WO2022004150A1 - 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

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WO2022004150A1
WO2022004150A1 PCT/JP2021/018372 JP2021018372W WO2022004150A1 WO 2022004150 A1 WO2022004150 A1 WO 2022004150A1 JP 2021018372 W JP2021018372 W JP 2021018372W WO 2022004150 A1 WO2022004150 A1 WO 2022004150A1
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single crystal
diamond
crystal diamond
synthetic single
less
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French (fr)
Japanese (ja)
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均 角谷
真和 李
三記 寺本
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Priority to CN202180040021.4A priority Critical patent/CN115698393B/zh
Priority to US18/009,728 priority patent/US20230219818A1/en
Priority to JP2022533717A priority patent/JP7658373B2/ja
Priority to EP21831884.8A priority patent/EP4174222A4/en
Publication of WO2022004150A1 publication Critical patent/WO2022004150A1/ja
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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
    • 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
    • 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

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 diamonds of the present disclosure are A synthetic single crystal diamond containing nitrogen atoms at a concentration of 100 ppm or more and 1500 ppm or less based on the number of atoms.
  • the synthetic single crystal diamond contains an agglomerate consisting of one pore and three substituted nitrogen atoms present adjacent to the pore.
  • Raman shift ⁇ cm -1 shows the relationship of the following equation 1.
  • ⁇ '- ⁇ ⁇ 0 Equation 1 It is a synthetic single crystal diamond.
  • the method for producing synthetic single crystal diamond of the present disclosure is The above method for producing synthetic single crystal diamond.
  • the third step of obtaining the synthetic single crystal diamond by applying a pressure of 3 GPa or more and a temperature of 1850 ° C. or higher and 2300 ° C. or lower for 1 minute or more and 3600 minutes or less to the diamond single crystal after the second step. It is a method for producing synthetic single crystal diamond.
  • FIG. 1 is an example of the fluorescence spectrum of synthetic single crystal diamond according to the embodiment of the present disclosure.
  • 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 hardness and excellent fracture resistance.
  • the synthetic single crystal diamonds of the present disclosure can have high hardness and excellent fracture resistance.
  • the synthetic single crystal diamond of the present disclosure is A synthetic single crystal diamond containing nitrogen atoms at a concentration of 100 ppm or more and 1500 ppm or less based on the number of atoms.
  • the synthetic single crystal diamond contains an agglomerate consisting of one pore and three substituted nitrogen atoms present adjacent to the pore.
  • Raman shift ⁇ cm -1 shows the relationship of the following equation 1.
  • ⁇ '- ⁇ ⁇ 0 Equation 1 It is a synthetic single crystal diamond.
  • the synthetic single crystal diamond of the present disclosure can have high hardness and excellent fracture resistance.
  • the emission peak is present in one or both of the fluorescence wavelength range of 415 ⁇ 2 nm and the fluorescence wavelength range of 420 nm or more and 470 nm or less.
  • synthetic single crystal diamond can have high hardness and excellent fracture resistance.
  • the absorption peak exists in the range of wave number 1370 cm -1 or more and 1385 cm -1 or less.
  • synthetic single crystal diamond can have high hardness and excellent fracture resistance.
  • the Knoop hardness in the ⁇ 100> direction on the ⁇ 001 ⁇ plane of the synthetic single crystal diamond is preferably 100 GPa or more.
  • synthetic single crystal diamond can have excellent wear resistance.
  • the crack generation load is preferably 15 N or more.
  • synthetic single crystal diamond can have excellent fracture resistance.
  • the method for producing synthetic single crystal diamond disclosed in the present disclosure is as follows.
  • the above method for producing synthetic single crystal diamond The first step of synthesizing a diamond single crystal containing a nitrogen atom at a concentration of 100 ppm or more and 1500 ppm or less based on the number of atoms by a temperature difference method using a solvent metal.
  • the third step of obtaining the synthetic single crystal diamond by applying a pressure of 3 GPa or more and a temperature of 1850 ° C. or higher and 2300 ° C. or lower for 1 minute or more and 3600 minutes or less to the diamond single crystal after the second step. It is a method for producing synthetic single crystal diamond.
  • 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.
  • Nitrogen atoms in diamond crystals can be classified into isolated substitution type nitrogen atoms, aggregated nitrogen atoms, etc., depending on their existence form.
  • the isolated substitution type nitrogen atom exists at the position of the carbon atom in the diamond crystal by substituting the nitrogen atom in units of one atom.
  • the present inventors have found that when a diamond crystal contains an isolated substitution type nitrogen atom, a local tensile stress is generated in the crystal lattice around the diamond crystal, which becomes a starting point of plastic deformation or fracture, and the hardness is lowered to withstand. It is newly assumed that wear resistance and fracture resistance will decrease.
