WO2022097641A1 - 合成単結晶ダイヤモンド及びその製造方法 - Google Patents

合成単結晶ダイヤモンド及びその製造方法 Download PDF

Info

Publication number
WO2022097641A1
WO2022097641A1 PCT/JP2021/040399 JP2021040399W WO2022097641A1 WO 2022097641 A1 WO2022097641 A1 WO 2022097641A1 JP 2021040399 W JP2021040399 W JP 2021040399W WO 2022097641 A1 WO2022097641 A1 WO 2022097641A1
Authority
WO
WIPO (PCT)
Prior art keywords
single crystal
diamond
ppm
less
synthetic single
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/040399
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
均 角谷
真和 李
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Electric Industries Ltd
Original Assignee
Sumitomo Electric Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Priority to JP2022560786A priority Critical patent/JP7754107B2/ja
Priority to US18/034,235 priority patent/US20230383436A1/en
Publication of WO2022097641A1 publication Critical patent/WO2022097641A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • C01B32/28—After-treatment, e.g. purification, irradiation, separation or recovery
    • 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
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/02—Heat treatment
    • 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
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/04—After-treatment of single crystals or homogeneous polycrystalline material with defined structure using electric or magnetic fields or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/10—Metal solvents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/21—Attrition-index or crushing strength of granulates

