Method for manufacturing material having nitrogen-vacancy complex defect, manufacturing device, manufacturing program, and material having nitrogen-vacancy complex defect

Abstract

The present invention implements a method for manufacturing a material having a nitrogen-vacancy (NV) center with a higher NV center concentration. This method is for manufacturing a material having a heteroelement-vacancy complex defect and includes: a preparation step for preparing a material that includes a heteroelement as an impurity; an electron beam irradiation step for irradiating the material with an electron beam to form vacancies in the material; and a heat treatment step for heating the electron beam-irradiated material to form a heteroelement-vacancy complex defect in the material. The electron beam irradiation step and the heat treatment step are repeated alternately two or more times.

Description

Method for manufacturing a material having nitrogen-vacancy complex defects, manufacturing apparatus, manufacturing program, and material having nitrogen-vacancy complex defects

[0001] The present invention relates to a method for producing a material having a nitrogen-vacancy complex defect, a production apparatus, a production program, and a material having a nitrogen-vacancy complex defect.

[0002] Development of sensors using nitrogen-vacancy complex defects (hereinafter also referred to as "NV centers") is underway. For example, diamonds containing NV centers can be used to measure temperature, pH, electric fields, magnetic fields, and the like.

[0003] Non-Patent Document 1 discloses a technique for forming NV centers in synthetic diamond by irradiating the synthetic diamond with an electron beam.

[0004] Shames, Alexander I., et al. Fluence-dependent evolution of paramagnetic triplet centers in e-beam irradiated microcrystalline Ib type HPHT diamond. The Journal of Physical Chemistry C, 2017, 121.40: 22335-22346.

[0005] However, the concentration of NV centers formed by this technique is not necessarily sufficient. Although the concentration of NV centers increases with increasing electron beam irradiation dose, the increase tends to plateau (see Figure 4 in Non-Patent Document 1). One aspect of the present invention aims to realize a method for producing a material having NV centers with a high concentration of heteroelement-vacancy complex defects by suppressing the accumulation and increase of significant defects and strain in the material.

[0006] In order to solve the above-mentioned problems, a manufacturing method according to one aspect of the present invention is a method for manufacturing a material having a hetero element-vacancy complex defect, and includes: a preparation step of preparing a material containing a hetero element as an impurity; an electron beam irradiation step of irradiating the material with an electron beam to form vacancies in the material; and a heat treatment step of heating the material irradiated with the electron beam to form nitrogen-vacancy complex defects in the material, wherein the electron beam irradiation step and the heat treatment step are repeated alternately two or more times.

[0007] According to one aspect of the present invention, it is possible to realize a method for producing a material having an NV center in which a high concentration of hetero element-vacancy complex defects is achieved while suppressing the accumulation and increase of significant defects and strain in the material.

[0008] 1 is a diagram showing the configuration of a manufacturing apparatus according to one embodiment of the present invention; FIG. 2 is a flow chart showing an example of a manufacturing process according to one embodiment of the present invention; FIG. 3 is a schematic enlarged view showing an example of a material used in the manufacturing process according to one embodiment of the present invention; FIG. 4 is a diagram showing the fluorescence spectrum of a material manufactured by the manufacturing process according to Example 1; FIG. 5 is a diagram showing the relationship between the fluorescence intensity of a material manufactured by the manufacturing process according to Example 1 and the total electron irradiation dose; FIG. 6 is a diagram showing the fluorescence spectrum of a material manufactured by the manufacturing process according to Example 2; FIG. 7 is a diagram showing the relationship between the fluorescence intensity of a material manufactured by the manufacturing process according to Example 2 and the total electron irradiation dose; FIG. 8 is a diagram showing an ODMR measurement apparatus; FIG. 9 is a diagram showing the ODMR measurement results of a material manufactured by the manufacturing process according to Example 2; FIG. 10 is a diagram showing the relationship between the contrast of an ODMR signal of a material manufactured by the manufacturing process according to Example 2 and the total electron irradiation dose; FIG. 11 is a diagram showing the relationship between the fluorescence intensity and contrast of an ODMR signal of a material manufactured by the manufacturing process according to Example 2 and the total electron irradiation dose;