  • Synthetic single crystal diamond containing isolated substitutional nitrogen atoms shows the infrared absorption spectrum measured by Fourier transform infrared spectroscopy, near the wave number 1130 cm -1 (i.e., wave number 1130 ⁇ 2 cm -1) absorption peaks.
  • ESR Electron Spin Response, electron spin resonance
  • Aggregate nitrogen atoms are those in which two or more nitrogen atoms are aggregated and exist in a diamond crystal.
  • the present inventors have newly assumed that the aggregated nitrogen atom in the diamond crystal can suppress the plastic deformation and the growth of cracks that occur when a load is applied to the diamond crystal.
  • the present inventors have newly assumed that when a diamond crystal contains aggregated nitrogen atoms, the wear resistance and fracture resistance of the diamond crystal are greatly improved.
  • Aggregated nitrogen atoms include A center (nitrogen 2 atom pair), H3 center (nitrogen 2 atom aggregation), N3 center (nitrogen 3 atom aggregation), B center (nitrogen 4 atom condensation), B'center or platelet, etc. It exists inside.
  • the A center (two nitrogen atom pair) is an agglomerate consisting of two nitrogen atoms, and the two nitrogen atoms form a covalent bond and each nitrogen atom is replaced with a carbon atom constituting a diamond crystal.
  • Diamonds containing A-centers (2 nitrogen atom pairs) are called IAA type.
  • the H3 center (2 nitrogen atom agglomeration) is an agglomerate consisting of one vacancies and two nitrogen atoms existing adjacent to the vacancies, and each nitrogen atom is a carbon atom constituting a diamond crystal. It is replacing.
  • the "nitrogen atom existing adjacent to a vacancy” is a nitrogen atom having the shortest interatomic distance from the carbon atom (that is, assuming that a carbon atom exists at the position of the vacancy). It means the nearest atom. It is also synonymous with N3 center and B center, which will be described later.
  • Synthetic single crystal diamonds containing the H3 center have a fluorescence spectrum of around 503 nm (eg, fluorescence wavelength 503 ⁇ ) in a fluorescence spectrum obtained by irradiating with excitation light shorter than about 500 nm, for example, excitation light having a wavelength of 325 nm.
  • the emission peak is shown at 2 nm).
  • the N3 center (nitrogen 3-atom agglomeration) is an agglomerate consisting of one vacancies and three nitrogen atoms existing adjacent to the vacancies, and each nitrogen atom is a carbon atom constituting a diamond crystal. It is replacing.
  • Synthetic single crystal diamonds containing N3 centers have a fluorescence spectrum around 415 nm (eg, 415 ⁇ fluorescence wavelength) in a fluorescence spectrum obtained by irradiating with excitation light shorter than approximately 410 nm, for example, excitation light having a wavelength of 325 nm. 2 nm) and one or both of the fluorescence wavelengths within the range of 420 nm or more and 470 nm or less show emission peaks.
  • the B center (condensation of 4 nitrogen atoms) is an agglomerate consisting of one vacancies and four nitrogen atoms existing adjacent to the vacancies, and each nitrogen atom is a carbon atom constituting a diamond crystal. It is replacing.
  • Diamonds containing tetranitrogen agglomeration are called type IaB.
  • Nitrogen 4 synthetic single crystal diamond containing atoms aggregation shows the infrared absorption spectrum measured by Fourier transform infrared spectroscopy, near wavenumber 1175cm -1 (e.g., the wave number 1175 ⁇ 2 cm -1) absorption peaks.
  • the B'center (also called a platelet) is a plate-like aggregate composed of five or more nitrogen atoms and interstitial carbon, and is incorporated as inclusions in the crystal.
  • a diamond containing a B'center (platelet) is called an IaB'type.
  • the synthetic single crystal diamond containing the B'center (platelet) shows an absorption peak at a wave number of 1358 cm -1 or more and 1385 cm -1 or less in the infrared absorption spectrum measured by Fourier transform infrared spectroscopy.
  • the present inventors have diligently studied aggregated nitrogen atoms that can improve the characteristics of synthetic single crystal diamond, and newly found that the N3 center has the least crystal strain and the structure is stable. Then, it was newly found that the mechanical properties such as hardness, strength, wear resistance, and fracture resistance of the synthetic single crystal diamond can be further improved by forming the N3 center predominantly in the synthetic single crystal diamond. This disclosure has been completed.
