CN113694830A - Nitrogen-doped diamond and synthetic method thereof - Google Patents
Nitrogen-doped diamond and synthetic method thereofDownload PDFInfo
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Abstract
Translated fromChinese
Description
Technical Field
The application relates to the technical field of synthesis of diamond crystals, in particular to a nitrogen-doped diamond and a synthesis method thereof.
Background
Diamond (element composition C) is the hardest naturally occurring substance, has strong corrosion resistance and thermal conductivity up to 2000W/(m.K), and is widely used as a cutting knifeMaterials such as a protective film and a heat sink. Carbon atoms in diamond in sp3Hybrid mode of bonding, C-C bond length
The included angle between the keys is 109 degrees and 28 degrees, the directivity is strong, and the Bravais lattice is of a face-centered cubic structure. Among the existing major techniques for manufacturing diamond, the main manufacturing methods are Chemical Vapor Deposition (CVD) and High Temperature and High Pressure (HTHP).
Among them, the CVD method has the advantages that the reaction can be carried out at a temperature far lower than the melting point of carbon, the purity of the obtained product is extremely high, but the crystal growth speed is slow, the production efficiency is low, the requirement on the device is high, and the method is not easy to popularize and prepare in a large scale. The HTHP method has the advantages of high automation degree, higher synthesis efficiency than the CVD method, relatively lower cost and suitability for mass production.
The prior HTHP process typically uses a catalyst to convert graphite to diamond. However, this method tends to introduce catalyst atoms into the diamond lattice during growth, causing defects in the diamond crystal.
Disclosure of Invention
It has been found that the catalyst is generally a metal of face-centered cubic structure such as iron, cobalt, nickel or an alloy thereof, that the catalyst in a molten or semi-molten state initially dissolves graphite in the contact region, and that electrons from carbon atoms are guided from sp by the corresponding closely-packed surfaces2Pi state to sp3The state is changed, nucleation is separated out after the catalyst crystal lattice or the diamond seed crystal reaches the supersaturation state, and then the catalyst atom grows gradually, so that the catalyst atom is introduced into the diamond crystal lattice in the growth process to cause the defect of the diamond crystal.
Aiming at the defects of the prior art, the embodiment of the application provides the nitrogen-doped diamond and the synthesis method thereof, and the nitrogen-doped diamond is prepared by matching a high-temperature high-pressure method and a platinum tube without adding a catalyst.
In a first aspect, embodiments of the present application provide a method for synthesizing nitrogen-doped diamond, including: mixing adamantane, at least one of C22-C25 alkane and nitrogen-containing heterocyclic organic compound to obtain a mixture. And pre-pressing the mixture into a prefabricated blank body. And (3) placing the prefabricated blank body in a metal platinum container, enabling the surface of the prefabricated blank body to be in contact with the inner wall of the metal platinum container, and carrying out high-temperature high-pressure treatment for at least 20min under the conditions that the temperature is not lower than 900 ℃ and the pressure is not lower than 10 GPa.
Placing the prefabricated ligand in a platinum container for high-temperature and high-pressure reaction, selecting an organic matter (adamantane) with a diamond-like structure as a starting point of diamond growth, matching with platinum under the conditions that the temperature is not lower than 900 ℃ and the pressure is not lower than 10GPa, dehydrogenating C22-C25 alkane to form an unsaturated C bond, wherein the unsaturated C bond tends to approach amantadine, and supplementing a nitrogen source through a nitrogen-containing heterocyclic organic compound to ensure that nitrogen elements are uniformly doped in the finally obtained diamond crystal to obtain the nitrogen-doped diamond. And platinum has very high melting point and good chemical stability, and can not be introduced into diamond crystal lattices, so that other impurity elements can be prevented from being introduced into the diamond crystals. In the application, the nitrogen-doped diamond can be prepared by matching an organic matter with a platinum tube by a high-temperature high-pressure method without adding a catalyst.
