WO2016013588A1 - 単結晶ダイヤモンドおよびその製造方法、単結晶ダイヤモンドを含む工具、ならびに単結晶ダイヤモンドを含む部品 - Google Patents
単結晶ダイヤモンドおよびその製造方法、単結晶ダイヤモンドを含む工具、ならびに単結晶ダイヤモンドを含む部品 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
- B23B27/18—Cutting tools of which the bits or tips or cutting inserts are of special material with cutting bits or tips or cutting inserts rigidly mounted, e.g. by brazing
- B23B27/20—Cutting tools of which the bits or tips or cutting inserts are of special material with cutting bits or tips or cutting inserts rigidly mounted, e.g. by brazing with diamond bits or cutting inserts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B53/00—Devices or means for dressing or conditioning abrasive surfaces
- B24B53/04—Devices or means for dressing or conditioning abrasive surfaces of cylindrical or conical surfaces on abrasive tools or wheels
- B24B53/047—Devices or means for dressing or conditioning abrasive surfaces of cylindrical or conical surfaces on abrasive tools or wheels equipped with one or more diamonds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/26—Preparation
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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
- C23C16/02—Pretreatment of the material to be coated
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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
- 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
- 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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- 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
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/68—Crystals with laminate structure, e.g. "superlattices"
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
Definitions
- the present invention relates to a single crystal diamond suitably used for a cutting tool, a polishing tool, an optical component, an electronic component, a semiconductor material and the like, a manufacturing method thereof, a tool including a single crystal diamond, and a component including a single crystal diamond.
- Diamond has excellent properties such as high thermal conductivity, high carrier mobility, high dielectric breakdown electric field, and low induction loss, and is widely used for cutting tools and anti-abrasion tools because of its unparalleled high hardness.
- Conventionally, single crystal diamond synthesized by a natural or high temperature / high pressure method has been widely used, but in recent years, a single crystal diamond that can be thick and self-supported by chemical vapor deposition (CVD) can be synthesized. Application is awaited.
- CVD chemical vapor deposition
- Non-Patent Document 1 discloses a single crystal CVD diamond layer having a thickness larger than 2 mm and a high quality single crystal CVD diamond layer having excellent electronic properties. A method of synthesizing by a CVD method after reducing the defect density on the surface of a diamond substrate serving as a seed substrate is disclosed.
- Non-patent Document 1 Japanese translations of PCT publication No. 2004-503461
- CVD single crystal diamond a single crystal diamond
- the CVD single crystal diamond is more resistant to defects than natural single crystal diamond and single crystal diamond grown by a high temperature high pressure method (hereinafter also referred to as high temperature high pressure single crystal diamond).
- Non-patent Document 1 Non-patent Document 1
- JP-T-2004-503461 Patent Document 1
- single crystal diamond suitably used for cutting tools, polishing tools, optical parts, electronic parts, semiconductor materials and the like, a manufacturing method thereof, a tool containing single crystal diamond, and single crystal diamond It aims at providing the part containing.
- the single crystal diamond according to an aspect of the present invention has a crystal defect point that is a point of a tip where a crystal defect line showing a crystal defect line in the X-ray topography image of the crystal growth main surface reaches the crystal growth main surface.
- a plurality of crystal defect linear aggregate regions extending linearly in a direction within 30 ° from one direction that is arbitrarily specified by the aggregation of the groups are present in parallel.
- a method for producing a single crystal diamond according to another aspect of the present invention includes a step of preparing a diamond seed crystal having a seed crystal defect linear assembly region in which a group of seed crystal defect points aggregates and extends linearly on a main surface And a step of growing single crystal diamond on the main surface of the diamond seed crystal by chemical vapor deposition.
- a single crystal diamond suitably used for a cutting tool, a polishing tool, an optical component, an electronic component, a semiconductor material and the like, a manufacturing method thereof, a tool including the single crystal diamond, and a component including the single crystal diamond.
- a single crystal diamond according to an embodiment of the present invention has a crystal defect that is a point at a tip where a crystal defect line showing 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 points exists.
- the single crystal diamond of the present embodiment is suitably used for cutting tools, polishing tools, optical parts, electronic parts, semiconductor materials, and the like because generation of large defects is suppressed by stress relaxation due to a large number of crystal defect lines.
- a single crystal diamond according to an embodiment of the present invention has a crystal defect that is a point at a tip where a crystal defect line showing a crystal defect exists in an X-ray topography image of the crystal growth main surface reaches the crystal growth main surface.
- a plurality of crystal defect linear aggregate regions extending in a linear form in a direction within 30 ° from one direction arbitrarily specified by a collection of points are present in parallel.
- the single crystal diamond of the present embodiment is linear in a direction within 30 ° from one direction that is arbitrarily specified by a group of crystal defect points that are points at the tip where the crystal defect line reaches the crystal growth main surface. Since a plurality of extending crystal defect linear assembly regions exist in parallel, the generation of large defects is suppressed by stress relaxation due to a large number of crystal defect lines, and a plurality of parallelly existing ones from an arbitrarily specified direction existing in parallel Since the direction in which chipping hardly occurs can be controlled by the crystal defect linear assembly region extending linearly in a direction within 30 °, it is suitably used for cutting tools, polishing tools, optical components, electronic components, semiconductor materials, and the like.
- two or more crystal defect linear aggregate regions exist per 1 mm in a direction perpendicular to the direction in which the crystal defect linearly extends, and an interval in the linearly extending direction is 500 ⁇ m.
- the direction in which the crystal defect linear assembly region extends linearly refers to the one direction specified above, which is the average direction of the plurality of directions in which the plurality of crystal defect linear assembly regions extend.
- Such a single crystal diamond has two or more crystal defect linear aggregate regions per mm in a direction perpendicular to the direction in which the single crystal diamond extends linearly, and an interval in the linearly extending direction is 500 ⁇ m or less.
- the generation of large defects is suppressed by stress relaxation due to a large number of crystal defect lines, and a plurality of high-density crystal defects arranged in parallel in a direction within 30 ° from an arbitrarily specified direction existing in parallel
- the direction in which chipping is difficult can be controlled by the linear assembly region 20r.
- the crystal defect linear assembly region can include five or more long crystal defect linear assembly regions having a length of 300 ⁇ m or more per 1 cm 2 of the crystal growth main surface.
- Such single crystal diamond includes five or more long crystal defect linear aggregate regions having a length of 300 ⁇ m or more per 1 cm 2 of the crystal growth main surface. The strength of the whole crystal diamond is enhanced. From this viewpoint, the crystal defect linear assembly region can include 20 or more longer crystal defect linear assembly regions having a length of 500 ⁇ m or more per 1 cm 2 of the main surface.
- the density of crystal defect points can be made larger than 20 mm ⁇ 2 .
- the density of crystal defect points is larger than 20 mm ⁇ 2 , so that generation of large defects is suppressed by stress relaxation due to high-density crystal defect lines corresponding to high-density crystal defect points.
- the density of crystal defect points can be made larger than 300 mm ⁇ 2 . Since such single crystal diamond has a density of crystal defect points greater than 300 mm ⁇ 2 , the generation of large defects is further suppressed due to stress relaxation by a high density crystal defect line corresponding to a higher density crystal defect point.
- a composite dislocation point that is 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 reaches the crystal growth main surface.
- the density can be greater than 20 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, so that large defects are generated. Is further suppressed.
- a composite dislocation that is 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 reaches the crystal growth main surface.
- the point density can be greater than 30 mm -2 .
- Such a single crystal diamond has a large defect since 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 30 mm ⁇ 2 and the effect of stress relaxation by the composite dislocation is larger. Occurrence is further suppressed.
- the single crystal diamond of this embodiment can include a plurality of single crystal diamond layers. Since such single crystal diamond includes a plurality of single crystal diamond layers, the formation of crystal defect lines is promoted, so that the generation of large defects is further suppressed.
- the single crystal diamond of the present embodiment 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.
- the density can be made higher than the crystal defect points on the main surface opposite to the crystal growth main surface.
- crystal defect lines are newly generated or branched at the interface of each single crystal diamond layer, so that as the number of single crystal diamond layers increases, the number of crystal defect points on the crystal growth main surface increases. Therefore, the crystal defect points on the crystal growth main surface become higher in density than the crystal defect points on the main surface opposite to the crystal growth main surface, and the defect resistance becomes higher.
- the single crystal diamond of the present embodiment includes a plurality of single crystal diamond layers, and crystal defect lines are newly generated, disappeared, branched or merged at the interface of each single crystal diamond layer.
- the defect points and the crystal defect points on the crystal growth main surface opposite to the crystal growth main surface can be made higher in density than the crystal defect points at the interface of each single crystal diamond layer.
- crystal defect lines branch or merge at the interface of each single crystal diamond layer.
- the crystal defect point on the main surface of crystal growth and the opposite side Because the number of crystal defect points on the crystal growth main surface increases, the crystal defect points on the crystal growth main surface and the crystal defect points on the opposite crystal growth main surface are higher than the crystal defect points on the interface of each single crystal diamond layer. Thus, the occurrence of large defects on the main surfaces on both sides is suppressed, the chip resistance on the main surfaces on both sides is high, and the strength is increased.
- the single crystal diamond of this embodiment can contain 1 ppm or more of nitrogen atoms as impurity atoms.
- Such single-crystal diamond contains 1 ppm or more of nitrogen atoms as impurity atoms, and such nitrogen atoms are not isolated substitutional nitrogen atoms that do not cause cracks or cracks but are aggregated types that cause cracks or cracks.
