WO2019080001A1 - Structure d'aiguille de diamant à l'échelle nanométrique, son procédé de préparation et son application - Google Patents

Structure d'aiguille de diamant à l'échelle nanométrique, son procédé de préparation et son application

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Publication number
WO2019080001A1
WO2019080001A1 PCT/CN2017/107649 CN2017107649W WO2019080001A1 WO 2019080001 A1 WO2019080001 A1 WO 2019080001A1 CN 2017107649 W CN2017107649 W CN 2017107649W WO 2019080001 A1 WO2019080001 A1 WO 2019080001A1
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WIPO (PCT)
Prior art keywords
diamond
layer
nanoneedle
sccm
etching
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Ceased
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PCT/CN2017/107649
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English (en)
Chinese (zh)
Inventor
杨扬
唐永炳
张文军
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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Priority to PCT/CN2017/107649 priority Critical patent/WO2019080001A1/fr
Publication of WO2019080001A1 publication Critical patent/WO2019080001A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M1/00—Apparatus for enzymology or microbiology
    • 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

Definitions

  • the present invention belongs to the field of biomaterials, and particularly relates to a diamond nanoneedle structure and a preparation method and application thereof.
  • Diamond materials are based on excellent physical, chemical properties and biocompatibility, as well as the fluorescence properties of nanodiamonds and the modification of surface groups, which have led to widespread interest in the application of nanostructured diamond materials in biomedical applications.
  • the color center such as nitrogen-vacancy (NV) in diamond is a composite structure composed of a substitutional nitrogen atom (N) in diamond and a carbon vacancy (V) in the ortho position. Ultra-high light stability and thermal stability, its fluorescence is not affected by size and surface modification.
  • NV color centers are extremely sensitive to physical quantities such as magnetic fields, temperature, stress, and electric fields, and have long coherence and relaxation at room temperature, and are therefore often used for high sensitivity measurements of these physical quantity parameters.
  • diamond NV nanomaterials are ideal fluorescent probes for fluorescent labeling, 3D tracking, bioimaging, and biosensing of cells.
  • the preparation of high-quality NV color centers exists only in diamond nanoparticles and high-quality single crystal diamond sheets, which greatly limits the range of applications.
  • diamond nanoneedles In addition to nano-sized diamond particles, recently vertically aligned diamond nanoneedle arrays have been used for efficient intracellular transport and detection. Compared to chemical and biological methods to achieve this goal, diamond nanoneedles show significant advantages in cell transport, with versatility, simple operation, high efficiency, low cost and safety, enabling controlled transfer of materials to a specific organ within a cell. Mechanical piercing of cell membranes with high aspect ratio nanomaterials has become a promising means of delivering substances to cells and enabling intracellular detection. Studies have shown that silicon nanowires or silicon nanoneedle arrays can be used to achieve intracellular neural network detection and intracellular drug delivery applications. Compared to silicon nanomaterials, diamond nanowire structures retain very high Young's modulus, yield strength and rupture strength.
  • a device for transferring a substance into a cell using a diamond nanoneedle array is disclosed, and the biomolecule which needs to enter the cell can be directly and easily transmitted through the cell membrane by the method.
  • Chemotherapy drugs, antibodies, and other biomolecules can be delivered directly into the cytoplasm without the need to pass signaling pathways through traditional cells. Using this method can Successfully transfected with nerve cells, the transfection efficiency is as high as 45%, only 10 minutes, but the current commercial method of transfection is generally less than 5%, which requires a small number of defects.
  • the same purpose can be achieved by using nano-needles of materials such as diamond, cubic boron nitride, carbon nitride, boron nitride, boron boron nitride, and metal boride.
  • materials such as diamond, cubic boron nitride, carbon nitride, boron nitride, boron boron nitride, and metal boride.
  • the application of diamond nanoneedle arrays in these work is currently based on the excellent mechanical properties of diamonds and the ease of modification of the surface.
  • the diamond nanoneedle itself does not emit fluorescence, and it is necessary to modify the fluorescent protein as a marker on its surface. The operation process is cumbersome, and the selectivity and detection sensitivity of the biological probe molecular modification on the surface of the diamond nanoneedle can have a serious impact.
  • Zero-dimensional diamond nanoparticles and one-dimensional diamond nanostructures have shown increasing use in drug delivery, bioimaging, and biosensing.
  • the application of zero-dimensional diamond nanoparticles mainly utilizes the special fluorescent light-emitting characteristics such as NV color center
  • the one-dimensional diamond vertical nanoneedle array structure mainly utilizes the excellent mechanical properties of diamond to pierce the cell membrane to realize intracellular transmission and detection. Therefore, it is of great scientific significance to study the biosensing of intracellular cells with diamond nanomaterials such as NV color center and vertical array nanoneedle array structure, such as studying changes in intracellular temperature, magnetic field and electrophysiological properties. And application value.
  • the formation rate such as NV color center is low, and the depth distribution is very dispersed, that is, high quality color centers cannot be formed.
  • the object of the present invention is to overcome the above-mentioned deficiencies of the prior art, to provide a diamond nanoneedle structure, a preparation method thereof and an application thereof, so as to solve the problem that the existing diamond nanoneedle cannot integrate the high quality color core of the diamond, resulting in failure to Technical problems of excellent fluorescence luminescence properties and electron spin coherence properties.
  • a diamond nanoneedle structure comprises a diamond base layer and a plurality of diamond nanoneedles extending on a surface of the diamond base layer, adjacent to the diamond nanoneedles being spaced apart from each other, and a color center structure is also distributed in the diamond nanoneedle surface layer .
  • a method of making a diamond nanoneedle structure comprises the following steps:
  • the diamond nanoneedles grown with the delta-taste layer are subjected to electron beam irradiation treatment and then annealed in a protective atmosphere.
  • a method of applying the above-described diamond nanoneedle structure is provided.
  • the above-mentioned diamond nanoneedle structure has a color center structure distributed on the surface layer of the diamond nanoneedle, thereby imparting excellent mechanical properties to the diamond nanoneedle structure of the present invention, and also having excellent performance. Fluorescence properties and electron spin coherence properties. Moreover, the color center structure is distributed in the shallow layer of the diamond nanoneedle, thereby making the color center structure uniform and imparting excellent fluorescence and sensing properties to the diamond nanoneedle structure of the present invention.
  • the above method for preparing a diamond nanoneedle structure is to prepare a shallow color center structure by sequentially growing a sandwich layer delta-grained diamond layer of a diamond layer/de lta-grain layer/diamond layer on a diamond nanoneedle surface layer, thereby realizing effective control of diamond
  • the generation and distribution of the color center structure in the surface layer ensures the intensity, stability and sensitivity of the color center structure fluorescence emission.
  • the prepared diamond nanoneedle structure not only has the mechanical properties of the diamond nanoneedle, but also has excellent fluorescence luminescent properties and electron spin coherence characteristics.
  • the steps of the preparation method of the invention can be effectively controlled, thereby ensuring the stable performance of the prepared diamond nanoneedle structure, high efficiency, and industrial production.
  • the diamond nanoneedle structure further has a color center structure distributed in the surface layer of the diamond nanoneedle, the diamond nanoneedle structure can not only penetrate the cell membrane to realize the transmission and detection of the intracellular substance, but also can realize Biomedical applications such as biosensing and bioimaging are more widely used, especially to detect the response of nerve cells to external stimuli and intracellular activities, and to promote the diagnosis, treatment and rehabilitation of neurological diseases. research Development.
