CN115232615A - Preparation method of microcrystalline diamond crystal grain with adjustable silicon vacancy color center luminous intensity - Google Patents
Preparation method of microcrystalline diamond crystal grain with adjustable silicon vacancy color center luminous intensity Download PDFInfo
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- CN115232615A CN115232615A CN202210720391.9A CN202210720391A CN115232615A CN 115232615 A CN115232615 A CN 115232615A CN 202210720391 A CN202210720391 A CN 202210720391A CN 115232615 A CN115232615 A CN 115232615A
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- 239000010432 diamond Substances 0.000 title claims abstract description 146
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 146
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 99
- 239000010703 silicon Substances 0.000 title claims abstract description 99
- 239000013078 crystal Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 92
- 238000000034 method Methods 0.000 claims abstract description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010899 nucleation Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 230000007613 environmental effect Effects 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 238000000259 microwave plasma-assisted chemical vapour deposition Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004020 luminiscence type Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 238000001069 Raman spectroscopy Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 10
- 238000007781 pre-processing Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000013081 microcrystal Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/26—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/28—After-treatment, e.g. purification, irradiation, separation or recovery
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/274—Diamond only using microwave discharges
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
Abstract
The invention discloses a preparation method of microcrystalline diamond grains with adjustable silicon vacancy color center luminous intensity, which comprises the following steps: selecting an epitaxial substrate with a certain crystal orientation; carrying out organic cleaning on the substrate; carrying out ultrasonic seeding treatment on the cleaned substrate; preprocessing the substrate subjected to ultrasonic seeding treatment; the microcrystalline diamond grows on the substrate, and the orientation of crystal grains is regulated and controlled by adjusting the proportion of nitrogen and oxygen in a growth environment to form the microcrystalline diamond crystal grains with specific crystal orientation, so that the regulation and control of the luminous intensity of the silicon vacancy color center are realized. The preparation method provided by the invention can realize low-cost and strong-controllability silicon vacancy in the diamond without introducing other impurity gas sources, avoids the problem that the continuous diamond film blocks and etches silicon, does not need a post-treatment process, and has the advantages of short growth period, simple growth process, low cost, safety, environmental protection, and stable and controllable growth.
Description
Technical Field
The invention belongs to the technical field of diamond color centers, and particularly relates to a preparation method of microcrystalline diamond grains with adjustable silicon vacancy color center luminous intensity.
Background
The diamond color center has the optical characteristics of high quantum efficiency, little photobleaching, no photoflicker and the like, has wide application prospect in the fields of quantum information processing, optoelectronics, biological markers and the like, and attracts more and more researchers to research the color center defects in the diamond. The diamond silicon vacancy color center is one of the current related scientific research institutions, the zero phonon line of the diamond silicon vacancy color center is 738nm, the silicon vacancy color center has a narrower zero phonon band and a shorter luminous life compared with the diamond nitrogen vacancy color center, and 70% of photons of the silicon vacancy color center are concentrated at the zero phonon line, so that the diamond silicon vacancy color center has higher fluorescence resolution, and the diamond silicon vacancy color center has higher application potential in various fields.
At present, there are two main schemes for forming silicon vacancy in diamond, one is to introduce silane in the process of extending diamond by microwave plasma chemical vapor deposition method to form silicon-doped diamond, and then to form silicon vacancy. For example, patent document 1 (publication No. CN 111099586A) provides a method for preparing a high-brightness silicon vacancy color center in a nanodiamond, which achieves the purpose of adjusting the luminous intensity of a silicon vacancy color center of diamond by introducing tetramethylsilane during the growth of diamond to adjust the concentration of silicon impurities in diamond. The other is that in the MPCVD epitaxial diamond process, the unintended doped silicon impurity is introduced into the diamond epitaxial layer due to the etching action of the quartz cavity or the silicon substrate under the hydrogen plasma, and then the silicon vacancy is formed by annealing. For example, patent document 2 (publication No. CN 104831253A) provides a method of increasing the emission intensity of a color center of a silicon vacancy in diamond. According to the method, after diamond grains grow, annealing is carried out at 600 ℃ in an air environment so as to regulate and control the luminous intensity of the diamond silicon vacancy color center.