Definitions

  • single crystal diamond Since single crystal diamond has high hardness, it is widely used in tools such as cutting tools, grinding tools, and abrasion resistant tools.
  • Single crystal diamonds used in tools include natural diamonds and synthetic diamonds.
  • Natural diamonds contain aggregated nitrogen atoms as impurities (Type Ia). Aggregate nitrogen atoms in diamond crystals can prevent plastic deformation and crack growth that occur when diamond is used in tools. Therefore, natural diamond has high mechanical strength. However, the quality of natural diamond varies widely and the supply is not stable, so its use for industrial applications is limited.
  • Ordinary synthetic diamond contains isolated substitution nitrogen atoms as impurities (Ib type).
  • Ib type isolated substitution nitrogen atoms as impurities
  • type IIa synthetic diamond does not contain impurities or crystal defects that prevent the growth of cracks, it tends to cause chipping of the cutting edge when used in a tool.
  • Patent Document 1 International Publication No. 2019/077888 discloses a synthetic single crystal diamond having high hardness and excellent fracture resistance.
  • the synthetic single crystal diamond of the present disclosure is a synthetic single crystal diamond containing a bond of one pore and one boron atom. It is a synthetic single crystal diamond having a concentration based on the number of atoms of a boron atom of 0.1 ppm or more and 100 ppm or less.
  • the method for producing synthetic single crystal diamond of the present disclosure is the above-mentioned method for producing synthetic single crystal diamond.
  • a synthetic single crystal diamond comprising a third step of applying a temperature of 600 ° C. or higher and 1800 ° C. or lower for 1 minute or more and 3600 minutes or less to the diamond single crystal after the second step to obtain a synthetic single crystal diamond. It is a manufacturing method.
  • FIG. 1 is a diagram for explaining a noup indentation.
  • FIG. 2 is a schematic cross-sectional view showing an example of a sample chamber configuration used for producing synthetic single crystal diamond according to an embodiment of the present disclosure.
  • an object of the present invention is to provide a synthetic single crystal diamond having high toughness and hardness, excellent fracture resistance and wear resistance, and a method for producing the same. [Effect of this disclosure]
  • the synthetic single crystal diamond of the present disclosure has high toughness and hardness, and excellent fracture resistance and wear resistance.
  • the synthetic single crystal diamond of the present disclosure is a synthetic single crystal diamond containing a bond of one pore and one boron atom. It is a synthetic single crystal diamond having a concentration based on the number of atoms of a boron atom of 0.1 ppm or more and 100 ppm or less.
  • the synthetic single crystal diamond of the present disclosure has high toughness and hardness, and excellent fracture resistance and wear resistance.
  • the synthetic single crystal diamond is formed when the Knoop hardness is measured under the conditions of a temperature of 23 ° C. ⁇ 5 ° C. and a test load of 4.9 N in accordance with JIS Z 2251: 2009 (001). It is preferable that the ratio b / a of the length b of the shorter diagonal line to the length a of the longer diagonal line of the Knoop indentation in the ⁇ 110> direction on the surface is 0.08 or less.
  • synthetic single crystal diamond can have excellent toughness and fracture resistance.
  • the Knoop hardness in the ⁇ 100> direction in the (001) plane of the synthetic single crystal diamond is preferably 110 GPa or more.
  • synthetic single crystal diamond can have excellent wear resistance.
  • the crack generation load is preferably 12 N or more.
  • synthetic single crystal diamond can have excellent fracture resistance.
  • the method for producing synthetic single crystal diamond of the present disclosure is the above-mentioned method for producing synthetic single crystal diamond.
  • a synthetic single crystal diamond comprising a third step of applying a temperature of 600 ° C. or higher and 1800 ° C. or lower for 1 minute or more and 3600 minutes or less to the diamond single crystal after the second step to obtain a synthetic single crystal diamond. It is a manufacturing method.
  • the notation in the form of "A to B” means the upper and lower limits of the range (that is, A or more and B or less), and when there is no description of the unit in A and the unit is described only in B, A.
  • the unit of and the unit of B are the same.
  • the present inventors assumed the influence of boron atoms existing as impurities in the crystal as one of the factors for improving the toughness and hardness of diamond crystals, that is, the fracture resistance and wear resistance when used as a tool. ..