- the generation of large defects is suppressed because of stress relaxation due to a large number of crystal defect lines.
- the single crystal diamond of this embodiment containing 1 ppm or more of nitrogen atoms as impurity atoms is suitably used for cutting tools such as cutting tools and end mills, wear resistant tools such as dressers and wire drawing dies, and heat sinks. It is done.
- the single crystal diamond of the present embodiment can contain 3 ppm or more of nitrogen atoms as impurity atoms, and more than 30 ppm. Of nitrogen atoms. However, if the concentration of nitrogen atoms is too high, even if the density of crystal defect lines is high, the stress relaxation cannot be made in time, so the nitrogen atoms can be preferably 1000 ppm or less.
- the single crystal diamond of this embodiment can contain nitrogen atoms of less than 1 ppm as impurity atoms. Since such single crystal diamond contains less than 1 ppm of nitrogen atoms as impurity atoms, nitrogen atoms, which are foreign element atoms that disturb the extension of the chip when a strong stress is applied to a specific portion, have a low concentration. For this reason, large defects over long distances are likely to occur. However, since the extension of the defects is disturbed by a large number of crystal defect lines themselves and stress relaxation caused thereby, the generation of large defects is suppressed.
- the single crystal diamond of this embodiment containing nitrogen atoms of less than 1 ppm as impurity atoms is suitably used for applications such as optical parts such as window materials and lenses, sensors, and semiconductor substrates. Furthermore, as a range in which the above effect is greatly exhibited, the single crystal diamond of the present embodiment can contain a nitrogen atom of 0.3 ppm or less as an impurity atom, and can contain a nitrogen atom of 30 ppb or less. However, when there is no nitrogen atom at all, defects of the single crystal diamond cannot be suppressed, so the nitrogen atom can be preferably 0.01 ppb or more.
- the single crystal diamond of this embodiment can have a light transmittance of 400 nm or less when its thickness is 500 ⁇ m.
- the light transmittance when the thickness of the single crystal diamond 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.
- Such single crystal diamond absorbs light having a wavelength of 400 nm or less due to a synergistic effect of crystal defects and impurity atoms, and thus the transmittance of light having such a wavelength is lowered.
- Single crystal diamond having a light transmittance of 400 nm or less with a thickness of 500 ⁇ m having a thickness of 60% or less suppresses the generation of large defects.
- a method for producing a single crystal diamond according to another embodiment of the present invention prepares a diamond seed crystal having a seed crystal defect linear assembly region in which a group of seed crystal defect points gathers and extends linearly on a main surface. And a step of growing single crystal diamond on the main surface of the diamond seed crystal by chemical vapor deposition.
- the method for producing a single crystal diamond according to the present embodiment has a chemical vapor on the main surface of a diamond seed crystal having a seed crystal defect linear assembly region in which a group of seed crystal defect points gathers and extends linearly on the main surface.
- a direction within 30 ° from one direction in which a group of crystal defect points, which is a point at the tip where the crystal defect line reaches the crystal growth main surface, is gathered together by growing single crystal diamond by the phase deposition method.
- a single crystal diamond having a plurality of linearly extending crystal defect linear aggregate regions in parallel is obtained.
- Such single crystal diamond is a crystal in which generation of large defects is suppressed by stress relaxation due to a large number of crystal defect lines, and a plurality of crystals that extend in a line within a direction of 30 ° from an arbitrarily specified direction existing in parallel. Since the direction in which chipping is difficult to be controlled can be controlled by the defective linear assembly region, it is suitably used for cutting tools, polishing tools, optical components, electronic components, semiconductor materials, and the like.
- two or more seed crystal defect linear aggregate regions exist in a direction perpendicular to the direction in which the seed crystal defect linearly extends, and the direction extends linearly.
- the interval at can be 500 ⁇ m or less.
- the direction in which the seed crystal defect linear assembly region extends linearly refers to the one specified direction that is an average direction of the plurality of directions in which the plurality of seed crystal defect linear assembly regions extend.
- Such a method for producing single-crystal diamond has two or more seed crystal defect linear aggregate regions per mm in the direction perpendicular to the direction in which the seed crystal defects extend, and the interval in the direction in which the seed crystal defects extend in the linear direction is set.
- the thickness By setting the thickness to 500 ⁇ m or less, there are two or more crystal defect linear aggregate regions per mm in a direction perpendicular to the direction in which the crystal defects extend, and the interval in the direction extending in a linear manner is 500 ⁇ m or less. Since crystal diamond is obtained by chemical vapor deposition, the generation of large defects is suppressed by stress relaxation due to a large number of crystal defect lines, and a plurality of parallel high-density, arbitrarily specified directions within 30 °. A single crystal diamond in which the direction in which it is difficult to chip can be controlled by the crystal defect linear assembly region extending linearly in the direction can be obtained.
- the seed crystal defect linear assembly region can include five or more long seed crystal defect linear assembly regions having a length of 300 ⁇ m or more per 1 cm 2 of the main surface.
- Such a method for producing single crystal diamond includes five or more long seed crystal defect linear aggregate regions having a length of 300 ⁇ m or more per 1 cm 2 of the main surface, so that generation of defects in the single crystal diamond to be grown is suppressed. In addition, the strength of the entire single crystal diamond is enhanced. From this point of view, the seed crystal defect linear assembly region can include 20 or more longer seed crystal defect linear assembly regions having a length of 500 ⁇ m or more per 1 cm 2 of the main surface.
- the density of seed crystal defect points can be made larger than 10 mm ⁇ 2 .
- the density of seed defect points is set to be larger than 10 mm ⁇ 2 , so that the density of crystal defect points, which is the point at which the crystal defect line reaches the crystal growth main surface, is greater than 20 mm ⁇ 2 . Since a large single crystal diamond can be obtained by chemical vapor deposition, a single crystal diamond can be obtained in which the generation of large defects is suppressed by stress relaxation due to high-density crystal defect lines. Furthermore, in the method for producing single crystal diamond of the present embodiment, the density of seed crystal defect points can be made larger than 100 mm ⁇ 2 .
- the density of seed defect points is made larger than 100 mm -2 , so that the density of crystal defect points, which are the point at which the crystal defect line reaches the crystal growth main surface, is more than 300 mm -2 . Since large single crystal diamond can be obtained by chemical vapor deposition, single crystal diamond can be obtained in which the generation of large defects is further suppressed by stress relaxation due to high-density crystal defect lines. Furthermore, from the viewpoint of further suppressing large defects of single crystal diamond, the density of seed crystal defect points can be made larger than 1000 mm ⁇ 2 and can be made larger than 1 ⁇ 10 4 mm ⁇ 2 .
- the density of the seed crystal defect points is preferably 1 ⁇ 10 6 mm. Can be smaller than -2 .
- the single crystal diamond to be grown has a crystal growth main surface in which a composite dislocation in which at least one of a plurality of edge dislocations and a plurality of screw dislocations is combined among the crystal defect points.
- the density of the composite dislocation point which is the point of the tip reaching the diameter, can be made larger than 20 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, so that large defects are generated. Is further suppressed.
- the density of complex dislocation points can be preferably greater than 30 mm ⁇ 2 , more preferably greater than 300 cm ⁇ 2 .
- the density of the seed crystal damage point indicating the point where crystal damage exists in the secondary electron image of the electron microscope after the main surface of the diamond seed crystal is hydrogen-terminated is 3 mm ⁇ .
- the density of seed crystal damage points that cause a large number of crystal defect lines in single crystal diamond grown by chemical vapor deposition, among the seed crystal defect points is made larger than 3 mm ⁇ 2 .
- single crystal diamond having a high density of crystal defect lines can be obtained by chemical vapor deposition, so that single crystal diamond in which large defects are suppressed by stress relaxation by the high density crystal defect lines can be obtained.
- the density of the seed crystal damage point indicating the point where crystal damage is present in the secondary electron image of the electron microscope after the main surface of the diamond seed crystal is terminated with hydrogen is 30 mm. Can be larger than -2 .
- the density of seed crystal damage points that cause a large number of crystal defect lines in single crystal diamond grown by chemical vapor deposition among the seed crystal defect points is made larger than 30 mm ⁇ 2 .
- single crystal diamond having a high density of crystal defect lines can be obtained by chemical vapor deposition, so that single crystal diamond in which large defects are further suppressed by stress relaxation by the high density crystal defect lines can be obtained.
- a tool according to yet another embodiment of the present invention includes a cutting tool, a milling wiper, an end mill, a drill, a reamer, a cutter, a dresser, and a wire guide, which include the single crystal diamond of the above-described embodiment in a contact portion with a work material.
- a component according to still another embodiment of the present invention is a component selected from the group consisting of an optical component including the single crystal diamond of the above embodiment, a heat sink, a biochip, a sensor, and a semiconductor substrate. Since such a component includes the single crystal diamond of the above-described embodiment, large defects are suppressed, and the resistance to defects is high and the strength is high.
- the single crystal diamond 20 of the present embodiment has a crystal defect line 20dq indicating a line where the crystal defect 20d exists in an X-ray topography image of the crystal growth main surface 20m.
- a group of crystal defect points 20dp which is a point at the tip reaching the crystal growth principal surface 20m, is present in an aggregate.