  • DRAWINGS 1 is a schematic view showing a process flow of a method for preparing a diamond nanoneedle structure according to an embodiment of the present invention
  • 2 is a sandwich structure of a pure diamond layer/delta-dense layer/pure diamond layer sequentially grown on the surface of a diamond nanoneedle during the preparation of a diamond nanoneedle structure;
  • Figure 3 is an enlarged view of a portion shown in A of Figure 2;
  • FIG. 4 is a schematic view showing the structure of a diamond nanoneedle according to an embodiment of the present invention.
  • an embodiment of the present invention provides a diamond nanoneedle structure having a color center structure.
  • the diamond nanoneedle structure is as shown in Fig. 4, which comprises a diamond substrate layer 1 and a plurality of diamond nanoneedles 2 extending on the surface of the diamond substrate layer 1.
  • the diamond matrix layer 1 contained in the diamond nanoneedle structure has at least a bonded surface.
  • the diamond matrix layer 1 is an electron-grade purity diamond flake or a preferentially oriented polycrystalline diamond thick film.
  • the use of this type of diamond matrix layer can effectively ensure the formation of diamond nanoneedles 2, such as etching, avoiding the complicated processes of cutting, etching thinning, polishing, etc., and very limited size (usually 3). -5 mm) , which satisfies the need of etching diamond nanoneedle 2 for intracellular material transport and detection.
  • the diamond nanoneedle 2 obtained by the same method is a single crystal structure, and there are very few impurities and defects inside, which do not affect diamond. Fluorescence luminescence and spin coherence properties of the center of the color center contained in the surface layer of the nanoneedle 2.
  • the diamond nanoneedle 2 contained in the diamond nanoneedle structure extends from the surface of the diamond base layer, specifically, from the surface of the diamond base layer 1 and along a direction away from the surface of the diamond base layer 1, that is, That is, the diamond nanoneedle 2 is at an angle to the surface of the diamond substrate layer 1, and the angle of the angle may be a conventional range, such as 60 ° to 90 °, preferably 90 ° in the embodiment of the present invention. .
  • the diamond nanoneedles 2 are spaced apart on the surface of the diamond matrix layer 1, that is, the two adjacent diamond nanoneedles 2 are spaced apart from each other, as in an embodiment,
  • the diamond nanoneedles 2 constitute a diamond nanoneedle array.
  • the diamond nanoneedles 2 are distributed
  • the diamond substrate layer 1 has a density of 10 4 - 10 9 needles / cm 2 .
  • the diamond nanoneedle 2 has a diameter of 100-2000 nm and a height of 2-10 ⁇ m. In another embodiment, the diamond nanoneedle 2 has a aspect ratio of 10-70. Wherein, the diameter of the diamond nanoneedle 2 refers to the diameter of the trunk portion of the diamond nanoneedle 2.
  • the color center structure 3 is also distributed in the surface layer of the diamond nanoneedle 2, that is, the color center structure 3 is distributed in the shallow layer on the surface of the diamond nanoneedle 2.
  • the density of the core structure 3 in the surface layer of the diamond nanoneedle 2 is 1-5000 per needle, preferably 500-5000 per needle. Among them, when the color center structure 3 is concentrated on the tip end portion of the diamond nanoneedle 2, it may have a small amount of distribution.
  • the distance of the core structure 3 from the surface of the diamond nanoneedle 2 is less than or equal to 100 nm.
  • the distance should be understood as the distance from the geometric midpoint to a face, specifically the distance from the color center structure 3 to the surface of the diamond nanoneedle 2.
  • the color center structure 3 is a color center structure formed by at least one of N, Si, P, and B, specifically, such as an NV color center structure.
  • the diamond nanoneedle 2 contained in the diamond nanoneedle structure in each of the above embodiments has not only a high aspect ratio, but also less impurities and defects, high purity, and preferably a single crystal structure, and has excellent mechanical properties;
  • the color center structure 3 distributed in the shallow layer of the diamond nanoneedle 2 is uniform, and has excellent fluorescence luminescent properties and electron spin coherence characteristics.
  • embodiments of the present invention also provide a method of fabricating the diamond nanoneedle structure described above.
  • the process of preparing the diamond nanoneedle structure described above is as shown in FIG. 1, combined with the diamond nanoneedle structure shown in FIG. 2-4, and the preparation method thereof comprises the following steps:
  • Step S01 The diamond film layer is etched to form a diamond nanoneedle: etching the diamond film layer, etching to form a plurality of diamond nanoneedles 2;
  • Step S02. growing a delta-difficult layer on the surface of the diamond nanoneedle: sequentially growing a first pure diamond layer 31, a delta-difficult layer 32 and a second pure diamond layer 33 on the surface of the diamond nanoneedle 2;
  • Step S03 Electron beam irradiation and annealing treatment on the delta-difficult layer: the delta-miscible growth will be grown The diamond nanoneedles of the layer are subjected to electron beam irradiation treatment to produce vacancies required to form a color center, and then annealed in a protective atmosphere.
  • the diamond film layer is used for etching to form the diamond nanoneedles 2.
  • etching process should be such that the formed diamond nanoneedles 2 are spaced apart from each other, and the sides of the diamond nanoneedles 2 are perpendicular to the surface of the diamond substrate layer.
  • the method of etching to form the diamond nanoneedles 2 may be a conventional etching method.
  • the etching method uses an ECR-assisted microwave plasma etching or an ICP etching device to perform a nano-etching structure on the surface of the diamond film layer, wherein the etching gas may be but not only hydrogen gas. At least one of argon, oxygen, CF 4 , SF 6 , etc., and other common etching gases.
  • the reactive ion etching process is a process of physical etching and chemical etching, and needs to be balanced by the adjustment of the process conditions.
  • the lower pressure in the ECR plasma can obtain diamond nanometers with higher aspect ratio.
  • the needle when the addition of Ar gas and the enhancement of microwave power make the sidewalls more vertical. The nanodiamonds and defects at the grain boundaries are first etched away, resulting in a diamond nanoneedle 2.
  • the conditions of the ECR-assisted microwave plasma etching are:
  • Total gas flow rate 10-50 sccm, Ar gas 0-50 ⁇ 3 ⁇ 4, H 2 gas 50-100%, Air pressure: (5-8) xl0 3 mTorr, Microwave power: 700-1000 W, Substrate plus DC
  • the negative bias voltage is -190 ⁇ -230V, the etching time is 2-6 hours, and the magnetic field strength of the ECR area is 875 Gauss;
  • the conditions of the ECR-assisted microwave plasma etching are: the etching gas is hydrogen/argon gas, and the hydrogen/argon gas flow rate is: 11 sccm/9 sccm, total gas flow rate: 20 sccm; : (5-8)xl0 3 mTorr, microwave power: 700-1000W, substrate plus DC negative bias -190 ⁇ - 230V, 2-6 ⁇ between etched turns, 875 Gauss in ECR .
  • the ICP etching conditions are as follows:
  • the flow rate of the reaction gas is 5 to 200 sccm
  • the reaction Air pressure is 0.1 ⁇ 10Pa
  • the power supply of the ion body is 500 ⁇ 3000W
  • the RF power on the substrate stage is 50 ⁇ 300W
  • the etching time is 10 ⁇ 600 min.