  • An isolated substitution type boron atom is known as an existing form of the boron atom.
  • the isolated-substituted boron atom is one in which a boron atom is substituted at the position of a carbon atom in a diamond crystal in units of one atom.
  • the present inventors assumed that the presence of pores adjacent to the above-mentioned boron atom in a diamond crystal can more effectively prevent the growth of cracks and the progress of plastic deformation in the crystal. It is believed that the intervention of vacancies alleviates the excessive compressive stress that can be the starting point of fracture in the lattice compared to the boron atom alone.
  • the synthetic single crystal diamond of the present embodiment is a synthetic single crystal diamond containing a bond of one pore and one boron atom, and the concentration based on the number of atoms of the boron atom is 0.1 ppm or more and 100 ppm or less. Is.
  • the synthetic single crystal diamond of the present embodiment can have high toughness, hardness, fracture resistance and wear resistance. The reason for this is not clear, but it is presumed to be as described in (i) and (ii) below.
  • the synthetic single crystal diamond of the present embodiment contains a boron atom and pores. According to this, the synthetic single crystal diamond tends to form a bond between one pore and one boron atom, and the bond prevents the growth of cracks and the progress of plastic deformation in the crystal. In addition, the presence of vacancies alleviates the excessive compressive stress that can be the starting point of fracture caused by the aggregation of boron atoms alone, thereby improving the wear resistance and fracture resistance of the synthetic single crystal diamond.
  • the synthetic single crystal diamond of the present embodiment contains a boron atom at a concentration of 0.1 ppm or more and 100 ppm or less on an atomic number basis. Compressive stress is appropriately generated in the synthetic single crystal diamond, and the wear resistance and fracture resistance of the synthetic single crystal diamond are improved.
  • the synthetic single crystal diamond of this embodiment contains a boron atom.
  • the concentration of boron atoms in synthetic single crystal diamond based on the number of atoms (hereinafter, also referred to as “boron atom concentration”) is 0.1 ppm or more and 100 ppm or less.
  • the boron atom in the synthetic single crystal diamond means all the boron atoms contained in the synthetic single crystal diamond, and the existence form thereof does not matter.
  • the boron atom concentration is 0.1 ppm or more, the effect due to the presence of the boron atom can be easily obtained, and the synthetic single crystal diamond can have high hardness and excellent fracture resistance.
  • the boron atom concentration is 100 ppm or less, the internal stress in the synthetic single crystal diamond is appropriate, and the decrease in hardness and the decrease in fracture resistance due to the generation of excessive lattice defects are suppressed.
  • the lower limit of the boron atom concentration in synthetic single crystal diamond can be 0.1 ppm or more, 0.3 ppm or more, 0.5 ppm or more, 2 ppm or more, and 10 ppm or more.
  • the upper limit of the boron atom concentration in the synthetic single crystal diamond can be 100 ppm or less, 80 ppm or less, and 50 ppm or less.
  • Boron atom concentration in synthetic single crystal diamond is 0.1ppm or more and 100ppm or less, 0.3ppm or more and 100ppm or less, 0.3ppm or more and 80ppm or less, 0.5ppm or more and 100ppm or less, 0.5ppm or more and 80ppm or less, 0.5ppm or more.
  • It can be 50 ppm or less, 2 ppm or more and 100 ppm or less, 2 ppm or more and 80 ppm or less, 2 ppm or more and 50 ppm or less, 10 ppm or more and 100 ppm or less, 10 ppm or more and 80 ppm or less, and 10 ppm or more and 50 ppm or less.
  • the concentration of boron atoms in synthetic single crystal diamond is measured by secondary ion mass spectrometry (SIMS: Secondary Ion Mass Spectrometry).
  • SIMS Secondary Ion Mass Spectrometry
  • the synthetic single crystal diamond of this embodiment contains a bond of one pore and one boron atom.
  • the conjugate is also referred to as "BV".
  • the inclusion of a composite of one pore and one boron atom in a synthetic single crystal diamond is, for example, fluorescence obtained by irradiating the synthetic single crystal diamond with excitation light having a wavelength of 488 nm or a wavelength of 514 nm or a wavelength of 532 nm. In the spectrum, it is confirmed by the presence of an emission peak within the range of the fluorescence wavelength of 776.4 ⁇ 1 nm.