- the single crystal diamond 20 of the present embodiment is a point at the tip where the crystal defect line 20dq indicating the line where the crystal defect 20d exists in the X-ray topography image of the crystal growth main surface 20m reaches the crystal growth main surface 20m.
- FIG. 1 schematically shows a transmission type X-ray topography image, in order to make it easy to understand a crystal defect point 20dp, which is a point at the tip where the crystal defect line 20dq reaches the crystal growth main surface 20m. Shown with black dots.
- Ib-type single crystal diamond grown by high-temperature and high-pressure methods widely used as cutting tools, wear-resistant tools, etc. is an isolated substitution type containing nitrogen impurities, and the isolated substitution type nitrogen atom is the starting point of plastic deformation. This prevents a large defect from occurring.
- single-crystal diamond grown by CVD CVD single-crystal diamond
- CVD single-crystal diamond is difficult to contain nitrogen atoms in the isolated substitution type, and is contained in the form of agglomeration with vacancies and multiple nitrogen atoms. This is the cause of the loss.
- the present inventors for such a CVD single crystal diamond, gather a group of crystal defect points 20dp and extend linearly in a direction within 30 ° from one direction arbitrarily specified.
- the stress is relieved, so that a fine wear is promoted and cannot be used as a cutting tool.
- the present inventors have found that Ib type single crystal diamond grown by a high temperature and high pressure method is difficult to introduce dislocations dispersed like CVD single crystal diamond, and a large number of dislocations diffuse radially from the seed crystal. It has been found that the defect defect resistance is not improved or the defect resistance is not improved, and the improvement in the defect resistance by the introduction of dislocations is unique to CVD single crystal diamond.
- the crystal defect line 20dq is a direction within 30 ° from one direction that is arbitrarily specified by a group of crystal defect points 20dp, which is a point at the tip where the crystal defect line 20dq reaches the crystal growth main surface 20m. Since a plurality of crystal defect linear assembly regions 20r extending linearly exist in parallel to each other, generation of large defects is suppressed by stress relaxation caused by a large number of crystal defect lines 20dq, and a plurality of crystal defect linear assembly regions 20r exist arbitrarily in parallel. Since the direction in which chipping is difficult can be controlled by the crystal defect linear assembly region 20r extending linearly in a direction within 30 ° from one specified direction, it is suitable for cutting tools, polishing tools, optical components, electronic components, semiconductor materials, etc. Used.
- the arbitrarily specified one direction is an average direction in which a group of crystal defect lines gather and extend linearly.
- a ⁇ 110> direction having high wear resistance may be used.
- the ⁇ 100> direction in which wear is easy may be used, and selection can be made according to the application and usage method.
- the direction in which the group of crystal defect lines gather and extend linearly may be dispersed to some extent, but the defect resistance is more effectively improved by making ⁇ shown in FIG. 2 within 30 °. I found it.
- the presence of the crystal defect point 20dp and the crystal defect line 20dq is shown in the X-ray topography image on the crystal growth main surface 20m. That is, since the crystal defect point 20dp and the crystal defect line 20dq have higher X-ray reflection intensity than other portions of the crystal (portions with fewer defects, that is, portions with high crystallinity), X-ray topography
- the presence of a positive image 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 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 consisting of these crystal defects 20d is newly generated or stops when the crystal growth main surface 20m is reached.
- the tip of the crystal defect line 20dq that reaches 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.
- 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 Count crystal defects and convert to mm -2 units.
- the region where the crystal defect points are counted is always a portion including the crystal defect line assembly region. If you do not know which side of the crystal defect line has stopped reaching the crystal growth main surface, change the incident angle and diffraction surface of the transmission X-ray topography image, or change the reflection X-ray topography Crystal defects are clarified by taking pictures.
- 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 in which the crystal defect 20d exists, gathers linearly on the crystal growth main surface 20m. .
- the crystal defect linear assembly region 20r is an X-ray topography image measured in a transmission type in a direction parallel to the crystal growth direction of the single crystal diamond 20 (that is, a direction perpendicular to the crystal growth main surface 20m).
- the X-ray topography image can be measured by the reflection type, but the X-ray topography image measured by the reflection type is an image in which the crystal defect lines 20dq are overlapped. Because it becomes difficult to do.
- 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 crystal defect point In the measurement of the X-ray topography image of the single crystal diamond of this embodiment, it is necessary to observe high-density crystal defect points, and therefore it is preferable to use X-rays of emitted light.
- 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 lower in order to avoid an increase in noise. After development, an image is captured with an optical microscope, and crystal defect points and crystal defect lines are quantified.
- the crystal growth direction of the single crystal diamond 20 corresponds to the average direction of the plurality of crystal defect lines 20dq.
- the crystal growth main surface 20m of single crystal diamond means the outermost main surface of crystal growth, and is generally a main surface perpendicular to the crystal growth direction.
- the direction in which the crystal defect linear assembly region 20r extends linearly one direction that is arbitrarily specified as a reference is preferably the ⁇ 100> direction, and a direction within 30 ° from the ⁇ 100> direction is preferable. A direction within 15 ° is more preferable. Since the single crystal diamond is easily cleaved in the ⁇ 111> direction, the defect of the single crystal diamond 20 can be further suppressed by setting the direction in which the crystal defect linear assembly region 20r extends linearly in the above range. In addition, since the diamond seed crystal used when growing the single crystal diamond 20 by the CVD method is often an Ib type single crystal grown by the high-temperature and high-pressure method, the main surface is a single crystal parallel to the ⁇ 100> direction.
- the crystal defect linear assembly region 20r is linear in the ⁇ 110> direction. It shall be the direction of elongation.
- the crystal defect linear assembly region 20r has a linear extension direction (an average direction of a plurality of directions in which each of the plurality of crystal defect linear assembly regions extends, i.e., specified above. It is preferable that there are two or more per 1 mm in a direction perpendicular to the one direction, and the distance D in the linearly extending direction is 500 ⁇ m or less.
- the single crystal diamond 20 has two or more crystal defect linear aggregate regions 20r per 1 mm in a direction perpendicular to the direction in which the single crystal diamond 20 extends linearly, and an interval in the linearly extending direction is 500 ⁇ m or less.
- the generation of large defects is suppressed by stress relaxation caused by a large number of crystal defect lines 20dq, and a plurality of high-density linearly extending in a direction within 30 ° from an arbitrarily specified direction existing in parallel.
- the direction in which chipping is difficult to control can be controlled by the crystal defect linear assembly region 20r.
- crystal defect linear gathering regions 20r per mm there are four or more crystal defect linear gathering regions 20r per mm in a direction perpendicular to the direction in which the crystal defects linearly extend, and / or the distance D in the direction extending in the linear form. More preferably, it is 100 ⁇ m or less.
- the pitch P between a plurality of parallel crystal defect linear aggregate regions 20r is preferably 500 ⁇ m or less, and more preferably 250 ⁇ m or less.
- the crystal defect linear assembly region 20r is a long crystal defect linear assembly region having a length L of 300 ⁇ m or more shown in FIG. 2 per 1 cm 2 of the crystal growth main surface 20m. It is preferable to include more than one. Since the single crystal diamond 20 includes five or more long crystal defect linear aggregate regions having a length of 300 ⁇ m or more per 1 cm 2 of the crystal growth main surface 20 m, generation of defects in the single crystal diamond 20 is suppressed. At the same time, the strength of the entire single crystal diamond 20 is enhanced. From this point of view, the crystal defect linear assembly region 20r more preferably includes 20 or more longer crystal defect linear assembly regions having a length L of 500 ⁇ m or more shown in FIG.
- the density of the crystal defect points 20 dp is preferably greater than 20 mm ⁇ 2, more preferably greater than 300 mm ⁇ 2 , still more preferably greater than 1000 mm ⁇ 2. Particularly preferred is greater than 4 mm ⁇ 2 .
- the density of the crystal defect point 20dp is larger than 20 mm ⁇ 2 , generation of large defects is suppressed by stress relaxation by the high-density crystal defect line 20dq corresponding to the high-density crystal defect point 20dp.
- the density of the crystal defect points 20 dp is larger than 1000 mm ⁇ 2 , the chipping resistance is excellent even in intermittent cutting such as a wiper tip.
- the density of the crystal defect point 20dp is preferably smaller than 1 ⁇ 10 6 mm ⁇ 2 .
- a composite dislocation where a composite dislocation in which at least one of a plurality of edge dislocations and a plurality of helical dislocations is combined among the crystal defect points 20dp is a point at the tip reaching the crystal growth main surface 20m.
- the density of dislocation points is preferably greater than 20 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 single crystal diamond 20 has a large defect because the density of the composite dislocation point, which is the point at which the composite dislocation reaches the crystal growth principal surface 20 m, is larger than 20 mm ⁇ 2 , and the effect of stress relaxation by the composite dislocation is large. Is further suppressed. Furthermore, when the density of complex dislocation points is larger than 300 mm ⁇ 2 , the chipping resistance is excellent even in intermittent cutting such as a wiper tip. However, if the composite dislocation points are too close, a stress increasing effect is added, so that the density of the composite dislocation points is preferably smaller than 3 ⁇ 10 5 mm ⁇ 2 .
- the composite dislocation can be observed by changing the X-ray diffraction direction (g vector) in the X-ray topography.
- the (001) plane which is the crystal growth main surface 20 m of a diamond single crystal
- the [4-40] direction orthogonal to the g vector can be observed.
- it cannot be observed with the g vector it is an edge dislocation, but when it can be observed with a plurality of g vectors orthogonal to each other, such as the [440] direction and the [4-40] direction, it is a composite dislocation.