  • the synthetic single crystal diamond of the present disclosure is a synthetic single crystal diamond containing a nitrogen atom at a concentration of 100 ppm or more and 1500 ppm or less on the basis of the number of atoms, and the synthetic single crystal diamond has one hole and is adjacent to the hole.
  • the Raman shift ⁇ cm -1 of the peak in the primary Raman scattering spectrum of the synthetic IIa single crystal diamond containing the following concentrations shows the relationship of the following formula 1.
  • ⁇ '- ⁇ ⁇ 0 Equation 1 It is a synthetic single crystal diamond.
  • the synthetic single crystal diamond of the present disclosure can have high hardness and fracture resistance. The reason for this is not clear, but it is presumed to be as follows (i) to (iii).
  • the synthetic single crystal diamond of the present disclosure contains nitrogen atoms at a concentration of 100 ppm or more and 1500 ppm or less based on the atomic number. According to this, nitrogen atoms in the synthetic single crystal diamond tend to aggregate with each other. Therefore, the synthetic single crystal diamond tends to contain aggregated nitrogen atoms, and the wear resistance and fracture resistance of the diamond crystal are improved.
  • the synthetic single crystal diamond of the present disclosure contains an agglomerate consisting of one pore and three substituted nitrogen atoms existing adjacent to the pore. That is, the synthetic single crystal diamonds of the present disclosure include N3 centers. The N3 center can suppress the plastic deformation and crack growth that occur when a load is applied to the synthetic single crystal diamond. Therefore, the synthetic single crystal diamond has improved fracture resistance.
  • the N3 center has the least crystal strain and the structure is stable. Therefore, the synthetic single crystal diamond of the present disclosure including the N3 center can have high hardness and excellent wear resistance.
  • the above formula 1 is satisfied, there is almost no tensile stress, and compressive stress is generated. Therefore, even if an isolated substitution type nitrogen atom is present, the isolated substitution type nitrogen atom does not serve as a starting point for plastic deformation or fracture. Therefore, the synthetic single crystal diamond of the present disclosure can have excellent strength and fracture resistance. The details of the relationship between the above formula 1 and the internal stress of the synthetic single crystal diamond will be described later.
  • the synthetic single crystal diamond of the present disclosure contains a nitrogen atom at a concentration of 100 ppm or more and 1500 ppm or less (hereinafter, also referred to as “nitrogen atom concentration”) based on the number of atoms.
  • nitrogen atom concentration 100 ppm or more
  • the nitrogen atoms in the synthetic single crystal diamond tend to form aggregated nitrogen atoms.
  • the synthetic single crystal diamond can have high hardness and excellent fracture resistance.
  • the lower limit of the nitrogen atom concentration in synthetic single crystal diamond can be 100 ppm or more, 200 ppm or more, and 300 ppm or more.
  • the upper limit of the nitrogen atom concentration in the synthetic single crystal diamond can be 1500 ppm or less, 1400 ppm or less, and 1300 ppm or less.
  • the nitrogen atom concentration in synthetic single crystal diamond is 100 ppm or more and 1500 ppm or less, 100 ppm or more and 1400 ppm or less, 100 ppm or more and 1300 ppm or less, 200 ppm or more and 1500 ppm or less, 200 ppm or more and 1400 ppm or less, 200 ppm or more and 1300 ppm or less, 300 ppm or more and 1500 ppm or less, 300 ppm or more and 1400 ppm or less. , 300 ppm or more and 1300 ppm or less.
  • the nitrogen atom concentration in the synthetic single crystal diamond can be measured by secondary ion mass spectrometry (SIMS: Secondary Ion Mass Spectrometry).
  • the synthetic single crystal diamond of the present disclosure comprises an agglomerate consisting of one vacancies and three substituted nitrogen atoms present adjacent to the vacancies. That is, the synthetic single crystal diamonds of the present disclosure include N3 centers.
  • the N3 center can suppress the plastic deformation and crack growth that occur when a load is applied to the synthetic single crystal diamond. Therefore, the synthetic single crystal diamond has improved fracture resistance.
  • the N3 center has the least crystal strain and the structure is stable. Therefore, the synthetic single crystal diamond of the present disclosure including the N3 center can have high hardness and excellent wear resistance.
  • the inclusion of the N3 center in the synthetic single crystal diamond can be confirmed by the fluorescence spectrum obtained by irradiating the synthetic single crystal diamond with an excitation light shorter than about 410 nm, for example, an excitation light having a wavelength of 325 nm. Specifically, in the fluorescence spectrum obtained by irradiating synthetic single crystal diamond with excitation light having a wavelength of 325 nm, one or both of the fluorescence wavelength within the range of 415 ⁇ 2 nm and the fluorescence wavelength within the range of 420 nm or more and 470 nm or less. If an emission peak is present in, the synthetic single crystal diamond is determined to contain an N3 center.
