Heteroatom-doped nanodiamond

Abstract

To provide a novel heteroatom-doped nanodiamond.SOLUTION: The present invention provides a heteroatom-doped nanodiamond, the heteroatom-doped nanodiamond being doped with at least one heteroatom, the heteroatom-doped nanodiamond satisfying criteria (i) and / or (ii) below: (i) a BET specific surface area being from 20 to 900 m2 / g, and (ii) an average size of primary particles being from 2 to 70 nm.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to heteroatom doped nanodiamonds. [Background technology]

[0002] Diamond luminescence centers are nano-sized, chemically stable fluorescent chromophores that do not decompose, fade, or blink in vivo, as is the case with many organic fluorescent materials, and so are expected to be used as fluorescence imaging probes. In addition, because it is sometimes possible to measure the spin information of electrons excited in the luminescence center from outside, they are also expected to be used in ODMR (Optically Detected Magnetic Resonance) and as quantum bits.

[0003] The SiV center, which is one type of luminescence center in diamond, has a sharp peak called the Zero Phonon Level (ZPL) in its emission spectrum (Non-Patent Document 1).

[0004] Silicon-doped diamond is produced by a CVD method or the like (Patent Documents 1 and 2).

[0005] Non-Patent Document 2 analyzes nanodiamonds in meteorites, but does not produce nanodiamonds with SiV (Silicon-Vacancy) centers. Non-Patent Document 2 shows through simulations that SiV centers in nanodiamonds of 1.1 nm to 1.8 nm are thermodynamically stable.

[0006] Figure 1 in Non-Patent Document 3 discloses nanodiamonds with SiV centers prepared by CVD using an AFM. In the graph in the upper right corner of Figure 1, the vertical axis indicates height (nm) and the horizontal axis indicates position (microns). It is clear that the peak height is about 9 nm, but the width (position) is at least 70 nm.

[0007] Non-Patent Document 4 discloses that nanodiamonds with an average particle size of 73 nm containing SiV centers can be obtained by using 3-4 nm nanodiamonds as a seed solution and growing them on a silicon wafer by the MWPECVD method. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Special table 2014-504254 [Patent Document 2] Patent Publication No. 2004-176132 [Non-patent literature]

[0009] [Non-Patent Document 1] E. Neu et al. APPLIED PHYSICS LETTERS 98, 243107 (2011) [Non-Patent Document 2] Nat Nanotechnol. 2014 Jan;9(1):54-8. doi: 10.1038 / nnano.2013.255. Epub 2013 Dec 8. [Non-Patent Document 3] Adv Sci Lett. 2011 Feb 1;4(2):512-515. [Non-Patent Document 4] Diamond and Related Materials, Volume 65, 2016, Pages 87-90 Summary of the Invention [Problem to be solved by the invention]

[0010] One object of the present invention is to provide a novel nanodiamond doped with a foreign atom. [Means for solving the problem]

[0011] The present invention provides the following heteroatom-doped nanodiamond. Item 1. The following (i) and / or (ii) doped with at least one heteroatom: (i) BET specific surface area is 20–900 m 2 / g, (ii) the average size of the primary particles is 2 to 70 nm; A heteroatom doped nanodiamond that meets the requirements. Item 2. A heteroatom-doped nanodiamond according to Item 1, wherein the heteroatom includes at least one selected from the group consisting of Group 14 elements, phosphorus and boron. Item 3. A heteroatom-doped nanodiamond according to item 1 or 2, having a fluorescence emission peak. Item 4. A heteroatom-doped nanodiamond according to any one of Items 1 to 3, wherein the fluorescence emission peak is derived from at least one type of heteroatom-Vacancy center. Item 5. A 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. A heteroatom-doped nanodiamond according to any one of Items 1 to 5, having a fluorescence emission peak in the range of 720 to 770 nm, and the heteroatom containing silicon. Item 7. A heteroatom-doped nanodiamond according to any one of Items 1 to 5, having a fluorescence emission peak in the range of 580 to 630 nm, and the heteroatom containing germanium. Item 8. A heteroatom-doped nanodiamond according to any one of Items 1 to 5, having a fluorescence emission peak in the range of 590 to 650 nm, and the heteroatom containing tin. Item 9. A nanodiamond according to any one of Items 1 to 5, having a fluorescence emission peak in the range of 540 to 600 nm and containing lead as a heteroatom. Item 10. A heteroatom-doped nanodiamond according to any one of items 1 to 9, which includes fluorescent emission due to a Nitrogen-Vacancy (NV) center. Item 11. A heteroatom-doped nanodiamond according to any one of Items 1 to 10, wherein the nanodiamond has a spherical, ellipsoidal or polyhedral shape. Item 12. A heteroatom-doped nanodiamond according to any one of Items 1 to 11, having a carbon content of 70 to 99 mass%, a hydrogen content of 0.1 to 5 mass%, and a nitrogen content of 0.1 to 5 mass%. Item 13. A heteroatom-doped nanodiamond according to any one of Items 1 to 12, wherein the ratio (D / G) of the diamond peak area (D) to the graphite peak area (G) in Raman spectroscopy is 0.2 to 9. Item 14. A heteroatom-doped nanodiamond according to any one of Items 1 to 13, wherein the ratio (H / D) of the peak area (H) of the surface hydroxyl group (OH) to the peak area (D) of the diamond in Raman spectroscopy is 0.1 to 5. Item 15. A heteroatom-doped nanodiamond according to any one of Items 1 to 14, wherein the ratio (C / D) of the peak area (C) of the surface carbonyl group (CO) to the peak area (D) of the diamond in Raman spectroscopy is 0.01 to 1.5. Item 16. A heteroatom-doped nanodiamond according to any one of items 1 to 15, having at least one type of oxygen-containing functional group end and / or at least one type of hydrogen-containing functional group end. Item 17. At least one heteroatom V center has a concentration of 1×10 10 / cm 3 17. The heteroatom-doped nanodiamond according to any one of items 1 to 16, wherein: Effect of the Invention

[0012] The known method of growing a nanodiamond layer doped with foreign atoms such as Si or B by CVD of undoped nanodiamond particles placed on a silicon substrate results in nanodiamond particles with a large average primary particle size and / or a small specific surface area and irregular shapes.

[0013] On the other hand, for example, heteroatom-doped nanodiamonds produced by the detonation method have a small average primary particle size and / or a large specific surface area, and are useful as fluorescent imaging probes because they are chemically stable at nano size and do not decompose, fade, or blink in vivo. Furthermore, since it may be possible to measure the information of the spin of electrons excited in the heteroatom V (Vacancy) luminescence center from outside, they are expected to be used in ODMR (Optically Detected Magnetic Resonance) and as quantum bits. [Brief description of the drawings]

[0014] [Figure 1] (a) 738 nm bright spot imaging image of nanodiamonds obtained by adding 1 mass% of triphenylsilanol as a heteroatom compound, (b) fluorescence measurement results of the bright spot in Figure 1(a), (c) XRD measurement results of the sample after mixed acid and alkali treatment. In Figure 1(b), a fluorescent side band (shoulder peak) is present around 750 nm, but this side band may not be present depending on the sample. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The heteroatom-doped nanodiamond of the present invention has 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 to 70 nm; Meet the requirements of.