In some embodiments herein, the adamantane is amantadine; the nitrogen-containing heterocyclic organic compound is triazine nitrogen-containing heterocyclic organic matter; the C22-C25 alkane is n-tetracosane. The three organic matters are selected as raw materials to prepare the nitrogen-doped diamond, so that the preparation conditions are easier to achieve, and the synthesis time is shortened.
In some embodiments of the present application, the triazine nitrogen-containing heterocyclic organic compound is melamine.
In some examples of the application, the mass ratio of amantadine to tetracosan to melamine is 5 (1-2) to (0.5-1) in sequence. This ratio may result in more uniform nitrogen doping in the diamond crystal.
In some embodiments of the present application, the preform is processed at a temperature of 1000-1200 deg.C and a pressure of 11-20GPa for 20-80 min. The preparation of the nitrogen-doped diamond under the condition can ensure that the yield is higher and the nitrogen doping is more uniform.
In some examples of the present application, a mixture of a C22-C25 alkane and a nitrogen-containing heterocyclic organic compound is dissolved in a solvent, then dried, then mixed with amantadine, milled in a solvent, and dried to obtain a mixture. The raw materials can be mixed more uniformly.
In some embodiments of the present application, the high temperature and high pressure treatment is performed in a multi-facer press. The multi-aspect press is easy to form a high-temperature and high-pressure environment so as to prepare the nitrogen-doped diamond.
In some embodiments of the present application, after the high temperature and high pressure treatment, the method further comprises reducing the temperature and releasing the pressure, removing the synthesized product, and subjecting the synthesized product to ultrasonic cleaning. Through the mode of ultrasonic cleaning separation, can clear away the impurity in the diamond of nitrogen doping, obtain more pure diamond of nitrogen doping.
In some embodiments of the present application, the pre-pressing is performed for 1-5min under a pressure chamber of 1-30 MPa.
In a second aspect, embodiments of the present application provide a nitrogen-doped diamond synthesized by the above-described method for synthesizing a nitrogen-doped diamond. The diamond crystal of the nitrogen-doped diamond is relatively uniformly doped with nitrogen elements.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a process flow diagram of a method for synthesizing nitrogen-doped diamond according to an embodiment of the present disclosure;
fig. 2 is a cross-sectional view of a high-pressure composite block of a double-sided press according to an embodiment of the present invention;
FIG. 3 is a photograph under an optical microscope of a synthetic product provided herein;
FIG. 4 is a Raman spectrum characterization chart of the synthesized product;
FIG. 5 is a photograph under a scanning electron microscope of a synthetic product provided herein;
FIG. 6 is a PL spectral test chart of a synthesized product provided in example 3 of the present application after electron irradiation and annealing treatment.
Icon: 110-magnesium oxide octahedra; 120-zirconium dioxide round tubes; 131-tantalum round tubes; 132-tantalum wafer; 140-zirconium dioxide plugs; 151-hexagonal boron nitride round tube; 152-hexagonal boron nitride wafer; 161-metal platinum round tubes; 162-a platinum metal disc; 210-preform body.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the present application are described below clearly and completely.
Fig. 1 is a process flow chart of a method for synthesizing nitrogen-doped diamond according to this embodiment. Referring to fig. 1, the present application provides a method for synthesizing a nitrogen-doped diamond, comprising the following steps:
s110, mixing at least one of adamantane and C22-C25 alkane and a nitrogen-containing heterocyclic organic compound to obtain a mixture.
Wherein, the adamantane can be one or more of amantadine, adamantane and diamantane; the heterocyclic nitrogen-containing organic compound may be melamine. The alkane may be one or more of didodecane, tricosane, tetracosane, and pentacosane; the number of branches in the alkane is not limited in this application, and may be unbranched or branched, such as: the alkane may be n-alkane, iso-alkane, neoalkane, etc., and the present application is not limited thereto. Optionally, the mass ratio of the adamantane, the C22-C25 alkane and the nitrogen-containing heterocyclic organic compound is 5 (1-2) to 0.5-1 in sequence.
