WO2020195997A1 - 異原子ドープナノダイヤモンド - Google Patents

異原子ドープナノダイヤモンド Download PDF

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WO2020195997A1
WO2020195997A1 PCT/JP2020/011336 JP2020011336W WO2020195997A1 WO 2020195997 A1 WO2020195997 A1 WO 2020195997A1 JP 2020011336 W JP2020011336 W JP 2020011336W WO 2020195997 A1 WO2020195997 A1 WO 2020195997A1
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heteroatomic
doped
nanodiamond
compounds
mass
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French (fr)
Japanese (ja)
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智明 間彦
有都 牧野
明彦 鶴井
明 劉
正浩 西川
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Daicel Corp
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Daicel Corp
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Priority to CN202080024646.7A priority Critical patent/CN113631512A/zh
Priority to EP20778201.2A priority patent/EP3950586A4/en
Priority to AU2020249853A priority patent/AU2020249853B2/en
Priority to KR1020217032670A priority patent/KR102806657B1/ko
Priority to SG11202108007RA priority patent/SG11202108007RA/en
Priority to CA3134678A priority patent/CA3134678A1/en
Application filed by Daicel Corp filed Critical Daicel Corp
Priority to JP2021509072A priority patent/JPWO2020195997A1/ja
Priority to US17/598,001 priority patent/US12351463B2/en
Priority to IL286397A priority patent/IL286397B2/en
Publication of WO2020195997A1 publication Critical patent/WO2020195997A1/ja
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Definitions

  • the present invention relates to heteroatomic doped nanodiamonds.
  • the diamond luminescence center is a nano-sized, chemically stable fluorescent chromophore, and is expected as a probe for fluorescence imaging because it does not show in vivo degradation, fading, or blinking that is often found in organic phosphors. ing.
  • the spin information of electrons excited in the light emitting center can be measured from the outside, so it is expected to be used as ODMR (Optically Detected Magnetic Resonance) or qubit.
  • the SiV center which is one of the emission centers of diamond, has a sharp peak called ZPL (Zero Phonon Level) in the emission spectrum (Non-Patent Document 1).
  • Silicon-doped diamond is manufactured by the CVD method or the like (Patent Documents 1 and 2).
  • Non-Patent Document 2 analyzes nanodiamonds in meteorites, but does not manufacture nanodiamonds having a SiV (Silicon-Vacancy) center.
  • Non-Patent Document 2 shows that the SiV center is thermodynamically stable in nanodiamonds of 1.1 nm to 1.8 nm by simulation.
  • Figure 1 of Non-Patent Document 3 discloses nanodiamonds having a SiV center adjusted by the CVD method by AFM, but in the upper right graph of Figure 1, the vertical axis is the height (nm) and the horizontal axis is the position ( Micron) is described and its peak height is about 9 nm, but it is clear that the width (position) is at least 70 nm.
  • Non-Patent Document 4 discloses that nanodiamonds having an average particle size of 73 nm including a SiV center can be obtained by using nanodiamonds having a diameter of 3-4 nm as a seed solution and growing them on a silicon wafer by the MWPECVD method.
  • One object of the present invention is to provide novel nanodiamonds doped with different atoms.
  • the present invention provides the following heteroatomic doped nanodiamonds.
  • Item 1. The following (i) and / or (ii) doped with at least one different atom (i) BET specific surface area is 20-900 m 2 / g, (ii) The average size of the primary particles is 2-70 nm, Heteroatomic-doped nanodiamonds that meet the requirements of.
  • Item 2. Item 2. The heteroatomic-doped nanodiamond according to Item 1, wherein the heteroatom contains at least one selected from the group consisting of Group 14 elements, phosphorus and boron.
  • Item 3. Item 2.
  • Item 4. Item 2.
  • Item 5. Item 2. The heteroatom-doped nanodiamond according to any one of Items 1 to 4, wherein the fluorescent heteroatom-doped nanodiamond is further doped with phosphorus and / or boron.
  • Item 6. Item 2. The heteroatomic-doped nanodiamond according to any one of Items 1 to 5, which has a fluorescence emission peak in the range of 720 to 770 nm and contains silicon as a heteroatom.
  • Item 7. Item 2.
  • Item 2. The heteroatomic-doped nanodiamond according to any one of Items 1 to 5, which has a fluorescence emission peak in the range of 590 to 650 nm and contains tin as a heteroatom.
  • Item 11. Item 2. The heteroatomic-doped nanodiamond according to any one of Items 1 to 10, wherein the shape of the nanodiamond is spherical, ellipsoidal or polyhedral.
  • Item 12. Item 2. The heteroatomic-doped nanodiamond according to any one of Items 1 to 11, wherein the carbon content is 70 to 99% by mass, the hydrogen content is 0.1 to 5% by mass, and the nitrogen content is 0.1 to 5% by mass.
  • Item 13. Item 2.
  • the heteroatomic-doped nanodiamond according to any one of Items 1 to 12, wherein the ratio (D / G) of the peak area (D) of diamond to the peak area (G) of graphite in Raman spectroscopy is 0.2 to 9. .. Item 14. Item 2. The item 1 to 13 in which the ratio (H / D) of the peak area (H) of the surface hydroxy group (OH) to the peak area (D) of diamond in Raman spectroscopy is 0.1 to 5. Different atom-doped nanodiamond. Item 15. Item 2.
  • the average size of the primary particles is large and /
  • the nanodiamond particles have a small specific surface area, and the shape becomes distorted.
  • heteroatomic-doped nanodiamonds produced by the roaring method become nanodiamond particles having a small average size of primary particles and / or a large specific surface area, and are nano-sized, chemically stable, and in vivo. It is useful as a probe for fluorescence imaging because it does not show decomposition, fading, or blinking in.
  • ODMR Optically Detected Magnetic Resonance
  • qubits can be measured from the outside by measuring the spin information of electrons excited in the heteroatomic V (Vacancy) light emitting center. It is also expected to be used as.
  • the nanodiamonds doped with different atoms of the present invention have the following (i) and / or (ii): (i) BET specific surface area is 20-900 m 2 / g, (ii) The average size of the primary particles is 2-70 nm, Meet the requirements of.
  • the heteroatomic compound is a compound containing at least one different atom (atom other than carbon), and may be either an organic compound or an inorganic compound.