- the single crystal diamond 20 of the present embodiment preferably includes a plurality of single crystal diamond layers 21 and 22. Since the single crystal diamond 20 includes a plurality of single crystal diamond layers 21 and 22, formation of the crystal defect lines 21dq and 22dq is promoted, and thus generation of large defects is further suppressed.
- 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 20 The tip reaching 20 m of the crystal growth main surface becomes a crystal defect point 20 dp.
- 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, as the number of single crystal diamond layers 21 and 22 increases, the crystal defect point 20dp of the single crystal diamond 20 increases. Become more.
- FIG. 5C shows a single crystal diamond 20 obtained by removing the diamond seed crystal 10 from the single crystal diamond 20 grown on the main surface 10 m of the diamond seed crystal 10 as shown in FIG.
- FIG. 5D shows the removal of the diamond seed crystal 10 from the single crystal diamond 20 including a plurality of single crystal diamond layers 21 and 22 grown on the main surface 10 m of the diamond seed crystal 10 as shown in FIG.
- a single crystal diamond 20 including a plurality of single crystal diamond layers 21 and 22 is shown.
- the single crystal diamond 20 of the present embodiment includes a plurality of single crystal diamond layers 21 and 22, and crystal defect lines 21dq, 22 dq is newly generated or branched, and the crystal defect points 20 dp on the crystal growth main surface 20 m have a higher density than the crystal defect points 20 ndp on the main surface 20 n opposite to the crystal growth main surface 20 m.
- the crystal defect lines 21 dp and 22 dp are newly generated or branched at the interfaces between the single crystal diamond layers 21 and 22.
- the crystal defect point 20dp on the crystal growth main surface 20m increases, the crystal defect point 20dp on the crystal growth main surface 20m has a higher density than the crystal defect point 20ndp on the main surface 20n on the opposite side of the crystal growth main surface 20m. The deficiency becomes higher. As shown in FIG. 5D, a newly generated crystal defect line may branch and extend.
- FIG. 6 shows a single crystal diamond obtained by growing a further single crystal diamond on the main surface 20n opposite to the crystal growth main surface 20m of the single crystal diamond 20 shown in FIG. 5 (C).
- 7 shows a plurality of single crystal diamond layers on the main surface 20n opposite to the crystal growth main surface 20m of the single crystal diamond 20 including the plurality of single crystal diamond layers 21 and 22 shown in FIG. 1 shows a single crystal diamond obtained by growing a further single crystal diamond containing
- a single crystal diamond 20 of the present embodiment includes a plurality of single crystal diamond layers 20a, 20b, 21a, 21b, 22a, 22b, and each single crystal diamond layer 20a, 20b, 21a. , 21b, 22a, 22b, the crystal defect lines 20adq, 20bdq, 21adq, 21bdq, 22adq, 22bdq are newly generated, disappeared, branched or merged, and the crystal of the crystal growth main surface 20am
- the crystal defect point 20bdp on the crystal growth main surface 20bm opposite to the defect point 20adp and the crystal growth main surface 20am is the crystal of the interface 20i, 212ai, 212bi of each single crystal diamond layer 20a, 20b, 21a, 21b, 22a, 22b.
- crystal defect lines 20adq, 20bdq, 21adq, 21bdq, 22adq, 22bdq are newly generated at the interfaces 20i, 212ai, 212bi of the single crystal diamond layers 20a, 20b, 21a, 21b, 22a, 22b.
- the crystal defect point 20apd of the crystal growth main surface 20am and the crystal growth main on the opposite side are increased.
- the crystal defect point 20bdp on the surface 20bm increases, the crystal defect point 20adp on the crystal growth main surface 20am and the crystal defect point 20bdp on the opposite crystal growth main surface 20bm correspond to the single crystal diamond layers 20a, 20b, 21a, 21b, 22a, 22b interfaces 20i, 212ai, 21 Higher than the high density crystalline defects point bi, generation of a large defect on either side of the main surface is suppressed, breakage of the sides of the main surface is high, the strength is high.
- the disappearance of the crystal defect line means the disappearance of some of the plurality of crystal defect lines.
- the single crystal diamond 20 shown in FIGS. 6 and 7 is obtained by growing the single crystal diamond layers 20a and 20b from the interface 20i to the crystal growth main surfaces 20am and 20bm. Therefore, crystal defect lines 20adq and 20bdq are newly generated or branched in the direction from the interface 20i to both crystal growth main surfaces 20am and 20bm. That is, crystal defect lines 20adq, 21adq, 22adq disappear or merge from one crystal growth main surface 20am to the interface 20i in the direction from one crystal growth main surface 20am through the interface 20i to the other crystal growth main surface 20bm. In addition, crystal defect lines 20bdq, 21bdq, and 22bdq are newly generated or branched from the interface 20i to the other crystal growth main surface 20bm.
- the cross section may be another direction such as the (110) plane.
- the defect resistance on the crystal growth main surface 20m side is increased by increasing the density of the crystal defect points 20dp on the crystal growth main surface 20m.
- the chipping resistance on the main surface 20n side opposite to the crystal growth main surface 20m does not increase.
- the density of the crystal defect point 20adp of the crystal growth main surface 20am and the density of 20bdp of the crystal defect point of the opposite crystal growth main surface 20bm are high.
- the chipping resistance on both main surfaces increases.
- the single crystal diamond layer 21, 21 a, 21 b, 22, 22 a, 22 b includes a plurality of single crystal diamond layers 21, 21 a, 21 b, 22, 22 a, 22 b as compared with single crystal diamond in which crystal defect lines are uniformly distributed in the thickness direction.
- Single crystal diamond including both a layer having few and many crystal defect lines 21dq, 21adq, 21bdq, 22dq, 22adq, and 22bdq has higher defect resistance even at the same crystal defect density.
- single crystal diamond with non-uniform distribution of crystal defect lines in the thickness direction is a material that has both a rake face and a brazing surface that are strong and is less prone to chipping and brazing. Obtainable.
- the single crystal diamond 20 of the present embodiment preferably contains 1 ppm or more of nitrogen atoms as impurity atoms.
- the single crystal diamond 20 contains 1 ppm or more of nitrogen atoms as impurity atoms, and the nitrogen atoms are not isolated substitutional nitrogen atoms that do not start from cracks or cracks, but aggregates that start from chips or cracks. Although it is a type of nitrogen atom, the generation of large defects is suppressed due to stress relaxation due to a large number of crystal defect lines.
- Aggregation-type nitrogen atoms are those existing in a diamond single crystal adjacent to a plurality of nitrogen atoms and / or vacancies, such as A Center, B Center, N3 Center, H3 Center, and NV Center.
- the nitrogen atom contained as impurity atoms in the single crystal diamond 20 is more preferably 3 ppm or more, further preferably 10 ppm or more, and particularly preferably 30 ppm or more. Furthermore, when the concentration of nitrogen atoms is 10 ppm or more, excellent fracture resistance is exhibited even in intermittent cutting. However, if the concentration of nitrogen atoms is too high, even if the density of crystal defect lines is high, the stress relaxation cannot be made in time, so 1000 ppm or less is preferable.
- the single crystal diamond 20 of the present embodiment preferably contains less than 1 ppm of nitrogen atoms as impurity atoms. Since the single crystal diamond 20 contains less than 1 ppm of nitrogen atoms as impurity atoms, nitrogen atoms, which are different element atoms that disturb the extension of the chip when a strong stress is applied to a specific portion, have a low concentration. For this reason, large defects over a long distance are likely to occur. However, since the extension of the defects is disturbed by a large number of crystal defect lines 20dq itself and stress relaxation caused thereby, the generation of large defects is suppressed.
- the nitrogen atom contained as impurity atoms in the single crystal diamond 20 is more preferably 0.3 ppm or less, further preferably 0.1 ppm or less, and particularly preferably 0.03 ppm or less. Furthermore, in the case of 0.1 ppm or less, it has excellent cracking resistance in applications that undergo repeated thermal shocks, such as laser window materials. However, when there is no nitrogen atom at all, the defect of the single crystal diamond cannot be suppressed, so the nitrogen atom is preferably 0.01 ppb or more.
- the nitrogen concentration is measured by, for example, secondary ion mass spectrometry (SIMS) or electron spin resonance analysis (ESR). At this time, the isolated substituted nitrogen measured by ESR is 50% or less, preferably 10% or less, more preferably 1% or less of the total nitrogen amount measured by SIMS.
- SIMS secondary ion mass spectrometry
- ESR electron spin resonance analysis
- the single crystal diamond 20 of the present embodiment preferably has a light transmittance of 400 nm when its thickness is 500 ⁇ m, preferably 60% or less, more preferably 30% or less, and 10%. The following is more preferable, and 5% or less is particularly preferable.
- the light transmittance when the thickness of the single crystal diamond 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.
- Single crystal diamond having a low light transmittance of 400 nm or less contains many crystal defect lines and / or nitrogen atoms, and as a result, cracks are suppressed and defect resistance is high.
- the light transmittance is a substantial transmittance with respect to incident light, and is not a transmittance only within the interior excluding the reflectance. Therefore, 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 size of the main surface of the single crystal diamond 20 of the present embodiment is preferably 3 mm or more, more preferably 6 mm or more, and even more preferably 10 mm or more from the viewpoint of a high effect of improving fracture resistance. Note that the single crystal diamond having a main surface size of 10 mm or more in diameter and having no crystal defect linear aggregate region of this embodiment is easily lost during cutting of a cutting tool or the like.