However, the introduction of silane is toxic and flammable, and the controllable doping of silicon is difficult, which results in high preparation cost, difficulty and high safety and environmental protection risks. And by adopting the mode of unintended doping and annealing, as the concentration of unintended doping is uncontrollable, and in the epitaxial process of the silicon substrate, after the surface diamond is continuously formed into a film, the etching effect of the silicon substrate cannot be formed, so that the silicon doping is reduced, and the controllability of the scheme is poor.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of microcrystalline diamond grains with adjustable silicon vacancy color center luminous intensity. The technical problem to be solved by the invention is realized by the following technical scheme:
the invention provides a preparation method of microcrystalline diamond grains with adjustable silicon vacancy color center luminous intensity, which comprises the following steps:
step 1: selecting an epitaxial substrate with a certain crystal orientation;
step 2: carrying out organic cleaning on the substrate;
and step 3: carrying out ultrasonic seeding treatment on the cleaned substrate;
and 4, step 4: preprocessing the substrate subjected to ultrasonic seeding treatment;
and 5: and growing the microcrystalline diamond on the substrate, and regulating and controlling the grain orientation by regulating the proportion of nitrogen and oxygen in a growth environment to form microcrystalline diamond grains with a specific crystal orientation, thereby realizing the regulation and control of the luminous intensity of the silicon vacancy color center.
In one embodiment of the invention, the substrate is an intrinsic silicon substrate with a resistivity greater than 2000 Ω · cm, a thickness of 1-3mm, and a silicon crystal orientation of 100, 110 or 111.
In one embodiment of the present invention, step 3 comprises:
preparing a diamond powder suspension solution with the diamond particle size of 3-50nm as an ultrasonic solution;
putting the cleaned substrate into the ultrasonic solution for ultrasonic treatment for 10-30min to form uniformly distributed diamond seed crystals on the substrate;
taking out the substrate and placing the substrate on a heating table heated to 50-100 ℃ for heating and drying.
In one embodiment of the present invention, step 4 comprises:
placing the silicon substrate subjected to ultrasonic treatment into an MPCVD device, and pumping the pressure of a cavity to be not more than 0.001mbar;
introducing H into MPCVD equipment 2 ，H 2 The flow rate is 100-800sccm;
when the air pressure of the cavity reaches 10-25mbar, turning on a microwave source to ensure that the air pressure of the cavity is increased to 120-200mbar, the power is 3000-5000W, and the temperature of the surface of the substrate is 800-1000 ℃;
and pretreating the substrate for 5-20min under the environmental conditions.
In one embodiment of the present invention, step 5 comprises:
introducing CH into an MPCVD device 4 While adding N 2 And/or O 2 To grow microcrystalline diamond grains on the substrate;
adjusting N 2 And O 2 The ratio of the silicon vacancy center luminous intensity to the crystal orientation of the formed microcrystalline diamond grains is controlled, and the microcrystalline diamond grains with different silicon vacancy center luminous intensities are realized;
wherein, the CH 4 The flow rate of (2) is 5-20sccm, and the growth time is 90-120 minutes.
In one embodiment of the present invention, said N 2 The flow rate of (A) is 0-0.1sccm 2 The flow rate of (A) is 0 to 2.0sccm.
In one embodiment of the present invention, step 5 comprises:
introducing CH into MPCVD equipment 4 While adding 0.02sccm of N 2 Thereby forming uniformly distributed microcrystalline diamond grains having crystal orientations of 100 and 111.
In one embodiment of the present invention, step 5 comprises:
introducing CH into an MPCVD device 4 While adding 0.03sccm of N 2 And 0.75sccm of O 2 Thereby forming microcrystalline diamond grains having crystal orientations of 100 and 111 and having 100 as a main component.
In one embodiment of the present invention, step 5 comprises:
introducing CH into an MPCVD device 4 While adding 0.06sccm of N 2 And 2sccm of O 2 Thereby forming microcrystalline diamond grains having a crystal orientation of 100.