  • the emission peak exists within the range of the fluorescence wavelength of 776.4 ⁇ 1 nm is determined by comparing the intensity with the intensity of the Raman peak of diamond appearing in the vicinity of 521.9 nm in the case of excitation with a wavelength of 488 nm, for example. You can check. Specifically, for example, when irradiated with excitation light having a wavelength of 488 nm, the peak intensity IA existing in the range of the fluorescence wavelength of 776.4 ⁇ 1 nm and the intensity IB of the Raman peak of diamond appearing in the vicinity of the wavelength of 521.9 nm. When the intensity IA is larger than the intensity IB, it is determined that "the emission peak exists within the range of the fluorescence wavelength of 776.4 ⁇ 1 nm".
  • the synthetic single crystal diamond of this embodiment can contain an isolated substituted boron atom.
  • the lower limit of the concentration based on the number of atoms of the isolated substituted boron atom of the synthetic single crystal diamond of this embodiment is 0 ppm or more, 0.01 ppm or more, 0.03 ppm or more, 0.06 ppm or more, 0.08 ppm or more, 0.09 ppm. As mentioned above, it can be 0.1 ppm or more, 0.6 ppm or more, 1.2 ppm or more, 1.6 ppm or more, 3 ppm or more, and 6 ppm or more.
  • the upper limit of the atomic number-based concentration of the isolated substituted boron atom of the synthetic single crystal diamond can be 70 ppm or less, 60 ppm or less, 30 ppm or less, and 10 ppm or less.
  • the atomic number-based concentrations of isolated substituted boron atoms in synthetic single crystal diamonds are 0 ppm or more and 70 ppm or less, 0.01 ppm or more and 70 ppm or less, 0.03 ppm or more and 70 ppm or less, 0.06 ppm or more and 70 ppm or less, 0.08 ppm or more and 70 ppm or less.
  • ppm or more and 70 ppm or less 0.09 ppm or more and 70 ppm or less, 0.1 ppm or more and 70 ppm or less, 0.6 ppm or more and 70 ppm or less, 1.2 ppm or more and 70 ppm or less, 1.6 ppm or more and 70 ppm or less, 3 ppm or more and 70 ppm or less, 6 ppm or more and 70 ppm or less, 0 ppm or more and 30 ppm or less.
  • it can be 1.6 ppm or more and 10 ppm or less, 3 ppm or more and 10 ppm or less, and 6 ppm or more and 10 ppm or less, 0.
  • the concentration based on the atomic number of the isolated substituted boron atom of the synthetic single crystal diamond of the present embodiment is measured by the following procedures (A1) to (A3).
  • A1 Synthetic single crystal diamond is processed into a plate shape with a thickness of about 1 mm to 0.1 mm, two surfaces that transmit light are mirror-polished, and then the wave number is measured by Fourier transform infrared spectroscopy (FT-IR method). Absorbance measurement at 800-5000 cm -1 is performed to create an infrared absorption spectrum.
  • FT-IR method Fourier transform infrared spectroscopy
  • the (111) growth sector portion which tends to contain boron is evaluated.
  • A2 In the above infrared absorption spectrum, the absorption peak height H 2800 having a wave number of 2800 cm -1 is calculated.
  • H 2800 (cm -1 ) indicates the FT-IR absorption height.
  • H 2458 (cm -1 ) and H 1290 (cm -1 ) indicate the FT-IR absorption height.
  • the synthetic single crystal diamond of the present embodiment is formed in accordance with JIS Z 2251: 2009 on the (001) plane formed when Knoop hardness is applied under the conditions of a temperature of 23 ° C. ⁇ 5 ° C. and a test load of 4.9 N.
  • the ratio b / a of the length b of the shorter diagonal line to the length a of the longer diagonal line of the Knoop indentation in the ⁇ 110> direction hereinafter, also referred to as "(001) ⁇ 110> Knoop indentation"). Is preferably 0.08 or less.
  • Knoop hardness is known as one of the measures for expressing the hardness of industrial materials as specified in JIS Z2251: 2009, and a Knoop indenter is used at a predetermined temperature and a predetermined load (test load). The hardness of the material to be measured is obtained by pressing it against the material to be measured.
  • the noup indenter is a diamond indenter whose bottom surface is in the shape of a diamond-shaped quadrangular prism.
  • the rhombus on the bottom surface is defined as having a ratio b'/ a'of the length b'of the shorter diagonal line to the length a'of the longer diagonal line of the diagonal line of 0.141.
  • the noup indentation refers to a trace remaining at a position where the noup indenter is released immediately after the noup indenter is pressed against the material to be measured (synthetic single crystal diamond in the present embodiment) at the above temperature and test load.
  • indentations are made in the ⁇ 110> direction in the (001) plane of the synthetic single crystal diamond under the conditions of a temperature of 23 ° C. ⁇ 5 ° C. and a test load of 4.9 N in accordance with JIS Z 2251: 2009. Make (Noop indentation).