[0016] The heteroatom compound is a compound that contains at least one type of heteroatom (atom other than carbon), and may be either an organic compound or an inorganic compound.

[0017] The heteroatom is selected from the group consisting of B, P, Si, S, Cr, Sn, Al, Ge, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl, Pb, As, Sb, Bi, Se, Te, Co, Xe, F, Y, and lanthanoids, 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, more preferably selected from the group consisting of Si, Ge, Sn, B, P, Ni, Ti, Co, Xe, Cr, W, Ta, Zr, Zn, Ag, and Pb.

[0018] Preferred heteroatoms to be 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 and P.

[0019] In one preferred embodiment, the nanodiamond of the present invention comprises at least one element selected from the group consisting of Si, Ge, Sn and Pb, a group consisting of B, P and Ni, and at least one other heteroatom.

[0020] In another preferred embodiment, the nanodiamond of the present invention comprises at least one selected from the group consisting of Si, B, P, and Ni, and at least one other heteroatom. The number of heteroatoms doped into the nanodiamond is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1, 2, or 3.

[0021] The heteroatom-doped nanodiamond of a preferred embodiment of the present invention has a fluorescence emission peak. The heteroatom-doped nanodiamond of another preferred embodiment of the present invention contains at least one heteroatom V center, thereby having a fluorescence emission peak. The wavelength of the fluorescence emission peak is preferably 720 to 770 nm, more preferably 730 to 760 nm, when the heteroatom contains silicon, preferably 580 to 630 nm, more preferably 590 to 620 nm, when the heteroatom contains germanium, preferably 590 to 650 nm, more preferably 600 to 640 nm, when the heteroatom contains tin, and preferably 540 to 600 nm, more preferably 550 to 590 nm, when the heteroatom contains lead.

[0022] In one preferred embodiment of the present invention, the doped nanodiamond emitting fluorescence from a heteroatom-Vacancy center in which the heteroatom is other than phosphorus and boron may be further doped with phosphorus and / or boron. It is considered that the introduction of these atoms (B and / or P) has the effect of adjusting the charge of the heteroatom-V center other than B and / or P and defects (luminescence centers) derived from other doped heteroatoms, and stabilizing the fluorescence. In addition, the heteroatom-doped nanodiamond of the present invention may contain fluorescence emission from an NV center. The NV center is a luminescence center due to nitrogen and a vacancy (vacancy), and has a wide fluorescence spectrum with a peak due to the ZPL (zero phonon line) near 575 nm and / or near 637 nm, and has a wide fluorescence spectrum of about 550 to 800 nm when excited at 532 nm. For example, when doping with a heteroatom that is not directly related to fluorescence, such as phosphorus or boron, the NV center intensity may be increased, which is preferable. In a more preferred embodiment of the present invention, the fluorescence emission peak of nanodiamonds in which the heteroatom is Si includes a sharp peak at about 738 nm, known as the Zero Phonon Level (ZPL).

[0023] The concentration of at least one heteroatom V center in the heteroatom-doped nanodiamond of the present invention is preferably 1×10 10 / cm3 More preferably, it is 2×10 10 ~1×10 19 / cm 3 This heteroatomic V center concentration is the total concentration when the nanodiamond contains two or more heteroatomic V centers. It is presumed that the heteroatomic V center concentration can be determined, for example, by using a confocal laser microscope or a fluorescence absorption spectroscopy device. For the determination of the heteroatomic V center concentration by fluorescence absorption analysis, please refer to the literature (DOI 10.1002 / pssa.201532174).

[0024] The BET specific surface area of ​​the heteroatom-doped nanodiamond is preferably 20 to 900 m 2 / g, more preferably 25 to 800 m 2 / g, more preferably 30 to 700 m 2 / g, particularly preferably 35 to 600 m 2 / g. The BET specific surface area can be measured by nitrogen adsorption. An example of a measuring device for the BET specific surface area is BELSORP-miniII (manufactured by Microtrack-Bell Co., Ltd.), and the BET specific surface area can be measured, for example, under the following conditions. ·Measured powder amount: 40mg Pre-drying: 120℃, vacuum treatment for 3 hours Measurement temperature: -196℃ (liquid nitrogen temperature) The average size of the primary particles of the heteroatom-doped nanodiamond 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 from the analysis results of powder X-ray diffraction (XRD) using Scherrer's formula. The XRD measuring device can be, for example, a fully automatic multipurpose X-ray diffractometer (manufactured by Rigaku Corporation).

[0025] The carbon content of the heteroatom-doped nanodiamond of the present invention is preferably 70 to 99 mass %, more preferably 75 to 98 mass %, and further preferably 80 to 97 mass %.

[0026] The hydrogen content of the heteroatom-doped nanodiamond of the present invention is preferably 0.1 to 5 mass %, more preferably 0.2 to 4.5 mass %, and even more preferably 0.3 to 4.0 mass %.

[0027] The nitrogen content of the heteroatom-doped nanodiamond of the present invention is preferably 0.1 to 5 mass %, more preferably 0.2 to 4.5 mass %, and even more preferably 0.3 to 4.0 mass %.

[0028] The carbon, hydrogen and nitrogen contents of the heteroatom doped nanodiamonds can be measured by elemental analysis.

[0029] The heteroatom content of the heteroatom-doped nanodiamond of the present invention is preferably 0.0001-10.0% by mass, more preferably 0.0001-5.0% by mass, and even more preferably 0.0001-1.0% by mass. The heteroatom content can be measured, for example, by inductively coupled plasma atomic emission spectrometry (ICP-AES), XRF, or SIMS (secondary ion mass spectrometry), and the heteroatom-doped nanodiamond can be quantified as an acidic solution after alkali fusion. In addition, when the nanodiamond contains two or more heteroatoms, the heteroatom content is the total content of the heteroatoms.

[0030] In a preferred embodiment of the present invention, the heteroatom-doped nanodiamond can identify peaks characteristic of diamond, graphite, surface hydroxyl groups (OH), and surface carbonyl groups (CO) in the Raman shift chart by Raman spectroscopy. The peak characteristic of diamond in the Raman shift chart is 1100 to 1400 cm -1 The characteristic peak of graphite is 1450-1700 cm -1 The characteristic peak of the surface hydroxyl group (OH) is 1500-1750 cm -1 The characteristic peak of the surface carbonyl group (CO) is 1650-1800 cm -1The areas of the peaks characteristic of diamond, graphite, surface hydroxyl groups (OH), and surface carbonyl groups (CO) are shown by a Raman spectrometer. The laser wavelength of the Raman light source is, for example, 325 nm or 488 nm. As the Raman spectrometer, a confocal microscopic Raman spectrometer (for example, trade name: Microscopic Laser Raman Spectrophotometer LabRAM HR Evolution, manufactured by Horiba, Ltd.) can be used.

[0031] In a preferred embodiment of the heteroatom-doped nanodiamond of the present invention, the ratio (D / G) of the diamond peak area (D) to the graphite peak area (G) is preferably 0.2 to 9, more preferably 0.3 to 8, and even more preferably 0.5 to 7.