The invention also provides a microcrystalline diamond crystal grain prepared by the preparation method in the embodiment, wherein the size of the microcrystalline diamond crystal grain is 3-10 μm, and the normalized intensity ratio of the fluorescence peak intensity of diamond color centers with different crystal directions to the diamond Raman peak is 7-84.
The invention has the beneficial effects that:
1. the preparation method provided by the invention can realize low-cost and strong-controllability silicon vacancy in the diamond without introducing other impurity gas sources, avoids the problem that the continuous diamond film blocks and etches silicon, does not need a post-treatment process, and has the advantages of short growth period, simple growth process, low cost, safety, environmental protection, and stable and controllable growth;
2. the preparation method provided by the invention can realize stable regulation and control of the crystallite orientation of the diamond by adjusting the change of the process parameters, thereby realizing the growth of diamond materials with different silicon vacancy luminous intensities; compared with the existing scheme of regulating and controlling the concentration of the in-situ doped silicon impurity and the like, the method has the advantages of strong controllability, simple process and low cost;
3. the diamond microcrystal grain size prepared by the preparation method provided by the invention can directly meet the requirement of system application such as quantum detection on the diamond size, does not need secondary processing, and has low cost, stability and reliability.
The present invention will be described in further detail with reference to the drawings and examples.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing microcrystalline diamond grains with adjustable silicon vacancy color center luminescence intensity according to an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of microcrystalline diamond grains grown in example two in which the (111) crystal orientation and the (100) crystal orientation are uniformly in proportion;
FIG. 3 is a scanning electron micrograph of microcrystalline diamond grains grown in example III, in which the (100) aspect ratio is higher than the (111) aspect ratio;
FIG. 4 is a scanning electron micrograph of (100) oriented microcrystalline diamond grains grown according to example four;
FIG. 5 is a graph of the difference N 2 And O 2 Photoluminescence spectra of the grown microcrystalline diamond with different grain orientations.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example one
Referring to fig. 1, fig. 1 is a schematic flow chart of a method for preparing microcrystalline diamond grains with adjustable silicon vacancy color center luminous intensity according to an embodiment of the present invention, including:
step 1: an epitaxial substrate with a certain crystal orientation is selected.
In this embodiment, in order not to introduce interference of other elements with diamond growth, an intrinsic silicon substrate is preferable as an epitaxial substrate. Wherein the intrinsic silicon substrate has a resistivity of more than 2000 Ω · cm, a thickness of 1-3mm, and a silicon crystal orientation of (100), (110), or (111).
And 2, step: and carrying out organic cleaning on the substrate.
Specifically, the selected substrate is ultrasonically cleaned for 5-30 minutes by sequentially adopting acetone, ethanol (or isopropanol) and deionized water, and finally washed in flowing deionized water and finally dried by a nitrogen gun.
And step 3: and carrying out ultrasonic seeding treatment on the cleaned substrate.
Firstly, preparing a diamond powder suspension solution as an ultrasonic solution; wherein the diamond particle size is 3-50nm.
And then, putting the cleaned substrate into an ultrasonic solution for ultrasonic treatment for 10-30min to form uniformly distributed diamond seed crystals on the substrate.
Finally, in order to prevent the diamond seed crystals which are uniformly distributed from being redistributed due to the evaporation of the solution, the substrate is taken out and placed on a heating table which is heated to 50-100 ℃ to rapidly heat and dry the solution.
And 4, step 4: and (4) preprocessing the substrate subjected to the ultrasonic seeding treatment.
Specifically, the silicon substrate after ultrasonic treatment is placed in an MPCVD device, and the air pressure of a cavity is pumped to be not more than 0.001mbar so as to reduce the influence of other impurities on the growth of diamond; introducing H into MPCVD equipment 2 ，H 2 The flow rate is 100-800sccm; when the air pressure of the cavity reaches 10-25mbar, the microwave source is switched on, so that the air pressure of the cavity is increased to 120-200mbar, the power is 3000-5000W, and the temperature of the surface of the substrate is 800-1000 ℃.