[0009] An embodiment of the present invention will be described in detail below with reference to FIG. 1 . FIG. 1 is a diagram showing the configuration of a manufacturing apparatus 10 according to an embodiment of the present invention. The manufacturing apparatus 10 has a mounting unit 11, an electron beam irradiation unit 12, a heat treatment unit 13, and a control unit 14, and forms heteroelement-vacancy complex defects (e.g., nitrogen-vacancy complex defects: NV centers) in a material M. A heteroelement refers to an element other than carbon and hydrogen, such as nitrogen (N), silicon (Si), or germanium (Ge). In other words, examples of heteroelement-vacancy complex defects include nitrogen-vacancy complex defects (NV centers), silicon-vacancy complex defects (SiV centers), and germanium-vacancy complex defects (GeV centers).

[0010] The material M is a material containing a hetero element (for example, nitrogen) as an impurity, such as synthetic diamond, for example, fine particles of synthetic diamond. Synthetic diamond can be produced, for example, by high-pressure high-temperature deposition (HPHT), chemical vapor deposition (CVD), or detonation deposition, and it is relatively easy to control the impurity composition, concentration, crystal distortion, size, shape, etc. Synthetic diamond contains nitrogen as an impurity at a concentration of, for example, about 100 ppm. The following description will be given using nitrogen as an example of a hetero element, but a material containing a SiV center or a GeV center may also be produced using the material M containing a hetero element other than nitrogen, for example, silicon or germanium, as an impurity.

[0011] The synthetic diamond particles have a roughly crushed stone shape (shape like crushed stone) with a diameter of, for example, about 5 nm to about 1000 nm (for example, 50 nm).

[0012] The mounting unit 11 is a table on which the material M is placed when the material M is irradiated with the electron beam EB. When the electron beam irradiation is performed at room temperature (e.g., room temperature), the mounting unit 11 can function as a cooling table, using its heat capacity, to cool the material M that is heated by the electron beam irradiation.

[0013] The mounting portion 11 is preferably conductive to prevent charging due to irradiation with the electron beam EB. The material M is mounted on the mounting portion 11 directly or indirectly via a conductive boat or the like. When the material M is fine particles (powder), the material M is preferably wrapped in a thin film (e.g., aluminum foil) of a conductive material such as aluminum, platinum, or gold and then mounted on the mounting portion 11. This is to prevent the material M from scattering.

[0014] The electron beam irradiation unit 12 accelerates electrons and irradiates the electron beam EB onto the material M. For example, the electrons are accelerated to 2 MeV, and irradiated with an electron current of 6 mA at a time of, for example, 1*10 １7 ~1*10 １９ cm －２ The electrons are irradiated with a dose of .

[0015] The heat treatment section 13 holds the material M after the electron beam EB irradiation in an internal space, here, a heat-resistant tube CT (e.g., an alumina tube), and performs heat treatment. At this time, the material M is held in a heat-resistant container, for example, an alumina port, and is held in the internal space of the heat treatment section 13.

[0016] The manufacturing apparatus 10 may have a camera for checking the material M, and a manipulator for placing the material M on the mounting section 11 and moving the material M irradiated with the electron beam from the mounting section 11 to the heat treatment section 13.

[0017] The control unit 14 includes a processor 141, a primary memory 142, a secondary memory 143, an input / output interface 144, and a bus 145. The processor 141, the primary memory 142, the secondary memory 143, and the input / output interface 144 are connected to each other via the bus 145.

[0018] A manufacturing program P1 is stored (non-volatilely stored) in the secondary memory 143. The processor 141 loads the manufacturing program P1 stored in the secondary memory 143 onto the primary memory 142. The processor 141 then controls the electron beam irradiation unit 12 and the heat treatment unit 13 (and the manipulator in some cases) in accordance with instructions contained in the manufacturing program P1 loaded onto the primary memory 142, thereby executing each step (steps S12, S13, and S14) included in the manufacturing process described below.