[0032] In a preferred embodiment of the heteroatom-doped nanodiamond of the present invention, the ratio (H / D) of the peak area (H) of the surface hydroxyl groups (OH) to the peak area (D) of the diamond is preferably 0.1 to 5, more preferably 0.1 to 4.0, and even more preferably 0.1 to 3.0.

[0033] In a preferred embodiment of the heteroatom-doped nanodiamond of the present invention, 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, and even more preferably 0.05 to 1.0.

[0034] For Raman analysis of nanodiamonds, please refer to the literature (e.g., Vadym N. Mochalin et al., NATURE NANOTECHNOLOGY, 7(2012)11-23, especially Figure 3).

[0035] In another preferred embodiment of the present invention, the surface of the heteroatom-doped nanodiamond may have at least one type of oxygen functional group terminal and / or at least one type of hydrogen terminal. The oxygen functional group terminal may be OH, COOH, CONH2, C=O, CHO, etc., and OH, C=O, COOH are preferred. The hydrogen terminal may be an alkyl group having 1 to 20 carbon atoms.

[0036] The presence of at least one type of oxygen functional group termination on the surface of the heteroatom-doped nanodiamond is preferable because it suppresses the aggregation of nanodiamond particles. The presence of at least one type of hydrogen termination on the surface of the heteroatom-doped nanodiamond is preferable because it makes the zeta potential positive and makes the nanodiamond stable and highly dispersible in an acidic aqueous solution.

[0037] In another preferred embodiment of the present invention, the heteroatom-doped nanodiamond of the present invention may have a core-shell structure. The core of the heteroatom-doped nanodiamond of the core-shell structure is a nanodiamond particle doped with at least one heteroatom. This core preferably has a heteroatom V center and emits fluorescence. The shell is a non-diamond coating layer, which may contain sp2 carbon and preferably further 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, and even more preferably 1 nm or less. The shell may have a hydrophilic functional group on the surface.

[0038] The heteroatom-doped nanodiamond can be preferably produced by the detonation method. The shape of the heteroatom-doped nanodiamond is preferably spherical, ellipsoidal, or a polyhedral shape close thereto.

[0039] Circularity is a number that expresses the complexity of a figure drawn in an image, etc. The maximum circularity is 1, and the more complex the figure, the smaller the number becomes. Circularity can be calculated, for example, by analyzing a TEM image of a heteroatom-doped nanodiamond with image analysis software (e.g., winROOF) and using the following formula. Circularity = 4π x (area) ÷ (perimeter) ^ 2 For example, in the case of a perfect circle with a radius of 10, the formula is "4π×(10×10×π)÷(10×2×π)^2", resulting in a circularity of 1 (maximum value). In other words, a perfect circle is the least complicated shape in terms of circularity. The circularity of heteroatom-doped nanodiamond is preferably 0.2 or more, more preferably 0.3 or more, and even more preferably 0.35 or more.

[0040] In a preferred embodiment of the present invention, the center of the heteroatom-doped nanodiamond particle has a diamond structure that includes sp3 carbon and doped heteroatoms, and its surface is covered with an amorphous layer that is composed of sp2 carbon.In a more preferred embodiment, the outside of the amorphous layer may be covered with a graphite oxide layer.In addition, a hydration layer may be formed between the amorphous layer and the graphite oxide layer.

[0041] In a preferred embodiment of the present invention, the heteroatom-doped nanodiamond has a positive or negative zeta potential. The zeta potential of the heteroatom-doped nanodiamond is preferably -70 to 70 mV, more preferably -60 to 30 mV.

[0042] The heteroatom-doped nanodiamond of the present invention can be produced by a production method including mixing an explosive composition containing at least one explosive and at least one heteroatom compound, and detonating the resulting mixture in a closed container. The container can be a metal container or a synthetic resin container. The explosive and the heteroatom compound are preferably formed by pressing or casting. Methods for producing particles (dry powder) of the explosive and the heteroatom compound include crystallization, crushing, and spray flash evaporation.

[0043] When the explosive composition is formed by the compression or casting method, the explosive and the heteroatom compound are mixed in a dry powder or melt state or with the aid of a solvent. The state of the mixture of the explosive and the heteroatom compound may be any of the following four combinations: Explosives (dry powder) and heteroatom compounds (dry powder) Explosives (dry powder) and heteroatom compounds (molten state) Explosives (molten state) and heteroatomic compounds (dry powders) Explosives (molten state) and heteroatomic compounds (molten state) The explosive and the heteroatom compound may be mixed in the presence or absence of a solvent, and after mixing, the mixture can be molded by a pressing method or a pouring method.

[0044] The average particle size of the explosives and heteroatom compounds is preferably 10 mm or less, more preferably 5 mm or less, and further preferably 1 mm or less. The average particle size can be measured by a laser diffraction / scattering method, an optical microscope, or a Raman method.

[0045] The product obtained by the explosion can be further subjected to a purification step and a post-treatment step. The purification step can include one or both of a mixed acid treatment and an alkali treatment. The preferred purification step is the mixed acid treatment step.

[0046] When an explosive composition containing explosives and heteroatom compounds is exploded in a container, graphite, metal impurities, heteroatom elements, heteroatom oxides, etc. are generated in addition to heteroatom-doped nanodiamonds. Graphite and metal impurities can be removed by mixed acid treatment, and when the heteroatom is a group 14 element such as Si, Ge, Sn, or Pb, group 14 element elements (Si, Ge, Sn, Pb) and group 14 element oxides (SiO2, GeO2, SnO, SnO2, PbO, PbO2, etc.) can be removed by alkali treatment.

[0047] The mixed acid may be a mixture of concentrated sulfuric acid and concentrated nitric acid, preferably a mixture of concentrated sulfuric acid:concentrated nitric acid=1:1 (volume ratio). The mixed acid treatment temperature is 50 to 200° C., and the mixed acid treatment time is 0.5 to 24 hours.

[0048] The alkali may be an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, etc. The alkali treatment temperature is 30 to 150° C., and the alkali treatment time is 0.5 to 24 hours.

[0049] The post-treatment process can include annealing and vapor phase oxidation. The annealing process allows the doped heteroatoms in the heteroatom-doped nanodiamond to meet with vacancies, forming heteroatom V centers. The vapor phase oxidation can also thin or remove the graphite layer formed on the surface of the heteroatom-doped nanodiamond. Although this is an optional process, a vacancy formation process may be performed before annealing. The vacancy formation process is performed by ion beam or electron beam irradiation. Although heteroatom V centers can be formed by annealing even without the vacancy formation process, more heteroatom V centers can be formed by annealing after the vacancy formation process. The upper limit of the vacancy density introduced by ion beam or electron beam irradiation is the concentration at which diamond is destroyed (>1×10 21 / cm 3 The lower limit is, for example, 1×10 16 / cm 3 That's it, plus 1x10 18 / cm 3 That is all. The ion beam is preferably a hydrogen (H) or helium (He) ion beam. For example, the energy of the hydrogen ion beam is preferably 10 to 1500 keV, and the energy of the helium ion beam is preferably 20 to 2000 keV. The energy of the electron beam is preferably 500 to 5000 keV.