In the application, the adamantane is amantadine, the alkane is n-tetracosan, and the nitrogen-containing heterocyclic organic compound is triazine nitrogen-containing heterocyclic organic matter. The preparation of the nitrogen-doped diamond by selecting amantadine, n-tetracosan and triazine nitrogen-containing heterocyclic organic compounds can enable the preparation conditions to be more easily achieved and shorten the synthesis time. Optionally, the triazine nitrogen-containing heterocyclic organic compound is melamine.
Optionally, the mass ratio of the amantadine to the tetracosane to the melamine is 5 (1-2) to (0.5-1) in sequence. Illustratively, the mass ratio of amantadine, n-tetracosan and melamine is 5:1:0.5, 5:2:0.5, 5:1.5:0.5, 5:1:0.8, 5:2:0.8, 5:1.5:0.8, 5:1:1, 5:2:1 or 5:1.5:1, in that order.
The three raw materials can be placed in a solvent for mixing in a magnetic stirring mode, so that the mixture is more uniform. Optionally, dissolving the mixture of C22-C25 alkane and nitrogen heterocycle organic in a solvent (such as ethanol) (such as magnetic stirring and mixing), and drying after fully dissolving; then mixing it with amantadine and grinding in solvent (such as ethanol) to form suspension, and drying to obtain mixed powder.
And S120, pre-pressing the mixture into a prefabricated blank body. Optionally, the pre-pressing is carried out for 1-5min under the condition that the pressure cavity is 1-30 MPa.
Optionally, the pre-pressing pressure is 1-10MPa, or the pre-pressing pressure is 10-20MPa, or the pre-pressing pressure is 20-30 MPa. Illustratively, the pre-pressing pressure is 1MPa, 5MPa, 10MPa15MPa, 20MPa, 25MPa or 30 MPa; the pre-pressing time can be 1min, 2min, 3min, 4min or 5 min.
It should be noted that: the shape of the preform body is not limited as long as it can be fitted to the shape of the sample chamber in the apparatus to be subsequently subjected to high-temperature high-pressure treatment.
S130, placing the prefabricated blank body in a metal platinum container, enabling the surface of the prefabricated blank body to be in contact with the inner wall of the metal platinum container, and carrying out high-temperature high-pressure treatment for at least 20min under the conditions that the temperature is not lower than 900 ℃ and the pressure is not lower than 10 GPa. Optionally, the prefabricated blank body is processed for 20-80min under the conditions that the temperature is 1000-1200 ℃ and the pressure is 11-20 GPa.
Illustratively, the temperature of the high-temperature high-pressure treatment is 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃ or 1400 ℃; the pressure of the high-temperature high-pressure treatment is 10GPa, 11GPa, 12GPa, 14GPa, 16GPa, 18GPa, 20GPa, 22GPa or 24 GPa.
In the application, the high-temperature and high-pressure treatment is carried out in a multi-aspect top press, the prefabricated blank is firstly placed in the high-pressure synthetic block, and then the high-pressure synthetic block is placed in a synthetic cavity of the multi-aspect top press for high-temperature and high-pressure treatment.
Alternatively, the multi-face press may be a two-face press, a four-face press, a cubic press, or a octahedral press, etc., and the present application is not limited thereto, as long as the equipment capable of providing the corresponding pressure and temperature is within the scope of the present application.