  • the diamond nanoneedle 2 formed by etching has a higher aspect ratio, such as etching formed in the diamond nanoneedle structure as described above.
  • the diamond nanoneedle 2 is preferably such that the sidewall of the diamond nanoneedle 2 formed by etching is perpendicular to the surface of the diamond substrate layer 1.
  • molybdenum and molybdenum carbide particles are spontaneously formed on the surface of the diamond film layer due to the bombardment and sputtering of the surface of the molybdenum substrate on the surface of the etched diamond film layer. The mask of the eclipse.
  • the etched diamond film layer may be a conventional diamond film.
  • an electronic grade purity diamond flake or a preferential orientation polycrystalline diamond thick film is selected as an embodiment.
  • the etched diamond film layer avoids the complicated process of cutting, etching thinning, polishing, etc., and very limited size (usually 3-5 mm), which is used for CVD single crystal diamond, and is suitable for diamond nanoneedle 2
  • the need for intracellular material transport and detection, the diamond nanoneedle 2 obtained by the same method is a single crystal structure, the sidewall is smooth, and there are very few impurities and defects existing inside, which does not affect the fluorescence luminescence and spin coherence characteristics of the NV center.
  • the preferentially oriented polycrystalline diamond thick film may be prepared as follows: [0040] prepared by microwave plasma chemical vapor deposition (MPCVD) or hot filament chemical vapor deposition (HFCVD), film The bias assisted nucleation is first performed in the pre-growth stage. Taking HFCVD as an example, double-biased hot wire chemical vapor deposition is used. During nucleation, a positive bias is applied to the gate above the hot wire, and a negative bias is applied to the substrate. For microwave plasma CVD, a negative bias is applied to the substrate. During the nucleation process, the proportion of methane is slightly higher.
  • the bias power supply is turned off, and the methane concentration and other process parameters are adjusted to the conditions suitable for the growth of the preferred oriented diamond film.
  • the [001] oriented diamond film is first selectively grown such that the grown diamond seed has a higher ⁇ 001> orientation of the vertical substrate, and then the process parameters are adjusted such that ⁇ 001 ⁇ The surface is expanded to obtain a (001) preferred oriented diamond film.
  • the above preferred orientation polycrystalline diamond thick film preparation can be prepared by the method of the step S11 in the following Example 1.
  • step S02 when the surface of the diamond nanoneedle 2 formed by etching in the above step S01 is sequentially followed by the first pure diamond layer 31, the delta-dense layer 32 and the second pure diamond layer 33, then in the diamond nano
  • the sandwich structure of the pure corundum layer/delta-dense layer/pure diamond layer is grown on the surface of the needle 2, as shown in Figs. 2 and 3.
  • the first pure diamond layer 31 and the second pure diamond layer 33 may be grown by a method capable of growing pure diamond, and the method of growing the delta-difficult layer 32 may also adopt a method capable of growing a delta-discrete layer.
  • the first pure diamond layer 31, the delta-taste layer 32, and the second pure diamond layer 33 are formed by CVD deposition, specifically but not exclusively by microwave plasma chemical vapor deposition.
  • the condition of growing the first pure diamond layer 31 on the surface of the diamond nanoneedle 2 by using a microwave plasma chemical vapor deposition method and/or growing the second pure diamond layer 33 on the surface of the delta-taste layer 32 is :
  • the base vacuum is >10 - 6 Pa, and the substrate temperature is 600 to 900.
  • C total flow rate of diamond carbon source gas/hydrogen gas mixture: 200 ⁇ 2000 sccm, wherein the volume percentage of diamond carbon source gas is 0.01 ⁇ 0.5 ⁇ 3 ⁇ 4, hydrogen volume percentage is 99.5 99.9%, gas pressure: 20-40 Torr, microwave power: 500-1200W, 2-20 hours after deposition.
  • the conditions for growing the first pure diamond layer 31 and/or growing the second pure diamond layer 33 by microwave plasma chemical vapor deposition are:
  • the base vacuum is >10 - 6 Pa, and the substrate temperature is 800.
  • the diamond carbon source gas is methane, acetylene, acetone, ethanol At least one of them.
  • the methane is a 12 CH 4 isotope gas.
  • I2CH 4 using isotope gas can be effectively reduced spin 1/2 of I3C, and 12 C is zero spin, and therefore can not be detected 12 C nuclear magnetic resonance and the like.
  • the coherent diurnal and dephasing phases of the color center are very long.
  • the conditions for the delta-grain layer 32 on the surface of the first pure diamond layer 31 by microwave plasma chemical vapor deposition are:
  • the base vacuum is >10 - 6 Pa, and the substrate temperature is 600 to 900.
  • the volume percentage of the diamond carbon source gas is 0.01 to 0.5%
  • the volume percentage of the hydrogen is 80 to 9 9%
  • the mass ratio of the impurity element to the carbon element is 1 to 20 ⁇ 3 ⁇ 4 (1000-10000).
  • the conditions for the delta-discrete layer 32 by microwave plasma chemical vapor deposition are:
  • the substrate temperature is 800. C, diamond carbon source gas / hydrogen / miscellaneous element gas mixed gas total flow rate: 0.1 sccm / 390 sccm / 10 sccm, total gas flow: 400 sccm, gas pressure: 30 Torr, microwave power: 1200W.
  • the diamond carbon source gas is at least one of methane, acetylene, acetone, and ethanol.
  • methane is a 12 CH 4 isotope gas.
  • the miscellaneous element used in the method of growing the delta-taste layer 32 is at least one of N, Si, P, B.
  • N can be N 2 , specifically 15 N 2 .
  • the use of 15 N is sufficient to avoid the effects of nitrogen-vacancy defects inherent in the diamond nanoneedle 2.
  • Si may be provided as a gaseous compound of Si such as silane (SiH 4 ), trimethylsilane (TMS), tetraethyl orthosilicate, and the like.
  • P may be provided as a gaseous compound of P, such as phosphine (PH 3 ), trimethylphosphane (TMP), trimethyl phosphate, and the like.
  • B may be provided as a gaseous compound of B, such as diborane (B 2 H 6 ), trimethylborane (TMB), trimethyl borate, etc.
  • the first pure diamond layer 31, the delta-dummy layer 32, and the second pure diamond layer 33 are controlled by the conditions of growing the first pure diamond layer 31, the delta-taste layer 32, and the second pure diamond layer 33.
  • the growth rate is preferably a slow growth rate (as in the specific embodiment described above, a growth rate of about 10 nm/h), an epitaxial mass and thickness, and a delta-difficult layer 32. Therefore, it is ensured that the generated color center structure 3 is evenly distributed in the shallow layer of the diamond nanoneedle 2 after being processed by the above step S03.
  • the density and depth of the color center structure 3 can be controlled by controlling the density of the color center structure 3 in the shallow layer of the diamond nanoneedle 2.
  • each layer can be calibrated using a secondary ion mass spectrometer (SIMS), and the impurity concentration of the delta-taste layer 32 can be measured.