[0050] The annealing temperature is preferably 800° C. or higher, and the annealing time is 30 minutes or longer.

[0051] The gas phase oxidation can be carried out in an air atmosphere, the gas phase oxidation temperature is preferably 300° C. or higher, and the gas phase oxidation time is 2 hours or longer.

[0052] The explosive is not particularly limited, and a wide variety of known explosives can be used. Specific examples include trinitrotoluene (TNT), cyclotrimethylenetrinitramine (hexogen, RDX), cyclotetramethylenetetranitramine (octogen), trinitrophenylmethylnitramine (tetryl), pentaerythritol tetranitrate (PETN), tetranitromethane (TNM), triamino-trinitrobenzene, hexanitrostilbene, and diaminodinitrobenzofuroxan, which can be used alone or in combination of two or more.

[0053] The heteroatom compounds described below as specific examples are merely illustrative, and a wide variety of known heteroatom compounds can be used.

[0054] When the heteroatom is silicon, the organic silicon compounds are: Silanes with lower alkyl groups, such as acetoxytrimethylsilane, diacetoxydimethylsilane, triacetoxymethylsilane, acetoxytriethylsilane, diacetoxydiethylsilane, triacetoxyethylsilane, acetoxytripropylsilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, ethoxytrimethylsilane, diethoxydimethylsilane, triethoxymethylsilane, ethoxytriethylsilane, diethoxydiethylsilane, triethoxyethylsilane, and trimethylphenoxysilane;

[0055] ·Trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, trichloroethylsilane, dichlorodiethylsilane, chlorotriethylsilane, trichlorophenylsilane, dichlorodiphenylsilane, chlorotriphenylsilane, dichlorodiphenylsilane, dichloromethylphenylsilane, dichloroethylphenylsilane, chlorodifluoromethylsilane, dichlorofluoromethylsilane, chlorofluorodimethylsilane, chloroethyldifluorosilane, dichloroethylfluorosilane, chlorodifluoropropylsilane, dichlorofluoropropyl silanes having halogen atoms such as pyrsilane, trifluoromethylsilane, difluorodimethylsilane, fluorotrimethylsilane, ethyltrifluorosilane, diethyldifluorosilane, triethylfluorosilane, trifluoropropylsilane, fluorotripropylsilane, trifluorophenylsilane, difluorodiphenylsilane, fluorotriphenylsilane, tribromomethylsilane, dibromodimethylsilane, bromotrimethylsilane, bromotriethylsilane, bromotripropylsilane, dibromodiphenylsilane, and bromotriphenylsilane;

[0056] Polysilanes such as hexamethyldisilane, hexaethyldisilane, hexapropyldisilane, hexaphenyldisilane, and octaphenylcyclotetrasilane Silazane such as triethylsilazane, tripropylsilazane, triphenylsilazane, hexamethyldisilazane, hexaethyldisilazane, hexaphenyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexaethylcyclotrisilazane, octaethylcyclotetrasilazane, and hexaphenylcyclotrisilazane; Aromatic silanes such as silabenzene and disilabenzene, which have silicon atoms incorporated in the aromatic ring Hydroxyl-containing silanes such as trimethylsilanol, dimethylphenylsilanol, triethylsilanol, diethylsilanediol, tripropylsilanol, dipropylsilanediol, triphenylsilanol, and diphenylsilanediol

[0057] Alkyl or aryl substituted silanes such as tetramethylsilane, ethyltrimethylsilane, trimethylpropylsilane, trimethylphenylsilane, diethyldimethylsilane, triethylmethylsilane, methyltriphenylsilane, tetraethylsilane, triethylphenylsilane, diethyldiphenylsilane, ethyltriphenylsilane, and tetraphenylsilane; Carboxylic acid-containing silanes such as triphenylsilyl carboxylic acid, trimethylsilyl acetic acid, trimethylsilyl propionic acid, and trimethylsilyl butyric acid,

[0058] Siloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, and hexaphenyldisiloxane, Silanes having an alkyl or 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(nitratomethyl)silane, etc.

[0059] Examples of inorganic silicon compounds include silicon oxide, silicon oxynitride, silicon nitride, silicon carbide oxide, silicon carbide nitride, silane, and carbon materials doped with silicon, etc. Examples of carbon materials doped with silicon include graphite, activated carbon, carbon black, ketjen black, coke, soft carbon, hard carbon, acetylene black, carbon fiber, and mesoporous carbon.

[0060] Examples of the boron compound include inorganic boron compounds and organic boron compounds.

[0061] Examples of inorganic boron compounds include orthoboric acid, diboron dioxide, diboron trioxide, tetraboron trioxide, tetraboron pentoxide, boron tribromide, tetrafluoroboric acid, ammonium borate, and magnesium borate.

[0062] Examples of organic boron compounds include triethylborane, (R)-5,5-diphenyl-2-methyl-3,4-propano-1,3,2-oxazaborolidine, triisopropyl borate, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, bis(hexylene glycolato)diboron, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole, tert-butyl-N-[4-(4,4,5,5-tetramethyl-1,2,3-dioxaborolan-2-yl)phenyl]carbamate, phenylboronic acid, 3-acetylphenylboronic acid, boron trifluoride acetate complex, boron trifluoride sulfolane complex, 2-thiopheneboronic acid, and tris(trimethylsilyl)borate.

[0063] Examples of the phosphorus compound include inorganic phosphorus compounds, organic phosphorus compounds, etc. Examples of the inorganic phosphorus compound include ammonium polyphosphate.

[0064] The organic phosphorus compounds include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl)p-tolyl phosphate, tritolyl phosphate, di(dodecyl)p-tolyl phosphate, tris(2-butoxyethyl)phosphate, tricyclohexyl phosphate, triphenyl phosphate, ethyl diphenyl phosphate, dibutyl phosphoric acid esters such as phenyl phosphate, phenyl bis dodecyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, p-tolyl bis (2,5,5'-trimethylhexyl) phosphate, cresyl-2,6-xylenyl phosphate, trixylenyl phosphate, hydroxyphenyl diphenyl phosphate, tris (t-butylphenyl) phosphate, tris (i-propylphenyl) phosphate, 2-ethylhexyl diphenyl phosphate, bis (2-ethylhexyl) phenyl phosphate, tri (nonylphenyl) phosphate, and phenyl bis neopentyl phosphate; Condensed phosphate esters such as 1,3-phenylene bis(diphenyl phosphate), 1,4-phenylene bis(dixylenyl phosphate), 1,3-phenylene bis(3,5,5'-trimethylhexyl phosphate), bisphenol A bis(diphenyl phosphate), 4,4'-biphenyl bis(dixylenyl phosphate), and 1,3,5-phenylene tris(dixylenyl phosphate); Phosphite esters such as trimethyl phosphite, triethyl phosphite, triphenyl phosphite, and tricresyl phosphite; Examples of phosphite esters include 1,3-phenylene bis(diphenyl phosphite), 1,3-phenylene bis(dixylenyl phosphite), 1,4-phenylene bis(3,5,5'-trimethylhexyl phosphite), bisphenol A bis(diphenyl phosphite), 4,4'-biphenyl bis(dixylenyl phosphite), and 1,3,5-phenylene tris(dixylenyl phosphite).