- Embodiment 2 Method for producing single crystal diamond
- a diamond having a seed crystal defect linear assembly region in which a group of seed crystal defect points 10dp gathers and extends linearly on main surface 10m A step of preparing the seed crystal 10 (FIG. 5A), a step of growing the single crystal diamond 20 on the main surface 10m of the diamond seed crystal 10 by chemical vapor deposition (FIG. 5B), Is provided.
- the main surface 10m of the diamond seed crystal 10 having a seed crystal defect linear assembly region in which a group of seed crystal defect points 10dp is gathered and extends linearly on the main surface 10m.
- a group of crystal defect points 20dp which is the point at which the crystal defect line 20dq reaches the crystal growth principal surface 20m, is gathered and arbitrarily specified.
- Single crystal diamond 20 is obtained in which a plurality of crystal defect linear aggregate regions 20r extending linearly in a direction within 30 ° from one direction are present in parallel.
- the single crystal diamond 20 is restrained from generating large defects due to stress relaxation caused by a large number of crystal defect lines 20dq, and is linearly formed in a direction within 30 ° from an arbitrarily specified direction existing in parallel. Since the extending direction of the crystal defect linear gathering region 20r can control the direction in which chipping is difficult, it can be suitably used for cutting tools, polishing tools, optical components, electronic components, semiconductor materials, and the like.
- two or more seed crystal defect linear aggregate regions exist per 1 mm in a direction perpendicular to the direction in which the seed crystal defects extend linearly, and extend linearly.
- the interval in the direction is preferably 500 ⁇ m or less.
- Such a method for producing a single crystal diamond 20 includes two or more seed crystal defect linear aggregate regions per mm in the direction perpendicular to the direction in which the seed crystal defects extend, and the spacing in the direction in which the seed crystal defects 20 extend in the linear shape. Is set to 500 ⁇ m or less, two or more crystal defect linear aggregate regions 20r shown in FIG. 1 and FIG. 2 exist in a direction perpendicular to the direction in which the crystal defects extend, and extend linearly.
- the single crystal diamond 20 having a distance in the direction of 500 ⁇ m or less is obtained, the generation of large defects is suppressed by stress relaxation by a large number of crystal defect lines 20dq, and a plurality of arbitrarily arranged high-density one direction
- the single crystal diamond 20 in which the direction in which it is difficult to be chipped can be controlled by the crystal defect linear assembly region 20r extending linearly in a direction within 30 ° from the angle is obtained.
- the pitch between the plurality of seed crystal defect linear assembly regions arranged in parallel is preferably 500 ⁇ m or less, and more preferably 250 ⁇ m or less.
- the seed crystal defect linear assembly region includes five or more long seed crystal defect linear assembly regions having a length of 300 ⁇ m or more per 1 cm 2 of the main surface.
- Such a method for producing the single crystal diamond 20 includes five or more long seed crystal defect linear aggregate regions having a length of 300 ⁇ m or more per 1 cm 2 of the main surface, so that defects are generated in the single crystal diamond 20 to be grown. In addition to being suppressed, the strength of the entire single crystal diamond 20 is enhanced. From this viewpoint, it is more preferable that the seed crystal defect linear assembly region includes 20 or more longer seed crystal defect linear assembly regions having a length of 500 ⁇ m or more per 1 cm 2 of the main surface.
- the density of the seed crystal defect point 10dp is larger than 10 mm ⁇ 2 .
- the density of the crystal defect point 20dp which is the point at which the crystal defect line 20dq reaches the crystal growth main surface 20m, is set by making the density of the seed crystal defect point 10dp larger than 10 mm ⁇ 2. Since single crystal diamond having a diameter greater than 20 mm ⁇ 2 is obtained by chemical vapor deposition, single crystal diamond 20 is obtained in which generation of large defects is suppressed by stress relaxation by high-density crystal defect lines 20dq.
- the density of the seed crystal defect point 10 dp more preferably greater than 100 mm -2, more preferably greater than 1000 mm -2, and particularly preferably greater than 1 ⁇ 10 4 mm -2.
- the species by the density of crystal defects point 10dp larger than 100 mm -2, the density of the point of the tip is a crystal defect point 20dp crystal defects line 20dq reaches the crystal growth major surface 20m is 300 mm -2 larger single crystals Diamond is obtained by chemical vapor deposition.
- the seed crystal defect point 10 dp and the seed crystal defect linear assembly region are X-ray topography measured in a transmission type in a direction perpendicular to the main surface 10 m of the diamond seed crystal 10. It is preferably shown in a photographic image (that is, an X-ray topography image of the major surface 10 m of the diamond seed crystal 10).
- the method for manufacturing single crystal diamond 20 of the present embodiment crystal damage is observed in the secondary electron image of the electron microscope after the main surface 10m of diamond seed crystal 10 is terminated with hydrogen. It is preferable to make the density of the seed crystal damage points indicating the point where the water is present larger than 3 mm ⁇ 2 .
- Such a method for producing the single crystal diamond 20 has a seed crystal damage point density of 3 mm ⁇ 2 that causes a large number of crystal defect lines 20dq in the single crystal diamond 20 grown by the chemical vapor deposition method among the seed crystal defect points.
- single crystal diamond 20 having high-density crystal defect lines 20dq can be obtained by chemical vapor deposition, so that single crystal in which large defects are suppressed by stress relaxation by high-density crystal defect lines 20dq. Diamond is obtained. From this point of view, it is more preferable to increase the density of seed crystal damage points, which indicates the point where crystal damage exists in the secondary electron image of the electron microscope after the main surface 10m of the diamond seed crystal 10 is hydrogen-terminated, to more than 30 mm ⁇ 2 preferable.
- the method of hydrogen-termination of the main surface 10m of the diamond seed crystal 10 is not particularly limited, but from the viewpoint of efficient treatment, 2.400 GHz to 2.497 GHz in a reduced-pressure atmosphere in which hydrogen gas is supplied.
- the main surface 10 m of the diamond seed crystal 10 is irradiated with hydrogen plasma generated by introduction of a microwave of 902 MHz to 928 MHz or heating by a hot filament.
- the temperature of the diamond seed crystal 10 at this time is preferably 800 ° C. or less, and more preferably 600 ° C. or less from the viewpoint of preventing the shape change of the main surface 10 m of the diamond seed crystal 10.
- 400 degreeC or more is preferable from a viewpoint which a hydrogen termination process advances.
- the hydrogen termination treatment time is preferably 3 minutes or more from the viewpoint of reliably performing the hydrogen termination treatment, and preferably 15 minutes or less from the viewpoint of preventing etching.
- the main surface 10m of the diamond seed crystal 10 terminated with hydrogen as described above has a negative electronegativity
- carriers excited by primary electrons of an electron microscope can be easily detected as secondary electrons.
- a secondary electron image can be observed as a distribution of defects trapping carriers inside the crystal. Therefore, not only when there is a clear defect such as a crack on the main surface 10m as shown in FIG. 8, but also when there is no clear defect on the main surface 10m as shown in FIG.
- the crystal damage and its density including fine cracks and fine strains is observed as a fine crack as a dark portion and a fine strain as a change in light and dark.
- the acceleration voltage of the primary electrons is preferably 15 kV or less in order to increase the sensitivity to the seed crystal damage point existing on the surface of the diamond seed crystal.
- the size of the main surface of the diamond seed crystal is preferably 3 mm or more, more preferably 6 mm or more, and 10 mm in diameter from the viewpoint of growing a large-diameter single crystal diamond. The above is more preferable.
- Step 10 (Preparation process of a diamond seed crystal having a seed crystal defect linear assembly region) Referring to FIG. 5A, a step of 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 linearly assembled on the main surface 10m and extends linearly.
- Ib type single crystal diamond, IIa type single crystal diamond, Ib type single crystal diamond, or IIa type single crystal diamond grown by a high temperature high pressure method is used as the diamond seed crystal 10.
- Single crystal diamond grown by the CVD method is prepared as a crystal.
- the seed crystal defect point 10dp includes a seed crystal point.
- Defect point, seed crystal dislocation point 10dd edge dislocation, screw dislocation, tip point where dislocation such as compound dislocation in which at least one of a plurality of edge dislocations and a plurality of screw dislocations is combined
- seed Various defect points such as a crystal defect point 10dv, a seed crystal crack point, and a seed crystal damage point 10di are included.
- the method for forming the seed crystal defect linear assembly region is not particularly limited.
- a linear mask is formed using a photolithography method, and then plasma etching is performed on a portion where the mask is not formed. It may be formed. Further, it may be formed by laser processing. You may form by the mechanical grinding
- RIE reactive ion etching
- microwave plasma etching or ion milling after such mechanical polishing
- carbon tetrafluoride (CF 4 ) with a flow rate (unit: sccm) of 1% or less with respect to the flow rate (unit: sccm) of oxygen (O 2 ) and O 2 is used.
- Dry etching is preferable. This is because acicular irregularities are easily formed after dry etching, and are likely to be the starting point of crystal defect lines after CVD growth.
- the direction in which the seed crystal defect linear assembly region extends linearly is 30 ° from the ⁇ 100> direction from the viewpoint of growing the single crystal diamond 20 having the crystal defect linear assembly region 20r extending linearly in a preferred direction.
- Direction is preferable, and a direction within 15 ° is more preferable.