  • SIMS secondary ion mass spectrometer
  • step S03 the diamond nanoneedle 2 having the delta-taste layer grown on the surface in step S02 is subjected to electron beam irradiation treatment and annealing treatment, and then formed in the shallow layer of the diamond nanoneedle 2 surface layer. Colored core structure 3. Wherein, after the electron beam irradiation treatment, the vacancies required to form the color center structure 3 are generated in the delta-difficult layer. Annealing results in a color center structure 3 in the delta-taste layer.
  • step S03 the diamond nanoneedle 2 ⁇ having a delta-grain layer grown on the surface is treated by electron beam irradiation, and the condition of the electron beam irradiation treatment is: the irradiation energy is 2-4 MeV, The dose is (1-9) x 10 14 cm 2 ; as in the specific embodiment, the conditions of the electron beam irradiation treatment are: irradiation energy of 2 MeV and dose of 10 14 cm -2 .
  • the vacancies required to form the color center are generated by high-energy electron beam irradiation, thereby increasing the generation rate of the color center structure 3.
  • the annealing treatment has a temperature of 800. Above C, the daytime is 2-4 hours. As a specific example, the annealing treatment temperature is 850. C, the day is 2 hours. Under this condition, it is effective to ensure that the color center structure 3 is formed in the shallow layer of the diamond nanoneedle 2.
  • the protective atmosphere in the annealing treatment may be an argon protective atmosphere or a vacuum protective atmosphere to ensure the formation of the color center structure 3 in the annealing treatment.
  • step S03 further comprising the step of subjecting the annealed diamond nanoneedle to oxidation treatment in an acid solution. Since the surface termination has a great influence on the luminescence characteristics of the color center structure 3, the oxygen termination of the surface negative potential is obtained by the oxidation treatment, and the luminescence stability of the color center structure 3 is ensured. Further, the photodetection magnetic resonance spectrum can be used to measure the coherence between the coherent turns and the electric field of the color center structure 3 obtained by the above-described preparation method.
  • the oxidation treatment after the annealing treatment in the step S03 is performed by placing the annealed diamond nanoneedle in a mixed acid solution to be heated to 200. C, maintained for more than 30 minutes, wherein the mixed acid solution comprises a mixed acid of H 2 S0 4 , HN 0 3 and 1100 4 in a volume ratio of 1: (1-3): (1-3).
  • the mixed acid solution and the temperature and the oxidation treatment between the crucibles the oxygen terminal of the negative potential of the surface of the diamond nanoneedle 2 is effectively obtained, and the luminescent stability of the color center structure 3 is provided.
  • the above method for preparing a diamond nanoneedle structure sequentially grows gold in the surface layer of the diamond nanoneedle 2
  • the layered delta-tough diamond layer of the corrugated layer/delta-difficult layer/diamond layer is used to prepare the shallow color center structure 3, thereby effectively controlling the generation and distribution of the color center structure 3 in the diamond surface layer, thereby ensuring the color center structure 3
  • the intensity, stability and sensitivity of fluorescent light The prepared diamond nanoneedle structure not only has the mechanical properties of the diamond nanoneedle 2, but also has excellent fluorescence luminescence properties and electron spin coherence characteristics.
  • each step of the above preparation method can be effectively controlled, thereby ensuring stable performance of the prepared diamond nanoneedle structure, high efficiency, and industrial production.
  • embodiments of the present invention also provide an apparatus for delivering a substance to a cell.
  • the device can include conventionally necessary components, such as diamond nanoneedle structural components, that deliver the device to the cells.
  • the diamond nanoneedle structural member is the diamond nanoneedle structure of the embodiment of the present invention as shown in Fig. 4 described above or the diamond nanoneedle structure prepared by the above-described diamond nanoneedle structure preparation method.
  • the diamond nanoneedle 2 contained in the diamond nanoneedle structure described above has a high aspect ratio with few impurities and defects, and is preferably a single crystal structure so that the surface thereof is smooth, Excellent mechanical properties; at the same time, the color center structure 3 distributed in the shallow layer of the diamond nanoneedle 2 is uniform, and has excellent fluorescence luminescence properties and electron spin coherence characteristics. Therefore, the above-mentioned diamond nanoneedle structure has excellent fluorescence and sensing properties on the basis of excellent mechanical properties.
  • This embodiment provides a diamond nanoneedle structure and a preparation method thereof.
  • the structure of the diamond nanoneedle structure is as shown in FIG. 4, which comprises a diamond base layer 1 and a plurality of diamond nanoneedle 2 arrays extending on the surface of the diamond base layer 1, the adjacent diamond nanoneedles 2 are spaced apart from each other, and The side surface of the diamond nanoneedle 2 is perpendicular to the surface of the diamond base layer 1, and the color center structure 3 is also distributed in the surface layer of the diamond nanoneedle 1.
  • the preparation method of the diamond nanoneedle structure of this embodiment is as follows:
  • a 5-10 micron thick diamond film layer was prepared on a l-5 cmxl-5 cm, (001) silicon wafer by microwave plasma CVD. Before the growth, the silicon wafer was placed in a hydrofluoric acid solution for 2 minutes to remove the oxide layer on the surface, and then the silicon wafer was ultrasonically cleaned for 10 minutes in an acetone solution, ultrasonically cleaned in deionized water for 10 minutes, and ultrasonically cleaned in an alcohol solution.
  • the cleaned silicon substrate is placed on a molybdenum substrate and placed in a C VD device, evacuated to a temperature below 10 - 5 Pa; a residual oxide layer on the surface of the wafer with hydrogen plasma before film growth Wash again with other impurities: Air pressure: 30 Torr, Microwave power: 1200 W, Silicon substrate temperature: 800. C, 30 minutes in the daytime. Subsequently, the diamond film nucleation stage is started.
  • the specific parameters of the microwave plasma CVD are as follows: A hospital/hydrogen flow: 10 sccm/190 sccm, total gas flow: 200 sccm, air pressure: 16 Torr, microwave power: 800 W, silicon lining Bottom temperature: 800.
  • the microwave power source and the gas source are turned off, the substrate temperature is lowered to room temperature, the vacuum is evacuated to 10 5 Pa, and then the hydrogen is recharged to 7 mTorr, and the ECR microwave plasma mode is applied, and the electromagnetic is applied.
  • the magnetic field provided by the coil has an intensity of 875 Gauss in the ECR zone.
  • the specific parameters of reactive ion etching in the ECR-assisted microwave plasma are as follows: Hydrogen/argon flow: 11 sccm/9 sccm, total gas flow: 20 sccm, air pressure: 7xlO - 3 mTorr, microwave power: 800W, substrate plus DC negative bias -200V, 2 turns after etching; after biasing, turn off bias voltage, microwave power, electromagnetic coil power, turn off gas, get Single crystal diamond nanoneedle array 2;
  • the delta-disintegrating diamond layer is continuously grown in the microwave plasma CVD mode; firstly, a high-purity epitaxial diamond is grown on the surface of the diamond nanoneedle array 2.
  • Layer 31, 12 CH 4 isotope gas (purity 99.999%) is used in the growth process.
  • very slow growth conditions are used, and the growth rate is about 10 nm/h.
  • the specific process conditions are as follows: Basic vacuum >10 - 6 ? &, substrate temperature 800.
  • a hospital / hydrogen gas flow ratio 0.1 sccm/400 sccm, total gas flow 400 sccm, pressure 30 Torr, microwave power 1200 W, deposition of 5 ⁇ between turns; then growth of nitrogen miscellaneous layer 32 on the surface of high-purity epitaxial diamond layer 31, using 15N 2 isotope gas (Purity > 98%)
  • the process conditions for the cumbersome growth are: substrate temperature 800.