[0065] Examples of germanium compounds include organic germanium compounds such as methylgermane, ethylgermane, trimethylgermanium methoxide, dimethylgermanium diacetate, tributylgermanium acetate, tetramethoxygermanium, tetraethoxygermanium, isobutylgermane, alkylgermanium trichloride, and dimethylaminogermanium trichloride; examples of germanium compounds include germanium complexes such as nitrotriphenol complex (Ge2(ntp)2O), catechol complex (Ge(cat)2), and aminopyrene complex (Ge2(ap)2Cl2); and germanium alkoxides such as germanium ethoxide and germanium tetrabutoxide.

[0066] Examples of tin compounds include inorganic tin compounds such as tin(II) oxide, tin(IV) oxide, tin(II) sulfide, tin(IV) sulfide, tin(II) chloride, tin(IV) chloride, tin(II) bromide, tin(II) fluoride, tin acetate, and tin sulfate; alkyl tin compounds such as tetramethyltin; monoalkyl tin oxide compounds such as monobutyltin oxide; dialkyl tin oxide compounds such as dibutyltin oxide; aryl tin compounds such as tetraphenyltin; and organic tin compounds such as dimethyltin maleate, hydroxybutyltin oxide, and monobutyltin tris(2-ethylhexanoate).

[0067] Examples of nickel compounds include divalent nickel halides such as nickel chloride(II), nickel bromide(II), and nickel iodide(II); inorganic nickel compounds such as nickel acetate(II) and nickel carbonate(II); and organic nickel compounds such as nickel bis(ethylacetoacetate) and nickel bis(acetylacetonate).

[0068] Examples of titanium compounds include inorganic titanium compounds such as titanium dioxide, titanium nitride, strontium titanate, lead titanate, barium titanate, and potassium titanate; tetraalkoxy titanium compounds such as tetraethoxy titanium, tetraisopropoxy titanium, and tetrabutyloxy titanium; tetraethylene glycol titanate, di-n-butyl bis(triethanolamine) titanate, di-isopropoxy titanium bis(acetylacetonate), isopropoxy titanium octanoate, isopropyl titanium trimethacrylate, isopropyl titanium triacrylate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris(butylmethylpyrophosphate) titanate, tetraisopropyl di(dilauryl phosphite) titanate, dimethacryloxy acetate titanate, diacryloxy acetate titanate, di(dioctylphosphate) ethylene titanate, triisopropyl phosphate titanate, dimethacryl ... (Dioctyl phosphate) isopropoxy titanium, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, tris(dioctyl pyrophosphate)ethyl Examples of the organic titanium compounds include lenthitanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryloyl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctylphosphate) titanate, isopropyl tricumylphenyl titanate, and isopropyl tri(N-aminoethyl-aminoethyl) titanate.

[0069] Examples of the cobalt compounds include inorganic cobalt compounds such as inorganic acid salts of cobalt, cobalt halides, cobalt oxide, cobalt hydroxide, dicobalt octacarbonyl, cobalt hydrogen tetracarbonyl, tetracobalt dodecacarbonyl, and alkylidynetricobalt nonacarbonyl; cobalt tris(ethylacetoacetate), cobalt tris(acetylacetonate); organic acid salts of cobalt (e.g., acetate, propionate, cyanate, naphthenate, and stearate); and alkylsulfonates such as methanesulfonate, ethanesulfonate, octane sulfonate, and dodecanesulfonate (e.g., C 6-18 alkylsulfonates; arylsulfonates which may be substituted with an alkyl group, such as benzenesulfonates, p-toluenesulfonates, naphthalenesulfonates, decylbenzenesulfonates, and dodecylbenzenesulfonates (e.g., C 6-18 Examples of the ligands constituting the complex include OH (hydroxo), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acyl (acetyl, propionyl, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), acetylacetonate, cyclopentadienyl group, halogen atom (chlorine, bromine, etc.), CO, CN, oxygen atom, H2O (aquo), phosphorus compounds such as phosphine (triarylphosphine, etc.), NH3 (ammine), NO, NO2 (nitro), NO3 (nitrato), ethylenediamine, diethylenetriamine, pyridine, and nitrogen-containing compounds such as phenanthroline.

[0070] Examples of xenon compounds include fluorides such as XeF2, XeF4, XeF6, XeOF2, XeOF4, and XeO2F4, oxides such as XeO3 and XeO4, xenonic acid Xe(OH)6 and its salt Ba3XeO6, perxenic acid H4XeO6 and its salt Na4XeO6, complexes with metal carbonyls M(CO)5Xe (M = Cr, Mo, W), and hydrates.

[0071] Examples of chromium compounds include chromium acetylacetone complexes such as acetylacetonate chromium, chromium alkoxides such as chromium(III) isopropoxide, organic acid chromium compounds such as chromium(II) acetate and hydroxychromium(III) diacetate, tris(allyl)chromium, tris(methallyl)chromium, tris(crotyl)chromium, bis(cyclopentadienyl)chromium (i.e., chromocene), bis(pentamethylcyclopentadienyl)chromium (i.e., decamethylchromocene), bis(benzene)chromium, Included are organic chromium compounds such as bis(ethylbenzene)chromium, bis(mesitylene)chromium, bis(pentadienyl)chromium, bis(2,4-dimethylpentadienyl)chromium, bis(allyl)tricarbonylchromium, (cyclopentadienyl)(pentadienyl)chromium, tetra(1-norbornyl)chromium, (trimethylenemethane)tetracarbonylchromium, bis(butadiene)dicarbonylchromium, (butadiene)tetracarbonylchromium, and bis(cyclooctatetraene)chromium.

[0072] Examples of the tungsten compound include inorganic tungsten compounds such as tungsten trioxide, ammonium tungstate, and sodium tungstate; boron atom-coordinated tungsten complexes such as ethylborylethylidene ligands; carbon atom-coordinated tungsten complexes such as carbonyl ligands, cyclopentadienyl ligands, alkyl group ligands, and olefin-based ligands; nitrogen atom-coordinated tungsten complexes such as pyridine ligands and acetonitrile ligands; phosphorus atom-coordinated tungsten complexes coordinated with phosphine ligands, phosphite ligands, and the like; and organic tungsten compounds such as sulfur atom-coordinated tungsten complexes coordinated with diethylcarbamodithiolato ligands.

[0073] Examples of thallium compounds include inorganic thallium compounds such as thallium nitrate, thallium sulfate, thallium fluoride, thallium chloride, thallium bromide, and thallium iodide; trialkylthallium compounds such as trimethylthallium, triethylthallium, and triisobutylthallium; arylthallium compounds such as dialkylthallium halides, alkenyldialkylthallium, alkynyldialkylthallium, triphenylthallium, and tritolylthallium; diarylthallium halides; thallium 2-ethylhexanoate, thallium malonate, thallium formate, thallium ethoxide, and thallium acetylacetonate; and organic thallium compounds such as thallium acetylacetonate.