And (3) pretreating the substrate for 5-20min under the environmental conditions to ensure the cleanness of the surface of the silicon substrate and provide initial temperature for subsequent diamond growth.
And 5: the microcrystalline diamond grows on the substrate, and the orientation of crystal grains is regulated and controlled by adjusting the proportion of nitrogen and oxygen in a growth environment to form the microcrystalline diamond crystal grains with specific crystal orientation, so that the regulation and control of the luminous intensity of the silicon vacancy color center are realized.
First, CH was introduced into the MPCVD apparatus 4 While adding N 2 And/or O 2 To do so byMicrocrystalline diamond grains are grown on a substrate.
Then, adjust N 2 And O 2 The ratio of the silicon vacancy center luminous intensity to the crystal orientation of the formed microcrystalline diamond grains is controlled, and the microcrystalline diamond grains with different silicon vacancy center luminous intensities are realized.
Wherein, CH 4 The flow rate of (A) is 5-20sccm, N 2 The flow rate of (A) is 0-0.1sccm 2 The flow rate of the growth medium is 0-2.0sccm, and the growth time is 90-120 minutes; the pressure and power are reduced to 0 within 30-40 minutes after the growth is finished.
According to the preparation method provided by the embodiment, other impurity gas sources are not required to be introduced, the silicon vacancy in the diamond with low cost and strong controllability can be realized, the problem that the continuous diamond film blocks and etches silicon is avoided, a post-treatment process is not required, and the preparation method has the advantages of short growth period, simple growth process, low cost, safety, environmental friendliness, and stable and controllable growth.
Meanwhile, the method can realize the stable regulation and control of the crystallite orientation of the diamond by adjusting the change of the process parameters, thereby realizing the growth of the diamond materials with different silicon vacancy luminous intensities; compared with the existing scheme of regulating and controlling the in-situ doped silicon impurity concentration and the like, the method has the advantages of strong controllability, simple process and low cost.
Example two
The method of the present invention will be described in detail below, taking intrinsic silicon having a crystal orientation of (111) as an epitaxial substrate, and taking the preparation of microcrystalline diamond grains having uniformly distributed microcrystalline diamond grains having crystal orientations of (100) and (111) as an example.
The method comprises the following steps: an intrinsic silicon substrate with a crystal orientation of (111) is selected, the resistivity of the intrinsic silicon substrate is 2000 omega cm, and the thickness of the intrinsic silicon substrate is 1.5mm.
Step two: carrying out organic cleaning on the surface of the intrinsic silicon substrate;
specifically, the selected substrate is ultrasonically cleaned for 5 minutes by sequentially adopting acetone, ethanol (or isopropanol) and deionized water, and finally washed in flowing deionized water and finally dried by a nitrogen gun.
Step three: carrying out nanocrystalline diamond ultrasonic seeding operation on a silicon substrate;
specifically, a diamond powder suspension solution with the diamond particle size of 7nm is used as an ultrasonic solution, the ultrasonic time is 10min, and then the silicon substrate is placed on a heating table heated to 60 ℃ to be heated and dried.
Step four: preprocessing a substrate before the growth of diamond microcrystals;
placing the ultrasonically treated intrinsic silicon substrate into an MPCVD device, and pumping the air pressure of a cavity to be less than 0.001mbar so as to reduce the influence of other impurities on the growth of diamond; after the vacuum condition meets the requirement of diamond growth, H begins to be introduced 2 ，H 2 The flow rate is 200sccm, when the air pressure of the cavity reaches 12mbar, the microwave source is turned on, the pressure of the cavity is raised to 175mbar, the power is 4000W, the temperature of the substrate surface is 920 ℃, and the pretreatment time is 5min.