  • Different atoms are B, P, Si, S, Cr, Sn, Al, Ge, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Selected from the group consisting of Mn, Fe, Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl, Pb, As, Sb, Bi, Se, Te, Co, Xe, F, Y and lanthanoids. It is preferably selected from the group consisting of Si, Ge, Sn, B, P, Ni, Ti, Co, Xe, Cr, W, Ta, Zr, Zn, Ag, Pb and lanthanoids, and more preferably Si, Ge, Sn. , B, P, Ni, Ti, Co, Xe, Cr, W, Ta, Zr, Zn, Ag and Pb.
  • Preferred heteroatoms doped into nanodiamonds are Group 14 elements selected from the group consisting of Si, Ge, Sn and Pb, B (boron), P (phosphorus) and Ni, and more preferred heteroatoms are Si. , B, P.
  • the nanodiamonds of the present invention differ from at least one selected from the group consisting of Group 14 elements, B, P, Ni selected from the group consisting of Si, Ge, Sn and Pb and others. Contains at least one of the atoms.
  • the nanodiamond of the present invention comprises at least one selected from the group consisting of Si, B, P, Ni and at least one other heteroatom.
  • the number of heteroatoms doped in nanodiamonds is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1, 2, or 3.
  • the heteroatomic doped nanodiamond of one preferred embodiment of the present invention has a fluorescence emission peak.
  • the heteroatomic-doped nanodiamonds of other preferred embodiments of the present invention contain at least one heteroatomic V-center, thereby having a fluorescence peak.
  • the wavelength of the fluorescence emission peak is preferably 720 to 770 nm, more preferably 730 to 760 nm when the foreign atom contains silicon, and preferably 580 to 630 nm, more preferably when the foreign atom contains germanium.
  • the doped nanodiamonds that fluoresce at the different atom-Vacancy center where the different atoms are other than phosphorus and boron may be further doped with phosphorus and / or boron.
  • the charge of the foreign atom-V center other than B and / or P and the defect (emission center) derived from other doped foreign atoms is adjusted. It is considered to have the effect of stabilizing fluorescence.
  • the heteroatomic doped nanodiamond of the present invention may include fluorescence emission by the NV center.
  • the NV center is a emission center due to nitrogen and vacancy, and has a wide fluorescence spectrum with a peak due to ZPL (zero phonon line) near 575 nm and / or 637 nm.
  • ZPL zero phonon line
  • the NV center intensity may be increased, which is preferable.
  • the fluorescence emission peak of nanodiamond whose heteroatom is Si includes a sharp peak of about 738 nm called ZPL (Zero Phonon Level).
  • the concentration of at least one heteroatomic V-center in the heteroatomic-doped nanodiamonds of the present invention is preferably 1 ⁇ 10 10 / cm 3 or more, more preferably 2 ⁇ 10 10 to 1 ⁇ 10 19 / cm 3 . is there.
  • the concentration of this heteroatomic V center is the total concentration of nanodiamonds containing two or more heteroatomic V centers. It is estimated that the concentration of the heteroatomic V center can be specified by using, for example, a confocal laser scanning microscope or a fluorescence absorption spectroscope. For the determination of the concentration of different atom V center by fluorescence absorption analysis, refer to the literature (DOI 10.1002 / pssa.201532174).
  • the BET specific surface area of heteroatomic doped nanodiamonds is preferably 20-900 m 2 / g, more preferably 25-800 m 2 / g, even more preferably 30-700 m 2 / g, particularly preferably 35-600 m. It is 2 / g.
  • the BET specific surface area can be measured by nitrogen adsorption. Examples of the BET specific surface area measuring device include BELSORP-miniII (manufactured by Microtrac Bell Co., Ltd.), and the BET specific surface area can be measured under the following conditions, for example.
  • the average size of the primary particles of heteroatomic doped nanodiamonds is preferably 2 to 70 nm, more preferably 2.5 to 60 nm, even more preferably 3 to 55 nm, and particularly preferably 3.5 to 50 nm.
  • the average size of the primary particles can be determined by Scheller's equation from the analysis results of powder X-ray diffraction (XRD). Examples of the XRD measuring device include a fully automatic multipurpose X-ray diffractometer (manufactured by Rigaku Co., Ltd.).
  • the carbon content of the heteroatomic-doped nanodiamond of the present invention is preferably 70 to 99% by mass, more preferably 75 to 98% by mass, and even more preferably 80 to 97% by mass.
  • the hydrogen content of the heteroatomic-doped nanodiamond of the present invention is preferably 0.1 to 5% by mass, more preferably 0.2 to 4.5% by mass, and further preferably 0.3 to 4.0% by mass.
  • the nitrogen content of the heteroatomic-doped nanodiamond of the present invention is preferably 0.1 to 5% by mass, more preferably 0.2 to 4.5% by mass, and further preferably 0.3 to 4.0% by mass.
  • the carbon, hydrogen, and nitrogen contents of heteroatomic-doped nanodiamonds can be measured by elemental analysis.
  • the heteroatomic content of the heteroatomic-doped nanodiamonds of the present invention is preferably 0.0001 to 10.0% by mass, more preferably 0.0001 to 5.0% by mass, and even more preferably 0.0001 to 1.0% by mass.
  • the heteroatomic content can be measured, for example, by inductively coupled plasma atomic emission spectrometry (ICP-AES), XRF, SIMS (secondary ion mass spectrometry), and heteroatom-doped nanodiamonds are quantified as acidic solutions after alkali melting. can do.
  • the heteroatomic content is the total content of nanodiamonds when they contain two or more heteroatoms.
  • the heteroatom-doped nanodiamonds of one preferred embodiment of the present invention identify peaks characteristic of diamond, graphite, surface hydroxy groups (OH), and surface carbonyl groups (CO) on Raman shift charts by Raman spectroscopy. It can.
  • Raman peaks characteristic of diamond in the shift chart is 1100 ⁇ 1400 cm -1
  • characteristic peaks graphite is 1450 ⁇ 1700 cm -1
  • characteristic peaks in the surface hydroxyl group (OH) is 1500 ⁇ 1750 cm It is -1
  • the peak characteristic of the surface carbonyl group (CO) is 1650 to 1800 cm -1 .
  • the area of peaks characteristic of diamond, graphite, surface hydroxy groups (OH), and surface carbonyl groups (CO) is indicated by Raman spectroscopy.
  • the laser wavelength of the Raman light source is, for example, 325 nm or 488 nm.