[0019] An example of a device that can be used as the processor 141 is a CPU (Central Processing Unit). An example of a device that can be used as the primary memory 142 is a semiconductor RAM (Random Access Memory). An example of a device that can be used as the secondary memory 143 is a HDD (Hard Disk Drive).

[0020] An input device and / or an output device are connected to the input / output interface 144. An example of an input device connected to the input / output interface 144 is a camera for checking the material M. Furthermore, output devices connected to the input / output interface 144 include the electron beam irradiation unit 12, the heat treatment unit 13, a manipulator, etc.

[0021] Examples of interfaces that can be used as the input / output interface 144 include a PCI (Peripheral Component Interconnect) interface and a USB (Universal Serial Bus).

[0022] The manufacturing program P1 may be recorded on a computer-readable, non-transitory, tangible recording medium. This recording medium may be the secondary memory 143 or another recording medium. For example, a tape, a disk, a card, a semiconductor memory, a programmable logic circuit, or the like may be used as the other recording medium.

[0023] (Manufacturing Process) Fig. 2 is a flow diagram showing an example of a manufacturing process according to one embodiment of the present invention. Fig. 3 is an enlarged view showing an example of a material M used in the manufacturing process according to one embodiment of the present invention. The manufacturing process will be described below with reference to Fig. 2.

[0024] (1) Preparation of material M (Step S11: Preparation step of preparing material M containing nitrogen) Prepare material M. As described above, material M is a material containing nitrogen, for example, synthetic diamond (for example, fine particles of synthetic diamond) (see FIG. 3A). As shown in FIG. 3A, synthetic diamond contains nitrogen (N) as an impurity.

[0025] In this case, the material M preferably contains 5 atomic ppm or more and 3000 atomic ppm or less of nitrogen, and more preferably 50 atomic ppm or more and 1000 atomic ppm or less of nitrogen (100 atomic ppm, as an example). The sensor or the like preferably has 1 atomic ppm or more of NV centers, and more preferably has 10 atomic ppm or more of NV centers. In other words, a relatively high concentration of nitrogen impurities facilitates the formation of NV centers, while an excessively high concentration of nitrogen impurities can deteriorate the characteristics (e.g., sensitivity) of the sensor or the like.

[0026] Furthermore, when the material is diamond microparticles, the average particle size of the microparticles is preferably 5 nm or more, and more preferably 10 nm or more (for example, 50 nm). This is because diamond microparticles with excessively small particle sizes reduce the efficiency of NV center formation during the heat treatment process. As an example, NDs with an average particle size of 50 nm can be used. The average particle size of the microparticles is measured by dynamic light scattering.

[0027] (2) Irradiating the material M with an electron beam (Step S12: Electron beam irradiation step of irradiating the material M with an electron beam EB to form vacancies V in the material M) The material M is placed on the mounting portion 11 and is irradiated with an electron beam. As a result, a portion (C1) of carbon C in the material M is removed from the lattice, forming vacancies V (see FIG. 3B).

[0028] At this time, it is preferable to accelerate the electrons to 300 keV or more and 3 MeV or less (for example, 2 MeV) in order to introduce vacancies V uniformly into the entire material M.

[0029] In each of the repeated electron beam irradiation steps (step S12), the irradiation amount (i.e., irradiation density) of the electrons irradiated onto the material M is 1*10 １２ cm －２ That's it, 1*10 １９ cm －２ The following (as an example, 4*10 １８ cm －２ ) is preferable. By setting the irradiation amount within this range, efficient NV coupling can be promoted during the subsequent heat treatment. In other words, by adjusting the irradiation amount, the concentration of the generated vacancies V can be made to correspond to the concentration of nitrogen impurities contained in the material M, and NV coupling can be generated efficiently.