Step five: growing diamond crystallites having a particular crystal orientation;
after the pretreatment of the substrate is finished, CH is introduced into the MPCVD equipment 4 ，CH 4 The flow rate is 10sccm, and N of 0.02sccm is added at the beginning of the diamond growth process 2 And growing the microcrystalline diamond grains on the substrate for 100 minutes. And within 30 minutes after the growth is finished, the pressure and the power are reduced to 0, so that the microcrystalline diamond grains with the crystal directions of (100) and (111) which are uniformly distributed are obtained.
Referring to fig. 2, fig. 2 is a scanning electron microscope image of the microcrystalline diamond grains with uniform ratio of (111) crystal orientation and (100) crystal orientation obtained by growth in this embodiment, and it is apparent that the ratio of (111) crystal orientation and (100) crystal orientation of diamond is approximately one-to-one.
EXAMPLE III
The method of the present invention will be described in detail below with reference to intrinsic silicon having a crystal orientation of (100) as an epitaxial substrate, microcrystalline diamond grains having crystal orientations of (100) and (111), and microcrystalline diamond grains mainly having a crystal orientation of (100) as an example.
Step A: an intrinsic silicon substrate with a crystal orientation of (100) is selected, the resistivity of the intrinsic silicon substrate is 2000 omega cm, and the thickness of the intrinsic silicon substrate is 2mm.
And B: organic cleaning of intrinsic silicon substrate surface
Specifically, the selected substrate is ultrasonically cleaned for 10 minutes by sequentially adopting acetone, ethanol (or isopropanol) and deionized water, and finally washed in flowing deionized water and finally dried by a nitrogen gun.
And C: carrying out nanocrystalline diamond ultrasonic seeding operation on a silicon substrate;
specifically, a diamond powder suspension solution with the diamond particle size of 10nm is used as an ultrasonic solution, the ultrasonic time is 12min, and then the silicon substrate is placed on a heating table heated to 70 ℃ to be heated and dried.
Step D: pre-treating a substrate before the growth of diamond microcrystals;
placing the ultrasonically treated intrinsic silicon substrate into an MPCVD device, and pumping the air pressure of a cavity to be less than 0.001mbar so as to reduce the influence of other impurities on the growth of diamond; after the vacuum condition meets the requirement of diamond growth, H begins to be introduced 2 ，H 2 The flow rate is 300sccm, when the chamber pressure reaches 20mbar, the microwave source is turned on, the chamber pressure is increased to 180mbar, the power is 4200W, the substrate surface temperature is 950 ℃, and the pretreatment time is 10min.
Step E: growing diamond crystallites having a particular crystal orientation;
after the pretreatment of the substrate is completed, CH is introduced into the MPCVD equipment 4 ，CH 4 The flow rate is 15sccm, and 0.03sccm of N is added at the beginning of the diamond growth process 2 And 0.75sccm of O 2 To grow microcrystalline diamond grains on the substrate for 110 minutes. Within 30 minutes after the growth, the pressure and power were reduced to 0, and thus microcrystalline diamond grains having crystal orientations of (100) and (111) and dominated by (100) were obtained.
Referring to fig. 3, fig. 3 is a scanning electron microscope image of the microcrystalline diamond grains grown in the present embodiment, wherein the (100) crystal orientation ratio is higher than the (111) crystal orientation ratio; the (111) and (100) crystal orientations of diamond can be clearly observed, with the (100) crystal orientation being dominant.
Example four
The method of the present invention will be described in detail below, taking intrinsic silicon having a crystal orientation of (111) as an epitaxial substrate, and taking the preparation of a microcrystalline diamond crystal having a microcrystalline diamond crystal orientation of (100) as an example.
Step a: an intrinsic silicon substrate with a crystal orientation of (111) is selected, the resistivity of the intrinsic silicon substrate is 2000 omega cm, and the thickness of the intrinsic silicon substrate is 3mm.
Step b: organic cleaning of intrinsic silicon substrate surface
Specifically, the selected substrate is ultrasonically cleaned for 15 minutes by sequentially adopting acetone, ethanol (or isopropanol) and deionized water, and finally is washed in flowing deionized water, and finally is dried by a nitrogen gun.