  • a confocal microscopic Raman spectroscope for example, trade name: microlaser Raman spectrophotometer LabRAM HR Evolution, manufactured by Horiba Seisakusho Co., Ltd.
  • LabRAM HR Evolution manufactured by Horiba Seisakusho Co., Ltd.
  • the ratio (D / G) of the peak area (D) of diamond to the peak area (G) of graphite is preferably 0.2-9, more preferably 0.3. It is ⁇ 8, more preferably 0.5-7.
  • the ratio (H / D) of the peak area (H) of the surface hydroxy group (OH) to the peak area (D) of the diamond is preferably 0.1 to 5. , More preferably 0.1 to 4.0, still more preferably 0.1 to 3.0.
  • the ratio (C / D) of the peak area (C) of the surface carbonyl group (CO) to the peak area (D) of the diamond is preferably 0.01 to 1.5. , More preferably 0.03 to 1.2, still more preferably 0.05 to 1.0.
  • the surface of the heteroatomic doped nanodiamond may have at least one oxygen functional group termination and / or at least one hydrogen termination.
  • hydrogen termination include alkyl groups having 1 to 20 carbon atoms.
  • the presence of at least one oxygen functional group termination on the surface of the heteroatomic-doped nanodiamond is preferable because the aggregation of nanodiamond particles is suppressed.
  • the presence of at least one hydrogen terminate on the surface of the heteroatomic-doped nanodiamond is preferable because the zeta potential becomes positive and is stable and highly dispersed in an acidic aqueous solution.
  • the heteroatomic doped nanodiamonds of the present invention may have a core-shell structure.
  • the core of a heteroatomic-doped nanodiamond with a core-shell structure is nanodiamond particles doped with at least one different atom.
  • This core preferably has a heteroatomic V-center and fluoresces.
  • the shell is a non-diamond coating layer, which may contain sp2 carbon and preferably contains oxygen atoms.
  • the shell may be a graphite layer.
  • the thickness of the shell is preferably 5 nm or less, more preferably 3 nm or less, still more preferably 1 nm or less.
  • the shell may have hydrophilic functional groups on its surface.
  • Heteroatomic doped nanodiamonds can preferably be produced by the detonation method.
  • the shape of the heteroatomic-doped nanodiamond is preferably spherical, ellipsoidal, or a polyhedron close to them.
  • the circularity is a numerical value for expressing the complexity of a figure drawn on an image or the like.
  • the maximum value of the circularity is 1, and the more complicated the figure, the smaller the value.
  • the circularity can be determined by, for example, analyzing a TEM image of heteroatomic-doped nanodiamonds with image analysis software (for example, winROOF) and using the following formula.
  • Circularity 4 ⁇ ⁇ (area) ⁇ (peripheral length) ⁇ 2
  • the formula is "4 ⁇ x (10 x 10 x ⁇ ) ⁇ (10 x 2 x ⁇ ) ⁇ 2"
  • the circularity is 1 (maximum value).
  • a perfect circle is the least complicated figure.
  • the circularity of the heteroatomic-doped nanodiamond is preferably 0.2 or more, more preferably 0.3 or more, still more preferably 0.35 or more.
  • the center of the heteroatom-doped nanodiamond particles has a diamond structure containing sp3 carbon and doped heteroatoms, the surface of which is covered with an amorphous layer composed of sp2 carbon. It has been.
  • the outside of the amorphous layer may be covered with a graphite oxide layer. Further, a hydrated layer may be formed between the amorphous layer and the graphite oxide layer.
  • the heteroatomic doped nanodiamond has a positive or negative zeta potential.
  • the zeta potential of the heteroatomic doped nanodiamond is preferably ⁇ 70 to 70 mV, more preferably ⁇ 60 to 30 mV.
  • the heteroatomic doped nanodiamond of the present invention is produced by a production method including a step of mixing an explosive composition containing at least one explosive and at least one heteroatomic compound, and a step of exploding the obtained mixture in a closed container.
  • a production method including a step of mixing an explosive composition containing at least one explosive and at least one heteroatomic compound, and a step of exploding the obtained mixture in a closed container.
  • the container include a metal container and a synthetic resin container.
  • Explosives and heteroatomic compounds are preferably molded by pressing or casting.
  • methods for producing particles (dry powder) of an explosive and a heteroatomic compound include a crystallization method, a crushing method, and a spray flash method (spray flash evaporation).
  • the explosive and the heteroatomic compound are mixed using a dry powder or a molten state or a solvent.
  • the mixed state of the explosive and the heteroatomic compound may be any of the following four combinations: ⁇ Explosives (dry powder) and heteroatomic compounds (dry powder) ⁇ Explosives (dry powder) and heteroatomic compounds (melted state) ⁇ Explosives (melted state) and heteroatomic compounds (dry powder) ⁇ Explosives (melted state) and heteroatomic compounds (melted state)
  • the mixture of the explosive and the heteroatomic compound may be in the presence or absence of a solvent, and can be molded by a pressing method or a filling method after mixing.
  • the average particle size of explosives and heteroatomic compounds is preferably 10 mm or less, more preferably 5 mm or less, and even more preferably 1 mm or less.
  • the average particle size of these particles can be measured by a laser diffraction / scattering method, an optical microscope, or a Raman method.
  • the product obtained by the explosion can be further subjected to a purification process and a post processing process.
  • the purification step can include one or both of mixed acid treatment and alkali treatment.
  • a preferred purification step is a mixed acid treatment step.
  • graphite, metal impurities, elemental foreign atoms, heteroatomic oxides, etc. are produced in addition to the heteroatomic doped nanodiamonds.
  • Graphite and metal impurities can be removed by mixed acid treatment, and when the different atom is a Group 14 element such as Si, Ge, Sn, Pb, the Group 14 element alone (Si, Ge, Sn, Pb) and the 14th group Group element oxides (SiO 2 , GeO 2 , SnO, SnO 2 , PbO, PbO 2, etc.) can be removed by alkaline treatment.
  • the temperature of the mixed acid treatment is 50 to 200 ° C., and the time of the mixed acid treatment is 0.5 to 24 hours.
  • alkali examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
  • the temperature of the alkali treatment is 30 to 150 ° C., and the time of the alkali treatment is 0.5 to 24 hours.
  • the post-treatment step can include annealing, vapor phase oxidation.
  • the annealing process the doped foreign atoms in the heteroatomic doped nanodiamond can meet with defects (Vacancy) to form a heteroatomic V center.