- the crack refers to a linear crack having a hole drilled to a depth of 1 ⁇ m or more and a length of 1 ⁇ m to 10 ⁇ m.
- the latter particularly refers to micro-cleavage that tends to enter mainly in the ⁇ 110> direction.
- the crack point refers to a point at the tip where the crack reaches the main surface 10 m.
- the crystal damage refers to a minute hole and a minute crack that are less than 1 ⁇ m deep, a crystal distortion, and the like.
- the crystal damage point refers to a point at the tip where the crystal damage reaches the main surface 10 m.
- the arithmetic average roughness Ra of the main surface 10 m after the seed crystal processing is preferably 0.1 nm to 30 nm.
- the main surface 10m preferably has an off angle of 2 ° to 15 ° from the (001) plane.
- the off direction of the main surface 10m is preferably within 15 ° from the ⁇ 100> direction or within 15 ° from the ⁇ 110> direction.
- the off angle from the (001) plane of the main surface 10m is less than 2 °, there is no particular limitation on the off direction, and the off angle from the (001) surface of the main surface 10m is 2 ° or more and 15 ° or less Compared to the above, it is preferable to perform the CVD growth under a higher pressure condition.
- the distance in the extending direction is 500 ⁇ m or less.
- the seed crystal defect point 10dp is larger than 10 mm ⁇ 2 by observing an optical microscope and / or an X-ray topography image. It is preferable to confirm. Further, after the main surface 10m of the diamond seed crystal 10 is terminated with hydrogen as described above, the density of the seed crystal damage point 10di is larger than 3 mm ⁇ 2 by observing a secondary electron image of the main surface 10m with an electron microscope. It is preferable to confirm this.
- the sub-process of changing the conditions to form the seed crystal defect linear assembly region Is preferably repeated. If at least one of the seed crystal defect point 10dp is larger than 1 ⁇ 10 6 mm ⁇ 2 and the density of the seed crystal damaged point 10di is larger than 5 ⁇ 10 5 mm ⁇ 2 , the seed crystal defect point is caused by etching or the like. It is preferable to reduce the density of at least one of the seed crystal damage points.
- the diamond seed crystal 10 is an n-type having a large number of donor atoms such as nitrogen atoms and phosphorus atoms, a band increases near the surface terminated with hydrogen, and emission of secondary electrons may be inhibited. Therefore, even if Ib type single crystal diamond is used as the diamond seed crystal, it is possible to observe the seed crystal damage point 10di, but the donor density of the diamond seed crystal 10 is preferably 30 ppm or less, and preferably 1 ppm or less. It is preferable to use IIa type single crystal diamond or single crystal diamond grown by a CVD method as the diamond seed crystal.
- the sub-process of forming the conductive layer region 10 c on the main surface 10 m side of the diamond seed crystal 10 is performed by implanting ions into the main surface 10 m side of the diamond seed crystal 10.
- ions carbon, hydrogen, lithium, boron, nitrogen, oxygen or phosphorus ions are preferably used.
- the step of growing single crystal diamond 20 is performed by growing single crystal diamond 20 on main surface 10m of diamond seed crystal 10 by chemical vapor deposition (CVD).
- 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 single crystal growth gas hydrogen, methane, argon, nitrogen, oxygen, oxygen dioxide, etc. are used, and the concentration of nitrogen atoms in the single crystal diamond is not particularly limited, and may be 1 ppm or more or less than 1 ppm. Although it is good, it is preferable to adjust so that it may become 3 ppm or more or 0.3 ppm or less.
- the region where the initial crystal growth thickness of the single crystal diamond 20 is 1 ⁇ m to 7 ⁇ m is preferably grown at least at a growth parameter ( ⁇ ) of 2 or more and the diamond seed crystal 10 at a temperature of 1100 ° C. or less.
- the thickness of the single crystal diamond 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, a polishing tool, an optical component, an electronic component, a semiconductor material, and the like. . From the viewpoint of preventing cracking due to stress in the diamond seed crystal 10, the thickness is preferably 1500 ⁇ m or less, and more preferably 1000 ⁇ m or less.
- the diamond seed crystal 10 is removed as described later, It is preferable to grow a second single crystal diamond layer 22 as an additional single crystal diamond 20 on one single crystal diamond layer 21.
- the first single crystal diamond layer 21 and the first single crystal diamond 20 are formed on the diamond seed crystal 10 as the single crystal diamond 20.
- Two single crystal diamond layers 22 can be grown continuously.
- a single crystal diamond 20 having a large thickness for example, a thickness greater than 1000 ⁇ m
- the method for manufacturing single crystal diamond 20 of the present embodiment can further include a step of removing diamond seed crystal 10 from the viewpoint of obtaining single crystal diamond 20 efficiently.
- the step of removing the diamond seed crystal 10 is preferably removed by laser cutting from the viewpoint of efficiently removing the diamond seed crystal 10. It is also preferable to remove the diamond seed crystal 10 by decomposing and removing the conductive layer region 10c formed by ion implantation into the diamond seed crystal 10 by electrochemical etching such as electrolytic etching.
- the method for manufacturing single crystal diamond 20 of the present embodiment grows by adding single crystal diamond 20 from the viewpoint of obtaining single crystal diamond 20 in which generation of large defects is further suppressed.
- the process of making it further can be provided.
- the second single crystal diamond layer 22 is formed on the main surface of the first single crystal diamond layer 21, which is the already grown single crystal diamond 20, by the CVD method. Do it by growing.
- a crystal defect line 21 dq that inherits the defect of the seed crystal defect point 10 dp on the main surface 10 m of the diamond seed crystal 10 extends in the crystal growth direction. ing.
- 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 20 The tip reaching 20 m of the crystal growth main surface becomes a crystal defect point 20 dp.
- 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, the crystal defect points 20dp of the single crystal diamond 20 increase as the number of the single crystal diamond layers 21, 22 increases. The occurrence of defects is further suppressed.
- a plurality of single-crystal diamond layers 21 and 22 are included, and crystal defect lines 21dq and 22dq are newly generated or branched at the interface 212i between the single-crystal diamond layers 21 and 22, respectively.
- a single crystal diamond 20 having a crystal defect point 20dp on the surface 20m higher in density than a crystal defect point 20ndp on the main surface 20n opposite to the crystal growth main surface 20m is obtained.
- the side opposite to crystal growth main surface 20 m of single crystal diamond 20 obtained in FIG. 5C is obtained. It can be performed by growing further single crystal diamond on the main surface 20n by the CVD method. In this way, as shown in FIG. 6, a plurality of single crystal diamond layers 20a and 20b are included, and crystal defect lines 20adq and 20bdq are newly generated and disappeared at the interface 20i of each single crystal diamond layer 20a and 20b.
- the crystal defect main point 20adp of the crystal growth main surface 20am and the crystal defect point 20bdp of the crystal growth main surface 20bm opposite to the crystal growth main surface 20am are branched or merged, and the interface 20i between the single crystal diamond layers 20a and 20b.
- the single crystal diamond 20 having a higher density than the crystal defect points is obtained.
- the side opposite to crystal growth main surface 20 m of single crystal diamond 20 obtained in FIG. 5D is obtained. It can be performed by growing further single crystal diamond on the main surface 20n by the CVD method. In this way, as shown in FIG. 7, a plurality of single crystal diamond layers 21a, 21b, 22a, 22b are included and crystals are formed at the interfaces 20i, 212ai, 212bi of the single crystal diamond layers 21a, 21b, 22a, 22b.
- Defect lines 21adq, 21bdq, 22adq, and 22bdq are newly generated, disappeared, branched, or merged, and the crystal defect point 20adp of the crystal growth main surface 20am and the crystal of the crystal growth main surface 20bm opposite to the crystal growth main surface 20am.
- the single crystal diamond 20 in which the defect points 20bdp are higher in density than the crystal defect points of the interfaces 20i, 212ai, 212bi of the single crystal diamond layers 21a, 21b, 22a, 22b is obtained.
- the tool of the present embodiment includes a cutting tool, a mill wiper, an end mill, a drill, a reamer, a cutter, a dresser, a wire guide, a wire drawing die, and a water jet that include the single crystal diamond of the first embodiment in contact with a work material.
- the component of this embodiment is a component selected from the group consisting of an optical component including the single crystal diamond of Embodiment 1, a heat sink, a biochip, a sensor, and a semiconductor substrate. Since such a component includes the single crystal diamond of the above-described embodiment, large defects are suppressed, and the resistance to defects is high and the strength is high.
- Example 1 (Sample 1 to Sample 5 and Sample 9 to Sample 12) 1. Preparation of Diamond Seed Crystal Having Seed Crystal Defect Linear Assembly Region on Main Surface
- a main surface 10m grown by a high-temperature high-pressure method as diamond seed crystal 10 is ⁇
- Nine diamond seed crystal substrates 5 mm ⁇ 5 mm ⁇ thickness 1 mm having an off angle of 2 ° to 10 ° in the 100> direction were prepared.
- Al serving as a mask is deposited on the main surface 10 m, and a linear photomask is formed by photolithography.
- the Al mask was formed by removing Al at a location where the seed crystal defect linear assembly region was formed by acid treatment using dilute hydrochloric acid.
- dry etching was performed using oxygen in a reduced-pressure atmosphere with a pressure of 0.1 Pa to 10 Pa to form needle-like protrusions with a height of 10 nm to 500 nm in the seed crystal defect linear assembly region. Thereafter, Al was removed by acid treatment using dilute hydrochloric acid.
