から、主面のオフ角は、10°未満が好ましく、7°未満がより好ましく、5°未満がさらに好ましく、3°未満がさらに好ましく、1°未満が特に好ましい。
本実施形態にかかる穿孔工具は、単結晶ダイヤモンドダイスにおける非置換型窒素原子の濃度が200ppm以下であり、非置換型窒素原子の濃度より置換型窒素原子の濃度が低く、かつ、伸線用の孔の方位に対する単結晶ダイスのミラー指数が-5以上5以下の整数で表示される低指数面の垂線のオフ角が20°以下である。かかる穿孔工具は、単結晶ダイヤモンドダイスの大きな欠損の発生が抑制されるとともに摩耗率のばらつきが小さい。
図4を参照して、本実施形態の単結晶ダイヤモンド材20の製造方法は、主面10m上に種結晶欠陥点10dpが集合している種結晶欠陥集合領域を有するダイヤモンド種結晶10を準備する工程(図4(A))と、ダイヤモンド種結晶10の主面10m上に、化学気相堆積法により単結晶ダイヤモンド材20を成長させる工程(図4(B))と、を備える。種結晶欠陥点10dpとは、ダイヤモンド種結晶10の主面10m上における種結晶欠陥点10dpの意味であり、種結晶欠陥集合領域とはダイヤモンド種結晶10の主面10m上に結晶欠陥点が集合している領域である。上記のダイヤモンド種結晶10の主面10m上の種結晶欠陥集合領域は、種結晶欠陥点10dpの群が集合していることがより好ましく、種結晶欠陥点10dpが集合して線状に延びていることがさらに好ましく、種結晶欠陥点10dpの群が集合して線状に延びている種結晶欠陥線状集合領域であることが特に好ましい。
図4(A)を参照して、主面10m上に種結晶欠陥点10dpの集合している種結晶欠陥集合領域を有するダイヤモンド種結晶10を準備する工程は、特に制限はないが、主面10m上に種結晶欠陥点10dpの群が集合して線状に延びる種結晶欠陥線状集合領域を有するダイヤモンド種結晶10を効率的に準備する観点から、ダイヤモンド種結晶10を準備するサブ工程と、ダイヤモンド種結晶10の主面10m上に種結晶欠陥点10dpが集合している種結晶欠陥集合領域を形成するサブ工程と、ダイヤモンド種結晶10の主面10m側に、イオンを注入することにより、イオン注入領域にダイヤモンドが破壊されてグラファイトに転化した導電層領域10cを形成するサブ工程と、を含むことができる。
図4(B)を参照して、単結晶ダイヤモンド材20を成長させる工程は、ダイヤモンド種結晶10の主面10m上に、CVD(化学気相堆積)法により、単結晶ダイヤモンド材20を成長させることにより行なう。CVD法としては、マイクロ波プラズマCVD法、DCプラズマCVD法、ホットフィラメントCVD法などが好適に用いられる。単結晶成長用ガスとしては、水素、メタン、アルゴン、窒素、酸素、二酸化炭素などを用いて、単結晶ダイヤモンド材中の非置換型窒素原子の濃度(全窒素原子濃度から置換型窒素原子濃度を差し引いた濃度)が、好ましくは1ppm以上、より好ましくは3ppm以上、さらに好ましくは5ppm以上、さらには好ましくは8ppm以上、さらに好ましくは10ppm以上、特に好ましくは30ppm以上になるように調整する。さらに、ジボラン、トリメチルボロン、ホスフィン、ターシャルブチルリン、シランなどのドーピングガスを添加してもよい。単結晶ダイヤモンド材20の結晶成長主面が(100)面方位であることが好ましく、結晶成長初期の厚さが1μm~7μmの領域は、少なくとも成長パラメーター(α)が2以上かつダイヤモンド種結晶10の温度が1100℃以下で成長することが好ましい。ここで、成長パラメーター(α)とは、<111>方向の結晶成長速度に対する<100>方向の結晶成長速度の比を√3倍した値である。
図4(C)を参照して、本実施形態の単結晶ダイヤモンド材20の製造方法は、効率よく単結晶ダイヤモンド材20を得る観点から、ダイヤモンド種結晶10を分離する工程をさらに備えることができる。
図4(D)を参照して、本実施形態の単結晶ダイヤモンド材20の製造方法は、大きな欠損の発生がさらに抑制される単結晶ダイヤモンド材20を得る観点から、単結晶ダイヤモンド材20を追加して成長させる工程をさらに備えることができる。