  • the graphite layer formed on the surface of the heteroatomic-doped nanodiamond can be thinned or removed by vapor phase oxidation.
  • a pore forming step may be performed before annealing. The pore forming step is performed by irradiation with an ion beam or an electron beam.
  • the heteroatomic V center is formed by annealing without performing the pore forming step, more heteroatomic V centers can be formed by performing annealing after the pore forming step.
  • the upper limit of the pore density introduced by ion beam irradiation or electron beam irradiation is limited by the concentration at which diamond is destroyed (the pore concentration of> 1 ⁇ 10 21 / cm 3 ), but the lower limit is, for example, 1 ⁇ . 10 16 / cm 3 or more, and 1 ⁇ 10 18 / cm 3 or more.
  • the ion beam is preferably a hydrogen (H) or helium (He) ion beam.
  • the energy of a hydrogen ion beam is preferably 10 to 1500 keV
  • the energy of a helium ion beam is preferably 20 to 2000 keV.
  • the energy of the electron beam is preferably 500 to 5000 keV.
  • the annealing temperature is preferably 800 ° C. or higher, and the annealing time is 30 minutes or longer.
  • the vapor phase oxidation can be carried out in an air atmosphere, the vapor phase oxidation temperature is preferably 300 ° C. or higher, and the vapor phase oxidation time is 2 hours or longer.
  • the explosive is not particularly limited, and a known explosive can be widely used. Specific examples include trinitrotoluene (TNT), cyclotrimethylene trinitramine (hexogen, RDX), cyclotetramethylenetetranitramine (octogen), trinitrophenylmethylnitramine (tetryl), pentaerythritol tetranitrate (PETN). ), Tetranitromethane (TNM), triamino-trinitrobenzene, hexanitrostilben, diaminodinitrobenzofloxane and the like, and these can be used alone or in combination of two or more.
  • TNT trinitrotoluene
  • RDX cyclotrimethylene trinitramine
  • octogen cyclotetramethylenetetranitramine
  • tetryl trinitrophenylmethylnitramine
  • PETN pentaerythritol tetranitrate
  • heteroatomic compounds whose specific examples are described below are merely examples, and known heteroatomic compounds can be widely used.
  • the organosilicon compound is -Acetoxytrimethylsilane, diacetoxydimethylsilane, triacetoxymethylsilane, acetoxytriethylsilane, diacetoxydiethylsilane, triacetoxyethylsilane, acetoxytripropylsilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, ethoxytrimethylsilane , Silanes with lower alkyl groups such as diethoxydimethylsilane, triethoxymethylsilane, ethoxytriethylsilane, diethoxydiethylsilane, triethoxyethylsilane, trimethylphenoxysilane,
  • -Polysilanes such as hexamethyldisilane, hexaethyldisilane, hexapropyldisilane, hexaphenyldisilane, octaphenylcyclotetrasilane-Triethylsilazane, tripropylsilazane, triphenylsilazane, hexamethyldisilazane, hexaethyldisilazane, hexaphenyldi Silazans such as silazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexaethylcyclotrisilazane, octaethylcyclotetrasilazane, hexaphenylcyclotrisilazane, etc.
  • -Aromatic silanes in which silicon atoms are incorporated into aromatic rings such as silabenzene and disilabenzene.
  • -Tetramethylsilane ethyltrimethylsilane, trimethylpropylsilane, trimethylphenylsilane, diethyldimethylsilane, triethylmethylsilane, methyltriphenylsilane, tetraethylsilane, triethylphenylsilane, diethyldiphenylsilane, ethyltriphenylsilane, tetraphenylsilane, etc.
  • Alkyl or aryl substituted silane -Carboxylic acid-containing silanes such as triphenylsilylcarboxylic acid, trimethylsilylacetic acid, trimethylsilylpropionic acid, and trimethylsilylbutyric acid,
  • ⁇ Siloxane such as hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, hexaphenyldisiloxane, etc.
  • -Silanes having an alkyl group or an aryl group and a hydrogen atom such as methylsilane, dimethylsilane, trimethylsilane, diethylsilane, triethylsilane, tripropylsilane, diphenylsilane, and triphenylsilane, -Tetrakis (chloromethyl) silane, tetrakis (hydroxymethyl) silane, tetrakis (trimethylsilyl) silane, tetrakis (trimethylsilyl) methane, tetrakis (dimethylsilanolyl) silane, tetrakis (tri (hydroxymethyl) silyl) silane, tetrakis (nitrate) Methyl) silane, And so on.
  • Examples of the inorganic silicon compound include silicon oxide, silicon oxynitride, silicon nitride, silicon oxide carbide, silicon nitride carbide, silane, and a carbon material doped with silicon.
  • Examples of the carbon-doped carbon material include graphite, graphite, activated carbon, carbon black, Ketjen black, coke, soft carbon, hard carbon, acetylene black, carbon fiber, and mesoporous carbon.
  • Examples of the boron compound include an inorganic boron compound and an organic boron compound.
  • inorganic boron compound examples include orthoboric acid, diboron dioxide, diboron trioxide, tetraboron trioxide, tetraboron pentoxide, boron tribromide, tetrafluoroboric acid, ammonium borate, magnesium borate and the like. Be done.
  • organoboron compound examples include triethylborane, (R) -5,5-diphenyl-2-methyl-3,4-propano-1,3,2-oxazaborolidine, triisopropyl borate, and 2-iso.
  • Examples of the phosphorus compound include an inorganic phosphorus compound and an organic phosphorus compound.
  • Examples of the inorganic phosphorus compound include ammonium polyphosphate.
  • Organophosphorus compounds include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, trypentyl phosphate, trihexyl phosphate, dimethyl ethyl phosphate, methyldibutyl phosphate, ethyldipropyl phosphate, 2-ethylhexyl di (p-tolyl) phosphate.
  • germanium compound examples include organic germaniums such as methyl germanium, ethyl germanium, trimethyl germanium methoxyde, dimethyl germanium diacetate, tributyl germanium acetate, tetramethoxy germanium, tetraethoxy germanium, isobutyl germanium, alkyl germanium trichloride, and dimethyl amino germanium trichloride.
  • organic germaniums such as methyl germanium, ethyl germanium, trimethyl germanium methoxyde, dimethyl germanium diacetate, tributyl germanium acetate, tetramethoxy germanium, tetraethoxy germanium, isobutyl germanium, alkyl germanium trichloride, and dimethyl amino germanium trichloride.