- a seed crystal defect linear assembly region is obtained from an X-ray topography image measured in a transmission type in a direction perpendicular to the main surface 10 m on which the seed crystal defect linear assembly region of each diamond seed crystal 10 is formed.
- Seed crystal defect lines having a line density perpendicular to the linearly extending direction (main ⁇ mm ⁇ 1 ), a maximum distance ( ⁇ m) in the linearly extending direction of the seed crystal defect linear assembly region, and a length of 300 ⁇ m or more.
- density of Jo accumulating region (present ⁇ cm -2), were calculated over the length 500 ⁇ m seed crystal defects linear aggregate areas density density of (present ⁇ cm -2) and the seed crystal defects point (mm -2).
- the main surface 10 m of the diamond seed crystal 10 is hydrogenated.
- the density (mm ⁇ 2 ) of the seed crystal damage point 10di was calculated from the secondary electron image in which the carriers excited by the primary electrons of the electron microscope were detected as secondary electrons. The results are summarized in Table 1.
- single crystal diamond is grown by microwave plasma CVD on the main surface 10 m on which the seed crystal defect linear assembly region of each diamond seed crystal 10 is formed.
- Crystalline diamond 20 was grown. Hydrogen gas, methane gas, and nitrogen gas were used as the crystal growth gas, and the concentration of methane gas with respect to hydrogen gas was 5 mol% to 20 mol%, and the concentration of nitrogen gas with respect to methane gas was 0 mol% to 5 mol%.
- the crystal growth pressure was 5 kPa to 15 kPa, and the crystal growth temperature (diamond seed crystal temperature) was 800 ° C. to 1200 ° C.
- each diamond seed crystal 10 from single crystal diamond 20 of each of samples 1 to 5 is electroconductively etched in diamond seed crystal 10.
- the diamond seed crystal 10 was removed by decomposing and removing the layer region 10c.
- Samples 9 to 12 were cut with an Nd: YAG laser to remove the seed crystals, and the cut surfaces were polished with a grindstone in which diamond abrasive grains were fixed with metal.
- the diffraction plane of X-rays was the (220) plane.
- the energy of X-ray used was 14.547 keV (wavelength 0.85 ⁇ ).
- Table 1 One of the values in the column of the density of the crystal defect point and the compound dislocation point of the sample 12 in Table 1 is a value on the crystal growth main surface, and the other is a value on the crystal growth main surface on the opposite side.
- single-crystal diamond 20 was further grown for Sample 2 to Sample 5 and Sample 10 to Sample 12.
- the crystal growth conditions in the additional growth were the same as the first crystal growth conditions described above.
- the single crystal diamonds 20 of Sample 2 to Sample 5 and Sample 10 to Sample 12 thus obtained were single crystal diamonds of three layers, two layers, five layers, three layers, three layers, five layers and three layers, respectively. Had a layer.
- FIG. 7 for sample 12, the main surface cut by laser is polished and acid cleaned (using aqua regia), and then oxygen (O 2 ) gas and hydrogen tetrafluoride (CF 4 ) gas are used. Were used for dry etching, and single crystal diamond composed of two single crystal diamond layers was additionally grown.
- the crystal growth conditions for these additional growths were the same as the first crystal growth conditions described above. The results are summarized in Table 1.
- Example 2 Next, for Samples 13 to 15, seed crystals were prepared in the same manner as in Example 1, and single-crystal diamond was grown so as to be as shown in Table 2 under conditions of low nitrogen concentration.
- gas for crystal growth hydrogen gas, methane gas, and carbon dioxide gas are used.
- concentration of methane gas with respect to hydrogen gas is 1 mol% to 20 mol%
- concentration of carbon dioxide gas with respect to methane gas is 1 mol% to 70 mol%. did.
- the crystal growth pressure was 5 kPa to 30 kPa
- the crystal growth temperature (diamond seed crystal temperature) was 800 ° C. to 1200 ° C.
- Example 2 After separating the seed substrate in the same manner as in Example 1, analysis and additional growth were performed in the same manner as in Example 1. Each single crystal diamond thus obtained was processed into a disk shape and attached to a flange to produce a window for CO 2 laser. For comparison, windows were made of AR-coated ZnSe. After repeating the processing for 2000 hours at a laser transmitter output of 40 kW, the window material surface was observed. The laser output of single crystal diamond at the start of use and after use was measured with a power meter. The results are summarized in Table 2.
- Samples 13 and 14 maintained good transmittance with no change at all when the laser output after use was 100% of the laser output at the start of use.
- the laser output decreased to 79% of the laser output at the start of use at the end. It turned out that the edge was blackened. From the occurrence of cracks due to thermal shock, it was found that diamond partially graphitized and the transmittance was lowered. Since ZnSe for comparison rapidly decreased the laser output to 50% of the laser output at the start of use in 700 hours, surface analysis was performed after stopping the laser coating. As a result, all of the AR coatings had surface roughness due to peeling heat.
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Abstract
Description
本発明のある実施形態にかかる単結晶ダイヤモンドは、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。
[実施形態1:単結晶ダイヤモンド]
図1、図2および図3を参照して、本実施形態の単結晶ダイヤモンド20は、結晶成長主面20mについてのX線トポグラフィー像において結晶欠陥20dが存在する線を示す結晶欠陥線20dqが結晶成長主面20mに達する先端の点である結晶欠陥点20dpの群が集合して存在する。また、本実施形態の単結晶ダイヤモンド20は、結晶成長主面20mについてのX線トポグラフィー像において結晶欠陥20dが存在する線を示す結晶欠陥線20dqが結晶成長主面20mに達する先端の点である結晶欠陥点20dpの群が集合して任意に特定される一方向から30°以内の方向に線状に延びる結晶欠陥線状集合領域20rが複数並列して存在する。この図1は透過型で撮影したX線トポグラフィー像を模式的に表したものであり、結晶欠陥線20dqが結晶成長主面20mに達する先端の点である結晶欠陥点20dpを分かりやすくするため黒丸点で示す。
図5を参照して、本実施形態の単結晶ダイヤモンド20の製造方法は、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を準備する工程(図5(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20を成長させる工程(図5(B))と、を備える。
図5(A)を参照して、主面10m上に種結晶欠陥点10dpの群が線状に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形成するサブ工程と、ダイヤモンド種結晶10の主面10m上の種結晶欠陥点10dpおよび種結晶損傷点10diの密度を確認するサブ工程と、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、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5(B)を参照して、単結晶ダイヤモンド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、化学気相堆積(CVD)法により、単結晶ダイヤモンド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、二酸化酸素などを用いて、単結晶ダイヤモンド中の窒素原子の濃度は、特に制限はなく、1ppm以上または1ppm未満であってもよいが、3ppm以上または0.3ppm以下になるように調整することが好ましい。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20の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(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。成長パラメータ(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30.5倍した値である。