[0030] The electron beam irradiation can be carried out at normal temperature (e.g., room temperature) in the atmosphere, but may also be carried out, for example, under reduced pressure (or inert gas flow) or under heating. Among these, under reduced pressure (or inert gas flow) and under heating is preferred. By simultaneously carrying out the electron beam irradiation and heating, it becomes possible to introduce vacancies V and form NV more efficiently than when heating is not carried out during the electron beam irradiation.

[0031] In the electron beam irradiation step (step S12), when the material M is a powder consisting of fine particles with a diameter of 1 μm or less, it is preferable that the material M be irradiated with the electron beam while covered with a conductive material to prevent the material M from scattering. This conductive material is, for example, a thin film of aluminum, platinum, gold, or the like (aluminum foil is one example).

[0032] (3) Heat Treatment of Material M (Step S13: Heat Treatment Step of Heating Material M Irradiated with Electron Beam EB to Form Nitrogen-Vacancy Complex Defects (NV Centers) in Material M) By heating material M in which vacancies V have been formed, the vacancies V are moved. As a result, NV centers in which nitrogen N and vacancies V are bonded are formed (see FIG. 3(c)). For example, vacancies V in diamond move approximately 46 nm (thermal diffusion length) by heat treatment at 900°C for 2 hours, and bond with nitrogen in the diamond. In FIGS. 3(b) and 3(c), vacancies V move to the position of carbon C in C2, and NV centers are formed.

[0033] The heat treatment process (step S13) preferably includes a heating step in which the temperature of the material M is maintained at 400°C or higher and 1400°C or lower for 1 second or longer and 12 hours or shorter, and more preferably, in this heating step, the temperature of the material M is maintained at 700°C or higher and 1100°C or lower (e.g., 900°C) for 1 hour or longer and 5 hours or shorter (e.g., 2 hours). The formation of NV centers requires atomic rearrangement through high-temperature heat treatment. On the other hand, excessively high-temperature or long-term heat treatment can cause adverse effects such as graphitization of the material M (diamond) and the formation of complex defects other than NV centers in the material M.

[0034] The heat treatment process (step S13) may include a cooling process for cooling the material M heated in the heating process, and a process for holding the material M cooled in the cooling process at a temperature of 300°C to 800°C (e.g., 575°C) in an oxygen atmosphere (e.g., in the air) for 1 minute to 24 hours (e.g., 3 hours) to form an oxide film on the material M. During this process, graphite is removed from the surface of the material M and carboxyl groups are formed. That is, forming an oxide film at a high temperature improves the efficiency of graphite removal and carboxyl group formation on the surface of the material M by the subsequent thermal mixed acid treatment. On the other hand, oxidation treatment at an excessively high temperature or for a long period of time can cause adverse effects such as graphitization of the material M (diamond) and crystal distortion.

[0035] (4) Repeating steps S12 and S13 and checking the number of repetitions (step S14: a step in which the electron beam irradiation step and the heat treatment step are alternately repeated two or more times). The electron beam irradiation and heat treatment steps S12 and S13 are repeated until the number of repetitions n reaches a predetermined value of two or more.

[0036] Here, in the repeated electron beam irradiation process (step S12), the total irradiation amount of electrons irradiated onto the material M is 1*10 １２ cm －２ That's it, 1*10 １９ cm －２ The following (as an example, 4*10 １８ cm －２ The concentration of vacancies V generated by the irradiation amount in this range corresponds to the concentration of nitrogen impurities in the material M, and enables efficient formation of NV coupling between the vacancies V and the nitrogen impurities.

[0037] The above manufacturing process forms a sample having NV centers. By repeating electron beam irradiation and heat treatment, it becomes possible to form high-concentration NV centers.

[0038] A material having a hetero element-vacancy complex (e.g., an NV center) emits fluorescence, and the amount of fluorescence changes when microwaves or the like are applied. For example, when a material having an NV center is irradiated with green light, red light is emitted as reflected light. Furthermore, when a material having an NV center is applied with microwaves having a wavelength of, for example, 2.8 GHz, the amount of fluorescence (red light) (emission intensity) decreases. For this reason, a material having a hetero element-vacancy complex can be used in sensors (quantum metrology, sensing). By using the manufacturing method according to this embodiment, the hetero element-vacancy complex (e.g., an NV center) can be concentrated while suppressing an increase in defects and strain in the material M, thereby increasing the sensitivity of a sensor using a hetero element-vacancy complex.