  • the diagonal ratio b / a of the noup indentation is 0.08 or less, which is preferably smaller than the original noup indenter ratio b'/ a'(0.141). .. This is because the material to be measured, that is, the synthetic single crystal diamond, has a large elastic deformability, and the indentation is elastically restored (elastic recovery).
  • FIG. 1 conceptually shows the indentation of Noup.
  • the cross section of the noup indenter and the noup indentation have the same shape (the part shown as the "original noup indentation" in FIG. 1).
  • the synthetic single crystal diamond of the present embodiment has high elastic deformability, elastic recovery occurs in the direction of the arrow in the figure, and the noup indentation thereof becomes a rhombus shown by the solid line in the figure. That is, the larger the return in the direction of the arrow in the figure, the smaller the value of the ratio b / a. The smaller the value of the ratio b / a, the greater the elastic deformability.
  • the synthetic single crystal diamond of the present embodiment has a large elastic deformability because the diagonal ratio b / a of the noup indentation is 0.08 or less.
  • the upper limit of the diagonal ratio b / a of the noup indentation can be 0.08 or less, 0.075 or less, 0.07 or less, 0.065 or less, 0.06 or less.
  • the diagonal ratio b / a of the noup indentation is 0 or more and 0.08 or less, 0 or more and 0.075 or less, 0 or more and 0.07 or less, 0 or more and 0.065 or less, 0 or more and 0.06 or less, 0 or more and 0.055.
  • it can be 0 or more and 0.05 or less, 0 or more and 0.045 or less, and 0 or more and 0.04 or less.
  • the Knoop hardness in the ⁇ 100> direction of the synthetic single crystal diamond of the present embodiment (hereinafter, also referred to as “(001) ⁇ 100> Knoop hardness”) is preferably 110 GPa or more.
  • (001) ⁇ 100> Synthetic single crystal diamond having a Knoop hardness of 110 GPa or more has a higher hardness than natural diamond containing nitrogen and is excellent in wear resistance.
  • the lower limit of Knoop hardness can be 110 GP or more, 113 GPa or more, 115 GPa or more, 118 GPa or more, 120 GPa or more, 122 GPa or more, 123 GPa or more, 125 GPa or more.
  • the upper limit of the Knoop hardness is not particularly limited, but can be, for example, 150 GPa or less from the viewpoint of manufacturing.
  • Knoop hardness of synthetic single crystal diamond is 110 GPa or more and 150 GPa or less, 113 GPa or more and 150 GPa or less, 115 GPa or more and 150 GPa or less, 118 GPa or more and 150 GPa or less, 120 GPa or more and 150 GPa or less, 122 GPa or more and 150 GPa or less, 123 GPa or more and 150 GPa or less, 125 GPa. It can be 150 GPa or less.
  • the unit is GPa) of synthetic single crystal diamond will be described.
  • an indentation is made in the ⁇ 100> direction in the (001) plane of the synthetic single crystal diamond with a load of 4.9 N.
  • the longer diagonal line a ( ⁇ m) of the obtained indentation is measured, and (001) ⁇ 100> Knoop hardness (HK) is calculated from the following formula A.
  • the Knoop hardness is measured at 23 ° C ⁇ 5 ° C.
  • the synthetic single crystal diamond of the present embodiment has a crack generation load of 12 N or more in a fracture strength test in which a spherical diamond indenter having a tip radius (R) of 50 ⁇ m is pressed against the surface of the synthetic single crystal diamond at a load speed of 100 N / min. Is preferable.
  • the crack generation load is 12 N or more, the synthetic single crystal diamond is excellent in fracture resistance and chipping resistance.
  • the cutting edge is less likely to be chipped even when cutting a hard difficult-to-cut material.
  • the lower limit of the crack generation load can be 12N or more, 13N or more, 14N or more, 15N or more, 16N or more, 17N or more, 18N or more, 20N or more, 22N or more.
  • the upper limit of the crack generation load is not particularly limited, but from a manufacturing point of view, it is, for example, 50 N or less.
  • the crack generation load of synthetic single crystal diamond is 12N or more and 50N or less, 13N or more and 50N or less, 14N or more and 50N or less, 15N or more and 50N or less, 16N or more and 50N or less, 17N or more and 50N or less, 18N or more and 50N or less, 20N or more and 50N or less. It can be 22N or more and 50N or less.
  • the specific method of the fracture strength test is as follows. A spherical diamond indenter with a tip radius (R) of 50 ⁇ m is pressed against the sample, a load is applied to the sample at a load rate of 100 N / min, and the load at the moment when a crack occurs in the sample (crack generation load) is measured. ..
  • the test temperature is 23 ° C ⁇ 5 ° C.
  • the moment when a crack occurs is measured by an AE sensor. The larger the crack generation load, the higher the strength of the sample and the better the fracture resistance.