  • the peak within the fluorescence wavelength range of 415 ⁇ 2 nm is the emission peak corresponding to the zero phonon line at the N3 center, and the emission peak within the fluorescence wavelength range of 420 nm or more and 470 nm or less corresponds to the subband (phonon side band) at the N3 center. It is a emission peak. Emission peaks having a fluorescence wavelength in the range of 420 nm or more and 470 nm or less are observed as one or more chevron peaks in the range. At least one of the chevron peaks shows maximum intensity within the range.
  • FIG. 1 shows an example of a fluorescence spectrum obtained by irradiating a synthetic single crystal diamond according to an embodiment of the present disclosure (hereinafter, also referred to as “the present embodiment”) with excitation light having a wavelength of 325 nm.
  • the X-axis indicates the fluorescence wavelength (nm)
  • the Y-axis indicates the emission intensity.
  • emission peaks in the fluorescence wavelength range of 415 ⁇ 2 nm (indicated by arrow N3) and emission peaks in the fluorescence wavelength range of 420 nm or more and 470 nm or less (indicated by arrow S) are shown. exist.
  • the synthetic single crystal diamond contains the N3 center.
  • the ultraviolet-visible spectroscopic spectrum when an absorption spectrum having a wavelength of 393 nm is present, it is determined that the synthetic single crystal diamond contains an N3 center.
  • the absorption peak exists in the range of wave number 1370 cm -1 or more and 1385 cm -1 or less.
  • the absorption peak is derived from the B'center (platelet) in the synthetic single crystal diamond.
  • synthetic single crystal diamond In the infrared absorption spectrum of synthetic single crystal diamond , when the absorption peak exists in the range of wave number 1370 cm -1 or more and 1385 cm -1 or less, the size of the aggregate of nitrogen atoms contained in the B'center (platelet) is appropriate. Therefore, it is possible to prevent plastic deformation and the growth of cracks, and it is unlikely to be the starting point of fracture. Therefore, synthetic single crystal diamond can have high hardness and excellent strength.
  • synthetic single crystal diamond containing a B'center shows an absorption peak at a wave number of 1358 cm -1 or more and 1385 cm -1 or less in an infrared absorption spectrum.
  • the absorption peak at a wavenumber of 1370 cm -1 is smaller than the range (less than a wavenumber 1358cm -1 or higher wavenumber 1370 cm -1) is present, B 'Center (platelets) in the crystal aggregates is too large, it becomes a starting point of fracture Not preferred. Therefore, in the infrared absorption spectrum of synthetic single crystal diamond, it is preferable that no absorption peak exists in the range of wave number 1358 cm -1 or more and wave number less than 1370 cm -1.
  • the synthetic single crystal diamond of the present disclosure can include an A center (nitrogen 2 atom pair), an H3 center (nitrogen 2 atom aggregation), a B center (nitrogen 4 atom aggregation), and a B'center. Aggregates of nitrogen atoms contained in these can suppress the propagation of cracks in single crystal diamond. Therefore, the synthetic single crystal diamond can have excellent fracture resistance.
  • the inclusion of the A center in the synthetic single crystal diamond can be confirmed by the infrared absorption spectrum measured by Fourier transform infrared spectroscopy. Specifically, in the infrared absorption spectrum, around wavenumber 1282cm -1 (e.g., 1282 ⁇ 2 cm -1) if there is absorption peak, said synthetic single-crystal diamond is determined to contain A center.
  • the inclusion of the H3 center in the synthetic single crystal diamond can be confirmed by the fluorescence spectrum obtained by irradiating the excitation light with a wavelength of 325 nm. Specifically, in the fluorescence spectrum, when the emission peak is present in the vicinity of the fluorescence wavelength of 503 nm (for example, 503 ⁇ 2 nm), it is determined that the synthetic single crystal diamond contains the H3 center.
  • the inclusion of the B center in the synthetic single crystal diamond can be confirmed by the infrared absorption spectrum measured by Fourier transform infrared spectroscopy. Specifically, in the infrared absorption spectrum, around wavenumber 1175cm -1 (e.g., 1175 ⁇ 2 cm -1) if there is absorption peak, said synthetic single-crystal diamond is determined to contain B centers.
  • the synthetic single crystal diamond of the present disclosure preferably does not contain an isolated substituted nitrogen atom (C center). According to this, the synthetic single crystal diamond of the present disclosure can have high hardness and excellent fracture resistance.
  • the absence of isolated substituted nitrogen atoms in synthetic single crystal diamond can be determined by the infrared absorption spectrum measured by Fourier transform infrared spectroscopy.