Step c: carrying out nanocrystalline diamond ultrasonic seeding operation on a silicon substrate;
specifically, a diamond powder suspension solution with the diamond particle size of 15nm is used as an ultrasonic solution, ultrasonic time is 15min, and then the silicon substrate is placed on a heating table heated to 70 ℃ for heating and drying.
Step d: preprocessing a substrate before the growth of diamond microcrystals;
placing the ultrasonically treated intrinsic silicon substrate into an MPCVD device, and pumping the air pressure of a cavity to be less than 0.001mbar so as to reduce the influence of other impurities on the growth of diamond; after the vacuum condition meets the requirement of diamond growth, H begins to be introduced 2 ，H 2 The flow rate is 400sccm, when the air pressure of the cavity reaches 25mbar, the microwave source is turned on, the pressure of the cavity is increased to 185mbar, the power is 4500W, the temperature of the surface of the substrate is 980 ℃, and the pretreatment time is 20min.
Step e: growing diamond crystallites having a particular crystal orientation;
after the pretreatment of the substrate is completed, CH is introduced into the MPCVD equipment 4 ，CH 4 The flow rate is 20sccm, and 0.06sccm of N is added at the beginning of the diamond growth process 2 And 2.0sccm of O 2 And growing the microcrystalline diamond grains on the substrate for 110 minutes. And within 30 minutes after the growth is finished, the pressure and the power are reduced to 0, so that the microcrystalline diamond crystal grain with the crystal orientation of (100) is obtained.
Referring to fig. 4, fig. 4 is a scanning electron microscope image of the microcrystalline diamond grains with (100) crystal orientation grown in the present embodiment; it can be observed that the diamond grains exist substantially only in the (100) crystal orientation.
Further, the photoluminescence spectra of the diamond grains with different crystal orientations prepared in the second, third and fourth examples were also tested, and the results are shown in fig. 5.
As can be seen from fig. 5, the diamond prepared in example two, in which the (111) crystal orientation and the (100) crystal orientation ratio are the same, has the highest luminous intensity of the silicon vacancy color center due to the sufficiently high (111) crystal orientation ratio, and the normalized intensity ratio of the fluorescence peak of the silicon vacancy color center of the diamond reaches 84. In the diamond prepared in the third example, in the (100) crystal orientation ratio higher than the (111) crystal orientation ratio, the luminous intensity of the silicon vacancy color center of the diamond is obviously reduced due to the reduction of the (111) crystal orientation ratio, and the normalized intensity ratio of the fluorescence peak of the silicon vacancy color center of the diamond is reduced to 31. The luminescence intensity of the silicon vacancy color centers of the diamond of only (100) crystal orientation prepared in example four continued to decrease, and the normalized intensity ratio of the fluorescence peaks of the silicon vacancy color centers of the diamond decreased to 7.
Thus, the N in the growth environment is regulated 2 And O 2 The proportion of (A) can realize diamond grains with different crystal directions, thereby realizing the regulation and control of the luminous intensity of the silicon vacancy color center.
EXAMPLE five
This example provides a microcrystalline diamond grain prepared using the preparation method of example one above. Wherein the crystallite size of the microcrystalline diamond grains is 3-10 mu m, and the normalized intensity ratio of the fluorescence peak intensity of the diamond color center with different crystal directions to the diamond Raman peak is 7-84. The diamond microcrystal grain size prepared by the preparation method provided by the invention can directly meet the requirement of system application such as quantum detection on the diamond size, does not need secondary processing, and has low cost, stability and reliability.
The foregoing is a further detailed description of the invention in connection with specific preferred embodiments and it is not intended to limit the invention to the specific embodiments described. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A preparation method of microcrystalline diamond grains with adjustable silicon vacancy color center luminous intensity is characterized by comprising the following steps:
step 1: selecting an epitaxial substrate with a certain crystal orientation;
step 2: carrying out organic cleaning on the substrate;
and 3, step 3: carrying out ultrasonic seeding treatment on the cleaned substrate;
and 4, step 4: pretreating the substrate subjected to ultrasonic seeding treatment;
and 5: and growing the microcrystalline diamond on the substrate, and regulating and controlling the grain orientation by regulating the proportion of nitrogen and oxygen in a growth environment to form microcrystalline diamond grains with a specific crystal orientation, thereby realizing the regulation and control of the luminous intensity of the silicon vacancy color center.