  • germanium complexes such as nitrotriphenol complex (Ge 2 (ntp) 2 O), catechol complex (Ge (cat) 2 ) or aminopyrene complex (Ge 2 (ap
  • tin compound examples include tin oxide (II), tin oxide (IV), tin sulfide (II), tin sulfide (IV), tin chloride (II), tin chloride (IV), tin bromide (II), and the like.
  • Inorganic tin compounds such as tin fluoride (II), tin acetate, tin sulfate, alkyl tin compounds such as tetramethyltin, monoalkyl tin oxide compounds such as monobutyl tin oxide, dialkyl tin oxide compounds such as dibutyl tin oxide, tetra.
  • aryltin compounds such as phenyltin, organotin compounds such as dimethyltinmaleate, hydroxybutyltin oxide, and monobutyltintris (2-ethylhexanoate).
  • nickel compound examples include divalent nickel halides such as nickel chloride (II), nickel bromide (II) and nickel iodide (II), and inorganic nickel such as nickel acetate (II) and nickel carbonate (II).
  • divalent nickel halides such as nickel chloride (II), nickel bromide (II) and nickel iodide (II)
  • inorganic nickel such as nickel acetate (II) and nickel carbonate (II).
  • examples thereof include compounds, organic nickel compounds such as nickel bis (ethylacetacetate) and nickel bis (acetylacetonate).
  • titanium compound examples include inorganic titanium compounds such as titanium dioxide, titanium nitride, strontium titanate, lead titanate, barium titanate and potassium titanate, and tetra such as tetraethoxytitanium, tetraisopropoxytitanium and tetrabutyloxytitanium.
  • inorganic titanium compounds such as titanium dioxide, titanium nitride, strontium titanate, lead titanate, barium titanate and potassium titanate
  • tetra such as tetraethoxytitanium, tetraisopropoxytitanium and tetrabutyloxytitanium.
  • cobalt compound examples include inorganic cobalt compounds such as cobalt inorganic acid salt, cobalt halide, cobalt oxide, cobalt hydroxide, dicobalt octacarbonyl, cobalt hydrogen tetracarbonyl, tetracobalt dodecacarbonyl, and alkylidine tricobalt nonacarbonyl.
  • inorganic cobalt compounds such as cobalt inorganic acid salt, cobalt halide, cobalt oxide, cobalt hydroxide, dicobalt octacarbonyl, cobalt hydrogen tetracarbonyl, tetracobalt dodecacarbonyl, and alkylidine tricobalt nonacarbonyl.
  • Cobalt Tris ethylacetate acetate
  • Cobalt Tris acetylacetonate
  • organic acid salts of cobalt eg acetate, propionate, bromate, naphthenate, stearate
  • methanesulphonate ethanesulfonic acid
  • Alkyl sulfonates such as salts, octane sulfonates, dodecane sulfonates (eg C 6-18 alkyl sulfonates); benzene sulfonates, p-toluene sulfonates, naphthalene sulfonates, decylbenzene sulfonates
  • aryl sulfonates for example, C 6-18 alkyl-aryl sulfonates
  • alkyl groups such as acid salts and dodecylbenzene sulfonates
  • organic cobalt complexes e
  • the ligands that make up the complex include OH (hydroxo), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acyl (acetyl, propionyl, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), acetylacetonate, etc.
  • cyclopentadienyl group a halogen atom (chlorine, bromine), CO, CN, oxygen atom, H 2 O (aquo), phosphine phosphorus compounds (such as triarylphosphines, such as triphenylphosphine), NH 3 (ammine) , NO, NO 2 (nitro), NO 3 (nitrat), ethylenediamine, diethylenetriamine, pyridine, nitrogen-containing compounds such as phenanthroline and the like.
  • Examples of the xenon compound include fluorides such as XeF 2 , XeF 4 , XeF 6 , XeOF 2 , XeOF 4 , XeO 2 F 4 , oxides such as XeO 3 , XeO 4 , and xenonic acid Xe (OH) 6 and the like.
  • the chromium compound examples include a chromium acetylacetone complex such as chromium acetylacetone, a chromium alkoxide such as chromium (III) isopropoxide, chromium organic acid such as chromium (II) acetate and hydroxychromium diacetate (III), and tris (allyl).
  • a chromium acetylacetone complex such as chromium acetylacetone
  • a chromium alkoxide such as chromium (III) isopropoxide
  • chromium organic acid such as chromium (II) acetate and hydroxychromium diacetate (III)
  • tris allyl
  • Chromium Tris (Metalyl) Chromium, Tris (Crotyl) Chromium, Bis (Cyclopentadienyl) Chromium (ie Chromosen), Bis (Pentamethylcyclopentadienyl) Chromium (ie Decamethylchromosen), Bis (benzene) ) Chromium, bis (ethylbenzene) chromium, bis (mesitylen) chromium, bis (pentadienyl) chromium, bis (2,4-dimethylpentadienyl) chromium, bis (allyl) tricarbonylchromium, (cyclopentadienyl) (pentadienyl) ) Chromium, tetra (1-norbornyl) chromium, (trimethylenemethane) tetracarbonyl chromium, bis (butadiene) dicarbonyl chromium, (butadiene) te
  • tungsten compound examples include inorganic tungsten compounds such as tungsten trioxide, ammonium tungstate, and sodium tungstate, and boron atomic coordination tungsten complexes such as ethylborylethylidene ligands; carbonyl ligands and cyclopentadi.
  • inorganic tungsten compounds such as tungsten trioxide, ammonium tungstate, and sodium tungstate
  • boron atomic coordination tungsten complexes such as ethylborylethylidene ligands; carbonyl ligands and cyclopentadi.
  • Carbon atom-coordinated tungsten complex such as enyl ligand, alkyl group ligand, olefin-based ligand; Nitrogen atom-coordinated tungsten complex such as pyridine ligand, acetonitrile ligand; phosphine ligand, phosphite Phosphorus atom-coordinated tungsten complexes coordinated with ligands and the like; organic tungsten compounds such as sulfur atom-coordinated tungsten complexes coordinated with diethylcarbamodithiolate ligands and the like can be mentioned.
  • thallium compound examples include inorganic thallium compounds such as thallium nitrate, thallium sulfate, thallium fluoride, thallium chloride, thallium bromide and thallium iodide, trialkyl thallium such as trimethyl thallium, triethyl thallium and triisobutyl thallium, and dialkyl thallium.