Fig. 2 is a cross-sectional view of a high pressure composite block of a double-faced press provided by the present application. Referring to fig. 2, the metal platinum container is a metal platinum tube (for example, a metal platinum round tube 161), the high-pressure synthesis block includes amagnesium oxide octahedron 110, a zirconiumdioxide round tube 120, atantalum round tube 131,tantalum wafers 132 disposed at two ends of thetantalum round tube 131, two zirconium dioxide plugs 140, a hexagonal boronnitride round tube 151, hexagonalboron nitride wafers 152 disposed at two ends of the hexagonal boronnitride round tube 151, the metalplatinum round tube 161, andmetal platinum wafers 162 disposed at two ends of the metalplatinum round tube 161, the sample cavity in the metalplatinum round tube 161 is used for accommodating thecylindrical preform 210.
The placing method of thepreform body 210 may be: putting the pressed cylinder prefabricated blank 210 into a metalplatinum round tube 161, wherein the upper end and the lower end of the metalplatinum round tube 161 are sealed by ametal platinum wafer 162; then placing the hexagonal boronnitride round tube 151 into the hexagonal boronnitride round tube 151, and sealing the upper end and the lower end of the hexagonal boronnitride round tube 151 with a hexagonalboron nitride wafer 152; then, the tantalum tube is placed into thetantalum tube 131, zirconium dioxide plugs 140 are respectively added to the two ends of the tantalum tube, and the upper and lower ports are sealed by thetantalum wafer 132. And then putting the blank into the zirconiumdioxide round tube 120 and themagnesium oxide octahedron 110 in sequence to realize the installation of the prefabricatedblank body 210. After the installation is finished, high-temperature and high-pressure treatment is carried out through a two-side jacking machine.
And S140, after the high-temperature high-pressure treatment is finished, cooling and releasing pressure, taking out the synthesized product, and carrying out ultrasonic cleaning on the synthesized product. Optionally, the synthetic product is put into a mortar, a small amount of alcohol is added for grinding, then the synthetic product is collected into a small plastic tube, the plastic tube is put into an ultrasonic machine for dispersion treatment, then the plastic tube is taken out and the liquid is evaporated to dryness, impurities are removed by clamping and picking with tweezers, fine needles and the like, and finally pure nitrogen-doped diamond powder is collected and the rest part is pure.
Through the mode of ultrasonic cleaning separation, can clear away some impurity in the diamond of nitrogen doping, obtain more pure diamond of nitrogen doping, can further get rid of impurity if carry out suitable pickling.
In the application, an organic matter (adamantane) with a diamond-like structure is selected as a starting point of diamond growth, the organic matter is matched with platinum under the conditions that the temperature is not lower than 900 ℃ and the pressure is not lower than 10GPa, C22-C25 alkane is dehydrogenated to form an unsaturated C bond, the unsaturated C bond tends to approach amantadine, and a nitrogen source is supplemented by a nitrogen-containing heterocyclic organic compound, so that nitrogen elements are uniformly doped in finally obtained diamond crystals, and the nitrogen-doped diamond is obtained. And platinum has very high melting point and excellent chemical stability, and can not be introduced into diamond crystal lattices, so that other impurity elements can be prevented from being introduced into the diamond crystals. In the application, the nitrogen-doped diamond can be prepared by matching an organic matter with a platinum tube by a high-temperature high-pressure method without adding a catalyst.
The mass ratio of amantadine to tetracosan to melamine is 5 (1-2) to (0.5-1) in sequence, and the preparation conditions can be more easily achieved and the synthesis time can be shortened by using the compound to prepare the nitrogen-doped diamond; and the doping of the nitrogen atoms is more uniform.
By the synthesis method, the finally obtained diamond crystal is uniformly doped with nitrogen elements, so that the nitrogen-doped diamond is obtained.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment provides a method for synthesizing nitrogen-doped diamond, which comprises the following steps:
(1) taking amantadine, tetracosan and melamine with the mass ratio of 5:2:1 in sequence as raw materials; and (2) placing the tetracosane and the melamine in a glass beaker, adding an ethanol solvent, stirring the solution by using a magnetic stirrer (the rotating speed is 200r/min), taking out the beaker after the solid is fully dissolved, and placing the beaker in an oven for drying. Pouring the obtained solid powder into a mortar, mixing the obtained solid powder with the amantadine, pouring a small amount of alcohol to form a suspension, grinding to accelerate alcohol volatilization, and drying in an oven again after almost no liquid is seen to obtain a mixture for later use.