  • an indenter with a tip radius (R) smaller than 50 ⁇ m is used as the measuring indenter, the sample will be plastically deformed before cracks occur, and accurate strength against cracks cannot be measured.
  • the load required to generate a crack increases, the contact area between the indenter and the sample increases, and the measurement accuracy is based on the surface accuracy of the sample.
  • the synthetic single crystal diamond of the present embodiment has high toughness and hardness, has excellent fracture resistance and wear resistance when used as a tool, has stable quality, and can be applied to various applications. ..
  • it can be used as a material for polishing tools such as dressers, wire drawing dies, stylus, scribing tools, and orifices for water jets, and cutting tools such as cutting tools for precision cutting and cutters for woodworking.
  • the tool using the synthetic single crystal diamond of the present embodiment is an excellent tool because it can perform stable machining for a long time as compared with the conventional synthetic diamond and those made from natural diamond or a diamond sintered body. Has a lifetime.
  • the method for producing synthetic single crystal diamond of the present embodiment is the method for producing synthetic single crystal diamond of Embodiment 1, and the boron atom is 0.1 ppm or more and 100 ppm based on the number of atoms by the temperature difference method using a solvent metal.
  • a third step of applying a temperature of 600 ° C. or higher and 1800 ° C. or lower for 1 minute or more and 3600 minutes or less to the diamond single crystal after the step to obtain a synthetic single crystal diamond is provided.
  • a diamond single crystal containing a boron atom at a concentration of 0.1 ppm or more and 100 ppm or less based on the number of atoms is synthesized by a temperature difference method using a solvent metal.
  • the diamond single crystal can be produced, for example, by a temperature difference method using a sample chamber 10 having the configuration shown in FIG.
  • the insulator 2, the carbon source 3, the solvent metal 4, and the seed crystal 5 are arranged in the space surrounded by the graphite heater 7.
  • a pressure medium 6 is arranged outside the graphite heater 7.
  • a vertical temperature gradient is provided inside the sample chamber 10
  • a carbon source 3 is arranged in a high temperature portion (T high )
  • a diamond seed crystal 5 is arranged in a low temperature portion (T low )
  • a carbon source 3 is provided.
  • a diamond single crystal is placed on the seed crystal 5 by arranging the solvent metal 4 between the seed crystal 5 and the seed crystal 5 and keeping the conditions above the pressure at which the diamond becomes thermally stable at the temperature at which the solvent metal 4 melts or higher. It is a synthetic method for growing 1.
  • diamond powder As the carbon source 3. Further, graphite (graphite) or pyrolytic carbon can also be used.
  • the solvent metal 4 one or more metals selected from iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn) and the like, or alloys containing these metals can be used. It is preferable to add an appropriate amount of an element having a high affinity for nitrogen, such as aluminum (Al) and titanium (Ti), as a nitrogen getter to the solvent metal so that nitrogen impurities are not mixed in the diamond single crystal.
  • boron powder (B), boron carbide (B 4 C or the like), iron carbide (Fe 2 B or the like) or the like is added as a simple substance or a mixture as a boron supply source. Can be done. Further, diamond powder or graphite containing a large amount of boron can be added to the carbon source 3. As a result, the diamond single crystal synthesized contains a boron atom. At this time, the boron atom in the diamond single crystal mainly exists as an isolated substitution type impurity.
  • the concentration of the boron supply source in the carbon source 3 or the solvent metal 4 is adjusted so that the concentration based on the number of atoms of the boron atom in the synthesized diamond single crystal is 0.1 ppm or more and 100 ppm or less.
  • the mass-based concentration of the boron atom derived from the boron source can be 5 ppm or more and 25,000 ppm or less.
  • the lower limit of the concentration of the boron atom of the boron-containing diamond single crystal which is the starting material of the synthetic single crystal diamond of the present embodiment, can be 0.1 ppm or more, 0.3 ppm or more, and 0.5 ppm or more. ..
  • the upper limit of the concentration based on the atomic number of the boron atom of the diamond single crystal can be 100 ppm or less, 80 ppm or less, and 50 ppm or less.
  • the concentration of the boron atom of the diamond single crystal based on the atomic number can be 0.1 ppm or more and 100 ppm or less, 0.3 ppm or more and 80 ppm or less, and 0.5 ppm or more and 50 ppm or less.