  • the diamond layer 33 is grown under the following conditions: substrate temperature 800.
  • the structure of the diamond layer 33 is as shown in Figures 2 and 3;
  • the diamond nanoneedle array 2 grown with the delta miscellaneous diamond layer in step S14 is irradiated by high energy electron beam to generate the vacancies required to form the NV color center 3, the irradiation energy is 2 MeV, and the dose is 10" cm -2 Subsequently, the NV color center is generated by high-temperature vacuum annealing, and the temperature of the vacuum annealing furnace is maintained at 850 ° C for two hours, and the diamond nanoneedle array is placed in a volume ratio of 1: 1: 1 H 2 SO 4 : HNO 3 : HC10 4 Heat in medium to boil to 200.
  • This embodiment provides a diamond nanoneedle structure and a preparation method thereof.
  • the structure of the diamond nanoneedle structure is as shown in FIG. 4, which comprises a diamond base layer 1 and a plurality of diamond nanoneedle 2 arrays extending on the surface of the diamond base layer 1, the adjacent diamond nanoneedles 2 are spaced apart from each other, and The side surface of the diamond nanoneedle 2 is perpendicular to the surface of the diamond base layer 1, and the color center structure 3 is also distributed in the surface layer of the diamond nanoneedle 1.
  • a 5-10 micron thick diamond film layer was prepared on a l-5 cmxl-5 cm, (001) silicon wafer by microwave plasma CVD. Before the growth, the silicon wafer was placed in a hydrofluoric acid solution for 2 minutes to remove the oxide layer on the surface, and then the silicon wafer was ultrasonically cleaned for 10 minutes in an acetone solution, ultrasonically cleaned in deionized water for 10 minutes, and ultrasonically cleaned in an alcohol solution.
  • the cleaned silicon substrate is placed on a molybdenum substrate and placed in a C VD device, evacuated to a temperature below 10 - 5 Pa; a residual oxide layer on the surface of the wafer with hydrogen plasma before film growth Wash again with other impurities: Air pressure: 30 Torr, Microwave power: 1200 W, Silicon substrate temperature : 800. C, 30 minutes in the daytime. Subsequently, the diamond film nucleation stage is started.
  • the specific parameters of the microwave plasma CVD are as follows: A hospital/hydrogen flow: 10 sccm/190 sccm, total gas flow: 200 sccm, air pressure: 16 Torr, microwave power: 800 W, silicon lining Bottom temperature: 800.
  • the microwave power source and the gas source are turned off, the substrate temperature is lowered to room temperature, the vacuum is evacuated to 10 5 Pa, and then the hydrogen is recharged to 7 mTorr, and the ECR microwave plasma mode is applied, and the electromagnetic is applied.
  • the magnetic field provided by the coil has an intensity of 875 Gauss in the ECR zone.
  • the specific parameters of reactive ion etching in the ECR-assisted microwave plasma are as follows: Hydrogen/argon flow: 11 sccm/9 sccm, total gas flow: 20 sccm, air pressure: 7xlO - 3 mTorr, microwave power: 800W, substrate plus DC negative bias -230V, etched dip is 4 hours; after the etching is completed, turn off the bias voltage, microwave power, electromagnetic coil power, turn off the gas, get Single crystal diamond nanoneedle array 2;
  • the delta-disintegrating diamond layer is continuously grown in the microwave plasma CVD mode; firstly, a high-purity epitaxial diamond is grown on the surface of the diamond nanoneedle array 2.
  • Layer 31, 12 CH 4 isotope gas (purity 99.999%) is used in the growth process.
  • very slow growth conditions are used, and the growth rate is about 10 nm/h.
  • the specific process conditions are as follows: Basic vacuum >10 -6 ? &, substrate temperature 800.
  • a hospital/hydrogen gas flow ratio 0.1 sccm/400 sccm, total gas flow 400 sccm, air pressure 30 Torr, microwave power 1200 W, deposition 10 ⁇ between turns; then growth of nitrogen on the surface of high-purity epitaxial diamond layer 31
  • the impurity layer 32, using i5N 2 isotope gas (purity > 98%), the process conditions for the cumbersome growth are: substrate temperature 800.
  • a hospital / hydrogen / nitrogen flow 0.1 sccm / 390 sccm / 10 sccm, total gas flow: 400 sccm, pressure: 30 Torr, microwave power: 1200W, deposition 0.5 ⁇ between the day; finally a high-purity epitaxy
  • the diamond layer 3 3 is grown under the following conditions: substrate temperature 800.
  • C A hospital/hydrogen gas flow ratio: 0.1 sccm/400 sccm, total gas flow 400 sccm, air pressure 30 Torr, microwave power 1200 W, 10 ⁇ between depositions; final growth diamond layer 31/nitrogen miscellaneous layer 32/
  • the structure of the diamond layer 33 is as shown in Figures 2 and 3; [0085] S14. Post-treatment to obtain a diamond N-center of the shallow NV center 3:
  • the diamond nanoneedle array 2 grown with the delta miscellaneous diamond layer in step S14 is subjected to high energy electron beam irradiation to generate the vacancies required to form the NV color center 3, the irradiation energy is 2 MeV, and the dose is 10" cm -2 Subsequently, the NV color center is generated by high-temperature vacuum annealing, and the temperature of the vacuum annealing furnace is maintained at 850 ° C for two hours, and the diamond nanoneedle array is placed in a volume ratio of 1:1:1 H 2 SO 4 :HNO 3 :HC10 4 Heat in medium to boil to 200.
  • This embodiment provides a diamond nanoneedle structure and a preparation method thereof.
  • the structure of the diamond nanoneedle structure is as shown in FIG. 4, which comprises a diamond base layer 1 and a plurality of diamond nanoneedle 2 arrays extending on the surface of the diamond base layer 1, the adjacent diamond nanoneedles 2 are spaced apart from each other, and The side surface of the diamond nanoneedle 2 is perpendicular to the surface of the diamond base layer 1, and the color center structure 3 is also distributed in the surface layer of the diamond nanoneedle 1.
  • a 5-10 micron thick diamond film layer was prepared on a l-5 C mxl-5 cm, (001) silicon wafer by microwave plasma CVD. Before the growth, the silicon wafer was placed in a hydrofluoric acid solution for 2 minutes to remove the oxide layer on the surface, and then the silicon wafer was ultrasonically cleaned for 10 minutes in an acetone solution, ultrasonically cleaned in deionized water for 10 minutes, and ultrasonically cleaned in an alcohol solution.
  • the cleaned silicon substrate is placed on a molybdenum substrate, placed in a C VD device, and evacuated to a temperature below 10 -5 p a ; residual oxidation of the silicon surface by hydrogen plasma before film growth
  • the layer and other impurities are washed again: Air pressure: 30 Torr, Microwave power: 1200 W, Silicon substrate temperature: 800. C, 30 minutes in the daytime. Subsequently, the diamond film nucleation stage is started.
  • the specific parameters of the microwave plasma CVD are as follows: A hospital/hydrogen flow: 10 sccm/190 sccm, total gas flow: 200 sccm, air pressure: 16 Torr, microwave power: 800 W, silicon lining Bottom temperature: 800.