[0074] Examples of the zirconium compound include inorganic zirconium compounds such as zirconium nitrate, zirconium sulfate, zirconium carbonate, zirconium hydroxide, zirconium fluoride, zirconium chloride, zirconium bromide, and zirconium iodide; and organic zirconium compounds such as zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium isopropoxide, zirconium ethoxide, zirconyl acetate, zirconium acetylacetonate, zirconium butoxyacetylacetonate, zirconium bisacetylacetonate, zirconium ethylacetoacetate, zirconium acetylacetonate bisethylacetoacetate, zirconium hexafluoroacetylacetonate, and zirconium trifluoroacetylacetonate.

[0075] Examples of zinc compounds include diethylzinc, dimethylzinc, zinc acetate, zinc nitrate, zinc stearate, zinc oleate, zinc palmitate, zinc myristate, zinc dodecanoate, zinc acetylacetonate, zinc chloride, zinc bromide, zinc iodide, and zinc carbamate.

[0076] Examples of silver compounds include organic silver compounds such as silver acetate, silver pivalate, silver trifluoromethanesulfonate, and silver benzoate; and inorganic silver compounds such as silver nitrate, silver fluoride, silver chloride, silver bromide, silver iodide, silver sulfate, silver oxide, silver sulfide, silver tetrafluoroborate, silver hexafluorophosphate (AgPF6), and silver hexafluoroantimonate (AgSbF6).

[0077] Examples of lead compounds include lead monoxide (PbO), lead dioxide (PbO2), red lead (Pb3O4), white lead (2PbCO3·Pb(OH)2), lead nitrate (Pb(NO3)2), lead chloride (PbCl2), lead sulfide (PbS), yellow lead (PbCrO4, Pb(SCr)O4, PbO·PbCrO4), lead carbonate (PbCO3), lead sulfate (PbSO4), lead fluoride (P Lead tetrafluoride (PbF2), lead tetrafluoride (PbF4), lead bromide (PbBr2), lead iodide (PbI2), and other inorganic lead compounds; lead acetate (Pb(CH3COO)2), lead tetracarboxylate (Pb(OCOCH3)4), tetraethyl lead (Pb(CH3CH2)4), tetramethyl lead (Pb(CH3)4), and tetrabutyl lead (Pb(C4H9)4).

[0078] Examples of the aluminum compound include inorganic aluminum compounds such as aluminum oxide, alkoxy compounds such as trimethoxyaluminum, triethoxyaluminum, isopropoxyaluminum, isopropoxydiethoxyaluminum, and tributoxyaluminum, acyloxy compounds such as triacetoxyaluminum, aluminum tristearate, and aluminum tributyrate, aluminum isopropylate, aluminum sec-butylate, aluminum tert-butylate, aluminum tris(ethylacetoacetate), tris(hexafluoroacetylacetonate)aluminum, tris(ethylacetoacetate)aluminum, and tris(n-propylacetoacetate). aluminum acetate), tris(iso-propylacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, trissalicylaldehyde aluminum, tris(2-ethoxycarbonylphenolate)aluminum, tris(acetylacetonate)aluminum, trimethylaluminum, triethylaluminum, triisobutylaluminum and other trialkylaluminums; dialkylaluminum halides; arylaluminums such as alkenyldialkylaluminum, alkynyldialkylaluminum, triphenylaluminum, and tritolylaluminum; and organic aluminum compounds such as diarylaluminum halides.

[0079] Examples of vanadium compounds include vanadic acid and metavanadic acid, as well as inorganic vanadium compounds such as alkali metal salts thereof; alkoxides such as triethoxyvanadyl, pentaethoxyvanadyl, triamyloxyvanadyl, and triisopropoxyvanadyl; acetonates such as bisacetylacetonate vanadyl, vanadium acetylacetonate, vanadyl acetylacetonate, and vanadium oxyacetylacetonate; and organic vanadium compounds such as vanadium stearate, vanadium pivalate, and vanadium acetate.

[0080] Examples of niobium compounds include halides such as niobium pentachloride and niobium pentafluoride, inorganic niobium compounds such as niobium sulfate, niobic acid and niobate salts, and organic niobium compounds such as niobium alkoxides.

[0081] Examples of tantalum compounds include inorganic tantalum compounds such as TaCl5 and TaF5, and organic tantalum compounds such as Ta(OC2H5)5, Ta(OCH3)5, Ta(OC3H7)5, Ta(OC4H9)5, (C5H5)2TaH3, and Ta(N(CH3)2)5.

[0082] Examples of the molybdenum compound include inorganic molybdenum compounds such as molybdenum trioxide, zinc molybdate, ammonium molybdate, magnesium molybdate, calcium molybdate, barium molybdate, sodium molybdate, potassium molybdate, phosphomolybdic acid, ammonium phosphomolybdate, sodium phosphomolybdate, silicomolybdic acid, molybdenum disulfide, molybdenum diselenide, molybdenum ditelluride, molybdenum boride, molybdenum disilicide, molybdenum nitride, and molybdenum carbide; and organic molybdenum compounds such as molybdenum dialkyldithiophosphate and molybdenum dialkyldithiocarbamate.

[0083] Examples of manganese compounds include inorganic manganese compounds such as manganese hydroxide, nitrate, acetate, sulfate, chloride and carbonate; manganese oxalate; acetylacetonate compounds; and organic manganese compounds including manganese alkoxides such as methoxide, ethoxide and butoxide.

[0084] Examples of iron compounds include iron fluoride (II), iron fluoride (III), iron chloride (II), iron chloride (III), iron bromide (II), iron bromide (III), iron iodide (II), Inorganic iron compounds such as iron(III) iodide, iron(II), iron(III), iron(III) oxide, iron(II) tetroxide, iron(III), iron(II) sulfate, iron(III) sulfate, iron(II) nitrate, iron(III) nitrate, iron(II) hydroxide, iron(III) hydroxide, iron(II) perchlorate, iron(III) perchlorate, ammonium iron(II) sulfate, ammonium iron(III) sulfate, iron(III) oxide tungstate, iron(III) tetravanadate, iron(III) selenide, iron(II) titanium trioxide, iron(III) titanium pentoxide, iron(II) sulfide, iron(III) sulfide, iron(II) phosphide, iron(III) phosphide, iron(III) phosphide; iron(II) acetate, iron(III) acetate, iron(II) formate, iron(III) triformate, iron(II) tartrate , sodium iron(III) tartrate, iron(II) lactate, iron(II) oxalate, iron(III) oxalate, ammonium iron(III) citrate, iron(III) laurate, iron(III) stearate, iron(III) tripalmitate, potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), bis(2,4-pentanedionato)diaquaferrate(II), iron(III) tris(2,4-pentanedionato), potassium tris(oxalato)ferrate(III), iron(III) tris(trifluoromethanesulfonate), iron(III) p-toluenesulfonate, iron(III) dimethyldithiocarbamate, iron(III) diethyldithiocarbamate, and organic iron compounds such as ferrocene.