  • inorganic thallium compounds such as thallium nitrate, thallium sulfate, thallium fluoride, thallium chloride, thallium bromide and thallium iodide, trialkyl thallium such as trimethyl thallium, triethyl thallium and triisobutyl thallium, and dialkyl thallium.
  • zirconium compound examples include inorganic zirconium compounds such as zirconium nitrate, zirconium sulfate, zirconium carbonate, zirconium hydroxide, zirconium fluoride, zirconium chloride, zirconium bromide and zirconium iodide, zirconium n-propoxide, zirconium n-butoxide.
  • inorganic zirconium compounds such as zirconium nitrate, zirconium sulfate, zirconium carbonate, zirconium hydroxide, zirconium fluoride, zirconium chloride, zirconium bromide and zirconium iodide, zirconium n-propoxide, zirconium n-butoxide.
  • Examples of zinc compounds include zinc diethyl, zinc acetate, zinc nitrate, zinc stearate, zinc oleate, zinc palmitate, zinc myristate, zinc dodecanoate, zinc acetylacetonate, zinc chloride, and zinc bromide. , Zinc iodide, zinc carbamate and the like.
  • silver compounds include organic silver compounds such as silver acetate, silver pivalate, silver trifluoromethanesulfonate, and silver benzoate; silver nitrate, silver fluoride, silver chloride, silver bromide, silver iodide, silver sulfate, and oxidation.
  • examples thereof include inorganic silver compounds such as silver, silver sulfide, silver tetrafluoroborate, silver hexafluorophosphate (AgPF 6 ), and silver hexafluoroantimonate (AgSbF6).
  • lead compounds include lead monoxide (PbO), lead dioxide (PbO 2 ), lead tan (Pb 3 O 4 ), lead white (2PbCO 3 ⁇ Pb (OH) 2 ), and lead nitrate (Pb (NO 3 )).
  • PbCl 2 Lead Chloride (PbCl 2 ), Lead Sulfide (PbS), Lead Yellow Lead (PbCrO 4 , Pb (SCr) O 4 , PbO / PbCrO 4 ), Lead Carbonate (PbCO 3 ), Lead Sulfate (PbSO 4 ), lead fluoride (PbF 2), 4 lead fluoride (PbF 4), lead bromide (PbBr 2), inorganic lead compounds such as lead iodide (PbI 2), lead acetate (Pb (CH 3 COO) 2 ), Lead tetracarboxylate (Pb (OCOCH 3 ) 4 ), tetraethyl lead (Pb (CH 3 CH 2 ) 4 ), tetramethyl lead (Pb (CH 3 ) 4 ), tetrabutyl lead (Pb (C 4 H 9 ) 4 ) Organic lead compounds such as.
  • PbI 2 lead iodide
  • aluminum compound examples include inorganic aluminum compounds such as aluminum oxide, alkoxy compounds such as trimethoxyaluminum, triethoxyaluminum, isopropoxyaluminum, isopropoxydiethoxyaluminum, and tributoxyaluminum; triacetoxyaluminum, tristeert aluminum, and tri.
  • inorganic aluminum compounds such as aluminum oxide, alkoxy compounds such as trimethoxyaluminum, triethoxyaluminum, isopropoxyaluminum, isopropoxydiethoxyaluminum, and tributoxyaluminum; triacetoxyaluminum, tristeert aluminum, and tri.
  • Asiloxy compounds such as butyrate aluminum; aluminum isopropyrate, aluminum sec-butyrate, aluminum tert-butyrate, aluminum tris (ethylacetacetate), tris (hexafluoroacetylacetonate) aluminum, tris (ethylacetacetate) aluminum, tris ( n-propyl acetoacetate) aluminum, tris (iso-propyl acetoacetate) aluminum, tris (n-butyl acetoacetate) aluminum, tris salicylaldehyde aluminum, tris (2-ethoxycarbonylphenylate) aluminum, tris (acetylacetonate)
  • Trialkylaluminum such as aluminum, trimethylaluminum, triethylaluminum, triisobutylaluminum, dialkylaluminum halide, alkenyldialkylaluminum, alkynyldialkylaluminum, triphenylaluminum, arylaluminum such as
  • vanadium compound examples include vanadium acid and metavanadium acid, and alkoxides such as these alkali metal salt inorganic vanadium compounds, triethoxyvanadyl, pentaethoxyvanadium, triamiloxyvanadyl, and triisopropoxyvanadyl; Acenates such as vanadium acetylacetonate, vanadylacetylacetonate, and vanadiumoxyacetylacetonate; organic vanadium compounds such as vanadium stearate, vanadium pivalate, and vanadium acetate can be mentioned.
  • alkoxides such as these alkali metal salt inorganic vanadium compounds, triethoxyvanadyl, pentaethoxyvanadium, triamiloxyvanadyl, and triisopropoxyvanadyl
  • Acenates such as vanadium acetylacetonate, vanadylacetylacetonate, and vana
  • niobium compound examples include halides such as niobium pentachloride and niobium pentafluoride, inorganic niobium compounds such as niobium sulfate, niobium acid and niobium acid salt, and organic niobium compounds such as niobium alkoxide.
  • halides such as niobium pentachloride and niobium pentafluoride
  • inorganic niobium compounds such as niobium sulfate, niobium acid and niobium acid salt
  • organic niobium compounds such as niobium alkoxide.
  • the tantalum compound examples include inorganic tantalum compounds such as TaCl 5 , TaF 5 , Ta (OC 2 H 5 ) 5 , Ta (OCH 3 ) 5 , Ta (OC 3 H 7 ) 5 , Ta (OC 4 H 9 ). Examples thereof include organic tantalum compounds such as 5 , (C 5 H 5 ) 2 TaH 3 , and Ta (N (CH 3 ) 2 ) 5 .
  • molybdenum compound examples include molybdenum trioxide, zinc molybdenum, ammonium molybdenum, magnesium molybdenum, calcium molybdenum, barium molybdenum, sodium molybdenum, potassium molybdenum, molybdenum acid, ammonium molybdenum, and molybdenum.
  • Inorganic molybdenum compounds such as sodium acid, molybdenum silicate, molybdenum disulfide, molybdenum diselene, molybdenum diterlude, molybdenum boride, molybdenum disilicate, molybdenum nitride, molybdenum carbide, molybdenum dialkyldithiophosphate, molybdenum dialkyldithiocarbamate Organic molybdenum compounds such as.