  • the microwave power source and the gas source are turned off, and the substrate temperature is lowered to room temperature, and the vacuum is applied to 10 5 Pa, then recharge the hydrogen to 7 mTorr, the ECR microwave plasma mode is applied, and the magnetic field provided by the electromagnetic coil is 875 Gauss in the ECR region, and the specific parameters of the reactive ion etching in the ECR assisted microwave plasma are performed.
  • the delta-disintegrating diamond layer is continuously grown in the microwave plasma CVD mode; firstly, a high-purity epitaxial diamond is grown on the surface of the diamond nanoneedle array 2.
  • Layer 31, 12 CH 4 isotope gas (purity 99.999%) is used in the growth process.
  • very slow growth conditions are used, and the growth rate is about 10 nm/h.
  • the specific process conditions are as follows: Basic vacuum >10 -6 ? &, substrate temperature 800.
  • a hospital/hydrogen gas flow ratio 0.1 sccm/400 sccm, total gas flow 400 sccm, air pressure 30 Torr, microwave power 1200 W, deposition of 5 ⁇ between turns; then growth of nitrogen on the surface of high-purity epitaxial diamond layer 31
  • the impurity layer 32, using 15N 2 isotope gas (purity > 98%), the process conditions for the cumbersome growth are: substrate temperature 800.
  • a hospital / hydrogen / nitrogen flow 0.1 sccm / 300 sccm / 100 sccm, total gas flow: 400 sccm, pressure: 30 Torr, microwave power: 1200W, 1 hour after deposition; finally a high-purity epitaxy
  • the diamond layer 33 is grown under the following conditions: substrate temperature 800.
  • a hospital / hydrogen gas flow ratio 0.1 sccm / 400 sccm, total gas flow 400 sccm, pressure 30 Torr, microwave power 1200 W, deposition time 20 hours; final growth diamond layer 31 / nitrogen miscellaneous layer 32 /
  • the structure of the diamond layer 33 is as shown in Figures 2 and 3;
  • the diamond nanoneedle array 2 grown with the delta miscellaneous diamond layer in step S14 is subjected to high energy electron beam irradiation to generate the vacancies required to form the NV color center 3, the irradiation energy is 2 MeV, and the dose is 10" cm -2 Subsequently, the NV color center is generated by high-temperature vacuum annealing, and the temperature of the vacuum annealing furnace is maintained at 850 ° C for two hours, and the diamond nanoneedle array is placed in a volume ratio of 1: 1: 1 H 2 SO 4 : HNO 3 : HC10 4 Heat in medium to boil to 200.
  • Example 4 provides a diamond nanoneedle structure and a preparation method thereof.
  • the structure of the diamond nanoneedle structure is as shown in FIG. 4, which comprises a diamond base layer 1 and a plurality of diamond nanoneedle 2 arrays extending on the surface of the diamond base layer 1, the adjacent diamond nanoneedles 2 are spaced apart from each other, and The side surface of the diamond nanoneedle 2 is perpendicular to the surface of the diamond base layer 1, and the color center structure 3 is also distributed in the surface layer of the diamond nanoneedle 1.
  • a 5-10 micron thick diamond film layer was prepared on a l-5 cmxl-5 cm, (001) silicon wafer by microwave plasma CVD. Before the growth, the silicon wafer was placed in a hydrofluoric acid solution for 2 minutes to remove the oxide layer on the surface, and then the silicon wafer was ultrasonically cleaned for 10 minutes in an acetone solution, ultrasonically cleaned in deionized water for 10 minutes, and ultrasonically cleaned in an alcohol solution.
  • the cleaned silicon substrate is placed on a molybdenum substrate, placed in a C VD device, and evacuated to a temperature below 10 -5 p a ; residual oxidation of the silicon surface by hydrogen plasma before film growth
  • the layer and other impurities are washed again: Air pressure: 30 Torr, Microwave power: 1200 W, Silicon substrate temperature: 800. C, 30 minutes in the daytime. Subsequently, the diamond film nucleation stage is started.
  • the specific parameters of the microwave plasma CVD are as follows: A hospital/hydrogen flow: 10 sccm/190 sccm, total gas flow: 200 sccm, air pressure: 16 Torr, microwave power: 800 W, silicon lining Bottom temperature: 800.
  • the microwave power source and the gas source are turned off, the substrate temperature is lowered to room temperature, the vacuum is evacuated to 10 5 Pa, and then the hydrogen is recharged to 7 mTorr, and the ECR microwave plasma mode is applied, and the electromagnetic is applied.
  • the magnetic field provided by the coil has an intensity of 875 Gauss in the ECR zone.
  • the specific parameters of reactive ion etching in the ECR-assisted microwave plasma are as follows: Hydrogen/argon flow: 11 sccm/9 sccm, total gas flow: 20 sccm, air pressure: 7xlO - 3 mTorr, microwave power: 800W, substrate plus DC negative bias -230V, etched dip is 4 hours; after the etching is completed, turn off the bias voltage, microwave power, electromagnetic coil power, turn off the gas, get Single crystal diamond nanoneedle array 2;
  • a hospital / hydrogen gas flow ratio 1.5 sccm / 298 sccm, total gas flow 300 sccm, pressure 30 Torr, microwave power 1200 W, deposition time 10 minutes; then on the surface of high purity epitaxial diamond layer 31 nitrogen is miscellaneous Layer 32, using 15 N 2 isotope gas (purity > 98%), the process conditions for the cumbersome growth are: substrate temperature 800.
  • a hospital / hydrogen / nitrogen flow 1.5 sccm / 258 sccm / 40 sccm, total gas flow: 300 sccm, pressure: 30 Torr, microwave power: 1200W, deposition time between 2 minutes; finally high-purity epitaxial diamond Layer 33, grown under conditions of: substrate temperature 800.
  • C A hospital / hydrogen gas flow ratio: 1.5 sccm / 298 sccm, total gas flow 300 sccm, pressure 30 Torr, microwave power 1200 W, deposition time 10 minutes; final growth diamond layer 31 / nitrogen miscellaneous layer 32 / diamond
  • the structure of layer 33 is shown in Figures 2 and 3;
  • the diamond nanoneedle array 2 grown with the delta cryptic diamond layer in step S14 is irradiated by high energy electron beam to generate the vacancies required to form the NV color center 3, the irradiation energy is 2 MeV, and the dose is 10" cm -2 Subsequently, the NV color center is generated by high-temperature vacuum annealing, and the temperature of the vacuum annealing furnace is maintained at 850 ° C for two hours, and the diamond nanoneedle array is placed in a volume ratio of 1: 1: 1 H 2 SO 4 : HNO 3 : HC10 4 Heat in medium to boil to 200.
  • This embodiment provides a diamond nanoneedle structure and a preparation method thereof.
  • the structure of the diamond nanoneedle structure is as shown in FIG. 4, which comprises a diamond base layer 1 and a plurality of diamond nanoneedle 2 arrays extending on the surface of the diamond base layer 1, the adjacent diamond nanoneedles 2 are spaced apart from each other, and The side surface of the diamond nanoneedle 2 is perpendicular to the surface of the diamond base layer 1, and the color center structure 3 is also distributed in the surface layer of the diamond nanoneedle 1.