  • Single crystal diamond containing isolated substitutional nitrogen atoms in the infrared absorption spectrum measured by Fourier transform infrared spectroscopy, a peak in the vicinity of a wave number of 1130 cm -1 (i.e., 1130 ⁇ 2cm -1). Therefore, in the infrared absorption spectrum of the synthetic single crystal diamond, the isolated substituted nitrogen atom is contained by confirming that the absorption peak derived from the isolated substituted nitrogen atom does not exist in the wave number range of 1130 ⁇ 2 cm -1. It can be judged that there is no such thing.
  • ⁇ Primary Raman scattering spectrum The Raman shift ⁇ 'cm -1 of the peak in the primary Raman scattering spectrum of the synthetic single crystal diamond of the present disclosure and the primary of the synthetic IIa type single crystal diamond of 1 ppm or less containing a nitrogen atom at a concentration of 1 ppm or less based on the number of atoms.
  • the Raman shift ⁇ cm -1 of the peak in the Raman scattering spectrum shows the relationship of the following equation 1. ⁇ '- ⁇ ⁇ 0 Equation 1
  • the state of internal stress in the crystal is the state of internal stress in the crystal.
  • tensile stress is present in a diamond crystal
  • plastic deformation or fracture of the diamond crystal is likely to occur starting from the point where the tensile stress is generated, and wear resistance and fracture resistance are lowered.
  • the presence of compressive stress in the diamond crystal improves fracture resistance. Therefore, the wear resistance and fracture resistance of single crystal diamond can be improved by reducing the tensile stress as much as possible or by making the compressive stress predominant in the state of the internal stress of the diamond crystal.
  • the state of internal stress of the synthetic single crystal diamond is a synthesis containing the Raman shift ⁇ '(cm -1 ) of the peak in the primary Raman scattering spectrum of the synthetic single crystal diamond at a concentration of 1 ppm or less based on the number of atomic atoms. It can be evaluated by comparing with the Raman shift ⁇ (cm -1 ) of the peak in the primary Raman scattering spectrum of the IIa type single crystal diamond (hereinafter, also referred to as a standard sample or a synthetic IIa type single crystal diamond). Specifically, the state of internal stress of the synthetic single crystal diamond can be evaluated by the magnitude of the peak position shift amount represented by the difference ( ⁇ '- ⁇ ) between ⁇ 'and ⁇ . The reason will be explained below.
  • the synthetic type IIa single crystal diamond used as a standard sample means a high-purity single crystal diamond having no lattice defects or internal strain, which is synthesized by a temperature difference method under high temperature and high pressure.
  • synthetic IIa type single crystal diamond has a concentration of nitrogen atom based on the number of atoms of 1 ppm or less, or 0 ppm or more and 1 ppm or less, and contains almost no nitrogen atom, so that there is no internal stress in the diamond crystal.
  • the synthetic IIa type single crystal diamond shows one sharp and strong peak in the primary Raman scattering spectrum.
  • Raman shift is a value measured at room temperature (20 ° C. or higher and 25 ° C. or lower).
  • the Raman shift shifts to the lower frequency side than the synthetic IIa type single crystal diamond. At this time, a tensile stress derived from the isolated substitution nitrogen atom is generated in the diamond crystal.
  • the Raman shift shifts to a higher frequency side than the synthetic IIa type single crystal diamond. At this time, no tensile stress is generated or compressive stress is generated in the diamond crystal.
  • the present inventors have determined the magnitude of the peak position shift amount represented by the difference ( ⁇ '- ⁇ ) between ⁇ '(cm -1 ) and ⁇ (cm -1), and the synthetic single crystal.
  • the synthetic single crystal diamond has high hardness and excellent fracture resistance. I found. ⁇ '- ⁇ ⁇ 0 Equation 1
  • the lower limit of ( ⁇ '- ⁇ ) can be 0 or more, 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, and 0.3 or more.
  • the upper limit of ( ⁇ '- ⁇ ) can be 2 or less and 1 or less.
  • ( ⁇ '- ⁇ ) is 0 or more and 2 or less, 0 or more and 1 or less, 0.05 or more and 2 or less, 0.05 or more and 1 or less, 0.1 or more and 2 or less, 0.1 or more and 1 or less, 0.15 or more. 2 or less, 0.15 or more and 1 or less, 0.2 or more and 2 or less, 0.2 or more and 1 or less, 0.25 or more and 2 or less, 0.25 or more and 1 or less, 0.3 or more and 2 or less, 0.3 or more 1 It can be as follows.