2. The method for preparing a microcrystalline diamond grain with a controllable color center luminescence intensity of silicon vacancies according to claim 1, wherein the substrate is an intrinsic silicon substrate, the resistivity of the intrinsic silicon substrate is more than 2000 Ω -cm, the thickness of the intrinsic silicon substrate is 1-3mm, and the crystal orientation of the intrinsic silicon substrate is 100, 110 or 111.
3. The method for preparing microcrystalline diamond grains with controllable silicon vacancy color center luminescence intensity according to claim 1, wherein the step 3 comprises the following steps:
preparing a diamond powder suspension solution with the diamond particle size of 3-50nm as an ultrasonic solution;
putting the cleaned substrate into the ultrasonic solution for ultrasonic treatment for 10-30min to form uniformly distributed diamond seed crystals on the substrate;
taking out the substrate and placing the substrate on a heating table heated to 50-100 ℃ for heating and drying.
4. The method for preparing microcrystalline diamond grains with controllable silicon vacancy color center luminescence intensity according to claim 1, wherein the step 4 comprises the following steps:
placing the silicon substrate subjected to ultrasonic treatment into an MPCVD device, and pumping the pressure of a cavity to be not more than 0.001mbar;
introducing H into MPCVD equipment 2 ，H 2 The flow rate is 100-800sccm;
when the air pressure of the cavity reaches 10-25mbar, turning on a microwave source to increase the air pressure of the cavity to 120-200mbar, wherein the power is 3000-5000W, and the surface temperature of the substrate is 800-1000 ℃;
and pretreating the substrate for 5-20min under the environmental conditions.
5. The method for preparing microcrystalline diamond grains with controllable silicon vacancy color center luminescence intensity according to claim 1, wherein the step 5 comprises the following steps:
introducing CH into MPCVD equipment 4 While adding N 2 And/or O 2 To grow microcrystalline diamond grains on the substrate;
adjusting N 2 And O 2 The ratio of the silicon vacancy center luminous intensity to the crystal orientation of the formed microcrystalline diamond grains is controlled, and the microcrystalline diamond grains with different silicon vacancy center luminous intensities are realized;
wherein, the CH 4 The flow rate of (2) is 5-20sccm, and the growth time is 90-120 minutes.
6. The method of claim 5, wherein the N is selected from the group consisting of 2 The flow rate of (A) is 0-0.1sccm 2 The flow rate of (A) is 0 to 2.0sccm.
7. The method for preparing microcrystalline diamond grains with controllable silicon vacancy color center luminescence intensity according to claim 1, wherein the step 5 comprises the following steps:
introducing CH into an MPCVD device 4 While adding 0.02sccm of N 2 Thereby forming microcrystalline diamond grains having uniformly distributed crystal orientations of 100 and 111.
8. The method of preparing microcrystalline diamond grains with controllable silicon vacancy color center luminous intensity as recited in claim 1, wherein step 5 comprises:
introducing CH into an MPCVD device 4 While adding 0.03sccm of N 2 And 0.75sccm of O 2 Thereby forming microcrystalline diamond grains having crystal orientations of 100 and 111 and having 100 as a main component.
9. The method of preparing microcrystalline diamond grains with controllable silicon vacancy color center luminous intensity as recited in claim 1, wherein step 5 comprises:
introducing CH into an MPCVD device 4 While adding 0.06sccm of N 2 And 2sccm of O 2 Thereby forming microcrystalline diamond grains having a crystal orientation of 100.
10. A microcrystalline diamond grain produced by the production method according to any one of claims 1 to 9, wherein the microcrystalline diamond grain has a size of 3 to 10 μm, and a normalized intensity ratio of fluorescence peak intensity of diamond color centers of different crystal directions to diamond raman peak is 7 to 84.
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