[0039] Example 1 Hereinafter, Example 1 will be described. ND having an average particle size of 50 nm was used as the material M. This is common to Examples 1 and 2.

[0040] In Example 1, electron beam irradiation and heat treatment were repeated. The energy of the irradiated electrons was 2 MeV, and the irradiation amount of the electron beam for each irradiation was constant (2*10 １８ cm －２ ), and the total irradiation dose of the electron beam is 1*10 １９ cm －２ On the other hand, in the comparative example, the electron beam irradiation and heat treatment were performed only once and were not repeated. The energy of the irradiated electrons was 2 MeV, and the irradiation amount of the electron beam was 2*10 １８ cm －２ In both Example 1 and Comparative Example, the electron beam irradiation was carried out at room temperature, and the heat treatment was carried out at 900° C. for 2 hours.

[0041] 4 is a graph showing the fluorescence spectra of materials produced by a manufacturing process according to one embodiment of the present invention. Graphs G11 to G13 show the fluorescence spectra of materials produced by a total electron dose of 4*10 １８ , 6*10 １８ , and 8*10 １８ cm －２ Graphs G11 to G13 show the fluorescence spectrum at NV ０ The fluorescence peak FL1 at 575 nm is due to the uncharged NV center, and the NV － A fluorescent peak FL2 at 637 nm due to the negatively charged NV center is observed. The light source used was a light source having a peak wavelength of 532 nm (HORIBA LabRAM HR Evolution / Excitation light in this example).

[0042] 5 is a graph showing the relationship between the fluorescence intensity and the total electron irradiation dose of the material produced by the production process according to Example 1. Graph G21 corresponds to Example 1, and graph G20 corresponds to the comparative example.

[0043] In Example 1, the fluorescence intensity tended to increase with increasing electron beam irradiation dose. １９ cm －２ On the other hand, in the comparative example in which the heat treatment is performed after the total irradiation amount reaches the target, the irradiation amount is 4*10 １８ cm－２ The fluorescence intensity increases linearly with the irradiation dose up to this point, but as the irradiation dose increases further, the fluorescence intensity decreases.

[0044] As mentioned above, in comparison with the comparative example, 4*10 １８ cm －２ It can be considered that irradiation with more electrons tends to inhibit the coupling between vacancies (defects) and nitrogen (formation of NV centers) in the material M. In contrast, in Example 1, the 2*10 １８ cm －２ Each time electron irradiation is performed, the material M is annealed to form NV centers. As a result, it is thought that a large amount of NV centers do not couple at once, and coupling is reliably formed by NV annealing after each irradiation. As a result, in Example 1, 2*10 １８ ~6*10 １８ cm －２ Although the intensity is inferior to that of continuous irradiation up to this point, the result is that the luminescence intensity remains high even when the irradiation dose reaches a high level.

[0045] As described above, by alternately performing electron beam irradiation and heat treatment, the luminescence intensity can be increased. Compared to a sample not irradiated with an electron beam, the fluorescence intensity can be increased by 300% or more. １８ cm －２ Up to an irradiation dose of about 1000, continuous irradiation can be used to produce a film in a shorter time than the case of irradiation with a fixed amount of light, and the luminescence intensity can be increased efficiently (200% more than that of unirradiated film).

[0046] (Example 2) In Example 2, electron beam irradiation and heat treatment were repeated. The energy of the irradiated electrons was 2 MeV, and the irradiation amount of the electron beam for each irradiation was constant (1*10 １８ cm －２ ), and the total irradiation dose of the electron beam is 7*10 １８ cm －２ The electron beam irradiation was carried out at room temperature, and the heat treatment was carried out at 900° C. for 2 hours.