(試料の作製)
1.ダイヤモンド種結晶の準備
図4(A)を参照して、ダイヤモンド種結晶10として、HPHT(高圧高温)法により成長させた主面が(001)面から<100>方向に2°のオフ角を有するサイズが4mm×4mmで表1に示す厚さのIb型単結晶ダイヤモンドを準備した。
次に、図4(B)を参照して、各々のダイヤモンド種結晶10の種結晶欠陥線状集合領域が形成された主面10m上に、マイクロ波プラズマCVD(化学気相堆積)法により、単結晶ダイヤモンド材20を成長させた。結晶成長用ガスとして、水素(H2)ガス、メタン(CH4)ガス、および窒素(N2)ガスを使用し、H2ガスに対するCH4ガスの濃度を5モル%~20モル%、CH4ガスに対するN2ガスの濃度を0~5モル%とした。結晶成長圧力は5kPa~15kPaとし、結晶成長温度(ダイヤモンド種結晶の温度)は800℃~1200℃とした。
次に、図4(C)および(D)を参照して、各々の単結晶ダイヤモンド材20から各々のダイヤモンド種結晶10を、電解エッチングにより、ダイヤモンド種結晶中の導電層領域を分解除去することにより、ダイヤモンド種結晶から分離した。あるいはイオン注入をしなかった場合にはレーザーを用いてスライスして、ダイヤモンド種結晶から分離した。イオン注入およびその後の電解エッチングにより得られた単結晶ダイヤモンド材の分離した面(結晶成長主面に反対側の主面)のうねりの最大高低差Dmおよび算術平均粗さRaは、白色走査型白色干渉型顕微鏡(キャノン社製ZYGO)により測定したところ、Dmは1μm/mm以下で、Raは10nm以下であった。レーザーを用いてスライスした場合は分離後に研磨を必要とし、研磨をすれば、単結晶ダイヤモンド材の分離した面(結晶成長主面に反対側の主面)のうねりの最大高低差Dmは1μm/mm以下で、算術平均粗さRaは10nm以下とすることができた。算術平均粗さRaを10nm以下とすることで、透過率評価において、散乱の影響をなくすことができた。レーザーを用いて分離した場合は、その平行度をできるだけ小さくするとともに、広がり角度を勘案して、成長面と分離面とのズレをなくしておき、研磨後にも維持する必要があるが、0.5°以下で実現した。イオン注入を用いた分離では、0.02°以下で実現した。例1-4のみレーザーを用いて分離し、その他の試料はイオン注入およびその後の電解エッチングを用いて分離した。以上のような精密な分離方法を用いない場合は、すでにこの時点で±2°以上のばらつきが生じた。光学測定のための研磨においては平行度を特に気にしなくともよかったが、オフ角のばらつきを小さく制御する本実施例では重要なポイントなので、イオン注入を用いた分離の方が好ましい。
表3および表4に示す条件以外は、実施例1と同様にして、例2-1~例2-12の単結晶ダイヤモンド材を作製し、それらの耐欠損性評価Iおよび耐欠損性評価IIを行なった。結果を表3および表4に示した。ここで、表3および4の研磨時の研磨方向の選び方について、注意して研磨を行ったので、その区別を記載した。表3および4中「回転→固定」というのは、一般的な方法で比較的平坦になった基板を、まずは回転(自転)させながら2時間研磨し、その後固定させて1時間研磨する手順のことである。線状に欠陥を導入しやすい。「固定→回転」というのは、一般的な方法で比較的平坦になった基板を、まずは固定して1時間研磨し、その後2時間回転して研磨する手順のことである。線状ではない集合した欠陥を導入しやすい。表3および4中の研磨時の荷重は、「回転→固定」、「固定→回転」中の荷重である。CVD法で形成した基板は、AsGrownの表面がきれいであるので、研磨をしなくとも成長させることができるので、研磨無しの条件のダイヤモンド種結晶についても実験した。
耐欠損性評価Iにおいて欠損数が1個以下の例2-1~例2-11の単結晶ダイヤモンド材について、ダイヤモンドチップとダイヤモンド穿孔工具を作製し、オフ角のばらつきと摩耗率のばらつきを評価した。結果を表5~表7にまとめた。また、対比のために、HPHT(高圧高温)法で作製したIb型の単結晶ダイヤモンド材および天然のIa型の単結晶ダイヤモンド材についても、ダイヤモンドチップとダイヤモンド穿孔工具を作製し、オフ角のばらつきと摩耗率のばらつきを評価した。結果を表6~表8にまとめた。