(2) And placing the ground mixture into a die, and pressing for 4min under the condition that the pressure is 5MPa to obtain a cylindrical blank.
(3) Putting the cylindrical blank into a metal platinum round tube, and sealing the upper end and the lower end of the metal platinum round tube by using a metal platinum wafer; then placing the hexagonal boron nitride round tube into a hexagonal boron nitride round tube, wherein the upper end and the lower end of the hexagonal boron nitride round tube are sealed by hexagonal boron nitride wafers; then the tantalum round tube is placed into the tantalum round tube, zirconium dioxide plugs are respectively added at two ends of the tantalum round tube, and the upper end port and the lower end port are sealed by the tantalum round plate. Then putting the zirconium dioxide round tube and the magnesium oxide octahedron in sequence. And carrying out heat preservation and pressure maintaining treatment for 30min under the conditions that the temperature is 1000 ℃ and the pressure is 11 GPa.
(4) The pressure relief and temperature reduction are carried out, the synthesized product is taken out, a small amount of alcohol is added into the mortar for grinding, then the synthesized product is collected into a small plastic pipe, the small plastic pipe is placed into an ultrasonic machine for dispersion treatment, then the synthesized product is taken out and the liquid is evaporated to dryness, impurities are removed by clamping and picking with tweezers, fine needles and the like, and finally pure nitrogen-doped diamond powder is collected.
Example 2
Example 2 differs from example 1 in that: the mass ratio of the amantadine to the tetracosane to the melamine is 5:1:1 in sequence. The other method has consistent processing steps.
Example 3
Example 3 differs from example 2 in that: the time for heat preservation and pressure maintaining is 70 min. The other method has consistent processing steps.
Example 4
Example 4 differs from example 2 in that: the time for heat preservation and pressure maintaining is 80 min. The other method has consistent processing steps.
Example 5
Example 5 differs from example 2 in that: and carrying out heat preservation and pressure maintaining treatment for 20min under the conditions that the temperature is 1200 ℃ and the pressure is 11 GPa. The other method has consistent processing steps.
Example 6
Example 6 differs from example 2 in that: the amantadine was replaced by adamantane.
Example 7
Example 7 differs from example 2 in that: n-tetracosan is replaced by n-tricosane.
Comparative example 1
Comparative example 1 differs from example 2 in that: in the raw materials, the mass ratio of amantadine to formaldehyde to aniline is 5:1:1.5 in sequence.
A certain amount of formaldehyde solution is taken out by using a liquid transfer gun and is placed in a glass beaker, the glass beaker is stirred by using a magnetic stirrer (the rotating speed is 200r/min), and then aniline is dripped into the formaldehyde solution by using the liquid transfer gun, wherein the volume ratio is 1: 1.5. The beaker is placed in a water bath, and the solution is heated in a water bath by the heating function of a magnetic stirrer, wherein the temperature is 90 ℃, and the stirring operation is kept during the period. Along with the reaction, the system will gradually form a light yellow hard colloidal solid (aniline-formaldehyde resin), when the light yellow hard colloidal solid is not increased basically, the heating is stopped, the solid is taken out and placed in a mortar, a certain amount of amantadine is taken out and mixed with the solid, a small amount of alcohol is poured to form suspension, then grinding is started to accelerate alcohol volatilization, and the suspension is placed in an oven to be dried again after almost no liquid is seen, so that a mixture is obtained for later use.
The other method has consistent processing steps.
Comparative example 2
Comparative example 2 differs from example 2 in that: in the raw materials, the mass ratio of the amantadine to the p-aminobenzoic acid is 5:2 in sequence.