[0047] 6 is a graph showing the fluorescence spectrum of the material produced by the production process according to Example 2. Graphs G51 to G57 show the fluorescence spectrum of the material produced by the production process according to Example 2, where the total electron irradiation dose is 0 to 7*10 １８cm －２ Graphs G11 to G13 show the fluorescence spectrum of Example 2 at NV ０ The fluorescence peak FL1 at 575 nm due to NV － A fluorescent peak FL2 at 637 nm due to the above phenomenon is observed. The light source used was the same as in Example 1, having a peak wavelength of 532 nm.

[0048] 7 is a graph showing the relationship between the fluorescence intensity and the total electron irradiation dose of the material produced by the production process according to Example 2. Graph G6 corresponds to Example 2.

[0049] FIG. 8 is a diagram illustrating an ODMR (optically detected magnetic resonance) measurement device. The measurement device includes a laser light source 21, a dichroic mirror 22, an objective lens 23, a filter 24, a camera 25, a microwave signal generator 26, a microwave oscillation antenna 27, and an I / O 28. Laser light L1 emitted from the laser light source 21 is reflected by the mirror 22, focused by the objective lens 23, and incident on the measurement object OB, i.e., a sample containing NV centers. Fluorescence L2 from the measurement object OB passes through the dichroic mirror 22 and the filter 24 and enters the camera 25. The microwave signal generator 26 generates a microwave signal P. The microwave oscillation antenna 27 irradiates the measurement object OB with microwaves based on this signal P. The camera 25 is synchronized with the microwave modulation and frequency sweep by the microwave signal generator 26 via the I / O 28. As a result, the change in the intensity of the fluorescence relative to the frequency of the microwave can be obtained as the contrast of the ODMR signal.

[0050] The contrast of an optically detected magnetic resonance (ODMR) signal can be defined as the absolute value of the maximum rate of change in fluorescence intensity in the ODMR signal. The ODMR signal is a plot of the ratio of the fluorescence intensity when microwaves are applied to the fluorescence intensity when no microwaves are applied, versus the microwave frequency. The ODMR signal can be obtained by detecting fluorescence from the object of measurement OB while applying microwaves with a frequency sweep to the object of measurement OB.

[0051] At the NV center, ODMR signals are acquired under the following conditions: (1) The wavelength of the excitation light source used to generate fluorescence is 532 nm; (2) A 1.5-turn coil with a diameter of 5 mm is used to apply microwaves to the OB under measurement, with a frequency sweep width of 2.83 GHz to 2.91 GHz; the microwave intensity is 10 mW to 10 W, and the excitation light intensity is 300 W / cm. ２ to 3 MW / cm ２ In the range of , the intensity at which the contrast of the ODMR signal is maximized is used.

[0052] 9 is a graph showing the ODMR measurement results for the material manufactured by the manufacturing process according to Example 2. Graphs G91 to G94 show the results when the total irradiation dose of the electron beam is 2*10 １８ , 4*10 １８ , 6*10 １８ , and 7*10 １８ cm －２ Graphs corresponding to

[0053] Fig. 10 is a diagram showing the relationship between the contrast of the ODMR signal and the total electron irradiation dose for the material produced by the production process according to Example 2. Fig. 11 is a diagram showing the relationship between the fluorescence intensity and the contrast of the ODMR signal for the material produced by the production process according to Example 2 and the total electron irradiation dose.

[0054] As described above, the intensity of the fluorescence and the NV － The contrast of the ODMR signal changes depending on the concentration of the ion beam. The ODMR signal tends to have lower contrast as the dose of irradiation increases.

[0055] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0056] (Summary) The manufacturing method of Aspect 1 is a manufacturing method of a material having hetero element-vacancy complex defects, and includes a preparation step of preparing a material containing a hetero element as an impurity, an electron beam irradiation step of irradiating the material with an electron beam to form vacancies in the material, and a heat treatment step of heating the electron beam-irradiated material to form hetero element-vacancy complex defects in the material, wherein the electron beam irradiation step and the heat treatment step are alternately repeated two or more times. This makes it possible to manufacture a material having a high concentration of hetero element-vacancy complex defects while suppressing an increase in defects and strain in the material.