[0085] Examples of copper compounds include organic copper compounds such as copper oxalate, copper stearate, copper formate, copper tartrate, copper oleate, copper acetate, copper gluconate, and copper salicylate; and inorganic copper compounds such as copper carbonate, copper chloride, copper bromide, copper iodide, copper phosphate, and natural minerals such as hydrotalcite, stichtite, and pyrolite.

[0086] Examples of cadmium compounds 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.

[0087] Examples of mercury compounds include inorganic mercury compounds such as mercuric chloride, mercuric sulfate, and mercuric nitrate, and organic mercury compounds such as methylmercury, methylmercury chloride, ethylmercury, ethylmercury chloride, phenylmercury acetate, thimerosal, mercuric parachlorobenzoate, and fluorescein mercuric acetate.

[0088] Examples of the gallium compound include organic gallium compounds such as tetraphenylgallium and tetrakis(3,4,5-trifluorophenyl)gallium, and inorganic gallium compounds such as gallium oxoates, gallium halides, gallium hydroxide, and gallium cyanide.

[0089] Examples of indium compounds include organic indium compounds such as triethoxyindium, indium 2-ethylhexanoate, and indium acetylacetonate, and inorganic indium compounds such as indium cyanide, indium nitrate, indium sulfate, indium carbonate, indium fluoride, indium chloride, indium bromide, and indium iodide.

[0090] Examples of arsenic compounds include inorganic arsenic compounds such as diarsenic trioxide, diarsenic pentoxide, arsenic trichloride, arsenic pentachloride, arsenous acid, arsenic acid, and salts thereof such as sodium arsenite, ammonium arsenite, potassium arsenite, ammonium arsenate, and potassium arsenate; and organic arsenic compounds such as cacodylic acid, phenylarsonic acid, diphenylarsonic acid, p-hydroxyphenylarsonic acid, p-aminophenylarsonic acid, and salts thereof such as sodium cacodylate and potassium cacodylate.

[0091] Examples of antimony compounds include inorganic antimony compounds such as antimony oxide, antimony phosphate, KSb(OH) and NH4SbF6, and organic antimony compounds such as antimony esters with organic acids, cyclic alkyl antimonites and triphenylantimony.

[0092] Examples of bismuth compounds include organic bismuth compounds such as triphenylbismuth, bismuth 2-ethylhexanoate, and bismuth acetylacetonate, and inorganic bismuth compounds such as bismuth nitrate, bismuth sulfate, bismuth acetate, bismuth hydroxide, bismuth fluoride, bismuth chloride, bismuth bromide, and bismuth iodide.

[0093] Examples of selenium compounds include organic selenium compounds such as selenomethionine, selenocysteine, and selenocystine, and inorganic selenium compounds including alkali metal selenates such as potassium selenate, and alkali metal selenites such as sodium selenite.

[0094] Examples of tellurium compounds include telluric acid and its salts, tellurium oxide, tellurium chloride, tellurium bromide, tellurium iodide, and tellurium alkoxides.

[0095] Examples of magnesium compounds include organic magnesium compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis(ethyl acetoacetate), alkyl acetoacetate magnesium monoisopropylate, and magnesium bis(acetylacetonate), and inorganic magnesium compounds such as magnesium oxide, magnesium sulfate, magnesium nitrate, and magnesium chloride.

[0096] Examples of calcium compounds include organic calcium compounds such as calcium 2-ethylhexanoate, calcium ethoxide, calcium methoxide, calcium methoxyethoxide, and calcium acetylacetonate, and inorganic calcium compounds such as calcium nitrate, calcium sulfate, calcium carbonate, calcium phosphate, calcium hydroxide, calcium cyanide, calcium fluoride, calcium chloride, calcium bromide, and calcium iodide.

[0097] As the heteroatom compound having a heteroatom of Li, Na, K, Cs, S, Sr, Ba, F, Y, or a lanthanoid, a known organic or inorganic compound can be used.

[0098] The heteroatom compounds may be used alone or in combination of two or more.

[0099] The ratio of the explosive in the mixture containing the explosive and the heteroatom compound is preferably 80 to 99.9999% by mass, more preferably 85 to 99.999% by mass, even more preferably 90 to 99.99% by mass, and particularly preferably 95 to 99.9% by mass. The ratio of the heteroatom compound is preferably 0.0001 to 20% by mass, more preferably 0.001 to 15% by mass, even more preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass. The heteroatom content in the mixture containing the explosive and the heteroatom compound is preferably 0.000005 to 10% by mass, more preferably 0.00001 to 8% by mass, even more preferably 0.0001 to 5% by mass, especially preferably 0.001 to 3% by mass, and most preferably 0.01 to 1% by mass.

[0100] When the explosive and the heteroatom compound are both solid, they may be mixed in powder form, melted, or dissolved or dispersed in a suitable solvent. Mixing may be performed by stirring, bead milling, ultrasonic waves, etc.

[0101] In a preferred embodiment, the explosive composition containing an explosive and a heteroatom compound further contains a cooling medium. The cooling medium may be any of solid, liquid, and gas. As a method using a cooling medium, a method of detonating a mixture of an explosive and a heteroatom compound in a cooling medium can be mentioned. Examples of the cooling medium include an inert gas (nitrogen, argon, CO), water, ice, liquid nitrogen, an aqueous solution of a salt containing a heteroatom, and a crystal hydrate. Examples of the salt containing a heteroatom include ammonium hexafluorosilicate, ammonium silicate, and tetramethylammonium silicate. In the case of water or ice, for example, it is preferable to use about 5 times the weight of the explosive as the cooling medium.

[0102] In one preferred embodiment of the present invention, the mixture containing explosives and heteroatomic compounds is converted into diamond by compression by shock waves under high pressure and high temperature conditions generated by the explosion of explosives (detonation method).During the explosion of explosives, heteroatoms are incorporated into diamond lattice.The carbon source of nanodiamonds can be explosives and organic heteroatomic compounds, but when the mixture containing explosives and heteroatomic compounds further contains carbon material that does not contain heteroatoms, this carbon material can also be the carbon source of nanodiamonds. EXAMPLES

[0103] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 6 By using TNT as the explosive and the dopant shown in Table 1 as the heteroatom compound in the number of moles shown in Table 1 per mole of TNT, and producing silicon-doped nanodiamonds by the conventional detonation method under the temperature (K) and pressure (GPa) conditions shown in Table 1, nanodiamonds doped with silicon in the ratio shown in Table 1 can be obtained.

[0104] The names and structural formulas of dopant molecules (silicon compounds) 1 to 6 used to dope silicon are shown below. Dopant molecule 1: silline Dopant molecule 2: Tetramethylsilane (SiMe4) Dopant molecule 3: Tetrakis(nitratomethyl)silane (SiPETN) Dopant molecule 4: Tetrakis(dimethylsilanolyl)silane (Si(SiMe2OH)4) Dopant molecule 5: Tetrakis(trimethylsilyl)silane (Si(SiMe3)4) Dopant molecule 6: Tetrakis(trimethylsilyl)methane (C(SiMe3)4)

[0105] [ka]

[0106] [Table 1]

[0107] As is clear from Table 1, it is clear that the present invention makes it possible to obtain nanodiamonds having a large number of silicon atoms introduced therein.