  • a 5-10 micron thick diamond film layer was prepared on a l-5 cmxl-5 cm, (001) silicon wafer by microwave plasma CVD. Before the growth, the silicon wafer was placed in a hydrofluoric acid solution for 2 minutes to remove the oxide layer on the surface.
  • the silicon wafer is ultrasonically cleaned in an acetone solution for 10 minutes, ultrasonically cleaned in deionized water for 10 minutes, and ultrasonically cleaned in an alcohol solution for 10 minutes; the cleaned silicon substrate is placed on a molybdenum substrate, and placed on In the C VD device, evacuate to 10 -5 p a or less; before the film growth, the residual oxide layer and other impurities on the surface of the silicon wafer are cleaned again with hydrogen plasma: gas pressure: 30 Torr, microwave power: 1200 W, silicon substrate Temperature: 800. C, 30 minutes in the daytime. Subsequently, the diamond film nucleation stage is started.
  • the specific parameters of the microwave plasma CVD are as follows: A hospital/hydrogen flow: 10 sccm/190 sccm, total gas flow: 200 sccm, air pressure: 16 Torr, microwave power: 800 W, silicon lining Bottom temperature: 800. C, substrate negative bias: -150 V, nucleation: 12 minutes.
  • the specific parameters for (001) preferred orientation diamond film growth in microwave plasma CVD are: A hospital / hydrogen flow: 1.5 sccm / 298 sccm, total gas flow: 300 sccm, gas pressure: 30 Torr, microwave power: 1200 W, silicon lining Bottom temperature: 850. C, deposition day: 20 hours;
  • the microwave power source and the gas source are turned off, the substrate temperature is lowered to room temperature, the vacuum is evacuated to 10 5 Pa, and then the hydrogen is recharged to 7 mTorr, and the ECR microwave plasma mode is applied, and the electromagnetic is applied.
  • the magnetic field provided by the coil has an intensity of 875 Gauss in the ECR zone.
  • the specific parameters of reactive ion etching in the ECR-assisted microwave plasma are as follows: Hydrogen/argon flow: 11 sccm/9 sccm, total gas flow: 20 sccm, air pressure: 7xlO - 3 mTorr, microwave power: 800W, substrate plus DC negative bias -230V, etched dip is 4 hours; after the etching is completed, turn off the bias voltage, microwave power, electromagnetic coil power, turn off the gas, get Single crystal diamond nanoneedle array 2;
  • the delta-disintegrating diamond layer is continuously grown in the microwave plasma CVD mode; firstly, a high-purity epitaxial diamond is grown on the surface of the diamond nanoneedle array 2.
  • Layer 31, 12 CH 4 isotope gas (purity 99.999%) is used in the growth process.
  • very slow growth conditions are used, and the growth rate is about 10 nm/h.
  • the specific process conditions are as follows: Basic vacuum >10 -6 ? &, substrate temperature 800.
  • a hospital/hydrogen gas flow ratio 0.1 sccm/400 sccm, total gas flow 400 sccm, air pressure 30 Torr, microwave power 1200 W, deposition of 5 ⁇ between turns; then growth of silicon on the surface of high-purity epitaxial diamond layer 31
  • the impurity layer 32 is a 29 Si H 4 isotope gas (purity > 98%), and the silane gas used here is a silicon gas/hydrogen mixed dilution gas in which the concentration of the silane is 1%.
  • the process conditions for the cumbersome growth are: substrate temperature 800.
  • the structure of the diamond layer 33 is as shown in Figures 2 and 3;
  • the diamond nanoneedle array 2 grown with the delta cryptic diamond layer in step S14 is irradiated by high energy electron beam to generate the vacancies required to form the SiV color center 3, the irradiation energy is 2 MeV, and the dose is 10 14 cm -2
  • the SiV color center is then produced by high temperature vacuum annealing, and the vacuum annealing furnace temperature is maintained at 850. C two small crucibles, the diamond nanoneedle array was placed in a volume ratio of 1: 1: 1 H 2 SO 4 : HNO 3 : HC10 4 was heated and boiled to 200.
  • This embodiment provides a diamond nanoneedle structure and a preparation method thereof.
  • the structure of the diamond nanoneedle structure is as shown in FIG. 4, which comprises a diamond base layer 1 and a plurality of diamond nanoneedle 2 arrays extending on the surface of the diamond base layer 1, the adjacent diamond nanoneedles 2 are spaced apart from each other, and The side surface of the diamond nanoneedle 2 is perpendicular to the surface of the diamond base layer 1, and the color center structure 3 is also distributed in the surface layer of the diamond nanoneedle 1.
  • a 5-10 micron thick diamond film layer was prepared on a l-5 cmxl-5 cm, (001) silicon wafer by microwave plasma CVD. Before the growth, the silicon wafer was placed in a hydrofluoric acid solution for 2 minutes to remove the oxide layer on the surface, and then the silicon wafer was ultrasonically cleaned for 10 minutes in an acetone solution, ultrasonically cleaned in deionized water for 10 minutes, and ultrasonically cleaned in an alcohol solution.
  • the cleaned silicon substrate is placed on a molybdenum substrate, placed in a C VD device, and evacuated to a temperature below 10 -5 p a ; residual oxidation of the silicon surface by hydrogen plasma before film growth
  • the layer and other impurities are washed again: Air pressure: 30 Torr, Microwave power: 1200 W, Silicon substrate temperature: 800. C, 30 minutes in the daytime. Subsequently, the diamond film nucleation stage is started.
  • the specific parameters of the microwave plasma CVD are as follows: A hospital/hydrogen flow: 10 sccm/190 sccm, total gas flow: 200 sccm, air pressure: 16 Torr, microwave power: 800 W, silicon lining Bottom temperature: 800.
  • the microwave power source and the gas source are turned off, the substrate temperature is lowered to room temperature, the vacuum is evacuated to 10 5 Pa, and then the hydrogen is recharged to 7 mTorr, and the ECR microwave plasma mode is applied, and the electromagnetic is applied.
  • the magnetic field provided by the coil has an intensity of 875 Gauss in the ECR zone.
  • the specific parameters of the reactive ion etching in the ECR-assisted microwave plasma are as follows: Hydrogen/argon flow: 1 1 sccm/9 sccm, total gas flow: 20 sccm, air pressure : 7x lO - 3 mTorr, microwave power: 800W, substrate plus DC negative bias -230V, 4 turns after etching; after biasing, turn off bias voltage, microwave power, electromagnetic coil power, turn off gas , obtaining a single crystal diamond nanoneedle array 2;
  • the delta-disintegrating diamond layer is continuously grown in the microwave plasma CVD mode; firstly, a high-purity epitaxial diamond is grown on the surface of the diamond nanoneedle array 2.
  • Layer 31, 12 CH 4 isotope gas (purity 99.999%) is used in the growth process.
  • very slow growth conditions are used, and the growth rate is about 10 nm/h.
  • the specific process conditions are as follows: Basic vacuum > 10 -6 ? &, substrate temperature 800.
  • a hospital/hydrogen gas flow ratio 0.2 sccm/400 sccm, total gas flow 400 sccm, air pressure 30 Torr, microwave power 1200 W, deposition of 5 ⁇ between turns; then growth of nitrogen on the surface of high-purity epitaxial diamond layer 31
  • the impurity layer 32 is made of i iB isotope trimethylborane gas (purity >98%), and the trimethylborane gas used here is a dilution gas of trimethylboron/hydrogen mixed gas, wherein trimethylborane The concentration is 0.1%.