[0057] In the manufacturing method of Aspect 2, in the manufacturing method of Aspect 1, the raw material is synthetic diamond. The synthetic diamond contains nitrogen as a hetero element, and it is possible to produce a material having a high concentration of hetero element-vacancy complex defects while suppressing an increase in defects and strain in the raw material.

[0058] In the production method of mode 3, in the production method of mode 1 or 2, the hetero element is nitrogen, and a material having an NV center as a hetero element-vacancy complex defect can be produced.

[0059] The manufacturing method of aspect 4 is the manufacturing method of any one of aspects 1 to 3, wherein the irradiation amount of electrons irradiated to the material in each of the repeated electron beam irradiation steps is 1*10 １2 cm －２ That's it, 1*10 １9 cm －２ This makes it possible to produce a material with a high concentration of hetero element-vacancy complex defects while suppressing the increase in defects and strain in the material.

[0060] A manufacturing method of aspect 5 is the manufacturing method of any one of aspects 1 to 4, wherein in the repeated electron beam irradiation steps, the total irradiation amount of electrons irradiated to the material is 1*10 12 cm －２ That's it, 1*10 19 cm －２ This makes it possible to produce a material with a high concentration of hetero element-vacancy complex defects while suppressing the increase in defects and strain in the material.

[0061] A manufacturing method of Aspect 6 is the manufacturing method of any one of Aspects 1 to 5, wherein in the electron beam irradiation step, the material is a powder made of fine particles having a diameter of 1 μm or less, and is irradiated with an electron beam while being covered with a conductive material. This makes it possible to manufacture a material having a high concentration of hetero element-vacancy complex defects while suppressing an increase in defects and strain in the material.

[0062] In the manufacturing method of Aspect 7, in the manufacturing method of any one of Aspects 1 to 6, the heat treatment step includes a heating step of maintaining the temperature of the material at 400°C or higher and 1400°C or lower for 1 second or higher and 12 hours or shorter.

[0063] A material of Aspect 8 is a material having a hetero element-vacancy complex defect produced by the production method of any one of Aspects 1 to 7, the material being a powder containing particles having an average particle size of less than 30 nm, the concentration of the hetero element-vacancy complex defect in the material being 0.2 ppm or more, and the contrast of the ODMR signal in the material being 2% or more.

[0064] A material of Aspect 9 is a material having a hetero element-vacancy complex defect produced by the production method of any one of Aspects 1 to 7, the material being a powder containing particles having an average particle size of 30 nm or more and less than 100 nm, the concentration of the hetero element-vacancy complex defect in the material being 1.5 ppm or more, and the contrast of the ODMR signal in the material being 2% or more.

[0065] A material according to aspect 10 is a material having a hetero element-vacancy complex defect produced by the production method according to any one of aspects 1 to 7, the material being a powder containing particles having an average particle size of 100 nm or more, the concentration of the hetero element-vacancy complex defect in the material being 1.5 ppm or more, and the contrast of the ODMR signal in the material being 5% or more.

[0066] The manufacturing apparatus of aspect 11 is a manufacturing apparatus for manufacturing a material having hetero element-vacancy complex defects, and includes an electron beam irradiation unit that irradiates an electron beam onto a material containing a hetero element as an impurity, a heat treatment unit that heats the material irradiated with the electron beam, and a control unit that controls the electron beam irradiation unit and the heat treatment unit, wherein the control unit controls the electron beam irradiation unit and the heat treatment unit to alternately repeat two or more times an electron beam irradiation step of irradiating the material with an electron beam to form vacancies in the material and a heat treatment step of heating the material irradiated with the electron beam to form hetero element-vacancy complex defects in the material. This makes it possible to manufacture a material having a high concentration of hetero element-vacancy complex defects while suppressing the accumulation and increase of significant defects and strain in the material.