Taking a certain amount of p-aminobenzoic acid out, placing the p-aminobenzoic acid in a glass beaker, placing a rotor, dripping sufficient ethanol solution, stirring the solution by using a magnetic stirrer (the rotating speed is 200r/min), then placing the beaker in a water bath, and heating the solution in a water bath by the heating function of the magnetic stirrer, wherein the temperature is 90 ℃, and the stirring operation is kept during the period. Stopping heating after a period of time, taking out the beaker, and drying the beaker in an oven at 60 ℃. And cooling to room temperature after drying, pouring the obtained solid powder into a mortar, taking out a certain amount of amantadine, mixing the amantadine with the solid powder, pouring a small amount of alcohol to form suspension, grinding to accelerate alcohol volatilization, and putting the mixture into an oven to be dried again after almost no liquid is seen, so as to obtain a mixture for later use.
The other method has consistent processing steps.
Comparative example 3
Comparative example 3 differs from example 2 in that: and performing heat preservation and pressure maintaining treatment for 120min under the conditions that the temperature is 800 ℃ and the pressure is 11 GPa. The other method has consistent processing steps.
Comparative example 4
Comparative example 4 differs from example 2 in that: and performing heat preservation and pressure maintaining treatment for 120min under the conditions that the temperature is 1400 ℃ and the pressure is 5 GPa. The other method has consistent processing steps.
Comparative example 5
Comparative example 5 differs from example 2 in that: and replacing the platinum round tube and the platinum round sheet in the high-pressure synthesis block with a steel round tube and a steel round sheet.
Comparative example 6
Comparative example 2 differs from example 2 in that: putting the cylindrical blank into a hexagonal boron nitride circular tube, and sealing the upper end and the lower end of the hexagonal boron nitride circular tube by using a hexagonal boron nitride wafer; then the tantalum round tube is placed into the tantalum round tube, zirconium dioxide plugs are respectively added at two ends of the tantalum round tube, and the upper end port and the lower end port are sealed by the tantalum round plate. Then putting the zirconium dioxide round tube and the magnesium oxide octahedron in sequence. And carrying out heat preservation and pressure maintaining treatment for 30min under the conditions that the temperature is 1000 ℃ and the pressure is 11 GPa.
Test example 1
The conditions for preparing the nitrogen-doped diamond and the results of the preparation provided in examples 1 to 7 and comparative examples 1 to 6 are shown in table 1.
TABLE 1 preparation conditions and results of nitrogen-doped diamond
As can be seen from table 1, in comparative example 1 (raw materials of amantadine, formaldehyde and aniline) and comparative example 2 (raw materials of amantadine and p-aminobenzoic acid), if the organic material is not selected from specific raw materials (adamantane, C22-C25 alkane and nitrogen-containing heterocyclic organic compound), the treatment under the conditions of high temperature and high pressure does not give nitrogen-doped diamond crystals.
Comparative example 3 (temperature 800 deg.c) and comparative example 4 (pressure 5GPa) it can be seen that the raw materials provided herein (adamantanes, C22-C25 alkanes and nitrogen-containing heterocyclic organic compounds) were selected for the preparation of nitrogen-doped diamond crystals, and if the temperature of the high-temperature high-pressure treatment was too low, nitrogen-doped diamond crystals could not be obtained.
Comparative examples 5 and 6 it can be seen that if the preform body is subjected to high temperature and high pressure treatment in a steel tube (comparative example 5) or a hexagonal boron nitride tube (comparative example 6), nitrogen-doped diamond crystals cannot be obtained.
Examples 1-7 it can be seen that nitrogen doped diamond crystals can be prepared by placing a preform in a platinum metal container and combining the preform with a high temperature and pressure treatment.