[0108] Example 7 Silicon-doped nanodiamonds were produced using approximately 60 g of explosive composition in which 10 parts by mass, 1 part by mass, or 0.1 part by mass of triphenylsilanol was added as a heteroatom compound to 100 parts by mass of explosive containing trinitrotoluene (TNT) and cyclotrimethylenetrinitramine (RDX), according to a conventional method for producing nanodiamonds. The silicon-doped nanodiamonds obtained were subjected to the following treatment. The amount of triphenylsilanol added in the explosive was 10% by mass, 1% by mass, or 0.1% by mass. (i) Mixed acid treatment 15 g of nanodiamonds obtained in the detonation test were added to 2,800 g of mixed acid of concentrated sulfuric acid: concentrated nitric acid = 11:1 (weight ratio), and treated with stirring at 150°C for 10 hours. (ii) Alkaline treatment 1 g of the nanodiamond treated with mixed acid was added to 100 mL of 8N aqueous sodium hydroxide solution and treated at 100°C for 10 hours with stirring. (iii) Annealing The alkaline-treated nanodiamonds were annealed at 800°C for 30 minutes in a vacuum atmosphere. (iv) Gas Phase Oxidation The annealed nanodiamond was subjected to gas phase oxidation treatment at 300°C for 2 hours in an air atmosphere to obtain the silicon-doped nanodiamond of the present invention. (v) Fluorescence analysis A 10 w / v% water suspension of the silicon-doped nanodiamond of the present invention obtained by gas-phase oxidation was dropped onto a glass substrate and dried to prepare an evaluation sample. The obtained evaluation sample was subjected to high-speed mapping using a microscopic Raman spectrometer (product name: Microscopic Laser Raman Spectrophotometer LabRAM HR Evolution, manufactured by Horiba, Ltd.) and 738 nm bright spot imaging was performed. Figure 1(a) shows a 738 nm bright spot image of a silicon-doped nanodiamond obtained using triphenylsilanol as a silicon compound and with an external ratio of 1 mass% added. Figure 1(b) shows the fluorescence spectrum of the bright spot in Figure 1(a). The zero phonon line (fluorescence peak) of the SiV center can be confirmed. The Si content of the obtained silicon-doped nanodiamond was 3.2 mass% when the amount of triphenylsilanol added in the explosive was 10 mass%, 0.15 mass% when it was 1 mass%, and 0.03 mass% when it was 0.1 mass%. From Figure 1 (b), it was confirmed that the silicon-doped nanodiamond of the present invention has 738 nm fluorescence derived from the SiV center. Furthermore, the average size of the primary particles and the BET specific surface area of ​​the obtained silicon-doped nanodiamond measured by XRD are shown in Table 2 below.

[0109] [Table 2]

[0110] -BET specific surface area measurement Equipment: BELSORP-miniII (Microtrack BEL Co., Ltd.) Measured powder amount: 40mg Pre-drying: 120℃, vacuum treatment for 3 hours Measurement temperature: -196℃ (liquid nitrogen temperature) -Measurement of the average size of primary particles (X-ray powder diffraction method (XRD)) Equipment: Fully automated multipurpose X-ray diffraction equipment (Rigaku Corporation) ·Measuring method for Si incorporation amount (XRF) Equipment: X-ray fluorescence analyzer ZSX Primus IV manufactured by Rigaku Corporation

[0111] 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 is used instead of 1 part by mass of triphenylsilanol in Example 7.

[0112] Example 9 Phosphorus-doped nanodiamonds can be obtained in the same manner as in Example 7, except that 1 part by mass of triphenylphosphine is used instead of 1 part by mass of triphenylsilanol in Example 7.

[0113] 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) is used instead of 1 part by mass of triphenylsilanol in Example 7.

[0114] Example 11 Nanodiamonds doped with silicon and boron can be obtained 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 are used instead of 1 part by mass of triphenylsilanol in Example 7.

[0115] Example 12 Nanodiamonds doped with silicon and phosphorus can be obtained 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 are used instead of 1 part by mass of triphenylsilanol in Example 7.

Claims

1. The following (i) and / or (ii) doped with at least one heteroatom: (i) BET specific surface area between 20 and 900 m 2 / g, (ii) the average size of the primary particles is between 2 and 70 nm; A heteroatom doped nanodiamond that meets the requirements.

2. The heteroatom-doped nanodiamond of claim 1, wherein the heteroatom comprises at least one selected from the group consisting of group 14 elements, phosphorus and boron.

3. The heteroatom-doped nanodiamond according to claim 1 or 2, having a fluorescence emission peak.

4. The heteroatom-doped nanodiamond according to any one of claims 1 to 3, wherein the fluorescence emission peak is derived from at least one heteroatom-Vacancy center.

5. The heteroatom-doped nanodiamond according to any one of claims 1 to 4, wherein the fluorescent heteroatom-doped nanodiamond is further doped with phosphorus and / or boron.

6. The heteroatom-doped nanodiamond according to any one of claims 1 to 5, having a fluorescence emission peak in the range of 720 to 770 nm, and the heteroatom includes silicon.

7. The heteroatom-doped nanodiamond according to any one of claims 1 to 5, having a fluorescence emission peak in the range of 580 to 630 nm, and the heteroatom includes germanium.

8. The heteroatom-doped nanodiamond according to any one of claims 1 to 5, having a fluorescence emission peak in the range of 590 to 650 nm, and the heteroatom includes tin.

9. The nanodiamond according to any one of claims 1 to 5, having a fluorescence emission peak in the range of 540 to 600 nm and containing lead as a foreign atom.

10. The heteroatom-doped nanodiamond according to any one of claims 1 to 9, comprising fluorescent emission due to a nitrogen-vacancy (NV) center.

11. The heteroatom-doped nanodiamond according to any one of claims 1 to 10, wherein the nanodiamond has a spherical, ellipsoidal or polyhedral shape.

12. A heteroatom-doped nanodiamond according to any one of claims 1 to 11, having a carbon content of 70 to 99 mass%, a hydrogen content of 0.1 to 5 mass%, and a nitrogen content of 0.1 to 5 mass%.

13. The heteroatom-doped nanodiamond according to any one of claims 1 to 12, wherein the ratio (D / G) of the diamond peak area (D) to the graphite peak area (G) in Raman spectroscopy is 0.2 to 9.

14. The heteroatom-doped nanodiamond according to any one of claims 1 to 13, wherein the ratio (H / D) of the peak area (H) of the surface hydroxyl group (OH) to the peak area (D) of the diamond in Raman spectroscopy is 0.1 to 5.

15. The heteroatom-doped nanodiamond according to any one of claims 1 to 14, wherein the ratio (C / D) of the peak area (C) of the surface carbonyl group (CO) to the peak area (D) of the diamond in Raman spectroscopy is 0.01 to 1.

5.

16. The heteroatom-doped nanodiamond according to any one of claims 1 to 15, having at least one oxygen-containing functional group end and / or at least one hydrogen-containing functional group end.

17. At least one heteroatom - Vacancy center with a concentration of 1×10 10 / cm 3 The heteroatom-doped nanodiamond according to any one of claims 1 to 16.

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