  • the Raman shift of the peak in the primary Raman scattering spectrum of synthetic single crystal diamond and standard sample can be measured by a micro Raman spectroscope. The measurement is performed at room temperature (20 ° C. or higher and 25 ° C. or lower) using a laser having a wavelength of 532 nm as excitation light.
  • ⁇ 'and ⁇ are wave numbers at which the first-order Raman scattering spectrum signal is the strongest.
  • the peak shape is evaluated by peak fitting processing with a Lorentz function or a Gaussian function.
  • the temperature change of the detector and optical system of the Raman spectroscope during the measurement of the sample and the standard sample is suppressed to ⁇ 1 ° C or less.
  • the peak position shift amount can be obtained.
  • the Knoop hardness in the ⁇ 100> direction (hereinafter, also referred to as “ ⁇ 001 ⁇ ⁇ 100> Knoop hardness”) on the ⁇ 001 ⁇ plane of the synthetic single crystal diamond according to the present embodiment is preferably 100 GPa or more.
  • the generic plane orientation including the crystal geometrically equivalent plane orientation is indicated by ⁇
  • the generic direction including the crystal geometrically equivalent direction is indicated by ⁇ >.
  • Synthetic single crystal diamond having a Knoop hardness of 100 GPa or more has a higher hardness than natural diamond containing nitrogen and is excellent in wear resistance.
  • Knoop hardness can be 105 GP or more, 110 GPa or more, and 115 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.
  • the ⁇ 001 ⁇ ⁇ 100> Knoop hardness of the synthetic single crystal diamond can be 100 GPa or more and 150 GPa or less, 105 GPa or more and 150 GPa or less, 110 GPa or more and 150 GPa or less, and 115 GPa or more and 150 GPa or less.
  • Knoop hardness (hereinafter, also referred to as HK.
  • the unit is GPa) 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 synthetic single crystal diamond of the present disclosure has a crack generation load of 15 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 rate of 100 N / min. It is preferable to have.
  • the crack generation load is 15 N or more, the synthetic single crystal diamond has excellent fracture strength and fracture resistance, and when used as a tool material, chipping of the cutting edge is unlikely to occur.
  • the lower limit of the crack generation load can be 17N or more, 20N or more, 25N or more, and 30N 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 the synthetic single crystal diamond can be 15N or more and 50N or less, 17N or more and 50N or less, 20N or more and 50N or less, 25N or more and 50N or less, and 30N 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 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 method for producing a synthetic single crystal diamond of the present disclosure is the method for producing a synthetic single crystal diamond according to the first embodiment, wherein the nitrogen atom has a concentration of 100 ppm or more and 1500 ppm or less based on the number of atoms by a temperature difference method using a solvent metal.
  • the diamond single crystal is provided with a third step of applying a pressure of 3 GPa or more and a temperature of 1850 ° C. or higher and 2300 ° C. or lower for 1 minute or more and 3600 minutes or less to obtain the synthetic single crystal diamond.
  • the diamond single crystal can be produced, for example, by a temperature difference method using a sample chamber 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), and a diamond seed crystal 5 is arranged in a low temperature portion (T low), and 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.
  • nitrogen supply sources for example, iron nitride (Fe 2 N, Fe 3 N), aluminum nitride (Al N), phosphorus nitride (P 3 N 4 ), silicon nitride (Si 3 N).
  • Nitride such as 4 ) and organic nitrogen compounds such as melamine and sodium azide can be added alone or as a mixture.
  • diamond or graphite containing a large amount of nitrogen may be added. As a result, nitrogen atoms are contained in the synthesized diamond single crystal. At this time, the nitrogen atom in the diamond single crystal mainly exists as an isolated substitution type nitrogen atom.
  • the concentration of the nitrogen 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 nitrogen atom in the synthesized diamond single crystal is 100 ppm or more and 1500 ppm or less.
  • the concentration of nitrogen atoms derived from a nitrogen supply source based on the number of atoms can be 200 ppm or more and 3000 ppm or less.
  • the solvent metal is an iron - cobalt - an alloy of nickel, if the nitrogen source is Fe 3 N, the concentration of the nitrogen source, 0.2 mass 0.01 mass% It can be less than or equal to%.
  • 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), Tantal (Ta), Tungsten (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 100 MGy or more and 1000 MGy or less. As a result, lattice defects are introduced in the diamond single crystal and pores are formed.
  • the amount of energy to be irradiated is less than 100 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 100 MGy or more and 1000 MGy or less.
  • a neutron beam or a proton beam can be used as the particle beam.
  • the irradiation conditions are not particularly limited as long as the diamond single crystal can be given energy of 100 MGy or more and 1000 MGy or less.