  • manganese compound examples include inorganic manganese compounds such as hydroxides, nitrates, acetates, sulfates, chlorides and carbonates of manganese, manganese oxalate, acetylacetonate compounds, and manganese such as methoxydo, ethoxyoxide and butoxide.
  • inorganic manganese compounds such as hydroxides, nitrates, acetates, sulfates, chlorides and carbonates of manganese, manganese oxalate, acetylacetonate compounds, and manganese such as methoxydo, ethoxyoxide and butoxide.
  • iron compound examples include iron (II) fluoride, iron (III) fluoride, iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, and iron iodide.
  • Examples of the copper compound include organic copper compounds such as copper oxalate, copper stearate, copper formate, copper tartrate, copper oleate, copper acetate, copper gluconate, and copper salicylate, copper carbonate, copper chloride, and copper bromide.
  • examples thereof include inorganic copper compounds such as natural minerals such as copper iodide, copper phosphate, hydrotalcite, stichtite and pyrolite.
  • cadmium compound examples include inorganic cadmium compounds such as cadmium fluoride, cadmium chloride, cadmium bromide, cadmium iodide, cadmium oxide and cadmium carbonate, and organic cadmium compounds such as cadmium phthalate and cadmium naphthalate.
  • inorganic cadmium compounds such as cadmium fluoride, cadmium chloride, cadmium bromide, cadmium iodide, cadmium oxide and cadmium carbonate
  • organic cadmium compounds such as cadmium phthalate and cadmium naphthalate.
  • the mercury compound examples include inorganic mercury compounds such as mercury chloride, mercury sulfate and mercury nitrate, methylmercury, methylmercury chloride, ethylmercury, ethylmercury chloride, phenylmercury acetate, timerosal, mercury parachlorobenzoate, and the like.
  • inorganic mercury compounds such as mercury chloride, mercury sulfate and mercury nitrate, methylmercury, methylmercury chloride, ethylmercury, ethylmercury chloride, phenylmercury acetate, timerosal, mercury parachlorobenzoate, and the like.
  • organic mercury compounds such as fluorescein mercury acetate.
  • gallium compounds include organic gallium compounds such as tetraphenyl gallium and tetrakis (3,4,5-trifluorophenyl) gallium, and inorganic gallium compounds such as gallium oxoate, gallium halide, gallium hydroxide, and gallium cyanide. Can be mentioned.
  • Examples of the indium compound include organic indium compounds such as triethoxyindium, indium 2-ethylhexanoate, and indium acetylacetonate, indium cyanide, indium nitrate, indium sulfate, indium carbonate, indium fluoride, indium chloride, and bromide. Examples thereof include inorganic indium compounds such as indium and indium iodide.
  • arsenic compounds include arsenic trioxide, arsenic pentoxide, arsenite trichloride, arsenic pentoxide, arsenous acid, and arsenite, and salts thereof include sodium arsenate, ammonium arsenate, and arsenic acid.
  • Inorganic arsenic compounds such as potassium acid, ammonium arsenous acid, potassium arsenate, cacodylic acid, phenylarsenic acid, diphenylarsenic acid, p-hydroxyphenylarsonic acid, p-aminophenylarsenic acid, and sodium cacodileate as salts thereof.
  • Organoarsenic compounds such as potassium cacodylate.
  • antimony compound examples include inorganic antimony compounds such as antimony oxide, antimony phosphate, KSb (OH), and NH 4 SbF 6 , antimony esters with organic acids, cyclic alkyl subantimony esters, and organic antimony compounds such as triphenylantimony. Can be mentioned.
  • the bismuth compound examples include organic bismuth compounds such as triphenylbismuth, bismuth 2-ethylhexanoate, and bismuth acetylacetonate, bismuth nitrate, bismuth sulfate, bismuth acetate, bismuth hydroxide, bismuth fluoride, bismuth chloride, and bromide.
  • organic bismuth compounds such as triphenylbismuth, bismuth 2-ethylhexanoate, and bismuth acetylacetonate, bismuth nitrate, bismuth sulfate, bismuth acetate, bismuth hydroxide, bismuth fluoride, bismuth chloride, and bromide.
  • inorganic bismuth compounds such as bismuth and bismuth iodide.
  • seleno compound examples include an organic selenium compound such as selenomethionine, selenocysteine, and selenocystine, an alkali metal selenate such as potassium selenate, and an inorganic selenium compound containing an alkali metal selenate such as sodium selenate. Can be mentioned.
  • tellurium compounds include telluric acid and salts thereof, tellurium oxide, tellurium chloride, tellurium bromide, tellurium iodide and tellurium alkoxide.
  • magnesium compounds include organic magnesium compounds such as ethyl acetoacetate magnesium monoisopropyrate, magnesium bis (ethyl acetoacetate), alkyl acetoacetate magnesium monoisopropylate, and magnesium bis (acetylacetonate), magnesium oxide, magnesium sulfate, and nitrate.
  • organic magnesium compounds such as ethyl acetoacetate magnesium monoisopropyrate, magnesium bis (ethyl acetoacetate), alkyl acetoacetate magnesium monoisopropylate, and magnesium bis (acetylacetonate), magnesium oxide, magnesium sulfate, and nitrate.
  • examples thereof include inorganic magnesium compounds such as magnesium and magnesium chloride.
  • Examples of the calcium compound include organic calcium compounds such as calcium 2-ethylhexanoate, calcium ethoxide, calcium methoxydo, calcium methoxyethoxydo, and calcium acetylacetonate, calcium nitrate, calcium sulfate, calcium carbonate, calcium phosphate, and water.
  • examples thereof include inorganic calcium compounds such as calcium oxide, calcium cyanide, calcium fluoride, calcium chloride, calcium bromide and calcium iodide.
  • heteroatomic compound having a heteroatomic Li Na, K, Cs, S, Sr, Ba, F, Y, or lanthanoid
  • a known organic or inorganic compound can be used as the heteroatomic compound having a heteroatomic Li, Na, K, Cs, S, Sr, Ba, F, Y, or lanthanoid.
  • the heteroatomic compound may be used alone or in combination of two or more.