Test example 2
Fig. 3 is a photograph under an optical microscope of a synthetic product provided herein. Wherein, the picture (a) in fig. 3 is a photo of the synthesized product provided in example 2 under an optical microscope; the picture (b) in fig. 3 is a photograph under an optical microscope of the synthesized product provided in example 3. As can be seen from fig. 3, the pictures (a) and (b) in fig. 3 both have glitter portions, which are very similar to the optical characteristics of diamond, and it can be inferred that the method provided by the present application can produce diamond crystals; and the content of the flash part in the picture (b) in fig. 3 is higher, it can be estimated that more diamond crystals are obtained, which indicates that the time of the high-temperature high-pressure treatment is prolonged, and more diamond crystals can be obtained.
FIG. 4 is a Raman spectrum characterization chart of the synthesized product. Wherein, the picture (a) in fig. 4 is a raman spectrum characterization chart of the synthetic product provided in comparative example 3; the picture (b) in fig. 4 is a raman spectrum characterization chart of the synthetic product provided in example 2; the graph (c) in fig. 4 is a raman spectrum characterization graph of the synthetic product provided in example 3; the graph (d) in fig. 4 is a raman spectrum characterization graph of the synthetic product provided in example 5; the graph (e) in fig. 4 is a raman spectrum characterization chart of the single crystal diamond. As can be seen from fig. 4, examples 2, 3 and 5 provided synthetic products having characteristic peaks of diamond, indicating that diamond crystals were obtained. Comparative example 1 provided a synthesized product having no characteristic peak of diamond, indicating that no diamond crystal was obtained. The full width at half maximum of the diamond characteristic peak of the picture (c) in fig. 4 is smaller than that of the diamond characteristic peak of the picture (b) in fig. 4; and the full width at half maximum of the characteristic diamond peak in the graph (b) in fig. 4 is smaller than that in the graph (d) in fig. 4, it is demonstrated that the degree of crystallinity of the diamond crystal is higher in the synthesized product provided in example 3.
Fig. 5 is a photograph under a scanning electron microscope of a synthetic product provided herein. Wherein, the picture (a) in fig. 5 is a photograph of the synthesized product provided in example 2 under a scanning electron microscope; the picture (b) in fig. 5 is a photograph under a scanning electron microscope of the synthesized product provided in example 3. As can be seen from fig. 5, the partially regular grains with the size of micrometer scale can be seen in both the picture (a) in fig. 5 and the picture (b) in fig. 5. The shape of the crystal grains appearing in the picture (a) in fig. 5 is not very regular, and the surface thereof is also stained with finer powder, and it can be presumed that the raw material is not completely converted into diamond crystals. The picture (b) in fig. 5 shows more regular grains, mostly octahedral structures of typical diamond crystals, and the {111} crystal face family is exposed at the outermost. Under the condition of the same experimental temperature (1000 ℃), the heat preservation time is prolonged by 40min, the shape of diamond grains in the product becomes very regular, the diamond grains are basically consistent with the octahedral structure of common artificial diamond, and no unreacted part is found, which shows that the heat preservation time is prolonged at the temperature to play an important role in synthesizing high-quality grains.
Test example 3
The synthetic product provided in example 3 was subjected to irradiation treatment under the following conditions: the irradiation dose is 700kGy, the irradiation voltage is 300kV, and the irradiation time is one week; then carrying out annealing treatment on the alloy, wherein the annealing conditions are as follows: vacuum annealing at 1000 deg.C with vacuum degree of 10-3Pa, and the time is 2 h. Then, the PL spectrum was measured, and a PL spectrum test pattern was obtained as shown in FIG. 6. It can be seen from fig. 6 that although there are defect levels in the sample, possibly due to incomplete removal of impurities, resulting in a poor line smoothness, the corresponding NV's consistent with this figure can still be found in repeated tests0PL characteristic peaks of a color center (575nm) and an NV-color center (638nm) show that the high-temperature high-pressure synthesis method successfully synthesizes the nitrogen-containing diamond and contains a large amount of NV0And NV-Color center, which shows that the nitrogen doping effect is better.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (10)
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