  • the process conditions for the cumbersome growth are: substrate temperature 800.
  • a hospital / hydrogen / trimethylborane flow 0.1 sccm / 390 sccm / 10 sccm, total gas flow: 400 sccm, pressure: 30 Torr, microwave power: 1200W, 1 hour after deposition; finally
  • the high-purity epitaxial diamond layer 33 is grown under the conditions of a substrate temperature of 800.
  • a hospital / hydrogen gas flow ratio 0.2 sccm / 400 sccm, total gas flow 400 sccm, pressure 30 Torr, microwave power 1200 W, 10 ⁇ between depositions; final growth diamond layer 31 / boron miscellaneous layer 32 /
  • the structure of the diamond layer 33 is as shown in Figures 2 and 3;
  • This embodiment provides a diamond nanoneedle structure and a preparation method thereof.
  • the structure of the diamond nanoneedle structure is as shown in FIG. 4, which comprises a diamond base layer 1 and a plurality of diamond nanoneedle 2 arrays extending on the surface of the diamond base layer 1, the adjacent diamond nanoneedles 2 are spaced apart from each other, and The side surface of the diamond nanoneedle 2 is perpendicular to the surface of the diamond base layer 1, and the color center structure 3 is also distributed in the surface layer of the diamond nanoneedle 1.
  • a 5-10 micron thick diamond film layer was prepared on a l-5 cmxl-5 cm, (001) silicon wafer by microwave plasma CVD. Before the growth, the silicon wafer was placed in a hydrofluoric acid solution for 2 minutes to remove the oxide layer on the surface, and then the silicon wafer was ultrasonically cleaned for 10 minutes in an acetone solution, ultrasonically cleaned in deionized water for 10 minutes, and ultrasonically cleaned in an alcohol solution.
  • the cleaned silicon substrate is placed on a molybdenum substrate, placed in a C VD device, and evacuated to a temperature below 10 -5 p a ; residual oxidation of the silicon surface by hydrogen plasma before film growth
  • the layer and other impurities are washed again: Air pressure: 30 Torr, Microwave power: 1200 W, Silicon substrate temperature: 800. C, 30 minutes in the daytime. Subsequently, the diamond film nucleation stage is started.
  • the specific parameters of the microwave plasma CVD are as follows: A hospital/hydrogen flow: 10 sccm/190 sccm, total gas flow: 200 sccm, air pressure: 16 Torr, microwave power: 800 W, silicon lining Bottom temperature: 800.
  • the microwave power source and the gas source are turned off, the substrate temperature is lowered to room temperature, the vacuum is evacuated to 10 5 Pa, and then the hydrogen is recharged to 7 mTorr, and the ECR microwave plasma mode is applied, and the electromagnetic is applied.
  • Coil The intensity of the magnetic field provided in the ECR zone is 875 Gauss.
  • the specific parameters of the reactive ion etching in the ECR assisted microwave plasma are as follows: Hydrogen/argon flow: 11 sccm/9 sccm, Total gas flow: 20 sccm, Air pressure: 7xlO - 3 mTorr, microwave power: 800W, substrate with DC negative bias -230V, etched for 4 hours; after switching, turn off bias, microwave power, solenoid power, shut off gas, get single Crystal diamond nanoneedle array 2;
  • the delta-disintegrating diamond layer is continuously grown in the microwave plasma CVD mode; first, a high-purity epitaxial diamond is grown on the surface of the diamond nanoneedle array 2.
  • Layer 31, 12 CH 4 isotope gas (purity 99.999%) is used in the growth process.
  • very slow growth conditions are used, and the growth rate is about 10 nm/h.
  • the specific process conditions are as follows: Basic vacuum >10 -6 ? &, substrate temperature 800.
  • a hospital/hydrogen gas flow ratio 0.1 sccm/400 sccm, total gas flow 400 sccm, air pressure 30 Torr, microwave power 1200 W, 10 ⁇ between depositions; then phosphorus growth on the surface of high-purity epitaxial diamond layer 31
  • the impurity layer 32 is made of 13 ⁇ 4 4 isotope gas (purity >98%), and the silane gas used here is a phosphorus gas/hydrogen mixed dilution gas in which the concentration of phosphane is 1%.
  • the process conditions for the cumbersome growth are: substrate temperature 800.
  • a hospital / hydrogen / phosphine flow 0.1 sccm / 390 sccm / 10 sccm, total gas flow: 400 sccm, pressure: 30 Torr, microwave power: 1200W, 1 hour after deposition; finally high purity
  • the epitaxial diamond layer 33 is grown under the following conditions: substrate temperature 800.
  • a hospital/hydrogen gas flow ratio 0.1 sccm/400 sccm, total gas flow 400 sccm, air pressure 30 Torr, microwave power 1200 W, 10 ⁇ between depositions; final growth diamond layer 31/phosphorus miscellaneous layer 32/
  • the structure of the diamond layer 33 is as shown in Figures 2 and 3;
  • the diamond nanoneedle array 2 grown with the delta cryptic diamond layer in step S14 is subjected to high energy electron beam irradiation to generate the vacancies required to form the PV color center 3, the irradiation energy is 2 MeV, and the dose is 10" cm -2 Subsequently, the PV color center is generated by high-temperature vacuum annealing, and the temperature of the vacuum annealing furnace is maintained at 850 ° C for two hours, and the diamond nanoneedle array is placed in a volume ratio of 1: 1: 1 H 2 SO 4 : HNO 3 : HC10 4 Heat in medium to boil to 200.
  • the diamond nanoneedle structure provided by the embodiment of the present invention has a high aspect ratio, excellent fluorescence luminescence property and electron spin coherence property, and can be used for the device for delivering substances to cells in the embodiment of the present invention.
  • the cell membrane to achieve the transmission and detection of substances in the cell, it can also provide a guarantee for a wide range of applications in biomedical fields such as biosensing and bioimaging.

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Abstract

La présente invention concerne une structure d'aiguille de diamant à l'échelle nanométrique qui comprend une couche de base de diamant (1) et une pluralité d'aiguilles de diamant à l'échelle nanométrique (2) s'étendant sur une surface de la couche de base de diamant (1), des aiguilles de diamant à l'échelle nanométrique adjacentes (2) étant espacées les unes des autres, et une structure de noyau coloré (3) étant en outre répartie dans la couche de surface d'aiguille de diamant à l'échelle nanométrique. La présente invention porte également sur un procédé de préparation de la structure d'aiguille de diamant à l'échelle nanométrique et sur une application de la structure de nano-aiguille pour préparer un dispositif pour distribuer un matériau dans des cellules.
PCT/CN2017/107649 2017-10-25 2017-10-25 Structure d'aiguille de diamant à l'échelle nanométrique, son procédé de préparation et son application Ceased WO2019080001A1 (fr)

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Cited By (2)

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CN117587381A (zh) * 2023-10-18 2024-02-23 吉林大学 一种纳米草金刚石膜的制备方法及作为高灵敏度电化学电极应用
CN120485724A (zh) * 2025-05-30 2025-08-15 南通威斯派尔半导体技术有限公司 一种基于真空溅射的铜表面纳米化界面制备方法

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