  • the proportion of the explosive in the mixture containing the explosive and the heteroatomic compound is preferably 80 to 99.9999% by mass, more preferably 85 to 99.999% by mass, still more preferably 90 to 99.99% by mass, and particularly preferably 90 to 99.99% by mass. It is 95 to 99.9% by mass, and the proportion of the heteroatomic compound is preferably 0.0001 to 20% by mass, more preferably 0.001 to 15% by mass, and further preferably 0.01 to 10% by mass. It is particularly preferably 0.1 to 5% by mass.
  • the heteroatomic content in the mixture containing the explosive and the heteroatomic compound is preferably 0.000005 to 10% by mass, more preferably 0.00001 to 8% by mass, still more preferably 0.0001 to 5% by mass, and particularly. It is preferably 0.001 to 3% by mass, and most preferably 0.01 to 1% by mass.
  • the explosive and the heteroatomic compound may be mixed by powder when both are solid, melted, or dissolved or dispersed in an appropriate solvent and mixed. Mixing can be performed by stirring, bead milling, ultrasonic waves, or the like.
  • the explosive composition comprising the explosive and the heteroatomic compound further comprises a cooling medium.
  • the cooling medium may be a solid, a liquid, or a gas.
  • Examples of the method using a cooling medium include a method of detonating a mixture of an explosive and a heteroatomic compound in the cooling medium.
  • Examples of the cooling medium include inert gas (nitrogen, argon, CO), water, ice, liquid nitrogen, an aqueous solution of an heteroatomic salt, crystalline hydrate and the like.
  • the heteroatomic salt include ammonium hexafluorosilicate, ammonium silicate, and tetramethylammonium silicate.
  • the cooling medium is preferably used about 5 times the weight of the explosive.
  • the mixture containing the explosive and the heteroatomic compound is converted to diamond by compression by a shock wave under high pressure and high temperature conditions produced by the explosion of the explosive (detonation method). During the explosive explosion, foreign atoms are incorporated into the diamond lattice.
  • the carbon source for nanodiamonds can be explosives and organic heteroatomic compounds, but if the mixture containing explosives and heteroatomic compounds further contains a carbon material that does not contain heteroatoms, this carbon material can also be a carbon source for nanodiamonds. ..
  • TNT was used as the explosive, and the dopant shown in Table 1 was used as the nanodiamond compound in the number of moles shown in Table 1 with respect to 1 mol of TNT.
  • the dopant shown in Table 1 was used as the nanodiamond compound in the number of moles shown in Table 1 with respect to 1 mol of TNT.
  • Dopant molecule 1 silline
  • Dopant molecule 2 Tetramethylsilane (SiMe 4 )
  • Dopant molecule 3 Tetrakis (nitrate methyl) silane (SiPETN)
  • Dopant molecule 4 Tetrakis (dimethylsilanolyl) silane (Si (SiMe 2 OH) 4 )
  • Dopant molecule 5 Tetrakis (trimethylsilyl) silane (Si (SiMe 3 ) 4 )
  • Dopant molecule 6 Tetrakis (trimethylsilyl) methane (C (SiMe 3 ) 4 )
  • Example 7 Approximately 60 g of an explosive composition containing 10 parts by mass, 1 part by mass or 0.1 parts by mass of triphenylsilanol as a nanodiamond compound added to 100 parts by mass of an explosive containing trinitrotoluene (TNT) and cyclotrimethylene trinitramine (RDX), respectively. was used to produce silicon-doped nanodiamonds according to the conventional method for producing nanodiamonds. The obtained silicon-doped nanodiamonds were subjected to the following treatments. The amount of triphenylsilanol added to the explosive was 10% by mass, 1% by mass, or 0.1% by mass.
  • TNT trinitrotoluene
  • RDX cyclotrimethylene trinitramine
  • FIG. 1 (a) shows a 738 nm bright spot imaging image of silicon-doped nanodiamonds obtained by using triphenylsilanol as the silicon compound and adding 1% by mass by external division.
  • the fluorescence spectrum of the bright spot in FIG. 1 (a) is shown in FIG. 1 (b). The zero phonon line (fluorescence peak) of the SiV center can be confirmed.
  • the Si content of the obtained silicon-doped nanodiamond is 3.2% by mass when the amount of triphenylsilanol added to the explosive is 10% by mass, 0.15% by mass when it is 1% by mass, and 0.1% by mass when it is 0.1% by mass. It was 0.03% by mass. From FIG. 1 (b), it was confirmed that the silicon-doped nanodiamond of the present invention has a fluorescence of 738 nm derived from the SiV center. Furthermore, the average size and BET specific surface area of the primary particles measured by XRD of the obtained silicon-doped nanodiamonds are shown in Table 2 below.
  • BET specific surface area measuring device BELSORP-miniII (manufactured by Microtrack Bell Co., Ltd.) Measured powder amount: 40 mg Pre-drying: 120 ° C, processed in vacuum for 3 hours Measurement temperature: -196 ° C (liquid nitrogen temperature) -Measurement of average size of primary particles (powder X-ray diffraction method (XRD)) Equipment: Fully automatic multipurpose X-ray diffractometer (manufactured by Rigaku Co., Ltd.) ⁇ Measurement method of Si introduction amount (XRF) Equipment: Fluorescent X-ray analyzer ZSX Primus IV Made by Rigaku Co., Ltd.
  • Example 8 Boron-doped nanodiamonds can be obtained in the same manner as in Example 7 except that 1 part by mass of phenylboronic acid was used instead of 1 part by mass of triphenylsilanol in Example 7.
  • Example 9 Phosphorus-doped nanodiamonds can be obtained in the same manner as in Example 7 except that 1 part by mass of triphenylphosphine was used instead of 1 part by mass of triphenylsilanol in Example 7.
  • Example 10 Nickel-doped nanodiamonds can be obtained in the same manner as in Example 7 except that 1 part by mass of nickel bis (acetylacetonate) was used instead of 1 part by mass of triphenylsilanol in Example 7.
  • Example 11 Silicon and boron were doped in the same manner as in Example 7 except that 0.5 parts by mass of triphenylsilanol and 0.5 parts by mass of phenylboronic acid were used instead of 1 part by mass of triphenylsilanol in Example 7. Nanodiamonds are obtained.
  • Example 12 Silicon and phosphorus were doped in the same manner as in Example 7 except that 0.5 parts by mass of triphenylsilanol and 0.5 parts by mass of triphenylphosphine were used instead of 1 part by mass of triphenylsilanol in Example 7. Nanodiamonds are obtained.

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