図5(C)を参照して、本実施形態の単結晶ダイヤモンド20の製造方法は、効率よく単結晶ダイヤモンド20を得る観点から、ダイヤモンド種結晶10を除去する工程をさらに備えることができる。
図5(D)を参照して、本実施形態の単結晶ダイヤモンド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20を得る観点から、単結晶ダイヤモンド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。
本実施形態の工具は、実施形態1の単結晶ダイヤモンドを被削材との接触部分に含む、切削バイト、フライスワイパー、エンドミル、ドリル、リーマー、カッター、ドレッサー、ワイヤーガイド、伸線ダイス、ウォータージェットノズル、ダイヤモンドナイフ、ガラス切りおよびスクライバーからなる群から選択される工具である。かかる工具は、非削材ろの接触部分に上記の実施形態の単結晶ダイヤモンドを含むため、大きな欠損抑制され、耐欠損性が高く強度が高い。
本実施形態の部品は、実施形態1の単結晶ダイヤモンドを含む光学部品、ヒートシンク、バイオチップ、センサーおよび半導体基板からなる群から選択される部品である。かかる部品は、上記の実施形態の単結晶ダイヤモンドを含むため、大きな欠損抑制され、耐欠損性が高く強度が高い。
(試料1~試料5および試料9~試料12)
1.主面に種結晶欠陥線状集合領域を有するダイヤモンド種結晶の準備
図5(A)を参照して、ダイヤモンド種結晶10として、高温高圧法により成長させた主面10mが(001)面から<100>方向に2°~10°のオフ角を有する5mm×5mm×厚さ1mmのダイヤモンド種結晶基板を9つ準備した。
次に、図5(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法により、単結晶ダイヤモンド20を成長させた。結晶成長用ガスとして、水素ガス、メタンガス、および窒素ガスを使用し、水素ガスに対するメタンガスの濃度を5モル%~20モル%、メタンガスに対する窒素ガスの濃度を0モル%~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5(C)を参照して、試料1~試料5の各々の単結晶ダイヤモンド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10中の導電層領域10cを分解除去することにより、ダイヤモンド種結晶10を除去した。試料9~試料12については、Nd:YAGレーザを用いて切断して種結晶を除去し、切断面をダイヤモンド砥粒をメタルで固定した砥石を用いて研磨した。
次に、図5(D)を参照して、試料2~試料5および試料10~試料12については、さらに、単結晶ダイヤモンド20を追加成長させた。かかる追加成長における結晶成長条件は、上記の最初の結晶成長条件と同じとした。このようにして得られた試料2~試料5および試料10~試料12の単結晶ダイヤモンド20は、それぞれ3層、2層、5層、3層、3層、5層および3層の単結晶ダイヤモンド層を有していた。さらに、図7を参照して、試料12については、レーザで切断した主面を研磨および酸洗浄(王水を使用)した後に、酸素(O2)ガスと四フッ化水素(CF4)ガスとを用いてドライエッチングを行い、2層の単結晶ダイヤモンド層で構成される単結晶ダイヤモンドを追加成長させた。これらの追加成長における結晶成長条件は、上記の最初の結晶成長条件と同じとした。結果を表1にまとめた。
このようにして得られた各々の単結晶ダイヤモンド20の(001)面である結晶成長主面20mについてこれに垂直な方向に透過型で測定されたX線トポグラフィー像により、結晶欠陥線状集合領域の線状に延びる方向に垂直な方向における線密度(本・mm-1)、結晶欠陥線状集合領域の線状に延びる方向における最大間隔(μm)、長さ300μm以上の結晶欠陥線状集合領域の密度(本・cm-2)、長さ500μm以上の結晶欠陥線状集合領域の密度(本・cm-2)、結晶欠陥点の密度(mm-2)および複合転位点の密度(mm-2)を算出した。ここで、X線の回折面は(220)面とした。使用したX線のエネルギーは、14.547keV(波長0.85Å)であった。結果を表1にまとめた。
上記で得られた各々の単結晶ダイヤモンド20をカッター刃の形状に加工し、ワーク(被切削材)の切削加工を行って耐欠損性を評価した。カッターは住友電工ハードメタル株式会社製RF4080Rを用い、ワイパーチップは同SNEW1204ADFR-WSを用いた。旋盤は株式会社森精機製のNV5000を用いた。切削速度は2000m/min、切込量0.05mm、送り量0.05mm/刃とした。ワークはアルミ材A5052を用い、ワークを30km切削した後に、カッター刃の5μm以上の欠損の数(欠損数)により耐欠損性の評価を行なった。欠損数の少ないほど耐欠損性が高い。結果を表1にまとめた。
比較のために、高温高圧法により成長させた3つの単結晶ダイヤモンドを、それぞれ、試料1~試料5の場合と同様にして、耐欠損性を評価した。これらの結果も、表1にまとめた。
次に試料13~15について、実施例1と同様の方法で種結晶を準備し、低窒素濃度となる条件で表2となるように単結晶ダイヤモンドを成長させた。結晶成長用ガスとして、水素ガス、メタンガス、および二酸化炭素ガスを使用し、水素ガスに対するメタンガスの濃度を1モル%~20モル%、メタンガスに対する二酸化炭素ガスの濃度を1モル%~70モル%とした。結晶成長圧力は5kPa~30kPa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。実施例1と同様の方法で種基板を分離した後、実施例1と同様の方法で分析と追加成長を行った。このようにして得られた各々の単結晶ダイヤモンドの円板形状の加工し、フランジに取り付けてCO2レーザ用の窓を作製した。比較用にはARコートしたZnSeで窓を作製した。レーザの発信機出力40kWで2000時間加工を繰り返した後、窓材表面を観察した。使用開始時と使用後の単結晶ダイヤモンドのレーザ出力をパワーメータで測定した。結果を表2にまとめた。
Claims (25)
- 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単結晶ダイヤモンド。
- 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任意に特定される一方向から30°以内の方向に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単結晶ダイヤモンド。
- 前記結晶欠陥線状集合領域は、それが線状に延びる方向に対して垂直な方向に1mm当たり2つ以上存在し、かつ、前記線状に延びる方向における間隔が500μm以下である請求項2に記載の単結晶ダイヤモンド。
- 前記結晶欠陥線状集合領域は、前記結晶成長主面の1cm2当たりに、長さ300μm以上の長い結晶欠陥線状集合領域を5本以上含む請求項2または請求項3に記載の単結晶ダイヤモンド。
- 前記結晶欠陥点の密度が20mm-2より大きい請求項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。
- 前記結晶欠陥点の密度が300mm-2より大きい請求項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。
- 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20mm-2より大きい請求項1から請求項6のいずれか1項に記載の単結晶ダイヤモンド。
- 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30mm-2より大きい請求項1から請求項6のいずれか1項に記載の単結晶ダイヤモンド。
- 複数の単結晶ダイヤモンド層を含む請求項1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。
- 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が、前記結晶成長主面と反対側の主面の前記結晶欠陥点より高密度である請求項9に記載の単結晶ダイヤモンド。 - 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、消滅、分岐または合流しており、
前記結晶成長主面の前記結晶欠陥点および前記結晶成長主面と反対側の結晶成長主面の前記結晶欠陥点が、各前記単結晶ダイヤモンド層の界面の前記結晶欠陥点より高密度である請求項9に記載の単結晶ダイヤモンド。 - 不純物原子として1ppm以上の窒素原子を含有する請求項1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。
- 不純物原子として3ppm以上の窒素原子を含有する請求項1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。
- 不純物原子として1ppm未満の窒素原子を含有する請求項1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。
- 不純物原子として0.3ppm以下の窒素原子を含有する請求項1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。
- 前記単結晶ダイヤモンドの厚さを500μmとしたときの400nmの光の透過率が60%以下である請求項1から請求項15のいずれか1項に記載の単結晶ダイヤモンド。
- 主面上に種結晶欠陥点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を準備する工程と、
前記ダイヤモンド種結晶の前記主面上に、化学気相堆積法により単結晶ダイヤモンドを成長させる工程と、
を備える単結晶ダイヤモンドの製造方法。 - 前記種結晶欠陥線状集合領域は、それが線状に延びる方向に対して垂直な方向に1mm当たり2つ以上存在し、かつ、前記線状に延びる方向における間隔が500μm以下である請求項17に記載の単結晶ダイヤモンドの製造方法。
- 前記種結晶欠陥線状集合領域は、前記主面の1cm2当たりに、長さ300μm以上の長い種結晶欠陥線状集合領域を5本以上含む請求項17または請求項18に記載の単結晶ダイヤモンドの製造方法。
- 前記種結晶欠陥点の密度が10mm-2より大きい請求項17から請求項19のいずれか1項に記載の単結晶ダイヤモンドの製造方法。
- 前記種結晶欠陥点の密度が100mm-2より大きい請求項17から請求項19のいずれか1項に記載の単結晶ダイヤモンドの製造方法。
- 前記ダイヤモンド種結晶の前記主面を水素終端した後の電子顕微鏡の2次電子像において、結晶損傷が存在する点を示す種結晶損傷点の密度が3mm-2より大きい請求項17から請求項21のいずれか1項に記載の単結晶ダイヤモンドの製造方法。
- 前記ダイヤモンド種結晶の前記主面を水素終端した後の電子顕微鏡の2次電子像において結晶損傷が存在する点を示す種結晶損傷点の密度が30mm-2より大きい請求項17から請求項21のいずれか1項に記載の単結晶ダイヤモンドの製造方法。
- 請求項1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を被削材との接触部分に含む、切削バイト、フライスワイパー、エンドミル、ドリル、リーマー、カッター、ドレッサー、ワイヤーガイド、伸線ダイス、ウォータージェットノズル、ダイヤモンドナイフ、ガラス切りおよびスクライバーからなる群から選択される工具。
- 請求項1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を含む光学部品、ヒートシンク、バイオチップ、センサーおよび半導体基板からなる群から選択される部品。
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EP15825061.3A EP3173510B1 (en) | 2014-07-22 | 2015-07-22 | Method for manufacturing a single-crystal diamond |
EP19170642.3A EP3575450A1 (en) | 2014-07-22 | 2015-07-22 | Single-crystal diamond |
US15/327,439 US10697058B2 (en) | 2014-07-22 | 2015-07-22 | Single-crystal diamond, method of producing same, tool including single-crystal diamond, and component including single-crystal diamond |
KR1020177004620A KR102392424B1 (ko) | 2014-07-22 | 2015-07-22 | 단결정 다이아몬드 및 그 제조 방법, 단결정 다이아몬드를 포함하는 공구, 및 단결정 다이아몬드를 포함하는 부품 |
JP2016535956A JP6708972B2 (ja) | 2014-07-22 | 2015-07-22 | 単結晶ダイヤモンドおよびその製造方法、単結晶ダイヤモンドを含む工具、ならびに単結晶ダイヤモンドを含む部品 |
CN201580039728.8A CN106574393B (zh) | 2014-07-22 | 2015-07-22 | 单晶金刚石及其制造方法、包含单晶金刚石的工具和包含单晶金刚石的部件 |
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WO2017014311A1 (ja) * | 2015-07-22 | 2017-01-26 | 住友電気工業株式会社 | 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 |
JP7042989B1 (ja) * | 2020-10-22 | 2022-03-28 | 住友電工ハードメタル株式会社 | ダイヤモンド焼結体、及びダイヤモンド焼結体を備える工具 |
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CN114729469A (zh) * | 2019-11-26 | 2022-07-08 | 住友电气工业株式会社 | 合成单晶金刚石、具备其的工具、及合成单晶金刚石的制造方法 |
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EP3173510A4 (en) | 2018-07-04 |
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US20170158514A1 (en) | 2017-06-08 |
US10697058B2 (en) | 2020-06-30 |
JPWO2016013588A1 (ja) | 2017-04-27 |
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JP6708972B2 (ja) | 2020-06-10 |
CN106574393B (zh) | 2019-10-08 |
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