Claims (25)
- 非置換型窒素原子の濃度が200ppm以下であり、前記非置換型窒素原子の濃度より置換型窒素原子の濃度が低く、かつ、結晶成長主面のオフ角が20°以下である単結晶ダイヤモンド材。
- 前記結晶成長主面のオフ角が7°未満である請求項1に記載の単結晶ダイヤモンド材。
- 置換型窒素原子の濃度が80ppm未満である請求項1または請求項2に記載の単結晶ダイヤモンド材。
- 前記非置換型窒素原子および前記置換型窒素原子の全体である全窒素原子の濃度が0.1ppm以上である請求項1から請求項3のいずれか1項に記載の単結晶ダイヤモンド材。
- 前記結晶成長主面に反対側の主面と前記結晶成長主面との平行からのずれ角が2°未満であり、前記結晶成長主面に反対側の主面は、そのうねりの最大高低差Dmが10μm/mm以下であり、かつ、その算術平均粗さRaが0.1μm以下である請求項1から請求項4のいずれか1項に記載の単結晶ダイヤモンド材。
- 前記結晶成長主面についてのX線トポグラフィー像において結晶欠陥が存在する線を示す結晶欠陥線が前記結晶成長主面に達する先端の点である結晶欠陥点の群が集合して存在する請求項1から請求項5のいずれか1項に記載の単結晶ダイヤモンド材。
- 前記結晶欠陥点の密度が2mm-2より大きい請求項6に記載の単結晶ダイヤモンド材。
- 前記結晶欠陥点のうち、複数の刃状転位および複数の螺旋転位の少なくともいずれかが複合した複合転位が前記結晶成長主面に達する先端の点である複合転位点の密度が2mm-2より大きい請求項6または請求項7に記載の単結晶ダイヤモンド材。
- 複数の単結晶ダイヤモンド層を含む請求項6から請求項8のいずれか1項に記載の単結晶ダイヤモンド材。
- 各前記単結晶ダイヤモンド層の界面で、前記結晶欠陥線が新たに発生または分岐しており、前記結晶成長主面の前記結晶欠陥点の密度が、前記結晶成長主面に反対側の主面の前記結晶欠陥点の密度より高い請求項9に記載の単結晶ダイヤモンド材。
- 前記結晶欠陥点の群が集合して線状に延びる結晶欠陥線状集合領域が複数並列に存在する請求項6から請求項10のいずれか1項に記載の単結晶ダイヤモンド材。
- 前記非置換型窒素原子の濃度が1ppm以上である請求項6から請求項11のいずれか1項に記載の単結晶ダイヤモンド材。
- 前記単結晶ダイヤモンド材の厚さを500μmとしたときの波長400nmの光の透過率が60%以下である請求項1から請求項12のいずれか1項に記載の単結晶ダイヤモンド材。
- 非置換型窒素原子の濃度が200ppm以下であり、前記非置換型窒素原子の濃度より置換型窒素原子の濃度が低く、かつ、単結晶ダイヤモンドチップの主面のオフ角が20°以下である単結晶ダイヤモンドチップ。
- 請求項1から請求項13のいずれか1項に記載の単結晶ダイヤモンド材から切り出された単結晶ダイヤモンドチップ。
- 前記単結晶ダイヤモンドチップの主面が、ミラー指数が-5以上5以下の整数で表示される低指数面である請求項14または請求項15に記載の単結晶ダイヤモンドチップ。
- 前記単結晶ダイヤモンドチップは、結晶成長主面および前記結晶成長主面に平行な主面のいずれかの主面についてのX線トポグラフィー像において結晶欠陥が存在する線を示す結晶欠陥線が前記結晶成長主面および前記結晶成長主面に平行な主面のいずれかの主面に達する先端の点である結晶欠陥点の群が集合して存在し、前記結晶欠陥点の密度が2mm-2より大きい、請求項14から請求項16のいずれか1項に記載の単結晶ダイヤモンドチップ。
- 単結晶ダイヤモンドダイスにおける非置換型窒素原子の濃度が200ppm以下であり、前記非置換型窒素原子の濃度より置換型窒素原子の濃度が低く、かつ、伸線用の孔の方位に対する前記単結晶ダイスのミラー指数が-5以上5以下の整数で表示される低指数面の垂線のオフ角が20°以下である前記単結晶ダイヤモンドダイスを含む穿孔工具。