  • the irradiation energy can be 4.6 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 1850 ° C. or higher, the movement of nitrogen atoms in the diamond single crystal is promoted, and one pore and three substituted nitrogen atoms existing adjacent to the pore are used. The formation of aggregates (N3 center) consisting of these is promoted. If the temperature of the third step is less than 1850 ° C., it is difficult to form an N3 center.
  • the upper limit of the temperature in the third step is preferably 2300 ° C. or lower from the viewpoint of cost and productivity.
  • the diamond single crystal when the diamond single crystal is heated to 1850 ° C. or higher under normal pressure, the diamond single crystal becomes graphitized.
  • the present inventors have applied a temperature of 1850 ° C. or higher for 1 minute or more and 3600 minutes or less under a high pressure of 3 GPa or higher to the diamond single crystal without graphitizing the diamond single crystal.
  • the time for applying a temperature of 1850 ° C. or higher to a diamond single crystal under a high pressure of 3 GPa or higher is 1 minute or more and 3600 minutes or less.
  • the time for applying the temperature of 1850 ° C. or higher to the diamond single crystal under a high pressure of 3 GPa or higher can be 60 minutes or more and 360 minutes or less.
  • the pressure at this time can be 3 GPa or more and 20 GPa 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 can promote the aggregation of isolated substituted nitrogen atoms in the diamond single crystal.
  • the synthetic single crystal diamonds of the present disclosure preferably do not contain isolated substituted nitrogen atoms. According to this, the hardness and fracture resistance of the synthetic single crystal diamond are further improved.
  • the nitrogen atom concentration in the synthetic single crystal diamond of the present disclosure can be 100 ppm or more and 1400 ppm or less.
  • the nitrogen atom concentration in the synthetic single crystal diamond of the present disclosure can be 100 ppm or more and 1300 ppm or less.
  • the nitrogen atom concentration in the synthetic single crystal diamond of the present disclosure can be 200 ppm or more and 1500 ppm or less.
  • the nitrogen atom concentration in the synthetic single crystal diamond of the present disclosure can be 200 ppm or more and 1400 ppm or less.
  • the nitrogen atom concentration in the synthetic single crystal diamond of the present disclosure can be 200 ppm or more and 1300 ppm or less.
  • the nitrogen atom concentration in the synthetic single crystal diamond of the present disclosure can be 300 ppm or more and 1500 ppm or less.
  • the nitrogen atom concentration in the synthetic single crystal diamond of the present disclosure can be 300 ppm or more and 1400 ppm or less.
  • the nitrogen atom concentration in the synthetic single crystal diamond of the present disclosure can be 300 ppm or more and 1300 ppm or less.
  • the above ( ⁇ '- ⁇ ) can be 0 or more and 2 or less. In the synthetic single crystal diamond of the present disclosure, the above ( ⁇ '- ⁇ ) can be 0 or more and 1 or less. In the synthetic single crystal diamond of the present disclosure, the above ( ⁇ '- ⁇ ) can be 0.05 or more and 2 or less. In the synthetic single crystal diamond of the present disclosure, the above ( ⁇ '- ⁇ ) can be 0.05 or more and 1 or less. In the synthetic single crystal diamond of the present disclosure, the above ( ⁇ '- ⁇ ) can be 0.1 or more and 2 or less. In the synthetic single crystal diamond of the present disclosure, the above ( ⁇ '- ⁇ ) can be 0.1 or more and 1 or less.
  • the above ( ⁇ '- ⁇ ) can be 0.15 or more and 2 or less. In the synthetic single crystal diamond of the present disclosure, the above ( ⁇ '- ⁇ ) can be 0.15 or more and 1 or less. In the synthetic single crystal diamond of the present disclosure, the above ( ⁇ '- ⁇ ) can be 0.2 or more and 2 or less. In the synthetic single crystal diamond of the present disclosure, the above ( ⁇ '- ⁇ ) can be 0.2 or more and 1 or less. In the synthetic single crystal diamond of the present disclosure, the above ( ⁇ '- ⁇ ) can be 0.25 or more and 2 or less. In the synthetic single crystal diamond of the present disclosure, the above ( ⁇ '- ⁇ ) can be 0.25 or more and 1 or less. In the synthetic single crystal diamond of the present disclosure, the above ( ⁇ '- ⁇ ) can be 0.3 or more and 2 or less. In the synthetic single crystal diamond of the present disclosure, the above ( ⁇ '- ⁇ ) can be 0.3 or more and 1 or less.
  • concentration of iron nitride in the solvent metal is shown in the "Iron nitride concentration in solvent metal (% by mass)" column of "Production conditions" in Table 1. For example, in sample 2, the concentration of iron nitride in the solvent metal is 0.02% by mass.