[0067] A manufacturing program of Aspect 12 is a manufacturing program for causing a computer to operate as a control unit of the manufacturing apparatus of Aspect 11, the manufacturing program causing a processor of the computer to control the electron beam irradiation unit and the heat treatment unit to alternately repeat the electron beam irradiation step and the heat treatment step two or more times. This makes it possible to manufacture a material having a high concentration of hetero element-vacancy complex defects while suppressing the accumulation and increase of significant defects and strain in the material.

[0068] A recording medium according to a thirteenth aspect is a computer-readable recording medium having the manufacturing program according to the twelfth aspect recorded thereon.

[0069] REFERENCE SIGNS LIST 10 Manufacturing device 11 Mounting section 12 Electron beam irradiation section 13 Heat treatment section 14 Control section

Claims

1. A method for producing a material having a hetero element-vacancy complex defect, comprising: a preparation step of preparing a material containing a hetero element as an impurity; an electron beam irradiation step of irradiating the material with an electron beam to form voids in the material; a heat treatment step of heating the material irradiated with the electron beam to form hetero element-vacancy complex defects in the material; Including, The electron beam irradiation step and the heat treatment step are alternately repeated two or more times.

2. The method of claim 1 , wherein the material is synthetic diamond.

3. The method according to claim 1 or 2, wherein the hetero element is nitrogen.

4. In each of the repeated electron beam irradiation steps, the irradiation amount of electrons irradiated to the material is 1*10 １２ cm －２ That's it, 1*10 １9 cm －２ The method according to claim 1 or 2, wherein:

5. In the repeated electron beam irradiation steps, the total irradiation amount of electrons irradiated to the material is 1*10 １２ cm －２ That's it, 1*10 １９ cm －２ The method according to claim 1 or 2, wherein:

6. 3. The manufacturing method according to claim 1, wherein in the electron beam irradiation step, the material is a powder made of fine particles having a diameter of 1 μm or less, and is irradiated with the electron beam while covered with a conductive material.

7. 3. The manufacturing method according to claim 1, wherein the heat treatment step comprises a heating step of maintaining the temperature of the material at 400° C. or higher and 1400° C. or lower for 1 second or higher and 12 hours or lower.

8. A material having a hetero element-vacancy complex defect produced by the production method according to claim 1 or 2, The material is a powder comprising particles having an average particle size of less than 30 nm, the concentration of hetero element-vacancy complex defects in the material is 0.2 ppm or more; A material in which the contrast of the ODMR signal in the material is 2% or greater.

9. A material having a hetero element-vacancy complex defect produced by the production method according to claim 1 or 2, The material is a powder containing particles having an average particle size of 30 nm or more and less than 100 nm, the concentration of heteroelement-vacancy complex defects in the material is 1.5 ppm or more; A material in which the contrast of the ODMR signal in the material is 2% or greater.

10. A material having a hetero element-vacancy complex defect produced by the production method according to claim 1 or 2, The material is a powder containing particles having an average particle size of 100 nm or more, the concentration of heteroelement-vacancy complex defects in the material is 1.5 ppm or more; A material in which the contrast of the ODMR signal in the material is 5% or greater.

11. A manufacturing apparatus for manufacturing a material having a hetero element-vacancy complex defect, comprising: an electron beam irradiation unit that irradiates an electron beam onto a material containing a hetero element as an impurity; a heat treatment section for heating the material irradiated with the electron beam; a control unit that controls the electron beam irradiation unit and the heat treatment unit; Equipped with The control unit controls the electron beam irradiation unit and the heat treatment unit, an electron beam irradiation step of irradiating the material with an electron beam to form voids in the material; a heat treatment step of heating the material irradiated with the electron beam to form hetero element-vacancy complex defects in the material; A manufacturing device that alternately repeats the above steps two or more times.

12. A manufacturing program for causing a computer to operate as a control unit of the manufacturing apparatus described in claim 11, the manufacturing program causing a processor provided in the computer to control the electron beam irradiation unit and the heat treatment unit to alternately repeat the electron beam irradiation process and the heat treatment process two or more times.

13. A computer-readable recording medium on which the manufacturing program according to claim 12 is recorded.