- 請求項14から請求項17のいずれか1項に記載の単結晶ダイヤモンドチップから形成される単結晶ダイヤモンドダイスを含む穿孔工具。
- 前記単結晶ダイヤモンドダイスは、結晶成長主面についてのX線トポグラフィー像において結晶欠陥が存在する線を示す結晶欠陥線が前記結晶成長主面に達する先端の点である結晶欠陥点の群が集合して存在し、前記結晶欠陥点の密度が2mm-2より大きい、請求項18または請求項19に記載の穿孔工具。
- 前記結晶欠陥点のうち、複数の刃状転位および複数の螺旋転位の少なくともいずれかが複合した複合転位が結晶成長主面に達する先端の点である複合転位点の密度が2mm-2より大きい、請求項20に記載の穿孔工具。
- 前記単結晶ダイヤモンドダイスは複数の単結晶ダイヤモンド層を含み、
各前記単結晶ダイヤモンド層の界面で、前記結晶欠陥線が新たに発生または分岐しており、前記結晶成長主面の前記結晶欠陥点の密度が、前記結晶成長主面に反対側の主面の前記結晶欠陥点の密度より高い、請求項20または請求項21に記載の穿孔工具。 - 前記単結晶ダイヤモンドダイスには、前記結晶欠陥点の群が集合して線状に延びる結晶欠陥線状集合領域が複数並列して存在する、請求項20から請求項22のいずれか1項に記載の穿孔工具。
- 前記単結晶ダイヤモンドダイスは、前記非置換型窒素原子の濃度が1ppm以上である請求項18から請求項23のいずれか1項に記載の穿孔工具。
- 前記単結晶ダイヤモンドダイスは、前記単結晶ダイヤモンドダイスの厚さを500μmとしたときの波長400nmの光の透過率が60%以下である請求項18から請求項24のいずれか1項に記載の穿孔工具。
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JP6996690B1 (ja) * | 2020-12-24 | 2022-01-17 | 住友電工ハードメタル株式会社 | ダイヤモンド工具中間体の製造方法および単結晶ダイヤモンドの判定方法 |
WO2022137429A1 (ja) * | 2020-12-24 | 2022-06-30 | 住友電工ハードメタル株式会社 | ダイヤモンド工具中間体の製造方法および単結晶ダイヤモンドの判定方法 |
US11878354B2 (en) | 2020-12-24 | 2024-01-23 | Sumitomo Electric Hardmetal Corp. | Method of manufacturing diamond tool intermediate and method of making determination for single-crystal diamond |
Also Published As
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EP3327179A4 (en) | 2019-01-23 |
EP3327179A1 (en) | 2018-05-30 |
SG11201704357TA (en) | 2017-06-29 |
JPWO2017014311A1 (ja) | 2017-07-20 |
WO2017014311A9 (ja) | 2017-05-11 |
KR20180034301A (ko) | 2018-04-04 |
JP6118954B1 (ja) | 2017-04-19 |
US10774442B2 (en) | 2020-09-15 |
KR102626684B1 (ko) | 2024-01-17 |
EP3327179B1 (en) | 2023-08-23 |
US20190218685A1 (en) | 2019-07-18 |
US20170241042A1 (en) | 2017-08-24 |
CN107109691B (zh) | 2021-05-25 |
US10287708B2 (en) | 2019-05-14 |
CN107109691A (zh) | 2017-08-29 |
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