  • the concentration of boron atoms in a diamond single crystal is measured by secondary ion mass spectrometry (SIMS).
  • the solvent metal 4 further includes titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), copper (Cu), zirconium (Zr), niobium (Nb), molybdenum (Mo), and ruthenium (Ru). ), Rodium (Rh), Hafnium (Hf), Tantalum (Ta), Tantalum (W), Osmium (Os), Iridium (Ir) and Platinum (Pt). You may.
  • the obtained diamond single crystal is irradiated with one or both of an electron beam and a particle beam that give energy of 10 MGy or more and 1000 MGy or less.
  • a particle beam a neutron beam or a proton beam can be used.
  • lattice defects are introduced in the diamond single crystal and pores are formed.
  • the amount of energy to be irradiated is less than 10 MGy, the introduction of lattice defects may be insufficient. On the other hand, if the amount of energy exceeds 1000 MGy, excessive pores may be generated and the crystallinity may be significantly deteriorated. Therefore, the amount of energy is preferably 10 MGy or more and 1000 MGy or less.
  • Irradiation conditions are not particularly limited as long as the diamond single crystal can be given energy of 10 MGy or more and 1000 MGy or less.
  • the irradiation energy can be 2 MeV or more and 4.8 MeV or less
  • the current can be 2 mA or more and 5 mA or less
  • the irradiation time can be 30 hours or more and 45 hours or less.
  • the temperature of the third step is 600 ° C. or higher, the formation of the above-mentioned conjugate is promoted. Below 600 ° C., many isolated pores remain and the hardness is greatly reduced.
  • the upper limit of the temperature in the third step is preferably 1800 ° C. or lower from the viewpoint of cost and productivity.
  • the time for applying a temperature of 600 ° C. or higher and 1800 ° C. or lower to a diamond single crystal is 1 minute or longer and 3600 minutes or lower. This time can be 60 minutes or more and 360 minutes or less.
  • the second step and the third step can be repeated for two or more cycles, with the case where each is performed once as one cycle. This makes it possible to promote the formation of the above-mentioned conjugate in the diamond single crystal.
  • the pressure was 5.5 GPa and the temperature of the low temperature part was controlled in the range of 1370 ° C ⁇ 10 ° C (1360 ° C to 1380 ° C) and held for 60 hours. Synthesize crystals.
  • the irradiation conditions are an irradiation line energy of 4.6 MeV, a current of 2 mA, and an irradiation time of 30 hours. This is an irradiation condition that gives an energy of 100 MGy to a diamond single crystal. If “Yes” is described in the "Electron beam irradiation (100MGy)" column of “Manufacturing conditions” in Table 1, electron beam irradiation is performed, and if "No” is described, electron beam irradiation is not performed. ..
  • “strong” means that an emission peak exists at a wavelength of 776.4 ⁇ 1 nm, and the intensity of the emission peak corresponds to the Raman scattered light of diamond (diamond Raman appearing near the wavelength 521.9 nm). It is 50% or more with respect to the intensity of the peak), indicating that the synthetic single crystal diamond contains a bond of one pore and one boron atom.
  • “Weak” means that an emission peak exists at a wavelength of 776.4 ⁇ 1 nm, and the intensity of the emission peak is 50% or less of the emission intensity of Raman scattered light of diamond appearing near a wavelength of 522 nm, and is a synthetic single crystal. It is shown that diamond contains a bond of one pore and one boron atom.
  • “None” means that there is no emission peak with a wavelength of 776.4 ⁇ 1 nm, and the synthetic single crystal diamond does not contain a bond of one pore and one boron atom.
  • Samples 3 to 8, sample 11 to sample 13, sample 15, sample 16, sample 18 and sample 19 correspond to Examples.
  • Sample 1, sample 2, sample 9, sample 10, sample 14, and sample 17 correspond to comparative examples.
  • the diagonal ratio b / a of the (001) ⁇ 110> noup indentation is smaller than that of the comparative example, the elastic deformability is large, the toughness is high, and the fracture resistance is excellent. Further, all of the examples have a high hardness of (001) ⁇ 100> Knoop hardness of 110 GPa or more, and are excellent in wear resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Carbon And Carbon Compounds (AREA)
PCT/JP2021/040399 2020-11-04 2021-11-02 合成単結晶ダイヤモンド及びその製造方法 Ceased WO2022097641A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2022560786A JP7754107B2 (ja) 2020-11-04 2021-11-02 合成単結晶ダイヤモンド及びその製造方法
US18/034,235 US20230383436A1 (en) 2020-11-04 2021-11-02 Synthetic single crystal diamond and method for producing same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020184564 2020-11-04
JP2020-184564 2020-11-04