  • the obtained diamond single crystal is irradiated with an electron beam.
  • 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.
  • the diamond single crystal after electron beam irradiation is subjected to normal pressure (Sample 4) or high pressure of 3 GPa or more (Sample 2, Samples 5 to 7, described as “high pressure” in Table 1).
  • the temperature described in the “third step (60 minutes)" column of "Production conditions” in Table 1 is applied for 60 minutes to obtain synthetic single crystal diamond.
  • a pressure of 3 GPa or more (high pressure) and a temperature of 2300 ° C. are applied to the diamond single crystal for 60 minutes.
  • sample 1 For sample 1, a diamond single crystal is synthesized by the same first step as sample 2. In sample 1, the second step and the third step are not performed.
  • Sample 3 synthesizes a diamond single crystal by the same first step as Sample 4. In sample 1, the second step and the third step are not performed.
  • Fluorescence spectrum After the surface of the synthetic single crystal diamond / diamond single crystal of each sample is mirror-polished, the fluorescence spectrum is measured by irradiating with excitation light having a wavelength of 325 nm.
  • the emission peak is "yes" within the fluorescence wavelength range of 415 ⁇ 2 nm, the emission intensity of the peak is shown in parentheses (). However, the emission intensity does not correspond to the content of the N3 center (the emission intensity changes depending on the state of other impurities and crystal defects).
  • the maximum emission intensity of the peak is shown in parentheses (). However, the maximum emission intensity does not correspond to the content of the N3 center (the emission intensity changes depending on the state of other impurities and crystal defects).
  • the N3 center indicates “yes” and the emission peak exists in any range. If not, the N center will be “none”.
  • the results are shown in the "N3 center” column of the "fluorescence spectrum” of "synthetic single crystal diamond / diamond single crystal” in Table 2.
  • the synthetic single crystal diamond containing the B'center (platelet) shows an absorption peak at a wave number of 1358 cm -1 or more and 1385 cm -1 or less in the infrared absorption spectrum.
  • the absorption peak at a wavenumber of 1370 cm -1 is smaller than the range (less than a wavenumber 1358cm -1 or higher wavenumber 1370 cm -1) is present, B 'Center (platelets) in the crystal aggregates is too large, it becomes a starting point of fracture Not preferred.
  • samples 1 to 7 there is no absorption peak below wavenumber 1358cm -1 or higher wavenumber 1370 cm -1.
  • I (1282) / I (2160) the value of I (1282) / I (2160) is larger in the sample 3 with the A center “without” than in the sample 2 with the A center “with”. This is because the sample 3 has a large amount of nitrogen in the C center, so that the absorption at the wave number 1282 cm -1 derived from the shoulder of the absorption spectrum of the C center is strong, and it does not indicate that the sample 3 contains the A center. No.
  • the sample 3 with the B center “without” is more than the sample 2 with the B center “with”, the sample 4 and the sample 5 with the I (1175) / I (2160).
  • the value is large. This is because the sample 3 has a large amount of nitrogen in the C center, so that the absorption at the wave number of 1175 cm -1 derived from the shoulder of the absorption spectrum of the C center is strong, and it does not indicate that the sample 3 contains the B center. No.
  • I (1130) / I (2160) the values of I (1130) / I (2160) are larger in the samples 4 to 7 with the C center “without” than in the sample 1 with the C center “with”. .. This is because Samples 4 to 7 contain a large amount of nitrogen in the A center and the B center, so that the absorption at the wave number of 1130 cm-1 derived from the shoulder of the absorption spectrum of the A center and the B center is strong, and the samples 4 to 7 are absorbed. It does not indicate that sample 7 contains a C center.
  • Sample 2 and Samples 5 to 7 correspond to Examples.
  • Sample 1, Sample 3, and Sample 4 correspond to Comparative Examples. It is confirmed that Sample 2 and Sample 5 to Sample 7 (Example) have higher hardness and excellent fracture resistance than Sample 1, Sample 3 and Sample 4 (Comparative Example). ..
  • Samples 5 to 7 have particularly high hardness and excellent fracture resistance. This is because in Samples 5 to 7, there is no C center (isolatedly substituted nitrogen atom) that causes a decrease in hardness and strength, and there is a platelet that contributes to suppressing plastic deformation and crack growth. Is considered to be.

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WO2025173239A1 (ja) * 2024-02-16 2025-08-21 住友電気工業株式会社 単結晶ダイヤモンドおよびそれを備える工具
WO2025173238A1 (ja) * 2024-02-16 2025-08-21 住友電気工業株式会社 単結晶ダイヤモンドおよび工具
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