Publications (1)

Publication Number Publication Date
WO2022097641A1 true WO2022097641A1 (ja) 2022-05-12

Family

ID=81457212

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/040399 Ceased WO2022097641A1 (ja) 2020-11-04 2021-11-02 合成単結晶ダイヤモンド及びその製造方法

Country Status (3)

Country Link
US (1) US20230383436A1 (https=)
JP (1) JP7754107B2 (https=)
WO (1) WO2022097641A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024210129A1 (ja) * 2023-04-03 2024-10-10 住友電気工業株式会社 合成単結晶ダイヤモンド、合成単結晶ダイヤモンドの製造方法および赤外光学部品

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012530676A (ja) * 2009-06-26 2012-12-06 エレメント シックス リミテッド ファンシーな橙色の単結晶ｃｖｄダイヤモンドの製造方法及び得られた製品
JP2018197178A (ja) * 2017-05-24 2018-12-13 住友電気工業株式会社 多結晶ダイヤモンドおよびその製造方法、スクライブツール、スクライブホイール、ドレッサー、回転工具、ウォータージェット用オリフィス、伸線ダイス、切削工具、電極ならびに多結晶ダイヤモンドを用いた加工方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI457475B (zh) * 2008-05-05 2014-10-21 Carnegie Inst Of Washington 超韌性單晶型摻硼鑽石
US9255009B2 (en) * 2009-06-26 2016-02-09 Element Six Technologies Limited Diamond material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012530676A (ja) * 2009-06-26 2012-12-06 エレメント シックス リミテッド ファンシーな橙色の単結晶ｃｖｄダイヤモンドの製造方法及び得られた製品
JP2015155377A (ja) * 2009-06-26 2015-08-27 エレメント シックス リミテッド 単結晶ｃｖｄダイヤモンドの処理方法及び得られた製品
JP2018197178A (ja) * 2017-05-24 2018-12-13 住友電気工業株式会社 多結晶ダイヤモンドおよびその製造方法、スクライブツール、スクライブホイール、ドレッサー、回転工具、ウォータージェット用オリフィス、伸線ダイス、切削工具、電極ならびに多結晶ダイヤモンドを用いた加工方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024210129A1 (ja) * 2023-04-03 2024-10-10 住友電気工業株式会社 合成単結晶ダイヤモンド、合成単結晶ダイヤモンドの製造方法および赤外光学部品

Also Published As

Publication number Publication date
JPWO2022097641A1 (https=) 2022-05-12
US20230383436A1 (en) 2023-11-30
JP7754107B2 (ja) 2025-10-15

Similar Documents

Publication Publication Date Title
JP7462419B2 (ja) 合成単結晶ダイヤモンド
JP7517347B2 (ja) 合成単結晶ダイヤモンド、それを備える工具、及び、合成単結晶ダイヤモンドの製造方法
JPWO2019077888A1 (ja) 合成単結晶ダイヤモンド、工具、及び、合成単結晶ダイヤモンドの製造方法
KR20130041884A (ko) 다이아몬드 공구
JP6582597B2 (ja) ダイヤモンド単結晶、工具およびダイヤモンド単結晶の製造方法
TWI896695B (zh) 合成單晶鑽石及其製造方法
JP7722370B2 (ja) 合成単結晶ダイヤモンド及びその製造方法
WO2022264706A1 (ja) 合成単結晶ダイヤモンド及びその製造方法
WO2022097641A1 (ja) 合成単結晶ダイヤモンド及びその製造方法
JP7760754B1 (ja) 単結晶ダイヤモンド素材および工具
JP7764631B1 (ja) 単結晶ダイヤモンドおよび工具
TW202314068A (zh) 合成單晶鑽石及其製造方法
JP2022139094A (ja) 合成単結晶ダイヤモンド及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21889194

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022560786

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 18034235

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21889194

Country of ref document: EP

Kind code of ref document: A1